WO2012098177A1 - Use of tallow alcohol ethoxylates in machine dish washing - Google Patents

Abstract

The invention relates to non-ionic surfactants made of ethoxylates of linear C₁₆-C₁₈ alcohols having on average 8.5 to 9.5 moles of ethylene oxide per mole of linear C₁₆-C₁₈ alcohol.

Description

 Use of tallow fatty alcohol ethoxylates in machine dishwashing

The invention relates to nonionic surfactants of tallow fatty alcohol ethoxylates, their use and dishwashing detergents containing the nonionic surfactants.

In the automatic dishwashing, the items to be washed in residue-free cleaned state with flawless glossy surface incurred, for which usually a cleaner, a rinse aid and Regeneriersalz must be used for water softening. The "3 in 1" dishwashing detergents introduced on the market since 2001 combine the function of detergent, rinse aid and regenerating salt in one product. In addition to cleaning components to remove stains on the items to be washed, they contain integrated rinse-aid surfactants, which ensure that the washware flows flat during the rinse and drying cycle, thus preventing limescale and water stains. In addition, they have components for binding the hardness-forming calcium and magnesium ions. This eliminates the need for the consumer refilling rinse aid and salt in the dishwasher. The incorporation of additional functions (eg protection against glass corrosion and silver tarnishing) led to the development of x in 1 (with eg x = 6 or 9) or "all in one" products WO 2008/132131 discloses the use a combination of at least one alcohol alkoxylate, at least one short-chain alcohol ethoxylate, at least one sulfonate group-containing polymer and / or at least one hydrophilically modified polycarboxylate and optionally a polycarboxylate, together with generally customary further constituents, for improving the final rinse performance in machine dishwashing detergents containing phosphate, even at significantly higher water hardness / 132,131 discloses the use of the same combination to improve the rinse performance in non-phosphate machine dishwashing detergents.

The alcohol alkoxylate has the general formula (I)

R ¹ - (OCH ₂ CHR ² ) _x (OCH ₂ CHR ³ ) _y -OR ⁴ (I) wherein

R is a linear or branched C ₆ -C ₂ 4-alkyl radical,

R ² , R ^{3 is} hydrogen or a linear or branched C 1 -C ₆ -alkyl radical,

R ^{4 is} hydrogen or a linear or branched C 1 -C ₈ -alkyl radical,

 , y has a mean value in the range of 0.5-80,

mean, wherein the individual alkylene oxide units may be present as a block or randomly distributed on.

Very particular preference is given to using as alcohol alkoxylates of the general formula (I):

Ci3- to Ci ₅ -Oxoalkohole + 10 units of ethylene oxide + 2 units of butylene oxide, iso-Cio alcohols + 10 units of ethylene oxide + 1, 5 units pentenoxide, Cur to Ci ₂ -fatty alcohols + 9 units of ethylene oxide + 5 units of propylene oxide, - Ci3- to C ₅ -oxoalcohols + 4.46 units of ethylene oxide + 0.86 units of butylene oxide, end-capped with a methyl group,

2-propylheptanol + 6 units of ethylene oxide + 4.5 units of propylene oxide or mixtures thereof. DE 102 33 834 A discloses as nonionic surfactants in machine dishwashing detergents alkoxylated, preferably ethoxylated primary alcohols having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol. Preferred are alcohol ethoxylates of alcohols of natural origin having 12 to 18 carbon atoms, such as coconut, palm, tallow or oleyl alcohol with an average of 2 to 8 moles of EO per mole of alcohol. Overall Nannt are described in detail, inter alia, C ₂ -C ₄ alcohols containing 3 or 4 EO, Cn alcohols with 7 EO, Cis-Cis alcohols containing 3, 5, 7 or 8 EO and C ₂ -C ₈ - Alcohols with 5 EO.

The object of the present invention is to improve the rinsing performance of dishwashing detergents, in particular so-called 3-in-1 dishwashing detergents, during dishwashing.

It is an object of the present invention, in particular, to increase the rinsing performance of dishwashing detergents in the case of water hardnesses of more than 14 ° dH. The object is achieved by nonionic surfactants from ethoxylates of linear Ci ₆ -Ci ₈ - alcohols with an average of 8.5 to 9.5 moles of ethylene oxide per mole of linear Ci ₆ -C ₈ -alcohol.

