EP0051986B1 - Reinigungsmittelzusammensetzungen - Google Patents

Reinigungsmittelzusammensetzungen Download PDF

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Publication number
EP0051986B1
EP0051986B1 EP81305266A EP81305266A EP0051986B1 EP 0051986 B1 EP0051986 B1 EP 0051986B1 EP 81305266 A EP81305266 A EP 81305266A EP 81305266 A EP81305266 A EP 81305266A EP 0051986 B1 EP0051986 B1 EP 0051986B1
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EP
European Patent Office
Prior art keywords
surfactant
alkyl
weight
composition
anionic surfactant
Prior art date
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EP81305266A
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English (en)
French (fr)
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EP0051986A2 (de
EP0051986A3 (en
Inventor
John George Bell
Richard Geoffrey Harris
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Procter and Gamble Ltd
Procter and Gamble Co
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Procter and Gamble Ltd
Procter and Gamble Co
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Priority to AT81305266T priority Critical patent/ATE13554T1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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

  • This invention relates to detergent compositions.
  • it relates to granular detergent compositions suitable for washing fabrics, clothes etc. in automatic washing machines with improved cleaning performance.
  • Cationic surfactants have been frequently incorporated into detergent compositions of various types. However, the inclusion of such cationic surfactants is generally for the purpose of providing some adjunct fabric care benefit, and not for the purpose of cleaning. For example, certain cationic surfactants have been included in detergent compositions for the purpose of yielding a germicidal or sanitization benefit to washed surfaces, as is disclosed in US-A-2,742,434, US ⁇ A ⁇ 3,539,520, and US-A-3,965,026.
  • cationic surfactants such as ditallowdimethylammonium chloride, have been included in detergent compositions for the purpose of yielding a fabric-softening benefit, as disclosed in US ⁇ A ⁇ 3,607,763 and US-A-3,644,203. Such components are also disclosed as being included in detergent compositions for the purpose of controlling static, as well as softening laundered fabrics, in US-A-3,951,879, and US-A-3,959,157.
  • compositions comprising mixtures of anionic, cationic and nonionic surfactants are also known in the art.
  • compositions conferring enhanced anti-static character to textiles washed therewith are described in GB-A-873,214 and BE-A-829,162 while compositions having enhanced germicidal and detergency performance are disclosed in GB-A-641,297; compositions containing cationic textile softeners are disclosed in FR-A-2,236,925; while compositions containing certain cationic surfactants as foam depressants are disclosed in FR-A-2,388,882.
  • EP-A-225 there is also disclosed a granular detergent composition
  • a granular detergent composition comprising a mixture of anionic, nonionic and water-soluble cationic surfactants providing improved cleaning performance, especially on greasy and oily soils.
  • these compositions require relatively high levels of the cationic and nonionic surfactant components in relation to the anionic surfactant level and this can result in a lack of "robustness", particularly in the areas of clay soil detergency and whiteness maintenance, when the compositions are used in multicycle wash-wear treatments in the presence of rinse-added cationic fabric softener.
  • cationic surfactant can also have a deleterious and intractible effect on the composition's foaming characteristics, thereby raising additional problems of automatic washing machine compatibility. If, on the other hand, the cationic surfactant component is reduced to a level at which foam regulation is no longer a problem, the beneficial grease detergency characteristics of prior art compositions are found to be greatly diminished, particularly when such compositions are used under realistic soil and fabric load/wash liquor ratio conditions.
  • the invention thus provides granular detergent compositions suitable for heavy duty laundering purposes having improved washing machine compatibility and improved cleaning performance especially on greasy and oily soils without detriment to detergency performance on clay soils and without detriment to the soil suspending or fabric whitening characteristics of the compositions, under realistic soil, fabric load and multi wash-rinse-wear cycle conditions.
  • a granular detergent composition comprising:
  • Detergent compositions of the present invention contain as an essential ingredient a multi-component active system comprising anionic surfactant, alkoxylated nonionic and water-soluble cationic surfactants.
  • the anionic surfactant in turn, comprises a mixture of sulfate and sulfonate surfactants or a mixture of sulfate/sulfonate surfactant with a fatty acid soap.
