FI73728C - Detergent composition containing a mixture of an anionic, cationic and possibly nonionic surfactant. - Google Patents

Description

1 73728

This invention relates to detergent compositions comprising a mixture of anionic, cationic and optionally nonionic surfactant components, wherein the anionic surfactant component comprises from 4 to 60% by weight of the detergent composition comprising a mixture of anionic, cationic and optionally nonionic surfactant components. % of the composition and comprises a mixture of sulfonate and sulfate-10 type anionic surfactants and the cationic surfactant component constitutes 0.25-12% by weight of the composition and comprises a monoquaternary ammonium salt, wherein the molar ratio of quaternary ammonium salt to anionic sulfonate is less than 15: 1 and wherein the composition optionally contains up to 70% by weight of detergent builder, for use in washing textiles. The compositions may take any form, such as granules, liquids, tablets or pastes. In a preferred embodiment, the detergent composition according to the invention comprises a detergent builder and / or a non-ionic surfactant and / or a fatty acid soap and / or enzymes.

Cationic surfactants have been added to detergent compositions for purposes other than cleaning; for example to destroy microorganisms or for sanitary purposes, to soften fabric or to combat static electricity. Recently, it has been shown that cationic surfactants together with anionic and / or nonionic surfactants are effective for purification purposes. U.S. Patent No. 4,235,759 to Ohbre et al. (November 25, 1980) is directed to liquid detergent compositions which are excellent detergents and which contain alkyl polyoxyalkylene ether sulfate as an anionic surfactant and mono-35 long chain alkyl quaternary ammonium. as an active agent, wherein the molar ratio of anionic surfactant to 2,73728 to cationic surfactant is 8: 1 to 1: 1.

U.S. Patent No. 4,321,165 to Smith et al. (March 23, 1982) discloses solid detergent compositions comprising 2-60% of a combination of surfactants containing a water-soluble anionic surfactant, a nonionic surfactant. an active alkoxylated alcohol and a water-soluble quaternary ammonium cationic surfactant, wherein the ratio of anionic surfactant to cationic surfactant is 5: 1 to 1: 3 and the ratio of nonionic surfactant to cationic surfactant is the ratio is 100: 1-2: 3. It has been shown that the greasy dirt removal ability of these compositions is improved.

EP Patent Application 26,529 to Snadini et al. (Published April 4, 1981) discloses detergent compositions containing 3-40% of an anionic surfactant, 0.5-15% of a quaternary mono-long chain alkylammonium compound or an aliphatic amine. and 1.5-45% of very fine, smectite-type clay, wherein the molar ratio of nitrogen compound to anionic surfactant is less than 1. It has been found that these compounds have good cleaning ability and also act as a softener for textiles.

U.S. Patent No. 4,333,862 to Smith et al. (June 8, 1982) discloses liquid detergent compositions comprising about 10-82% anionic surfactant, 10-82% nonionic surfactant alkoxylated alcohol, and about 4-35% of a water-soluble, quaternary salt of a cationic surfactant. It has been mentioned that the cleaning ability of these combinations for greasy and oily soils is improved.

The detergent compositions of the present invention, especially for washing textiles, achieve excellent soil removal, especially organic soil removal, with unusually low re-deposition of soil on textile surfaces.

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With the detergent compositions of the present invention, these advantages are achieved over a wide range of washing temperatures.

The detergent composition of the present invention is characterized in that a) the anionic surfactant sulfate comprises an aqueous alkali metal or ammonium salt of a primary C 1-6 alkyl sulfate or a secondary C 12-18 alkyl sulfate; a water-soluble substituted ammonium salt, b) the monoquaternary ammonium surfactant compound is i) a compound having one C 1-4 alkyl group and wherein the other groups are C 1-4 alkyl groups or C 1-4 alkyl groups. roxyalkyl groups, or ii) a compound having two C 1-6 alkyl groups, the total number of carbon atoms in the two groups being 10-14, and in which the other groups are methyl groups and / or hydroxyethyl groups; and c) the anionic surfactant sulfonate is

C 1-4 alkylbenzenesulfonate, C 1-4 paraffin sulfo-γ-8 8-24 sodium, C 0 -alkylglyceryl ether sulfonate, a sulfonated fatty acid ester 25 or ether containing 6-20 carbon atoms in the fatty acid group and 1-10 carbon atoms in the ester group. , a water-soluble salt of a C 1-6 alkyl or aryl sulfonate containing an ester or amide bond to a C 1-6 alkyl chain.

The detergent compositions of this invention essentially comprise a three component surfactant detergent system consisting of a particular alkyl sulfate, a particular sulfonate, and cationic surfactants. This three-component surfactant system is a very effective detergent. It is a particularly effective cleaner for organic soils, such as lipids, greasy and oily soils. In addition, with this system, re-precipitation of dirt is unusually low. Re-precipitation of dirt occurs when dirt removed from the textiles during washing in the washing solution re-precipitates on the textiles.

The detergent compositions of the invention provide the desired, excellent washing performance over a wide range of wash water conditions. The temperature of the wash water can be about 5-95 ° C.

It is advantageous if the initial pH of the washing solution, i.e. the pH of the mixture of detergent composition and wash water is greater than about 8 and most preferably about 9-11.

The detergent compositions of the invention may be of any form, for example granules, liquids, tablets or pastes, but granular compositions 3 are preferred. The density of the granules may be from about 0.15 g / cm 3 to about 0.8 g / cm 2.