It has surprisingly been found that nonionic surfactants based on tallow fatty alcohols (C ₆ -C ₈ -alcohols) with about 9 mol of ethylene oxide per mole of alcohol cause a significantly better rinse performance than those with about 7 or about 1 1 mol of ethylene oxide per mol of alcohol.

Preferably, nonionic surfactants of the invention ethoxylates of linear C ₆ -C ₈ alcohols contain the formula (I)

R ¹ - (OCH ₂ CH ₂ ) _x -OR ² (I) With

R ^{1 is} a linear C ₆ -C ₈ -alkyl radical,

R ^{2 is} hydrogen or a linear or branched C 1 -C ₆ -alkyl radical,

x 8, 9 or 10.

Especially preferred nonionic surfactants of the invention contain at least 80 wt .-% ethoxylates of linear C ₆ -C ₈ alcohols of the formula (I) with x = 8, 9 or 10 ethylene oxide units.

In particular, the nonionic surfactants contain at least 80% by weight of ethoxylates of linear C ₆ -C ₈ -alcohols of the formula (I) with x = 9 ethylene oxide units.

Preferred nonionic surfactants furthermore contain on average 8.8 to 9.2 mol of ethylene oxide, in particular 8.9 to 9, 1 mol of ethylene oxide per mole of linear Ci ₆ -C ₈ -alcohol.

Preferred linear C ₆ -C ₈ -alcohols are n-hexadecanol and n-octadecanol. These can be obtained by hydrogenation of natural tallow fat. Mixtures of linear Ci ₆ - and Ci ₈ -alcohols of natural origin are also known as tallow fatty alcohol. Tallow fatty alcohols include unsaturated units, in particular units of mono- or polyunsaturated C ₆ to a limited extent - and C ₈ alcohols. The iodine value of the tallow fatty alcohols is generally <5 g of I _2/100 g of alcohol, preferably <1 g of I _2/100 g alcohol. The compounds of general formula (I) according to the invention are obtained by alkoxylation of the C ₆ -C ₈ alcohols with alkylene oxides. In this case, if the radical R ^{2 is} not hydrogen, an etherification, for example with dimethyl sulfate, connect to the alkoxylation. Preferably, R ^{2 is} hydrogen or methyl.

The ethoxylation can be carried out, for example, using alkaline catalysts such as alkali metal hydroxides or alkali metal alkoxides. The use of these catalysts results in special properties, in particular the homolog distribution of the alkylene oxides.

The ethoxylation can also be carried out using Lewis acidic catalysts, in particular in the presence of BF ₃ × H ₃ PO ₄ , BF ₃ × dietherate, BF ₃ , SbCl ₅ , SnCl ₄ × 2 H ₂ O or hydrotalcite. The ethoxylation is preferably catalyzed by strong bases, which are expediently added in the form of an alkali metal hydroxide or alkaline earth metal hydroxide, generally in an amount of from 0.1 to 1% by weight, based on the amount of the alcohol R ¹ -OH. The alkoxylation can also be carried out with double metal cyanide catalysts. DMC compounds suitable as catalyst are described, for example, in WO 99/16775 and in DE-A-101 17 273.

The addition reaction is carried out at temperatures of about 90 to about 240 ° C, preferably from 120 to 180 ° C, in a closed vessel. Ethylene oxide is the mixture of Ci ₆ -Ci ₈ alcohol or mixture and alkali supplied under the prevailing at the selected reaction temperature vapor pressure of the alkylene oxide mixture. If desired, the alkylene oxide may be diluted with up to about 30 to 60% by volume of an inert gas. As a result, an explosive polyaddition or decomposition of the alkylene oxide can be prevented.

The invention also provides the use of nonionic surfactants of the invention comprising ethoxylates of linear C ₆ -C ₈ alcohols schirrreinigung having an average of 8.5 to 9.5 moles of ethylene oxide per mole of alcohol in detergent formulations for machine overall.