  • This active system is generally in the range from 4% to 20%, more preferably from 6% to 15% by weight of the compositions.
  • the weight ratio of anionic:cationic surfactant in the present compositions varies in the range from 5.1:1 to 50:1, especially from 6:1 to 20:1, the weight ratio of nonionic:nonionic surfactant from 20:1 to 1:1, especially from 10:1 to 1:1, and the weight ratio of anionic-nonionic surfactant from 5.9:1 to 1:3, especially from 4:1 to 1:1.
  • the cationic surfactant component of the composition of the invention is characterised as being water-soluble.
  • water solubility we refer in this context to the solubility of cationic surfactant in monomeric form, the limit of solubility being determined by the onset of micellisation and measured in terms of critical micelle concentration (C.M.C.).
  • the cationic surfactant should thus have a C.M.C. for the pure material greater than 200 p.p.m. and preferably greater than 500 p.p.m., specified at 30°C and in distilled water.
  • Literature values are taken where possible, especially surface tension or conductimetric values-see Critical Micelle Concentrations of Aqueous Surfactant Systems, P. Mukerjee and K. J. Mysels, NSRDS-NBS 36, (1971).
  • the system itself must be water-dispersible or water-soluble in combination with the remainder of the detergent composition. This implies that, in an equilibrium aqueous mixture of the detergent composition (containing 1000 p.p.m. of surfactant) the surfactant system exists in one or more liquid (as opposed to solid) surfactant/water phases. Expressed in another way, the surfactant system should have a Kraft point of no higher than 25°C.
  • Afurther essential component of the present compositions is at least 10%, preferably from 20% to 70% by weight of composition of a detergency builder, for example, a water-soluble inorganic or organic electrolyte.
  • Suitable electrolytes have an equivalent weight of less than 210, especially less than 100 and include the common alkaline polyvalent calcium ion sequestering agents.
  • Water-insoluble calcium ion exchange materials can also be used with advantage, however.
  • the grease removal performance of the present compositions depends sensitively on the ionic strength and the level of free hardness ions in the detergent liquor and these parameters must be closely controlled for optimum performance.
  • the builder:surfactant weight ratio is preferably greater than 1:3, more preferably greater than 4:1 and especially greater than 8:1.
  • Optimum grease and particulate detergency also depends sensitively on the choice of nonionic surfactant and especially desirable from the viewpoint of grease detergency are biodegradable nonionic surfactants having a lower consolute temperature in the range from 25°C to 65°C, more preferably from 30°C to 50°C.
  • biodegradable nonionic surfactants of this type have the general formula RO(CH 2 CH 2 0) n H wherein R is primary or secondary branched or unbranched C 9 -C '5 alkyl or alkenyl and n (the average degree of ethoxylation) is from 2 to 10, especially from 3 to 9.
  • More hydrophilic nonionic detergents can be employed for providing particulate detergency and anti-redeposition, however, for instance, nonionic detergents of the general formula given above wherein R is primary or secondary, branched or unbranched CS-C24 alkyl or alkenyl and n is from 11 to 40. Combinations of the two classes of nonionic surfactants can also be used with advantage of course.
  • compositions of the present invention are preferably formulated to have a pH of at least 6 in the laundry solution at conventional usage concentrations (about 1 % by weight) in order to optimize cleaning performance. More preferably, they are alkaline in nature when placed in the laundry solution and have a pH greater than 7, especially greater than 8.
  • the cationic surfactant is a water-soluble quaternary ammonium compound having a critical micelle concentration of at least 200 ppm at 30°C.
  • the preferred cationic surfactant comprises from 1 to 4 quaternary ammonium groups of which only one has the general formula:- wherein each R' is a hydrophobic alkyl, alkenyl or alkaryl group totalling from 10 to 14 carbon atoms optionally linked to the quaternary nitrogen via ether, alkoxy, ester or amide groups, and each R 2 is an alkyl group containing from one to four carbon atoms or a benzyl group with no more than one R 2 in a molecule being benzyl.
