EP1226226B1 - Paste-like detergent - Google Patents

Abstract

The invention relates to a paste-like detergent that contains up to 40 % by weight of an inorganic builder and/or an alkalifying agent and up to 15 % by weight, especially 3 % by weight to 10 % by weight, of an organic builder, and optionally bleaching agents, enzymes, an anti-graying polymer and/or other conventional ingredients. The inventive detergent is further characterized in that it contains 5 % by weight to 25 % by weight of a carbonic acid salt of the general formula (I) R<1>-COOM (I), wherein R<1> represents an alkyl or alkenyl group with 8 to 22 C atoms and M represents an alkali metal, 1 % by weight to 20 % by weight of a long-chain alcohol or alkylether of the general formula (II) R<2>-O-R<3> (II), wherein R<2> represents an alkyl or alkenyl group with 8 to 22 C atoms and R<3> represents hydrogen or an alkyl group with 1 to 6 C atoms, as well as 10 % by weight to 65 % by weight water and/or a short-chain polyol of the general formula (III) X-CH2-(CHY)n-CH2-Z (III), wherein n is an integer from 0 to 2 and X, Y and Z independently represent hydrogen or a hydroxyl group, with the proviso that at least 2 hydroxyl groups are present in the molecule. Although these agents are substantially devoid of non-ionic tenside containing alkoxy groups and of synthetic anion tenside of the sulfate and sulfonate type, they are characterized by excellent washing results.

Description

The present invention relates to paste detergents for use in commercial laundry and a process for their preparation.

Detergents used in the household are tailored to the needs that occur there; they are usually powdery or sufficiently liquid to pour and dose without any problem. One way of avoiding possible metering problems with insufficiently liquid agents is proposed in the European patent application EP 253 151 A2. From this document liquid, sometimes highly viscous detergents based on nonionic and anionic surfactants are known which contain polyethylene glycol as a hydrotrope and which do not have to be metered by the user in liquid form, but are portioned into bags of water-soluble material, for example polyvinyl alcohol.

The pasty detergent described in European Patent Specification EP 0 295 525 B1 consists of a liquid phase below 10 ° C which is formed from nonionic surfactant and a solid phase of certain particle size dispersed therein, which consists of wash alkalis, sequestering agents and optionally anionic surfactants becomes. For surfactants or their mixtures are used, the pour point (solidification point) must be below 5 ° C in order to avoid solidification of the paste at low transport and storage temperatures. This detergent paste is intended for commercial laundries and is so flowable that it can be conveyed via a suction line by means of a conventional feed pump.

Another paste-form detergent containing 40 to 70 wt .-% at room temperature, ethoxylated fatty alcohol having 10 to 20 carbon atoms and a moderate degree of ethoxylation of 1 to 8 and 20 to 50 wt .-% liquid at room temperature ethoxylated and propoxylated fatty alcohol as a nonionic surfactant Contains 10 to 20 carbon atoms and a mean degree of ethoxylation of 2 to 8 and an average degree of propoxylation of 1 to 6 and 1 to 10 wt .-% soap, in the international patent application WO 95/09229. This paste-like detergent or cleaning agent is so pseudoplastic that it is not flowable at room temperature under the action of gravity, but has a significantly lower viscosity in shear and then flow under the action of gravity. The dosage of this paste-like detergent or cleaner is preferably carried out by subjecting the shear-reducing agent to shear, and then metering the flowable agent by means of feed pumps.

In recent years, the demand for the waiver of not sufficiently biodegradable perceived detergent ingredients in commercial laundry. This requirement is particularly difficult to comply because the cleaning performance of the detergent in comparison to the conditions in the household linen much higher demands must be made. This is especially true for the very essential to the cleaning performance contributing surfactant ingredients in which in addition to the liquid phase of pasty agents essentially constituting nonionic surfactants synthetic anionic surfactants, in particular the type of sulfonated alkylbenzenes play an outstanding role in this regard.

It is an object of the present invention to provide a paste detergent for use in commercial laundry which exhibits good washing performance with good storage stability, although it has to do with normally required alkoxy-containing nonionic surfactants and synthetic anionic surfactants of the sulfate and sulfonate type largely omitted.

