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EP0008829A1 - Reinigungsmittelzusammensetzungen mit geregeltem Schaumverhalten - Google Patents

Reinigungsmittelzusammensetzungen mit geregeltem Schaumverhalten Download PDF

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Publication number
EP0008829A1
EP0008829A1 EP79200471A EP79200471A EP0008829A1 EP 0008829 A1 EP0008829 A1 EP 0008829A1 EP 79200471 A EP79200471 A EP 79200471A EP 79200471 A EP79200471 A EP 79200471A EP 0008829 A1 EP0008829 A1 EP 0008829A1
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EP
European Patent Office
Prior art keywords
alkyl
nonionic
group
weight
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP79200471A
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English (en)
French (fr)
Inventor
Ronald Edward Atkinson
David Alexander Ross
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Procter and Gamble Ltd
Procter and Gamble Co
Original Assignee
Procter and Gamble Ltd
Procter and Gamble Co
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Publication of EP0008829A1 publication Critical patent/EP0008829A1/de
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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
    • C11D1/86—Mixtures of anionic, cationic, and 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • Granular detergent compositions are employed in a wide range of washing conditions. Some garments are washed by hand, at temperatures ranging from nearly cold up to about 45-50°C, some are washed in upright washing machines, some in the more modern drum machines at temperatures ranging from cold to 40°C, 60°C and near boiling according to the machine wash cycle selected. As the user naturally prefers to be able to use a single washing product for all purposes, it is necessary to design products which have good performance in all washing conditions.
  • the sudsing properties of detergent compositions are very important features of their performance. Thus users expect a considerable degree of sudsing when they use the products for hand washing, i.e. at low temperatures with relatively mild agitation.
  • a granular built detergent composition having a controlled sudsing pattern characterised in that it comprises the following components, in per cent by weight:
  • the organic detergent component of the compositions of the invention consists of at least 50% by weight of nonionic and/or water-soluble cationic surfactants and may additionally contain anionic, zwitterionic and amphoteric surfactants.
  • Detergent compositions based upon predominantly anionic organic detergents when containing the ternary suds controlling systems of the invention tend to over-suds in drum washing machines at low or moderate temperature.
  • Preferred organic detergent mixtures comprises 35% to 99% of nonionic surfactants, of the types described more fully hereinafter.
  • a more preferred organic detergent mixture comprises a water-soluble or water-dispersible combination of ethoxylated nonionic, water-soluble quaternary ammonium cationic, and anionic surfactants wherein the weight ratio of anionic to cationic surfactant is no more than 5:1 and the weight to of nonionic to cationic surfactant is at least 2:3, and wherein the surfactant system contains anionic and cationic surfactants in an equivalent ratio of at least 1:1. Mixtures of this sort are described in copending European Patent Application 78 200 050.9.
  • the anionic and cationic surfactants have a combined total of no more than 34 carbon atoms counted in hydrophobic groups having at least 4 consecutive carbon atoms (e.g.
  • the number of such hydrophobic group carbon atoms totals from about 18 to 33, especially from about 26 to 32, with the anionic surfactant providing at least 12 of the carbon atoms.
  • the cationic surfactant is a water-soluble quaternary ammonium compound having a critical micelle concentration for the pure material of at least 200 p.p.m. and preferably at least 500 p.p.m. specified at 30°C and in distilled water.
  • Literature valves are taken where possible, especially surface tension or conductimetric values - see Critical Micelle Concentrations of Aqueous Surfactant System, P. Mukerjee and K.J. Mysels. NSRDS - NBS 36 (1971).
  • a highly preferred group of cationic surfactants of this type have the general formula: wherein R 1 is selected from C 8 -C 20 alkyl, alkenyl and alkanyl groups; R 2 is selected from C 1 -C 4 alkyl and benzyl groups; Z is an anion in number to give electrical neutrality; and m is 1, 2 or 3; provided that when m is 2 R 1 has less than carbon atoms and when m is 3, R has less than 9 carbon atoms.
