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EP1409625B1 - Dishwashing machine detergents containing surfactants with specific diffusion co-efficients - Google Patents

Dishwashing machine detergents containing surfactants with specific diffusion co-efficients Download PDF

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Publication number
EP1409625B1
EP1409625B1 EP02762357A EP02762357A EP1409625B1 EP 1409625 B1 EP1409625 B1 EP 1409625B1 EP 02762357 A EP02762357 A EP 02762357A EP 02762357 A EP02762357 A EP 02762357A EP 1409625 B1 EP1409625 B1 EP 1409625B1
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EP
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Prior art keywords
acid
weight
preferred
machine dishwashing
surfactants
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EP02762357A
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German (de)
French (fr)
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EP1409625A1 (en
Inventor
Arnd Kessler
Christian Nitsch
Rolf Bayersdörfer
Wolfgang Wick
Sven Müller
Peter Schmiedel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic

Definitions

  • the present invention relates to automatic dishwashing detergents and methods of using these agents.
  • the invention relates to automatic dishwashing detergents which contain nonionic surfactants which have particularly low viscosities in aqueous solution.
  • Machine dishwashing in home dishwashers is a process that is radically different from washing clothes in home washing machines. While in a washing machine the material to be cleaned is permanently moved in the liquor and in this way the cleaning is mechanically assisted, in a dishwasher the rinsing liquor is applied to the surfaces to be cleaned by a spray system. There, the cleaning liquor must automatically counteract even stubborn dirt, without any support by mechanical influences occurs. The level of performance of automatic dishwashing detergents must therefore be incomparably higher than that of conventional laundry detergents.
  • the agents to be provided should be superior to conventional agents even in comparison to lower doses, especially on greasy soils.
  • the funds should be used both as a conventional machine dishwashing detergent ("cleaner") in Powder or granule form or as a tablet or pourable offer form, as well as a combination product ("2in1" products which combine cleaners and rinse aid in combination and "3in1" products which combine cleaners, rinse aid and salt substitute) ,
  • automatic dishwashing detergents which satisfy the abovementioned requirement profile can be provided if they contain builders and certain nonionic surfactants and optionally further ingredients of detergents.
  • the present invention relates to automatic dishwashing compositions containing builder (s), surfactant (s) and optionally further ingredients, characterized in that they contain 0.1 to 50 wt .-% of one or more nonionic surfactants of the general formula I.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another represent integers from 1 to 6 which contain surfactants at a concentration of 0, 01 g / l in distilled water have a diffusion coefficient of at least 9 - 10 -11 m 2 s -1 .
  • Another object of the present invention is a machine dishwashing process in which a dishwashing detergent according to the invention is used.
  • the diffusion coefficient can be calculated according to the theory of Fainerman et al. (Colloids and Surfaces A, 90 (1994) 213-224 ) from the measurement of the dynamic surface tension.
  • the higher diffusion coefficients of the surfactant at high concentrations causes a significantly improved flow behavior of the overall formulation of surfaces treated with the cleaning agents.
  • the surfactants used according to the invention wet the surfaces quickly and, above all, uniformly, so that the film of the rinse solution runs off uniformly on the dishes and does not break open prematurely. In this way, stain and schlierenlose surfaces and thus improved rinse results are obtained.
  • the surfactant has even higher diffusion coefficients in a highly concentrated aqueous solution.
  • erfundgsfelde agents are preferred in which the / the nonionic (s) surfactant (s) at a concentration of 0.01 g / l in distilled water has a diffusion coefficient of at least 9.5 ⁇ 10 -11 m 2 s -1 , preferably of at least 1 ⁇ 10 -10 m 2 s -1 and in particular of at least 2.5 ⁇ 10 -10 m 2 s -1 .
  • Particularly preferred machine dishwasher detergents according to the invention contain one or more nonionic surfactant (s) which, at a concentration of 0.01 g / l in distilled water, have a diffusion coefficient of at least 5 ⁇ 10 -10 m 2 s -1 , preferably of at least 1 ⁇ 10 -9 m 2 s -1 and in particular of at least 5 ⁇ 10 -9 m 2 s -1 .
  • nonionic surfactant s
  • the diffusion coefficient of the present invention contained in the surfactants in aqueous solutions it may be advantageous for certain formulations when the surfactants are liquid at room temperature. This has, in addition to the easier processability with powdered or granular agents, the additional advantage that the surfactants do not have to be melted during processing, whereby the manufacturing costs can be further reduced.
  • Nonionic surfactants which have a diffusion coefficient of at least 9 ° 10 -11 m 2 s -1 at a concentration of 0.01 g / l in distilled water can have a molecular structure of different composition. Depending on the type and length of the hydrophobic and the hydrophilic radical in the molecule, the properties of the surfactants can be controlled so that desired properties are present.
  • nonionic surfactants having the properties described above are used in the inventive compositions in amounts of 0.1 to 50 wt .-%, each based on the total agent.
  • Preferred automatic dishwashing agents according to the invention contain the nonionic surfactant (s) in amounts of from 0.5 to 40% by weight, preferably from 1 to 30 Wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
  • Nonionic surfactants used in the context of the present invention are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units, one to ten EO or AO groups being bonded to one another before one block is followed by the other groups.
  • Automatic dishwashing agents according to the invention contain nonionic surfactant (s) surfactants of the general formula I.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
  • the nonionic surfactants of formula I can be prepared by known methods from the corresponding alcohols R 1 -OH and Ethlyne- or alkylene oxide.
  • the radical R 1 in the formula I above may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals.
  • R 1 in formula 1 is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from - CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable.
  • Preferred automatic dishwashing detergents are CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable.
  • Preferred automatic dishwashing agents are characterized in that R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.
  • nonionic surfactants which have a C 9-15 -alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • These surfactants have the required high diffusion coefficients in aqueous solution and can be used according to the invention with particular preference.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • nonionic surfactants contained in the agents according to the invention with respect to the radical R. 1 , the rests R 2 and R 3 and the indices w, x, y and z characterized.
  • Preferred agents according to the invention comprise one or more surfactants from the table below or mixtures of these.
  • the agents according to the invention may contain further surfactants from the groups containing nonionic, anionic, cationic or amphoteric surfactants.
  • additional nonionic surfactants it is preferred to use alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula (II)
  • RCO is an aliphatic acyl group having 6 to 22 carbon atoms
  • R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (III)
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the automatic dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above room temperature.
  • preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and more preferably between 26.6 and 43.3 ° C.
  • Suitable nonionic surfactants which have melting or softening points in the stated temperature range are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • ethoxylated nonionic surfactant consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols additionally having polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants are included.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • a further preferred rinse aid according to the invention contains nonionic surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ],
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2
  • R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5 stand. If the value x ⁇ 2, each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • rinse aids are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2
  • x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18, are particularly preferred.
  • Anionic, cationic and / or amphoteric surfactants may also be used in conjunction with the surfactants mentioned, these having only minor importance because of their foaming behavior in dishwasher detergents and usually only in amounts below 10% by weight, in most cases even below 5% by weight .%, For example, from 0.01 to 2.5 wt .-%, each based on the agent used.
  • the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which is a synthetic, on contain petrochemical base produced straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products of the Shell Oil Company under the name DAN ® , are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the agents according to the invention contain one or more builders.
  • Builders are used in the compositions of the invention especially for binding calcium and magnesium.
  • Common builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates.
  • Trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders from the class of alkali disilicates are preferably used for the cleaning agents according to the invention.
  • the potassium salts are preferable to the sodium salts because they often have a higher water solubility.
  • Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.
  • Particularly preferred automatic dishwashing agents contain as builders phosphates, preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate potassium phosphate primary or monobasic potassium phosphate, KDP
  • KH 2 PO 4 is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of Density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the detergent industry compared to corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.
  • alkali carriers may be present.
  • Suitable alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, preference being given for the purposes of this invention to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • compositions according to the invention may contain the builder (s), depending on the intended use, in different amounts.
  • automatic dishwashing agents according to the invention are preferred which contain the builder (s) in amounts of from 5 to 90% by weight, preferably from 7.5 to 85% by weight and in particular from 10 to 80% by weight, in each case on the entire remedy, included.
  • automatic dishwashing detergents In addition to builders, bleaches, bleach activators, enzymes, silver protectants, dyes and fragrances, etc., are preferred ingredients of automatic dishwashing detergents. In addition, further ingredients may be present, automatic dishwashing agents according to the invention being preferred which additionally contain one or more substances from the group of acidifying agents, chelating agents or coating-inhibiting polymers.
  • Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients.
  • the solid mono-, oligo-and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid.
  • the anhydrides of these acids can be used as Acidisersstoff, in particular maleic anhydride and succinic anhydride are commercially available.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • a commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.
  • Common and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • complex-forming polymers ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms generally with the formation of chelate complexes, can be used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals.
  • Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
  • polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA are preferred.
  • these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts.
  • alkali metal, ammonium or alkylammonium salts, in particular sodium salts are preferred.
  • Scale-inhibiting polymers can likewise be present in the agents according to the invention. These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.
  • Scale-inhibiting polymers may also have co-builder properties.
  • organic cobuilders it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the dishwasher detergents according to the invention. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, this group may in turn, the short-chain polyacrylates, the molar masses of 1000 to 10,000 g / mol, and particularly preferably from 1000 to 4000 g / mol, have to be preferred.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention.
  • the sulfonic acid group-containing copolymers are described in detail below.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives .
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • EDTMP hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • Builder is used from the class of phosphonates preferably HEDP.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the agents according to the invention may contain further customary ingredients of cleaning agents, in particular bleaching agents, bleach activators, enzymes, silver protectants, dyes and fragrances being of importance. These substances will be described below.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diper
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the machine dishwashing detergents according to the invention.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • Preferred automatic dishwashing agents according to the invention additionally contain bleaching agents in amounts of from 1 to 40% by weight, preferably from 2.5 to 30% by weight and in particular from 5 to 20% by weight, in each case based on the total composition.
  • bleach activators which aid in the action of the bleaches have already been mentioned above as a possible ingredient of the rinse aid particles.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes.
  • Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
  • bleach catalysts can also be incorporated into the rinse aid particles.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Bleach activators from the group of the polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOS
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.
  • Suitable enzymes in the detergents according to the invention are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants.
  • the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous,
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or For example, enzyme granules may be about 0.1 to 5 weight percent, preferably 0.5 to about 4.5 weight percent.
  • preferred automatic dishwashing detergents according to the invention are those which additionally comprise enzyme (s) in amounts of from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight and in particular from 0.5 to 6% by weight, in each case based on the total agent included.
  • Dyes and fragrances can be added to the machine dishwasher detergents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to performance.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals having 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionones, ⁇ -isomethylionone and methylcedryl ketone, among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the fragrances can be incorporated directly into the detergents according to the invention, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and provide a slower fragrance release for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • compositions made according to the invention may (or parts thereof) be colored with suitable dyes.
  • suitable dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.
  • the detergents according to the invention may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, active chlorine-containing agents are frequently found in cleaner formulations, which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. In order to obtain crystal-clear and spotless dishes, one uses therefore successfully today rinse aid.
  • the addition of rinse aid at the end of the washing program ensures that the water runs as completely as possible from the items to be washed, so that the different surfaces at the end of the washing program are residue-free and flawless gloss.
  • the automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses.
  • the pre-rinse cycle for heavily soiled dishes can be switched on, but only in Exceptionally chosen by the consumer, so that in most machines, a main rinse, an intermediate rinse with pure water and a rinse cycle are performed.
  • the temperature of the main wash cycle varies between 40 and 65 ° C, depending on the machine type and program level selection.
  • rinse aids are added from a dosing tank in the machine, which usually contain nonionic surfactants as the main constituent. Such rinse aids are in liquid form and are widely described in the art. Your task is primarily to prevent limescale and deposits on the dishes.
  • compositions according to the invention can be formulated as "normal" cleaners, which are used together with commercially available supplements (rinse aid, regenerating salt).
  • rinse aid regenerating salt
  • These so-called “2in1" products lead to a simplification of handling and relieve the consumer of the burden of additional dosage of two different products (cleaner and rinse aid).
  • the invention is characterized by an improved "cleanability" of the treated substrates in subsequent cleaning operations and by a significant reduction in the drying time compared to comparable agents without the use of sulfonic acid-containing polymers.
  • Drying time in the context of the teaching according to the invention is generally understood to mean the meaning of the word, ie the time that elapses until a dish surface treated in a dishwasher has dried, but in particular the time that elapses, up to 90% with a cleaning or Rinse aid is dried in concentrated or diluted form treated surface.
  • R 1 (R 2 ) C C (R 3 ) COOH (VII)
  • R 1 to R 3 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • R 5 (R 6 ) C C (R 7 ) -X-SO 3 H (VIII)
  • H 2 C CH-X-SO 3 H (VIIIa)
  • H 2 C C (CH 3 ) -X-SO 3 H (VIIIb)
  • HO 3 SX- (R 6 ) C C (R 7 ) -X-SO 3 H (VIIIc)
  • R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2
  • Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the content of the polymers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the Polymer.
  • Particularly preferred polymers to be used consist only of monomers of groups i) and ii).
  • copolymers according to the invention in the compositions may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii ) can be combined.
  • Particularly preferred polymers have certain structural units, which are described below.
  • These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the agents according to the invention is also preferred and characterized in that the agents contain one or more copolymers, the structural units of the formula X.
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • machine dishwashing detergents which comprise one or more copolymers as ingredient b), the structural units of the formulas IX and / or X and / or XI and / or XII and / or XIII and / or XIV - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (IX), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (X), - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XI), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XI), - [CH 2 -
  • the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions.
  • metal ions preferably alkali metal ions and especially sodium ions.
  • the monomer distribution of the copolymers used in the agents according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight. % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molecular weight of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the content of one or more copolymers in the compositions according to the invention can vary depending on the intended use and the desired product performance, preference being given to preferred automatic dishwashing compositions according to the invention in that they contain the copolymer (s) in amounts of from 0.25 to 50% by weight. %, preferably from 0.5 to 35 wt .-%, particularly preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.
  • polyacrylates As already mentioned above, in the agents according to the invention it is particularly preferable to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers.
  • the polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons.
  • Such polyacrylates are commercially available under the trade name Sokalan ® PA15 and Sokalan ® PA25 (BASF).
  • a mixture of surfactants 575 and 673 from the table in the specification text was prepared by ethoxylating an unbranched and saturated C 11 alcohol in the presence of KOH as a catalyst in an autoclave at 150 ° C with ethylene oxide. After the ethylene oxide had reacted, propylene oxide was fed to the autoclave and, after the reaction, the procedure was repeated with ethylene oxide followed by propylene oxide.
  • the resulting surfactant mixture can be defined by the formula CH 3 (CH 2 ) 10 -O- (CH 2 -CH 2 -O) 3 - (CH 2 -CH (CH 3 ) -O) 3 - (CH 2 -CH 2 -O) 2 - (CH 2 - CH (CH3) -O) 1.5 -H describe.
  • the surfactant mixture has a diffusion coefficient of 9.1 ⁇ 10 -11 m 2 s -1 at a concentration of 0.01 g / l in distilled water.
  • a plaque test is carried out in a 65 ° C. universal cleaning program in a Miele dishwasher which has been converted to continuous operation.
  • the program was carried out without commercially available rinse aid (storage tank of the dishwasher emptied) and with up to 21 ° d hardened water (bypassing the ion exchanger).
  • the evaluation of the covering test is made by visual inspection of the objects in a box whose walls are lined with black velvet, giving the marks 0-6. Higher values indicate less porous surfaces.
  • compositions E2 and V2 were used in a universal cleaning program.
  • the program was carried out without commercially available rinse aid (storage tank of the dishwasher emptied) and with up to 21 ° d hardened water (bypassing the ion exchanger).
  • Dishwasher Miele G575 Detergent: 24.9 g dosed in the main rinse cycle Water hardness: 21 ° dH Program: Universal 55 ° C Cycles: 3 Dirt load: 50g minced meat
  • formulation E2 is in part significantly superior to formulation V2 in filming and is at least equivalent to spotting.

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Abstract

Machine dishwashing detergents which contain builder(s), surfactant(s), and optionally further ingredients, which comprise 0.1 to 50% by weight of one or more nonionic surfactants which, at a concentration of 0.01 g/l in distilled water, have a diffusion coefficient of at least 9.10<SUP>-11</SUP>m<SUP>2</SUP>s<SUP>-1</SUP>.

Description

Die vorliegende Erfindung betrifft maschinelle Geschirrspülmittel und Methoden zur Anwendung dieser Mittel. Im Speziellen betrifft die Erfindung maschinelle Geschirrspülmittel, welche nichtionische Tenside enthalten, die in wäßriger Lösung besonders niedrige Viskositäten aufweisen.The present invention relates to automatic dishwashing detergents and methods of using these agents. In particular, the invention relates to automatic dishwashing detergents which contain nonionic surfactants which have particularly low viscosities in aqueous solution.

Maschinelles Geschirrspülen in Hauhaltsgeschirrspülmaschinen ist ein Prozeß, der sich vom Wäschewaschen in Haushaltswaschmaschinen grundlegend unterscheidet. Während in einer Waschmaschine das zu reinigende Gut permanent in der Flotte bewegt und auf diese Weise die Reinigung mechanisch unterstützt wird, wird in einer Geschirrspülmaschine die Spülflotte durch ein Sprühsystem auf die zu reinigenden Oberflächen aufgetragen. Dort muß die Reinigungsflotte selbsttätig auch hartnäckigen Verschmutzungen entgegenwirken, ohne daß eine Unterstützung durch mechanische Einflüsse eintritt. Das Leistungsniveau von maschinellen Geschirrspülmitteln muß deshalb ungleich höher sein als das herkömmlicher Textilwaschmittel.Machine dishwashing in home dishwashers is a process that is radically different from washing clothes in home washing machines. While in a washing machine the material to be cleaned is permanently moved in the liquor and in this way the cleaning is mechanically assisted, in a dishwasher the rinsing liquor is applied to the surfaces to be cleaned by a spray system. There, the cleaning liquor must automatically counteract even stubborn dirt, without any support by mechanical influences occurs. The level of performance of automatic dishwashing detergents must therefore be incomparably higher than that of conventional laundry detergents.

Zusätzlich geht der Trend beim maschinellen Geschirrspülen aus ökologischen Gründen zu immer niedrigeren Temperaturen, immer kürzeren Spülzyklen und einer reduzierten Dosierung von Reinigungsmitteln, wobei in einigen Ländern auch Restriktionen bezüglich des Einsatzes bestimmter Inhaltsstoffe (beispielsweise Phosphate) zu beachten sind.In addition, the trend in automatic dishwashing for ecological reasons to ever lower temperatures, increasingly shorter rinsing cycles and a reduced dosage of detergents, in some countries, restrictions on the use of certain ingredients (for example, phosphates) are observed.

Die Leistungsanforderungen an moderne maschinelle Geschirrspülmittel steigen unter den oben genannten Rahmenbedingungen stetig an. Im Zuge dieser erhöhten Leistungsanforderungen besteht ein ständiger Bedarf nach leistungsgesteigerten maschinellen Geschirrspülmitteln, die in niederiger Dosierung auch bei niedrigen Temperaturen und kurzen Spülzeiten hohe Reinigungsleistungen erzielen.The performance requirements of modern automatic dishwashing detergents are steadily increasing under the above mentioned conditions. In the course of these increased performance requirements there is a constant need for performance-enhanced automatic dishwashing detergents which achieve high cleaning performance in low doses even at low temperatures and short rinsing times.

So offenbart die internationale Anmeldung WO 98/11185 (Procter & Gamble) maschinelle Geschirrspülmittel, die nichtionische Tenside aus der Gruppe der alkoxylierten Fettalkohole enthalten.Thus, the international application discloses WO 98/11185 (Procter & Gamble) automatic dishwashing detergents containing nonionic surfactants from the group of alkoxylated fatty alcohols.

Der vorliegenden Erfindung lag die Aufgabe zugrunde, maschinelle Geschirrspülmittel bereitzustellen, die den erhöhten Leistungsanforderungen gerecht werden. Die bereitzustellenden Mittel sollten dabei insbesondere an fettigen Verschmutzungen herkömmlichen Mitteln auch bei im Vergleich geringerer Dosierung überlegen sein. Zusätzlich sollten die Mittel sowohl als herkömmliche maschinelle Geschirrspülmitttel ("Reiniger") in Pulver- oder Granulatform bzw. als Tablette oder gießbare Angebotsform bereitgestellt werden können, als auch als Kombinationsprodukt ("2in1"-Produkte, die Reiniger und Klarspüler in sich vereinen sowie "3in1"-Produkte, welche Reiniger, Klarspüler und Salzersatz in sich vereinen).It is an object of the present invention to provide automatic dishwashing detergents which meet the increased performance requirements. The agents to be provided should be superior to conventional agents even in comparison to lower doses, especially on greasy soils. In addition, the funds should be used both as a conventional machine dishwashing detergent ("cleaner") in Powder or granule form or as a tablet or pourable offer form, as well as a combination product ("2in1" products which combine cleaners and rinse aid in combination and "3in1" products which combine cleaners, rinse aid and salt substitute) ,

Es wurde nun gefunden, daß sich maschinelle Geschirrspülmittel, die dem vorstehend genannten Anforderungsprofil genügen, bereitstellen lassen, wenn sie Gerüststoffe und bestimmte nichtionische Tenside sowie optional weitere Inhaltsstoffe von Reinigungsmitteln enthalten.It has now been found that automatic dishwashing detergents which satisfy the abovementioned requirement profile can be provided if they contain builders and certain nonionic surfactants and optionally further ingredients of detergents.

Gegenstand der vorliegenden Erfindung sind maschinelle Geschirrspülmittel, enthaltend Gerüststoff(e), Tensid(e) sowie optional weitere Inhaltsstoffe, dadurch gekennzeichnet, daß sie 0,1 bis 50 Gew.-% eines oder mehrerer nichtionischer Tenside der allgemeinen Formel I enthalten

Figure imgb0001
in der R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R2 bzw. R3 unabhängig voneinander ausgewählt ist aus -CH3; -CH2CH3, -CH2CH2-CH3, CH(CH3)2 und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen, welche Tenside bei einer Konzentration von 0,01 g/l in destilliertem Wasser einen Diffusionskoeffizienten von mindestens 9 - 10-11 m2s-1 aufweisen.The present invention relates to automatic dishwashing compositions containing builder (s), surfactant (s) and optionally further ingredients, characterized in that they contain 0.1 to 50 wt .-% of one or more nonionic surfactants of the general formula I.
Figure imgb0001
 in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another represent integers from 1 to 6 which contain surfactants at a concentration of 0, 01 g / l in distilled water have a diffusion coefficient of at least 9 - 10 -11 m 2 s -1 .

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein maschinelles Geschirrspülverfahren, in dem ein Geschirrspülmittel gemäß der Erfindung eingesetzt wird.Another object of the present invention is a machine dishwashing process in which a dishwashing detergent according to the invention is used.

Der Diffusionskoeffizient läßt sich dabei nach der Theorie von Fainerman et al. (Colloids and Surfaces A, 90 (1994) 213 - 224 ) aus der Messung der dynamischen Oberflächenspannung bestimmen.The diffusion coefficient can be calculated according to the theory of Fainerman et al. (Colloids and Surfaces A, 90 (1994) 213-224 ) from the measurement of the dynamic surface tension.

Nach der Theorie von Fainerman, die bei kurzen Oberflächenaltern und kleinen Konzentrationen den Oberflächenfilm als ein ideales Gas modelliert, berechnet sich der Oberflächendruck P(t) = s0 - s(t) für kleine Oberflächenalter und kleine Oberflächenkonzentrationen zu Π t = σ 0 - σ t = 2 ⁢ RTc ⁢ Dt π

Figure imgb0002
According to the theory of Fainerman, who models the surface film as an ideal gas at short surface ages and small concentrations, the surface pressure P (t) = s 0 -s (t) is calculated for small surface ages and small surface concentrations Π t = σ 0 - σ t = 2 ⁢ RTc ⁢ dt π
Figure imgb0002

Daraus kann man den Diffusionskoeffizient durch die Gleichung D = π ⁢ m 2 ⁢ RTc 2

Figure imgb0003

berechnen, wobei m die Steigung der Geraden in einer Auftragung P gegen t1/2 ist.From this one can get the diffusion coefficient by the equation D = π ⁢ m 2 ⁢ RTc 2
Figure imgb0003
where m is the slope of the straight line in a plot P versus t 1/2 .

In den vorstehenden Formeln ist:

t:
Oberflächenalter
s(t)
Oberflächenspannung in Abhängigkeit vom Oberflächenalter
s0:
Oberflächenspannung des Wassers
P(t):
Oberflächendruck = s0 - s(t)
R:
Gaskonstante
c:
Molare Konzentration
T:
Temperatur
D:
DiffusionskoefFzient
In the above formulas:
t:
surface age
s (t)
Surface tension as a function of the surface age
s 0 :
Surface tension of the water
P (t):
Surface pressure = s 0 - s (t)
R:
gas constant
c:
Molar concentration
T:
temperature
D:
DiffusionskoefFzient

Die größeren Diffusionskoeffizienten des Tensids bei hohen Konzentrationen bewirkt ein deutlich verbessertes Ablaufverhalten der Gesamtformulierung von mit den Reinigungsmitteln behandelten Oberflächen. Die erfindungsgemäß eingesetzten Tenside benetzen dabei die Oberflächen schnell und vor allem gleichmäßig, so daß der Film der Klarspüllösung auf dem Geschirr gleichmäßig abläuft und nicht frühzeitig aufreißt. Auf diese Weise werden flecken- und schlierenlose Oberflächen und damit verbesserte Klarspülergebnisse erhalten.The higher diffusion coefficients of the surfactant at high concentrations causes a significantly improved flow behavior of the overall formulation of surfaces treated with the cleaning agents. The surfactants used according to the invention wet the surfaces quickly and, above all, uniformly, so that the film of the rinse solution runs off uniformly on the dishes and does not break open prematurely. In this way, stain and schlierenlose surfaces and thus improved rinse results are obtained.

In bevorzugten Ausführungsformen der vorliegenden Erfindung weist das Tensid in einer hochkonzentrierten wäßrigen Lösung noch höhere Diffusionskoeffizienten auf. Hier sind erfundgsgemäße Mittel bevorzugt, bei denen das/die nichtionische(n) Tensid(e) bei einer Konzentration von 0,01 g/l in destilliertem Wasser einen Diffusionskoeffizienten von mindestens 9,5 ∘ 10-11 m2s-1, vorzugsweise von mindestens 1 ∘ 10-10 m2s-1 und insbesondere von mindestens 2,5 ∘ 10-10 m2s-1 aufweisen.In preferred embodiments of the present invention, the surfactant has even higher diffusion coefficients in a highly concentrated aqueous solution. Here, erfundgsgemäße agents are preferred in which the / the nonionic (s) surfactant (s) at a concentration of 0.01 g / l in distilled water has a diffusion coefficient of at least 9.5 ∘ 10 -11 m 2 s -1 , preferably of at least 1 ∘ 10 -10 m 2 s -1 and in particular of at least 2.5 ∘ 10 -10 m 2 s -1 .

Besonders bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel enthalten ein oder mehrere nichtionische(s) Tensid(e), das/die bei einer Konzentration von 0,01 g/l in destilliertem Wasser einen Diffusionskoeffizienten von mindestens 5 ∘ 10-10 m2s-1, vorzugsweise von mindestens 1 ∘ 10-9 m2s-1 und insbesondere von mindestens 5 ∘ 10-9 m2s-1 aufweisen.Particularly preferred machine dishwasher detergents according to the invention contain one or more nonionic surfactant (s) which, at a concentration of 0.01 g / l in distilled water, have a diffusion coefficient of at least 5 × 10 -10 m 2 s -1 , preferably of at least 1 ∘ 10 -9 m 2 s -1 and in particular of at least 5 ∘ 10 -9 m 2 s -1 .

Unabhängig vom Diffusionskoeffizienten der erfindungsgemäß in den Mitteln enthaltenen Tenside in wäßrigen Lösungen kann es für bestimmte Formulierungen von Vorteil sein, wenn die Tenside bei Raumtemperatur flüssig sind. Dies hat neben der leichteren Verarbeitbarkeit bei pulver- oder granulatförmigen Mitteln den zusätzlichen Vorteil, daß die Tenside bei der Verarbeitung nicht aufgeschmolzen werden müssen, wodurch sich die Herstellkosten weiter senken lassen.Regardless of the diffusion coefficient of the present invention contained in the surfactants in aqueous solutions, it may be advantageous for certain formulations when the surfactants are liquid at room temperature. This has, in addition to the easier processability with powdered or granular agents, the additional advantage that the surfactants do not have to be melted during processing, whereby the manufacturing costs can be further reduced.

Nichtionische Tenside, die bei einer Konzentration von 0,01 g/l in destilliertem Wasser einen Diffusionskoeffizienten von mindestens 9 ° 10-11 m2s-1 aufweisen, können molekular unterschiedlich aufgebaut sein. Je nach Art und Länge des hydrophoben und des hydrophilen Restes im Molekül können die Eigenschaften der Tenside so gesteuert werden, daß wunschgemäße Eigenschaften vorliegen.Nonionic surfactants which have a diffusion coefficient of at least 9 ° 10 -11 m 2 s -1 at a concentration of 0.01 g / l in distilled water can have a molecular structure of different composition. Depending on the type and length of the hydrophobic and the hydrophilic radical in the molecule, the properties of the surfactants can be controlled so that desired properties are present.

Die nichtionischen Tenside mit den vorstehend beschriebenen Eigenschaften werden in den erfindungsgemäßen Mitteln in Mengen von 0,1 bis 50 Gew.-%, jeweils bezogen auf das gesamte Mittel, eingesetzt. Bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel enthalten das/die nichtionische(n) Tensid(e) in Mengen von 0,5 bis 40 Gew.-%, vorzugsweise von 1 bis 30 Gew.-%, besonders bevorzugt von 2,5 bis 25 Gew.-% und insbesondere von 5 bis 20 Gew.-%, jeweils bezogen auf das gesamte Mittel.The nonionic surfactants having the properties described above are used in the inventive compositions in amounts of 0.1 to 50 wt .-%, each based on the total agent. Preferred automatic dishwashing agents according to the invention contain the nonionic surfactant (s) in amounts of from 0.5 to 40% by weight, preferably from 1 to 30 Wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.

Als Niotenside werden im Rahmen der vorliegenden Erfindung schwachschäumende Niotenside eingesetzt, welche alternierende Ethylenoxid- und Alkylenoxideinheiten aufweisen, wobei jeweils eine bis zehn EO- bzw. AO-Gruppen aneinander gebunden sind, bevor ein Block aus den jeweils anderen Gruppen folgt. Erfindungsgemäße maschinelle Geschirrspülmittel enthalten nichionische(s) Tensid(e) Tenside der allgemeinen Formel I

Figure imgb0004
Nonionic surfactants used in the context of the present invention are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units, one to ten EO or AO groups being bonded to one another before one block is followed by the other groups. Automatic dishwashing agents according to the invention contain nonionic surfactant (s) surfactants of the general formula I.
Figure imgb0004

in der R1 für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C6-24-Alkyl- oder -Alkenylrest steht; jede Gruppe R2 bzw. R3 unabhängig voneinander ausgewählt ist aus -CH3; -CH2CH3, -CH2CH2-CH3, CH(CH3)2 und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.

Die Niotenside der Formel I lassen sich durch bekannte Methoden aus den entsprechenden Alkoholen R1-OH und Ethlyne- bzw. Alkylenoxid herstellen. Der Rest R1 in der vorstehenden Formel I kann je nach Herkunft des Alkohols variieren. Werden native Quellen genutzt, weist der Rest R1 eine gerade Anzahl von Kohlenstoffatomen auf und ist in der Regel unverzweigt, wobei die linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, bevorzugt sind. Aus sysnthetischen Quellen zugängliche Alkohole sind beispielsweise die Guerbetalkohole oder in 2-Stellung methylverzweigte bzw. lineare und methylverzweigte Reste im Gemisch, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Unanbhängig von der Art des zur Herstellung der erfindungsgemäß in den Mitteln enthaltenen Niotenside eingesetzten Alkohols sind erfindungsgemäße maschinelle Geschirrspülmittel bevorzugt, bei denen R1 in Formel 1 für einen Alkylrest mit 6 bis 24, vorzugsweise 8 bis 20, besonders bevorzugt 9 bis 15 und insbesondere 9 bis 11 Kohlenstoffatomen steht.The nonionic surfactants of formula I can be prepared by known methods from the corresponding alcohols R 1 -OH and Ethlyne- or alkylene oxide. The radical R 1 in the formula I above may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, automatic dishwasher detergents according to the invention are preferred in which R 1 in formula 1 is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

Als Alkylenoxideinheit, die alternierend zur Ethylenoxideinheit in den bevorzugten Niotensiden enthalten ist, kommt neben Propylenoxid insbesondere Butylenoxid in Betracht. Aber auch weitere Alkylenoxide, bei denen R2 bzw. R3 unabhängig voneinander ausgewählt sind aus - CH2CH2-CH3 bzw. CH(CH3)2 sind geeignet. Bevorzugte maschinelle Geschirrspülmittel sind CH2CH2-CH3 bzw. CH(CH3)2 sind geeignet. Bevorzugte maschinelle Geschirrspülmittel sind dadurch gekennzeichnet, daß R2 bzw. R3 für einen Rest -CH3, w und x unabhängig voneinander für Werte von 3 oder 4 und y und z unabhängig voneinander für Werte von 1 oder 2 stehen.As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R 2 or R 3 are independently selected from - CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable. Preferred automatic dishwashing detergents are CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are suitable. Preferred automatic dishwashing agents are characterized in that R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.

Zusammenfassend sind zum Einsatz in den erfindungsgemäßen Mitteln insbesondere nichtionische Tenside bevorzugt, die einen C9-15-Alkylrest mit 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten, gefolgt von1 bis 4 Ethylenoxideinheiten, gefolgt von1 bis 4 Propylenoxideinheiten aufweisen. Diese Tenside weisen in wäßriger Lösung die erforderliche hohen Diffusionskoeffizienten auf und sind erfindungsgemäß mit besonderem Vorzug einsetzbar.In summary, for use in the compositions of the invention, particular preference is given to nonionic surfactants which have a C 9-15 -alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required high diffusion coefficients in aqueous solution and can be used according to the invention with particular preference.