This could be essentially solved by the use of natural anionic surfactants in combination with a solubilizer system of linear and / or branched-chain long-chain alcohol or alkyl ether and short-chain polyol and / or water.

The present invention is a paste-form detergent for use in commercial laundry, containing 10 wt .-% to 40 wt .-%, in particular 10 wt .-% bis 30 wt .-% inorganic builder and / or alkalizing agent and up to 15 wt .-%, in particular 3 wt .-% to 10 wt .-% organic builder and optionally bleach, enzyme, graying-inhibiting polymer and / or other conventional ingredients, which characterized in that it contains 5% by weight to 25% by weight, in particular 8% by weight to 20% by weight, of a carboxylic acid salt of the general formula I,

R ¹ -COOM (I)

in which R ^{1 is} an alkyl or alkenyl radical having 8 to 22 C atoms and M is an alkali metal, 1 wt .-% to 20 wt .-%, in particular 3 wt .-% to 15 wt .-% linear and / or branched-chain long-chain alcohol or alkyl ether of the general formula II,

R ² -OR ³ (II),

in which R ^{2 is} a linear or branched alkyl or alkenyl radical having 8 to 22 C atoms and R ^{3 is} hydrogen or a linear or branched alkyl radical having 1 to 8 C atoms, 10% by weight to 65% by weight, in particular from 20% by weight to 60% by weight of water and / or short-chain polyol of the general formula III,

X-CH ₂ - (CHY) _n -CH ₂ -Z (III),

in which n is a number from 0 to 2 and X, Y and Z independently of one another denote hydrogen or a hydroxyl group, with the proviso that at least 2 hydroxyl groups are present in the molecule.

A paste detergent according to the invention is preferably substantially free of alkoxy group-containing nonionic surfactant and synthetic anionic surfactant of the sulfate and sulfonate type. Under alkoxy-containing nonionic surfactants are understood to be conventional ethoxylated, propoxylated and / or butoxylated compounds having surfactant character. The term "substantially free" should be understood to mean that at most small amounts, in particular less than 2 wt .-% based on the total agent, are present on such material. Preferably no such substances are incorporated into the compositions according to the invention, although the amounts which are contained, for example, for stabilization in other raw materials for the production of detergents according to the invention can be tolerated.

For example, high-strength zeolite slurries which, as is known, can be stabilized by the presence of small amounts of nonionic surfactant of the fatty alcohol-polyethoxylate type and which can be used in the preparation of compositions according to the invention.

In the case of the carboxylic acid salts of the formula I, the radical R ^{1 may be} linear or branched, for example methyl-branched in the 2-position, preference being given to linear radicals as are generally typical for fatty acids. Optionally, the radical R ^{1 may have} one or more double bonds. Preferably, R ¹ in formula I is a radical having 12 to 18, in particular 12 to 16 carbon atoms. In particular, the alkali metal salts of caprylic, pelargonic, capric, lauric, lauric, myristic, palmitic, palmitoleic, stearic, petroselic, petroselaidic, oleic, linoleic Erucic acid, brassidic acid, clupanodonic acid and mixtures thereof. Preferred alkali metals are sodium and potassium and mixtures of these. In the context of the preparation of compositions according to the invention, it is also possible to start from free carboxylic acids and convert them into the corresponding alkali metal salts by addition of alkalizing agents or other alkaline salts, in particular alkali hydroxides or alkali carbonates, contained in the composition according to the invention anyway.

For the alcohols or ethers of the general formula II, which contribute to the particularly good low-temperature stability of the compositions according to the invention and can additionally contribute to the washing performance, with respect to the radical R ² , the same applies above to the radical R ¹ . In addition to hydrogen, R ³ is preferably a methyl, ethyl, propyl or butyl group, with hydrogen and the methyl group being particularly preferred. In a preferred embodiment of the invention, the compositions contain up to 12% by weight, preferably 4% by weight to 10% by weight, of substances according to general formula II.

The polyols of the general formula III include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, 1,4-butylene glycol and mixtures thereof, with 1,2-propylene glycol being particularly preferred. The compositions according to the invention preferably contain 20% by weight to 35% by weight of water and / or 20% by weight to 55% by weight, in particular 30% by weight to 50% by weight, of substances according to general formula III , If both water and polyol according to formula III are present, their weight ratio is preferably in the range from 1: 1 to 6: 1. especially in the range of 2: 1 to 4: 1. In a preferred embodiment of the invention, the weight ratio of alcohol or alkyl ether of the general formula II to polyol of the general formula III is 1: 1 to 1:20, in particular 1: 2 to 1:15. Small amounts of short-chain monoalcohols, such as methanol, ethanol, propanol and / or isopropanol, may optionally be present in addition, their proportion in the total agent preferably not exceeding 6% by weight.