  • compositions of this mono-long chain type include those in which R 1 is a C 10 to C 16 alkyl group.
  • Particularly preferred compositions of this class include C 12 alkyl trimethylammonium halide and C 14 alkyl trimethylammonium halide.
  • the R 1 chains should have less than 14 carbon atoms.
  • ditallowdimethylammonium chloride and distearyldimethylammonium chloride which are used conventionally as fabric softeners and static control agents in detergent compositions, may not be used as the cationic component in the surfactant mixtures of the present invention.
  • Particularly preferred cationic materials of this class include di-C 8 alkyldimethylammonium halide and di-C 10 alkyldimethylammonium halide materials.
  • the R 1 chains should be less than 9 carbon atoms in length.
  • An example is trioctyl methyl ammonium chloride.
  • the reason for this chain length restriction, as is also the case with the di-long chain cationics described above, is the relative insolubility of these tri- and di-long chain materials.
  • R 1 is selected from C 6-24 alkyl or alkenyl groups and C 6-12 alkaryl groups; R is selected from C 1-12 alkyl or alkenyl groups and C 1-6 alkaryl groups.
  • m 2, however, it is preferred that the sum total of carbon atoms in R and R 3 3-m is no more than about 20 with R 1 representing a a C 8-18 alkyl or alkenyl gorup. More preferably the sum total of carbon atoms in R and R 1 3-m is no more than about 17 with R 1 representing a C10-16 alkyl or alkenyl group.
  • m it is again preferred that the sum total of carbon atoms in R 1 and R 3 3-m is no more than about 17 with R 1 representing a C 10-16 alkyl or alkaryl group.
  • the total number of alkoxy radicals in polyalkoxy groups (R 2 m ) directly attached to the cationic charge centre should be no more than 14.
  • the total number of such alkoxy groups is from 1 ta 7 with each polyalkoxy group ( R 2 ) independently containing from 1 to 7 alkoxy groups; more preferably, the total number of such alkoxy groups is from 1 to 5 with each polyalkoxy group ( R 2 ) independently containing from 1 to 3 alkoxy groups.
  • cationic surfactants having the formula: wherein R is as defined immediately above, n is 2 or 3 and m is 1, 2 or 3.
  • Particularly preferred cationic surfactants of the class having m equal to 1 are dodecyl dimethyl hydroxyethyl ammonium salts, dodecyl dimethyl hydroxypropyl ammonium salts, myristyl dimethyl hydroxyethyl ammonium salts and dodecyl dimethyl dioxyethylenyl ammonium salts.
  • particularly preferred cationic surfactants are dodecyl dihydroxyethyl methyl ammonium salts, dodecyl dihydroxypropyl methyl ammonium salts, dodecyl dihydroxyethyl ethyl ammonium salts, myristyl dihydroxyethyl methyl ammonium salts, cetyl dihydroxyethyl methyl ammonium salts, stearyl dihydroxyethyl methyl ammonium salts, oleyldi hydroxyethyl methyl ammonium salts, and dodecyl hydroxy ethyl hydroxypropyl methyl ammonium salts.
  • particularly preferred cationic surfactants are dodecyl trihydroxyethyl ammonium salts, myristyl trihydroxyethyl ammonium salts, cetyl trihydroxyethyl ammonium salts, stearyl trihydroxyethyl ammonium salts, oleyl trihydroxy ethyl ammonium salts, dodecyl dihydroxyethyl hydroxypropyl ammonium salts and dodecyl trihydroxy propyl ammonium salts.
  • salt counterions can be employed, for example, chlorides, bromides and borates.
  • Salt counterions can also be selected from organic acid anions, however, such as the anions derived from organic sulphonic acids and from sulphuric acid esters.
  • organic acid anion is a C 6-12 alkaryl sulphonate.
  • cationic surfactants especially preferred are dodecyl dimethyl hydroxyethyl ammonium salts and dodecyl dihydrowyethyl methyl ammonium salts.