Die angegebenen C-Kettenlängen sowie Ethoxylierungsgrade bzw. Alkoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Aufgrund der Herstellverfahren bestehen Handelsprodukte der genannten Formeln zumeist nicht aus einem individuellen Vertreter, sondern aus Gemischen, wodurch sich sowohl für die C-Kettenlängen als auch für die Ethoxylierungsgrade bzw. Alkoxylierungsgrade Mittelwerte und daraus folgend gebrochene Zahlen ergeben können. In der nachstehenden Tabelle sind besonders bevorzugt in den erfindungsgemäßen Mitteln enthaltene nichtionische Tenside bezüglich des Restes R1, der Reste R2 und R3 sowie der Indizes w, x, y und z charakterisiert. Bevorzugte erfindungsgemäße Mittel enthalten ein oder mehrere Tenside aus der nachstehenden Tabelle oder Gemische aus diesen. Nr. R1 R 2 R 3 w x y z 1 CH3-(CH2)8- CH3- CH3- 1 1 1 1 2 CH3-(CH2)8- CH3- CH3- 2 1 1 1 3 CH3-(CH2)8- CH3- CH3- 1 2 1 1 4 CH3-(CH2)8- CH3- CH3- 1 1 2 1 5 CH3-(CH2)8- CH3- CH3- 1 1 1 2 6 CH3-(CH2)8- CH3- CH3- 3 1 1 1 7 CH3-(CH2)8- CH3- CH3- 1 3 1 1 8 CH3-(CH2)8- CH3- CH3- 1 1 3 1 9 CH3-(CH2)8- CH3- CH3- 1 1 1 3 10 CH3-(CH2)8- CH3- CH3- 4 1 1 1 11 CH3-(CH2)8- CH3- CH3- 1 4 1 1 12 CH3-(CH2)8- CH3- CH3- 1 1 4 1 13 CH3-(CH2)8- CH3- CH3- 1 1 1 4 14 CH3-(CH2)8- CH3- CH3- 1 2 2 1 15 CH3-(CH2)8- CH3- CH3- 1 2 1 2 16 CH3-(CH2)8- CH3- CH3- 1 1 2 2 17 CH3-(CH2)8- CH3- CH3- 2 2 1 1 18 CH3-(CH2)8- CH3- CH3- 2 1 2 1 19 CH3-(CH2)8- CH3- CH3- 2 1 1 2 20 CH3-(CH2)8- CH3- CH3- 1 3 3 1 21 CH3-(CH2)8- CH3- CH3- 1 3 1 3 22 CH3-(CH2)8- CH3- CH3- 1 1 3 3 23 CH3-(CH2)8- CH3- CH3- 3 3 1 1 24 CH3-(CH2)8- CH3- CH3- 3 1 3 1 25 CH3-(CH2)8- CH3- CH3- 3 1 1 3 26 CH3-(CH2)8- CH3- CH3- 1 4 4 1 27 CH3-(CH2)8- CH3- CH3- 1 4 1 4 28 CH3-(CH2)8- CH3- CH3- 1 1 4 4 29 CH3-(CH2)8- CH3- CH3- 4 4 1 1 30 CH3-(CH2)8- CH3- CH3- 4 1 4 1 31 CH3-(CH2)8- CH3- CH3- 4 1 1 4 32 CH3-(CH2)8- CH3- CH3- 1 1 2 3 33 CH3-(CH2)8- CH3- CH3- 1 1 3 2 34 CH3-(CH2)8- CH3- CH3- 1 2 3 1 35 CH3-(CH2)8- CH3- CH3- 1 3 2 1 36 CH3-(CH2)8- CH3- CH3- 1 2 1 3 37 CH3-(CH2)8- CH3- CH3- 1 3 1 2 38 CH3-(CH2)8- CH3- CH3- 2 1 1 3 39 CH3-(CH2)8- CH3- CH3- 2 1 3 1 40 CH3-(CH2)8- CH3- CH3- 2 3 1 1 41 CH3-(CH2)8- CH3- CH3- 3 1 1 2 42 CH3-(CH2)8- CH3- CH3- 3 1 2 1 43 CH3-(CH2)8- CH3- CH3- 3 2 1 1 44 CH3-(CH2)8- CH3- CH3- 1 1 2 4 45 CH3-(CH2)8- CH3- CH3- 1 1 4 2 46 CH3-(CH2)8- CH3- CH3- 1 2 4 1 47 CH3-(CH2)8- CH3- CH3- 1 4 2 1 48 CH3-(CH2)8- CH3- CH3- 1 2 1 4 49 CHs-(CH2)8- CH3- CH3- 1 4 1 2 50 CH3-(CH2)8- CH3- CH3- 2 1 1 4 51 CH3-(CH2)8- CH3- CH3- 2 1 4 1 52 CH3-(CH2)8- CH3- CH3- 2 4 1 1 53 CH3-(CH2)8- CH3- CH3- 4 1 1 2 54 CH3-(CH2)8- CH3- CH3- 4 1 2 1 55 CH3-(CH2)8- CH3- CH3- 4 2 1 1 56 CH3-(CH2)8- CH3- CH3- 1 1 4 3 57 CH3-(CH2)8- CH3- CH3- 1 1 3 4 58 CH3-(CH2)8- CH3- CH3- 1 4 3 1 59 CH3-(CH2)8- CH3- CH3- 1 3 4 1 60 CH3-(CH2)8- CH3- CH3- 1 4 1 3 61 CH3-(CH2)8- CH3- CH3- 1 3 1 4 62 CH3-(CH2)8- CH3- CH3- 4 1 1 3 63 CH3-(CH2)8- CH3- CH3- 4 1 3 1 64 CH3-(CH2)8- CH3- CH3- 4 3 1 1 65 CH3-(CH2)8- CH3- CH3- 3 1 1 4 66 CH3-(CH2)8- CH3- CH3- 3 1 4 1 67 CH3-(CH2)8- CH3- CH3- 3 4 1 1 68 CH3-(CH2)8- CH3- CH3- 1 2 2 2 69 CH3-(CH2)8- CH3- CH3- 2 1 2 2 70 CH3-(CH2)8- CH3- CH3- 2 2 1 2 71 CH3-(CH2)8- CH3- CH3- 2 2 2 1 72 CH3-(CH2)8- CH3- CH3- 1 3 3 3 73 CH3-(CH2)8- CH3- CH3- 3 1 3 3 74 . CH3-(CH2)8- CH3- CH3- 3 3 1 3 75 CH3-(CH2)8- CH3- CH3- 3 3 3 1 76 CH3-(CH2)8- CH3- CH3- 1 4 4 4 77 CH3-(CH2)8- CH3- CH3- 4 1 4 4 78 CH3-(CH2)8- CH3- CH3- 4 4 1 4 79 CH3-(CH2)8- CH3- CH3- 4 4 4 1 80 CH3-(CH2)8- CH3- CH3- 2 2 1 3 81 CH3-(CH2)8- CH3- CH3- 2 2 3 1 82 CH3-(CH2)8- CH3- CH3- 2 1 2 3 83 CH3-(CH2)8- CH3- CH3- 2 3 2 1 84 CH3-(CH2)8- CH3- CH3- 2 1 3 2 85 CH3-(CH2)8- CH3- CH3- 2 3 1 2 86 CH3-(CH2)8- CH3- CH3- 1 2 2 3 87 CH3-(CH2)8- CH3- CH3- 1 2 3 2 88 CH3-(CH2)8- CH3- CH3- 1 3 2 2 89 CH3-(CH2)8- CH3- CH3- 3 2 2 1 90 CH3-(CH2)8- CH3- CH3- 3 2 1 2 91 CH3-(CH2)8- CH3- CH3- 3 1 2 2 92 CH3-(CH2)8- CH3- CH3- 2 2 1 4 93 CH3-(CH2)8- CH3- CH3- 2 2 4 1 94 CH3-(CH2)8- CH3- CH3- 2 1 2 4 95 CH3-(CH2)8- CH3- CH3- 2 4 2 1 96 CH3-(CH2)8- CH3- CH3- 2 1 4 2 97 CH3-(CH2)8- CH3- CH3- 2 4 1 2 98 CH3-(CH2)8- CH3- CH3- 1 2 2 4 99 CH3-(CH2)8- CH3- CH3- 1 2 4 2 100 CH3-(CH2)8- CH3- CH3- 1 4 2 2 101 CH3-(CH2)8- CH3- CH3- 4 2 2 1 102 CH3-(CH2)8- CH3- CH3- 4 2 1 2 103 CH3-(CH2)8- CH3- CH3- 4 1 2 2 104 CH3-(CH2)8- CH3- CH3- 2 2 4 3 105 CH3-(CH2)8- CH3- CH3- 2 2 3 4 106 CH3-(CH2)8- CH3- CH3- 2 4 2 3 107 CH3-(CH2)8- CH3- CH3- 2 3 2 4 108 CH3-(CH2)8- CH3- CH3- 2 4 3 2 109 CH3-(CH2)8- CH3- CH3- 2 3 4 2 110 CH3-(CH2)8- CH3- CH3- 4 2 2 3 111 CH3-(CH2)8- CH3- CH3- 4 2 3 2 112 CH3-(CH2)8- CH3- CH3- 4 3 2 2 113 CH3-(CH2)8- CH3- CH3- 3 2 2 4 114 CH3-(CH2)8- CH3- CH3- 3 2 4 2 115 CH3-(CH2)8- CH3- CH3- 3 4 2 2 116 CH3-(CH2)8- CH3- CH3- 3 3 1 2 117 CH3-(CH2)8- CH3- CH3- 3 3 2 1 118 CH3-(CH2)8- CH3- CH3- 3 1 3 2 119 CH3-(CH2)8- CH3- CH3- 3 2 3 1 120 CH3-(CH2)8- CH3- CH3- 3 1 2 3 121 CH3-(CH2)8- CH3- CH3- 3 2 1 3 122 CH3-(CH2)8- CH3- CH3- 1 3 3 2 123 CH3-(CH2)8- CH3- CH3- 1 3 2 3 124 CH3-(CH2)8- CH3- CH3- 1 2 3 3 125 CH3-(CH2)8- CH3- CH3- 2 3 3 1 126 CH3-(CH2)8- CH3- CH3- 2 3 1 3 127 CH3-(CH2)8- CH3- CH3- 2 1 3 3 128 CH3-(CH2)8- CH3- CH3- 3 3 1 4 129 CH3-(CH2)8- CH3- CH3- 3 3 4 1 130 CH3-(CH2)8- CH3- CH3- 3 1 3 4 131 CH3-(CH2)8- CH3- CH3- 3 4 3 1 132 CH3-(CH2)8- CH3- CH3- 3 1 4 3 133 CH3-(CH2)8- CH3- CH3- 3 4 1 3 134 CH3-(CH2)8- CH3- CH3- 1 3 3 4 135 CH3-(CH2)8- CH3- CH3- 1 3 4 3 136 CH3-(CH2)8- CH3- CH3- 1 4 3 3 137 CH3-(CH2)8- CH3- CH3- 4 3 3 1 138 CH3-(CH2)8- CH3- CH3- 4 3 1 3 139 CH3-(CH2)8- CH3- CH3- 4 1 3 3 140 CH3-(CH2)8- CH3- CH3- 3 3 4 2 141 CH3-(CH2)8- CH3- CH3- 3 3 2 4 142 CH3-(CH2)8- CH3- CH3- 3 4 3 2 143 CH3-(CH2)8- CH3- CH3- 3 2 3 4 144 CH3-(CH2)8- CH3- CH3- 3 4 2 3 145 CH3-(CH2)8- CH3- CH3- 3 2 4 3 146 CH3-(CH2)8- CH3- CH3- 4 3 3 2 147 CH3-(CH2)8- CH3- CH3- 4 3 2 3 148 CH3-(CH2)8- CH3- CH3- 4 2 3 3 149 CH3-(CH2)8- CH3- CH3- 2 3 3 4 150 CH3-(CH2)8- CH3- CH3- 2 3 4 3 151 CH3-(CH2)8- CH3- CH3- 2 4 3 3 152 CH3-(CH2)8- CH3- CH3- 4 4 1 2 153 CH3-(CH2)8- CH3- CH3- 4 4 2 1 154 CH3-(CH2)8- CH3- CH3- 4 1 4 2 155 CH3-(CH2)8- CH3- CH3- 4 2 4 1 156 CH3-(CH2)8- CH3- CH3- 4 1 2 4 157 CH3-(CH2)8- CH3- CH3- 4 2 1 4 158 CH3-(CH2)8- CH3- CH3- 1 4 4 2 159 CH3-(CH2)8- CH3- CH3- 1 4 2 4 160 CH3-(CH2)8- CH3- CH3- 1 2 4 4 161 CH3-(CH2)8- CH3- CH3- 2 4 4 1 162 CH3-(CH2)8- CH3- CH3- 2 4 1 4 163 CH3-(CH2)8- CH3- CH3- 2 1 4 4 164 CH3-(CH2)8- CH3- CH3- 4 4 1 3 165 CH3-(CH2)8- CH3- CH3- 4 4 3 1 166 CH3-(CH2)8- CH3- CH3- 4 1 4 3 167 CH3-(CH2)8- CH3- CH3- 4 3 4 1 168 CH3-(CH2)8- CH3- CH3- 4 1 3 4 169 CH3-(CH2)8- CH3- CH3- 4 3 1 4 170 CH3-(CH2)8- CH3- CH3- 1 4 4 3 171 CH3-(CH2)8- CH3- CH3- 1 4 3 4 172 CH3-(CH2)8- CH3- CH3- 1 3 4 4 173 CH3-(CH2)8- CH3- CH3- 3 4 4 1 174 CH3-(CH2)8- CH3- CH3- 3 4 1 4 175 CH3-(CH2)8- CH3- CH3- 3 1 4 4 176 CH3-(CH2)8- CH3- CH3- 4 4 3 2 177 CH3-(CH2)8- CH3- CH3- 4 4 2 3 178 CH3-(CH2)8- CH3- CH3- 4 3 4 2 179 CH3-(CH2)8- CH3- CH3- 4 2 4 3 180 CH3-(CH2)8- CH3- CH3- 4 3 2 4 181 CH3-(CH2)8- CH3- CH3- 4 2 3 4 182 CH3-(CH2)8- CH3- CH3- 3 4 4 2 183 CH3-(CH2)8- CH3- CH3- 3 4 2 4 184 CH3-(CH2)8- CH3- CH3- 3 2 4 4 185 CH3-(CH2)8- CH3- CH3- 2 4 4 3 186 CH3-(CH2)8- CH3- CH3- 2 4 3 4 187 CH3-(CH2)8- CH3- CH3- 2 3 4 4 188 CH3-(CH2)8- CH3- CH3- 1 2 3 4 189 CH3-(CH2)8- CH3- CH3- 1 2 4 3 190 CH3-(CH2)8- CH3- CH3- 1 3 2 4 191 CH3-(CH2)8- CH3- CH3- 1 3 4 2 192 CH3-(CH2)8- CH3- CH3- 1 4 2 3 193 CH3-(CH2)8- CH3- CH3- 1 4 3 2 194 CH3-(CH2)8- CH3- CH3- 2 1 3 4 195 CH3-(CH2)8- CH3- CH3- 2 1 4 3 196 CH3-(CH2)8- CH3- CH3- 2 3 1 4 197 CH3-(CH2)8- CH3- CH3- 2 3 4 1 198 CH3-(CH2)8- CH3- CH3- 2 4 1 3 199 CH3-(CH2)8- CH3- CH3- 2 4 3 1 200 CH3-(CH2)8- CH3- CH3- 3 1 2 4 201 CH3-(CH2)8- CH3- CH3- 3 1 4 2 202 CH3-(CH2)8- CH3- CH3- 3 2 1 4 203 CH3-(CH2)8- CH3- CH3- 3 2 4 1 204 CH3-(CH2)8- CH3- CH3- 3 4 1 2 205 CH3-(CH2)8- CH3- CH3- 3 4 2 1 206 CH3-(CH2)8- CH3- CH3- 4 1 2 3 207 CH3-(CH2)8- CH3- CH3- 4 1 3 2 208 CH3-(CH2)8- CH3- CH3- 4 2 1 3 209 CH3-(CH2)8- CH3- CH3- 4 2 3 1 210 CH3-(CH2)8- CH3- CH3- 4 3 1 2 211 CH3-(CH2)8- CH3- CH3- 4 3 2 1 212 CH3-(CH2)8- CH3- CH3- 2 3 3 2 213 CH3-(CH2)8- CH3- CH3- 2 3 2 3 214 CH3-(CH2)8- CH3- CH3- 2 2 3 3 215 CH3-(CH2)8- CH3- CH3- 3 3 2 2 216 CH3-(CH2)8- CH3- CH3- 3 2 3 2 217 CH3-(CH2)8- CH3- CH3- 3 2 2 3 218 CH3-(CH2)8- CH3- CH3- 2 4 4 2 219 CH3-(CH2)8- CH3- CH3- 2 4 2 4 220 CH3-(CH2)8- CH3- CH3- 2 2 4 4 221 CH3-(CH2)8- CH3- CH3- 4 4 2 2 222 CH3-(CH2)8- CH3- CH3- 4 2 4 2 223 CH3-(CH2)8- CH3- CH3- 4 2 2 4 224 CH3-(CH2)8- CH3- CH3- 3 4 4 3 225 CH3-(CH2)8- CH3- CH3- 3 4 3 4 226 CH3-(CH2)8- CH3- CH3- 3 3 4 4 227 CH3-(CH2)8- CH3- CH3- 4 4 3 3 228 CH3-(CH2)8- CH3- CH3- 4 3 4 3 229 CH3-(CH2)8- CH3- CH3- 4 3 3 4 230 CH3-(CH2)9- CH3- CH3- 1 1 1 1 231 CH3-(CH2)9- CH3- CH3- 2 1 1 1 232 CH3-(CH2)9- CH3- CH3- 1 2 1 1 233 CH3-(CH2)9- CH3- CH3- 1 1 2 1 234 CH3-(CH2)9- CH3- CH3- 1 1 1 2 235 CH3-(CH2)9- CH3- CH3- 3 1 1 1 236 CH3-(CH2)9- CH3- CH3- 1 3 1 1 237 CH3-(CH2)9- CH3- CH3- 1 1 3 1 238 CH3-(CH2)9- CH3- CH3- 1 1 1 3 239 CH3-(CH2)9- CH3- CH3- 4 1 1 1 240 CH3-(CH2)9- CH3- CH3- 1 4 1 1 241 CH3-(CH2)9- CH3- CH3- 1 1 4 1 242 CH3-(CH2)9- CH3- CH3- 1 1 1 4 243 CH3-(CH2)9- CH3- CH3- 1 2 2 1 244 CH3-(CH2)9- CH3- CH3- 1 2 1 2 245 CH3-(CH2)9- CH3- CH3- 1 1 2 2 246 CH3-(CH2)9- CH3- CH3- 2 2 1 1 247 CH3-(CH2)9- CH3- CH3- 2 1 2 1 248 CH3-(CH2)9- CH3- CH3- 2 1 1 2 249 CH3-(CH2)9- CH3- CH3- 1 3 3 1 250 CH3-(CH2)9- CH3- CH3- 1 3 1 3 251 CH3-(CH2)9- CH3- CH3- 1 1 3 3 252 CH3-(CH2)9- CH3- CH3- 3 3 1 1 253 CH3-(CH2)9- CH3- CH3- 3 1 3 1 254 CH3-(CH2)9- CH3- CH3- 3 1 1 3 255 CH3-(CH2)9- CH3- CH3- 1 4 4 1 256 CH3-(CH2)9- CH3- CH3- 1 4 1 4 257 CH3-(CH2)9- CH3- CH3- 1 1 4 4 258 CH3-(CH2)9- CH3- CH3- 4 4 1 1 259 CH3-(CH2)9- CH3- CH3- 4 1 4 1 260 CH3-(CH2)9- CH3- CH3- 4 1 1 4 261 CH3-(CH2)9- CH3- CH3- 1 1 2 3 262 CH3-(CH2)9- CH3- CH3- 1 1 3 2 263 CH3-(CH2)9- CH3- CH3- 1 2 3 1 264 CH3-(CH2)9- CH3- CH3- 1 3 2 1 265 CH3-(CH2)9- CH3- CH3- 1 2 1 3 266 CH3-(CH2)9- CH3- CH3- 1 3 1 2 267 CH3-(CH2)9- CH3- CH3- 2 1 1 3 268 CH3-(CH2)9- CH3- CH3- 2 1 3 1 269 CH3-(CH2)9- CH3- CH3- 2 3 1 1 270 CH3-(CH2)9- CH3- CH3- 3 1 1 2 271 CH3-(CH2)9- CH3- CH3- 3 1 2 1 272 CH3-(CH2)9- CH3- CH3- 3 2 1 1 273 CH3-(CH2)9- CH3- CH3- 1 1 2 4 274 CH3-(CH2)9- CH3- CH3- 1 1 4 2 275 CH3-(CH2)9- CH3- CH3- 1 2 4 1 276 CH3-(CH2)9- CH3- CH3- 1 4 2 1 277 CH3-(CH2)9- CH3- CH3- 1 2 1 4 278 CH3-(CH2)9- CH3- CH3- 1 4 1 2 279 CH3-(CH2)9- CH3- CH3- 2 1 1 4 280 CH3-(CH2)9- CH3- CH3- 2 1 4 1 281 CH3-(CH2)9- CH3- CH3- 2 4 1 1 282 CH3-(CH2)9- CH3- CH3- 4 1 1 2 283 CH3-(CH2)9- CH3- CH3- 4 1 2 1 284 CH3-(CH2)9- CH3- CH3- 4 2 1 1 285 CH3-(CH2)9- CH3- CH3- 1 1 4 3 286 CH3-(CH2)9- CH3- CH3- 1 1 3 4 287 CH3-(CH2)9- CH3- CH3- 1 4 3 1 288 CH3-(CH2)9- CH3- CH3- 1 3 4 1 289 CH3-(CH2)9- CH3- CH3- 1 4 1 3 290 CH3-(CH2)9- CH3- CH3- 1 3 1 4 291 CH3-(CH2)9- CH3- CH3- 4 1 1 3 292 CH3-(CH2)9- CH3- CH3- 4 1 3 1 293 CH3-(CH2)9- CH3- CH3- 4 3 1 1 294 CH3-(CH2)9- CH3- CH3- 3 1 1 4 295 CH3-(CH2)9- CH3- CH3- 3 1 4 1 296 CH3-(CH2)9- CH3- CH3- 3 4 1 1 297 CH3-(CH2)9- CH3- CH3- 1 2 2 2 298 CH3-(CH2)9- CH3- CH3- 2 1 2 2 299 CH3-(CH2)9- CH3- CH3- 2 2 1 2 300 CH3-(CH2)9- CH3- CH3- 2 2 2 1 301 CH3-(CH2)9- CH3- CH3- 1 3 3 3 302 CH3-(CH2)9- CH3- CH3- 3 1 3 3 303 CH3-(CH2)9- CH3- CH3- 3 3 1 3 304 CH3-(CH2)9- CH3- CH3- 3 3 3 1 305 CH3-(CH2)9- CH3- CH3- 1 4 4 4 306 CH3-(CH2)9- CH3- CH3- 4 1 4 4 307 CH3-(CH2)9- CH3- CH3- 4 4 1 4 308 CH3-(CH2)9- CH3- CH3- 4 4 4 1 309 CH3-(CH2)9- CH3- CH3- 2 2 1 3 310 CH3-(CH2)9- CH3- CH3- 2 2 3 1 311 CH3-(CH2)9- CH3- CH3- 2 1 2 3 312 CH3-(CH2)9- CH3- CH3- 2 3 2 1 313 CH3-(CH2)9- CH3- CH3- 2 1 3 2 314 CH3-(CH2)9- CH3- CH3- 2 3 1 2 315 CH3-(CH2)9- CH3- CH3- 1 2 2 3 316 CH3-(CH2)9- CH3- CH3- 1 2 3 2 317 CH3-(CH2)9- CH3- CH3- 1 3 2 2 318 CH3-(CH2)9- CH3- CH3- 3 2 2 1 319 CH3-(CH2)9- CH3- CH3- 3 2 1 2 320 CH3-(CH2)9- CH3- CH3- 3 1 2 2 321 CH3-(CH2)9- CH3- CH3- 2 2 1 4 322 CH3-(CH2)9- CH3- CH3- 2 2 4 1 323 CH3-(CH2)9- CH3- CH3- 2 1 2 4 324 CH3-(CH2)9- CH3- CH3- 2 4 2 1 325 CH3-(CH2)9- CH3- CH3- 2 1 4 2 326 CH3-(CH2)9- CH3- CH3- 2 4 1 2 327 CH3-(CH2)9- CH3- CH3- 1 2 2 4 328 CH3-(CH2)9- CH3- CH3- 1 2 4 2 329 CH3-(CH2)9- CH3- CH3- 1 4 2 2 330 CH3-(CH2)9- CH3- CH3- 4 2 2 1 331 CH3-(CH2)9- CH3- CH3- 4 2 1 2 332 CH3-(CH2)9- CH3- CH3- 4 1 2 2 333 CH3-(CH2)9- CH3- CH3- 2 2 4 3 334 CH3-(CH2)9- CH3- CH3- 2 2 3 4 335 CH3-(CH2)9- CH3- CH3- 2 4 2 3 336 CH3-(CH2)9- CH3- CH3- 2 3 2 4 337 CH3-(CH2)9- CH3- CH3- 2 4 3 2 338 CH3-(CH2)9- CH3- CH3- 2 3 4 2 339 CH3-(CH2)9- CH3- CH3- 4 2 2 3 340 CH3-(CH2)9- CH3- CH3- 4 2 3 2 341 CH3-(CH2)9- CH3- CH3- 4 3 2 2 342 CH3-(CH2)9- CH3- CH3- 3 2 2 4 343 CH3-(CH2)9- CH3- CH3- 3 2 4 2 344 CH3-(CH2)9- CH3- CH3- 3 4 2 2 345 CH3-(CH2)9- CH3- CH3- 3 3 1 2 346 CH3-(CH2)9- CH3- CH3- 3 3 2 1 347 CH3-(CH2)9- CH3- CH3- 3 1 3 2 348 CH3-(CH2)9- CH3- CH3- 3 2 3 1 349 CH3-(CH2)9- CH3- CH3- 3 1 2 3 350 CH3-(CH2)9- CH3- CH3- 3 2 1 3 351 CH3-(CH2)9- CH3- CH3- 1 3 3 2 352 CH3-(CH2)9- CH3- CH3- 1 3 2 3 353 CH3-(CH2)9- CH3- CH3- 1 2 3 3 354 CH3-(CH2)9- CH3- CH3- 2 3 3 1 355 CH3-(CH2)9- CH3- CH3- 2 3 1 3 356 CH3-(CH2)9- CH3- CH3- 2 1 3 3 357 CH3-(CH2)9- CH3- CH3- 3 3 1 4 358 CH3-(CH2)9- CH3- CH3- 3 3 4 1 359 CH3-(CH2)9- CH3- CH3- 3 1 3 4 360 CH3-(CH2)9- CH3- CH3- 3 4 3 1 361 CH3-(CH2)9- CH3- CH3- 3 1 4 3 362 CH3-(CH2)9- CH3- CH3- 3 4 1 3 363 CH3-(CH2)9- CH3- CH3- 1 3 3 4 364 CH3-(CH2)9- CH3- CH3- 1 3 4 3 365 CH3-(CH2)9- CH3- CH3- 1 4 3 3 366 CH3-(CH2)9- CH3- CH3- 4 3 3 1 367 CH3-(CH2)9- CH3- CH3- 4 3 1 3 368 CH3-(CH2)9- CH3- CH3- 4 1 3 3 369 CH3-(CH2)9- CH3- CH3- 3 3 4 2 370 CH3-(CH2)9- CH3- CH3- 3 3 2 4 371 CH3-(CH2)9- CH3- CH3- 3 4 3 2 372 CH3-(CH2)9- CH3- CH3- 3 2 3 4 373 CH3-(CH2)9- CH3- CH3- 3 4 2 3 374 CH3-(CH2)9- CH3- CH3- 3 2 4 3 375 CH3-(CH2)9- CH3- CH3- 4 3 3 2 376 CH3-(CH2)9- CH3- CH3- 4 3 2 3 377 CH3-(CH2)9- CH3- CH3- 4 2 3 3 378 CH3-(CH2)9- CH3- CH3- 2 3 3 4 379 CH3-(CH2)9- CH3- CH3- 2 3 4 3 380 CH3-(CH2)9- CH3- CH3- 2 4 3 3 381 CH3-(CH2)9- CH3- CH3- 4 4 1 2 382 CH3-(CH2)9- CH3- CH3- 4 4 2 1 383 CH3-(CH2)9- CH3- CH3- 4 1 4 2 384 CH3-(CH2)9- CH3- CH3- 4 2 4 1 385 CH3-(CH2)9- CH3- CH3- 4 1 2 4 386 CH3-(CH2)9- CH3- CH3- 4 2 1 4 387 CH3-(CH2)9- CH3- CH3- 1 4 4 2 388 CH3-(CH2)9- CH3- CH3- 1 4 2 4 389 CH3-(CH2)9- CH3- CH3- 1 2 4 4 390 CH3-(CH2)9- CH3- CH3- 2 4 4 1 391 CH3-(CH2)9- CH3- CH3- 2 4 1 4 392 CH3-(CH2)9- CH3- CH3- 2 1 4 4 393 CH3-(CH2)9- CH3- CH3- 4 4 1 3 394 CH3-(CH2)9- CH3- CH3- 4 4 3 1 395 CH3-(CH2)9- CH3- CH3- 4 1 4 3 396 CH3-(CH2)9- CH3- CH3- 4 3 4 1 397 CH3-(CH2)9- CH3- CH3- 4 1 3 4 398 CH3-(CH2)9- CH3- CH3- 4 3 1 4 399 CH3-(CH2)9- CH3- CH3- 1 4 4 3 400 CH3-(CH2)9- CH3- CH3- 1 4 3 4 401 CH3-(CH2)9- CH3- CH3- 1 3 4 4 402 CH3-(CH2)9- CH3- CH3- 3 4 4 1 403 CH3-(CH2)9- CH3- CH3- 3 4 1 4 404 CH3-(CH2)9- CH3- CH3- 3 1 4 4 405 CH3-(CH2)9- CH3- CH3- 4 4 3 2 406 CH3-(CH2)9- CH3- CH3- 4 4 2 3 407 CH3-(CH2)9- CH3- CH3- 4 3 4 2 408 CH3-(CH2)9- CH3- CH3- 4 2 4 3 409 CH3-(CH2)9- CH3- CH3- 4 3 2 4 410 CH3-(CH2)9- CH3- CH3- 4 2 3 4 411 CH3-(CH2)9- CH3- CH3- 3 4 4 2 412 CH3-(CH2)9- CH3- CH3- 3 4 2 4 413 CH3-(CH2)9- CH3- CH3- 3 2 4 4 414 CH3-(CH2)9- CH3- CH3- 2 4 4 3 415 CH3-(CH2)9- CH3- CH3- 2 4 3 4 416 CH3-(CH2)9- CH3- CH3- 2 3 4 4 417 CH3-(CH2)9- CH3- CH3- 1 2 3 4 418 CH3-(CH2)9- CH3- CH3- 1 2 4 3 419 CH3-(CH2)9- CH3- CH3- 1 3 2 4 420 CH3-(CH2)9- CH3- CH3- 1 3 4 2 421 CH3-(CH2)9- CH3- CH3- 1 4 2 3 422 CH3-(CH2)9- CH3- CH3- 1 4 3 2 423 CH3-(CH2)9- CH3- CH3- 2 1 3 4 424 CH3-(CH2)9- CH3- CH3- 2 1 4 3 425 CH3-(CH2)9- CH3- CH3- 2 3 1 4 426 CH3-(CH2)9- CH3- CH3- 2 3 4 1 427 CH3-(CH2)9- CH3- CH3- 2 4 1 3 428 CH3-(CH2)9- CH3- CH3- 2 4 3 1 429 CH3-(CH2)9- CH3- CH3- 3 1 2 4 430 CH3-(CH2)9- CH3- CH3- 3 1 4 2 431 CH3-(CH2)9- CH3- CH3- 3 2 1 4 432 CH3-(CH2)9- CH3- CH3- 3 2 4 1 433 CH3-(CH2)9- CH3- CH3- 3 4 1 2 434 CH3-(CH2)9- CH3- CH3- 3 4 2 1 435 CH3-(CH2)9- CH3- CH3- 4 1 2 3 436 CH3-(CH2)9- CH3- CH3- 4 1 3 2 437 CH3-(CH2)9- CH3- CH3- 4 2 1 3 438 CH3-(CH2)9- CH3- CH3- 4 2 3 1 439 CH3-(CH2)9- CH3- CH3- 4 3 1 2 440 CH3-(CH2)9- CH3- CH3- 4 3 2 1 441 CH3-(CH2)9- CH3- CH3- 2 3 3 2 442 CH3-(CH2)9- CH3- CH3- 2 3 2 3 443 CH3-(CH2)9- CH3- CH3- 2 2 3 3 444 CH3-(CH2)9- CH3- CH3- 3 3 2 2 445 CH3-(CH2)9- CH3- CH3- 3 2 3 2 446 CH3-(CH2)9- CH3- CH3- 3 2 2 3 447 CH3-(CH2)9- CH3- CH3- 2 4 4 2 448 CH3-(CH2)9- CH3- CH3- 2 4 2 4 449 CH3-(CH2)9- CH3- CH3- 2 2 4 4 450 CH3-(CH2)9- CH3- CH3- 4 4 2 2 451 CH3-(CH2)9- CH3- CH3- 4 2 4 2 452 CH3-(CH2)9- CH3- CH3- 4 2 2 4 453 CH3-(CH2)9- CH3- CH3- 3 4 4 3 454 CH3-(CH2)9- CH3- CH3- 3 4 3 4 455 CH3-(CH2)9- CH3- CH3- 3 3 4 4 456 CH3-(CH2)9- CH3- CH3- 4 4 3 3 457 CH3-(CH2)9- CH3- CH3- 4 3 4 3 458 CH3-(CH2)9- CH3- CH3- 4 3 3 4 459 CH3-(CH2)10- CH3- CH3- 1 1 1 1 460 CH3-(CH2)10- CH3- CH3- 2 1 1 1 461 CH3-(CH2)10- CH3- CH3- 1 2 1 1 462 CH3-(CH2)10- CH3- CH3- 1 1 2 1 463 CH3-(CH2)10- CH3- CH3- 1 1 1 2 464 CH3-(CH2)10- CH3- CH3- 3 1 1 1 465 CH3-(CH2)10- CH3- CH3- 1 3 1 1 466 CH3-(CH2)10- CH3- CH3- 1 1 3 1 467 CH3-(CH2)10- CH3- CH3- 1 1 1 3 468 CH3-(CH2)10- CH3- CH3- 4 1 1 1 469 CH3-(CH2)10- CH3- CH3- 1 4 1 1 470 CH3-(CH2)10- CH3- CH3- 1 1 4 1 471 CH3-(CH2)10- CH3- CH3- 1 1 1 4 472 CH3-(CH2)10- CH3- CH3- 1 2 2 1 473 CH3-(CH2)10- CH3- CH3- 1 2 1 2 474 CH3-(CH2)10- CH3- CH3- 1 1 2 2 475 CH3-(CH2)10- CH3- CH3- 2 2 1 1 476 CH3-(CH2)10- CH3- CH3- 2 1 2 1 477 CH3-(CH2)10- CH3- CH3- 2 1 1 2 478 CH3-(CH2)10- CH3- CH3- 1 3 3 1 479 CH3-(CH2)10- CH3- CH3- 1 3 1 3 480 CH3-(CH2)10- CH3- CH3- 1 1 3 3 481 CH3-(CH2)10- CH3- CH3- 3 3 1 1 482 CH3-(CH2)10- CH3- CH3- 3 1 3 1 483 CH3-(CH2)10- CH3- CH3- 3 1 1 3 484 CH3-(CH2)10- CH3- CH3- 1 4 4 1 485 CH3-(CH2)10- CH3- CH3- 1 4 1 4 486 CH3-(CH2)10- CH3- CH3- 1 1 4 4 487 CH3-(CH2)10- CH3- CH3- 4 4 1 1 488 CH3-(CH2)10- CH3- CH3- 4 1 4 1 489 CH3-(CH2)10- CH3- CH3- 4 1 1 4 490 CH3-(CH2)10- CH3- CH3- 1 1 2 3 491 CH3-(CH2)10- CH3- CH3- 1 1 3 2 492 CH3-(CH2)10- CH3- CH3- 1 2 3 1 493 CH3-(CH2)10- CH3- CH3- 1 3 2 1 494 CH3-(CH2)10- CH3- CH3- 1 2 1 3 495 CH3-(CH2)10- CH3- CH3- 1 3 1 2 496 CH3-(CH2)10- CH3- CH3- 2 1 1 3 497 CH3-(CH2)10- CH3- CH3- 2 1 3 1 498 CH3-(CH2)10- CH3- CH3- 2 3 1 1 499 CH3-(CH2)10- CH3- CH3- 3 1 1 2 500 CH3-(CH2)10- CH3- CH3- 3 1 2 1 501 CH3-(CH2)10- CH3- CH3- 3 2 1 1 502 CH3-(CH2)10- CH3- CH3- 1 1 2 4 503 CH3-(CH2)10- CH3- CH3- 1 1 4 2 504 CH3-(CH2)10- CH3- CH3- 1 2 4 1 505 CH3-(CH2)10- CH3- CH3- 1 4 2 1 506 CH3-(CH2)10- CH3- CH3- 1 2 1 4 507 CH3-(CH2)10- CH3- CH3- 1 4 1 2 508 CH3-(CH2)10- CH3- CH3- 2 1 1 4 509 CH3-(CH2)10- CH3- CH3- 2 1 4 1 510 CH3-(CH2)10- CH3- CH3- 2 4 1 1 511 CH3-(CH2)10- CH3- CH3- 4 1 1 2 512 CH3-(CH2)10- CH3- CH3- 4 1 2 1 513 CH3-(CH2)10- CH3- CH3- 4 2 1 1 514 CH3-(CH2)10- CH3- CH3- 1 1 4 3 515 CH3-(CH2)10- CH3- CH3- 1 1 3 4 516 CH3-(CH2)10- CH3- CH3- 1 4 3 1 517 CH3-(CH2)10- CH3- CH3- 1 3 4 1 518 CH3-(CH2)10- CH3- CH3- 1 4 1 3 519 CH3-(CH2)10- CH3- CH3- 1 3 1 4 520 CH3-(CH2)10- CH3- CH3- 4 1 1 3 521 CH3-(CH2)10- CH3- CH3- 4 1 3 1 522 CH3-(CH2)10- CH3- CH3- 4 3 1 1 523 CH3-(CH2)10- CH3- CH3- 3 1 1 4 524 CH3-(CH2)10- CH3- CH3- 3 1 4 1 525 CH3-(CH2)10- CH3- CH3- 3 4 1 1 526 CH3-(CH2)10- CH3- CH3- 1 2 2 2 527 CH3-(CH2)10- CH3- CH3- 2 1 2 2 528 CH3-(CH2)10- CH3- CH3- 2 2 1 2 529 CH3-(CH2)10- CH3- CH3- 2 2 2 1 530 CH3-(CH2)10- CH3- CH3- 1 3 3 3 531 CH3-(CH2)10- CH3- CH3- 3 1 3 3 532 CH3-(CH2)10- CH3- CH3- 3 3 1 3 533 CH3-(CH2)10- CH3- CH3- 3 3 3 1 534 CH3-(CH2)10- CH3- CH3- 1 4 4 4 535 CH3-(CH2)10- CH3- CH3- 4 1 4 4 536 CH3-(CH2)10- CH3- CH3- 4 4 1 4 537 CH3-(CH2)10- CH3- CH3- 4 4 4 1 538 CH3-(CH2)10- CH3- CH3- 2 2 1 3 539 CH3-(CH2)10- CH3- CH3- 2 2 3 1 540 CH3-(CH2)10- CH3- CH3- 2 1 2 3 541 CH3-(CH2)10- CH3- CH3- 2 3 2 1 542 CH3-(CH2)10- CH3- CH3- 2 1 3 2 543 CH3-(CH2)10- CH3- CH3- 2 3 1 2 544 CH3-(CH2)10- CH3- CH3- 1 2 2 3 545 CH3-(CH2)10- CH3- CH3- 1 2 3 2 546 CH3-(CH2)10- CH3- CH3- 1 3 2 2 547 CH3-(CH2)10- CH3- CH3- 3 2 2 1 548 CH3-(CH2)10- CH3- CH3- 3 2 1 2 549 CH3-(CH2)10- CH3- CH3- 3 1 2 2 550 CH3-(CH2)10- CH3- CH3- 2 2 1 4 551 CH3-(CH2)10- CH3- CH3- 2 2 4 1 552 CH3-(CH2)10- CH3- CH3- 2 1 2 4 553 CH3-(CH2)10- CH3- CH3- 2 4 2 1 554 CH3-(CH2)10- CH3- CH3- 2 1 4 2 555 CH3-(CH2)10- CH3- CH3- 2 4 1 2 556 CH3-(CH2)10- CH3- CH3- 1 2 2 4 557 CH3-(CH2)10- CH3- CH3- 1 2 4 2 558 CH3-(CH2)10- CH3- CH3- 1 4 2 2 559 CH3-(CH2)10- CH3- CH3- 4 2 2 1 560 CH3-(CH2)10- CH3- CH3- 4 2 1 2 561 CH3-(CH2)10- CH3- CH3- 4 1 2 2 562 CH3-(CH2)10- CH3- CH3- 2 2 4 3 563 CH3-(CH2)10- CH3- CH3- 2 2 3 4 564 CH3-(CH2)10- CH3- CH3- 2 4 2 3 565 CH3-(CH2)10- CH3- CH3- 2 3 2 4 566 CH3-(CH2)10- CH3- CH3- 2 4 3 2 567 CH3-(CH2)10- CH3- CH3- 2 3 4 2 568 CH3-(CH2)10- CH3- CH3- 4 2 2 3 569 CH3-(CH2)10- CH3- CH3- 4 2 3 2 570 CH3-(CH2)10- CH3- CH3- 4 3 2 2 571 CH3-(CH2)10- CH3- CH3- 3 2 2 4 572 CH3-(CH2)10- CH3- CH3- 3 2 4 2 573 CH3-(CH2)10- CH3- CH3- 3 4 2 2 574 CH3-(CH2)10- CH3- CH3- 3 3 1 2 575 CH3-(CH2)10- CH3- CH3- 3 3 2 1 576 CH3-(CH2)10- CH3- CH3- 3 1 3 2 577 CH3-(CH2)10- CH3- CH3- 3 2 3 1 578 CH3-(CH2)10- CH3- CH3- 3 1 2 3 579 CH3-(CH2)10- CH3- CH3- 3 2 1 3 580 CH3-(CH2)10- CH3- CH3- 1 3 3 2 581 CH3-(CH2)10- CH3- CH3- 1 3 2 3 582 CH3-(CH2)10- CH3- CH3- 1 2 3 3 583 CH3-(CH2)10- CH3- CH3- 2 3 3 1 584 CH3-(CH2)10- CH3- CH3- 2 3 1 3 585 CH3-(CH2)10- CH3- CH3- 2 1 3 3 586 CH3-(CH2)10- CH3- CH3- 3 3 1 4 587 CH3-(CH2)10- CH3- CH3- 3 3 4 1 588 CH3-(CH2)10- CH3- CH3- 3 1 3 4 589 CH3-(CH2)10- CH3- CH3- 3 4 3 1 590 CH3-(CH2)10- CH3- CH3- 3 1 4 3 591 CH3-(CH2)10- CH3- CH3- 3 4 1 3 592 CH3-(CH2)10- CH3- CH3- 1 3 3 4 593 CH3-(CH2)10- CH3- CH3- 1 3 4 3 594 CH3-(CH2)10- CH3- CH3- 1 4 3 3 595 CH3-(CH2)10- CH3- CH3- 4 3 3 1 596 CH3-(CH2)10- CH3- CH3- 4 3 1 3 597 CH3-(CH2)10- CH3- CH3- 4 1 3 3 598 CH3-(CH2)10- CH3- CH3- 3 3 4 2 599 CH3-(CH2)10- CH3- CH3- 3 3 2 4 600 CH3-(CH2)10- CH3- CH3- 3 4 3 2 601 CH3-(CH2)10- CH3- CH3- 3 2 3 4 602 CH3-(CH2)10- CH3- CH3- 3 4 2 3 603 CH3-(CH2)10- CH3- CH3- 3 2 4 3 604 CH3-(CH2)10- CH3- CH3- 4 3 3 2 605 CH3-(CH2)10- CH3- CH3- 4 3 2 3 606 CH3-(CH2)10- CH3- CH3- 4 2 3 3 607 CH3-(CH2)10- CH3- CH3- 2 3 3 4 608 CH3-(CH2)10- CH3- CH3- 2 3 4 3 609 CH3-(CH2)10- CH3- CH3- 2 4 3 3 610 CH3-(CH2)10- CH3- CH3- 4 4 1 2 611 CH3-(CH2)10- CH3- CH3- 4 4 2 1 612 CH3-(CH2)10- CH3- CH3- 4 1 4 2 613 CH3-(CH2)10- CH3- CH3- 4 2 4 1 614 CH3-(CH2)10- CH3- CH3- 4 1 2 4 615 CH3-(CH2)10- CH3- CH3- 4 2 1 4 616 CH3-(CH2)10- CH3- CH3- 1 4 4 2 617 CH3-(CH2)10- CH3- CH3- 1 4 2 4 618 CH3-(CH2)10- CH3- CH3- 1 2 4 4 619 CH3-(CH2)10- CH3- CH3- 2 4 4 1 620 CH3-(CH2)10- CH3- CH3- 2 4 1 4 621 CH3-(CH2)10- CH3- CH3- 2 1 4 4 622 CH3-(CH2)10- CH3- CH3- 4 4 1 3 623 CH3-(CH2)10- CH3- CH3- 4 4 3 1 624 CH3-(CH2)10- CH3- CH3- 4 1 4 3 625 CH3-(CH2)10- CH3- CH3- 4 3 4 1 626 CH3-(CH2)10- CH3- CH3- 4 1 3 4 627 CH3-(CH2)10- CH3- CH3- 4 3 1 4 628 CH3-(CH2)10- CH3- CH3- 1 4 4 3 629 CH3-(CH2)10- CH3- CH3- 1 4 3 4 630 CH3-(CH2)10- CH3- CH3- 1 3 4 4 631 CH3-(CH2)10- CH3- CH3- 3 4 4 1 632 CH3-(CH2)10- CH3- CH3- 3 4 1 4 633 CH3-(CH2)10- CH3- CH3- 3 1 4 4 634 CH3-(CH2)10- CH3- CH3- 4 4 3 2 635 CH3-(CH2)10- CH3- CH3- 4 4 2 3 636 CH3-(CH2)10- CH3- CH3- 4 3 4 2 637 CH3-(CH2)10- CH3- CH3- 4 2 4 3 638 CH3-(CH2)10- CH3- CH3- 4 3 2 4 639 CH3-(CH2)10- CH3- CH3- 4 2 3 4 640 CH3-(CH2)10- CH3- CH3- 3 4 4 2 641 CH3-(CH2)10- CH3- CH3- 3 4 2 4 642 CH3-(CH2)10- CH3- CH3- 3 2 4 4 643 CH3-(CH2)10- CH3- CH3- 2 4 4 3 644 CH3-(CH2)10- CH3- CH3- 2 4 3 4 645 CH3-(CH2)10- CH3- CH3- 2 3 4 4 646 CH3-(CH2)10- CH3- CH3- 1 2 3 4 647 CH3-(CH2)10- CH3- CH3- 1 2 4 3 648 CH3-(CH2)10- CH3- CH3- 1 3 2 4 649 CH3-(CH2)10- CH3- CH3- 1 3 4 2 650 CH3-(CH2)10- CH3- CH3- 1 4 2 3 651 CH3-(CH2)10- CH3- CH3- 1 4 3 2 652 CH3-(CH2)10- CH3- CH3- 2 1 3 4 653 CH3-(CH2)10- CH3- CH3- 2 1 4 3 654 CH3-(CH2)10- CH3- CH3- 2 3 1 4 655 CH3-(CH2)10- CH3- CH3- 2 3 4 1 656 CH3-(CH2)10- CH3- CH3- 2 4 1 3 657 CH3-(CH2)10- CH3- CH3- 2 4 3 1 658 CH3-(CH2)10- CH3- CH3- 3 1 2 4 659 CH3-(CH2)10- CH3- CH3- 3 1 4 2 660 CH3-(CH2)10- CH3- CH3- 3 2 1 4 661 CH3-(CH2)10- CH3- CH3- 3 2 4 1 662 CH3-(CH2)10- CH3- CH3- 3 4 1 2 663 CH3-(CH2)10- CH3- CH3- 3 4 2 1 664 CH3-(CH2)10- CH3- CH3- 4 1 2 3 665 CH3-(CH2)10- CH3- CH3- 4 1 3 2 666 CH3-(CH2)10- CH3- CH3- 4 2 1 3 667 CH3-(CH2)10- CH3- CH3- 4 2 3 1 668 CH3-(CH2)10- CH3- CH3- 4 3 1 2 669 CH3-(CH2)10- CH3- CH3- 4 3 2 1 670 CH3-(CH2)10- CH3- CH3- 2 3 3 2 671 CH3-(CH2)10- CH3- CH3- 2 3 2 3 672 CH3-(CH2)10- CH3- CH3- 2 2 3 3 673 CH3-(CH2)10- CH3- CH3- 3 3 2 2 674 CH3-(CH2)10- CH3- CH3- 3 2 3 2 675 CH3-(CH2)10- CH3- CH3- 3 2 2 3 676 CH3-(CH2)10- CH3- CH3- 2 4 4 2 677 CH3-(CH2)10- CH3- CH3- 2 4 2 4 678 CH3-(CH2)10- CH3- CH3- 2 2 4 4 679 CH3-(CH2)10- CH3- CH3- 4 4 2 2 680 CH3-(CH2)10- CH3- CH3- 4 2 4 2 681 CH3-(CH2)10- CH3- CH3- 4 2 2 4 682 CH3-(CH2)10- CH3- CH3- 3 4 4 3 683 CH3-(CH2)10- CH3- CH3- 3 4 3 4 684 CH3-(CH2)10- CH3- CH3- 3 3 4 4 685 CH3-(CH2)10- CH3- CH3- 4 4 3 3 686 CH3-(CH2)10- CH3- CH3- 4 3 4 3 687 CH3-(CH2)10- CH3- CH3- 4 3 3 4 688 CH3-(CH2)11- CH3- CH3- 1 1 1 1 689 CH3-(CH2)11- CH3- CH3- 2 1 1 1 690 CH3-(CH2)11- CH3- CH3- 1 2 1 1 691 CH3-(CH2)11- CH3- CH3- 1 1 2 1 692 CH3-(CH2)11- CH3- CH3- 1 1 1 2 693 CH3-(CH2)11- CH3- CH3- 3 1 1 1 694 CH3-(CH2)11- CH3- CH3- 1 3 1 1 695 CH3-(CH2)11- CH3- CH3- 1 1 3 1 696 CH3-(CH2)11- CH3- CH3- 1 1 1 3 697 CH3-(CH2)11- CH3- CH3- 4 1 1 1 698 CH3-(CH2)11- CH3- CH3- 1 4 1 1 699 CH3-(CH2)11- CH3- CH3- 1 1 4 1 700 CH3-(CH2)11- CH3- CH3- 1 1 1 4 701 CH3-(CH2)11- CH3- CH3- 1 2 2 1 702 CH3-(CH2)11- CH3- CH3- 1 2 1 2 703 CH3-(CH2)11- CH3- CH3- 1 1 2 2 704 CH3-(CH2)11- CH3- CH3- 2 2 1 1 705 CH3-(CH2)11- CH3- CH3- 2 1 2 1 706 CH3-(CH2)11- CH3- CH3- 2 1 1 2 707 CH3-(CH2)11- CH3- CH3- 1 3 3 1 708 CH3-(CH2)11- CH3- CH3- 1 3 1 3 709 CH3-(CH2)11- CH3- CH3- 1 1 3 3 710 CH3-(CH2)11- CH3- CH3- 3 3 1 1 711 CH3-(CH2)11- CH3- CH3- 3 1 3 1 712 CH3-(CH2)11- CH3- CH3- 3 1 1 3 713 CH3-(CH2)11- CH3- CH3- 1 4 4 1 714 CH3-(CH2)11- CH3- CH3- 1 4 1 4 715 CH3-(CH2)11- CH3- CH3- 1 1 4 4 716 CH3-(CH2)11- CH3- CH3- 4 4 1 1 717 CH3-(CH2)11- CH3- CH3- 4 1 4 1 718 CH3-(CH2)11- CH3- CH3- 4 1 1 4 719 CH3-(CH2)11- CH3- CH3- 1 1 2 3 720 CH3-(CH2)11- CH3- CH3- 1 1 3 2 721 CH3-(CH2)11- CH3- CH3- 1 2 3 1 722 CH3-(CH2)11- CH3- CH3- 1 3 2 1 723 CH3-(CH2)11- CH3- CH3- 1 2 1 3 724 CH3-(CH2)11- CH3- CH3- 1 3 1 2 725 CH3-(CH2)11- CH3- CH3- 2 1 1 3 726 CH3-(CH2)11- CH3- CH3- 2 1 3 1 727 CH3-(CH2)11- CH3- CH3- 2 3 1 1 728 CH3-(CH2)11- CH3- CH3- 3 1 1 2 729 CH3-(CH2)11- CH3- CH3- 3 1 2 1 730 CH3-(CH2)11- CH3- CH3- 3 2 1 1 731 CH3-(CH2)11- CH3- CH3- 1 1 2 4 732 CH3-(CH2)11- CH3- CH3- 1 1 4 2 733 CH3-(CH2)11- CH3- CH3- 1 2 4 1 734 CH3-(CH2)11- CH3- CH3- 1 4 2 1 735 CH3-(CH2)11- CH3- CH3- 1 2 1 4 736 CH3-(CH2)11- CH3- CH3- 1 4 1 2 737 CH3-(CH2)11- CH3- CH3- 2 1 1 4 738 CH3-(CH2)11- CH3- CH3- 2 1 4 1 739 CH3-(CH2)11- CH3- CH3- 2 4 1 1 740 CH3-(CH2)11- CH3- CH3- 4 1 1 2 741 CH3-(CH2)11- CH3- CH3- 4 1 2 1 742 CH3-(CH2)11- CH3- CH3- 4 2 1 1 743 CH3-(CH2)11- CH3- CH3- 1 1 4 3 744 CH3-(CH2)11- CH3- CH3- 1 1 3 4 745 CH3-(CH2)11- CH3- CH3- 1 4 3 1 746 CH3-(CH2)11- CH3- CH3- 1 3 4 1 747 CH3-(CH2)11- CH3- CH3- 1 4 1 3 748 CH3-(CH2)11- CH3- CH3- 1 3 1 4 749 CH3-(CH2)11- CH3- CH3- 4 1 1 3 750 CH3-(CH2)11- CH3- CH3- 4 1 3 1 751 CH3-(CH2)11- CH3- CH3- 4 3 1 1 752 CH3-(CH2)11- CH3- CH3- 3 1 1 4 753 CH3-(CH2)11- CH3- CH3- 3 1 4 1 754 CH3-(CH2)11- CH3- CH3- 3 4 1 1 755 CH3-(CH2)11- CH3- CH3- 1 2 2 2 756 CH3-(CH2)11- CH3- CH3- 2 1 2 2 757 CH3-(CH2)11- CH3- CH3- 2 2 1 2 758 CH3-(CH2)11- CH3- CH3- 2 2 2 1 759 CH3-(CH2)11- CH3- CH3- 1 3 3 3 760 CH3-(CH2)11- CH3- CH3- 3 1 3 3 761 CH3-(CH2)11- CH3- CH3- 3 3 1 3 762 CH3-(CH2)11- CH3- CH3- 3 3 3 1 763 CH3-(CH2)11- CH3- CH3- 1 4 4 4 764 CH3-(CH2)11- CH3- CH3- 4 1 4 4 765 CH3-(CH2)11- CH3- CH3- 4 4 1 4 766 CH3-(CH2)11- CH3- CH3- 4 4 4 1 767 CH3-(CH2)11- CH3- CH3- 2 2 1 3 768 CH3-(CH2)11- CH3- CH3- 2 2 3 1 769 CH3-(CH2)11- CH3- CH3- 2 1 2 3 770 CH3-(CH2)11- CH3- CH3- 2 3 2 1 771 CH3-(CH2)11- CH3- CH3- 2 1 3 2 772 CH3-(CH2)11- CH3- CH3- 2 3 1 2 773 CH3-(CH2)11- CH3- CH3- 1 2 2 3 774 CH3-(CH2)11- CH3- CH3- 1 2 3 2 775 CH3-(CH2)11- CH3- CH3- 1 3 2 2 776 CH3-(CH2)11- CH3- CH3- 3 2 2 1 777 CH3-(CH2)11- CH3- CH3- 3 2 1 2 778 CH3-(CH2)11- CH3- CH3- 3 1 2 2 779 CH3-(CH2)11- CH3- CH3- 2 2 1 4 780 CH3-(CH2)11- CH3- CH3- 2 2 4 1 781 CH3-(CH2)11- CH3- CH3- 2 1 2 4 782 CH3-(CH2)11- CH3- CH3- 2 4 2 1 783 CH3-(CH2)11- CH3- CH3- 2 1 4 2 784 CH3-(CH2)11- CH3- CH3- 2 4 1 2 785 CH3-(CH2)11- CH3- CH3- 1 2 2 4 786 CH3-(CH2)11- CH3- CH3- 1 2 4 2 787 CH3-(CH2)11- CH3- CH3- 1 4 2 2 788 CH3-(CH2)11- CH3- CH3- 4 2 2 1 789 CH3-(CH2)11- CH3- CH3- 4 2 1 2 790 CH3-(CH2)11- CH3- CH3- 4 1 2 2 791 CH3-(CH2)11- CH3- CH3- 2 2 4 3 792 CH3-(CH2)11- CH3- CH3- 2 2 3 4 793 CH3-(CH2)11- CH3- CH3- 2 4 2 3 794 CH3-(CH2)11- CH3- CH3- 2 3 2 4 795 CH3-(CH2)11- CH3- CH3- 2 4 3 2 796 CH3-(CH2)11- CH3- CH3- 2 3 4 2 797 CH3-(CH2)11- CH3- CH3- 4 2 2 3 798 CH3-(CH2)11- CH3- CH3- 4 2 3 2 799 CH3-(CH2)11- CH3- CH3- 4 3 2 2 800 CH3-(CH2)11- CH3- CH3- 3 2 2 4 801 CH3-(CH2)11- CH3- CH3- 3 2 4 2 802 CH3-(CH2)11- CH3- CH3- 3 4 2 2 803 CH3-(CH2)11- CH3- CH3- 3 3 1 2 804 CH3-(CH2)11- CH3- CH3- 3 3 2 1 805 CH3-(CH2)11- CH3- CH3- 3 1 3 2 806 CH3-(CH2)11- CH3- CH3- 3 2 3 1 807 CH3-(CH2)11- CH3- CH3- 3 1 2 3 808 CH3-(CH2)11- CH3- CH3- 3 2 1 3 809 CH3-(CH2)11- CH3- CH3- 1 3 3 2 810 CH3-(CH2)11- CH3- CH3- 1 3 2 3 811 CH3-(CH2)11- CH3- CH3- 1 2 3 3 812 CH3-(CH2)11- CH3- CH3- 2 3 3 1 813 CH3-(CH2)11- CH3- CH3- 2 3 1 3 814 CH3-(CH2)11- CH3- CH3- 2 1 3 3 815 CH3-(CH2)11- CH3- CH3- 3 3 1 4 816 CH3-(CH2)11- CH3- CH3- 3 3 4 1 817 CH3-(CH2)11- CH3- CH3- 3 1 3 4 818 CH3-(CH2)11- CH3- CH3- 3 4 3 1 819 CH3-(CH2)11- CH3- CH3- 3 1 4 3 820 CH3-(CH2)11- CH3- CH3- 3 4 1 3 821 CH3-(CH2)11- CH3- CH3- 1 3 3 4 822 CH3-(CH2)11- CH3- CH3- 1 3 4 3 823 CH3-(CH2)11- CH3- CH3- 1 4 3 3 824 CH3-(CH2)11- CH3- CH3- 4 3 3 1 825 CH3-(CH2)11- CH3- CH3- 4 3 1 3 826 CH3-(CH2)11- CH3- CH3- 4 1 3 3 827 CH3-(CH2)11- CH3- CH3- 3 3 4 2 828 CH3-(CH2)11- CH3- CH3- 3 3 2 4 829 CH3-(CH2)11- CH3- CH3- 3 4 3 2 830 CH3-(CH2)11- CH3- CH3- 3 2 3 4 831 CH3-(CH2)11- CH3- CH3- 3 4 2 3 832 CH3-(CH2)11- CH3- CH3- 3 2 4 3 833 CH3-(CH2)11- CH3- CH3- 4 3 3 2 834 CH3-(CH2)11- CH3- CH3- 4 3 2 3 835 CH3-(CH2)11- CH3- CH3- 4 2 3 3 836 CH3-(CH2)11- CH3- CH3- 2 3 3 4 837 CH3-(CH2)11- CH3- CH3- 2 3 4 3 838 CH3-(CH2)11- CH3- CH3- 2 4 3 3 839 CH3-(CH2)11- CH3- CH3- 4 4 1 2 840 CH3-(CH2)11- CH3- CH3- 4 4 2 1 841 CH3-(CH2)11- CH3- CH3- 4 1 4 2 842 CH3-(CH2)11- CH3- CH3- 4 2 4 1 843 CH3-(CH2)11- CH3- CH3- 4 1 2 4 844 CH3-(CH2)11- CH3- CH3- 4 2 1 4 845 CH3-(CH2)11- CH3- CH3- 1 4 4 2 846 CH3-(CH2)11- CH3- CH3- 1 4 2 4 847 CH3-(CH2)11- CH3- CH3- 1 2 4 4 848 CH3-(CH2)11- CH3- CH3- 2 4 4 1 849 CH3-(CH2)11- CH3- CH3- 2 4 1 4 850 CH3-(CH2)11- CH3- CH3- 2 1 4 4 851 CH3-(CH2)11- CH3- CH3- 4 4 1 3 852 CH3-(CH2)11- CH3- CH3- 4 4 3 1 853 CH3-(CH2)11- CH3- CH3- 4 1 4 3 854 CH3-(CH2)11- CH3- CH3- 4 3 4 1 855 CH3-(CH2)11- CH3- CH3- 4 1 3 4 856 CH3-(CH2)11- CH3- CH3- 4 3 1 4 857 CH3-(CH2)11- CH3- CH3- 1 4 4 3 858 CH3-(CH2)11- CH3- CH3- 1 4 3 4 859 CH3-(CH2)11- CH3- CH3- 1 3 4 4 860 CH3-(CH2)11- CH3- CH3- 3 4 4 1 861 CH3-(CH2)11- CH3- CH3- 3 4 1 4 862 CH3-(CH2)11- CH3- CH3- 3 1 4 4 863 CH3-(CH2)11- CH3- CH3- 4 4 3 2 864 CH3-(CH2)11- CH3- CH3- 4 4 2 3 865 CH3-(CH2)11- CH3- CH3- 4 3 4 2 866 CH3-(CH2)11- CH3- CH3- 4 2 4 3 867 CH3-(CH2)11- CH3- CH3- 4 3 2 4 868 CH3-(CH2)11- CH3- CH3- 4 2 3 4 869 CH3-(CH2)11- CH3- CH3- 3 4 4 2 870 CH3-(CH2)11- CH3- CH3- 3 4 2 4 871 CH3-(CH2)11- CH3- CH3- 3 2 4 4 872 CH3-(CH2)11- CH3- CH3- 2 4 4 3 873 CH3-(CH2)11- CH3- CH3- 2 4 3 4 874 CH3-(CH2)11- CH3- CH3- 2 3 4 4 875 CH3-(CH2)11- CH3- CH3- 1 2 3 4 876 CH3-(CH2)11- CH3- CH3- 1 2 4 3 877 CH3-(CH2)11- CH3- CH3- 1 3 2 4 878 CH3-(CH2)11- CH3- CH3- 1 3 4 2 879 CH3-(CH2)11- CH3- CH3- 1 4 2 3 880 CH3-(CH2)11- CH3- CH3- 1 4 3 2 881 CH3-(CH2)11- CH3- CH3- 2 1 3 4 882 CH3-(CH2)11- CH3- CH3- 2 1 4 3 883 CH3-(CH2)11- CH3- CH3- 2 3 1 4 884 CH3-(CH2)11- CH3- CH3- 2 3 4 1 885 CH3-(CH2)11- CH3- CH3- 2 4 1 3 886 CH3-(CH2)11- CH3- CH3- 2 4 3 1 887 CH3-(CH2)11- CH3- CH3- 3 1 2 4 888 CH3-(CH2)11- CH3- CH3- 3 1 4 2 889 CH3-(CH2)11- CH3- CH3- 3 2 1 4 890 CH3-(CH2)11- CH3- CH3- 3 2 4 1 891 CH3-(CH2)11- CH3- CH3- 3 4 1 2 892 CH3-(CH2)11- CH3- CH3- 3 4 2 1 893 CH3-(CH2)11- CH3- CH3- 4 1 2 3 894 CH3-(CH2)11- CH3- CH3- 4 1 3 2 895 CH3-(CH2)11- CH3- CH3- 4 2 1 3 896 CH3-(CH2)11- CH3- CH3- 4 2 3 1 897 CH3-(CH2)11- CH3- CH3- 4 3 1 2 898 CH3-(CH2)11- CH3- CH3- 4 3 2 1 899 CH3-(CH2)11- CH3- CH3- 2 3 3 2 900 CH3-(CH2)11- CH3- CH3- 2 3 2 3 901 CH3-(CH2)11- CH3- CH3- 2 2 3 3 902 CH3-(CH2)11- CH3- CH3- 3 3 2 2 903 CH3-(CH2)11- CH3- CH3- 3 2 3 2 904 CH3-(CH2)11- CH3- CH3- 3 2 2 3 905 CH3-(CH2)11- CH3- CH3- 2 4 4 2 906 CH3-(CH2)11- CH3- CH3- 2 4 2 4 907 CH3-(CH2)11- CH3- CH3- 2 2 4 4 908 CH3-(CH2)11- CH3- CH3- 4 4 2 2 909 CH3-(CH2)11- CH3- CH3- 4 2 4 2 910 CH3-(CH2)11- CH3- CH3- 4 2 2 4 911 CH3-(CH2)11- CH3- CH3- 3 4 4 3 912 CH3-(CH2)11- CH3- CH3- 3 4 3 4 913 CH3-(CH2)11- CH3- CH3- 3 3 4 4 914 CH3-(CH2)11- CH3- CH3- 4 4 3 3 915 CH3-(CH2)11- CH3- CH3- 4 3 4 3 916 CH3-(CH2)11- CH3- CH3- 4 3 3 4 917 CH3-(CH2)12- CH3- CH3- 1 1 1 1 918 CH3-(CH2)12- CH3- CH3- 2 1 1 1 919 CH3-(CH2)12- CH3- CH3- 1 2 1 1 920 CH3-(CH2)12- CH3- CH3- 1 1 2 1 921 CH3-(CH2)12- CH3- CH3- 1 1 1 2 922 CH3-(CH2)12- CH3- CH3- 3 1 1 1 923 CH3-(CH2)12- CH3- CH3- 1 3 1 1 924 CH3-(CH2)12- CH3- CH3- 1 1 3 1 925 CH3-(CH2)12- CH3- CH3- 1 1 1 3 926 CH3-(CH2)12- CH3- CH3- 4 1 1 1 927 CH3-(CH2)12- CH3- CH3- 1 4 1 1 928 CH3-(CH2)12- CH3- CH3- 1 1 4 1 929 CH3-(CH2)12- CH3- CH3- 1 1 1 4 930 CH3-(CH2)12- CH3- CH3- 1 2 2 1 931 CH3-(CH2)12- CH3- CH3- 1 2 1 2 932 CH3-(CH2)12- CH3- CH3- 1 1 2 2 933 CH3-(CH2)12- CH3- CH3- 2 2 1 1 934 CH3-(CH2)12- CH3- CH3- 2 1 2 1 935 CH3-(CH2)12- CH3- CH3- 2 1 1 2 936 CH3-(CH2)12- CH3- CH3- 1 3 3 1 937 CH3-(CH2)12- CH3- CH3- 1 3 1 3 938 CH3-(CH2)12- CH3- CH3- 1 1 3 3 939 CH3-(CH2)12- CH3- CH3- 3 3 1 1 940 CH3-(CH2)12- CH3- CH3- 3 1 3 1 941 CH3-(CH2)12- CH3- CH3- 3 1 1 3 942 CH3-(CH2)12- CH3- CH3- 1 4 4 1 943 CH3-(CH2)12- CH3- CH3- 1 4 1 4 944 CH3-(CH2)12- CH3- CH3- 1 1 4 4 945 CH3-(CH2)12- CH3- CH3- 4 4 1 1 946 CH3-(CH2)12- CH3- CH3- 4 1 4 1 947 CH3-(CH2)12- CH3- CH3- 4 1 1 4 948 CH3-(CH2)12- CH3- CH3- 1 1 2 3 949 CH3-(CH2)12- CH3- CH3- 1 1 3 2 950 CH3-(CH2)12- CH3- CH3- 1 2 3 1 951 CH3-(CH2)12- CH3- CH3- 1 3 2 1 952 CH3-(CH2)12- CH3- CH3- 1 2 1 3 953 CH3-(CH2)12- CH3- CH3- 1 3 1 2 954 CH3-(CH2)12- CH3- CH3- 2 1 1 3 955 CH3-(CH2)12- CH3- CH3- 2 1 3 1 956 CH3-(CH2)12- CH3- CH3- 2 3 1 1 957 CH3-(CH2)12- CH3- CH3- 3 1 1 2 958 CH3-(CH2)12- CH3- CH3- 3 1 2 1 959 CH3-(CH2)12- CH3- CH3- 3 2 1 1 960 CH3-(CH2)12- CH3- CH3- 1 1 2 4 961 CH3-(CH2)12- CH3- CH3- 1 1 4 2 962 CH3-(CH2)12- CH3- CH3- 1 2 4 1 963 CH3-(CH2)12- CH3- CH3- 1 4 2 1 964 CH3-(CH2)12- CH3- CH3- 1 2 1 4 965 CH3-(CH2)12- CH3- CH3- 1 4 1 2 966 CH3-(CH2)12- CH3- CH3- 2 1 1 4 967 CH3-(CH2)12- CH3- CH3- 2 1 4 1 968 CH3-(CH2)12- CH3- CH3- 2 4 1 1 969 CH3-(CH2)12- CH3- CH3- 4 1 1 2 970 CH3-(CH2)12- CH3- CH3- 4 1 2 1 971 CH3-(CH2)12- CH3- CH3- 4 2 1 1 972 CH3-(CH2)12- CH3- CH3- 1 1 4 3 973 CH3-(CH2)12- CH3- CH3- 1 1 3 4 974 CH3-(CH2)12- CH3- CH3- 1 4 3 1 975 CH3-(CH2)12- CH3- CH3- 1 3 4 1 976 CH3-(CH2)12- CH3- CH3- 1 4 1 3 977 CH3-(CH2)12- CH3- CH3- 1 3 1 4 978 CH3-(CH2)12- CH3- CH3- 4 1 1 3 979 CH3-(CH2)12- CH3- CH3- 4 1 3 1 980 CH3-(CH2)12- CH3- CH3- 4 3 1 1 981 CH3-(CH2)12- CH3- CH3- 3 1 1 4 982 CH3-(CH2)12- CH3- CH3- 3 1 4 1 983 CH3-(CH2)12- CH3- CH3- 3 4 1 1 984 CH3-(CH2)12- CH3- CH3- 1 2 2 2 985 CH3-(CH2)12- CH3- CH3- 2 1 2 2 986 CH3-(CH2)12- CH3- CH3- 2 2 1 2 987 CH3-(CH2)12- CH3- CH3- 2 2 2 1 988 CH3-(CH2)12- CH3- CH3- 1 3 3 3 989 CH3-(CH2)12- CH3- CH3- 3 1 3 3 990 CH3-(CH2)12- CH3- CH3- 3 3 1 3 991 CH3-(CH2)12- CH3- CH3- 3 3 3 1 992 CH3-(CH2)12- CH3- CH3- 1 4 4 4 993 CH3-(CH2)12- CH3- CH3- 4 1 4 4 994 CH3-(CH2)12- CH3- CH3- 4 4 1 4 995 CH3-(CH2)12- CH3- CH3- 4 4 4 1 996 CH3-(CH2)12- CH3- CH3- 2 2 1 3 997 CH3-(CH2)12- CH3- CH3- 2 2 3 1 998 CH3-(CH2)12- CH3- CH3- 2 1 2 3 999 CH3-(CH2)12- CH3- CH3- 2 3 2 1 1000 CH3-(CH2)12- CH3- CH3- 2 1 3 2 1001 CH3-(CH2)12- CH3- CH3- 2 3 1 2 1002 CH3-(CH2)12- CH3- CH3- 1 2 2 3 1003 CH3-(CH2)12- CH3- CH3- 1 2 3 2 1004 CH3-(CH2)12- CH3- CH3- 1 3 2 2 1005 CH3-(CH2)12- CH3- CH3- 3 2 2 1 1006 CH3-(CH2)12- CH3- CH3- 3 2 1 2 1007 CH3-(CH2)12- CH3- CH3- 3 1 2 2 1008 CH3-(CH2)12- CH3- CH3- 2 2 1 4 1009 CH3-(CH2)12- CH3- CH3- 2 2 4 1 1010 CH3-(CH2)12- CH3- CH3- 2 1 2 4 1011 CH3-(CH2)12- CH3- CH3- 2 4 2 1 1012 CH3-(CH2)12- CH3- CH3- 2 1 4 2 1013 CH3-(CH2)12- CH3- CH3- 2 4 1 2 1014 CH3-(CH2)12- CH3- CH3- 1 2 2 4 1015 CH3-(CH2)12- CH3- CH3- 1 2 4 2 1016 CH3-(CH2)12- CH3- CH3- 1 4 2 2 1017 CH3-(CH2)12- CH3- CH3- 4 2 2 1 1018 CH3-(CH2)12- CH3- CH3- 4 2 1 2 1019 CH3-(CH2)12- CH3- CH3- 4 1 2 2 1020 CH3-(CH2)12- CH3- CH3- 2 2 4 3 1021 CH3-(CH2)12- CH3- CH3- 2 2 3 4 1022 CH3-(CH2)12- CH3- CH3- 2 4 2 3 1023 CH3-(CH2)12- CH3- CH3- 2 3 2 4 1024 CH3-(CH2)12- CH3- CH3- 2 4 3 2 1025 CH3-(CH2)12- CH3- CH3- 2 3 4 2 1026 CH3-(CH2)12- CH3- CH3- 4 2 2 3 1027 CH3-(CH2)12- CH3- CH3- 4 2 3 2 1028 CH3-(CH2)12- CH3- CH3- 4 3 2 2 1029 CH3-(CH2)12- CH3- CH3- 3 2 2 4 1030 CH3-(CH2)12- CH3- CH3- 3 2 4 2 1031 CH3-(CH2)12- CH3- CH3- 3 4 2 2 1032 CH3-(CH2)12- CH3- CH3- 3 3 1 2 1033 CH3-(CH2)12- CH3- CH3- 3 3 2 1 1034 CH3-(CH2)12- CH3- CH3- 3 1 3 2 1035 CH3-(CH2)12- CH3- CH3- 3 2 3 1 1036 CH3-(CH2)12- CH3- CH3- 3 1 2 3 1037 CH3-(CH2)12- CH3- CH3- 3 2 1 3 1038 CH3-(CH2)12- CH3- CH3- 1 3 3 2 1039 CH3-(CH2)12- CH3- CH3- 1 3 2 3 1040 CH3-(CH2)12- CH3- CH3- 1 2 3 3 1041 CH3-(CH2)12- CH3- CH3- 2 3 3 1 1042 CH3-(CH2)12- CH3- CH3- 2 3 1 3 1043 CH3-(CH2)12- CH3- CH3- 2 1 3 3 1044 CH3-(CH2)12- CH3- CH3- 3 3 1 4 1045 CH3-(CH2)12- CH3- CH3- 3 3 4 1 1046 CH3-(CH2)12- CH3- CH3- 3 1 3 4 1047 CH3-(CH2)12- CH3- CH3- 3 4 3 1 1048 CH3-(CH2)12- CH3- CH3- 3 1 4 3 1049 CH3-(CH2)12- CH3- CH3- 3 4 1 3 1050 CH3-(CH2)12- CH3- CH3- 1 3 3 4 1051 CH3-(CH2)12- CH3- CH3- 1 3 4 3 1052 CH3-(CH2)12- CH3- CH3- 1 4 3 3 1053 CH3-(CH2)12- CH3- CH3- 4 3 3 1 1054 CH3-(CH2)12- CH3- CH3- 4 3 1 3 1055 CH3-(CH2)12- CH3- CH3- 4 1 3 3 1056 CH3-(CH2)12- CH3- CH3- 3 3 4 2 1057 CH3-(CH2)12- CH3- CH3- 3 3 2 4 1058 CH3-(CH2)12- CH3- CH3- 3 4 3 2 1059 CH3-(CH2)12- CH3- CH3- 3 2 3 4 1060 CH3-(CH2)12- CH3- CH3- 3 4 2 3 1061 CH3-(CH2)12- CH3- CH3- 3 2 4 3 1062 CH3-(CH2)12- CH3- CH3- 4 3 3 2 1063 CH3-(CH2)12- CH3- CH3- 4 3 2 3 1064 CH3-(CH2)12- CH3- CH3- 4 2 3 3 1065 CH3-(CH2)12- CH3- CH3- 2 3 3 4 1066 CH3-(CH2)12- CH3- CH3- 2 3 4 3 1067 CH3-(CH2)12- CH3- CH3- 2 4 3 3 1068 CH3-(CH2)12- CH3- CH3- 4 4 1 2 1069 CH3-(CH2)12- CH3- CH3- 4 4 2 1 1070 CH3-(CH2)12- CH3- CH3- 4 1 4 2 1071 CH3-(CH2)12- CH3- CH3- 4 2 4 1 1072 CH3-(CH2)12- CH3- CH3- 4 1 2 4 1073 CH3-(CH2)12- CH3- CH3- 4 2 1 4 1074 CH3-(CH2)12- CH3- CH3- 1 4 4 2 1075 CH3-(CH2)12- CH3- CH3- 1 4 2 4 1076 CH3-(CH2)12- CH3- CH3- 1 2 4 4 1077 CH3-(CH2)12- CH3- CH3- 2 4 4 1 1078 CH3-(CH2)12- CH3- CH3- 2 4 1 4 1079 CH3-(CH2)12- CH3- CH3- 2 1 4 4 1080 CH3-(CH2)12- CH3- CH3- 4 4 1 3 1081 CH3-(CH2)12- CH3- CH3- 4 4 3 1 1082 CH3-(CH2)12- CH3- CH3- 4 1 4 3 1083 CH3-(CH2)12- CH3- CH3- 4 3 4 1 1084 CH3-(CH2)12- CH3- CH3- 4 1 3 4 1085 CH3-(CH2)12- CH3- CH3- 4 3 1 4 1086 CH3-(CH2)12- CH3- CH3- 1 4 4 3 1087 CH3-(CH2)12- CH3- CH3- 1 4 3 4 1088 CH3-(CH2)12- CH3- CH3- 1 3 4 4 1089 CH3-(CH2)12- CH3- CH3- 3 4 4 1 1090 CH3-(CH2)12- CH3- CH3- 3 4 1 4 1091 CH3-(CH2)12- CH3- CH3- 3 1 4 4 1092 CH3-(CH2)12- CH3- CH3- 4 4 3 2 1093 CH3-(CH2)12- CH3- CH3- 4 4 2 3 1094 CH3-(CH2)12- CH3- CH3- 4 3 4 2 1095 CH3-(CH2)12- CH3- CH3- 4 2 4 3 1096 CH3-(CH2)12- CH3- CH3- 4 3 2 4 1097 CH3-(CH2)12- CH3- CH3- 4 2 3 4 1098 CH3-(CH2)12- CH3- CH3- 3 4 4 2 1099 CH3-(CH2)12- CH3- CH3- 3 4 2 4 1100 CH3-(CH2)12- CH3- CH3- 3 2 4 4 1101 CH3-(CH2)12- CH3- CH3- 2 4 4 3 1102 CH3-(CH2)12- CH3- CH3- 2 4 3 4 1103 CH3-(CH2)12- CH3- CH3- 2 3 4 4 1104 CH3-(CH2)12- CH3- CH3- 1 2 3 4 1105 CH3-(CH2)12- CH3- CH3- 1 2 4 3 1106 CH3-(CH2)12- CH3- CH3- 1 3 2 4 1107 CH3-(CH2)12- CH3- CH3- 1 3 4 2 1108 CH3-(CH2)12- CH3- CH3- 1 4 2 3 1109 CH3-(CH2)12- CH3- CH3- 1 4 3 2 1110. CH3-(CH2)12- CH3- CH3- 2 1 3 4 1111 CH3-(CH2)12- CH3- CH3- 2 1 4 3 1112 CH3-(CH2)12- CH3- CH3- 2 3 1 4 1113 CH3-(CH2)12- CH3- CH3- 2 3 4 1 1114 CH3-(CH2)12- CH3- CH3- 2 4 1 3 1115 