In addition to the surfactants mentioned, the agents according to the invention may contain amphoteric surfactants and / or nonionic surfactants in the form of alkyl glycosides of the general formula R ⁴ O (G) _x in which R ^{4 is} a primary straight-chain or methyl-branched, especially methyl-branched, aliphatic radical in the 2-position with 8 to 22, preferably 12 to 18 carbon atoms and G is a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number-the size of which can be determined to be analytically determined-which may also be broken values-between 1 and 10; preferably x is 1.2 to 1.4. Such additional surfactant is preferably present in quantities not exceeding 20% by weight, especially in amounts of from 1% to 12% by weight.

The solid phase of the composition according to the invention is essentially formed by the alkalizing agents and builders, it being possible for further particulate auxiliaries to be present if appropriate. The solid phase should be dispersed as homogeneously as possible in the liquid phase. The components of the pasty agent contained as a solid phase should preferably be finely divided and have an average particle size in the range of 5 microns to 200 microns, with at most 10% of the particles Grain size of more than 200 microns have. Surprisingly, it is possible to incorporate relatively coarse-grained solids, for example those containing 20% to 50% of particles with particle sizes greater than 100 μm, into the pasty compositions without any disadvantage. The mean particle size of the particles forming the solid phase is preferably 10 .mu.m to 80 .mu.m and in particular 10 .mu.m to 60 .mu.m, the maximum particle size being less than 300 .mu.m, in particular less than 250 .mu.m. Preferably, 90% by weight of the solid powdery constituents are smaller than 200 μm, in particular smaller than 140 μm. The average particle size can be determined by known methods (for example by means of laser diffraction or Coulter Counter).

The alkalizing agents contained in agents according to the invention are often also referred to as wash alkalis. As stated above, they are at least predominantly associated with the solid phase. Under conditions of use, they provide for a pH in the alkaline range, which is normally in the range from 9 to 13, in particular from 10 to 12 (each measured in 1 weight percent solution of the agent in ion-exchanged water). In addition to alkali metal hydroxide, the preferred alkalizing agent is amorphous alkali metal silicate, in particular sodium metasilicate of the composition Na ₂ O: SiO _{2 of} from 1: 0.8 to 1: 1.3, preferably 1: 1, which is used in particular for preparing anhydrous inventive composition in anhydrous form. In addition to the alkali metal silicate and alkali metal bicarbonate or alkali metal bicarbonate are suitable, but due to absorption processes requires larger amounts of liquid phase and therefore less preferred. The proportion of the agents in alkalizing agents is preferably from 12% by weight to 30% by weight and in particular from 15% by weight to 25% by weight. The alkalizing agent component of the agent according to the invention may consist solely of silicate. Alkalicarbonate or alkali metal bicarbonate is preferably at most up to 30 wt .-%, in particular less than 25 wt .-% present. In particular when a phosphate content is ecologically harmless when using agents according to the invention (for example in the case of a wastewater purification which eliminates phosphates), pasty agents according to the invention may also optionally contain polymeric alkali metal phosphates, such as sodium tripolyphosphate, to be present. Their proportion is preferably up to 30 wt .-%, in particular 15 wt .-% to 25 wt .-%, based on the total agent, wherein the proportion of other solids, for example, the alkali metal silicate and / or aluminosilicate, if appropriate, accordingly can be reduced.