  • Another group of useful caticnic compounds are the polyammonium salts cf the general formula: wherein R 3 is selected from C 8 to C 20 alkyl, alkenyl and alkaryl groups; each R 2 is C 1-4 alkyl; n is from 1 to 6; and m is from 1 to 3.
  • a further preferred type of cationic component which is described in U.S. Patent Application Serial No. 811218 Letton, filed June 29th, 1977, and incorporated herein by reference, has the formula:
  • this particular cationic component is environmentally desirable, since it is biodegradable, both in terms of its long alkyl chain and its nitrogen-containing segment.
  • Particularly preferred cationic surfactants of this type are the choline ester derivatives having the following formula: as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.
  • p may be from 0 to 20.
  • the preferred choline-derivative cationic substances may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material.
  • the choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize triethanolamine, forming the desired cationic component.
  • each R 1 is a 2 C 1 to C 4 alkyl group, preferably a methyl group.
  • Each R 2 is either hydrogen or C 1 to C 3 alkyl, preferably hydrogen.
  • R is a C 4 to C 30 straight or branched chain alkyl, alkenyl, or alkyl benzyl group, preferably a 4 C 8 to C 18 alkyl group, most preferably a C 12 alkyl group.
  • R is a C 1 to C 10 alkylene or alkenylene group.
  • n is from 2 to 4, preferably 2; y is from 1 to 20, preferably from about 1 to 10, most preferably about 7; a may be 0 or 1; t may be 0 or 1; and m is from 1 to 5, preferably 2.
  • Z 1 and Z 2 are each selected from the group consisting of: and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide.
  • X is an anion which will make the compound water-soluble and is selected from the group consisting of . nalides, methylsulfate, hydroxide and nitrate, particularly chloride, bromide and iodide.
  • surfactants when used in the compositions of the present invention, yield excellent particulate soil, body soil, and grease and oil soil removal.
  • the detergent compositions control static and soften the fabrics laundered therewith, and inhibit the transfer of dyes in the washing solution.
  • these cationic surfactants are environmentally desirable, since both their long chain alkyl segments and their nitrogen segments are biodegradable.
  • Preferred embodiments of this type of cationic component are the choline esters (R 1 is a methyl group and Z 2 is an ester or reverse ester group), particular formulas of which are given below in which t is O or 1 and y is from 1 to 20.
  • the preferred choline derivatives may be prepared by the reaction of a long chain alkyl polyalkoxy (preferably polyethoxy) carboxylate, having an alkyl chain of desired length, with oxalyl chloride, to form the corresponding acid chloride.
  • the acid chloride is then reacted with dimethylaminoethanol to form the appropriate amine ester, which is then quaternized with a methyl halide to form the desired choline ester compound.
  • Another way of preparing these compounds is by the direct esterification of the appropriate long chain ethoxylated carboxylic acid together with 2-haloethanol or dimethyl aminoethanol, in the presence of heat and an acid catalyst.
  • the reaction product formed is then quaternized with methylhalide or used to quaternize trimethylamine to form the desired choline ester compounds.
  • compositions of the invention comprise at least 50% by weight of the surfactant mixture of nonionic and/or water-soluble cationic surfactants.
  • a highly preferred mixture of surfactants comprises by weight thereof
  • Another highly preferred mixture of surfactants comprises 90%-99.5% by weight of an ethoxylated primary or secondary alcohol having from 9-15 carbon atoms in the alkyl group and containing from 4-9 ethylene oxide groups per mole of alcohol and from 0.5%-10% of a water-soluble organic sulphate or sulphonate salt in which the organic group is a C 8-22 alkyl or alkaryl radicle.
  • Water-soluble salts of the higher fatty acids can be used as the anionic detergent component of the compositions herein.
  • This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids containing from about 8 to aobut 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of fats and soils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixture of fatty acids derived from coconut oil and tallow, i.e. sodium or potassium tallow and coconut soap.
  • a highly preferred class of anionic detergents includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts, or orqanic sulfuric reaction products having in their molecular structure an alkyl or alkaryl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups).
  • Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols tC8-18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g. those of the type described in USP 2,220, 099 and 2,477,383.
  • Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as C 11.8 LA S.
  • a preferred alkyl ether sulfate surfactant component of the present invention is a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean) carbon chain length within the range of about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide.
  • anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkylphenol ethylene oxide ether sulfate containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
  • Other useful anionic detergent compounds herein include the water-soluble salts of esters of ⁇ -sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group, and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of2-acyloxy-alkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; water-soluble salts of paraffin sulfonates containing from about 8 to 24, especially 14 to 18 carbon atoms, and ⁇ -alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the' alky
  • Anionic surfactant mixtures can also be employed, for example 5:1 to 1:5 mixtures of an alkyl benzene sulfonate having from 9 to 15 carbon atoms in the alkyl radical and mixtures thereof, the cation being an alkali metal preferably sodium; and from about 2% to about 15% by weight of an alkyl ethoxy sulfate having from 10 to 20 carbon atoms in the alkyl radical and from 1 to 30 ethoxy groups and mixtures thereof, having an alkali metal cation, preferably sodium.
  • a water-soluble nonionic synthetic detergent is a further essential component of the instant compositions.
  • Such nonionic detergent materials can be broadly defined as compounds produced by.the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Suitable nonionic detergents include:
  • compositions of the invention also contain from 10% to 96.9% of detergency builders, preferably from 20 to 60% thereof.
  • Suitable detergent builder salts useful herein can be of the polyvalent inorganic and polyvalent organic types, or mixtures thereof.
  • suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, polyphosphates, tripolyphosphates, bicarbonates and sulfates.
  • Suitable organic alkaline detergency builder salts are:
  • Mixtures of organic and/or inorganic builders can be used herein.
  • One such mixture of builders is disclosed in Canadian Patent No. 755,038, e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
  • a further class of builder salts is the insoluble alumino silicate type which functions by cation exchange to remove polyvalent mineral hardness and heavy metal ions from solution.
  • a preferred builder of this type has the formulation Na (A10 2 ) z (SiO 2 ) y .xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5 and x is an integer fiom about 15 to about 264.
  • Compositions incorporating builder salts of this type form the subject of British Patent. Specification No. 1,429,143 published March 24, 1976, German Patent Application No. OLS 2,433,485 published February 6, 1975, and OLS 2,525,778 published January 2, 1976. the disclosures of which are incorporated herein- by reference.
  • a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product.
  • the suds suppressing system consists of a mixture of wax, hydrophilic nonionic dispersant and hydrophobic silica in the proportions discussed hereinbefore. Preferably it contains from 60% to 85% of wax, from 5% to 15% of dispersant and from 5% to 15% of silica. Silicones should preferably be absent as they tend to cause suds suppression in hand wash conditions.
  • Preferred waxes are petroleum waxes of the micro- crystalline type, melting generally in the temperature range from 35°C to 110°C. Paraffin waxes may also be used, but preferred hydrocarbon wax mixtures comprise not more than 70% paraffin wax.
  • Suitable micro-crystalline waxes include Shell micro-crystalline wax - HMP, and -W4, and micro-crystalline waxes sold by Witco, and many other suppliers. Paraffin waxes are widely commerically available.
  • waxes include Fischer-Tropsch and oxidised Fischer-Tropsch waxes, ozokerite, ceresin, montan wax, beeswax, candelilla, and carnauba wax, and spermacetti, and other ester waxes having a saponification value less than 100.
  • Other waxy materials which may be employed, preferably constituting less than 50% of the wax component, are partial esters of polyhydric alcohols such as C 12 to C 20 acid esters of glycerol and sorbitan. Glycerol monostearate is a preferred member of this class. Mixtures of these waxes and waxy materials may be employed.
  • the dispersing agent is a hydrophilic nonionic surfactant having a hydrophilic-lipophilic balance (HLB) in the range from 14 to 19. These substances are too hydrophilic to function effectively as organic detergent components.