CH3-(CH2)12- CH3- CH3- 2 4 3 1 1116 CH3-(CH2)12- CH3- CH3- 3 1 2 4 1117 CH3-(CH2)12- CH3- CH3- 3 1 4 2 1118 CH3-(CH2)12- CH3- CH3- 3 2 1 4 1119 CH3-(CH2)12- CH3- CH3- 3 2 4 1 1120 CH3-(CH2)12- CH3- CH3- 3 4 1 2 1121 CH3-(CH2)12- CH3- CH3- 3 4 2 1 1122 CH3-(CH2)12- CH3- CH3- 4 1 2 3 1123 CH3-(CH2)12- CH3- CH3- 4 1 3 2 1124 CH3-(CH2)12- CH3- CH3- 4 2 1 3 1125 CH3-(CH2)12- CH3- CH3- 4 2 3 1 1126 CH3-(CH2)12- CH3- CH3- 4 3 1 2 1127 CH3-(CH2)12- CH3- CH3- 4 3 2 1 1128 CH3-(CH2)12- CH3- CH3- 2 3 3 2 1129 CH3-(CH2)12- CH3- CH3- 2 3 2 3 1130 CH3-(CH2)12- CH3- CH3- 2 2 3 3 1131 CH3-(CH2)12- CH3- CH3- 3 3 2 2 1132 CH3-(CH2)12- CH3- CH3- 3 2 3 2 1133 CH3-(CH2)12- CH3- CH3- 3 2 2 3 1134 CH3-(CH2)12- CH3- CH3- 2 4 4 2 1135 CH3-(CH2)12- CH3- CH3- 2 4 2 4 1136 CH3-(CH2)12- CH3- CH3- 2 2 4 4 1137 CH3-(CH2)12- CH3- CH3- 4 4 2 2 1138 CH3-(CH2)12- CH3- CH3- 4 2 4 2 1139 CH3-(CH2)12- CH3- CH3- 4 2 2 4 1140 CH3-(CH2)12- CH3- CH3- 3 4 4 3 1141 CH3-(CH2)12- CH3- CH3- 3 4 3 4 1142 CH3-(CH2)12- CH3- CH3- 3 3 4 4 1143 CH3-(CH2)12- CH3- CH3- 4 4 3 3 1144 CH3-(CH2)12- CH3- CH3- 4 3 4 3 1145 CH3-(CH2)12- CH3- CH3- 4 3 3 4 1146 CH3-(CH2)13- CH3- CH3- 1 1 1 1 1147 CH3-(CH2)13- CH3- CH3- 2 1 1 1 1148 CH3-(CH2)13- CH3- CH3- 1 2 1 1 1149 CH3-(CH2)13- CH3- CH3- 1 1 2 1 1150 CH3-(CH2)13- CH3- CH3- 1 1 1 2 1151 CH3-(CH2)13- CH3- CH3- 3 1 1 1 1152 CH3-(CH2)13- CH3- CH3- 1 3 1 1 1153 CH3-(CH2)13- CH3- CH3- 1 1 3 1 1154 CH3-(CH2)13- CH3- CH3- 1 1 1 3 1155 CH3-(CH2)13- CH3- CH3- 4 1 1 1 1156 CH3-(CH2)13- CH3- CH3- 1 4 1 1 1157 CH3-(CH2)13- CH3- CH3- 1 1 4 1 1158 CH3-(CH2)13- CH3- CH3- 1 1 1 4 1159 CH3-(CH2)13- CH3- CH3- 1 2 2 1 1160 CH3-(CH2)13- CH3- CH3- 1 2 1 2 1161 CH3-(CH2)13- CH3- CH3- 1 1 2 2 1162 CH3-(CH2)13- CH3- CH3- 2 2 1 1 1163 CH3-(CH2)13- CH3- CH3- 2 1 2 1 1164 CH3-(CH2)13- CH3- CH3- 2 1 1 2 1165 CH3-(CH2)13- CH3- CH3- 1 3 3 1 1166 CH3-(CH2)13- CH3- CH3- 1 3 1 3 1167 CH3-(CH2)13- CH3- CH3- 1 1 3 3 1168 CH3-(CH2)13- CH3- CH3- 3 3 1 1 1169 CH3-(CH2)13- CH3- CH3- 3 1 3 1 1170 CH3-(CH2)13- CH3- CH3- 3 1 1 3 1171 CH3-(CH2)13- CH3- CH3- 1 4 4 1 1172 CH3-(CH2)13- CH3- CH3- 1 4 1 4 1173 CH3-(CH2)13- CH3- CH3- 1 1 4 4 1174 CH3-(CH2)13- CH3- CH3- 4 4 1 1 1175 CH3-(CH2)13- CH3- CH3- 4 1 4 1 1176 CH3-(CH2)13- CH3- CH3- 4 1 1 4 1177 CH3-(CH2)13- CH3- CH3- 1 1 2 3 1178 CH3-(CH2)13- CH3- CH3- 1 1 3 2 1179 CH3-(CH2)13- CH3- CH3- 1 2 3 1 1180 CH3-(CH2)13- CH3- CH3- 1 3 2 1 1181 CH3-(CH2)13- CH3- CH3- 1 2 1 3 1182 CH3-(CH2)13- CH3- CH3- 1 3 1 2 1183 CH3-(CH2)13- CH3- CH3- 2 1 1 3 1184 CH3-(CH2)13- CH3- CH3- 2 1 3 1 1185 CH3-(CH2)13- CH3- CH3- 2 3 1 1 1186 CH3-(CH2)13- CH3- CH3- 3 1 1 2 1187 CH3-(CH2)13- CH3- CH3- 3 1 2 1 1188 CH3-(CH2)13- CH3- CH3- 3 2 1 1 1189 CH3-(CH2)13- CH3- CH3- 1 1 2 4 1190 CH3-(CH2)13- CH3- CH3- 1 1 4 2 1191 CH3-(CH2)13- CH3- CH3- 1 2 4 1 1192 CH3-(CH2)13- CH3- CH3- 1 4 2 1 1193 CH3-(CH2)13- CH3- CH3- 1 2 1 4 1194 CH3-(CH2)13- CH3- CH3- 1 4 1 2 1195 CH3-(CH2)13- CH3- CH3- 2 1 1 4 1196 CH3-(CH2)13- CH3- CH3- 2 1 4 1 1197 CH3-(CH2)13- CH3- CH3- 2 4 1 1 1198 CH3-(CH2)13- CH3- CH3- 4 1 1 2 1199 CH3-(CH2)13- CH3- CH3- 4 1 2 1 1200 CH3-(CH2)13- CH3- CH3- 4 2 1 1 1201 CH3-(CH2)13- CH3- CH3- 1 1 4 3 1202 CH3-(CH2)13- CH3- CH3- 1 1 3 4 1203 CH3-(CH2)13- CH3- CH3- 1 4 3 1 1204 CH3-(CH2)13- CH3- CH3- 1 3 4 1 1205 CH3-(CH2)13- CH3- CH3- 1 4 1 3 1206 CH3-(CH2)13- CH3- CH3- 1 3 1 4 1207 CH3-(CH2)13- CH3- CH3- 4 1 1 3 1208 CH3-(CH2)13- CH3- CH3- 4 1 3 1 1209 CH3-(CH2)13- CH3- CH3- 4 3 1 1 1210 CH3-(CH2)13- CH3- CH3- 3 1 1 4 1211 CH3-(CH2)13- CH3- CH3- 3 1 4 1 1212 CH3-(CH2)13- CH3- CH3- 3 4 1 1 1213 CH3-(CH2)13- CH3- CH3- 1 2 2 2 1214 CH3-(CH2)13- CH3- CH3- 2 1 2 2 1215 CH3-(CH2)13- CH3- CH3- 2 2 1 2 1216 CH3-(CH2)13- CH3- CH3- 2 2 2 1 1217 CH3-(CH2)13- CH3- CH3- 1 3 3 3 1218 CH3-(CH2)13- CH3- CH3- 3 1 3 3 1219 CH3-(CH2)13- CH3- CH3- 3 3 1 3 1220 CH3-(CH2)13- CH3- CH3- 3 3 3 1 1221 CH3-(CH2)13- CH3- CH3- 1 4 4 4 1222 CH3-(CH2)13- CH3- CH3- 4 1 4 4 1223 CH3-(CH2)13- CH3- CH3- 4 4 1 4 1224 CH3-(CH2)13- CH3- CH3- 4 4 4 1 1225 CH3-(CH2)13- CH3- CH3- 2 2 1 3 1226 CH3-(CH2)13- CH3- CH3- 2 2 3 1 1227 CH3-(CH2)13- CH3- CH3- 2 1 2 3 1228 CH3-(CH2)13- CH3- CH3- 2 3 2 1 1229 CH3-(CH2)13- CH3- CH3- 2 1 3 2 1230 CH3-(CH2)13- CH3- CH3- 2 3 1 2 1231 CH3-(CH2)13- CH3- CH3- 1 2 2 3 1232 CH3-(CH2)13- CH3- CH3- 1 2 3 2 1233 CH3-(CH2)13- CH3- CH3- 1 3 2 2 1234 CH3-(CH2)13- CH3- CH3- 3 2 2 1 1235 CH3-(CH2)13- CH3- CH3- 3 2 1 2 1236 CH3-(CH2)13- CH3- CH3- 3 1 2 2 1237 CH3-(CH2)13- CH3- CH3- 2 2 1 4 1238 CH3-(CH2)13- CH3- CH3- 2 2 4 1 1239 CH3-(CH2)13- CH3- CH3- 2 1 2 4 1240 CH3-(CH2)13- CH3- CH3- 2 4 2 1 1241 CH3-(CH2)13- CH3- CH3- 2 1 4 2 1242 CH3-(CH2)13- CH3- CH3- 2 4 1 2 1243 CH3-(CH2)13- CH3- CH3- 1 2 2 4 1244 CH3-(CH2)13- CH3- CH3- 1 2 4 2 1245 CH3-(CH2)13- CH3- CH3- 1 4 2 2 1246 CH3-(CH2)13- CH3- CH3- 4 2 2 1 1247 CH3-(CH2)13- CH3- CH3- 4 2 1 2 1248 CH3-(CH2)13- CH3- CH3- 4 1 2 2 1249 CH3-(CH2)13- CH3- CH3- 2 2 4 3 1250 CH3-(CH2)13- CH3- CH3- 2 2 3 4 1251 CH3-(CH2)13- CH3- CH3- 2 4 2 3 1252 CH3-(CH2)13- CH3- CH3- 2 3 2 4 1253 CH3-(CH2)13- CH3- CH3- 2 4 3 2 1254 CH3-(CH2)13- CH3- CH3- 2 3 4 2 1255 CH3-(CH2)13- CH3- CH3- 4 2 2 3 1256 CH3-(CH2)13- CH3- CH3- 4 2 3 2 1257 CH3-(CH2)13- CH3- CH3- 4 3 2 2 1258 CH3-(CH2)13- CH3- CH3- 3 2 2 4 1259 CH3-(CH2)13- CH3- CH3- 3 2 4 2 1260 CH3-(CH2)13- CH3- CH3- 3 4 2 2 1261 CH3-(CH2)13- CH3- CH3- 3 3 1 2 1262 CH3-(CH2)13- CH3- CH3- 3 3 2 1 1263 CH3-(CH2)13- CH3- CH3- 3 1 3 2 1264 CH3-(CH2)13- CH3- CH3- 3 2 3 1 1265 CH3-(CH2)13- CH3- CH3- 3 1 2 3 1266 CH3-(CH2)13- CH3- CH3- 3 2 1 3 1267 CH3-(CH2)13- CH3- CH3- 1 3 3 2 1268 CH3-(CH2)13- CH3- CH3- 1 3 2 3 1269 CH3-(CH2)13- CH3- CH3- 1 2 3 3 1270 CH3-(CH2)13- CH3- CH3- 2 3 3 1 1271 CH3-(CH2)13- CH3- CH3- 2 3 1 3 1272 CH3-(CH2)13- CH3- CH3- 2 1 3 3 1273 CH3-(CH2)13- CH3- CH3- 3 3 1 4 1274 CH3-(CH2)13- CH3- CH3- 3 3 4 1 1275 CH3-(CH2)13- CH3- CH3- 3 1 3 4 1276 CH3-(CH2)13- CH3- CH3- 3 4 3 1 1277 CH3-(CH2)13- CH3- CH3- 3 1 4 3 1278 CH3-(CH2)13- CH3- CH3- 3 4 1 3 1279 CH3-(CH2)13- CH3- CH3- 1 3 3 4 1280 CH3-(CH2)13- CH3- CH3- 1 3 4 3 1281 CH3-(CH2)13- CH3- CH3- 1 4 3 3 1282 CH3-(CH2)13- CH3- CH3- 4 3 3 1 1283 CH3-(CH2)13- CH3- CH3- 4 3 1 3 1284 CH3-(CH2)13- CH3- CH3- 4 1 3 3 1285 CH3-(CH2)13- CH3- CH3- 3 3 4 2 1286 CH3-(CH2)13- CH3- CH3- 3 3 2 4 1287 CH3-(CH2)13- CH3- CH3- 3 4 3 2 1288 CH3-(CH2)13- CH3- CH3- 3 2 3 4 1289 CH3-(CH2)13- CH3- CH3- 3 4 2 3 1290 CH3-(CH2)13- CH3- CH3- 3 2 4 3 1291 CH3-(CH2)13- CH3- CH3- 4 3 3 2 1292 CH3-(CH2)13- CH3- CH3- 4 3 2 3 1293 CH3-(CH2)13- CH3- CH3- 4 2 3 3 1294 CH3-(CH2)13- CH3- CH3- 2 3 3 4 1295 CH3-(CH2)13- CH3- CH3- 2 3 4 3 1296 CH3-(CH2)13- CH3- CH3- 2 4 3 3 1297 CH3-(CH2)13- CH3- CH3- 4 4 1 2 1298 CH3-(CH2)13- CH3- CH3- 4 4 2 1 1299 CH3-(CH2)13- CH3- CH3- 4 1 4 2 1300 CH3-(CH2)13- CH3- CH3- 4 2 4 1 1301 CH3-(CH2)13- CH3- CH3- 4 1 2 4 1302 CH3-(CH2)13- CH3- CH3- 4 2 1 4 1303 CH3-(CH2)13- CH3- CH3- 1 4 4 2 1304 CH3-(CH2)13- CH3- CH3- 1 4 2 4 1305 CH3-(CH2)13- CH3- CH3- 1 2 4 4 1306 CH3-(CH2)13- CH3- CH3- 2 4 4 1 1307 CH3-(CH2)13- CH3- CH3- 2 4 1 4 1308 CH3-(CH2)13- CH3- CH3- 2 1 4 4 1309 CH3-(CH2)13- CH3- CH3- 4 4 1 3 1310 CH3-(CH2)13- CH3- CH3- 4 4 3 1 1311 CH3-(CH2)13- CH3- CH3- 4 1 4 3 1312 CH3-(CH2)13- CH3- CH3- 4 3 4 1 1313 CH3-(CH2)13- CH3- CH3- 4 1 3 4 1314 CH3-(CH2)13- CH3- CH3- 4 3 1 4 1315 CH3-(CH2)13- CH3- CH3- 1 4 4 3 1316 CH3-(CH2)13- CH3- CH3- 1 4 3 4 1317 CH3-(CH2)13- CH3- CH3- 1 3 4 4 1318 CH3-(CH2)13- CH3- CH3- 3 4 4 1 1319 CH3-(CH2)13- CH3- CH3- 3 4 1 4 1320 CH3-(CH2)13- CH3- CH3- 3 1 4 4 1321 CH3-(CH2)13- CH3- CH3- 4 4 3 2 1322 CH3-(CH2)13- CH3- CH3- 4 4 2 3 1323 CH3-(CH2)13- CH3- CH3- 4 3 4 2 1324 CH3-(CH2)13- CH3- CH3- 4 2 4 3 1325 CH3-(CH2)13- CH3- CH3- 4 3 2 4 1326 CH3-(CH2)13- CH3- CH3- 4 2 3 4 1327 CH3-(CH2)13- CH3- CH3- 3 4 4 2 1328 CH3-(CH2)13- CH3- CH3- 3 4 2 4 1329 CH3-(CH2)13- CH3- CH3- 3 2 4 4 1330 CH3-(CH2)13- CH3- CH3- 2 4 4 3 1331 CH3-(CH2)13- CH3- CH3- 2 4 3 4 1332 CH3-(CH2)13- CH3- CH3- 2 3 4 4 1333 CH3-(CH2)13- CH3- CH3- 1 2 3 4 1334 CH3-(CH2)13- CH3- CH3- 1 2 4 3 1335 CH3-(CH2)13- CH3- CH3- 1 3 2 4 1336 CH3-(CH2)13- CH3- CH3- 1 3 4 2 1337 CH3-(CH2)13- CH3- CH3- 1 4 2 3 1338 CH3-(CH2)13- CH3- CH3- 1 4 3 2 1339 CH3-(CH2)13- CH3- CH3- 2 1 3 4 1340 CH3-(CH2)13- CH3- CH3- 2 1 4 3 1341 CH3-(CH2)13- CH3- CH3- 2 3 1 4 1342 CH3-(CH2)13- CH3- CH3- 2 3 4 1 1343 CH3-(CH2)13- CH3- CH3- 2 4 1 3 1344 CH3-(CH2)13- CH3- CH3- 2 4 3 1 1345 CH3-(CH2)13- CH3- CH3- 3 1 2 4 1346 CH3-(CH2)13- CH3- CH3- 3 1 4 2 1347 CH3-(CH2)13- CH3- CH3- 3 2 1 4 1348 CH3-(CH2)13- CH3- CH3- 3 2 4 1 1349 CH3-(CH2)13- CH3- CH3- 3 4 1 2 1350 CH3-(CH2)13- CH3- CH3- 3 4 2 1 1351 CH3-(CH2)13- CH3- CH3- 4 1 2 3 1352 CH3-(CH2)13- CH3- CH3- 4 1 3 2 1353 CH3-(CH2)13- CH3- CH3- 4 2 1 3 1354 CH3-(CH2)13- CH3- CH3- 4 2 3 1 1355 CH3-(CH2)13- CH3- CH3- 4 3 1 2 1356 CH3-(CH2)13- CH3- CH3- 4 3 2 1 1357 CH3-(CH2)13- CH3- CH3- 2 3 3 2 1358 CH3-(CH2)13- CH3- CH3- 2 3 2 3 1359 CH3-(CH2)13- CH3- CH3- 2 2 3 3 1360 CH3-(CH2)13- CH3- CH3- 3 3 2 2 1361 CH3-(CH2)13- CH3- CH3- 3 2 3 2 1362 CH3-(CH2)13- CH3- CH3- 3 2 2 3 1363 CH3-(CH2)13- CH3- CH3- 2 4 4 2 1364 CH3-(CH2)13- CH3- CH3- 2 4 2 4 1365 CH3-(CH2)13- CH3- CH3- 2 2 4 4 1366 CH3-(CH2)13- CH3- CH3- 4 4 2 2 1367 CH3-(CH2)13- CH3- CH3- 4 2 4 2 1368 CH3-(CH2)13- CH3- CH3- 4 2 2 4 1369 CH3-(CH2)13- CH3- CH3- 3 4 4 3 1370 CH3-(CH2)13- CH3- CH3- 3 4 3 4 1371 CH3-(CH2)13- CH3- CH3- 3 3 4 4 1372 CH3-(CH2)13- CH3- CH3- 4 4 3 3 1373 CH3-(CH2)13- CH3- CH3- 4 3 4 3 1374 CH3-(CH2)13- CH3- CH3- 4 3 3 4 1375 CH3-(CH2)14- CH3- CH3- 1 1 1 1 1376 CH3-(CH2)14- CH3- CH3- 2 1 1 1 1377 CH3-(CH2)14- CH3- CH3- 1 2 1 1 1378 CH3-(CH2)14- CH3- CH3- 1 1 2 1 1379 CH3-(CH2)14- CH3- CH3- 1 1 1 2 1380 CH3-(CH2)14- CH3- CH3- 3 1 1 1 1381 CH3-(CH2)14- CH3- CH3- 1 3 1 1 1382 CH3-(CH2)14- CH3- CH3- 1 1 3 1 1383 CH3-(CH2)14- CH3- CH3- 1 1 1 3 1384 CH3-(CH2)14- CH3- CH3- 4 1 1 1 1385 CH3-(CH2)14- CH3- CH3- 1 4 1 1 1386 CH3-(CH2)14- CH3- CH3- 1 1 4 1 1387 CH3-(CH2)14- CH3- CH3- 1 1 1 4 1388 CH3-(CH2)14- CH3- CH3- 1 2 2 1 1389 CH3-(CH2)14- CH3- CH3- 1 2 1 2 1390 CH3-(CH2)14- CH3- CH3- 1 1 2 2 1391 CH3-(CH2)14- CH3- CH3- 2 2 1 1 1392 CH3-(CH2)14- CH3- CH3- 2 1 2 1 1393 CH3-(CH2)14- CH3- CH3- 2 1 1 2 1394 CH3-(CH2)14- CH3- CH3- 1 3 3 1 1395 CH3-(CH2)14- CH3- CH3- 1 3 1 3 1396 CH3-(CH2)14- CH3- CH3- 1 1 3 3 1397 CH3-(CH2)14- CH3- CH3- 3 3 1 1 1398 CH3-(CH2)14- CH3- CH3- 3 1 3 1 1399 CH3-(CH2)14- CH3- CH3- 3 1 1 3 1400 CH3-(CH2)14- CH3- CH3- 1 4 4 1 1401 CH3-(CH2)14- CH3- CH3- 1 4 1 4 1402 CH3-(CH2)14- CH3- CH3- 1 1 4 4 1403 CH3-(CH2)14- CH3- CH3- 4 4 1 1 1404 CH3-(CH2)14- CH3- CH3- 4 1 4 1 1405 CH3-(CH2)14- CH3- CH3- 4 1 1 4 1406 CH3-(CH2)14- CH3- CH3- 1 1 2 3 1407 CH3-(CH2)14- CH3- CH3- 1 1 3 2 1408 CH3-(CH2)14- CH3- CH3- 1 2 3 1 1409 CH3-(CH2)14- CH3- CH3- 1 3 2 1 1410 CH3-(CH2)14- CH3- CH3- 1 2 1 3 1411 CH3-(CH2)14- CH3- CH3- 1 3 1 2 1412 CH3-(CH2)14- CH3- CH3- 2 1 1 3 1413 CH3-(CH2)14- CH3- CH3- 2 1 3 1 1414 CH3-(CH2)14- CH3- CH3- 2 3 1 1 1415 CH3-(CH2)14- CH3- CH3- 3 1 1 2 1416 CH3-(CH2)14- CH3- CH3- 3 1 2 1 1417 CH3-(CH2)14- CH3- CH3- 3 2 1 1 1418 CH3-(CH2)14- CH3- CH3- 1 1 2 4 1419 CH3-(CH2)14- CH3- CH3- , 1 1 4 2 1420 CH3-(CH2)14- CH3- CH3- 1 2 4 1 1421 CH3-(CH2)14- CH3- CH3- 1 4 2 1 1422 CH3-(CH2)14- CH3- CH3- 1 2 1 4 1423 CH3-(CH2)14- CH3- CH3- 1 4 1 2 1424 CH3-(CH2)14- CH3- CH3- 2 1 1 4 1425 CH3-(CH2)14- CH3- CH3- 2 1 4 1 1426 CH3-(CH2)14- CH3- CH3- 2 4 1 1 1427 CH3-(CH2)14- CH3- CH3- 4 1 1 2 1428 CH3-(CH2)14- CH3- CH3- 4 1 2 1 1429 CH3-(CH2)14- CH3- CH3- 4 2 1 1 1430 CH3-(CH2)14- CH3- CH3- 1 1 4 3 1431 CH3-(CH2)14- CH3- CH3- 1 1 3 4 1432 CH3-(CH2)14- CH3- CH3- 1 4 3 1 1433 CH3-(CH2)14- CH3- CH3- 1 3 4 1 1434 CH3-(CH2)14- CH3- CH3- 1 4 1 3 1435 CH3-(CH2)14- CH3- CH3- 1 3 1 4 1436 CH3-(CH2)14- CH3- CH3- 4 1 1 3 1437 CH3-(CH2)14- CH3- CH3- 4 1 3 1 1438 CH3-(CH2)14- CH3- CH3- 4 3 1 1 1439 CH3-(CH2)14- CH3- CH3- 3 1 1 4 1440 CH3-(CH2)14- CH3- CH3- 3 1 4 1 1441 CH3-(CH2)14- CH3- CH3- 3 4 1 1 1442 CH3-(CH2)14- CH3- CH3- 1 2 2 2 1443. CH3-(CH2)14- CH3- CH3- 2 1 2 2 1444 CH3-(CH2)14- CH3- CH3- 2 2 1 2 1445 CH3-(CH2)14- CH3- CH3- 2 2 2 1 1446 CH3-(CH2)14- CH3- CH3- 1 3 3 3 1447 CH3-(CH2)14- CH3- CH3- 3 1 3 3 1448 CH3-(CH2)14- CH3- CH3- 3 3 1 3 1449 CH3-(CH2)14- CH3- CH3- 3 3 3 1 1450 CH3-(CH2)14- CH3- CH3- 1 4 4 4 1451 CH3-(CH2)14- CH3- CH3- 4 1 4 4 1452 CH3-(CH2)14- CH3- CH3- 4 4 1 4 1453 CH3-(CH2)14- CH3- CH3- 4 4 4 1 1454 CH3-(CH2)14- CH3- CH3- 2 2 1 3 1455 CH3-(CH2)14- CH3- CH3- 2 2 3 1 1456 CH3-(CH2)14- CH3- CH3- 2 1 2 3 1457 CH3-(CH2)14- CH3- CH3- 2 3 2 1 1458 CH3-(CH2)14- CH3- CH3- 2 1 3 2 1459 CH3-(CH2)14- CH3- CH3- 2 3 1 2 1460 CH3-(CH2)14- CH3- CH3- 1 2 2 3 1461 CH3-(CH2)14- CH3- CH3- 1 2 3 2 1462 CH3-(CH2)14- CH3- CH3- 1 3 2 2 1463 CH3-(CH2)14- CH3- CH3- 3 2 2 1 1464 CH3-(CH2)14- CH3- CH3- 3 2 1 2 1465 CH3-(CH2)14- CH3- CH3- 3 1 2 2 1466 CH3-(CH2)14- CH3- CH3- 2 2 1 4 1467 CH3-(CH2)14- CH3- CH3- 2 2 4 1 1468 CH3-(CH2)14- CH3- CH3- 2 1 2 4 1469 CH3-(CH2)14- CH3- CH3- 2 4 2 1 1470 CH3-(CH2)14- CH3- CH3- 2 1 4 2 1471 CH3-(CH2)14- CH3- CH3- 2 4 1 2 1472 CH3-(CH2)14- CH3- CH3- 1 2 2 4 1473 CH3-(CH2)14- CH3- CH3- 1 2 4 2 1474 CH3-(CH2)14- CH3- CH3- 1 4 2 2 1475 CH3-(CH2)14- CH3- CH3- 4 2 2 1 1476 CH3-(CH2)14- CH3- CH3- 4 2 1 2 1477 CH3-(CH2)14- CH3- CH3- 4 1 2 2 1478 CH3-(CH2)14- CH3- CH3- 2 2 4 3 1479 CH3-(CH2)14- CH3- CH3- 2 2 3 4 1480 CH3-(CH2)14- CH3- CH3- 2 4 2 3 1481 CH3-(CH2)14- CH3- CH3- 2 3 2 4 1482 CH3-(CH2)14- CH3- CH3- 2 4 3 2 1483 CH3-(CH2)14- CH3- CH3- 2 3 4 2 1484 CH3-(CH2)14- CH3- CH3- 4 2 2 3 1485 CH3-(CH2)14- CH3- CH3- 4 2 3 2 1486 CH3-(CH2)14- CH3- CH3- 4 3 2 2 1487 CH3-(CH2)14- CH3- CH3- 3 2 2 4 1488 CH3-(CH2)14- CH3- CH3- 3 2 4 2 1489 CH3-(CH2)14- CH3- CH3- 3 4 2 2 1490 CH3-(CH2)14- CH3- CH3- 3 3 1 2 1491 CH3-(CH2)14- CH3- CH3- 3 3 2 1 1492 CH3-(CH2)14- CH3- CH3- 3 1 3 2 1493 CH3-(CH2)14- CH3- CH3- 3 2 3 1 1494 CH3-(CH2)14- CH3- CH3- 3 1 2 3 1495 CH3-(CH2)14- CH3- CH3- 3 2 1 3 1496 CH3-(CH2)14- CH3- CH3- 1 3 3 2 1497 CH3-(CH2)14- CH3- CH3- 1 3 2 3 1498 CH3-(CH2)14- CH3- CH3- 1 2 3 3 1499 CH3-(CH2)14- CH3- CH3- 2 3 3 1 1500 CH3-(CH2)14- CH3- CH3- 2 3 1 3 1501 CH3-(CH2)14- CH3- CH3- 2 1 3 3 1502 CH3-(CH2)14- CH3- CH3- 3 3 1 4 1503 CH3-(CH2)14- CH3- CH3- 3 3 4 1 1504 CH3-(CH2)14- CH3- CH3- 3 1 3 4 1505 CH3-(CH2)14- CH3- CH3- 3 4 3 1 1506 CH3-(CH2)14- CH3- CH3- 3 1 4 3 1507 CH3-(CH2)14- CH3- CH3- 3 4 1 3 1508 CH3-(CH2)14- CH3- CH3- 1 3 3 4 1509 CH3-(CH2)14- CH3- CH3- 1 3 4 3 1510 CH3-(CH2)14- CH3- CH3- 1 4 3 3 1511 CH3-(CH2)14- CH3- CH3- 4 3 3 1 1512 CH3-(CH2)14- CH3- CH3- 4 3 1 3 1513 CH3-(CH2)14- CH3- CH3- 4 1 3 3 1514 CH3-(CH2)14- CH3- CH3- 3 3 4 2 1515 CH3-(CH2)14- CH3- CH3- 3 3 2 4 1516 CH3-(CH2)14- CH3- CH3- 3 4 3 2 1517 CH3-(CH2)14- CH3- CH3- 3 2 3 4 1518 CH3-(CH2)14- CH3- CH3- 3 4 2 3 1519 CH3-(CH2)14- CH3- CH3- 3 2 4 3 1520 CH3-(CH2)14- CH3- CH3- 4 3 3 2 1521 CH3-(CH2)14- CH3- CH3- 4 3 2 3 1522 CH3-(CH2)14- CH3- CH3- 4 2 3 3 1523 CH3-(CH2)14- CH3- CH3- 2 3 3 4 1524 CH3-(CH2)14- CH3- CH3- 2 3 4 3 1525 CH3-(CH2)14- CH3- CH3- 2 4 3 3 1526 CH3-(CH2)14- CH3- CH3- 4 4 1 2 1527 CH3-(CH2)14- CH3- CH3- 4 4 2 1 1528 CH3-(CH2)14- CH3- CH3- 4 1 4 2 1529 CH3-(CH2)14- CH3- CH3- 4 2 4 1 1530 CH3-(CH2)14- CH3- CH3- 4 1 2 4 1531 CH3-(CH2)14- CH3- CH3- 4 2 1 4 1532 CH3-(CH2)14- CH3- CH3- 1 4 4 2 1533 CH3-(CH2)14- CH3- CH3- 1 4 2 4 1534 CH3-(CH2)14- CH3- CH3- 1 2 4 4 1535 CH3-(CH2)14- CH3- CH3- 2 4 4 1 1536 CH3-(CH2)14- CH3- CH3- 2 4 1 4 1537 CH3-(CH2)14- CH3- CH3- 2 1 4 4 1538 CH3-(CH2)14- CH3- CH3- 4 4 1 3 1539 CH3-(CH2)14- CH3- CH3- 4 4 3 1 1540 CH3-(CH2)14- CH3- CH3- 4 1 4 3 1541 CH3-(CH2)14- CH3- CH3- 4 3 4 1 1542 CH3-(CH2)14- CH3- CH3- 4 1 3 4 1543 CH3-(CH2)14- CH3- CH3- 4 3 1 4 1544 CH3-(CH2)14- CH3- CH3- 1 4 4 3 1545 CH3-(CH2)14- CH3- CH3- 1 4 3 4 1546 CH3-(CH2)14- CH3- CH3- 1 3 4 4 1547 CH3-(CH2)14- CH3- CH3- 3 4 4 1 1548 CH3-(CH2)14- CH3- CH3- 3 4 1 4 1549 CH3-(CH2)14- CH3- CH3- 3 1 4 4 1550 CH3-(CH2)14- CH3- CH3- 4 4 3 2 1551 CH3-(CH2)14- CH3- CH3- 4 4 2 3 1552 CH3-(CH2)14- CH3- CH3- 4 3 4 2 1553 CH3-(CH2)14- CH3- CH3- 4 2 4 3 1554 CH3-(CH2)14- CH3- CH3- 4 3 2 4 1555 CH3-(CH2)14- CH3- CH3- 4 2 3 4 1556 CH3-(CH2)14- CH3- CH3- 3 4 4 2 1557 CH3-(CH2)14- CH3- CH3- 3 4 2 4 1558 CH3-(CH2)14- CH3- CH3- 3 2 4 4 1559 CH3-(CH2)14- CH3- CH3- 2 4 4 3 1560 CH3-(CH2)14- CH3- CH3- 2 4 3 4 1561 CH3-(CH2)14- CH3- CH3- 2 3 4 4 1562 CH3-(CH2)14- CH3- CH3- 1 2 3 4 1563 CH3-(CH2)14- CH3- CH3- 1 2 4 3 1564 CH3-(CH2)14- CH3- CH3- 1 3 2 4 1565 CH3-(CH2)14- CH3- CH3- 1 3 4 2 1566 CH3-(CH2)14- CH3- CH3- 1 4 2 3 1567 CH3-(CH2)14- CH3- CH3- 1 4 3 2 1568 CH3-(CH2)14- CH3- CH3- 2 1 3 4 1569 CH3-(CH2)14- CH3- CH3- 2 1 4 3 1570 CH3-(CH2)14- CH3- CH3- 2 3 1 4 1571 CH3-(CH2)14- CH3- CH3- 2 3 4 1 1572 CH3-(CH2)14- CH3- CH3- 2 4 1 3 1573 CH3-(CH2)14- CH3- CH3- 2 4 3 1 1574 CH3-(CH2)14- CH3- CH3- 3 1 2 4 1575 CH3-(CH2)14- CH3- CH3- 3 1 4 2 1576 CH3-(CH2)14- CH3- CH3- 3 2 1 4 1577 CH3-(CH2)14- CH3- CH3- 3 2 4 1 1578 CH3-(CH2)14- CH3- CH3- 3 4 1 2 1579 CH3-(CH2)14- CH3- CH3- 3 4 2 1 1580 CH3-(CH2)14- CH3- CH3- 4 1 2 3 1581 CH3-(CH2)14- CH3- CH3- 4 1 3 2 1582 CH3-(CH2)14- CH3- CH3- 4 2 1 3 1583 CH3-(CH2)14- CH3- CH3- 4 2 3 1 1584 CH3-(CH2)14- CH3- CH3- 4 3 1 2 1585 CH3-(CH2)14- CH3- CH3- 4 3 2 1 1586 CH3-(CH2)14- CH3- CH3- 2 3 3 2 1587 CH3-(CH2)14- CH3- CH3- 2 3 2 3 1588 CH3-(CH2)14- CH3- CH3- 2 2 3 3 1589 CH3-(CH2)14- CH3- CH3- 3 3 2 2 1590 CH3-(CH2)14- CH3- CH3- 3 2 3 2 1591 CH3-(CH2)14- CH3- CH3- 3 2 2 3 1592 CH3-(CH2)14- CH3- CH3- 2 4 4 2 1593 CH3-(CH2)14- CH3- CH3- 2 4 2 4 1594 CH3-(CH2)14- CH3- CH3- 2 2 4 4 1595 CH3-(CH2)14- CH3- CH3- 4 4 2 2 1596 CH3-(CH2)14- CH3- CH3- 4 2 4 2 1597 CH3-(CH2)14- CH3- CH3- 4 2 2 4 1598 CH3-(CH2)14- CH3- CH3- 3 4 4 3 1599 CH3-(CH2)14- CH3- CH3- 3 4 3 4 1600 CH3-(CH2)14- CH3- CH3- 3 3 4 4 1601 CH3-(CH2)14- CH3- CH3- 4 4 3 3 1602 CH3-(CH2)14- CH3- CH3- 4 3 4 3 1603 CH3-(CH2)14- CH3- CH3- 4 3 3 4 The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers. In the table below, particular preference is given to nonionic surfactants contained in the agents according to the invention with respect to the radical R.1, the rests R2 and R3 and the indices w, x, y and z characterized. Preferred agents according to the invention comprise one or more surfactants from the table below or mixtures of these. No. R 1 R 2 R 3 w x y z 1 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 1 1 2 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 1 1 3 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 1 1 4 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 2 1 5 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 1 2 6 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 1 1 7 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 1 1 8th CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 3 1 9 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 1 3 10 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 1 1 11 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 1 1 12 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 4 1 13 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 1 4 14 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 2 1 15 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 1 2 16 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 2 2 17 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 1 1 18 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 2 1 19 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 1 2 20 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 3 1 21 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 1 3 22 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 3 3 23 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 1 1 24 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 3 1 25 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 1 3 26 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 4 1 27 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 1 4 28 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 4 4 29 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 1 1 30 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 4 1 31 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 1 4 32 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 2 3 33 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 3 2 34 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 3 1 35 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 2 1 36 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 1 3 37 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 1 2 38 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 1 3 39 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 3 1 40 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 1 1 41 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 1 2 42 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 2 1 43 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 1 1 44 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 2 4 45 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 4 2 46 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 4 1 47 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 2 1 48 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 1 4 49 CH s - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 1 2 50 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 1 4 51 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 4 1 52 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 1 1 53 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 1 2 54 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 2 1 55 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 1 1 56 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 4 3 57 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 1 3 4 58 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 3 1 59 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 4 1 60 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 1 3 61 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 1 4 62 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 1 3 63 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 3 1 64 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 1 1 65 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 1 4 66 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 4 1 67 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 1 1 68 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 2 2 69 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 2 2 70 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 1 2 71 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 2 1 72 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 3 3 73 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 3 3 74. CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 1 3 75 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 3 1 76 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 4 4 77 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 4 4 78 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 1 4 79 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 4 1 80 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 1 3 81 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 3 1 82 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 2 3 83 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 2 1 84 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 3 2 85 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 1 2 86 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 2 3 87 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 3 2 88 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 2 2 89 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 2 1 90 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 1 2 91 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 2 2 92 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 1 4 93 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 4 1 94 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 2 4 95 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 2 1 96 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 4 2 97 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 1 2 98 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 2 4 99 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 4 2 100 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 2 2 101 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 2 1 102 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 1 2 103 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 2 2 104 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 4 3 105 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 3 4 106 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 2 3 107 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 2 4 108 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 3 2 109 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 4 2 110 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 2 3 111 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 3 2 112 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 2 2 113 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 2 4 114 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 4 2 115 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 2 2 116 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 1 2 117 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 2 1 118 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 3 2 119 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 3 1 120 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 2 3 121 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 1 3 122 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 3 2 123 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 2 3 124 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 3 3 125 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 3 1 126 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 1 3 127 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 3 3 128 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 1 4 129 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 4 1 130 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 3 4 131 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 3 1 132 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 4 3 133 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 1 3 134 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 3 4 135 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 4 3 136 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 3 3 137 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 3 1 138 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 1 3 139 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 3 3 140 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 4 2 141 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 2 4 142 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 3 2 143 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 3 4 144 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 2 3 145 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 4 3 146 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 3 2 147 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 2 3 148 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 3 3 149 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 3 4 150 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 4 3 151 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 3 3 152 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 1 2 153 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 2 1 154 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 4 2 155 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 4 1 156 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 2 4 157 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 1 4 158 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 4 2 159 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 2 4 160 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 4 4 161 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 4 1 162 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 1 4 163 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 4 4 164 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 1 3 165 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 3 1 166 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 4 3 167 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 4 1 168 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 3 4 169 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 1 4 170 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 4 3 171 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 3 4 172 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 4 4 173 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 4 1 174 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 1 4 175 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 4 4 176 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 3 2 177 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 2 3 178 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 4 2 179 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 4 3 180 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 2 4 181 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 3 4 182 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 4 2 183 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 2 4 184 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 4 4 185 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 4 3 186 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 3 4 187 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 4 4 188 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 3 4 189 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 2 4 3 190 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 2 4 191 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 3 4 2 192 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 2 3 193 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 1 4 3 2 194 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 3 4 195 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 1 4 3 196 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 1 4 197 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 4 1 198 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 1 3 199 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 3 1 200 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 2 4 201 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 1 4 2 202 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 1 4 203 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 4 1 204 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 1 2 205 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 2 1 206 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 2 3 207 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 1 3 2 208 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 1 3 209 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 3 1 210 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 1 2 211 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 2 1 212 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 3 2 213 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 3 2 3 214 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 3 3 215 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 2 2 216 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 3 2 217 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 2 2 3 218 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 4 2 219 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 4 2 4 220 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 2 2 4 4 221 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 2 2 222 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 4 2 223 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 2 2 4 224 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 4 3 225 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 4 3 4 226 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 3 3 4 4 227 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 4 3 3 228 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 4 3 229 CH 3 - (CH 2 ) 8 - CH 3 - CH 3 - 4 3 3 4 230 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 1 1 231 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 1 1 232 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 1 1 233 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 2 1 234 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 1 2 235 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 1 1 236 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 1 1 237 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 3 1 238 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 1 3 239 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 1 1 240 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 1 1 241 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 4 1 242 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 1 4 243 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 2 1 244 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 1 2 245 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 2 2 246 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 1 1 247 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 2 1 248 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 1 2 249 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 3 1 250 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 1 3 251 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 3 3 252 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 1 1 253 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 3 1 254 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 1 3 255 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 4 1 256 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 1 4 257 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 4 4 258 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 1 1 259 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 4 1 260 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 1 4 261 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 2 3 262 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 3 2 263 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 3 1 264 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 2 1 265 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 1 3 266 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 1 2 267 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 1 3 268 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 3 1 269 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 1 1 270 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 1 2 271 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 2 1 272 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 1 1 273 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 2 4 274 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 4 2 275 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 4 1 276 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 2 1 277 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 1 4 278 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 1 2 279 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 1 4 280 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 4 1 281 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 1 1 282 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 1 2 283 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 2 1 284 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 1 1 285 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 4 3 286 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 1 3 4 287 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 3 1 288 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 4 1 289 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 1 3 290 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 1 4 291 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 1 3 292 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 3 1 293 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 1 1 294 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 1 4 295 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 4 1 296 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 1 1 297 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 2 2 298 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 2 2 299 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 1 2 300 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 2 1 301 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 3 3 302 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 3 3 303 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 1 3 304 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 3 1 305 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 4 4 306 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 4 4 307 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 1 4 308 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 4 1 309 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 1 3 310 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 3 1 311 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 2 3 312 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 2 1 313 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 3 2 314 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 1 2 315 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 2 3 316 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 3 2 317 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 2 2 318 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 2 1 319 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 1 2 320 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 2 2 321 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 1 4 322 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 4 1 323 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 2 4 324 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 2 1 325 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 4 2 326 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 1 2 327 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 2 4 328 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 4 2 329 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 2 2 330 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 2 1 331 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 1 2 332 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 2 2 333 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 4 3 334 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 3 4 335 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 2 3 336 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 2 4 337 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 3 2 338 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 4 2 339 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 2 3 340 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 3 2 341 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 2 2 342 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 2 4 343 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 4 2 344 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 2 2 345 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 1 2 346 