  • a highly preferred group of cationic surfactants of this type has the general formula:- wherein R 1 is selected from C 10 ⁇ C 14 alkyl, alkenyl and alkaryl groups; R is selected from C,-C 4 alkyl and benzyl groups with no more than one R 2 being benzyl; and Z is an anion in number to give electrical neutrality.
  • compositions of this mono-long chain type include those in which R I is a C 10 ⁇ C 14 alkyl group and R 2 is methyl.
  • Particularly preferred compositions of this class include C 12 alkyl trimethylammonium halide, C 14 alkyl trimethylammonium halide and coconut alkyl trimethylammonium halide.
  • the anionic surfactant component of the present compositions preferably comprises either a mixture of sulfonate and sulfate surfactant in a weight ratio of from 5:1 to 1:5, more preferably from 5:1 to 1:1, especially from 4:1 to 1.5:1, or a mixture of sulfonate/sulfate surfactants with a fatty acid soap.
  • Such mixtures preferably have a weight ratio of sulfate or sulfonate surfactant to soap of at least 1:1, especially from 1:1 to 20:1.
  • fatty acid soap i.e., a water-soluble salt of a higher fatty acid
  • this can be selected from the ordinary alkali metal (sodium, potassium), ammonium, and alkylolammonium salts of higher fatty acids containing from 8 to 24, preferably from 10 to 22 and especially from 16 to 22 carbon atoms in the alkyl chain.
  • Suitable fatty acids can be obtained from natural sources such as, for instance, from plant or animal esters (e.g. soybean oil, caster oil, tallow, whale and fish oils, grease, lard and mixtures thereof).
  • the fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process).
  • Resin acids are suitable such as rosin and those resin acids in tall oil. Naphthenic acids are also suitable.
  • Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from tallow and hydrogenated fish oil.
  • the sulfate or sulfonate anionic surfactants for use herein can be defined generally as water-soluble salts, particularly alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 8 to 22, especially from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl” is the alkyl portion of acyl groups).
  • Suitable synthetic anionic surfactants are water-soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin sulfonates, alpha-sulfo-carboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2-agyloxy-alkane-1-sulfonate, and betaalkyloxy alkane sulfonate.
  • Examples of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 87 -C is 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 9 to 15 carbon atoms, in straight chain or branched chain configuration, e.g. those of the type described in US-A-2,220,099 and US-A-2,477,383 and those prepared by alkylation with straight chain chloroparaffins (using aluminium trichloride catalysis) or straight chain olefins (using hydrogen fluoride catalysis).
  • 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, 1 . 8 LAS.
  • 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 12 to 16 carbon atoms, preferably from 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from 1 to 4 mols 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 alkyl phenol ethylene oxide ether sulfate containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain 8 to 12 carbon atoms.
  • Other useful anionic detergent compounds herein include the water-soluble salts of esters of a-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from 12 to 24 carbon atoms; water-soluble salts of paraffin sulfonates containing from 8 to'24, especially 14 to 18 carbon atoms, and (3-atkytoxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in
  • Anionic sulfate/sulfonate surfactant mixtures preferred herein include 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 either an alkyl sulfate having from 10 to 20 carbon atoms in the alkyl radical or an 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.
  • the 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:
  • a highly preferred mixture of surfactants comprises a C S - 22 alkyl benzene sulfonate and a C 9-15 alkanol ethoxylated with from 3 to 9 moles of ethylene oxide per mole of alkanol.
  • a specific preferred mixture comprises C, 2 alkyl benzene sulfonate and C 14-15 alcohol-(7)-ethoxylate.
  • a C 1S - 22 fatty acid soap can also be included.
  • the detergent composition of the invention also contains at least 10% by weight thereof of a detergency builder, especially a water-soluble inorganic or organic electrolyte.
  • Suitable electrolytes have an equivalent weight of less than 210, especially less than 100 and include the common alkaline polyvalent calcium ion sequestering agents.
  • the builder can also include water-insoluble calcium ion exchange materials, however.
  • suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates, sulfates and chlorides. Specific examples of such salts include sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphates, orthophosphates, pyrophosphates, hexametaphosphates and sulfates.
  • Mixtures of organic and/or inorganic builders can be used herein.