Particularly suitable organic builders are monomeric polycarboxylic acids or hydroxycarboxylic acids, such as citric acid or gluconic acid or salts thereof, and also those from the class of aminopolycarboxylic acids and polyphosphonic acids. The aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologs, with N, N-bis (carboxymethyl) aspartic acid being preferably used. Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and their higher homologs, such as diethylenetetramine tetra (methylenephosphonic acid). The abovementioned acids are usually used in the form of their alkali metal salts, in particular the sodium or potassium salts. The builders which can also be used include homopolymeric and / or copolymeric carboxylic acids or their alkali metal salts, the sodium or potassium salts being particularly preferred here as well. Particularly suitable are polymeric carboxylates or polymeric carboxylic acids having a molecular weight of at least 350, in the form of their water-soluble salts, in particular in the form of sodium and / or potassium salts, as oxidized polysaccharides according to International Patent Application WO 93/08251, polyacrylates , Polymethacrylates, polymaleates and in particular copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those of 50 to 70% of acrylic acid and 50 to 10% of maleic acid, as are characterized, for example, in European Patent EP 022 551. The molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, although less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers. Vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-%. As polymeric carboxylates or carboxylic acids, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C _3- C ₄ monocarboxylic acid, in particular of the (meth) acrylic acid. The second acidic monomer or its salt may be a derivative of a C ₄ -C ₈ dicarboxylic acid, with maleic acid being preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred terpolymers contain from 60 to 95 wt .-%, in particular 70 to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 to 40 wt .-%, preferably 10 to 30% by weight of vinyl alcohol and / or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth) acrylic acid to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2.5: 1 , Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain 40 to 60 wt .-%, in particular 45 to 55 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 wt .-% to 30 wt .-%, preferably 15 Wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide be mono-, di- or oligosaccharides are preferred. Particularly preferred is sucrose. Through the use of the third monomer, predetermined breaking points are incorporated into the polymer, which are probably responsible for the good biodegradability of such polymers. Preference is also given to using those polymers which are neutralized either completely or at least partially, in particular more than 50%, based on the carboxyl groups present. Particularly preferred polymeric polycarboxylates are prepared by methods described in German Patent Application DE 43 00 772 and German Patent DE 42 21 381. Also useful are polyacetal carboxylic acids such as described in US Pat. Nos. 4,144,226 and 4,146,495 which are obtained by polymerization of esters of glycolic acid, introduction of stable terminal end groups, and saponification to the sodium or potassium salts. Also suitable are polymeric acids which are obtained by polymerization of acrolein and disproportionation of the polymer to Canizzaro by means of strong alkalis. They are composed essentially of acrylic acid units and vinyl alcohol units or acrolein units. The proportion of organic builder materials in the pasty agent of the invention is preferably up to 10 wt .-% and in particular 2 wt .-% to 8 wt .-%.

Suitable inorganic builders for use in compositions according to the invention are, in addition to the abovementioned phosphate, crystalline alkali metal silicates and finely divided alkali metal aluminosilicates, in particular zeolites of the NaA, X and / or P type. Suitable zeolites normally have a calcium binding level in the range of 100 to 200 mg CaO / g, which can be determined according to the information in German Patent DE 24 12 837 on. Their particle size is usually in the range of 1 .mu.m to 10 .mu.m. They are preferably used in dry form. The water contained in bound form in the zeolites does not interfere in the present case. Crystalline silicates which may be present alone or in a mixture with said aluminosilicates are preferably crystalline phyllosilicates of the formula NaMSi _x O _{2 +} xyH ₂ O, in which M is hydrogen or sodium, x is a number from 1.9 to 4 and y is a number from 0 to 20. Preferred values for x are 2, 3 and 4. Such crystalline sheet silicates are For example, in European Patent Application EP 164 514 described. In particular, both β- and ###- sodium disilicates Na ₂ Si ₂ O ₅ yH ₂ O are preferred, whereby β-sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171. Useful crystalline silicates are commercially available under the names SKS-6 (manufacturer Hoechst) and Nabion® 15 (manufacturer Rhone-Poulenc). The content of inorganic builder material in the paste according to the invention may optionally be up to 40% by weight, preferably up to 25% by weight and in particular 10% by weight to 20% by weight.

In addition, a paste-form agent according to the invention may contain chlorine and / or oxygen-containing oxidizing agent and optionally bleach activator. Alkali hypochlorites and inorganic peroxygen compounds are used in particular as the oxidizing agent, with hydrogen peroxide and also sodium perborate tetrahydrate and sodium perborate monohydrate being of particular importance in addition to sodium percarbonate. Further suitable oxidizing agents are, for example, persulfates, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid. Preference is given to using sodium hypochlorite, sodium percarbonate, sodium persulfate and / or sodium perborate monohydrate. Oxidizing agents may preferably be present in agents according to the invention in amounts of up to 25% by weight and in particular of 10% by weight to 20% by weight.