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 2 1 347 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 3 2 348 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 3 1 349 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 2 3 350 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 1 3 351 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 3 2 352 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 2 3 353 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 3 3 354 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 3 1 355 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 1 3 356 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 3 3 357 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 1 4 358 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 4 1 359 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 3 4 360 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 3 1 361 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 4 3 362 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 1 3 363 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 3 4 364 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 4 3 365 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 3 3 366 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 3 1 367 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 1 3 368 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 3 3 369 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 4 2 370 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 2 4 371 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 3 2 372 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 3 4 373 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 2 3 374 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 4 3 375 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 3 2 376 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 2 3 377 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 3 3 378 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 3 4 379 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 4 3 380 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 3 3 381 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 1 2 382 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 2 1 383 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 4 2 384 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 4 1 385 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 2 4 386 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 1 4 387 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 4 2 388 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 2 4 389 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 4 4 390 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 4 1 391 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 1 4 392 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 4 4 393 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 1 3 394 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 3 1 395 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 4 3 396 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 4 1 397 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 3 4 398 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 1 4 399 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 4 3 400 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 3 4 401 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 4 4 402 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 4 1 403 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 1 4 404 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 4 4 405 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 3 2 406 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 2 3 407 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 4 2 408 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 4 3 409 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 2 4 410 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 3 4 411 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 4 2 412 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 2 4 413 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 4 4 414 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 4 3 415 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 3 4 416 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 4 4 417 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 3 4 418 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 2 4 3 419 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 2 4 420 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 3 4 2 421 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 2 3 422 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 1 4 3 2 423 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 3 4 424 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 1 4 3 425 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 1 4 426 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 4 1 427 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 1 3 428 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 3 1 429 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 2 4 430 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 1 4 2 431 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 1 4 432 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 4 1 433 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 1 2 434 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 2 1 435 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 2 3 436 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 1 3 2 437 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 1 3 438 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 3 1 439 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 1 2 440 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 2 1 441 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 3 2 442 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 3 2 3 443 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 3 3 444 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 2 2 445 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 3 2 446 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 2 2 3 447 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 4 2 448 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 4 2 4 449 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 2 2 4 4 450 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 2 2 451 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 4 2 452 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 2 2 4 453 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 4 3 454 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 4 3 4 455 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 3 3 4 4 456 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 4 3 3 457 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 4 3 458 CH 3 - (CH 2 ) 9 - CH 3 - CH 3 - 4 3 3 4 459 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 1 1 460 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 1 1 461 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 1 1 462 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 2 1 463 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 1 2 464 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 1 1 465 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 1 1 466 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 3 1 467 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 1 3 468 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 1 1 469 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 1 1 470 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 4 1 471 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 1 4 472 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 2 1 473 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 1 2 474 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 2 2 475 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 1 1 476 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 2 1 477 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 1 2 478 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 3 1 479 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 1 3 480 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 3 3 481 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 1 1 482 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 3 1 483 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 1 3 484 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 4 1 485 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 1 4 486 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 4 4 487 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 1 1 488 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 4 1 489 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 1 4 490 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 2 3 491 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 3 2 492 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 3 1 493 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 2 1 494 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 1 3 495 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 1 2 496 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 1 3 497 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 3 1 498 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 1 1 499 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 1 2 500 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 2 1 501 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 1 1 502 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 2 4 503 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 4 2 504 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 4 1 505 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 2 1 506 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 1 4 507 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 1 2 508 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 1 4 509 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 4 1 510 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 1 1 511 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 1 2 512 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 2 1 513 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 1 1 514 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 4 3 515 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 1 3 4 516 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 3 1 517 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 4 1 518 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 1 3 519 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 1 4 520 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 1 3 521 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 3 1 522 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 1 1 523 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 1 4 524 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 4 1 525 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 1 1 526 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 2 2 527 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 2 2 528 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 1 2 529 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 2 1 530 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 3 3 531 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 3 3 532 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 1 3 533 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 3 1 534 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 4 4 535 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 4 4 536 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 1 4 537 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 4 1 538 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 1 3 539 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 3 1 540 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 2 3 541 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 2 1 542 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 3 2 543 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 1 2 544 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 2 3 545 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 3 2 546 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 2 2 547 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 2 1 548 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 1 2 549 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 2 2 550 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 1 4 551 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 4 1 552 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 2 4 553 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 2 1 554 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 4 2 555 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 1 2 556 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 2 4 557 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 4 2 558 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 2 2 559 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 2 1 560 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 1 2 561 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 2 2 562 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 4 3 563 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 3 4 564 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 2 3 565 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 2 4 566 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 3 2 567 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 4 2 568 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 2 3 569 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 3 2 570 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 2 2 571 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 2 4 572 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 4 2 573 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 2 2 574 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 1 2 575 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 2 1 576 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 3 2 577 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 3 1 578 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 2 3 579 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 1 3 580 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 3 2 581 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 2 3 582 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 3 3 583 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 3 1 584 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 1 3 585 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 3 3 586 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 1 4 587 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 4 1 588 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 3 4 589 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 3 1 590 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 4 3 591 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 1 3 592 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 3 4 593 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 4 3 594 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 3 3 595 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 3 1 596 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 1 3 597 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 3 3 598 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 4 2 599 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 2 4 600 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 3 2 601 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 3 4 602 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 2 3 603 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 4 3 604 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 3 2 605 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 2 3 606 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 3 3 607 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 3 4 608 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 4 3 609 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 3 3 610 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 1 2 611 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 2 1 612 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 4 2 613 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 4 1 614 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 2 4 615 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 1 4 616 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 4 2 617 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 2 4 618 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 4 4 619 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 4 1 620 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 1 4 621 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 4 4 622 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 1 3 623 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 3 1 624 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 4 3 625 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 4 1 626 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 3 4 627 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 1 4 628 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 4 3 629 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 3 4 630 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 4 4 631 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 4 1 632 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 1 4 633 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 4 4 634 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 3 2 635 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 2 3 636 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 4 2 637 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 4 3 638 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 2 4 639 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 3 4 640 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 4 2 641 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 2 4 642 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 4 4 643 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 4 3 644 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 3 4 645 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 4 4 646 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 3 4 647 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 2 4 3 648 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 2 4 649 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 3 4 2 650 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 2 3 651 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 1 4 3 2 652 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 3 4 653 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 1 4 3 654 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 1 4 655 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 4 1 656 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 1 3 657 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 3 1 658 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 2 4 659 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 1 4 2 660 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 1 4 661 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 4 1 662 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 1 2 663 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 2 1 664 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 2 3 665 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 1 3 2 666 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 1 3 667 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 3 1 668 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 1 2 669 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 2 1 670 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 3 2 671 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 3 2 3 672 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 3 3 673 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 2 2 674 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 3 2 675 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 2 2 3 676 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 4 2 677 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 4 2 4 678 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 2 2 4 4 679 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 2 2 680 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 4 2 681 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 2 2 4 682 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 4 3 683 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 4 3 4 684 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 3 3 4 4 685 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 4 3 3 686 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 4 3 687 CH 3 - (CH 2 ) 10 - CH 3 - CH 3 - 4 3 3 4 688 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 1 1 689 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 1 1 690 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 1 1 691 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 2 1 692 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 1 2 693 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 1 1 694 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 1 1 695 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 3 1 696 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 1 3 697 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 1 1 698 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 1 1 699 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 4 1 700 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 1 4 701 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 2 1 702 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 1 2 703 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 2 2 704 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 1 1 705 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 2 1 706 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 1 2 707 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 3 1 708 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 1 3 709 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 3 3 710 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 1 1 711 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 3 1 712 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 1 3 713 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 4 1 714 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 1 4 715 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 4 4 716 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 1 1 717 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 4 1 718 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 1 4 719 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 2 3 720 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 3 2 721 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 3 1 722 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 2 1 723 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 1 3 724 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 1 2 725 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 1 3 726 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 3 1 727 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 1 1 728 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 1 2 729 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 2 1 730 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 1 1 731 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 2 4 732 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 4 2 733 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 4 1 734 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 2 1 735 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 1 4 736 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 1 2 737 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 1 4 738 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 4 1 739 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 1 1 740 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 1 2 741 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 2 1 742 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 1 1 743 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 4 3 744 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 1 3 4 745 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 3 1 746 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 4 1 747 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 1 3 748 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 1 4 749 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 1 3 750 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 3 1 751 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 1 1 752 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 1 4 753 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 4 1 754 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 1 1 755 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 2 2 756 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 2 2 757 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 1 2 758 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 2 1 759 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 3 3 760 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 3 3 761 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 1 3 762 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 3 1 763 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 4 4 764 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 4 4 765 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 1 4 766 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 4 1 767 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 1 3 768 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 3 1 769 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 2 3 770 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 2 1 771 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 3 2 772 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 1 2 773 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 2 3 774 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 3 2 775 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 2 2 776 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 2 1 777 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 1 2 778 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 2 2 779 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 1 4 780 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 4 1 781 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 2 4 782 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 2 1 783 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 4 2 784 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 1 2 785 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 2 4 786 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 4 2 787 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 2 2 788 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 2 1 789 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 1 2 790 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 2 2 791 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 4 3 792 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 3 4 793 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 2 3 794 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 2 4 795 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 3 2 796 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 4 2 797 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 2 3 798 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 3 2 799 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 2 2 800 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 2 4 801 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 4 2 802 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 2 2 803 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 1 2 804 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 2 1 805 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 3 2 806 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 3 1 807 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 2 3 808 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 1 3 809 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 3 2 810 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 2 3 811 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 3 3 812 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 3 1 813 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 1 3 814 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 3 3 815 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 1 4 816 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 4 1 817 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 3 4 818 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 3 1 819 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 4 3 820 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 1 3 821 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 3 4 822 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 4 3 823 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 3 3 824 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 3 1 825 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 1 3 826 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 3 3 827 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 4 2 828 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 2 4 829 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 3 2 830 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 3 4 831 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 2 3 832 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 4 3 833 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 3 2 834 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 2 3 835 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 3 3 836 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 3 4 837 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 4 3 838 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 3 3 839 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 1 2 840 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 2 1 841 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 4 2 842 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 4 1 843 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 2 4 844 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 1 4 845 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 4 2 846 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 2 4 847 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 4 4 848 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 4 1 849 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 1 4 850 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 4 4 851 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 1 3 852 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 3 1 853 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 4 3 854 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 4 1 855 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 3 4 856 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 1 4 857 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 4 3 858 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 3 4 859 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 4 4 860 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 4 1 861 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 1 4 862 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 4 4 863 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 3 2 864 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 2 3 865 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 4 2 866 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 4 3 867 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 2 4 868 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 3 4 869 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 4 2 870 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 2 4 871 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 4 4 872 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 4 3 873 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 3 4 874 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 4 4 875 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 3 4 876 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 2 4 3 877 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 2 4 878 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 3 4 2 879 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 2 3 880 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 1 4 3 2 881 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 3 4 882 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 1 4 3 883 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 1 4 884 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 4 1 885 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 1 3 886 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 3 1 887 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 2 4 888 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 1 4 2 889 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 1 4 890 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 4 1 891 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 1 2 892 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 2 1 893 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 2 3 894 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 1 3 2 895 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 1 3 896 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 3 1 897 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 1 2 898 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 2 1 899 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 3 2 900 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 3 2 3 901 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 3 3 902 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 2 2 903 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 3 2 904 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 2 2 3 905 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 4 2 906 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 4 2 4 907 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 2 2 4 4 908 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 2 2 909 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 4 2 910 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 2 2 4 911 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 4 3 912 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 4 3 4 913 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 3 3 4 4 914 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 4 3 3 915 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 4 3 916 CH 3 - (CH 2 ) 11 - CH 3 - CH 3 - 4 3 3 4 917 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 1 1 918 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 1 1 919 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 1 1 920 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 2 1 921 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 1 2 922 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 1 1 923 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 1 1 924 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 3 1 925 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 1 3 926 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 1 1 927 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 1 1 928 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 4 1 929 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 1 4 930 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 2 1 931 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 1 2 932 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 2 2 933 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 1 1 934 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 2 1 935 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 1 2 936 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 3 1 937 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 1 3 938 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 3 3 939 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 1 1 940 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 3 1 941 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 1 3 942 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 4 1 943 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 1 4 944 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 4 4 945 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 1 1 946 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 4 1 947 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 1 4 948 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 2 3 949 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 3 2 950 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 3 1 951 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 2 1 952 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 1 3 953 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 1 2 954 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 1 3 955 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 3 1 956 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 1 1 957 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 1 2 958 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 2 1 959 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 1 1 960 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 2 4 961 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 4 2 962 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 4 1 963 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 2 1 964 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 1 4 965 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 1 2 966 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 1 4 967 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 4 1 968 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 1 1 969 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 1 2 970 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 2 1 971 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 1 1 972 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 4 3 973 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 1 3 4 974 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 3 1 975 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 4 1 976 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 1 3 977 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 1 4 978 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 1 3 979 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 3 1 980 