  • One such mixture of builders is disclosed in CA-A-755.038, e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
  • 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.
  • a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in BE-A-814,874.
  • This patent discloses and claims detergent compositions containing sodium aluminosilicates having the formula wherein z and.y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to about 0.5:1, and X is an integer from 15 to 264, said aluminosilicates having a calcium ion exchange capacity of at least 200 milligrams equivalent/gram and a calcium ion exchange rate of at least 2 grains/gallon/minute/ gram (0.09 g/I/min/g/I).
  • a preferred material is
  • 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 0.1% to 10% by weight such as water-soluble salts of carboxymethyl-cellulose, carboxyhydroxymethyl cellulose, and polyethylene glycols having a molecular weight of 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 discussed in US-A-3,519,570 and US-A-3,533,139.
  • Anionic fluorescent brightening agents are well-known materials, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate, disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate, disodium 4,4'-bis(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate, sodium 4,4'-bis-(2-anilino-4-(N-methyl N-2-hydroxyethyl- amino)-s-triazin-6-ylamino)stilbene-2,2'-disulphonate, disodium 4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)stilbene-2,2'-disulphonate, diso
  • alkali metal, or alkaline earth metal, silicate can also be present.
  • the alkali metal silicate preferably is used in an amount from 0.5% to 10% preferably from 3% to 8%.
  • Suitable silicate solids have a molar ratio of SiO 2 /alkali metal 2 O in the range from 0.5 to 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.
  • the present compositions also contain additional suds regulating components in an amount of from 0.05% to 3%.
  • Preferred are microcrystalline waxes having a melting point in the range from 35°C-115°C and saponification value of less than 100.
  • the microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants.
  • Preferred microcrystalline waxes have a melting point from 65°C to 100°C, a molecular weight in the range from 400-1000; and a penetration value of at least 6, measured at 77°C by ASTM-D1321.
  • Suitable examples of the above waxes include microcrystalline and oxidized microcrystalline petrolatum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax, candelilla; and carnauba wax.
  • the granular detergent compositions herein can also advantageously contain a peroxy bleaching component in an amount from 3% to 40% by weight, preferably from 8% to 33% by weight.
  • a peroxy bleaching component for use herein include perborates, persulfates, persilicates, perphosphates, percarbonates, and more generally all inorganic and organic peroxy bleaching agents which are known to be adapted for use in the subject compositions.
  • the composition can also advantageously include a bleach activator which is normally an organic compound containing an N-acyl, or an O-acyl (preferably acetyl) group.
  • Preferred materials are N,N,N',N'-tetraacetyl ethylene diamine and N,N,N',N'-tetracetylglycouril.
  • the bleach activator is preferably added at a level from 0.5% to 5% by weight of composition.
  • a further preferred ingredient of the instant compositions is from 0.01 to 4%, especially from 0.1 to 1.0% by weight of a polyphosphonic acid or salt thereof which is found to provide bleachable stain detergency benefits.
  • Especially preferred polyphosphonates have the formula:- wherein each R is CH 2 P0 3 H 2 or a water-soluble salt thereof and n is from 0 to 2.
  • Examples of compounds within this class are aminotri-(methylenephosphonic acid), ethylene diamine tetra (methylenephosphonic acid) and diethylene triamine penta (methylene phosphonic acid). Of these, ethylene diamine tetra (methylene phosphonic acid) is particularly preferred.
  • a further optional component is from 0.1% to 3%, especially from 0.25% to 1.5% of a polymeric material having a molecular weight of from 2000 to 2,000,000 and which is a copolymer of maleic acid or anhydride and a polymerisable monomer selected from C l -C l , alkyl vinyl ethers, acrylic and methacrylic acid and C,-C 2o esters thereof, alkenes having from 2 to 12 carbon atoms, N-vinyl pyrrolidone and styrene.
  • carboxylates are 1:1 styrene/maleic acid copolymer, di-isobutylene/ maleic acid copolymers and methyl vinyl ether/maleic acid copolymers.
  • Other suitable polycarboxylates are poly-a-hydroxy acrylates and lactones thereof as described in BE-A-817,678 and GB-A-1,425,307.