Without wishing to be bound by theory, it is believed that the detergent compositions of the present invention obtain advantageous excellent performance against organic soils because the alkyl sulfate surfactant and the sulfonate surfactant both form an electrically neutral complex with the cationic surfactant. The organic dirt removal mechanism is assumed to be based on the absorption of the surfactant on the dirt surface, whereby the surface tension of the dirt / water interface is reduced to such an extent that the mechanical action in the washing process removes dirt from the textile surfaces. Because the complexes formed are electrically neutral and thus do not repel each other, they can pack tightly when absorbed onto the surface of the dirt. This results in a significantly lower stress on the dirt / water interface pin-30 and thus very efficient dirt removal. It should be noted that in order to achieve the desired excellent efficacy of this invention, both an alkyl sulfate surfactant and a sulfonate surfactant detergent must be present. However, the experimental results show that it is essential that the molar ratio of cationic surfactant to sulfonate surfactant detergent be less than about 1.5. Otherwise, the desired excellent effect cannot be achieved.

In addition, it is preferred that the molar amount of the sum of the alkyl sulfate detergent surfactant and the sulfonate surfactant surfactant is greater than to ensure the removal of the proteinaceous and finely soiled dirt of the cationic surfactant and the removal of the textile-separated dirt suspension into the wash solution. Such a dirt suspension prevents re-precipitation of dirt.

The following is a detailed description of the essential and optional ingredients of the detergents of the invention. All percentages, proportions and ratios are by weight unless otherwise indicated.

Cationic Surfactant The cationic surfactant is an essential ingredient in the compositions of the invention. Without the cationic surfactant, an electrically neutral complex can be formed with the alkyl sulfate detergent and / or the sulfonate surfactant detergent, and thus the desired excellent effect cannot be obtained. Although in theory, in principle, any cationic surfactant can be used to achieve this advantage, nitrogen-containing surfactants which are cationic or capable of being present in cationic form are most useful. The cationic surfactants of the invention may be saturated or unsaturated.

The cationic surfactants of the invention are selected from the group consisting of monoquaternary ammonium surfactants selected from the group consisting of: i) compounds having one C 1-12 alkyl group and the other groups being C 1-6 alkyl groups or C 2-4 alkyl groups; -hydroxyalkyl groups, and ii) compounds having two N-alkyl groups, the total number of carbon atoms in the two groups being 6,73728 1C-14, and in which the other groups are methyl and / or hydroxyethyl groups.

The most preferred cationic surfactants are C 1-4 alkyltrimethylammonium surfactants, C 1-4 alkylhydroxyethyldimethylammonium surfactants, C 1-4 alkylmethyldi-O "12 hydroxyethylammonium surfactants, Chloride, bromide and methyl sulfates of alkoxytrimethylammonium surfactants, C 1-4 alkoxide hydroxyethylmethylammonium surfactants and C 1-4 alkoxyhydroxyethyldimethylammonium surfactants.

If desired, salts of cationic surfactants may be prepared by forming a precomplex of the cationic surfactant with an anionic surfactant within the scope of the invention instead of forming such a complex in a washing solution.

These nitrogen-containing cationic surfactants are preferred when using cold wash water, i. pe-20 at a summer temperature below 45 ° C, because when used in combination with a surfactant sulfate and a surfactant sulfonate, the electrically neutral complex formed therefrom does not crystallize or become too viscous. It has been found that an electrically neutral complex with a cationic surfactant such as C 2 -C 2 trimethylanonium chloride formed under cold wash water conditions causes this complex to crystallize or become highly viscous and is thus less effective.

The most preferred cationic surfactants are the chloride, bromide and methyl sulfate salts with quaternary alkyl ammonium surfactants.

The amount of cationic surfactant within the scope of the invention is determined by the amount of surfactant sulfonate. The molar ratio of cationic surfactant to surfactant sulfonate is at most about 1.5: 1 and preferably less than about 1: 1. It is preferred to use a small molar excess of surfactant sulfonate because it is effective in removing fabric softeners that have precipitated on textile surfaces in previous washing steps. The sum of equimolar amounts of the cationic surfactant and the surfactant sulfonate is preferably at least 2%, more preferably at least 5% and most preferably more than 10% of the total amount of anionic surfactant used. This excess of anionic surfactant is preferred, ensuring the removal of proteinaceous and finely soiled dirt and the removal of the dirt removed from the textiles in the washing solution.

The amount of cationic surfactant in the present invention is 0.5 to 8, preferably 0.5 to 6%. Anionic Sulfate Surfactant Anionic surfactant sulfate is an essential ingredient in the detergent composition of the invention.

Detergent compositions that do not contain anionic sulfate surfactant do not achieve the desired excellent performance. These compositions poorly remove finely divided dirt and increase the re-precipitation of dirt. It is believed that the anionic sulfate surfactant, in addition to forming an electrically neutral complex with the cationic surfactant, is particularly effective for this purpose. In addition, only certain anionic alkyl sulfates with surfactants achieve the desired excellent washing performance. The washing performance is poor when using an alkyl sulfate surfactant in which the alkyl chain contains more than about 15 carbon atoms in the linear portion of the chain from the end group and / or more than about four ethoxy groups. The anionic surfactant sulfate to be used in accordance with the present invention comprises a primary C, n-alkyl sulfate or a secondary C, n-al-12-1-7 i 2 -1 salt or a water-soluble substituted ammonium salt.

Preferred substituted arammonium cations are mono- and diethanolammonium cations.