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 1 1 981 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 1 4 982 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 4 1 983 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 1 1 984 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 2 2 985 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 2 2 986 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 1 2 987 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 2 1 988 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 3 3 989 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 3 3 990 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 1 3 991 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 3 1 992 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 4 4 993 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 4 4 994 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 1 4 995 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 4 1 996 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 1 3 997 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 3 1 998 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 2 3 999 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 2 1 1000 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 3 2 1001 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 1 2 1002 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 2 3 1003 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 3 2 1004 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 2 2 1005 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 2 1 1006 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 1 2 1007 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 2 2 1008 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 1 4 1009 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 4 1 1010 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 2 4 1011 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 2 1 1012 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 4 2 1013 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 1 2 1014 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 2 4 1015 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 4 2 1016 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 2 2 1017 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 2 1 1018 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 1 2 1019 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 2 2 1020 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 4 3 1021 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 3 4 1022 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 2 3 1023 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 2 4 1024 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 3 2 1025 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 4 2 1026 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 2 3 1027 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 3 2 1028 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 2 2 1029 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 2 4 1030 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 4 2 1031 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 2 2 1032 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 1 2 1033 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 2 1 1034 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 3 2 1035 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 3 1 1036 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 2 3 1037 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 1 3 1038 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 3 2 1039 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 2 3 1040 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 3 3 1041 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 3 1 1042 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 1 3 1043 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 3 3 1044 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 1 4 1045 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 4 1 1046 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 3 4 1047 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 3 1 1048 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 4 3 1049 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 1 3 1050 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 3 4 1051 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 4 3 1052 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 3 3 1053 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 3 1 1054 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 1 3 1055 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 3 3 1056 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 4 2 1057 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 2 4 1058 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 3 2 1059 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 3 4 1060 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 2 3 1061 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 4 3 1062 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 3 2 1063 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 2 3 1064 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 3 3 1065 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 3 4 1066 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 4 3 1067 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 3 3 1068 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 1 2 1069 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 2 1 1070 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 4 2 1071 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 4 1 1072 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 2 4 1073 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 1 4 1074 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 4 2 1075 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 2 4 1076 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 4 4 1077 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 4 1 1078 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 1 4 1079 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 4 4 1080 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 1 3 1081 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 3 1 1082 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 4 3 1083 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 4 1 1084 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 3 4 1085 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 1 4 1086 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 4 3 1087 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 3 4 1088 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 4 4 1089 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 4 1 1090 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 1 4 1091 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 4 4 1092 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 3 2 1093 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 2 3 1094 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 4 2 1095 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 4 3 1096 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 2 4 1097 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 3 4 1098 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 4 2 1099 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 2 4 1100 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 4 4 1101 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 4 3 1102 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 3 4 1103 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 4 4 1104 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 3 4 1105 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 2 4 3 1106 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 2 4 1107 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 3 4 2 1108 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 2 3 1109 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 1 4 3 2 1110th CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 3 4 1111 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 1 4 3 1112 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 1 4 1113 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 4 1 1114 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 1 3 1115 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 3 1 1116 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 2 4 1117 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 1 4 2 1118 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 1 4 1119 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 4 1 1120 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 1 2 1121 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 2 1 1122 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 2 3 1123 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 1 3 2 1124 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 1 3 1125 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 3 1 1126 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 1 2 1127 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 2 1 1128 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 3 2 1129 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 3 2 3 1130 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 3 3 1131 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 2 2 1132 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 3 2 1133 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 2 2 3 1134 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 4 2 1135 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 4 2 4 1136 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 2 2 4 4 1137 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 2 2 1138 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 4 2 1139 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 2 2 4 1140 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 4 3 1141 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 4 3 4 1142 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 3 3 4 4 1143 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 4 3 3 1144 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 4 3 1145 CH 3 - (CH 2 ) 12 - CH 3 - CH 3 - 4 3 3 4 1146 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 1 1 1147 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 1 1 1148 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 1 1 1149 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 2 1 1150 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 1 2 1151 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 1 1 1152 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 1 1 1153 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 3 1 1154 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 1 3 1155 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 1 1 1156 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 1 1 1157 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 4 1 1158 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 1 4 1159 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 2 1 1160 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 1 2 1161 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 2 2 1162 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 1 1 1163 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 2 1 1164 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 1 2 1165 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 3 1 1166 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 1 3 1167 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 3 3 1168 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 1 1 1169 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 3 1 1170 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 1 3 1171 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 4 1 1172 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 1 4 1173 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 4 4 1174 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 1 1 1175 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 4 1 1176 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 1 4 1177 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 2 3 1178 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 3 2 1179 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 3 1 1180 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 2 1 1181 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 1 3 1182 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 1 2 1183 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 1 3 1184 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 3 1 1185 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 1 1 1186 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 1 2 1187 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 2 1 1188 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 1 1 1189 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 2 4 1190 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 4 2 1191 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 4 1 1192 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 2 1 1193 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 1 4 1194 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 1 2 1195 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 1 4 1196 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 4 1 1197 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 1 1 1198 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 1 2 1199 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 2 1 1200 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 1 1 1201 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 4 3 1202 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 1 3 4 1203 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 3 1 1204 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 4 1 1205 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 1 3 1206 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 1 4 1207 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 1 3 1208 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 3 1 1209 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 1 1 1210 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 1 4 1211 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 4 1 1212 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 1 1 1213 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 2 2 1214 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 2 2 1215 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 1 2 1216 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 2 1 1217 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 3 3 1218 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 3 3 1219 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 1 3 1220 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 3 1 1221 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 4 4 1222 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 4 4 1223 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 1 4 1224 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 4 1 1225 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 1 3 1226 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 3 1 1227 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 2 3 1228 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 2 1 1229 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 3 2 1230 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 1 2 1231 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 2 3 1232 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 3 2 1233 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 2 2 1234 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 2 1 1235 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 1 2 1236 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 2 2 1237 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 1 4 1238 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 4 1 1239 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 2 4 1240 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 2 1 1241 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 4 2 1242 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 1 2 1243 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 2 4 1244 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 4 2 1245 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 2 2 1246 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 2 1 1247 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 1 2 1248 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 2 2 1249 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 4 3 1250 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 3 4 1251 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 2 3 1252 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 2 4 1253 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 3 2 1254 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 4 2 1255 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 2 3 1256 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 3 2 1257 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 2 2 1258 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 2 4 1259 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 4 2 1260 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 2 2 1261 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 1 2 1262 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 2 1 1263 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 3 2 1264 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 3 1 1265 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 2 3 1266 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 1 3 1267 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 3 2 1268 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 2 3 1269 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 3 3 1270 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 3 1 1271 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 1 3 1272 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 3 3 1273 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 1 4 1274 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 4 1 1275 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 3 4 1276 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 3 1 1277 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 4 3 1278 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 1 3 1279 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 3 4 1280 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 4 3 1281 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 3 3 1282 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 3 1 1283 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 1 3 1284 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 3 3 1285 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 4 2 1286 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 2 4 1287 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 3 2 1288 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 3 4 1289 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 2 3 1290 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 4 3 1291 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 3 2 1292 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 2 3 1293 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 3 3 1294 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 3 4 1295 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 4 3 1296 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 3 3 1297 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 1 2 1298 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 2 1 1299 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 4 2 1300 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 4 1 1301 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 2 4 1302 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 1 4 1303 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 4 2 1304 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 2 4 1305 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 4 4 1306 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 4 1 1307 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 1 4 1308 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 4 4 1309 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 1 3 1310 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 3 1 1311 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 4 3 1312 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 4 1 1313 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 3 4 1314 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 1 4 1315 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 4 3 1316 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 3 4 1317 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 4 4 1318 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 4 1 1319 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 1 4 1320 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 4 4 1321 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 3 2 1322 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 2 3 1323 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 4 2 1324 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 4 3 1325 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 2 4 1326 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 3 4 1327 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 4 2 1328 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 2 4 1329 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 4 4 1330 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 4 3 1331 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 3 4 1332 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 4 4 1333 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 3 4 1334 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 2 4 3 1335 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 2 4 1336 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 3 4 2 1337 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 2 3 1338 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 1 4 3 2 1339 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 3 4 1340 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 1 4 3 1341 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 1 4 1342 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 4 1 1343 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 1 3 1344 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 3 1 1345 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 2 4 1346 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 1 4 2 1347 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 1 4 1348 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 4 1 1349 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 1 2 1350 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 2 1 1351 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 2 3 1352 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 1 3 2 1353 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 1 3 1354 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 3 1 1355 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 1 2 1356 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 2 1 1357 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 3 2 1358 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 3 2 3 1359 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 3 3 1360 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 2 2 1361 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 3 2 1362 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 2 2 3 1363 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 4 2 1364 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 4 2 4 1365 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 2 2 4 4 1366 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 2 2 1367 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 4 2 1368 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 2 2 4 1369 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 4 3 1370 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 4 3 4 1371 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 3 3 4 4 1372 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 4 3 3 1373 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 4 3 1374 CH 3 - (CH 2 ) 13 - CH 3 - CH 3 - 4 3 3 4 1375 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 1 1 1376 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 1 1 1377 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 1 1 1378 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 2 1 1379 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 1 2 1380 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 1 1 1381 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 1 1 1382 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 3 1 1383 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 1 3 1384 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 1 1 1385 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 1 1 1386 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 4 1 1387 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 1 4 1388 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 2 1 1389 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 1 2 1390 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 2 2 1391 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 1 1 1392 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 2 1 1393 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 1 2 1394 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 3 1 1395 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 1 3 1396 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 3 3 1397 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 1 1 1398 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 3 1 1399 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 1 3 1400 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 4 1 1401 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 1 4 1402 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 4 4 1403 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 1 1 1404 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 4 1 1405 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 1 4 1406 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 2 3 1407 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 3 2 1408 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 3 1 1409 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 2 1 1410 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 1 3 1411 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 1 2 1412 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 1 3 1413 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 3 1 1414 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 1 1 1415 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 1 2 1416 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 2 1 1417 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 1 1 1418 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 2 4 1419 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 -, 1 1 4 2 1420 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 4 1 1421 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 2 1 1422 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 1 4 1423 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 1 2 1424 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 1 4 1425 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 4 1 1426 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 1 1 1427 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 1 2 1428 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 2 1 1429 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 1 1 1430 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 4 3 1431 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 1 3 4 1432 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 3 1 1433 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 4 1 1434 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 1 3 1435 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 1 4 1436 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 1 3 1437 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 3 1 1438 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 1 1 1439 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 1 4 1440 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 4 1 1441 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 1 1 1442 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 2 2 1,443th CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 2 2 1444 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 1 2 1445 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 2 1 1446 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 3 3 1447 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 3 3 1448 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 1 3 1449 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 3 1 1450 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 4 4 1451 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 4 4 1452 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 1 4 1453 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 4 1 1454 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 1 3 1455 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 3 1 1456 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 2 3 1457 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 2 1 1458 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 3 2 1459 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 1 2 1460 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 2 3 1461 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 3 2 1462 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 2 2 1463 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 2 1 1464 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 1 2 1465 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 2 2 1466 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 1 4 1467 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 4 1 1468 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 2 4 1469 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 2 1 1470 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 4 2 1471 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 1 2 1472 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 2 4 1473 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 4 2 1474 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 2 2 1475 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 2 1 1476 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 1 2 1477 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 2 2 1478 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 4 3 1479 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 3 4 1480 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 2 3 1481 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 2 4 1482 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 3 2 1483 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 4 2 1484 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 2 3 1485 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 3 2 1486 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 2 2 1487 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 2 4 1488 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 4 2 1489 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 2 2 1490 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 1 2 1491 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 2 1 1492 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 3 2 1493 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 3 1 1494 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 2 3 1495 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 1 3 1496 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 3 2 1497 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 2 3 1498 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 3 3 1499 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 3 1 1500 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 1 3 1501 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 3 3 1502 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 1 4 1503 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 4 1 1504 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 3 4 1505 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 3 1 1506 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 4 3 1507 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 1 3 1508 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 3 4 1509 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 4 3 1510 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 3 3 1511 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 3 1 1512 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 1 3 1513 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 3 3 1514 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 4 2 1515 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 2 4 1516 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 3 2 1517 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 3 4 1518 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 2 3 1519 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 4 3 1520 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 3 2 1521 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 2 3 1522 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 3 3 1523 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 3 4 1524 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 4 3 1525 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 3 3 1526 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 1 2 1527 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 2 1 1528 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 4 2 1529 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 4 1 1530 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 2 4 1531 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 1 4 1532 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 4 2 1533 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 2 4 1534 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 4 4 1535 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 4 1 1536 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 1 4 1537 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 4 4 1538 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 1 3 1539 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 3 1 1540 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 4 3 1541 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 4 1 1542 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 3 4 1543 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 1 4 1544 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 4 3 1545 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 3 4 1546 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 4 4 1547 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 4 1 1548 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 1 4 1549 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 4 4 1550 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 3 2 1551 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 2 3 1552 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 4 2 1553 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 4 3 1554 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 2 4 1555 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 3 4 1556 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 4 2 1557 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 2 4 1558 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 4 4 1559 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 4 3 1560 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 3 4 1561 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 4 4 1562 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 3 4 1563 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 2 4 3 1564 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 2 4 1565 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 3 4 2 1566 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 2 3 1567 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 1 4 3 2 1568 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 3 4 1569 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 1 4 3 1570 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 1 4 1571 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 4 1 1572 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 1 3 1573 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 3 1 1574 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 2 4 1575 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 1 4 2 1576 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 1 4 1577 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 4 1 1578 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 1 2 1579 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 2 1 1580 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 2 3 1581 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 1 3 2 1582 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 1 3 1583 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 3 1 1584 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 1 2 1585 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 2 1 1586 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 3 2 1587 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 3 2 3 1588 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 3 3 1589 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 2 2 1590 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 3 2 1591 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 2 2 3 1592 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 4 2 1593 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 4 2 4 1594 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 2 2 4 4 1595 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 2 2 1596 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 4 2 1597 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 2 2 4 1598 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 4 3 1599 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 4 3 4 1600 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 3 3 4 4 1601 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 4 3 3 1602 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 4 3 1603 CH 3 - (CH 2 ) 14 - CH 3 - CH 3 - 4 3 3 4