The oxidizing power of such oxidizing agents can be improved by the use of bleach activators which form peroxycarboxylic acids under perhydrolysis conditions. For such bleach activators are numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, sodium isononanoyl-oxybenzolsulfonat and triacetin (glycerol triacetate), and acylated sugar derivatives, such as pentaacetylglucose, have become known in the literature. Preferably, a bleach activator is used which forms peracetic acid under the washing conditions, with tetraacetylethylenediamine being particularly preferred. Agents according to the invention preferably contain up to 10% by weight, in particular from 3% by weight to 8% by weight, of bleach activator. By adding bleach activators, the bleaching action of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C., substantially the same effects as with the peroxide liquor occur at 95 ° C. alone. Particularly at even lower temperatures, the use of transition metal salts and complexes, as described, for example, in European Patent Applications EP 0 392 592, EP 0 443 651, EP 0 458 397, EP 0 544 490, EP 0 549 271, EP 0 630 964 or EP 0 693 550, as so-called bleach catalysts in addition to or instead of the conventional bleach activators, result in an increase in the bleaching performance. Also suitable are, in particular, the transition metal complexes known from German patent applications DE 195 29 905, DE 195 36 082, DE 196 05 688, DE 196 20 411 and DE 196 20 267 as bleach-activating catalysts. Bleach activating transition metal complexes, in particular with the central atoms Mn, Fe. Co. Cu, Mo, V, Ti and / or Ru, are contained in compositions of the invention in amounts of preferably not more than 1 wt .-%, in particular from 0.0025 wt .-% to 0.25 wt .-%.

In addition, an agent according to the invention may contain further washing auxiliaries, which may normally be present in amounts of up to about 15% by weight, based on the finished composition. For example, enzymes, grayness inhibitors, soil release agents, optical brighteners, foam regulators and / or dyes and fragrances can be used as such laundry aids. As far as fragrances are contained, which are generally liquid, they go into the liquid phase of the invention means. Due to their small amount, however, they have no significant influence on the flow behavior of the pastes.

Enzymes optionally present in the compositions according to the invention are, in particular, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, Xylanases, hemicellulases. Cellulases, peroxidases and oxidases or mixtures thereof, wherein the use of protease, amylase, lipase and / or cellulase is particularly preferred. The proportion is preferably 0.1 wt .-% to 1.5 wt .-%, in particular 0.3 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner to carriers and / or embedded in coating substances or incorporated as concentrated, optionally anhydrous liquid formulations in the pastes. Useful proteases are described, for example, in International Patent Applications WO 91/02792, WO 92/21760, WO 93/05134, WO 93/07276, WO 93/18140, WO 93/24623, WO 94/02618, WO 94/23053, WO 94 / 25579, WO 94/25583, WO 95/02044, WO 95/05477, WO 95/07350, WO 95/10592, WO 95/10615, WO 95/20039, WO 95/20663, WO 95/23211, WO 95 / 27049, WO 95/30010, WO 95/30011, WO 95/30743 and WO 95/34627. Enzymes stabilized against oxidative damage, for example the proteases or amylases known under the trade names Durazym® or Purafect® OxP or Duramyl® or Purafect® OxAm, are preferably used.

Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preferably, sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Dirt-releasing copolyesters of the type mentioned as well as their use in detergents have been known for a long time. For example, German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. German laid-open specification DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. German laid-open specification DT 22 53 063 mentions acidic textile auxiliaries which are a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol. European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. European Patent EP 185,427 discloses methyl or ethyl end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer. European Patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units. The proportion of grayness inhibitors and / or soil-release active ingredients in compositions according to the invention is generally not more than 2% by weight and is preferably from 0.5% by weight to 1.5% by weight. In a preferred embodiment of the invention, the agent is free of such agents.

As an optical brightener for particular textiles made of cellulose fibers (for example, cotton), for example, derivatives of diaminostilbene disulfonic acid or their alkali metal salts may be included. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Further, brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. For polyamide fibers, brighteners of the 1,3-diaryl-2-pyrazolines type are particularly suitable, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similarly structured compounds. The content of the composition of optical brighteners or Aufliellergemischen is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%. In a preferred embodiment of the invention, the agent is free of such agents.