  • compositions of the invention are used as aqueous solutions containing from 100 to 3000 p.p.m., especially from 500 to 1500 p.p.m. of surfactant.
  • the detergent compositions of the invention are made by spray-drying a crutcher mix containing the anionic, cationic and builder components and subsequently absorbing the nonionic surfactant in liquid or molten form into the spray-dried granules.
  • compositions of the invention can also be formulated as special prewash compositions designed for use before the main wash stage of the conventional laundering cycle.
  • compositions are prepared by spray-drying an aqueous slurry of the ingredients except for the Dobanol-derived nonionic surfactants which is sprayed onto the spray-dried granules, and the sodium perborate, TAED and enzyme which are dry mixed into the composition.
  • Dobanol-derived nonionic surfactants which is sprayed onto the spray-dried granules, and the sodium perborate, TAED and enzyme which are dry mixed into the composition.
  • N.B The level of Zeolite A is given on an anhydrous basis; the material contains 21% water of crystallisation.
  • lauryl or myristyl trimethyl ammonium chloride in the above examples can be replaced by lauryl or myristyl-trimethyl ammonium bromide, decyl trimethyl ammonium chloride, or coconut alkyl benzyl dimethyl ammonium chloride.

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Claims (9)

1. Eine Reinigungsmittelzusammensetzung, enthaltend:
(a) 2 Gew.-% bis 30 Gew.-% der Zusammensetzung eines oberflächenaktiven Systems, enthaltend:
(i) anionisches oberflächenaktives Mittel,
(ii) alkoxyliertes, nichtionisches oberflächenaktives Mittel und
(iii) 0,2 Gew.-% bis 2 Gew.-% der Zusammensetzung an wasserlöslichem, kationischem Mono-C10― C,4-alkyl-, -alkenyl- oder -alkarylquaternären Ammonium-oberflächenaktivem Mittel, und
(b) wenigstens 10 Gew.-% der Zusammensetzung an Detergensgerüststoff, dadurch gekennzeichnet, daß das Gewichtsverhältnis von anionischem oberflächenaktivem Mittel:kationischem oberflächenaktivem Mittel 5,1:1 bis 50:1 beträgt, und das Gewichtsverhältnis von anionischem oberflächenaktivem Mittel:nichtionischem oberflächenaktivem Mittel 5,9:1 bis 1:3 beträgt.
2. Eine Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das anionische oberflächenaktive Mittel ein Sulfat- oder Sulfonat-oberflächenaktives Mittel oder ein Gemisch davon mit Fettsäureseife in einem Gewichtsverhältnis von wenigstens 1:1 enthält.
3. Eine Zusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das anionische oberflächenaktive Mittel ein Gemisch von Sulfonat- und Sulfat-oberflächenaktiven Mitteln in einem Gewichtsverhältnis von 1:1 bis 5:1, vorzugsweise von 1,5:1 bis 4:1, enthält.
4. Eine Zusammensetzung nach Anspruch 2 oder 3, dadurch gekennzeichnet, daß das anionische Sulfat- oder Sulfonatoberflächenaktive Mittel eine C10―C20-Alkyl- oder -Alkarylgruppe aufweist, und die Seife ein wasserlösliches Salz einer C16―C22-Fettsäure ist, wobei das Gewichtsverhältnis von Sulfat- oder Sulfonat-oberflächenaktivem Mittel zu Seife im Bereich von 1:1 bis 20:1 liegt.
5. Eine Zusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das kationische oberflächenaktive Mittel 1 bis 4 quaternäre Ammoniumgruppen enthält, von weichen nicht mehr als eine die allgemeine Formel
Figure imgb0010
aufweist, worin R' eine hydrophobe Alkyl-, Alkenyl- oder Alkarylgruppe mit insgesamt 10 bis 14 Kohlenstoffatomen ist, die gegebenenfalls an den quaternären Stickstoff über Ether-, Alkoxy-, Ester- oder Amidgruppen gebunden ist, und jeder Rest R2 eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen oder eine Benzylgruppe ist, wobei nicht mehr als ein Rest R2 in einem Molekül Benzyl ist.