Preferably, the sulfate surfactant is not ethoxylated. Preferred sulphate surfactants are the sodium and potassium salts of the primary C 1-6 and secondary C 1-6 alkyl sulfates. The most preferred sulfate surfactants are the sodium and potassium salts of linear and methyl-branched C 1-4 alkyl sulfates.

In cold wash water conditions, i.e. when the temperature of the wash water is below about 45 ° C, the preferred surfactant sulfates are secondary and lower alkyl chain surfactants.

The amount of anionic surfactant sulfate used in accordance with the present invention is 3 to 30%, preferably 5 to 20%.

Anionic Surfactant Sulfonate Anionic surfactant sulfonate is an essential ingredient in the compositions of the invention. Compositions which do not contain a surfactant sulfonate according to the invention do not achieve the desired excellent washing performance.

The range of surfactant sulfonates useful in the compositions of the invention is very wide. However, it is assumed that the alkyl chain portion of these substances should be saturated. For example, O-olefin sulfonates with an unsaturated carbon-30 bond do not achieve the desired excellent washing performance.

Suitable anionic surfactant sulfonates include C 1-4 alkylbenzenesulfonates, C 8-2 paraffinic sulfonates, C 1-4 alkylglyceryl ether sulfonates, fatty acid sulfonates containing 6-20 carbon atoms in the fatty acid group and 1-10 carbon atoms in the ester group. and water-soluble salts of C 1-4 alkyl and aryl sulfonates containing an ether, ester or amide bond to the alkyl chain.

Preferred surfactant sulfonates are secondary alkylbenzene sulfonates having 59 to 15, preferably 11 to 13 carbon atoms in the alkyl chain.

Suitable paraffin sulfonates contain about 8 to 24 carbon atoms and preferably 12 to 18 carbon atoms. Alkyl glyceryl ether sulfonates are ethers of C8-8 g alcohols, for example those derived from tallow and coconut oil. Suitable esters of χ, -sulfonated fatty acids contain from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group.

Suitable alkyl sulfonates having an ether, ester or amide bond are of the general formula: R7-A-R8-SO3-7, wherein R is an alkyl chain having 7 to 15 carbon atoms, R is 1 to 6 carbon atoms or a benzyl group The alkyl chain containing 20 and A is selected from the group consisting of:

O OH

M II I

-C-O-, -C-N- and -O- Under cold wash water conditions, i. with a wash water temperature below about 45 ° C, lower alkyl chain surfactant sulfonates are preferred.

The amount of anionic surfactant sulfonate of the invention is such that the molar ratio of cationic surfactant to surfactant sulfonate is less than about 1.5: 1, and preferably less than about 1: 1. The sum of equimolar amounts of cationic surfactant and sulfonate surfactant is at least 2%, preferably at least 5%, and most preferably greater than about 10% of the total amount of anionic surfactant used.

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In the detergent compositions of the present invention, the amount of anionic surfactant sulfonate is 2-30%, preferably 3-20%.

Detergent Materials 5 A highly preferred embodiment of the detergent compositions of the invention comprises a detergent material. The detergent compositions have a structural content of 0-70%, preferably 10-60% and most preferably 20-50%.

Preferred detergent builders include water-soluble metal ion complexing agents such as tripolyphosphates, hexametaphosphates, and more polymerized species, citrates, nitrilotriacetates, and water-soluble polyacetals, as disclosed in U.S. Patent Nos. 4,144,266 and 4,246,595 to The most preferred detergent builders are tripolyphosphates, nitrilotriacetates and water-soluble polyacetals and mixtures thereof.

Aqueous solutions of inorganic or organic electrolytes are suitable building materials. The electrolytes have an equivalent weight of less than 210, in particular less than 100, and contain the usual basic polyvalent calcium ion sequestrants. Detergent builders can also be water-insoluble calcium ion exchange materials: examples of suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, bicarbonates, silicates, and sulfates. Examples of these salts are sodium and potassium tetraborates, perborates, bicarbonates, carbonates, percarbonates, orthophosphates, pyrophosphates and sulfates.

Examples of suitable organic alkaline detergent builders include: 1) water-soluble aminocarboxylates and aminopolyacetates, for example sodium and potassium glycinates, ethylenediaminetetraacetates and N- (2-hydroxyethyl) nitrilodiacetates and diethylene; li 73728 2) water-soluble salts of inositol hexaphosphoric acid, for example sodium and calcium phytates; 3) water-soluble knephosphonates, including sodium, potassium and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; sodium, potassium and lithium salts of ethylenediphosphonic acid; and the like; 4) water-soluble polycarboxylates such as lactic acid, succinic acid, malic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid, 2-oxa-1,1,3-propanetricarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, cyclopentane, cyclopentane salts of tetracarboxylic acid, mellitic acid and pyromellitic acid; 5) water-soluble organic amines and amine salts such as monoethanolamine, diethanolamine and triethanolamine and their salts; G) water-soluble kneal acetals disclosed in U.S. Patent Nos. 4,144,266 and 4,246,495, and 7) water-soluble salts of fatty acids, e.g., salts of C 1-6 fatty acids, lz-lo

Another type of detergent builder useful in these compositions comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness-increasing cations, preferably in combination with seed crystals capable of forming growth sites for said reaction product. Compositions containing these "inoculated enhancers" are extensively disclosed in GB Patent No. 1,424,406.