Zusätzlich zu den erfindungsgemäß in den Mitteln enthaltenen Niotensiden mit hohen Diffusionskoeffizienten können die erfindungsgemäßen Mittel weitere Tenside aus den Gruppen der nichtionischen, anionischen, kationischen oder amphoteren Tenside enthalten. Als zusätzliche nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO oder 4 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 5 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO.In addition to the nonionic surfactants having high diffusion coefficients contained in the compositions according to the invention, the agents according to the invention may contain further surfactants from the groups containing nonionic, anionic, cationic or amphoteric surfactants. As additional nonionic surfactants it is preferred to use alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette.Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.

Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel (II),

Figure imgb0005
Further suitable surfactants are polyhydroxy fatty acid amides of the formula (II)
Figure imgb0005

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R1 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (III),

Figure imgb0006
The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)
Figure imgb0006

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R1 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R2 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Als bevorzugte zusätzliche Tenside werden schwachschäumende nichtionische Tenside eingesetzt. Mit besonderem Vorzug enthalten die erfindungsgemäßen maschinellen Geschirrspülmittel ein nichtionisches Tensid, das einen Schmelzpunkt oberhalb Raumtemperatur aufweist. Demzufolge sind bevorzugte Mittel dadurch gekennzeichnet, daß sie nichtionische(s) Tensid(e) mit einem Schmelzpunkt oberhalb von 20°C, vorzugsweise oberhalb von 25°C, besonders bevorzugt zwischen 25 und 60°C und insbesondere zwischen 26,6 und 43,3°C, enthalten.Low-foaming nonionic surfactants are used as preferred additional surfactants. With particular preference, the automatic dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and more preferably between 26.6 and 43.3 ° C.

Geeignete zusätzlich zu den erfindungsgemäß in den Mitteln enthaltenen Niitenside nichtionische Tenside, die Schmelz- bzw. Erweichungspunkte im genannten Temperaturbereich aufweisen, sind beispielsweise schwachschäumende nichtionische Tenside, die bei Raumtemperatur fest oder hochviskos sein können. Werden bei Raumtemperatur hochviskose Niotenside eingesetzt, so ist bevorzugt, daß diese eine Viskosität oberhalb von 20 Pas, vorzugsweise oberhalb von 35 Pas und insbesondere oberhalb 40 Pas aufweisen. Auch Niotenside, die bei Raumtemperatur wachsartige Konsistenz besitzen, sind bevorzugt.Suitable nonionic surfactants which have melting or softening points in the stated temperature range, in addition to the nickel surfactants present in the compositions according to the invention, are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.

Bevorzugt als bei Raumtemperatur feste einzusetzende Niotenside stammen aus den Gruppen der alkoxylierten Niotenside, insbesondere der ethoxylierten primären Alkohole und Mischungen dieser Tenside mit strukturell komplizierter aufgebauten Tensiden wie Polyoxypropylen/Polyoxyethylen/Polyoxypropylen (PO/EO/PO)-Tenside. Solche (PO/EO/PO)-Niotenside zeichnen sich darüber hinaus durch gute Schaumkontrolle aus.Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung ist das nichtionische Tensid mit einem Schmelzpunkt oberhalb Raumtemperatur ein ethoxyliertes Niotensid, das aus der Reaktion von einem Monohydroxyalkanol oder Alkylphenol mit 6 bis 20 C-Atomen mit vorzugsweise mindestens 12 Mol, besonders bevorzugt mindestens 15 Mol, insbesondere mindestens 20 Mol Ethylenoxid pro Mol Alkohol bzw. Alkylphenol hervorgegangen ist.In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

Ein besonders bevorzugtes bei Raumtemperatur festes, einzusetzendes Niotensid wird aus einem geradkettigen Fettalkohol mit 16 bis 20 Kohlenstoffatomen (C16-20-Alkohol), vorzugsweise einem C18-Alkohol und mindestens 12 Mol, vorzugsweise mindestens 15 Mol und insbesondere mindestens 20 Mol Ethylenoxid gewonnen. Hierunter sind die sogenannten "narrow range ethoxylates" (siehe oben) besonders bevorzugt.A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Demnach enthalten besonders bevorzugte erfindungsgemäße Mittel ethoxylierte(s) Niotensid(e), das/die aus C6-20-Monohydroxyalkanolen oder C6-20-Alkylphenolen oder C16-20-Fettalkoholen und mehr als 12 Mol, vorzugsweise mehr als 15 Mol und insbesondere mehr als 20 Mol Ethylenoxid pro Mol Alkohol gewonnen wurde(n).Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

Das Niotensid besitzt vorzugsweise zusätzlich Propylenoxideinheiten im Molekül. Vorzugsweise machen solche PO-Einheiten bis zu 25 Gew.-%, besonders bevorzugt bis zu 20 Gew.-% und insbesondere bis zu 15 Gew.-% der gesamten Molmasse des nichtionischen Tensids aus. Besonders bevorzugte nichtionische Tenside sind ethoxylierte Monohydroxyalkanole oder Alkylphenole, die zusätzlich Polyoxyethylen-Polyoxypropylen Blockcopolymereinheiten aufweisen. Der Alkohol- bzw. Alkylphenolteil solcher Niotensidmoleküle macht dabei vorzugsweise mehr als 30 Gew.-%, besonders bevorzugt mehr als 50 Gew.-% und insbesondere mehr als 70 Gew.-% der gesamten Molmasse solcher Niotenside aus. Bevorzugte Klarspülmittel sind dadurch gekennzeichnet, daß sie ethoxylierte und propoxylierte Niotenside enthalten, bei denen die Propylenoxideinheiten im Molekül bis zu 25 Gew.-%, bevorzugt bis zu 20 Gew.-% und insbesondere bis zu 15 Gew.-% der gesamten Molmasse des nichtionischen Tensids ausmachen, enthalten.The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols additionally having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred rinse aids are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants are included.

Weitere besonders bevorzugt einzusetzende Niotenside mit Schmelzpunkten oberhalb Raumtemperatur enthalten 40 bis 70% eines Polyoxypropylen/Polyoxyethylen/Polyoxypropylen-Blockpolymerblends, der 75 Gew.-% eines umgekehrten Block-Copolymers von Polyoxyethylen und Polyoxypropylen mit 17 Mol Ethylenoxid und 44 Mol Propylenoxid und 25 Gew.-% eines Block-Copolymers von Polyoxyethylen und Polyoxypropylen, initiiert mit Trimethylolpropan und enthaltend 24 Mol Ethylenoxid und 99 Mol Propylenoxid pro Mol Trimethylolpropan.More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nichtionische Tenside, die mit besonderem Vorzug eingesetzt werden können, sind beispielsweise unter dem Namen Poly Tergent® SLF-18 von der Firma Olin Chemicals erhältlich.Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.

Ein weiter bevorzugtes erfindungsgemäßes Klarspülmittel enthält nichtionische Tenside der Formel

        R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2],

A further preferred rinse aid according to the invention contains nonionic surfactants of the formula

R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ],

in der R1 für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 18 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x für Werte zwischen 0,5 und 1,5 und y für einen Wert von mindestens 15 steht.in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

Weitere bevorzugt einsetzbare Niotenside sind die endgruppenverschlossenen Poly(oxyalkylierten) Niotenside der Formel

        R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2

in der R1 und R2 für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen, R3 für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, x für Werte zwischen 1 und 30, k und j für Werte zwischen 1 und 12, vorzugsweise zwischen 1 und 5 stehen. Wenn der Wert x ≥ 2 ist, kann jedes R3 in der obenstehenden Formel unterschiedlich sein. R1 und R2 sind vorzugsweise lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. Für den Rest R3 sind H, -CH3 oder-CH2CH3 besonders bevorzugt. Besonders bevorzugte Werte für x liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15.in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5 stand. If the value x ≥ 2, each R 3 in the above formula may be different. R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R 3 , H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

Wie vorstehend beschrieben, kann jedes R3 in der obenstehenden Formel unterschiedlich sein, falls x ≥ 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht x beispielsweise für 3, kann der Rest R3 ausgewählt werden, um Ethylenoxid- (R3 = H) oder Propylenoxid- (R3 = CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefügt sein können, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 für x ist hierbei beispielhaft gewählt worden und kann durchaus größer sein, wobei die Variationsbreite mit steigenden x-Werten zunimmt und beispielsweise eine große Anzahl (EO)-Gruppen, kombiniert mit einer geringen Anzahl (PO)-Gruppen einschließt, oder umgekehrt.As described above, each R 3 in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R 3 can be selected to form ethylene oxide (R 3 = H) or propylene oxide (R 3 = CH 3 ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Insbesondere bevorzugte endgruppenverschlossenen Poly(oxyalkylierte) Alkohole der obenstehenden Formel weisen Werte von k = 1 und j = 1 auf, so daß sich die vorstehende Formel zu

        R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2

vereinfacht. In der letztgenannten Formel sind R1, R2 und R3 wie oben definiert und x steht für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesonders von 6 bis 18. Besonders bevorzugt sind Tenside, bei denen die Reste R1 und R2 9 bis 14 C-Atome aufweisen, R3 für H steht und x Werte von 6 bis 15 annimmt.Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to

R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2

simplified. In the last-mentioned formula, R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.

Faßt man die letztgenannten Aussagen zusammen, sind erfindungsgemäße Klarspülmittel bevorzugt, die endgruppenverschlossenen Poly(oxyalkylierten) Niotenside der Formel

        R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2

enthalten, in der R1 und R2 für lineare oder verzweigte, gesättigte oder ungesättigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen, R3 für H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, x für Werte zwischen 1 und 30, k und j für Werte zwischen 1 und 12, vorzugsweise zwischen 1 und 5 stehen, wobei Tenside des Typs

        R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2

Summarizing the latter statements, rinse aids according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2

in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type

R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2

in denen x für Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesonders von 6 bis 18 steht, besonders bevorzugt sind.in which x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18, are particularly preferred.

In Verbindung mit den genannten Tensiden können auch anionische, kationische und/oder amphotere Tenside eingesetzt werden, wobei diese wegen ihres Schaumverhaltens in maschinellen Geschirrspülmitteln nur untergeordnete Bedeutung besitzen und zumeist nur in Mengen unterhalb von 10 Gew.-%, meistens sogar unterhalb von 5 Gew.%, beispielsweise von 0,01 bis 2,5 Gew.-%, jeweils bezogen auf das Mittel, eingesetzt werden. Die erfindungsgemäßen Mittel können somit als Tensidkomponente auch anionische, kationische und/oder amphotere Tenside enthalten.Anionic, cationic and / or amphoteric surfactants may also be used in conjunction with the surfactants mentioned, these having only minor importance because of their foaming behavior in dishwasher detergents and usually only in amounts below 10% by weight, in most cases even below 5% by weight .%, For example, from 0.01 to 2.5 wt .-%, each based on the agent used. The agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.

Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Ebenso sind auch die Ester von a-Sulfofettsäuren (Estersulfonate), z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren geeignet.As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fettsäureglycerinester sind dabei die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure.Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate, welche als Handelsprodukte der Shell Oil Company unter dem namen DAN® erhalten werden können, sind geeignete Aniontenside.Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which is a synthetic, on contain petrochemical base produced straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of the Shell Oil Company under the name DAN ® , are suitable anionic surfactants.

Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21-Alkohole, wie 2-Methyl-verzweigte C9-11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-18-Fettalkohole mit 1 bis 4 EO, sind geeignet. Sie werden in Reinigungsmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt.The sulfuric acid monoesters of straight-chain or branched C 7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Weitere geeignete Aniontenside sind auch die Salze der Alkylsulfobemsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobemsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8-18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische.As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Als kationische Aktivsubstanzen können die erfindungsgemäßen Mittel beispielsweise kationische Verbindungen der Formeln IV, V oder VI enthalten:

Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
 worin jede Gruppe R1 unabhängig voneinander ausgewählt ist aus C1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R2 unabhängig voneinander ausgewählt ist aus C8-28-Alkyl-oder -Alkenylgruppen; R3 = R1 oder (CH2)n-T-R2; R4= R1 oder R2 oder (CH2)n-T-R2; T = -CH2-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, the agents according to the invention may contain, for example, cationic compounds of the formulas IV, V or VI:
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
 wherein each R 1 group is independently selected from C 1-6 alkyl, alkenyl or hydroxyalkyl groups; each R 2 group is independently selected from C 8-28 alkyl or alkenyl groups; R 3 = R 1 or (CH 2 ) n -TR 2 ; R 4 = R 1 or R 2 or (CH 2 ) n -TR 2 ; T = -CH 2 -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Als weiteren Inhaltsstoff enthalten die erfindungsgemäßen Mittel einen oder mehrere Gerüststoff(e). Gerüststoffe werden in den erfindungsgemäßen Zusammensetzungen vor allem zum Binden von Calcium und Magnesium eingesetzt. Übliche Builder sind die niedermolekularen Polycarbonsäuren und ihre Salze, die homopolymeren und copolymeren Polycarbonsäuren und ihre Salze, die Carbonate, Phosphate und Natrium- und Kaliumsilikate. Für die erfindungsgemäßen Reinigungsmittel werden bevorzugt Trinatriumcitrat und/oder Pentanatriumtripolyphosphat und silikatische Builder aus der Klasse der Alkalidisilikate eingesetzt. Generell sind bei den Alkalimetallsalzen die Kaliumsalze den Natriumsalzen vorzuziehen, da sie oftmals eine höherer Wasserlöslichkeit besitzen. Bevorzugte wasserlösliche Gerüststoffe sind beispielsweise Trikaliumcitrat, Kaliumcarbonat und die Kaliwassergläser.As a further ingredient, the agents according to the invention contain one or more builders. Builders are used in the compositions of the invention especially for binding calcium and magnesium. Common builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates. Trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders from the class of alkali disilicates are preferably used for the cleaning agents according to the invention. In general, with the alkali metal salts, the potassium salts are preferable to the sodium salts because they often have a higher water solubility. Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.

Besonders bevorzugte maschinelle Geschirrspülmittel enthalten als Gerüststoffe Phosphate, vorzugsweise Alkalimetallphosphate unter besonderer Bevorzugung von Pentanatrium- bzw. Pentakaliumtriphosphat (Natrium- bzw. Kaliumtripolyphosphat).Particularly preferred automatic dishwashing agents contain as builders phosphates, preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).

Alkalimetallphosphate ist dabei die summarische Bezeichnung für die Alkalimetall- (insbesondere Natrium- und Kalium-) -Salze der verschiedenen Phosphorsäuren, bei denen man Metaphosphorsäuren (HPO3)n und Orthophosphorsäure H3PO4 neben höhermolekularen Vertretern unterscheiden kann. Die Phosphate vereinen dabei mehrere Vorteile in sich: Sie wirken las Alkaliträger, verhindern Kalkbeläge und tragen überdies zur Reinigungsleistung bei.Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits and also contribute to the cleaning performance.

Natriumdihydrogenphosphat, NaH2PO4, existiert als Dihydrat (Dichte 1,91 gcm-3, Schmelzpunkt 60°) und als Monohydrat (Dichte 2,04 gcm-3). Beide Salze sind weiße, in Wasser sehr leicht lösliche Pulver, die beim Erhitzen das Kristallwasser verlieren und bei 200°C in das schwach saure Diphosphat (Dinatriumhydrogendiphosphat, Na2H2P2O7), bei höherer Temperatur in Natiumtrimetaphosphat (Na3P3O9) und Maddrellsches Salz (siehe unten), übergehen. NaH2PO4 reagiert sauer; es entsteht, wenn Phosphorsäure mit Natronlauge auf einen pH-Wert von 4,5 eingestellt und die Maische versprüht wird. Kaliumdihydrogenphosphat (primäres oder einbasiges Kaliumphosphat, Kaliumbiphosphat, KDP), KH2PO4, ist ein weißes Salz der Dichte 2,33 gcm-3, hat einen Schmelzpunkt 253° [Zersetzung unter Bildung von Kaliumpolyphosphat (KPO3)x] und ist leicht löslich in Wasser.Sodium dihydrogen phosphate, NaH 2 PO 4 , exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below). NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH 2 PO 4 , is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.

Dinatriumhydrogenphosphat (sekundäres Natriumphosphat), Na2HPO4, ist ein farbloses, sehr leicht wasserlösliches kristallines Salz. Es existiert wasserfrei und mit 2 Mol. (Dichte 2,066 gcm-3, Wasserverlust bei 95°), 7 Mol. (Dichte 1,68 gcm-3, Schmelzpunkt 48° unter Verlust von 5 H2O) und 12 Mol. Wasser (Dichte 1,52 gcm-3, Schmelzpunkt 35° unter Verlust von 5 H2O), wird bei 100° wasserfrei und geht bei stärkerem Erhitzen in das Diphosphat Na4P2O7 über. Dinatriumhydrogenphosphat wird durch Neutralisation von Phosphorsäure mit Sodalösung unter Verwendung von Phenolphthalein als Indikator hergestellt. Dikaliumhydrogenphosphat (sekundäres od. zweibasiges Kaliumphosphat), K2HPO4, ist ein amorphes, weißes Salz, das in Wasser leicht löslich ist.Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.

Trinatriumphosphat, tertiäres Natriumphosphat, Na3PO4, sind farblose Kristalle, die als Dodecahydrat eine Dichte von 1,62 gcm-3 und einen Schmelzpunkt von 73-76°C (Zersetzung), als Decahydrat (entsprechend 19-20% P2O5) einen Schmelzpunkt von 100°C und in wasserfreier Form (entsprechend 39-40% P2O5) eine Dichte von 2,536 gcm-3 aufweisen. Trinatriumphosphat ist in Wasser unter alkalischer Reaktion leicht löslich und wird durch Eindampfen einer Lösung aus genau 1 Mol Dinatriumphosphat und 1 Mol NaOH hergestellt. Trikaliumphosphat (tertiäres oder dreibasiges Kaliumphosphat), K3PO4, ist ein weißes, zerfließliches, körniges Pulver der Dichte 2,56 gcm-3, hat einen Schmelzpunkt von 1340° und ist in Wasser mit alkalischer Reaktion leicht löslich. Es entsteht z.B. beim Erhitzen von Thomasschlacke mit Kohle und Kaliumsulfat. Trotz des höheren Preises werden in der Reinigungsmittel-Industrie die leichter löslichen, daher hochwirksamen, Kalium- phosphate gegenüber entsprechenden Natrium-Verbindungen vielfach bevorzugt.Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 , are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of Density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the detergent industry compared to corresponding sodium compounds.

Tetranatriumdiphosphat (Natriumpyrophosphat), Na4P2O7, existiert in wasserfreier Form (Dichte 2,534 gcm-3, Schmelzpunkt 988°, auch 880° angegeben) und als Decahydrat (Dichte 1,815-1,836 gcm-3, Schmelzpunkt 94° unter Wasserverlust). Bei Substanzen sind farblose, in Wasser mit alkalischer Reaktion lösliche Kristalle. Na4P2O7 entsteht beim Erhitzen von Dinatriumphosphat auf >200° oder indem man Phosphorsäure mit Soda im stöchiometrischem Verhältnis umsetzt und die Lösung durch Versprühen entwässert. Das Decahydrat komplexiert Schwermetall-Salze und Härtebildner und verringert daher die Härte des Wassers. Kaliumdiphosphat (Kaliumpyrophosphat), K4P2O7, existiert in Form des Trihydrats und stellt ein farbloses, hygroskopisches Pulver mit der Dichte 2,33 gcm-3 dar, das in Wasser löslich ist, wobei der pH-Wert der 1%igen Lösung bei 25° 10,4 beträgt.Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Durch Kondensation des NaH2PO4 bzw. des KH2PO4 entstehen höhermol. Natrium- und Kaliumphosphate, bei denen man cyclische Vertreter, die Natrium- bzw. Kaliummetaphosphate und kettenförmige Typen, die Natrium- bzw. Kaliumpolyphosphate, unterscheiden kann. Insbesondere für letztere sind eine Vielzahl von Bezeichnungen in Gebrauch: Schmelz- oder Glühphosphate, Grahamsches Salz, Kurrolsches und Maddrellsches Salz. Alle höheren Natrium-und Kaliumphosphate werden gemeinsam als kondensierte Phosphate bezeichnet.Condensation of NaH 2 PO 4 or KH 2 PO 4 results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

Das technisch wichtige Pentanatriumtriphosphat, Na5P3O10 (Natriumtripolyphosphat), ist ein wasserfrei oder mit 6 H2O kristallisierendes, nicht hygroskopisches, weißes, wasserlösliches Salz der allgemeinen Formel NaO-[P(O)(ONa)-O]n-Na mit n=3. In 100 g Wasser lösen sich bei Zimmertemperatur etwa 17 g, bei 60° ca. 20 g, bei 100° rund 32 g des kristallwasserfreien Salzes; nach zweistündigem Erhitzen der Lösung auf 100° entstehen durch Hydrolyse etwa 8% Orthophosphat und 15% Diphosphat. Bei der Herstellung von Pentanatriumtriphosphat wird Phosphorsäure mit Sodalösung oder Natronlauge im stöchiometrischen Verhältnis zur Reaktion gebracht und die Lsg. durch Versprühen entwässert. Ähnlich wie Grahamsches Salz und Natriumdiphosphat löst Pentanatriumtriphosphat viele unlösliche Metall-Verbindungen (auch Kalkseifen usw.). Pentakaliumtriphosphat, K5P3O10 (Kaliumtripolyphosphat), kommt beispielsweise in Form einer 50 Gew.-%-igen Lösung (> 23% P2O5, 25% K2O) in den Handel. Die Kaliumpolyphosphate finden in der Wasch- und Reinigungsmittel-Industrie breite Verwendung.The technically important pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate), is an anhydrous or with 6 H 2 O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.

Weitere wichtige Gerüststoffe sind insbesondere die Carbonate, Citrate und Silikate. Bevorzugt werden Trinatriumcitrat und/oder Pentanatriumtripolyphosphat und/oder Natriumcarbonat und/oder Natriumbicarbonat und/oder Gluconate und/oder silikatische Builder aus der Klasse der Disilikate und/oder Metasilikate eingesetzt.Other important builders are in particular the carbonates, citrates and silicates. Prefers For example, trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicatic builders from the class of disilicates and / or metasilicates are used.

Als weitere Bestandteile können Alkaliträger zugegen sein. Als Alkaliträger gelten Alkalimetallhydroxide, Alkalimetallcarbonate, Alkalimetallhydrogencarbonate, Alkalimetallsesquicarbonate, Alkalisilikate, Alkalimetasilikate, und Mischungen der vorgenannten Stoffe, wobei im Sinne dieser Erfindung bevorzugt die Alkalicarbonate, insbesondere Natriumcarbonat, Natriumhydrogencarbonat oder Natriumsesquicarbonat eingesetzt werden.As further constituents alkali carriers may be present. Suitable alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, preference being given for the purposes of this invention to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.

Besonders bevorzugt ist ein Buildersystem enthaltend eine Mischung aus Tripolyphosphat und Natriumcarbonat.Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate.

Ebenfalls besonders bevorzugt ist ein Buildersystem enthaltend eine Mischung aus Tripolyphosphat und Natriumcarbonat und Natriumdisilikat.Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.

Die erfindungsgemäßen Mittel können den bzw. die Gerüststoffe je nach Anwendungszweck in unterschiedlichen Mengen enthalten. Hier sind erfindungsgemäße maschinelle Geschirrspülmittel bevorzugt, die den/die Gerüststoff(e) in Mengen von 5 bis 90 Gew.-%, vorzugsweise von 7,5 bis 85 Gew.-% und insbesondere von 10 bis 80 Gew.-%, jeweils bezogen auf das gesamte Mittel, enthalten.The compositions according to the invention may contain the builder (s), depending on the intended use, in different amounts. Here, automatic dishwashing agents according to the invention are preferred which contain the builder (s) in amounts of from 5 to 90% by weight, preferably from 7.5 to 85% by weight and in particular from 10 to 80% by weight, in each case on the entire remedy, included.

Neben den Gerüststoffen sind insbesondere Bleichmittel, Bleichaktivatoren, Enzyme, Silberschutzmittel, Farb- und Duftstoffe usw. bevorzugte Inhaltsstoffe von maschinellen Geschirrspülmitteln. Daneben können weitere Inhaltsstoffe zugegen sein, wobei erfindungsgemäße maschinelle Geschirrspülmittel bevorzugt sind, die zusätzlich einen oder mehrere Stoffe aus der Gruppe der Acidifizierungsmittel, Chelatkomplexbildner oder der belagsinhibierenden Polymere enthalten.In addition to builders, bleaches, bleach activators, enzymes, silver protectants, dyes and fragrances, etc., are preferred ingredients of automatic dishwashing detergents. In addition, further ingredients may be present, automatic dishwashing agents according to the invention being preferred which additionally contain one or more substances from the group of acidifying agents, chelating agents or coating-inhibiting polymers.

Als Acidifizierungsmittel bieten sich sowohl anorganische Säuren als auch organische Säuren an, sofern diese mit den übrigen Inhaltsstoffen verträglich sind. Aus Gründen des Verbraucherschutzes und der Handhabungssicherheit sind insbesondere die festen Mono-, Oligo-und Polycarbonsäuren einsetzbar. Aus dieser Gruppe wiederum bevorzugt sind Citronensäure, Weinsäure, Bernsteinsäure, Malonsäure, Adipinsäure, Maleinsäure, Fumarsäure, Oxalsäure sowie Polyacrylsäure. Auch die Anhydride dieser Säuren können als Acidifizierungsmittel eingesetzt werden, wobei insbesondere Maleinsäureanhydrid und Bernsteinsäureanhydrid kommerziell verfügbar sind. Organische Sulfonsäuren wie Amidosulfonsäure sind ebenfalls einsetzbar. Kommerziell erhältlich und als Acidifizierungsmittel im Rahmen der vorliegenden Erfindung ebenfalls bevorzugt einsetzbar ist Sokalan® DCS (Warenzeichen der BASF), ein Gemisch aus Bernsteinsäure (max. 31 Gew.-%), Glutarsäure (max. 50 Gew.-%) und Adipinsäure (max. 33 Gew.-%).Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients. For reasons of consumer protection and handling safety in particular the solid mono-, oligo-and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid. Also, the anhydrides of these acids can be used as Acidifizierungsmittel, in particular maleic anhydride and succinic anhydride are commercially available. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).