The invention further provides a cleaning formulation for machine dishwashing containing as components: a) 0, 1 to 20 wt .-% of nonionic surfactants from ethoxylates of linear Ci ₆ -Ci ₈ - alcohols with an average of 8.5 to 9.5 mol ethylene oxide per mole of C ₆ -C ₈ alcohol, b) 0 to 10 wt .-% further nonionic surfactants, c) 0 to 20 wt .-% of component c), various polycarboxylates, d) 0 to 50 wt .-% complexing , e) 0 to 70% by weight of phosphates, f) 0 to 60% by weight of further builders and cobuilders, g) 0 to 30% by weight of bleaching agent and optionally bleach activators and bleach catalysts, h) 0 to 8% by weight of enzymes, i) 0 to 50% by weight of one or more further additives, such as anionic or zwitterionic surfactants, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents, tableting aids, disintegrating,

Thickener, solubilizer and water, wherein the sum of components a) to i) gives 100 wt .-%. The cleaning formulations according to the invention preferably contain from 0.5 to 15% by weight, particularly preferably from 1 to 10% by weight, of the nonionic surfactants a).

In addition to the nonionic surfactants of component a) according to the invention, the cleaning formulations may contain up to 10% by weight of component a) various other nonionic surfactants, usually weak or low foaming nonionic surfactants. If present, they are contained in amounts of from 0.1 to 10% by weight, preferably from 0.25 to 5% by weight.

Suitable further nonionic surfactants include the surfactants of the general formula (II)

R ⁴ -O- (CH ₂ CH ₂ O) p- (CHR ³ CH ₂ O) _m -R ⁵ (II) in which R ^{4 is} a linear or branched alkyl radical having 8 to 22 C atoms,

R ³ and R ⁵ independently of one another are hydrogen or a linear or branched alkyl radical having 1-10 C atoms or H, where R ^{3 is} preferably methyl,

p and m are independently 0 to 300. Preferably, p = 1 - 100 and

m = 0-30.

The surfactants of formula (III) may be both random copolymers and block copolymers, preferably block copolymers.

Further, di- and multiblock copolymers composed of ethylene oxide and propylene oxide, are used which (BASF Corporation) are commercially available, for example under the name Pluronic ^® (BASF SE) or Tetronic ^®. Furthermore, reaction products of sorbitan esters with ethylene oxide and / or propylene oxide can be used. Also suitable are amine oxides or alkyl glycosides. An overview of suitable further nonionic surfactants is provided by EP-A 851 023 and DE-A 198 19 187.

It may also contain mixtures of several different nonionic surfactants. As component c), the cleaning formulations according to the invention may contain from 0 to 20% by weight of one or more different polycarboxylates. These may be hydrophilic or hydrophobic modified. If included, they are generally contained in amounts of 0.1 to 20% by weight.

Suitable are alkali metal salts of homo- and copolymers of acrylic acid or methacrylic acid. For copolymerization, monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid are suitable. A suitable polymer is in particular polyacrylic acid, which preferably has a molar mass of from 2000 to 40 000 g / mol. Because of their superior solubility, the short-chain polyacrylic acid, which has molar masses of from 2000 to 10 000 g / mol, in particular from 3000 to 8000 g / mol, may be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

It may also be copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated C ₃ -C ₀ mono- or dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least one hydrophilic or hydrophobic modified Monomers can be used.

Examples of suitable hydrophobic monomers are isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-doses, 1-tetracoses and 1 -hexacoses, C ₂ 2-alpha-olefin, a mixture of C ₂ oC ₂ 4-alpha-olefins and polyisobutene with an average of 12 to 100 carbon atoms.

Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples include: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate,

 Ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate. The polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-one methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene 1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and salts of said acids, such as their sodium, potassium or ammonium salts.

Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.

In addition, amphoteric and cationic polymers can also be used. As component d), the cleaning formulations according to the invention may contain from 0 to 50% by weight of one or more complexing agents. If complexing agents are contained, they are present in amounts of from 0.1 to 50% by weight, preferably from 1 to 45% by weight and more preferably from 1 to 40% by weight. Preferred complexing agents are selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid and methylglycinediacetic acid, glutamic acid diacid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediamine disuccinic acid, aspartic acid diacetic acid and salts thereof. Particularly preferred complexing agents e) are methylglycinediacetic acid and its salts.