The customary foam regulators that can be used in the compositions according to the invention include, for example, polysiloxane-silica mixtures, the compositions contained therein finely divided silica is preferably silanated. The polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof. Further defoamers are paraffin hydrocarbons, in particular M-icroparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 C atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each have 12 to 22 carbon atoms. Particular preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate with C ₁₆ - to C ₁₈ -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight. In many cases, a suitable selection of the surfactants can reduce the tendency for foaming, so that the use of defoaming agents in a preferred embodiment of the invention can be completely dispensed with.

The paste-form detergents according to the invention are preferably substantially free of water and organic solvents in the presence of bleaches, that is to say in this case preferably polyol instead of water according to formula (III) is present. By "substantially free of water" is meant a state in which the content of free, that is not in the form of water of hydration and water of constitution lying water below 3 wt .-%, preferably below 2 wt .-% and in particular below 1 % By weight. Dehydrating agents, for example in the form of water-crystal-binding salts such as anhydrous sodium acetate, calcium sulfate, calcium chloride, sodium hydroxide, magnesium silicate, or metal oxides such as CaO, MgO, P can also be used to increase the physical stability and also the chemical stability of the bleaching component component present and optionally present ₄ O ₁₀ or Al ₂ O ₃ , are used. Such dehydrating agents with which the water content of inventive compositions can be reduced to particularly low levels are in amounts of preferably 1 wt .-% to 10 wt .-% and in particular 2 wt .-% to 8 wt .-% in the compositions according to the invention available.

In the preparation of inventive paste-form detergent expediently the carboxylic acid salts of the formula I and the solubilization system of the alcohols or ethers of formula II and water and / or the polyols of formula III are mixed to a homogeneous premix and incorporated into this premix, the solids and optionally other ingredients , If the particulate solids are not sufficiently finely divided, one or more milling steps may be inserted.

A paste-form agent according to the invention preferably has a viscosity in the range from 80,000 mPa · s to 250,000 mPa · s, in particular 100,000 mPas to 250,000 mPas, measured at 25 ° C. with a Brookfield rotational viscometer (spindle No. 7) at 5 Revolutions per minute. Under otherwise identical conditions, the viscosity at 50 revolutions per minute is preferably 20,000 mPas to 80,000 mPas. The paste-form detergent and cleaner in a particular embodiment of the invention preferably has a viscosity at room temperature such that it is not flowable under the action of gravity. Preferably, it is then particularly structurally viscous, that is, it has a significantly lower viscosity in shear and is flowable under the action of gravity, and it is particularly preferred a viscosity in the range of 8,000 mPas to 45,000 mPas at 25 ° C and a shear rate of 0.01 s ^-1 , to be determined using a CS rheometer CVO from Bohlin with measuring system plate / plate, plate spacing 2 mm. When sufficient shear forces are exerted, a composition according to the invention preferably has a considerable, generally 100 to 2000 times lower viscosity, which lies at a shear rate of 10 s ^-1 and otherwise identical measuring conditions, in particular in the range from 40 mPas to 60 mPas. The numerical values for the viscosity refer to the reading after a measuring time of 3 minutes in order to take into account any thixotropic effect of the paste. The reduction in viscosity under shear is largely reversible, that is, after completion of the shear, the agent goes back to its original physical state without the occurrence of segregation. In this context, it should be noted that the viscosities mentioned are not based on measurements directly after preparation of the paste, but on stored, so to speak, in equilibrium pastes, since the shear forces acting in the context of the manufacturing process lead to a lower paste viscosity, which only increases over time to the definitive final viscosity. Storage periods of 1 month are generally sufficient.

An agent according to the invention normally has a density in the range from 1.2 kg / l to 1.4 kg / l. The composition according to the invention can be metered in with conventional equipment for metering pastes, as described, for example, in International Patent Application WO 95/29282, German Patent Application DE 196 05 906, German Patent DE 44 30 418 or European Patents EP 0 295 525 or EP 0 356 707 have been described. A device which is particularly well suited for the metering of pseudoplastic paste-form detergents is known, for example, from International Patent Application WO 95/09263 and is preferably used for the metering of pseudoplastic pastes according to the invention. If appropriate, the washing and cleaning agents according to the invention can also be filled into foil pouches in advance, with water-soluble foils being used in the case of essentially anhydrous compositions according to the invention. Such films are described, for example, in European Patent Application EP 0 253 151.