  • HLB hydrophilic-lipophilic balance
  • Many nonionic surfactants having HLB in the above range are known, and a list is given in McCutcheons Detergents and Emulsifiers, North American Edition, 1977 - pages 22-26.
  • Preferred nonionic surfactants for this purpose are relatively highly ethoxylated alcohols and alkyl phenols. Preferred are ethoxylated C 12 to C 20 preferably C 16 to C18, alcohols with 15 to 100 preferably 20 to 80 ethoxy groups per molecule.
  • the alcohol portion may be branched or unbranched, primary or secondary. Tallow alcohol ethoxylates are most preferred.
  • Suitable silicas are microfine hydrophobic, particulate silicas. These silicas usually have an average primary particle diameter from about 5 millimicrons (m ⁇ ) to about 100 m ⁇ , preferably from 10 m ⁇ to 30 m ⁇ The primary particles can form aggregates frequently termed secondary particles having frequently an average particle diameter in the range from about 0.3 ⁇ to about 3 ⁇ .
  • Suitable silica components can additionally be characterized by a specific surface area from about 50m 2 /g to about 400m 2 /g, preferably from 100m 2 /g to 200m 2 /g. The specific surface area can be determined with the aid of the N 2 -adsorption method.
  • the preferred silica component herein can additionally be defined in having a pH in the range from a to 12, to thus be better compatible with the usually alkaline laundry solution.
  • Generally preferred herein are precipitated hydrophobic microfine silicas with preferred species commercially available under the Trade Names QUSO WR82 and QUSO WR50 from Philadelphia Quartz Company.
  • Additional examples of suitable silicas herein can include pyrogenic silica and aerogel and xerogel silicas provided their general physical properties are as set forth above.
  • the silica can be rendered hydrophobic through one of the well-known treatments such as e.g. disclosed in U.S. Patent 3,207,698.
  • the mechanism of operation of the suds suppression system is not fully understood, it appears that the system has little or no suds suppressing effect at temperatures below its softening point.
  • the softening point which is that of the wax-dispersant mixture
  • the mixture disperses in the wash liquor, the dispersion being aided by the dispersing agent, and the mixture then acts as a suds suppressant.
  • the softening point is suitably chosen, as by selection of wax and the dispersant and the proportions of each, little or no depression of hand wash suds is caused. In a drum washing machine, suds tend to increase continuously as the temperature of the wash liquor increases.
  • This increase in suds can be reversed at a chosen temperature by choosing, once again, the temperature at which the suds controlling system softens.
  • the softening point is in the range from about 40°C to about 70°C, preferably about 50°C.
  • the softening point can be determined by warming a sample of wax or the mixture in the hot stage of a microscope and observing the temperature at which the crystal structure of the wax begins to break down to a substantial degree.
  • compositions of the present invention can be supplemented by all manner of detergent components, either by including such components in the aqueous slurry to be dried or by admixing such components with the compositions of the invention following the drying step.
  • Soil-suspending agents at about 0.1% to 10% by weight such as water-soluble salts of carboxymethyl-cellulose, carboxyhydroxymethyl cellulose, and polyethylene glycols having a molecular weight of about 400 to 10,000 are common components of the present invention.
  • Dyes, pigment optical brighteners, and perfumes can be added in varying amounts as desired.
  • Enzymes suitable for use herein include those di.scussed in U.S. Patents 3,519,570 and 3,533,139 to McCarty and McCarty et al issued July 7, 1970 and January 5, 1971, respectively.
  • Anionic fluorescent brightening agents are well-known materials, examples of which are disodium 4,4'-bis-(2- diathanolajuino-4-amino-4-triazin-6-ylamino)stilbene-2:2' disolphonate, disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2'-3disulphonate, 4, 4'- bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate, disodium 4,4'-bis-(2-anilino-4-(N-methyl-N-2- sydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2' - disulphonate, disodium 4,4'-bis-(4-phenyl-2,1,3-triazol-2- yl)-stilbene-2,2'-disul
  • alkali metal, or alkaline earth metal, silicate can so be present.