6. Eine Zusammensetzung nach Anspruch 5, dadurch gekennzeichnet, daß das kationische oberflächenaktive Mittel die allgemeine Formel:
Figure imgb0011
hat, worin R' aus C10―C14-Alkyl-, -Alkenyl- und -Alkarylgruppen ausgewählt ist; RZ aus C1―4-Alkyl- und Benzylgruppen-wobei nicht mehr als ein Rest RZ Benzyl ist-ausgewählt ist; und Z ein Anion solcher Zahl ist, daß elektrische Neutralität gegeben ist.
7. Eine Zusammensetzung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das nichtionische oberflächenaktive Mittel die allgemeine Formel RO(CH2CH2O)nH hat, worin R primäres oder sekundäres, verzweigtes oder unverzweigtes C9―C15-Alkyl oder -Alkenyl ist und n, der durchschnittliche Ethoxylierungsgrad, 2 bis 10 ist.
8. Eine Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Gewichtsverhältnis von anionischem oberflächenaktivem Mittel zu kationischem oberflächenaktivem Mittel 6:1 bis 20:1 beträgt, das Gewichtsverhältnis von anionischem oberflächenaktivem Mittel zu nichtionischem oberflächenaktivem Mittel 4:1 bis 1:1 beträgt und das oberflächenaktive System 4 Gew.-% bis 20 Gew.-% der Reinigungsmittelzusammensetzung ausmacht.
9. Eine Zusammensetzung nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß sie zusätzlich 3 Gew.-% bis 40 Gew.-% der Zusammensetzung an Peroxybleichmittel und 0,5 Gew.-% bis 5 Gew.-% der Zusammensetzung eines Precursors für ein organisches Peroxysäurebleichmittel enthält.
EP81305266A 1980-11-06 1981-11-06 Reinigungsmittelzusammensetzungen Expired EP0051986B1 (de)

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AT396479B (de) * 1986-01-27 1993-09-27 Colgate Palmolive Co Teilchenförmiges wasch- und weichmachungsmittel

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US4561998A (en) * 1982-05-24 1985-12-31 The Procter & Gamble Company Near-neutral pH detergents containing anionic surfactant, cosurfactant and fatty acid
ZA837830B (en) * 1982-11-05 1985-06-26 Colgate Palmolive Co Detergent softener composition
FR2620728B1 (fr) * 1986-01-27 1994-04-01 Colgate Palmolive Cy Article detergent et assouplissant pour tissus, composition detergente, son procede de fabrication et procede de lavage
US4818422A (en) * 1987-09-17 1989-04-04 Colgate-Palmolive Co. Fabric softening detersive article
AU4712189A (en) * 1989-01-03 1990-07-12 Amway Corporation Nonionic laundry detergent composition
CA2226621A1 (en) * 1995-07-08 1997-01-30 The Procter & Gamble Company Detergent compositions
GB2303147A (en) * 1995-07-08 1997-02-12 Procter & Gamble Detergent compositions
GB2303150A (en) * 1995-07-08 1997-02-12 Procter & Gamble Laundry washing method
GB2303144A (en) * 1995-07-08 1997-02-12 Procter & Gamble Detergent compositions
GB9513999D0 (en) * 1995-07-08 1995-09-06 Procter & Gamble Detergent compositions
AR007837A1 (es) * 1996-07-08 1999-11-24 Procter & Gamble Composicion detergente para lavado que comprende una combinacion de surfactantes
BR9810933A (pt) * 1997-06-23 2000-09-26 Procter & Gamble Composição detergente granular contendo um sistema tensoativo ótimo para lavagem de roupa em temperatura fria
US11512268B2 (en) * 2017-11-29 2022-11-29 Basf Se Storage-stable enzyme preparations, their production and use

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AT396479B (de) * 1986-01-27 1993-09-27 Colgate Palmolive Co Teilchenförmiges wasch- und weichmachungsmittel

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DE3170763D1 (en) 1985-07-04
EP0051986A2 (de) 1982-05-19
EP0051986A3 (en) 1982-07-21

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