Examples

The following table gives examples of the composition of inventive detergents ( M1 to M8 ). The pasty detergents had very good storage stability and, despite the absence of alkoxy group-containing nonionic surfactant and synthetic anionic surfactant, had excellent cleaning performance at least equal to that of known pasty detergent containing alkoxy group-containing nonionic surfactant and synthetic anionic surfactant. <u> Table 1: Composition of paste detergent (% by weight) </ u> M1 M2 M3 M4 M5 M6 M7 M8 M9 M10 M11 Soap ^a) - 16 10 - - - - - - - - Fatty acid ^b) 16 - - 8th 8th 8th 8th 8th 15 10 5 lauric acid - - 4 4 4 4 4 4 - - - lsotridecanol 6 6 6 6 6 6 - 6 3 3 3 2-hexyl-decan-1-ol - - 1.5 1.5 1.5 - 1.5 - - - - 2-butyl-octan-1-ol - - - - - 1.5 6 1.5 3 3 3 Di-n-octyl ether - - 2.5 2.5 2.5 2.5 2.5 2.5 - - - 1.2-propylene glycol 40 40 21.7 20.1 5 5 20.1 5 - - - ethanol - - 4 4 4 4 4 4 - - - water - - - - 23.4 27.4 - 18.4 34.5 29.5 24.5 Polyglucoside I ^c ) - - - - 2 - - 3 2 2 2 Polyglucoside II ^d ) - - - - 4 - - - - - - Amphoteric surfactant ^e) - - - - 2 4 - 4 - - - sodium citrate 4 4 3 3 3 3 3 3 3.5 3.5 3.5 Org. Builder ^f) 3 3 3 3 3 3 3 3 6 6 6 metasilicate 19.7 25.2 - 10 10 - 15 20 5 5 - sodium - - 15 5 5 15 - - 10.3 10.3 15.3 Zeolite Na-A - - 4 4 4 4 4 4 2 2 2 Sodium hydroxide ^g) 5.5 - - 3.6 3.6 3.6 3.6 3.6 10 20 30 Na-perborate - - 12 12 - - 12 - - - - TAED - - 4 4 - 4 - - - - Complexing agent I ^h) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2 2 2 Complexing agent II ⁱ⁾ - - 3 3 3 - - - Sodium nitrilotriacetate - - - - - 3 3 3 - - - CMC / MC ^j) 1 1 1 1 1 1 1 1 - - - Perfume ^k) 3 3 3 3 3 3 3 3 0.2 0.2 0.2 Opt. Brightener 0.3 0.3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 protease - - 0.3 0.3 - - 0.3 - - - - a) coconut fatty acid Na salt (Edenor® K 12/18, manufacturer Henkel KGaA) b) palm kernel fatty acid (Edenor® PK 1805, manufacturer Henkel KGaA) c) C _8-10 -alkyl glucoside, degree of oligomerization about 1.2 d) C _12-14 -alkyl glucoside, degree of oligomerization about 1.2 e) N, N-dimethyl-N (C _8-18 cocoamidopropyl) ammonium acetobetaine based on C _8-18 fatty acid f) Polymeric polycarboxylate (Norasol®, manufacturer Norsohaas AG) g) 50% in water h) phosphonate (Turpinal® 2 NZ, manufacturer Henkel KGaA) i) Na iminodisuccinate (manufacturer Bayer AG) j) carboxymethylcellulose-methylcellulose mixture (2.5: 1) k) citruster oil (96% d-limonene)

Claims (17)

1. A pasty washing agent for use in commercial washing, including from 10 wt.-% to 40 wt.-% inorganic builder and/or alkalizing agent and up to 15 wt.-%, particularly from 3 wt.-% to 10 wt.-% organic builder and optionally bleaching agent, enzyme, graying inhibitor polymer and/or other usual ingredients, characterized in that it includes from 5 wt.-% to 25 wt.-% of a carboxylic acid salt of general formula I
   