As component e), the cleaning agents according to the invention may contain from 0 to 70% by weight of phosphates. If the cleaning agent contains phosphates, it generally contains these in amounts of from 1 to 70% by weight, preferably from 5 to 60% by weight, particularly preferably from 20 to 55% by weight.

Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are the most important in the detergent and cleaner industry.

Suitable phosphates for dishwashing detergents are, in particular, alkali metal phosphates and polymeric alkali metal phosphates, which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of such phosphates are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium tripolyphosphate, so-called sodium hexametaphosphate, oligomeric Trisodium phosphate having a degree of oligomerization of 5 to 1000, preferably 5 to 50, and the corresponding potassium salts, or mixtures of sodium hexametaphosphate and the corresponding potassium salts, or mixtures of the sodium and potassium salts. Particularly preferred are tripolyphosphate salts.

As component f), the cleaning agents according to the invention may contain from 0 to 60% by weight of builder and cobuilder. If the detergent contains builders and cobuilders, it generally contains them in amounts of from 0.1 to 60% by weight. Builders and co-builders are water-soluble or water-insoluble substances whose main task is the binding of calcium and magnesium ions.

These may be low molecular weight carboxylic acids and their salts, such as alkali citrates, in particular anhydrous trisodium citrate or trisodium citrate dihydrate, alkali metal succinates, alkali malonates, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate and .alpha.-hydroxypropionic acid.

Another class of substances with cobuilder properties which may be present in the cleansing compositions according to the invention are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. 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 the neutral reacting sodium salts, e.g. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. The builder used here is preferably HEDP from the class of phosphonates. 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.

Another class of substances in the builder system are the silicates. Crystalline layered silicates with the general formula NaMSi _x 0 _{2x +} i ^' yH ₂ O, where M is sodium or hydrogen, x may be a number from 1, 9 to 22, preferably from 1, 9 to 4, with particularly preferred values for x is 2, 3 or 4, and y is a number from 0 to 33, preferably 0 to 20. In addition, amorphous sodium silicates with a Si0 ₂ : Na ₂ 0 ratio of 1 to 3.5, preferably from 1, 6 to 3 and especially from 2 to 2.8 are used. Furthermore, carbonates and bicarbonates are used, of which the alkali metal salts, in particular sodium salts, are preferred.

As component g), the cleaning formulations according to the invention may contain from 0 to 30% by weight of bleach, optionally bleach activators and optionally bleach catalysts. If the cleaning formulations contain bleaches, bleach activators or bleach catalysts, they contain these in amounts of from 0.1 to 30% by weight, preferably from 1 to 30% by weight and more preferably from 5 to 30% by weight. Bleaching agents are subdivided into oxygen bleaching agents and chlorine-containing bleaching agents. Use as oxygen bleach find alkali metal perborates and their hydrates and alkali metal percarbonates. Preferred bleaching agents here are sodium perborate in the form of the mono- or tetrahydrate, sodium percarbonate or the hydrates of sodium percarbonate. Also used as oxygen bleach are persulfates and hydrogen peroxide.

Typical oxygen bleaches are also organic peracids such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauric acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxoisophthalic acid or 2-decyldiperoxybutane-1,4-diacid.

In addition, the following oxygen bleaches may also be used in the detergent formulation: cationic peroxyacids described in patent applications US 5,422,028, US 5,294,362 and US 5,292,447, and sulfonyl peroxyacids described in patent application US 5,039,447.

Chlorine-containing bleaches as well as the combination of chlorine-containing bleach with peroxide-containing bleaches may also be used. Known chlorine-containing bleaching agents are for example 1, 3-dichloro-5,5-dimethylhydantoin, N-Chlorosulfamid, chloramine T, dichloramine T, chloramine B, Ν, Ν ^{'-Dichlorbenzoylharnstoff,} p-toluene- or sulfondichloroamid Trichlorethylamin. Preferred chlorine-containing bleaching agents are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium dichloroisocyanurate or sodium dichloroisocyanurate.