Eine weitere mögliche Gruppe von Inhaltsstoffen stellen die Chelatkomplexbildner dar. Chelatkomplexbildner sind Stoffe, die mit Metallionen cyclische Verbindungen bilden, wobei ein einzelner Ligand mehr als eine Koordinationsstelle an einem Zentralatom besetzt, d. h. mind. "zweizähnig" ist. In diesem Falle werden also normalerweise gestreckte Verbindungen durch Komplexbildung über ein Ion zu Ringen geschlossen. Die Zahl der gebundenen Liganden hängt von der Koordinationszahl des zentralen Ions ab.Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.

Gebräuchliche und im Rahmen der vorliegenden Erfindung bevorzugte Chelatkomplexbilder sind beispielsweise Polyoxycarbonsäuren, Polyamine, Ethylendiamintetraessigsäure (EDTA) und Nitrilotriessigsäure (NTA). Auch komplexbildende Polymere, also Polymere, die entweder in der Hauptkette selbst oder seitenständig zu dieser funktionelle Gruppen tragen, die als Liganden wirken können und mit geeigneten Metall-Atomen in der Regel unter Bildung von ChelatKomplexen reagieren, sind erfindungsgemäß einsetzbar. Die Polymer-gebundenen Liganden der entstehenden Metall-Komplexe können dabei aus nur einem Makromolekül stammen oder aber zu verschiedenen Polymerketten gehören. Letzteres führt zur Vernetzung des Materials, sofern die komplexbildenden Polymere nicht bereits zuvor über kovalente Bindungen vernetzt waren.Common and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also, complex-forming polymers, ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms generally with the formation of chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Komplexierende Gruppen (Liganden) üblicher komplexbildender Polymere sind Iminodiessigsäure-, Hydroxychinolin-, Thioharnstoff-, Guanidin-, Dithiocarbamat-, Hydroxamsäure-, Amidoxim-, Aminophosphorsäure-, (cycl.) Polyamino-, Mercapto-, 1,3-Dicarbonyl- und Kronenether-Reste mit z. T. sehr spezif. Aktivitäten gegenüber Ionen unterschiedlicher Metalle. Basispolymere vieler auch kommerziell bedeutender komplexbildender Polymere sind Polystyrol, Polyacrylate, Polyacrylnitrile, Polyvinylalkohole, Polyvinylpyridine und Polyethylenimine. Auch natürliche Polymere wie Cellulose, Stärke od. Chitin sind komplexbildende Polymere. Darüber hinaus können diese durch polymeranaloge Umwandlungen mit weiteren Ligand-Funktionalitäten versehen werden.Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals. Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.

Besonders bevorzugt sind im Rahmen der vorliegenden Erfindung maschinelle Geschirrspülmittel, die ein oder mehrere Chelatkomplexbildner aus den Gruppen der

  1. (i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
  2. (ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,
  3. (iii) geminalen Diphosphonsäuren,
  4. (iv) Aminophosphonsäuren,
  5. (v) Phosphonopolycarbonsäuren,
  6. (vi) Cyclodextrine
In the context of the present invention, particular preference is given to automatic dishwasher detergents which contain one or more chelate complexing agents from the groups of
  1. (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,
  2. (ii) nitrogen-containing mono- or polycarboxylic acids,
  3. (iii) geminal diphosphonic acids,
  4. (iv) aminophosphonic acids,
  5. (v) phosphonopolycarboxylic acids,
  6. (vi) cyclodextrins

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.%, jeweils bezogen auf das Gewicht des Geschirrspülmittels, enthalten.in amounts above 0.1 wt .-%, preferably above 0.5 wt .-%, more preferably above 1 wt .-% and in particular above 2.5 wt.%, in each case based on the weight of the dishwashing detergent , contain.

Im Rahmen der vorliegenden Erfindung können alle Komplexbildner des Standes der Technik eingesetzt werden. Diese können unterschiedlichen chemischen Gruppen angehören. Vorzugsweise werden einzeln oder im Gemisch miteinander eingesetzt:

  1. a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
  2. b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
  3. c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
  4. d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methyfenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
  5. e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
  6. f) Cyclodextrine.
In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:
  1. a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
  2. b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di (β-hydroxyethyl) glycine, N- (1,2- Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
  3. c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,
  4. d) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylphosphonic acid) or nitrilotri (methylenephosphonic acid),
  5. e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
  6. f) cyclodextrins.

Als Polycarbonsäuren a) werden im Rahmen dieser Patentanmeldung Carbonsäuren -auch Monocarbonsäuren- verstanden, bei denen die Summe aus Carboxyl- und den im Molekül enthaltenen Hydroxylgruppen mindestens 5 beträgt. Komplexbildner aus der Gruppe der stickstoffhaltigen Polycarbonsäuren, insbesondere EDTA, sind bevorzugt. Bei den erfindungsgemäß erforderlichen alkalischen pH-Werten der Behandlungslösungen liegen diese Komplexbilner zumindest teilweise als Anionen vor. Es ist unwesentlich, ob sie in Form der Säuren oder in Form von Salzen eingebracht werden. Im Falle des Einsatzes als Salze sind Alkali-, Ammonium- oder Alkylammoniumsalze, insbesondere Natriumsalze, bevorzugt.For the purposes of this patent application, polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Belagsinhibierende Polymere können ebenfalls in den erfindungsgemäßen Mitteln enthalten sein.
Diese Stoffe, die chemisch verschieden aufgebaut sein könne, stammen beispielsweise aus den Gruppen der niedermolekularen Polyacrylate mit Molmassen zwischen 1000 und 20.000 Dalton, wobei Polymere mit Molmassen unter 15.000 Dalton bevorzugt sind.Scale-inhibiting polymers can likewise be present in the agents according to the invention.
These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.

Belagsinhibierende Polymere können auch Cobuildereigenschaften aufweisen. Als organische Cobuilder können in den erfindungsgemäßen maschinellen Geschirrspülmitteln insbesondere Polycarboxylate / Polycarbonsäuren, polymere Polycarboxylate, Asparaginsäure, Polyacetale, Dextrine, weitere organische Cobuilder (siehe unten) sowie Phosphonate eingesetzt werden. Diese Stoffklassen werden nachfolgend beschrieben.Scale-inhibiting polymers may also have co-builder properties. As organic cobuilders, it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the dishwasher detergents according to the invention. These classes of substances are described below.

Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen.Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- oder Reinigungsmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Als Builder bzw. Belagsinhibitor sind weiter polymere Polycarboxylate geeignet, dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 70000 g/mol.As a builder or coating inhibitor further polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.

Bei den für polymere Polycarboxylate angegebenen Molmassen handelt es sich im Sinne dieser Schrift um gewichtsmittlere Molmassen Mw der jeweiligen Säureform, die grundsätzlich mittels Gelpermeationschromatographie (GPC) bestimmt wurden, wobei ein UV-Detektor eingesetzt wurde. Die Messung erfolgte dabei gegen einen externen Polyacrylsäure-Standard, der aufgrund seiner strukturellen Verwandtschaft mit den untersuchten Polymeren realistische Molgewichtswerte liefert. Diese Angaben weichen deutlich von den Molgewichtsangaben ab, bei denen Polystyrolsulfonsäuren als Standard eingesetzt werden. Die gegen Polystyrolsulfonsäuren gemessenen Molmassen sind in der Regel deutlich höher als die in dieser Schrift angegebenen Molmassen.For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 500 bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 1000 bis 10000 g/mol, und besonders bevorzugt von 1000 bis 4000 g/mol, aufweisen, bevorzugt sein.Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, this group may in turn, the short-chain polyacrylates, the molar masses of 1000 to 10,000 g / mol, and particularly preferably from 1000 to 4000 g / mol, have to be preferred.

Besonders bevorzugt werden in den erfindungsgemäßen Mitteln sowohl Polyacrylate als auch Copolymere aus ungesättigten Carbonsäuren, Sulfonsäuregruppen-haltigen Monomeren sowie gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren eingesetzt. Die Sulfonsäuregruppen-haltigen Copolymere werden weiter unten ausführlich beschrieben.Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention. The sulfonic acid group-containing copolymers are described in detail below.

Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 2000 bis 70000 g/mol, vorzugsweise 20000 bis 50000 g/mol und insbesondere 30000 bis 40000 g/mol.Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

Die (co-)polymeren Polycarboxylate können entweder als Pulver oder als wäßrige Lösung eingesetzt werden. Der Gehalt der Mittel an (co-)polymeren Polycarboxylaten beträgt vorzugsweise 0,5 bis 20 Gew.-%, insbesondere 3 bis 10 Gew.-%.The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

Insbesondere bevorzugt sind auch biologisch abbaubare Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder die als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten. Weitere bevorzugte Copolymere sind solche, die als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat aufweisen.Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives , Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Ebenso sind als weitere bevorzugte Buildersubstanzen polymere Aminodicarbonsäuren, deren Salze oder deren Vorläufersubstanzen zu nennen. Besonders bevorzugt sind Polyasparaginsäuren bzw. deren Salze und Derivate, die neben Cobuilder-Eigenschaften auch eine bleichstabilisierende Wirkung aufweisen.Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.

Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Weitere geeignete organische Buildersubstanzen sind Dextrine, beispielsweise Oligomere bzw. Polymere von Kohlenhydraten, die durch partielle Hydrolyse von Stärken erhalten werden können. Die Hydrolyse kann nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden. Vorzugsweise handelt es sich um Hydrolyseprodukte mit mittleren Molmassen im Bereich von 400 bis 500000 g/mol. Dabei ist ein Polysaccharid mit einem Dextrose-Äquivalent (DE) im Bereich von 0,5 bis 40, insbesondere von 2 bis 30 bevorzugt, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Polysaccharids im Vergleich zu Dextrose, welche ein DE von 100 besitzt, ist. Brauchbar sind sowohl Maltodextrine mit einem DE zwischen 3 und 20 und Trockenglucosesirupe mit einem DE zwischen 20 und 37 als auch sogenannte Gelbdextrine und Weißdextrine mit höheren Molmassen im Bereich von 2000 bis 30000 g/mol.Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

Bei den oxidierten Derivaten derartiger Dextrine handelt es sich um deren Umsetzungsprodukte mit Oxidationsmitteln, welche in der Lage sind, mindestens eine Alkoholfunktion des Saccharidrings zur Carbonsäurefunktion zu oxidieren. Ein an C6 des Saccharidrings oxidiertes Produkt kann besonders vorteilhaft sein.The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized to C 6 of the saccharide ring may be particularly advantageous.

Auch Oxydisuccinate und andere Derivate von Disuccinaten, vorzugsweise Ethylendiamindisuccinat, sind weitere geeignete Cobuilder. Dabei wird Ethylendiamin-N,N'-disuccinat (EDDS) bevorzugt in Form seiner Natrium- oder Magnesiumsalze verwendet. Weiterhin bevorzugt sind in diesem Zusammenhang auch Glycerindisuccinate und Glycerintrisuccinate. Geeignete Einsatzmengen liegen in zeolithhaltigen und/oder silicathaltigen Formulierungen bei 3 bis 15 Gew.-%.Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Weitere brauchbare organische Cobuilder sind beispielsweise acetylierte Hydroxycarbonsäuren bzw. deren Salze, welche gegebenenfalls auch in Lactonform vorliegen können und welche mindestens 4 Kohlenstoffatome und mindestens eine Hydroxygruppe sowie maximal zwei Säuregruppen enthalten.Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Eine weitere Substanzklasse mit Cobuildereigenschaften stellen die Phosphonate dar. Dabei handelt es sich insbesondere um Hydroxyalkan- bzw. Aminoalkanphosphonate. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung als Cobuilder. Es wird vorzugsweise als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch (pH 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugsweise in Form der neutral reagierenden Natriumsalze, z. B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa-Natriumsalz der DTPMP, eingesetzt. Als Builder wird dabei aus der Klasse der Phosphonate bevorzugt HEDP verwendet. Die Aminoalkanphosphonate besitzen zudem ein ausgeprägtes Schwermetallbindevermögen. Dementsprechend kann es, insbesondere wenn die Mittel auch Bleiche enthalten, bevorzugt sein, Aminoalkanphosphonate, insbesondere DTPMP, einzusetzen, oder Mischungen aus den genannten Phosphonaten zu verwenden.Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. When Builder is used from the class of phosphonates preferably HEDP. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

Zusätzlich zu den Stoffen aus den genannten Stoffklassen können die erfindungsgemäßen Mittel weitere übliche Inhaltsstoffe von Reinigungsmitteln enthalten, wobei insbesondere Bleichmittel, Bleichaktivatoren, Enzyme, Silberschutzmittel, Farb- und Duftstoffe von Bedeutung sind. Diese Stoffe werden nachstehend beschrieben.In addition to the substances from the mentioned substance classes, the agents according to the invention may contain further customary ingredients of cleaning agents, in particular bleaching agents, bleach activators, enzymes, silver protectants, dyes and fragrances being of importance. These substances will be described below.

Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Erfindungsgemäße Reinigungsmittel können auch Bleichmittel aus der Gruppe der organischen Bleichmittel enthalten. Typische organische Bleichmittel sind die Diacylperoxide, wie z.B. Dibenzoylperoxid. Weitere typische organische Bleichmittel sind die Peroxysäuren, wobei als Beispiele besonders die Alkylperoxysäuren und die Arylperoxysäuren genannt werden. Bevorzugte Vertreter sind (a) die Peroxybenzoesäure und ihre ringsubstituierten Derivate, wie Alkylperoxybenzoesäuren, aber auch Peroxy-α-Naphtoesäure und Magnesiummonoperphthalat, (b) die aliphatischen oder substituiert aliphatischen Peroxysäuren, wie Peroxylaurinsäure, Peroxystearinsäure, ε-Phthalimidoperoxycapronsäure [Phthaloiminoperoxyhexansäure (PAP)], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipinsäure und N-nonenylamidopersuccinate, und (c) aliphatische und araliphatische Peroxydicarbonsäuren, wie 1,12-Diperoxycarbonsäure, 1,9-Diperoxyazelainsäure, Diperocysebacinsäure, Diperoxybrassylsäure, die Diperoxyphthalsäuren, 2-Decyldiperoxybutan-1,4-disäure, N,N-Terephthaloyl-di(6-aminopercapronsäue) können eingesetzt werden.Among the compounds serving as bleaches in water H 2 O 2 , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1,4-diene diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

Als Bleichmittel in den erfindungsgemäßen Reinigungsmitteln für das maschinelle Geschirrspülen können auch Chlor oder Brom freisetzende Substanzen eingesetzt werden. Unter den geeigneten Chlor oder Brom freisetzenden Materialien kommen beispielsweise heterocyclische N-Brom- und N-Chloramide, beispielsweise Trichlorisocyanursäure, Tribromisocyanursäure, Dibromisocyanursäure und/oder Dichlorisocyanursäure (DICA) und/oder deren Salze mit Kationen wie Kalium und Natrium in Betracht. Hydantoinverbindungen, wie 1,3-Dichlor-5,5-dimethylhydanthoin sind ebenfalls geeignet.Chlorine or bromine-releasing substances can also be used as bleaching agents in the machine dishwashing detergents according to the invention. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel enthalten zusätzlich Bleichmittel in Mengen von 1 bis 40 Gew.-%, vorzugsweise von 2,5 bis 30 Gew.-% und insbesondere von 5 bis 20 Gew.-%, jeweils bezogen auf das gesamte Mittel.Preferred automatic dishwashing agents according to the invention additionally contain bleaching agents in amounts of from 1 to 40% by weight, preferably from 2.5 to 30% by weight and in particular from 5 to 20% by weight, in each case based on the total composition.

Bleichaktivatoren, die die Wirkung der Bleichmittel unterstützen, wurden bereits weiter oben als möglicher Inhaltsstoff der Klarspülerpartikel erwähnt. Bekannte Bleichaktivatoren sind Verbindungen, die eine oder mehrere N- bzw. O-Acylgruppen enthalten, wie Substanzen aus der Klasse der Anhydride, der Ester, der Imide und der acylierten Imidazole oder Oxime. Beispiele sind Tetraacetylethylendiamin TAED, Tetraacetylmethylendiamin TAMD und Tetraacetylhexylendiamin TAHD, aber auch Pentaacetylglucose PAG, 1,5-Diacetyl-2,2-dioxo-hexahydro-1,3,5-triazin DADHT und Isatosäureanhydrid ISA.Bleach activators which aid in the action of the bleaches have already been mentioned above as a possible ingredient of the rinse aid particles. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder lsononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran, n-Methyl-Morpholinium-Acetonitril-Methylsulfat (MMA), und Enolester sowie acetyliertes Sorbitol und Mannitol beziehungsweise deren Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfructose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam. Hydrophil substituierte Acylacetale und Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden.As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), and enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose and also acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl capr olactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

Zusätzlich zu den konventionellen Bleichaktivatoren oder an deren Stelle können auch sogenannte Bleichkatalysatoren in die Klarspülerpartikel eingearbeitet werden. Bei diesen Stoffen handelt es sich um bleichverstärkende Übergangsmetallsalze bzw. Übergangsmetallkomplexe wie beispielsweise Mn-, Fe-, Co-, Ru - oder Mo-Salenkomplexe oder -carbonylkomplexe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu-Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe-, Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren verwendbar.In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the rinse aid particles. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Bevorzugt werden Bleichaktivatoren aus der Gruppe der mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder lsononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), n-Methyl-Morpholinium-Acetonitril-Methylsulfat (MMA), vorzugsweise in Mengen bis 10 Gew.-%, insbesondere 0,1 Gew.-% bis 8 Gew.-%, besonders 2 bis 8 Gew.-% und besonders bevorzugt 2 bis 6 Gew.-% bezogen auf das gesamte Mittel, eingesetzt.Bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.

Bleichverstärkende Übergangsmetallkomplexe, insbesondere mit den Zentralatomen Mn, Fe, Co, Cu, Mo, V, Ti und/oder Ru, bevorzugt ausgewählt aus der Gruppe der Mangan und/oder Cobaltsalze und/oder -komplexe, besonders bevorzugt der Cobalt(ammin)-Komplexe, der Cobalt(acetat)-Komplexe, der Cobalt(Carbonyl)-Komplexe, der Chloride des Cobalts oder Mangans, des Mangansulfats werden in üblichen Mengen, vorzugsweise in einer Menge bis zu 5 Gew.-%, insbesondere von 0,0025 Gew.-% bis 1 Gew.-% und besonders bevorzugt von 0,01 Gew.-% bis 0,25 Gew.-%, jeweils bezogen auf das gesamte Mittel, eingesetzt. Aber in spezielle Fällen kann auch mehr Bleichaktivator eingesetzt werden.Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.

Als Enzyme kommen in den erfindungsgemäßen Reinigungsmitteln insbesondere solche aus der Klassen der Hydrolasen wie der Proteasen, Esterasen, Lipasen bzw. lipolytisch wirkende Enzyme, Amylasen, Glykosylhydrolasen und Gemische der genannten Enzyme in Frage. Alle diese Hydrolasen tragen zur Entfernung von Anschmutzungen wie protein-, fett- oder stärkehaltigen Verfleckungen bei. Zur Bleiche können auch Oxidoreduktasen eingesetzt werden. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen wie Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus und Humicola insolens sowie aus deren gentechnisch modifizierten Varianten gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase bzw. lipolytisch wirkenden Enzymen oder aus Protease, Amylase und Lipase bzw. lipolytisch wirkenden Enzymen oder Protease, Lipase bzw. lipolytisch wirkenden Enzymen, insbesondere jedoch Protease und/oder Lipase-haltige Mischungen bzw. Mischungen mit lipolytisch wirkenden Enzymen von besonderem Interesse. Beispiele für derartige lipolytisch wirkende Enzyme sind die bekannten Cutinasen. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Zu den geeigneten Amylasen zählen insbesondere alpha-Amylasen, lso-Amylasen, Pullulanasen und Pektinasen.Suitable enzymes in the detergents according to the invention are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.

Die Enzyme können an Trägerstoffe adsorbiert oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Der Anteil der Enzyme, Enzymmischungen oder Enzymgranulate kann beispielsweise etwa 0,1 bis 5 Gew.-%, vorzugsweise 0,5 bis etwa 4,5 Gew.-% betragen.The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or For example, enzyme granules may be about 0.1 to 5 weight percent, preferably 0.5 to about 4.5 weight percent.

Besonders bevorzugt ist im Rahmen der vorliegenden Erfindung der Einsatz flüssiger Enzymformulierungen. Hier sind erfindungsgemäße maschinelle Geschirspülmittel bevorzugt, die zusätzlich Enzym(e) in Mengen von 0,01 bis 15 Gew.-%, vorzugsweise von 0,1 bis 10 Gew.-% und insbesondere von 0,5 bis 6 Gew.-%, jeweils bezogen auf das gesamte Mittel, enthalten.Particularly preferred in the context of the present invention is the use of liquid enzyme formulations. Here, preferred automatic dishwashing detergents according to the invention are those which additionally comprise enzyme (s) in amounts of from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight and in particular from 0.5 to 6% by weight, in each case based on the total agent included.

Farb- und Duftstoffe können den erfindungsgemäßen maschinellen Geschirrspülmitteln zugesetzt werden, um den ästhetischen Eindruck der entstehenden Produkte zu verbessern und dem Verbraucher neben der Leistung ein visuell und sensorisch "typisches und unverwechselbares" Produkt zur Verfügung zu stellen. Als Parfümöle bzw. Duftstoffe können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyclohexylacetat, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethylmethylphenylglycinat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethern zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8-18 C-Atomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone, α-Isomethylionon und Methylcedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene wie Limonen und Pinen. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pine-, Citrus-, Jasmin-, Patchouly-, Rosen- oder Ylang-Ylang-Öl. Ebenfalls geeignet sind Muskateller, Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeeröl, Vetiveröl, Olibanumöl, Galbanumöl und Labdanumöl sowie Orangenblütenöl, Neroliol, Orangenschalenöl und Sandelholzöl.Dyes and fragrances can be added to the machine dishwasher detergents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to performance. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionones, α-isomethylionone and methylcedryl ketone, among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

Die Duftstoffe können direkt in die erfindungsgemäßen Reinigungsmittel eingearbeitet werden, es kann aber auch vorteilhaft sein, die Duftstoffe auf Träger aufzubringen, die die Haftung des Parfüms auf der Wäsche verstärken und durch eine langsamere Duftfreisetzung für langanhaltenden Duft der Textilien sorgen. Als solche Trägermaterialien haben sich beispielsweise Cyclodextrine bewährt, wobei die Cyclodextrin-Parfüm-Komplexe zusätzlich noch mit weiteren Hilfsstoffen beschichtet werden können.The fragrances can be incorporated directly into the detergents according to the invention, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and provide a slower fragrance release for long-lasting fragrance of the textiles. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

Um den ästhetischen Eindruck der erfindungsgemäß hergestellten Mittel zu verbessern, kann es (oder Teile davon) mit geeigneten Farbstoffen eingefärbt werden. Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, besitzen eine hohe Lagerstabilität und Unempfindlichkeit gegenüber den übrigen Inhaltsstoffen der Mittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber den mit den Mitteln zu behandelnden Substraten wie Glas, Keramik oder Kunststoffgeschirr, um diese nicht anzufärben.In order to improve the aesthetics of the compositions made according to the invention, it may (or parts thereof) be colored with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.

Die erfindungsgemäßen Reinigungsmittel können zum Schutze des Spülgutes oder der Maschine Korrosionsinhibitoren enthalten, wobei besonders Silberschutzmittel im Bereich des maschinellen Geschirrspülens eine besondere Bedeutung haben. Einsetzbar sind die bekannten Substanzen des Standes der Technik. Allgemein können vor allem Silberschutzmittel ausgewählt aus der Gruppe der Triazole, der Benzotriazole, der Bisbenzotriazole, der Aminotriazole, der Alkylaminotriazole und der Übergangsmetallsalze oder -komplexe eingesetzt werden. Besonders bevorzugt zu verwenden sind Benzotriazol und/oder Alkylaminotriazol. Man findet in Reinigerformutierungen darüber hinaus häufig aktivchlorhaltige Mittel, die das Korrodieren der Silberoberfläche deutlich vermindern können. In chlorfreien Reinigern werden besonders Sauerstoff- und stickstoffhaltige organische redoxaktive Verbindungen, wie zwei- und dreiwertige Phenole, z. B. Hydrochinon, Brenzkatechin, Hydroxyhydrochinon, Gallussäure, Phloroglucin, Pyrogallol bzw. Derivate dieser Verbindungsklassen. Auch salz- und komplexartige anorganische Verbindungen, wie Salze der Metalle Mn, Ti, Zr, Hf, V, Co und Ce finden häufig Verwendung. Bevorzugt sind hierbei die Übergangsmetallsalze, die ausgewählt sind aus der Gruppe der Mangan und/oder Cobaltsalze und/oder -komplexe, besonders bevorzugt der Cobalt(ammin)-Komplexe, der Cobalt(acetat)-Komplexe, der Cobalt-(Carbonyl)-Komplexe, der Chloride des Cobalts oder Mangans und des Mangansulfats. Ebenfalls können Zinkverbindungen zur Verhinderung der Korrosion am Spülgut eingesetzt werden.The detergents according to the invention may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, active chlorine-containing agents are frequently found in cleaner formulations, which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

An maschinell gespültes Geschirr werden heute häufig höhere Anforderungen gestellt als an manuell gespültes Geschirr. So wird auch ein von Speiseresten völlig gereinigtes Geschirr dann als nicht einwandfrei bewertet, wenn es nach dem maschinellen Geschirrspülen noch weißliche, auf Wasserhärte oder anderen mineralischen Salzen beruhende Flecken aufweist, die mangels Netzmittel aus eingetrockneten Wassertropfen stammen. Um glasklares und fleckenloses Geschirr zu erhalten, setzt man daher heute mit Erfolg Klarspüler ein. Der Zusatz von Klarspüler am Ende des Spülprogramms sorgt dafür, daß das Wasser möglichst vollständig vom Spülgut abläuft, so daß die unterschiedlichen Oberflächen am Ende des Spülprogramms rückstandsfrei und makellos glänzend sind. Das maschinelle Reinigen von Geschirr in Haushaltsgeschirrspülmaschinen umfaßt üblicherweise einen Vorspülgang, einen Hauptspülgang und einen Klarspülgang, die von Zwischenspülgängen unterbrochen werden. Bei den meisten Maschinen ist der Vorspülgang für stark verschmutztes Geschirr zuschaltbar, wird aber nur in Ausnahmefällen vom Verbraucher gewählt, so daß in den meisten Maschinen ein Hauptspülgang, ein Zwischenspülgang mit reinem Wasser und ein Klarspülgang durchgeführt werden. Die Temperatur des Hauptspülgangs variiert dabei je nach Maschinentyp und Programmstufenwahl zwischen 40 und 65°C. Im Klarspülgang werden aus einem Dosiertank in der Maschine Klarspülmittel zugegeben, die üblicherweise als Hauptsbestandteil nichtionische Tenside enthalten. Solche Klarspüler liegen in flüssiger Form vor und sind im Stand der Technik breit beschrieben. Ihre Aufgabe besteht vornehmlich darin, Kalkflecken und Beläge auf dem Geschirr zu verhindern.Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets. In order to obtain crystal-clear and spotless dishes, one uses therefore successfully today rinse aid. The addition of rinse aid at the end of the washing program ensures that the water runs as completely as possible from the items to be washed, so that the different surfaces at the end of the washing program are residue-free and flawless gloss. The automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses. On most machines, the pre-rinse cycle for heavily soiled dishes can be switched on, but only in Exceptionally chosen by the consumer, so that in most machines, a main rinse, an intermediate rinse with pure water and a rinse cycle are performed. The temperature of the main wash cycle varies between 40 and 65 ° C, depending on the machine type and program level selection. In the rinse cycle, rinse aids are added from a dosing tank in the machine, which usually contain nonionic surfactants as the main constituent. Such rinse aids are in liquid form and are widely described in the art. Your task is primarily to prevent limescale and deposits on the dishes.

Die erfindungsgemäßen Mittel können als "normale" Reiniger formuliert werden, welche zusammen mit handelsüblichen Ergänzungsmitteln (Klarspüler, Regeneriersalz) eingesetzt werden. Mit besonderem Vorteil kann aber mit den erfindungsgemäßen Produkten auf die zusätzliche Dosierung von Klarspülmitteln verzichtet werden, da die erfindungsgemäß in den Mitteln enthaltenen Tenside mit hohen Diffusionskoeffizienten hervorragende Ablaufeigenschaften der Spülflotte bedingen und Beläge auf dem Geschirr im Vergleich zu herkömmlichen Tensiden deutlich verringern. Diese sogenannten "2in1"-Produkte führen zu einer Vereinfachung der Handhabung und nehmen dem Verbraucher die Last der zusätzlichen Dosierung zweier unterschiedlicher Produkte (Reiniger und Klarspüler) ab.The compositions according to the invention can be formulated as "normal" cleaners, which are used together with commercially available supplements (rinse aid, regenerating salt). With particular advantage but can be dispensed with the products of the invention to the additional dosage of rinse agents, since the invention contained in the surfactants with high diffusion coefficients cause excellent flow properties of the rinse and significantly reduce deposits on the dishes compared to conventional surfactants. These so-called "2in1" products lead to a simplification of handling and relieve the consumer of the burden of additional dosage of two different products (cleaner and rinse aid).

Selbst beim Einsatz von "2in1"-Produkten sind zum Betrieb einer Haushaltsgeschirrspülmaschine in Zeitabständen zwei Dosiervorgänge erforderlich, da nach einer bestimmten Anzahl von Spülvorgängen das Regeneriersalz im Wasserenthärtungssystem der Maschine nachgefüllt werden muß. Diese Wasserenthärtungssysteme bestehen aus lonenaustauscherpolymeren, welche das der Maschine zulaufende Hartwasser enthärten und im Anschluß an das Spülprogramm durch eine Spülung mit Salzwasser regeneriert werden.Even with the use of "2in1" products, two dosing operations are required at regular intervals to operate a domestic dishwasher, because after a certain number of rinses, the regeneration salt must be replenished in the water softening system of the machine. These water softening systems consist of ion exchange polymers which soften the hard water entering the machine and are regenerated by a rinsing with salt water following the washing program.

Es lassen sich aber auch erfindungsgemäße Produkte, welche als sogenannte "3in1"-Produkte die herkömmlichen Reiniger, Klarspüler und eine Salzersatzfunktion in sich vereinen, bereitstellen. Hierzu sind erfindungsgemäße maschinelle Geschirrspülmittel bevorzugt, die zusätzlich 0,1 bis 70 Gew.-% an Copolymeren aus

  • i) ungesättigten Carbonsäuren
  • ii) Sulfonsäuregruppen-haltigen Monomeren
  • iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
enthalten.However, it is also possible to provide products according to the invention which, as so-called "3in1" products, combine the conventional cleaners, rinse aids and a salt replacement function. For this purpose, automatic dishwashing agents according to the invention are preferred which additionally comprise from 0.1 to 70% by weight of copolymers
  • i) unsaturated carboxylic acids
  • ii) sulfonic acid group-containing monomers
  • iii) optionally further ionic or nonionic monomers
contain.

Diese Copolymere bewirken, daß die mit solchen Mitteln behandelten Geschirrteile bei nachfolgenden Reinigungsvorgängen deutlich sauberer werden, als Geschirrteile, die mit herkömmlichen Mitteln gespült wurden.These copolymers cause the dishware treated with such agents to become significantly cleaner in subsequent cleanings than do the dishware which has been rinsed by conventional means.

Als zusätzlicher positiver Effekt tritt eine Verkürzung der Trocknungszeit der mit dem Reinigungsmittel behandelten Geschirrteile auf, d.h. der Verbraucher kann nach dem Ablauf des Reinigungsprogramms das Geschirr früher aus der Maschine nehmen und wiederbenutzen.As an additional positive effect, a shortening of the drying time of the dishes treated with the detergent occurs, i. the consumer can take the dishes from the machine earlier and reuse them after the cleaning program has ended.

Die Erfindung zeichnet sich durch eine verbesserte "Reinigbarkeit" der behandelten Substrate bei späteren Reinigungsvorgängen und durch ein erhebliche Verkürzung der Trocknungszeit gegenüber vergleichbaren Mitteln ohne den Einsatz Sulfonsäuregruppen-haltiger Polymere aus.The invention is characterized by an improved "cleanability" of the treated substrates in subsequent cleaning operations and by a significant reduction in the drying time compared to comparable agents without the use of sulfonic acid-containing polymers.

Unter Trocknungszeit wird im Rahmen der erfindungsgemäßen Lehre im allgemeinen die wortsinngemäße Bedeutung verstanden, also die Zeit, die verstreicht, bis eine in einer Geschirrspülmaschine behandelte Geschirroberfläche getrocknet ist, im besonderen aber die Zeit, die verstreicht, bis 90 % einer mit einem Reinigungs- oder Klarspülmittel in konzentrierter oder verdünnter Form behandelten Oberfläche getrocknet ist. Drying time in the context of the teaching according to the invention is generally understood to mean the meaning of the word, ie the time that elapses until a dish surface treated in a dishwasher has dried, but in particular the time that elapses, up to 90% with a cleaning or Rinse aid is dried in concentrated or diluted form treated surface.

Im Rahmen der vorliegenden Erfindung sind ungesättigte Carbonsäuren der Formel VII als Monomer bevorzugt,

        R1(R2)C=C(R3)COOH     (VII),

in der R1 bis R3 unabhängig voneinander für -H -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein-oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder - COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder - COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist.In the context of the present invention, unsaturated carboxylic acids of the formula VII are preferred as the monomer,

R 1 (R 2 ) C = C (R 3 ) COOH (VII),

in the R 1 to R 3 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Unter den ungesättigten Carbonsäuren, die sich durch die Formel 1 beschreiben lassen, sind insbesondere Acrylsäure (R1 = R2 = R3 = H), Methacrylsäure (R1 = R2 = H; R3 = CH3) und/oder Maleinsäure (R1 = COOH; R2 = R3 = H) bevorzugt.Among the unsaturated carboxylic acids which can be described by the formula 1 are in particular acrylic acid (R 1 = R 2 = R 3 = H), methacrylic acid (R 1 = R 2 = H, R 3 = CH 3 ) and / or maleic acid (R 1 = COOH; R 2 = R 3 = H) is preferred.

Bei den Sulfonsäuregruppen-haltigen Monomeren sind solche der Formel VIII bevorzugt,

        R5(R6)C=C(R7)-X-SO3H     (VIII),

in der R5 bis R7 unabhängig voneinander für -H -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein-oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder - COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder - COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2- und -C(O)-NH-CH(CH2CH3)-.In the sulfonic acid-containing monomers, those of the formula VIII are preferred,

R 5 (R 6 ) C = C (R 7 ) -X-SO 3 H (VIII),

in R 5 to R 7 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 - and -C (O) -NH-CH (CH 2 CH 3 ) -.