           R¹-COOM     (I),
   
   wherein R¹ represents an alkyl or alkenyl residue with 8 to 22 C atoms and M represents an alkali metal, from 1 wt.-% to 20 wt.-% of a linear and/or branched long-chain alcohol or alkyl ether of general formula II
   
           R²-O-R³     (II),
   
   wherein R² represents a linear or branched alkyl or alkenyl residue with 8 to 22 C atoms and R³ represents hydrogen or a linear or branched alkyl residue with 1 to 8 C atoms, from 10 wt.-% to 65 wt.-% water and/or short-chain polyol of general formula III
   
           X-CH₂-(CHY)_n-CH₂-Z     (III),
   
   wherein n represents a number from 0 to 2, and X, Y and Z independently represent hydrogen or a hydroxyl group, with the proviso that at least 2 hydroxyl groups are present in the molecule.
2. The agent according to claim 1, characterized in that it includes from 8 wt.-% to 20 wt.-% of said carboxylic acid salt of general formula I.
3. The agent according to claim 1 or 2, characterized in that R¹ in said carboxylic acid salt in accordance with formula I represents a residue with 12 to 18, particularly 12 to 16 carbon atoms.
4. The agent according to any of claims 1 to 3, characterized in that the surfactant in accordance with formula I is selected from the alkali metal salts of caprylic acid, pelargonic acid, capric acid, lauric acid, lauroleic acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, stearic acid, petroselic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, eleostearic acid, arachic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid and mixtures thereof.
5. The agent according to any of claims 1 to 4, characterized in that it includes from 3 wt.-% to 15 wt.-% of long-chain alcohol or alkyl ether of general formula II.
6. The agent according to any of claims 1 to 5, characterized in that it includes from 20 wt.-% to 35 wt.-% water and/or from 20 wt.-% to 55 wt.-%, particularly from 30 wt.-% to 50 wt.-% substances in accordance with general formula III.
7. The agent according to any of claims 1 to 6, characterized in that it includes water and polyol in accordance with formula III at a weight ratio ranging from 1:1 to 6:1, particularly from 2:1 to 4:1.
8. The agent according to any of claims 1 to 7, characterized in that the weight ratio of alcohol or alkyl ether of general formula II to polyol of general formula III is from 1:1 to 1:20, particularly from 1:2 to 1:15.
9. The agent according to any of claims 1 to 8, characterized in that it includes from 10 wt.-% to 30 wt.-% inorganic builder and/or alkalizing agent and/or from 3 wt.-% to 10 wt.-% organic builder.
10. The agent according to any of claims 1 to 9, characterized in that it includes from 12 wt.-% to 30 wt.-%, particularly from 15 wt.-% to 25 wt.-% alkalizing agent.
11. The agent according to any of claims 1 to 10, characterized in that it includes up to 25 wt.-%, particularly from 10 wt.-% to 20 wt.-% inorganic builder.
12. The agent according to any of claims 1 to 11, characterized in that the components of the pasty agent included as solid phase are finely particulate, having a mean grain size ranging from 5 µm to 200 µm, particularly from 10 µm to 80 µm.
13. The agent according to any of claims 1 to 12, characterized in that a maximum of 10% of the particles of the components included as solid phase have a grain size of greater than 200 µm.
14. The agent according to any of claims 1 to 13, characterized in that it includes from 0.1 wt.-% to 1.5 wt.-%, particularly from 0.5 wt.-% to 1 wt.-% enzyme, especially protease, amylase, lipase and/or cellulase.
15. The agent according to any of claims 1 to 6 or 8 to 14, characterized in that it includes from 1 wt.-% to 10 wt.-%, particularly from 2 wt.-% to 8 wt.-% dehydrating agent.
16. The agent according to any of claims 1 to 15, characterized in that it has a viscosity at 25°C of from 80,000 mPa·s to 250,000 mPa·s, measured with a Brookfield rotational viscometer (spindle No. 7) at 5 revolutions per minute and, under otherwise identical conditions, a viscosity of from 20,000 mPa·s to 80,000 mPa·s at 50 revolutions per minute.
17. A method for the production of pasty washing agents according to any of claims 1 to 16 by mixing the carboxylic acid salts of formula I and the solubilizer system comprising the alcohols or ethers of formula II and water and/or polyols of formula lll into a homogeneous premix, followed by incorporating the solids and optionally further components in said premix.