Chlorine-containing bleaching agents are used in amounts of generally from 0.1 to 20% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.3 to 8% by weight, based on the total detergent formulation , Furthermore, bleach stabilizers such as phosphonates, borates, metaborates, metasilicates or magnesium salts can be added in small amounts.

Bleach activators are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or substituted perbenzoic acid. Suitable compounds are those which contain one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, for example substances from the class of the anhydrides, esters, imides, acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acylimides such as N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates such as n-nonanoyl or isononanoyloxybenzenesulfonates (n- or n-nonanoyl) iso-NOBS), pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (DADHT) or isatoic anhydride (ISA). Also suitable as bleach activators are nitrile quats, such as, for example, N-methyl-morpholinium-acetonitrile salts (MMA salts) or trimethylammonium acetonitrile salts (TMAQ salts).

Bleach activators are preferably suitable from the group consisting of polyacylated alkylenediamines, particularly preferably TAED, N-acylimides, particularly preferably NOSI, acylated phenolsulfonates, more preferably n- or iso-NOBS, MMA and TMAQ.

Bleach activators are used in amounts of generally from 0.1 to 10% by weight, preferably from 1 to 9% by weight, particularly preferably from 1.5 to 8% by weight, based on the total detergent formulation.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts may also be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, manganese, iron, cobalt, ruthenium or molybdenum salt complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.

As component h), the cleaning formulations according to the invention may contain from 0 to 8% by weight of enzymes. If the cleaning formulations contain enzymes, they generally contain them in amounts of 0, 1 to 8 wt .-%. Enzymes can be added to the detergent to increase the performance of the detergents or to ensure the same level of cleaning performance under milder conditions. To The most commonly used enzymes include lipases, amylases, cellulases and proteases. Furthermore, for example, esterases, pectinases, lactases and peroxidases can be used. Furthermore, the cleaning agents according to the invention as component i) 0 to 50 wt .-% one or more other additives such as anionic or zwitterionic surfactants, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents, tabletting, Disintegrationsmittel, thickener, soluble - Contain mediator and water. If the cleaning formulation contains further additives, these are generally contained in amounts of from 0.1 to 50% by weight.

The formulations may contain anionic or zwitterionic surfactants, preferably in admixture with nonionic surfactants. Suitable anionic and zwitterionic surfactants are mentioned in EP-A 851 023 and DE-A 198 19 187.

As further constituents of the cleaner formulation, alkali carriers may be present. In addition to the ammonium or alkali metal carbonates already mentioned in the case of the builder substances, ammonium or alkali metal bicarbonates and ammonium or alkali metal sesquicarbonates, suitable alkali carriers may also be ammonium or alkali metal hydroxides, ammonium or alkali silicates and ammonium or alkali metal silicates and mixtures of the abovementioned substances ,

As corrosion inhibitors, it is possible to use silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes.

Glass corrosion inhibitors are used to prevent glass corrosion, which is manifested by clouding, iridescence, streaks and lines on the glasses. Preferred glass corrosion inhibitors are from the group of magnesium-zinc and bismuth salts and complexes.

Paraffin oils and silicone oils can optionally be used as defoamers and for the protection of plastic and metal surfaces. Defoamers are generally used in proportions of 0.001 wt .-% to 5 wt .-%. In addition, dyes such as patent blue, preservatives such as Kathon CG, perfumes and other perfumes of the cleaning formulation of the invention may be added.

A suitable filler is, for example, sodium sulfate. The cleaning formulations according to the invention can be provided in liquid or solid form, single- or multiphase, as tablets or in the form of other dosage units, packaged or unpackaged.

The invention is explained in more detail by the following examples.

Examples

The nonionic surfactants T 9, T 7 and T 1 1 were tested in the following phosphate-free formulations PF1 and in the phosphate-based formulation P1.

T 9: tallow fatty alcohol ethoxylate with an average of 9 moles of ethylene oxide per mole of alcohol;

 T 11: tallow fatty alcohol ethoxylate having on average 11 moles of ethylene oxide per mole of alcohol;

 T 7: tallow fatty alcohol ethoxylate with an average of 7 moles of ethylene oxide per mole of alcohol.

 15

 The composition of the formulations is given in Table 1 (in% by weight).