  • the alkali metal silicate preferably is ed in an amount from 0.5% to 10% preferably from 3% to 8%.
  • itable siiicate solids have a molar ratio of SiO 2 /alkali metal 2 O in the range from about 0.5 to about 4.0, but much more preferably from 1.0 to 1.8,. especially about 1.6.
  • the alkali metal silicates suitable herein can be commercial preparations of the combination of silicon dioxide and alkali metal oxide, fused together in varying proportions. Preparing The Composition
  • the granular detergent compositions of the invention may be prepared in any effective way, for instance by granulating techniques.
  • a spray dried base powder is prepared containing some or all of the non-heat sensitive components, and the other components are added to it, by dry blending or spray on or like means as appropriate.
  • the anionic and nonionic surfactants and the builder and filler components can be spray dried in conventional manner to form a base powder composition and the cationic component can then be added to the base powder either as an approximately 1:1 mixture with part of the builder or filler components retained for that purpose, or as an inclusion complex of, for instance, urea.
  • the cationic surfactant can be sprayed onto the base powder, or added as a dry mixed prill agglomerated with an inorganic or organic agglomerating aid, or can be separately spray dried and added to the base powder as a dry mixed granule.
  • the cationic surfactant and base powder compositions can be individually spray dried in separate stages of a multi-stage spray drying tower.
  • the spray dried base powder contains the anionic and cationic detergents, builders etc., and the nonionic surfactant is sprayed onto the base powder.
  • the suds-controlling system must be present as a uniform dispersion and be in admixture with preformed granules comprising some or all of the organic detergent and/or detergency builder components of the composition. That is to say, the suds-controlling system is prepared in the form of a premix by intimately mixing the dispersing agent, silica and wax, and the suds-suppressor premix is then added to a granular base composition comprising organic detergent and/or detergency builder.
  • the suds controlling system is prepared by melting together the wax and the dispersing agent and raising the temperature to at least that at which they form a single phase, dispersing the silica in the mixture by suitable mixing means, and cooling the mixture rapidly so that the separation does not take place before the mixture freezes.
  • a small amount of an emulsifier may be added to or included in the wax to inhibit phase separation of the wax and the hydrophilic dispersant during cooling of the molten mixture.
  • Suitable emulsifiers are nonionic surfactants of low HLB viz less than about 6, e.g. glycerine monostearate and'like substances. Cooling may be performed by spray cooling or by cooling a film of the melt on chilling rolls, or by like methods.
  • the fluid dispersion may be sprayed onto the cool spray dried base powder or onto a particulate carrier which is then dry mixed with base powder and forms part of the detergent composition.
  • the suds controlling system is preformed in particulate form, either alone or on a particulate carrier.
  • a spray dried detergent base powder was prepared containing the following ingredients, in parts by weight.
  • the resulting granular product was dry mixed with, in parts by weight:- to provide 100 parts of a detergent composition according to the invention.
  • the suds controlling system contained, by weight:
  • the product was used at 0.5% concentration in a wash liquor for hand washing clothes at 40°C, and formed copious suds.
  • the product was also used in a wash liquor at 0.75% concentration in the boil wash cycle of a Miele domestic washing machine.
  • Corresponding product lacking the suds controlling system gave equal suds in the hand wash but over-sudsed in the machine wash.
  • a spray dried detergent base powder was prepared containing the following ingredients, in parts by weight:-
  • the resulting granular product was dry mixed with, in parts by weight:- to provide 100 parts of a detergent composition according to the invention.
  • the suds controlling system was as in Example 1.
  • Example 1 When used as in Example 1, this composition provided adequate suds in hand washing conditions and acceptable freedom from oversudsing in the boil wash cycle of a domestic washing machine. Corresponding product wherein the above suds controlling system was replaced by an equal weight of powdered microcrystalline wax oversudsed in the machine wash.