Insoluble sodium aluminosilicates, particularly those disclosed in BE Patent 814,874, issued November 12, 1974, comprise the following class of detergent building materials useful in the present invention. This patent discloses detergent compositions comprising the formula:

Sodium aluminosilicates according to Na (A10 „) (SiO_) XH„ 0 7, 2z 2 y 2 12 7 3 7 2 8, where z and y are integers having a value of at least 6, the molar ratio z: y is in the range 1.0: 1 - about 0.5: 1 and X is an integer from about 15 to 264, wherein said aluminosil-5 edges have a calcium ion exchange capacity of at least 200 milligrams per gram and a calcium ion exchange rate of at least about 0.034 g / l / in / g. The preferred material is: 10 Na- ^ 2 (SiO2AlO2) - ^ 2 ^ H2O

Non-ionic surfactant

If desired, the compositions of the invention may contain a nonionic surfactant. These surfactants used herein consist of those typical surfactants well known in the detergent art. Preferred nonionic surfactants are fatty acid amides, amine oxides and ethoxylated alcohols.

Suitable surfactant fatty acid amides include ammonia amides, monoethanolamides, diethanolamides and ethoxylated amides. The formula for the preferred amides is:

O H

n 1 y RCN - // * (CH 2 CH 2 O) 2 CH 2 CH 2 OH / x 25 where R is a Cy_QQ alkyl group, x + y = 2 and a range from 0 to about 5. Particularly preferred amides are those in which the alkyl group contains about 10-16 carbon atoms, such as coconut -alkyl monoethanol or diethanolamide. These 30 compounds are commercially available under the tradename

Super-Amide L-9 and GR, sold by Onyx Chemical Company, Jersey City, NJ; Super-Amide F-3, sold by Ryco, inc., Conshohocken, PA and Gafamide CDD-518, sold by GAF Corp., New York, NY.

The amine oxide-35 surfactants useful in this invention form compounds of the formula: 13 7372 8 R2 r1 (OC2h4) n1 - * 0 R3 and mixtures thereof, wherein R1 is an alkyl, hydroxyalkyl, alkoxyhydroxypropyl radical, alkoxyhydroxyethyl , alkylamido or alkyl carboxylate, in which the alkyl and alkoxy groups are 2 '. R and RJ are methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or together form a heterocyclic ring, for example a morpholino ring in which the nitrogen is part of the ether ring and n is from 0 to about 10.

Examples of suitable surface-active amine oxides include: dimetyy1idodekyy1iamiinioksidi, dimethyl tetradokyy1iamiinioksidi 15, etyylimotyylitetradekyvliamiinioksidi, setyylidimetyvliamiinioksidi, dimetyylistearyyli-amine oxide, setyylietyylipropyyliamiinioksidi, diethyl-dodecylamine in ioksidi, dietyylitetradekyy1iamiinioksidi, dipropyy1idodekyy1iami inioksidi, bis (2-hydroxyethyl) -20 dodekyyliamiinioksidi bis (2-hydroxyethyl) -3-dodecoxy-2-hydroxypropylamine oxide, (2-hydroxypropyl) methyl -tetradecylamine oxide, dimethyloleylamine oxide, dimethyl- (2-hydroxydodecyl) amine oxide, C2-20 alkyl- (α-α-dimethylamine oxide) and carboxylate oecyl, hexadecyl and octadecyl homologues of the aforementioned compounds. A particularly preferred material is dimethyl i-C, .., ..- and 1-alkylamine oxide.

12-ib · The ethoxylated alcohols useful in this invention have the formula: R (OC2H40) ..O-R1 wherein R is alkyl, hydroxyalkyl, alkylene, hydroxyalkylene, acyl or hydroxyacyl groups containing 8-22 n L atoms or an alkylioenzene group, 14 73 72 8 wherein the alkyl group contains about 6-15 carbon atoms or mixtures thereof; X is a number between about 2-30; and R 1 is selected from the group consisting of H, alkyl groups having 2 to 4 carbon atoms, acyl groups having about 2 to 4 carbon atoms, and mixtures thereof. These nonionic surfactants preferably have an HLB value of from about 5 to 20, most preferably from about 8 to 14.

Other suitable nonionic surfactants include: 1) condensation products of ethylene oxide formed with a hydrophobic base by condensing propylene oxide and propylene glycol, and 2) condensation products of ethylene oxide with a product obtained by the reaction of propylene oxide with ethylenediamine. These surfactants are sold by BASF Wyandotte under the trade names Pluronic and Tetronic, respectively.

The content of the nonionic surfactant to be used is about 0 to about 50%, preferably about 0.5 to 10%, and most preferably about 1 to 5%.

Miscellaneous ingredients

In addition to the ingredients mentioned above, the compositions of this invention may contain all conventional ingredients of detergent compositions, including those disclosed in LiS Patent No. 3,936,537 to Baskerviile et al., Which is incorporated herein by reference. These ingredients include color particles, bleaches, bleach activators, foam builders, foam dampers, corrosion inhibitors and / or antifoulants, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, microorganisms, microorganisms and microorganisms. , alkalizing agents, hydrotropes, antioxidants, enzymes, enzyme stabilizers, ha- 35

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1 D

In addition to acting as builders for the detergent, water-soluble salts of fatty acids can be added as part of the surfactant system. Surprisingly, they are most effective in cold wash water conditions. Suitable water-soluble fatty acid salts contain about 8 to 18 carbon atoms. Preferred water-soluble salts of fatty acids are the sodium, potassium and magnesium salts of C 1-4 fatty acids. Their concentration can be up to about 1C percent.