Unter diesen Monomeren bevorzugt sind solche der Formeln VIIIa, VIIIb und/oder Vlllc,

        H2C=CH-X-SO3H     (VIIIa),

        H2C=C(CH3)-X-SO3H     (VIIIb),

        HO3S-X-(R6)C=C(R7)-X-SO3H     (VIIIc),

in denen R6 und R7 unabhängig voneinander ausgewählt sind aus -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2 und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2- und -C(O)-NH-CH(CH2CH3)-.Preferred among these monomers are those of the formulas VIIIa, VIIIb and / or VIIIc,

H 2 C = CH-X-SO 3 H (VIIIa),

H 2 C = C (CH 3 ) -X-SO 3 H (VIIIb),

HO 3 SX- (R 6 ) C =C (R 7 ) -X-SO 3 H (VIIIc),

in which R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 and X is an optional spacer group which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 - and - C (O) -NH-CH (CH 2 CH 3 ) -.

Besonders bevorzugte Sulfonsäuregruppen-haltige Monomere sind dabei 1-Acrylamido-1-propansulfonsäure (X = -C(O)NH-CH(CH2CH3) in Formel IIa), 2-Acrylamido-2-propansulfonsäure (X = -C(O)NH-C(CH3)2 in Formel VIIIa), 2-Acrylamido-2-methyl-1-propansulfonsäure (X = - C(O)NH-CH(CH3)CH2- in Formel VIIIa), 2-Methacrylamido-2-methyl-1-propansulfonsäure (X = - C(O)NH-CH(CH3)CH2- in Formel VIIIb), 3-Methacrylamido-2-hydroxy-propansulfonsäure (X = - C(O)NH-CH2CH(OH)CH2- in Formel VIIIb), Allylsulfonsäure (X = CH2 in Formel VIIIa), Methallylsulfonsäure (X = CH2 in Formel IIb), Allyloxybenzolsulfonsäure (X = -CH2-O-C6H4- in Formel VIIIa), Methallyloxybenzolsulfonsäure (X = -CH2-O-C6H4- in Formel VIIIb), 2-Hydroxy-3-(2-propenyloxy)propansulfonsäure, 2-Methyl-2-propenl-sulfonsäure (X = CH2 in Formel VIIIb), Styrolsulfonsäure (X = C6H4 in Formel VIIIa), Vinylsulfonsäure (X nicht vorhanden in Formel VIIIa), 3-Sulfopropylacrylat (X = -C(O)NH-CH2CH2CH2- in Formel VIIIa), 3-Sulfopropylmethacrylat (X = -C(O)NH-CH2CH2CH2- in Formel VIIIb), Sulfomethacrylamid (X = -C(O)NH- in Formel VIIIb), Sulfomethylmethacrylamid (X = -C(O)NH-CH2- in Formel VIIIb) sowie wasserlösliche Salze der genannten Säuren.Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH 2 CH 3 ) in formula IIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH 3 ) 2 in formula VIIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = - C (O) NH-CH (CH 3 ) CH 2 - in formula VIIIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH 3 ) CH 2 - in formula VIIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH 2 CH (OH) CH 2 - in formula VIIIb), allylsulfonic acid (X = CH 2 in formula VIIIa), methallylsulfonic acid (X = CH 2 in formula IIb), allyloxybenzenesulfonic acid (X = -CH 2 -OC 6 H 4 - in formula VIIIa), methallyloxybenzenesulfonic acid (X = -CH 2 -OC 6 H 4 - in formula VIIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid (X = CH 2 in formula VIIIb), styrenesulfonic acid (X = C 6 H 4 in formula VIIIa), vinylsulfonic acid (X not present in formula VIIIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH 2 CH 2 CH 2 in formula VIIIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH 2 CH 2 CH 2 - in formula VIIIb), sulfomethacrylamide (X = -C (O) NH- in formula VIIIb), sulfomethylmethacrylamide (X = -C (O) NH-CH 2 - in formula VIIIb) and water-soluble salts of said acids.

Als weitere ionische oder nichtionogene Monomere kommen insbesondere ethylenisch ungesättigte Verbindungen in Betracht. Vorzugsweise beträgt der Gehalt der erfindungsgemäß eingesetzten Polymere an Monomeren der Grupp iii) weniger als 20 Gew.-%, bezogen auf das Polymer. Besonders bevorzugt zu verwendende Polymere bestehen lediglich aus Monomeren der Gruppen i) und ii).Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of the polymers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the Polymer. Particularly preferred polymers to be used consist only of monomers of groups i) and ii).

Zusammenfassend sind Copolymere aus

  1. i) ungesättigten Carbonsäuren der Formel VII.

            R1(R2)C=C(R3)COOH     (VII),

    in der R1 bis R3 unabhängig voneinander für -H -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein-oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder - COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder - COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
  2. ii) Sulfonsäuregruppen-haltigen Monomeren der Formel VIII

            R5(R6)C=C(R7)-X-SO3H     (VIII),

    in der R5 bis R7 unabhängig voneinander für -H -CH3, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein-oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH2, -OH oder - COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder - COOR4 steht, wobei R4 ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2- und -C(O)-NH-CH(CH2CH3)-
  3. iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
    besonders bevorzugt.
In summary, copolymers are made of
  1. i) unsaturated carboxylic acids of the formula VII.

    R 1 (R 2 ) C = C (R 3 ) COOH (VII),

    in the R 1 to R 3 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
  2. ii) sulfonic acid group-containing monomers of the formula VIII

    R 5 (R 6 ) C = C (R 7 ) -X-SO 3 H (VIII),

    in R 5 to R 7 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 - and -C (O) -NH-CH (CH 2 CH 3 ) -
  3. iii) optionally further ionic or nonionic monomers
    particularly preferred.

Besonders bevorzugte Copolymere bestehen aus

  1. i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
  2. ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln VIIIa, VIIIb und/oder VIIIc:

            H2C=CH-X-SO3H     (VIIIa),

            H2C=C(CH3)-X-SO3H     (VIIIb),

            HO3S-X-(R6)C=C(R7)-X-SO3H     (VIIIc),

    in der R6 und R7 unabhängig voneinander ausgewählt sind aus -H, -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2 und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus - (CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2- und -C(O)-NH-CH(CH2CH3)-
  3. iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.
Particularly preferred copolymers consist of
  1. i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
  2. ii) one or more sulfonic acid group-containing monomers of the formulas VIIIa, VIIIb and / or VIIIc:

    H 2 C = CH-X-SO 3 H (VIIIa),

    H 2 C = C (CH 3 ) -X-SO 3 H (VIIIb),

    HO 3 SX- (R 6 ) C =C (R 7 ) -X-SO 3 H (VIIIc),

    in which R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2 and X is an optional spacer group which is selected from - (CH 2 ) n - with n = 0 to 4, -COO- (CH 2 ) k - with k = 1 to 6, -C (O) -NH-C (CH 3 ) 2 - and - C (O) -NH-CH (CH 2 CH 3 ) -
  3. iii) optionally further ionic or nonionic monomers.

Die erfindungsgemäß in den Mitteln anthaltenen Copolymere können die Monomere aus den Gruppen i) und ii) sowie gegebenenfalls iii) in variierenden Mengen enthalten, wobei sämtliche Vertreter aus der gruppe i) mit sämtlichen Vertretern aus der Gruppe ii) und sämtlichen Vertretern aus der Gruppe iii) kombiniert werden können. Besonders bevorzugte Polymere weisen bestimmte Struktureinheiten auf, die nachfolgend beschrieben werden.The copolymers according to the invention in the compositions may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii ) can be combined. Particularly preferred polymers have certain structural units, which are described below.

So sind beispielsweise erfindungsgemäße Mittel bevorzugt, die dadurch gekennzeichnet sind, daß sie ein oder mehrere Copolymere enthalten, die Struktureinheiten der Formel IX

        -[CH2-CHCOOH]m-[CH2-CHC(O)-Y-SO3H]p-     (IX),

enthalten, in der m und p jeweils für eine ganze natürliche Zahl zwischen 1 und 2000 sowie Y für eine Spacergruppe steht, die ausgewählt ist aus substituierten oder unsubstituierten aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffresten mit 1 bis 24 Kohlenstoffatomen, wobei Spacergruppen, in denen Y für -O-(CH2)n- mit n = 0 bis 4, für -O-(C6H4)-, für -NH-C(CH3)2- oder -NH-CH(CH2CH3)- steht, bevorzugt sind.Thus, for example, agents according to the invention are preferred, which are characterized in that they contain one or more copolymers, the structural units of the formula IX

- [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (IX),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH 2 ) n - with n = 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH-CH (CH 2 CH 3 ) - stands, are preferred.

Diese Polymere werden durch Copolymerisation von Acrylsäure mit einem Sulfonsäuregruppen-haltigen Acrylsäurederivat hergestellt. Copolymerisiert man das Sulfonsäuregruppen-haltige Acrylsäurederivat mit Methacrylsäure, gelangt man zu einem anderen Polymer, dessen Einsatz in den erfindungsgemäßen Mitteln ebenfalls bevorzugt und dadurch gekennzeichnet ist, daß die Mittel ein oder mehrere Copolymere enthalten, die Struktureinheiten der Formel X

        -[CH2-C(CH3)COOH]m-[CH2-CHC(O)-Y-SO3H]p-     (X),

enthalten, in der m und p jeweils für eine ganze natürliche Zahl zwischen 1 und 2000 sowie Y für eine Spacergruppe steht, die ausgewählt ist aus substituierten oder unsubstituierten aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffresten mit 1 bis 24 Kohlenstoffatomen, wobei Spacergruppen, in denen Y für -O-(CH2)n- mit n = 0 bis 4, für -O-(C6H4)-, für -NH-C(CH3)2- oder -NH-CH(CH2CH3)- steht, bevorzugt sind.These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the agents according to the invention is also preferred and characterized in that the agents contain one or more copolymers, the structural units of the formula X.

- [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (X),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH 2 ) n - with n = 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH-CH (CH 2 CH 3 ) - stands, are preferred.

Völlig analog lassen sich Acrylsäure und/oder Methacrylsäure auch mit Sulfonsäuregruppen-haltigen Methacrylsäurederivaten copolymerisieren, wodurch die Struktureinheiten im Molekül verändert werden. So sind erfindungsgemäße Mittel, die ein oder mehrere Copolymere enthalten, welche Struktureinheiten der Formel XI

        -[CH2-CHCOOH]m-[CH2-C(CH3)C(O)-Y-SO3H]p-     (XI),

enthalten, in der m und p jeweils für eine ganze natürliche Zahl zwischen 1 und 2000 sowie Y für eine Spacergruppe steht, die ausgewählt ist aus substituierten oder unsubstituierten aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffresten mit 1 bis 24 Kohlenstoffatomen, wobei Spacergruppen, in denen Y für -O-(CH2)n- mit n = 0 bis 4, für -O-(C6H4)-, für -NH-C(CH3)2- oder -NH-CH(CH2CH3)- steht, bevorzugt sind, ebenfalls eine bevorzugte Ausführungsform der vorliegenden Erfindung, genau wie auch Mittel bevorzugt sind, die dadurch gekennzeichnet sind, daß sie ein oder mehrere Copolymere enthalten, die Struktureinheiten der Formel XII

        -[CH2-C(CH3)COOH]m-[CH2-C(CH3)C(O)-Y-SO3H]p-     (XII),

enthalten, in der m und p jeweils für eine ganze natürliche Zahl zwischen 1 und 2000 sowie Y für eine Spacergruppe steht, die ausgewählt ist aus substituierten oder unsubstituierten aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffresten mit 1 bis 24 Kohlenstoffatomen, wobei Spacergruppen, in denen Y für -O-(CH2)n- mit n = 0 bis 4, für -O-(C6H4)-, für -NH-C(CH3)2- oder-NH-CH(CH2CH3)- steht, bevorzugt sind.Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, agents according to the invention which comprise one or more copolymers which are structural units of the formula XI

- [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XI),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH 2 ) n - with n = 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH-CH (CH 2 CH 3 ) - are, preferably, also a preferred embodiment of the present invention, just as preferred are agents which are characterized in that they contain one or more copolymers, the structural units of the formula XII

- [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XII),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH 2 ) n - with n = 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH-CH (CH 2 CH 3 ) - stands, are preferred.

Anstelle von Acrylsäure und/oder Methacrylsäure bzw. in Ergänzung hierzu kann auch Maleinsäure als besonders bevorzugtes Monomer aus der Gruppe i) eingesetzt werden. Man gelangt auf diese Weise zu erfindungsgemäß bevorzugten Mitteln, die dadurch gekennzeichnet sind, daß sie ein oder mehrere Copolymere enthalten, die Struktureinheiten der Formel XIII

        -[HOOCCH-CHCOOH]m-[CH2-CHC(O)-Y-SO3H]p-     (XIII),

enthalten, in der m und p jeweils für eine ganze natürliche Zahl zwischen 1 und 2000 sowie Y für eine Spacergruppe steht, die ausgewählt ist aus substituierten oder unsubstituierten aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffresten mit 1 bis 24 Kohlenstoffatomen, wobei Spacergruppen, in denen Y für -O-(CH2)n- mit n = 0 bis 4, für -O-(C6H4)-, für -NH-C(CH3)2- oder -NH-CH(CH2CH3)- steht, bevorzugt sind und zu Mitteln, welche dadurch gekennzeichnet sind, daß sie ein oder mehrere Copolymere enthalten, die Struktureinheiten der Formel XIV

        -[HOOCCH-CHCOOH]m-[CH2-C(CH3)C(O)O-Y-SO3H]p-     (XIV),

enthalten, in der m und p jeweils für eine ganze natürliche Zahl zwischen 1 und 2000 sowie Y für eine Spacergruppe steht, die ausgewählt ist aus substituierten oder unsubstituierten aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffresten mit 1 bis 24 Kohlenstoffatomen, wobei Spacergruppen, in denen Y für -O-(CH2)n- mit n = 0 bis 4, für -O-(C6H4)-, für -NH-C(CH3)2- oder -NH-CH(CH2CH3)- steht, bevorzugt sind.Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred agents, which are characterized in that they contain one or more copolymers, the structural units of the formula XIII

- [HOOCCH-CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (XIII)

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH 2 ) n - with n = 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH-CH (CH 2 CH 3 ) - are, are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula XIV

- [HOOCCH-CHCOOH] m - [CH 2 -C (CH 3 ) C (O) OY-SO 3 H] p - (XIV),

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH 2 ) n - with n = 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH-CH (CH 2 CH 3 ) - stands, are preferred.

Zusammenfassend sind erfindungsgemäße maschinelle Geschirrspülmittel bevorzugt, die als Inhaltsstoff b) ein oder mehrere Copolymere enthält, die Struktureinheiten der Formeln IX und/oder X und/oder XI und/oder XII und/oder XIII und/oder XIV

        -[CH2-CHCOOH]m-[CH2-CHC(O)-Y-SO3H]p-     (IX),

        -[CH2-C(CH3)COOH]m-[CH2-CHC(O)-Y-SO3H]p-     (X),

        -[CH2-CHCOOH]m-[CH2-C(CH3)C(O)-Y-SO3H]p-     (XI),

        -[CH2-C(CH3)COOH]m-[CH2-C(CH3)C(O)-Y-SO3H]p-     (XII),

        -[HOOCCH-CHCOOH]m-[CH2-CHC(O)-Y-SO3H]p-     (XIII),

        -[HOOCCH-CHCOOH]m-[CH2-C(CH3)C(O)O-Y-SO3H]p     (XIV),

enthalten, in denen m und p jeweils für eine ganze natürliche Zahl zwischen 1 und 2000 sowie Y für eine Spacergruppe steht, die ausgewählt ist aus substituierten oder unsubstituierten aliphatischen, aromatischen oder araliphatischen Kohlenwasserstoffresten mit 1 bis 24 Kohlenstoffatomen, wobei Spacergruppen, in denen Y für -O-(CH2)n- mit n = 0 bis 4, für -O-(C6H4)-, für -NH-C(CH3)2- oder -NH-CH(CH2CH3)- steht, bevorzugt sind.In summary, machine dishwashing detergents according to the invention are preferred which comprise one or more copolymers as ingredient b), the structural units of the formulas IX and / or X and / or XI and / or XII and / or XIII and / or XIV

- [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (IX),

- [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (X),

- [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XI),

- [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XII),

- [HOOCCH-CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (XIII)

- [HOOCCH-CHCOOH] m - [CH 2 -C (CH 3 ) C (O) OY-SO 3 H] p (XIV),

in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH 2 ) n - with n = 0 to 4, for -O- (C 6 H 4 ) -, for -NH-C (CH 3 ) 2 - or -NH-CH (CH 2 CH 3 ) - stands, are preferred.

In den Polymeren können die Sulfonsäuregruppen ganz oder teilweise in neutralisierter Form vorliegen, d.h. daß das acide Wasserstoffatom der Sulfonsäuregruppe in einigen oder allen Sulfonsäuregruppen gegen Metallionen, vorzugsweise Alkalimetallionen und insbesondere gegen Natriumionen, ausgetauscht sein kann. Entsprechende Mittel, die dadurch gekennzeichnet sind, daß die Sulfonsäuregruppen im Copolymer teil- oder vollneutralisiert vorliegen, sind erfindungsgemäß bevorzugt.In the polymers, the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. Appropriate means, which are characterized that the sulfonic acid groups are partially or fully neutralized in the copolymer are preferred according to the invention.

Die Monomerenverteilung der in den erfindungsgemäßen Mitteln eingesetzten Copolymeren beträgt bei Copolymeren, die nur Monomere aus den Gruppen i) und ii) enthalten, vorzugsweise jeweils 5 bis 95 Gew.-% i) bzw. ii), besonders bevorzugt 50 bis 90 Gew.-% Monomer aus der Gruppe i) und 10 bis 50 Gew.-% Monomer aus der Gruppe ii), jeweils bezogen auf das Polymer.The monomer distribution of the copolymers used in the agents according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight. % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.

Bei Terpolymeren sind solche besonders bevorzugt, die 20 bis 85 Gew.-% Monomer aus der Gruppe i), 10 bis 60 Gew.-% Monomer aus der Gruppe ii) sowie 5 bis 30 Gew.-% Monomer aus der Gruppe iii) enthalten.In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

Die Molmasse der in den erfindungsgemäßen Mitteln eingesetzten Polymere kann variiert werden, um die Eigenschaften der Polymere dem gewünschten Verwendungszweck anzupassen. Bevorzugte maschinelle Geschirrspülmittel sind dadurch gekennzeichnet, daß die Copolymere Molmassen von 2000 bis 200.000 gmol-1, vorzugsweise von 4000 bis 25.000 gmol-1 und insbesondere von 5000 bis 15.000 gmol-1 aufweisen.The molecular weight of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired use. Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .

Der Gehalt an einem oder mehreren Copolymeren in den erfindungsgemäßen Mitteln kann je nach Anwendungszweck und gewünschter Produktleistung varieren, wobei bevorzugte erfindungsgemäße maschinelle Geschirrspülmittel dadurch gekennzeichnet sind, daß sie das bzw. die Copolymer(e) in Mengen von 0,25 bis 50 Gew.-%, vorzugsweise von 0,5 bis 35 Gew.-%, besonders bevorzugt von 0,75 bis 20 Gew.-% und insbesondere von 1 bis 15 Gew.-% enthalten.The content of one or more copolymers in the compositions according to the invention can vary depending on the intended use and the desired product performance, preference being given to preferred automatic dishwashing compositions according to the invention in that they contain the copolymer (s) in amounts of from 0.25 to 50% by weight. %, preferably from 0.5 to 35 wt .-%, particularly preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.

Wie bereits weiter oben erwähnt, werden in den erfindungsgemäßen Mitteln besonders bevorzugt sowohl Polyacrylate als auch die vorstehend beschriebenen Copolymere aus ungesättigten Carbonsäuren, Sulfonsäuregruppen-haltigen Monomeren sowie gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren eingesetzt. Die Polyacrylate wurden dabei weiter oben ausführlich beschrieben. Besonders bevorzugt sind Kombinationen aus den vorstehend beschriebenen Sulfonsäuregruppen-haltigen Copolymeren mit Polyacrylaten niedriger Molmasse, beispielsweise im Bereich zwischen 1000 und 4000 Dalton. Solche Polyacrylate sind kommerziell unter dem Handelsnamen Sokalan® PA15 bzw. Sokalan® PA25 (BASF) erhältlich.As already mentioned above, in the agents according to the invention it is particularly preferable to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers. The polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons. Such polyacrylates are commercially available under the trade name Sokalan ® PA15 and Sokalan ® PA25 (BASF).

Beispiele:Examples:

Ein Gemisch der Tenside 575 und 673 aus der Tabelle im Beschreibungstext wurde hergestellt, indem ein unverzweigter und gesättigter C11-Alkohol bei Anwesenheit von KOH als Katalysator in einem Autoklaven bei 150°C mit Ethylenoxid ethoxyliert wurde. Nachdem das Ethylenoxid abreagiert hatte, wurde Propylenoxid in den Autoklaven eingespeist und nach dessen Reaktion die Prozedur mit Ethylenoxid und anschließen mit Propylenoxid wiederholt. Das resultierende Tensidgemisch läßt sich durch die Formel

        CH3(CH2)10-O-(CH2-CH2-O)3-(CH2-CH(CH3)-O)3-(CH2-CH2-O)2-(CH2-CH(CH3)-O)1,5-H

beschreiben. Das Tensidgemisch weist bei einer Konzentration von 0,01 g/l in destilliertem Wasser einen Diffusionskoeffizienten von 9,1 ∘10-11 m2s-1 auf.A mixture of surfactants 575 and 673 from the table in the specification text was prepared by ethoxylating an unbranched and saturated C 11 alcohol in the presence of KOH as a catalyst in an autoclave at 150 ° C with ethylene oxide. After the ethylene oxide had reacted, propylene oxide was fed to the autoclave and, after the reaction, the procedure was repeated with ethylene oxide followed by propylene oxide. The resulting surfactant mixture can be defined by the formula

CH 3 (CH 2 ) 10 -O- (CH 2 -CH 2 -O) 3 - (CH 2 -CH (CH 3 ) -O) 3 - (CH 2 -CH 2 -O) 2 - (CH 2 - CH (CH3) -O) 1.5 -H

describe. The surfactant mixture has a diffusion coefficient of 9.1 × 10 -11 m 2 s -1 at a concentration of 0.01 g / l in distilled water.

Durch Granulation in einem 130-Liter-Pflugscharmischer der Firma Lödige wurden granulare maschinelle Geschirrspülmittel der in Tabelle 1 angegebenen Zusammensetzung hergestellt. Tabelle 1: granulare maschinelle Geschirrspülmittel [Gew.-%] erfindungsgemäß E1 Vergleichsbeispiel V1 Trinatriumphosphat 30,44% 30,44% Natriumperborat 3,00% 3,00% TAED 1,07% 1,07% Niotensid* 5,27% 5,27% Natriumcarbonat 54,11% 54,11% polymerer Cobuilder 3,78% 3,78% Enzyme 2,22% 2,22% Parfüm 0,11% 0,11% * Im erfindungsgemäßen Beispiel E1 wurde das vorstehend beschreibene Niotensid eingesetzt; im Vergleichsbeispiel V1 wurde Poly Tergent® SLF 18 B-45 der Firma Olin eingesetzt, das bei einer Konzentration von 0,01 g/l in destilliertem Wasser einen Diffusionskoeffizienten von 5 ∘ 10-11 m2s-1 aufweist. By granulation in a 130-liter ploughshare mixer company Lödige granular machine dishwashing detergent of the composition shown in Table 1 were prepared. <b> Table 1 </ b>: granular machine dishwashing detergent [wt%] according to the invention E1 Comparative Example C1 trisodium phosphate 30.44% 30.44% sodium 3.00% 3.00% TAED 1.07% 1.07% nonionic surfactant * 5.27% 5.27% sodium 54.11% 54.11% polymeric cobuilder 3.78% 3.78% enzymes 2.22% 2.22% Perfume 0.11% 0.11% * In Example E1 according to the invention, the above-described nonionic surfactant was used; in Comparative Example C1 Poly Tergent® SLF 18 B-45 Olin was used, which has a diffusion coefficient of 5 ∘ 10 -11 m 2 s -1 at a concentration of 0.01 g / l in distilled water.

Leistungsbewertung:Performance evaluation: a) Belagstesta) coating test

Zur Leistungsbewertung der Rezepturen E1 (Einsatz des erfindungsgemäßen Mittels) und V1 wird ein Belagstest in einem 65°C Universal-Reinigungsprogramm in einer auf kontinuirlichen Betrieb umgebauten Miele Geschirrspülmaschine durchgeführt. Dabei wurde das Programm ohne handelsüblichen Klarspüler (Vorratstank der Geschirrspülmaschine entleert) und mit auf 21°d aufgehärtetem Wasser (Umgehung des Ionentauschers) durchgeführt.To evaluate the performance of the formulations E1 (use of the agent according to the invention) and V1, a plaque test is carried out in a 65 ° C. universal cleaning program in a Miele dishwasher which has been converted to continuous operation. The program was carried out without commercially available rinse aid (storage tank of the dishwasher emptied) and with up to 21 ° d hardened water (bypassing the ion exchanger).

Testbedingungentest conditions

  • Spülmaschine: Miele KontiDishwasher: Miele Konti
  • Reinigungsmittel: 45g im Hauptspülgang dosiertDetergent: 45g dosed in the main rinse cycle
  • Wasserhärte: 21 °dHWater hardness: 21 ° dH
  • Programm: Universal 65°CProgram: Universal 65 ° C
  • Zyklen: 30Cycles: 30
  • Schmutzbelastung: 50g Flüssigschmutz im Hauptspülgang dosiert
    Zusammensetzung:
    30% Protein/Eiweiß
    30% Stärke
    30% Fett
    10% Wasser/Emulgator
    Dirt load: 50g liquid dirt dosed in the main rinse cycle
    Composition:
    30% protein / protein
    30% strength
    30% fat
    10% water / emulsifier

Die Bewertung des Belagsversuchs erfogt durch visuelle Betrachtung der Objekte in einem Kasten, dessen Wände mit schwarzem Samt ausgekleidet sind, wobei die Noten 0-6 vergeben werden. Höhere Werte zeigen belagfreiere Oberflächen an.The evaluation of the covering test is made by visual inspection of the objects in a box whose walls are lined with black velvet, giving the marks 0-6. Higher values indicate less porous surfaces.

Die Ergebnisse zeigt die nachfolgende Grafik:

Figure imgb0011
The results are shown in the following graphic:
Figure imgb0011

Durch Herstellung zweier teilchenförmiger Vorgemische und nachfolgendes Verpressen wurden zweischichtige Reinigungsmitteltabletten für das maschinelle Geschirrspülen der in Tabelle 2 angegebenen Zusammensetzung hergestellt. Tabelle 2: zweiphasige Reinigungsmitteltabletten für das maschinelle Geschirrspülen [Gew.-%] erfindungsgemäß E2 Vergleichsbeispiel V2 Oberphase Natriumperborat 10,44% 10,44% TAED 2,01% 2,01% Niotensid* 7,23% 7,23% Hydroxyethan-1,1-diphosphonsäure, Na-Salz 0,68% 0,68% Natriumcarbonat 10,04% 10,04% Benzotriazol 0,12% 0,12% polymerer Cobuilder 16,06% 16,06% Schichtsilikat (SKS6®) 1,61% 1,61% tri-Natriumcitrat 16,06% 16,06% Natriumhydrogencarbonat 6,02% 6,02% Unterphase Trinatriumphosphat 25,42% 25,42% Enzyme 2,85% 2,85% Parfüm 0,08% 0,08% Niotensid 1,37% 1,37% * Im erfindungsgemäßen Beispiel E2 wurde das vorstehend beschreibene Niotensid eingesetzt; im Vergleichsbeispiel V2 wurde Poly Tergent® SLF 18 B-45 der Firma Olin eingesetzt, das bei einer Konzentration von 0,01 g/l in destilliertem Wasser einen Diffusionskoeffizienten von 5 ° 10-11 m2s-1 aufweist. By preparing two particulate premixes and then pressing, two-layer automatic dishwashing detergent tablets of the composition shown in Table 2 were prepared. <b> Table 2: </ b> two-phase automatic dishwashing detergent tablets [wt%] according to the invention E2 Comparative Example V2 upper phase sodium 10.44% 10.44% TAED 2.01% 2.01% nonionic surfactant * 7.23% 7.23% Hydroxyethane-1,1-diphosphonic acid, Na salt 0.68% 0.68% sodium 10.04% 10.04% benzotriazole 0.12% 0.12% polymeric cobuilder 16.06% 16.06% Phyllosilicate (SKS6 ® ) 1.61% 1.61% tri-sodium citrate 16.06% 16.06% sodium 6.02% 6.02% under phase trisodium phosphate 25.42% 25.42% enzymes 2.85% 2.85% Perfume 0.08% 0.08% nonionic surfactant 1.37% 1.37% In example E2 according to the invention, the above-described nonionic surfactant was used; in Comparative Example C2 Poly Tergent® SLF 18 B-45 Olin was used, which has a diffusion coefficient of 5 ° 10 -11 m 2 s -1 at a concentration of 0.01 g / l in distilled water.

b) Klarspültestb) rinse test

zur Bewertung des Klarspüleffekts wurden die Zusammensetzungen E2 und V2 in einem Universal-Reinigungsprogramm eingesetzt. Dabei wurde das Programm ohne handelsüblichen Klarspüler (Vorratstank der Geschirrspülmaschine entleert) und mit auf 21 °d aufgehärtetem Wasser (Umgehung des Ionentauschers) durchgeführt.to evaluate the rinse effect, compositions E2 and V2 were used in a universal cleaning program. The program was carried out without commercially available rinse aid (storage tank of the dishwasher emptied) and with up to 21 ° d hardened water (bypassing the ion exchanger).

Testbedingungentest conditions

Spülmaschine: Miele G575
Reinigungsmittel: 24,9g im Hauptspülgang dosiert
Wasserhärte: 21°dH
Programm: Universal 55°C
Zyklen: 3
Schmutzbelastung: 50g HackfleischanschmutzungDishwasher: Miele G575
Detergent: 24.9 g dosed in the main rinse cycle
Water hardness: 21 ° dH
Program: Universal 55 ° C
Cycles: 3
Dirt load: 50g minced meat

Die Bewertung des Klarspüleffekts erfolgt durch visuelle Betrachtung in einem Kasten, dessen Wände mit schwarzem Samt ausgekleidet sind, wobei die Noten 0-4 für Tropfen- und Belagsbildung (Spotting/Filming) getrennt vergeben werden. Die Bewertung folgt folgendem Schema:

Spotting:
4 = keine Tropfen
3 = 1-4 Tropfen
2 = mehr als 4 Tropfen, bis zu 25% der Oberfläche mit Tropfen belegt
1 = 25-50% der Oberfläche mit Tropfen belegt
0 = mehr als 50% der Oberfläche mit Tropfen belegt
Filming:
4 = kein Belag bis 0 = sehr starker Belag
Glas Edelstahl Porzellan Spotting Filming Spotting Filming Spotting Filming E2 3,7 2,3 3,8 2,8 3,8 4 V2 3,2 1,0 3,2 1,3 3,8 3,7 Melamin PE SAN Spotting Filming Spotting Filming Spotting Filming E2 3 3 2,2 3,0 2,0 2,3 V2 3 2,3 2,2 1,7 2,0 1,0 The rinse effect is evaluated by visual inspection in a box lined with black velvet walls, with 0-4 grading separately for spotting / filming. The evaluation follows the following scheme:
Spotting:
4 = no drops
3 = 1-4 drops
2 = more than 4 drops, up to 25% of the surface covered with drops
1 = 25-50% of the surface covered with drops
0 = more than 50% of the surface covered with drops
Filming:
4 = no coating up to 0 = very strong coating
Glass stainless steel porcelain spotting Filming spotting Filming spotting Filming E2 3.7 2.3 3.8 2.8 3.8 4 V2 3.2 1.0 3.2 1.3 3.8 3.7 melamine PE SAN spotting Filming spotting Filming spotting Filming E2 3 3 2.2 3.0 2.0 2.3 V2 3 2.3 2.2 1.7 2.0 1.0

Die Tabelle zeigt, daß die Rezeptur E2 der Rezeptur V2 zum Teil deutlich beim Filming überlegen und beim Spotting mindestens gleichwertig ist.The table shows that formulation E2 is in part significantly superior to formulation V2 in filming and is at least equivalent to spotting.

Claims (10)

  1. Machine dishwashing detergents comprising builder(s), surfactant(s), and optionally further ingredients, characterized in that they comprise 0.1 to 50% by weight of one or more nonionic surfactants of the general formula I
    Figure imgb0013
     in which R1 is a straight-chain or branched, saturated or mono- or polyunsaturated C6-24-alkyl or -alkenyl radical; each group R2 and R3, independently of one another, is chosen from -CH3, -CH2CH3, -CH2CH2-CH3, CH(CH3)2 and the indices w, x, y, z, independently of one another, are integers from 1 to 6, which surfactants, at a concentration of 0.01 g/l in distilled water, have a diffusion coefficient of at least 9 · 10-11m2s-1.
  2. Machine dishwashing detergents according to Claim 1, characterized in that the nonionic surfactant(s), at a concentration of 0.01 g/l in distilled water, have a diffusion coefficient of at least 9.5 · 10-11m2s-1, preferably of at least 1 · 10-10m2s-1 and in particular of at least 2.5 · 10-10m2s-1.
  3. Machine dishwashing detergents according to either of Claims 1 and 2, characterized in that the nonionic surfactant(s), at a concentration of 0.01 g/l in distilled water, have a diffusion coefficient of at least 5 · 10-10m2s-1, preferably of at least 1 · 10-9m2s-1 and in particular of at least 5 · 10-9m2s-1.
  4. Machine dishwashing detergents according to any of Claims 1 to 3, characterized in that the nonionic surfactant(s) are present in amounts of from 0.5 to 40% by weight, preferably from 1 to 30% by weight, particularly preferably from 2.5 to 25% by weight and in particular from 5 to 20% by weight, in each case based on the total composition.
  5. Machine dishwashing detergents according to Claim 1, characterized in that R1 is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11, carbon atoms.
  6. Machine dishwashing detergents according to either of Claims 1 and 5, characterized in that R2 and R3 are a radical -CH3, w and x, independently of one another, are values of 3 or 4 and y and z, independently of one another, are values of 1 or 2.
  7. Machine dishwashing detergents according to any of Claims 1 to 6, characterized in that they comprise the builder(s) in amounts of from 5 to 90% by weight, preferably from 7.5 to 85% by weight and in particular from 10 to 80% by weight, in each case based on the total composition.
  8. Machine dishwashing detergents according to any of Claims 1 to 7, characterized in that they additionally comprise enzyme(s) in amounts of from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight and in particular from 0.5 to 6% by weight, in each case based on the total composition.
  9. Machine dishwashing detergents according to any of Claims 1 to 8, characterized in that they additionally comprise bleaches in amounts of from 1 to 40% by weight, preferably from 2.5 to 30% by weight and in particular from 5 to 20% by weight, in each case based on the total compositions.
  10. Machine dishwashing process using a machine dishwashing detergent according to any of Claims 1 to 9.
EP02762357A 2001-07-24 2002-07-13 Dishwashing machine detergents containing surfactants with specific diffusion co-efficients Expired - Lifetime EP1409625B1 (en)

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DE10136001A1 (en) * 2001-07-24 2003-02-13 Henkel Kgaa Automatic dishwashing detergent with low viscosity surfactants
DE10136000A1 (en) * 2001-07-24 2003-02-13 Henkel Kgaa Automatic dishwashing detergent with surfactants with low dynamic surface tension
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