  • a granular detergent composition is prepared substantially as described in Example I consisting of, per cent by weight:-
  • This composition provides good sudsing in hand wash conditions and does not over-suds in a drum type automatic washing machine even in the 95°C wash cycle.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP79200471A 1978-09-09 1979-08-28 Reinigungsmittelzusammensetzungen mit geregeltem Schaumverhalten Withdrawn EP0008829A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7836241 1978-09-09
GB3624178 1978-09-09

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EP0008829A1 true EP0008829A1 (de) 1980-03-19

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0051986A3 (en) * 1980-11-06 1982-07-21 The Procter & Gamble Company Detergent compositions
EP0091802A1 (de) * 1982-04-13 1983-10-19 The Procter & Gamble Company Schaumkontrollierende Detergenszusatzzusammensetzungen und ihre Verwendung in Detergenszusammensetzungen
EP0094250A1 (de) * 1982-05-11 1983-11-16 Unilever Plc Verfahren zur Herstellung von Antischaummittel auf Silikonbasis enthaltenden Granulaten
EP0150386A1 (de) * 1984-01-02 1985-08-07 Henkel Kommanditgesellschaft auf Aktien Zur Verwendung in tensidhaltigen Mitteln geeignetes Schaumregulierungsmittel
EP0150387A1 (de) * 1984-01-02 1985-08-07 Henkel Kommanditgesellschaft auf Aktien Verwendung von paraffinhaltigen Entschäumungskompositionen in Mitteln für das maschinelle Reinigen von Gegenständen mit harten Oberflächen
EP0151936A2 (de) 1984-01-25 1985-08-21 REWO Chemische Werke GmbH Waschmittel mit Weichspüleigenschaften und Verfahren zu seiner Herstellung
GB2169308A (en) * 1985-01-07 1986-07-09 Kao Corp Mould removing composition
US4732694A (en) * 1983-08-27 1988-03-22 The Procter & Gamble Company Suds suppressor compositions and their use in detergent compositions
US4801401A (en) * 1986-03-08 1989-01-31 Henkel Kommanditsegellschaft auf Aktien Process for the production of a foam inhibitor mixture
US4818292A (en) * 1985-09-04 1989-04-04 Lever Brothers Company Antifoam ingredient for detergent compositions
US5780410A (en) * 1993-07-14 1998-07-14 The Procter & Gamble Company Detergent compositions containing percarbonate and making processes thereof
US6017867A (en) * 1998-06-05 2000-01-25 The Procter & Gamble Company Detergent compositions containing percarbonate and making processes thereof
US6200498B1 (en) 1997-08-29 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Process for producing paraffin-containing foam regulators
WO2002044310A3 (de) * 2000-11-29 2002-09-19 Henkel Kgaa Granuläre konditioniermittel
US7078373B2 (en) 2002-11-04 2006-07-18 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Laundry detergent composition
WO2008129026A1 (en) * 2007-04-24 2008-10-30 Unilever Plc Improvements relating to laundry cleaning compositions
CN101668841B (zh) * 2007-04-24 2011-10-19 荷兰联合利华有限公司 关于衣物洗涤用组合物的改进

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT267024B (de) * 1964-07-10 1968-12-10 Unilever Nv Waschmittelzusammensetzung und Verfahren zu deren Herstellung
DE2124526A1 (de) * 1970-05-20 1971-12-02 Procter & Gamble European Technical Center, Strombeek-Bever (Belgien) Wasch- und Reinigungsmittelmischungen mit geregeltem Schaum verhalten
FR2231743A1 (de) * 1973-06-01 1974-12-27 Henkel & Cie Gmbh
FR2231745A1 (de) * 1973-05-28 1974-12-27 Henkel & Cie Gmbh
FR2264086A2 (de) * 1974-03-11 1975-10-10 Procter & Gamble