The enzymes are expected to be particularly effective in the detergent compositions of this invention. Enzyme-containing detergent compositions are particularly effective against enzyme-sensitive soils such as grass and blood while maintaining cleansing properties on greasy and oily soils. Suitable enzymes include, for example, those disclosed in U.S. Patent No. 4,176,079 to Guerry et al. (November 27, 1979), which is incorporated herein by reference. The amount of enzymes added is about 0.02-3%, preferably about 0.1-1%.

Examples of suitable bleaching agents are sodium perborate (as monohydrate or tetrahydrate), sodium percarbonate and other perhydrates in concentrations of about 5-35% by weight of the composition, and activators therefor, such as tetraacetylethylene-diamine and tetraacetyl and stabilizers therefor, such as magnesium silicate and ethylenediaraine tetraacetate. Peroxycarboxylic acids, such as those disclosed in U.S. Patent No. 4,091,544 to Hutchins (May 30, 1975), are particularly useful.

Preferred optional ingredients include washing solution modifiers, especially those of the foam damping type, for example silicones and silicon ionic alloys.

35 U.S. Patent Nos. 3,933,672, issued January 20, 1976 (Bartolotta et al.) And 4,136,045, issued January 23, 1972 (Gault et al.), Incorporated herein by reference, relate to silicones. washing solution adjusters. Silicone materials can be represented by alkylated polysiloxane materials, such as silicon aerogels and xerogels, and various types of hydrophobic silicon materials. The silicone material can be represented by the formula:

R

10 -SiO- 1 as a siloxane according to R x, wherein x is a number between about 20-2000 and R and R 1 are each alkyl or aryl, especially methyl, ethyl, propyl, butyl and phenyl. Polydimethylsiloxanes (R and R "1" are both methyl) having a molecular weight in the range of about 200 to 2,000,000 or greater are all useful soap solution modifiers. Other suitable silicone materials in which the side chain groups R and R 1 are alkyl, aryl or mixed alkyl or aryl hydrocarbyl groups have useful washing solution control properties. Examples of these ingredients include diethyl, dipropyl, dibutyl, methyl, ethyl, phenylmethylpolysiloxanes and the like. Other useful siloxane wash solution modifiers may be a mixture of an alkylated siloxane, as mentioned above, and solid silicon. These alloys are prepared by attaching silox-30 to a solid silicon surface. The preferred silicone-containing washing solution adjuster is hydrophobic silanized (most preferably trimethylsilacinated) silicon having a particle size in the range of about 10 millimicrometers to about 20 millimicrometers and a specific surface area greater than about 50 m / g, thoroughly mixed with dimethyl the molecular weight is in the range of about 500 to 200,000, wherein the weight ratio of silicone to silanized silicon is about 19: 1 to 1: 2. The silicone suds suppressor is preferably freely added to a water-soluble or water-dispersible, substantially non-surfactant, detergent-impermeable carrier.

Particularly useful defoamers include self-emulsifying silicone defoamers disclosed in U.S. Patent No. 4,073,118 to Gault et al., Issued February 21, 1978, which is incorporated herein by reference. An example of such a compound is DB-344, sold by Dow Corning, which is a siloxane / Gly coli copolymer.

The above wash solution modifiers are used in concentrations up to about 2%, preferably from about 0.1% to about 1% by weight of the surfactant.

Microcrystalline waxes having a m.p. are in the range of 35-20115 ° C and a saponification number of less than 100, represent other examples of detergent control ingredients for use in the present compositions and are detailed in U.S. Patent No. 4,056,481, Tate, issued October 1, 1977, which is incorporated herein by reference. nittakoon. Microcrystalline waxes are substantially insoluble in water, but can be dispersed in water in the presence of organic surfactants. The m.p. of the recommended microcrystalline waxes is about 65-100 ° C, has a molecular weight in the range of 400-1000 and a penetration value of v-30 measured at 25 ° C according to the ASTM-D1321 procedure. Suitable examples of the aforementioned waxes include: microcrystalline and oxidized microcrystalline rock oil waxes; Fischer-Tropsch and oxidized Fischer-Tropsch wadding; ozokerite; ceresin; montan; beeswax 35 and carnauba wax.

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Alkyl phosphate esters represent the following preferred detergent modifiers that may be used herein. These Preferred Phosphate Esters are primarily monostearyl phosphate and may additionally contain di- and tristearyl phosphates and mono-oleyl phosphate which may contain di- and trioleyl phosphate.

Alkyl phosphate esters often contain some trialkyl phosphate. Thus, the preferred phosphate ester 10 may contain up to about 50 mole percent dialkyl phosphate and up to about 5 mole percent trialkyl phosphate in addition to the monoalkyl ester, e.g., monostearyl phosphate.

Small amounts of amphoteric and / or ampholytic surfactants may be added, but since the washing performance properties of the compositions of this invention are excellent, surfactants in addition to the required ingredients are generally not required.

The following examples are intended to illustrate the compositions of kek-20 according to the invention and their parameters. All values of the compositions refer to percentages by weight.

Example 1

A water wash solution was prepared with the following oil composition: 25______A____________B______C___

C8-alkyltrimethylammonium chloride 0 0 3.0

C 12 alkyltrimethylammonium chloride 3.0 0 0

Sodium C 1-6 linear alkylbenzenesulfonate (C 1-4 LAS) 4.9 5.1 4.9

Sodium C1-methyl-branched alkyl sulphate (C1-AS) 12.6 13.5 12.6

C 1-4 alkyl polyethoxy-35αa ^ 12.5T + ^ 91 ^ 2.5T ^ 3.3 3.4 3.3

Sodium carbonate 24.6 25.4 24.7 ίο 73728

_ A_B___C

Sodium tripolyphosphate 28.1 29.1 28.2

Sodium nitrilotriacetate 8.6 8.9 8.6

Sodium sulphate 12.3 12.7 12.3 5 Sodium silicate (1.6 r) 2.0 2.0 2.0

Optical brightener 0.29_0.30_0.29 +)

Deleted low ethoxylated fractions and fatty alcohol.