Table 1

 20

 The following test conditions were observed:

Dishwasher: Miele G 1222 SCL

 Program: 50 ° C with R-time 2 [8 min] (without prewash)

25 dishes: 3 knives (WMF Tafelmesser Berlin, Monoblock) 3 drinking glasses Amsterdam 0.2L

 3 BREAKFAST "OCEAN BLUE" (MELAMINE)

 3 Porcelain plate FLAG FLAG 19 CM Arrangement: Knife in the cutlery drawer, glasses in the upper basket, plates in the lower basket

 Dishwashing detergent: 21 g

Dirt addition: 100 g of rinse aid dirt (contains egg, starch and fat) is dosed frozen

 Rinse temperature: 65 ° C

Water hardness: 21 ° dH (Ca / Mg): HC0 ₃ (3: 1): 1.35

 Rinse cycles: 6; between each 1 h break (10 min open door, 50 min closed door)

 Evaluation: Visually after 6 rinsing cycles

The washware was evaluated after 6 cycles in a darkened chamber under light behind a pinhole using a grading scale from 10 (very good) to 1 (very poor). Grades from 1 - 10 were given for spotting (very many, intense spots = 1 to no spots = 10) as well as for covering (filming) the scores 1 - 10 (1 = very strong pad, 10 = no pad).

The test results are summarized in Table 2.

Table 2

As can be seen from the table, the T9 surfactant scores significantly better in terms of spotting than the comparison surfactants T7 and T11. During filming, comparably good results are obtained with all 3 surfactants.

Claims

claims 1. Non-ionic surfactants of ethoxylates of linear C ₆ -C ₈ alcohols with an average of 8.5 to 9.5 mol of ethylene oxide per mole of linear C ₆ -C ₈ alcohol. 2. Nonionic surfactants according to claim 1 containing ethoxylates of linear Ci ₆ -Ci ₈ - alcohols of the formula (I) R ¹ - (OCH ₂ CH ₂ ) _x -OR ² (I) with R ^{1 is} a linear C ₆ -C ₈ -alkyl radical, R ^{2 is} hydrogen or a linear or branched C 1 -C ₆ -alkyl radical,  x 8, 9 or 10. 3. Nonionic surfactant according to claim 2 containing at least 80 wt .-% ethoxylates of linear Ci ₆ -Ci ₈ -alcohols of the formula (I) with x = 8, 9 or 10 ethylene oxide units. 4. Nonionic surfactant according to claim 3 containing at least 80 wt .-% Ethoxylates of linear C ₆ -C ₈ -alcohols of the formula (I) with x = 9 ethylene oxide units. 5. Nonionic surfactant according to one of claims 1 to 4 containing an average of 8.8 - 9.2 moles of ethylene oxide per mole of linear Ci ₆ -Ci ₈ alcohol. 6. Use of ethoxylates of linear C ₆ -C ₈ -alcohols with an average of 8.5 to 9.5 mol of ethylene oxide per mole of linear C ₆ -C ₈ -alcohol as nonionic surfactants in cleaning formulations for machine dishwashing. 7. Cleaning formulations for machine dishwashing containing a) 0, 1 to 20 wt .-% of nonionic surfactants from ethoxylates of linear Ci ₆ - Ci ₈ -alcohols with an average of 8.5 to 9.5 moles of ethylene oxide per mole of linear Ci ₆ - Ci ₈ - alcohol according to any one of claims 1 to 5, b) 0 to 10 wt .-% further nonionic surfactants, c) 0 to 20 wt .-% polycarboxylates, d) 0 to 50% by weight of complexing agent, e) 0 to 70% by weight of phosphates, f) 0 to 60% by weight of further builders and cobuilders, g) 0 to 30% by weight of bleaching agent and optionally bleach activators and H) 0 to 8 wt .-% enzymes, i) 0 to 50 wt .-% one or more other additives such as anionic or zwitterionic surfactants, alkali carriers, corrosion inhibitors, defoamers, dyes, fragrances, fillers, organic solvents, tableting aids, Disintegrating agent, thickener, solubilizer and water, wherein the sum of the components a) to i) gives 100 wt .-%.