FR2380340A1 (fr) * 1977-02-10 1978-09-08 Basf Ag Utilisation d'esters d'acides dicarboxyliques comme agents antimousse dans des produits de nettoyage acides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT267024B (de) * 1964-07-10 1968-12-10 Unilever Nv Waschmittelzusammensetzung und Verfahren zu deren Herstellung
DE2124526A1 (de) * 1970-05-20 1971-12-02 Procter & Gamble European Technical Center, Strombeek-Bever (Belgien) Wasch- und Reinigungsmittelmischungen mit geregeltem Schaum verhalten
FR2231745A1 (de) * 1973-05-28 1974-12-27 Henkel & Cie Gmbh
FR2231743A1 (de) * 1973-06-01 1974-12-27 Henkel & Cie Gmbh
FR2264086A2 (de) * 1974-03-11 1975-10-10 Procter & Gamble
FR2380340A1 (fr) * 1977-02-10 1978-09-08 Basf Ag Utilisation d'esters d'acides dicarboxyliques comme agents antimousse dans des produits de nettoyage acides

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0051986A3 (en) * 1980-11-06 1982-07-21 The Procter & Gamble Company Detergent compositions
EP0091802A1 (de) * 1982-04-13 1983-10-19 The Procter & Gamble Company Schaumkontrollierende Detergenszusatzzusammensetzungen und ihre Verwendung in Detergenszusammensetzungen
EP0094250A1 (de) * 1982-05-11 1983-11-16 Unilever Plc Verfahren zur Herstellung von Antischaummittel auf Silikonbasis enthaltenden Granulaten
US4732694A (en) * 1983-08-27 1988-03-22 The Procter & Gamble Company Suds suppressor compositions and their use in detergent compositions
EP0150386A1 (de) * 1984-01-02 1985-08-07 Henkel Kommanditgesellschaft auf Aktien Zur Verwendung in tensidhaltigen Mitteln geeignetes Schaumregulierungsmittel
EP0150387A1 (de) * 1984-01-02 1985-08-07 Henkel Kommanditgesellschaft auf Aktien Verwendung von paraffinhaltigen Entschäumungskompositionen in Mitteln für das maschinelle Reinigen von Gegenständen mit harten Oberflächen
US4590237A (en) * 1984-01-02 1986-05-20 Henkel Kommanditgesellschaft Auf Aktien Foam regulators containing paraffin hydrocarbons and hydrophobic silica
US4599189A (en) * 1984-01-02 1986-07-08 Henkel Kommanditgesellschaft Auf Aktien Paraffin-containing defoaming compositions and detergent compositions containing same
EP0151936A2 (de) 1984-01-25 1985-08-21 REWO Chemische Werke GmbH Waschmittel mit Weichspüleigenschaften und Verfahren zu seiner Herstellung
EP0151936A3 (en) * 1984-01-25 1986-11-20 Rewo Chemische Werke Gmbh Powdery laundry softening agent, process for its production and washing agent containing the same
GB2169308A (en) * 1985-01-07 1986-07-09 Kao Corp Mould removing composition
US4818292A (en) * 1985-09-04 1989-04-04 Lever Brothers Company Antifoam ingredient for detergent compositions
US4801401A (en) * 1986-03-08 1989-01-31 Henkel Kommanditsegellschaft auf Aktien Process for the production of a foam inhibitor mixture
US5780410A (en) * 1993-07-14 1998-07-14 The Procter & Gamble Company Detergent compositions containing percarbonate and making processes thereof
US6200498B1 (en) 1997-08-29 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Process for producing paraffin-containing foam regulators
US6017867A (en) * 1998-06-05 2000-01-25 The Procter & Gamble Company Detergent compositions containing percarbonate and making processes thereof
WO2002044310A3 (de) * 2000-11-29 2002-09-19 Henkel Kgaa Granuläre konditioniermittel
US7078373B2 (en) 2002-11-04 2006-07-18 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Laundry detergent composition
WO2008129026A1 (en) * 2007-04-24 2008-10-30 Unilever Plc Improvements relating to laundry cleaning compositions
CN101668841B (zh) * 2007-04-24 2011-10-19 荷兰联合利华有限公司 关于衣物洗涤用组合物的改进

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