Three groups were prepared, each containing four 7.5 x 7.5 cm standard fabric pieces.

7 M

L ta dirty with normal.l la.

A wash portion consisting of one group of sample cloth pieces along with six clean, terry cloth towels and one terry cloth towel soiled with a mixture of fine soil and oily soil was placed in a mini wash system. The amount of laundry was then washed with an amount of Composition A corresponding to the detergent concentration used in the conventional automatic washing method. A mini wash system using such a load corresponds to a conventional automatic washing process. The wash water temperature was 35 ° C and contained 0.086 g / l of water curing agents.

This washing treatment was repeated two more times, once with a second group of fabric samples and composition 13 and once with a third group of fabric samples and 7 with composition C.

Each of the four fabric sample types was then compared to a similar sample washed with a different detergent composition to determine relative soil removal. A rating scale of -4-4, 0 f) was used, with -4 corresponding to very little soil removal, 0 indicating no difference and 4 indicating very high soil removal.

The above procedure as a whole, comprising preparing three groups of a fabric sample containing them, and the three washing cycles were then repeated four more times. To this end, each fabric nipple type of each detergent composition was evaluated a total of four times. These four estimates were then averaged. Finally, the average of these averages was calculated for each detergent composition. This average is called the purification index.

The results were as follows:

__________ A_B_C

Cleaning index ΰ -0.56 +0.38 10 Smallest significant difference (0.05) 0.41 0.41 0.41

Compositions A and C achieved significantly higher soil removal than Composition B, which did not contain the necessary cationic surfactant. Example 2 Wash water solutions were prepared having the following compositions:

Sodium C 1-6 alkyl-3-_A_B_C_D_E_F

sulphate 0 00 0 5,1 0 20 Sodium olefin sulphonate 0 0 0 5,5 0 0 ck sulphonated coconut fatty acid hexyl ester 0 0 6,40 0 0 25 Sodium C 1-6 alkyl paraffin sulphonate 0 5 .4 0 0 0 0 C ^ LAS 5.4 0 0 0 0 5.4 C ~ -AS 11.7 11.7 11.6 11.7 11.7 11.7 30 ammonium chloride 3.1 3.1 3 .0 3.1 3.1 3.1

Cg3AE2 3.1 3.1 3.0 3.1 3.1 3.1

Sodium carbonate 22.4 22.5 22.3 22.4 23.0 22.4

Sodium tripolyphosphate 36.3 36.4 36.1 36.3 36.6 36.3

Sodium nitrilotriacetate 5.7 5.7 5.6 5.7 5.7 5.7 35 Sodium sulphate 9.9 9.9 9.8 9.9 9.9 9.9 il 2i 73728

_A_B_C_D_E_F

Sodium silicate (1.6r) 1.8 1.8 1.8 1.8 1.8

Optical brightener 0.27 0.27 0.27 0.27 0.27 0.27

The soil removal performance of Compositions A-D was then compared by determining the cleaning index according to the procedure set forth in Example 1. The same comparison was then performed for compositions E and F. The results were as follows:

_A_B_C_D E_F

Cleaning index 0 -0.3 -0.4 -0.9 -0.48 0 10 Smallest significant difference (0.05) 0.46 0.46 0.46 0.46 0.31 0.31

Compositions A, B and C achieved significantly higher soil removal than composition D, which did not contain a sulfonate surfactant according to the invention. Composition F provided significantly greater soil removal than Composition E. Thus, it is apparent that sodium C 1-6 alkyl 4-sulfate cannot "replace" the sulfonate surfactant of the invention.

20 Example 3

Wash water solutions were prepared having the following composition:

___A_B_C

C13LAS 5.3 10.6 17.6 25 C45AS 12.3 7 0

C 1-2 alkyltrimethylammonium chloride 3.1 3.1 3.1 ^ 91 ^ 2 5T 3.1 3.1 3.1

Sodium carbonate 22.4 22.4 22.4 30 Sodium tripolyphosphate 36.3 36.3 36.3

Sodium nitrilotriacetate 5.7 5.7 5.7

Sodium sulphate 9.9 9.9 9.9

Sodium silicate (1.6r) 1.8 1.8 1.8

Optical brightener 0.27 0.27 0.27 35 Six 7.5 x 7.5 cm fabric samples of different textile types were prepared. Six cloth samples and six clean terry cloth towels were placed in the mini wash system. The amount of laundry was then washed with washing water containing lipid-dirty dirt and finely divided organic and inorganic dirt with an amount of Composition A corresponding to the detergent content used in the conventional automatic washing method. The textiles were then dried. The same fabric samples and terry cloth towels were washed five more times according to this procedure.

10 After the sixth wash, six fabric samples were measured for difference in "Hunter Whiteness Units Filtered" (Δ HWUF). This measurement corresponds to the amount of dirt that has precipitated on the fabric samples, with a lower number indicating a greater re-precipitation of the dirt. Mean Δ HWUF values were calculated for six samples, ke sk im. AHWUF.

The above treatment was repeated twice more, once with composition B and once with composition C. The results were as follows:

2 0 _A_B_C

Avg. Δ -HWUF -10.5 -14.0 -26.5

The smallest significant difference (C, 05) 2.5 2.5 2.5

The re-precipitation of dirt on the fabric samples was significantly less with Compositions A and B than with Composition C. This result indicates that the surfactant alkyl sul. The phosphate detergent, which was not included in composition C, is essential to prevent re-precipitation of dirt. The dirt precipitation of composition B was also slightly higher than that of composition A.

This is due to the lower content of alkyl sulphate surfactant in composition B.

Example 4

Wash water solutions were prepared with the following composition: 23 7 3 7 2 8 _A_B_C__

Sodium olefin sulfonate 0 0 12.1

Sodium C 1-6 alkyl paraffin-5 sulfonate 0 12.1 0 C - ^ ^ LAS 5.1 5.6 5.6 C45AS 12.1 0 0

C12-allyltrimethylammonium chloride 3.1 3.1 3.1 10 C91AE2.5T 3.1 3'3 3.1

Sodium carbonate 22.5 22.5 22.5

Sodium tripolyphosphate

Sodium nitrilotriacetate 5.7 5.7 5.7

Sodium sulphate 9.9 9.9 9.9 15 Sodium silicate (1.6r) 1.8 1.8 1.8

Optical brightener 0.27 0.27 0.27

The soil removal performance of each composition was then compared by determining the cleaning index as described in Example 1. The results were as follows:

2 0___A B C

Cleaning index 0 -1.06 -0.66

The smallest significant difference (0.05) 0.31 0.31 0.31

Composition A provided significantly higher soil removal than Compositions B and C. It is believed that this is due to the fact that Compositions B and C did not contain an alkyl sulfate surfactant. Thus, an alkyl sulfate surfactant is also necessary to remove dirt.

Example 5 Wash water solutions were prepared corresponding to the following compositions: 73728

/. '-I

A_B_C___D

Sodium tallow -specific alkyl sulphate 0 1]., 8 0 0 linear primary 5 AS 0 0 0 12.8 C13LAS 5.0 5.0 5.5 5.5 C45AS 11.8 0 12.8 0

C 1 H 2 Nitrile triethyl ether ammonium chloride 3.1 3.1 3.3 3.3 10 C91A £ 2 ^ 5t 3.1 3.1 3.3 3.3

Sodium carbonate 22.6 22.6 24.9 24.9

Sodium tripolyphosphate 36.7 36.7 28.4 23.4

Sodium trilotriacetate 5.7 5.7 8.8 8.8

Sodium sulphate 10.5 10.0 10.8 10.8 15 Sodium silicate (1.6r) 1.8 1.8 2.0 2.0

Optical brightener 0.27 0.27 0.27 0.27

The soil removal capacity of Composition A was compared to the soil removal capacity of Composition B by determining the cleaning index according to the procedure described in Example 1. This comparison was also performed between compositions C and D. The results were as follows: ____ A_§_C_D_

Cleaning index 0 -0.96 0 -1.2

The smallest significant difference (0.05) 0.55 0.55 0.7 0.7 25 The soil release performance of Composition A was significantly better than that of Composition B, and Composition C achieved significantly higher soil removal than Composition D. This result is due to the fact that Compositions B and The length of the first portion of the surfactant alkyl sulfate detergent pi-30 is too long.

Example 6

Aqueous washing solutions were prepared corresponding to the following composition: 25 73728

_A_B_C

C13LAS 0 2.4 5.0 C, - AS 16.7 14.3 11.7 4 _> C ^ 2 ~ a 1k yy 1 itr imit ty 1 i - 5 ammonium chloride 3.0 3.0 3.0 C91AE2 ςπ; 3.0 3.0 3.0

Sodium carbonate 22.9 22.9 22.9

Sodium tripolyphosphate 36.6 36.6 36.6

Sodium nitrilotriacetate 5.7 5.7 5.7 10 Sodium sulphate 9.9 9.9 9.9

Sodium silicate (1.6r) 1.8 1.8 1.8

Optical brightener 0.23 0.23 0.23

The soil removal performance of each composition was then compared by determining the swelling index according to the procedure set forth in Example 1-15. The results were as follows:

____________A B_C

Cleaning index _ -0.76 -0.61 0

The smallest significant difference (0.05) 0.35 0.35 0.35

Molecular weight C 1-4 alkyltrimethylammonium chloride: C 1-3 LAS 0 1.7 0.82

Composition C provided significantly better soil removal than Compositions A and B. It is assumed that this was due to the fact that Compositions Λ and B did not contain a sufficient amount of C ^ LAS material to form a sufficient concentration of cationic pin-25 ta-surfactant and alkyl sulfonate surfactant complex. .

_Example 7

Aqueous washing solutions were prepared corresponding to the following compositions:

______________________________________ B

C13LAS 7.3 7.5 C.r AE, S 5.4 5.6 4 b 1 C45AS 5.5 5.7 1 C

_____A_B

r -3 -3 n

91 2.5T U

Sodium carbonate 24.9 25.7

Sodium tripolyphosphate 28.4 29.4 5 Sodium nitrilotriacetate 8.7 9.1

Sodium sulphate 10.8 11.2

Sodium silicate 2.0 2.0

Optical brightener

The soil removal performance of each composition was then compared by determining the cleaning index using the procedure set forth in Example 1. The results were as follows:

_A_B

Cleaning index 0 -0.5

Minimum Significant Difference (0.05) 0.50 0.50 15 Composition A, which contained an optional nonionic surfactant, had only slightly better soil removal performance than Composition B.

Example 8

Wash water solutions were prepared corresponding to the following compositions:

_A_B

C13LAS 5.4 5.5 C45AS 10.1 10.2 C12-alkyltrimethylammonium chloride 2.6 0 25 C ^ 2 “Primary amine (pKa value 10.8) 0 1.8 C91AE2.5T 3.1 3tl

Na trium carbonate 23.4 23.5

Sodium tripolyphosphate

Sodium nitrilotriacetate 5.8 5.9 30 Sodium sulphate 10.1 10.2

Sodium silicate (1,6r)

Optical brightener 0.2 0.2

The soil removal performance of each composition was then compared by determining the cleaning index according to the procedure set forth in Example 1. The initial pH of the washing solution was 10.1. The results were as follows: 27,73728 _A_B_

Cleaning index 0 -0.40

The smallest significant difference (0.05) was 0.97 0.97

Composition B, which contains the amine-5 surfactant material, does not remove significantly less dirt than Composition A, which contains an alkylammonium surfactant.

If dihexyldimethylammonium chloride is replaced by C 1-6 alkylammonium chloride, the performance in cold water, e.g. at 20 ° C, is improved.

Example 9

The following is a composition according to the invention containing a water-soluble salt of a fatty acid: Sodium laurate 5.7 C10H21O- (CH2) 3N r (CH2J) 2OH / 2 2.7 C45AS 7.2 C13LAS 3.9

Sodium sulphate 29.0

Sodium carbonate 16.1 20 Sodium tripolyphosphate 32.2

Sodium silicate (1.6r) 3.0

Optical brightener 0.2

Example 10

The following is a granular detergent composition of the invention having a density of about 0.73 g / cm 3:

C 1-2 alkyltrimethylammonium chloride 3.0 C13LAS 4.9 C4CAS 11.3 C4jAE7 1.6 Sodium carbonate 22.3

Sodium tripolyphosphate 27.5

Sodium nitrilotriacetate 7.8

Sodium sulphate 12.9

Sodium silicate (1.6r) 1.8 35 Optical brightener 0.22 ,, 73728

Z 'J

Example 11

The following is the enzyme-containing detergent composition of the invention:

Enzymes (Alcalase) 0.8 5 C13LAS 5.2 C45AS 13.5 C1-2alkyltrimethylammonium chloride 3.5 C91AE2.5T X'7

Sodium carbonate 13.1 10 Sodium tripolyphosphate 42.0

Sodium nitrilotriacetate 6.6

Sodium sulphate 11.4

Sodium silicate (1.6 r) 2.1

Optical brightener 0.26 15 This composition achieves the desired excellent cleaning ability with respect to conventional soils and is also very effective against enzyme-sensitive stains.

Example 12 The following is a composition according to the invention containing a water-soluble salt of a fatty acid:

Sodium laurate 5.7 C12-alkyltrimethylammonium chloride 2.7 C AE 15 ^ 23 6.5 '25 C45AS 7.2 C13LAS 3.9

Sodium sulphate 27.5

Sodium carbonate 16.1

Sodium tripolyphosphate 32.2 Sodium silicate (1.6 r) 3.0

Optical brightener 0.2

Example 13

_A_B

C13LAS 7.5 7.5 35 C45AS 7.5 7.5 29 7 372 8

_ A__B

C12 alkyltrimethylammonium chloride 2 2 C00AE, c 22 2 3 6.5 5 Na2CO3 20 15

Sodium nitrilotriacetate 0 15

Hydrogenated sodium zeolite A (1-3 μm) 25 20

Na2SO4 25 20 10 Sodium silicate (1.6 r) 2.5 2.5

Other small amounts, water, etc. rest the rest

Claims (3)

30 73728 A detergent composition comprising a mixture of anionic, cationic and optionally nonionic surfactant components, wherein the anionic surfactant component comprises from 4 to 60% by weight of the composition and comprises sulfonate and sulphate type anionic surfactants. and the cationic surfactant component constitutes from 0.25 to 12% by weight of the composition and comprises a monoquaternary ammonium salt, the molar ratio of quaternary ammonium salt to anionic sulfonate being less than 1: 1 and optionally containing up to 70% by weight of the composition. by weight of detergent builder, characterized in that a) the anionic surfactant sulfate comprises a water-soluble alkali metal or ammonium salt or a water-soluble substituted ammonium salt of a primary C 1 -C 5 alkyl sulfate or a secondary C 12-20 alkyl sulfate; B) the monoquaternary ammonium surfactant compound is i) a compound having one C 1-4 alkyl group and the other groups being C 1-4 alkyl groups or C 2-4 hydroxyalkyl groups, or ii) a compound having two C 1-4 alkyl groups; A C 4 -C 4 alkyl group in which the total number of carbon atoms in the two groups is 10 to 14, and in which the other groups are methyl groups and / or hydroxyethyl groups; and c) the anionic surfactant sulfonate is a C-sulfonated fatty acid ester or an ether-containing fatty acid ester having a C 35 A water-soluble salt of a C 1-6 alkyl or aryl sulfonate. Composition according to Claim 1, characterized in that the sum of the equirolar amounts of cationic surfactant and sulfonate surfactant is at least 2%, preferably at least 5% of the total amount of anionic surfactant. Composition according to Claim 1 or 2, characterized in that it contains 3-30%, preferably 5-20%, of alkyl sulphate surfactant, 0.5-8%, preferably 0.5-6% of cationic surfactant and surfactant sulfonate 2-30%, preferably 3-20%. 32 73728