EP0876470A1

EP0876470A1 - Paste-form washing and cleaning agents

Info

Publication number: EP0876470A1
Application number: EP96931801A
Authority: EP
Inventors: Thomas Merz; Khalil Shamayeli; Günther Amberg; Heinz-Manfred Wilsberg
Original assignee: Henkel Ecolab GmbH and Co KG
Current assignee: Ecolab GmbH and Co OHG
Priority date: 1995-09-21
Filing date: 1996-09-13
Publication date: 1998-11-11
Also published as: US6187739B1; PL324968A1; DE19535082A1; WO1997011150A1; CA2232574A1; BR9610591A; NO981123L; NO981123D0

Abstract

Described is a paste-form washing and cleaning agent including 20 to 58 % by wt. of, in particular non-ionic, surfactants, 2 to 40 % by wt. of builders and 2 to 40 % by wt. of a bleach containing a peroxy oxidizing agent and a bleach activator.

Description

Paste-like detergent and cleaning agent

The invention relates to bleach-containing, paste-like detergents and cleaning agents and to a process for their production.

Detergents used in the household are tailored to the needs occurring there; they are usually powdery or sufficiently liquid to be poured out and dosed easily. Since liquid detergents of this type are also said to be stable in storage within relatively wide temperature ranges, additions of organic solvents and / or hydrotropes are frequently added, but these do not themselves contribute to the washing or cleaning result and are therefore undesirable. A possibility for circumventing possible dosing problems with insufficiently liquid agents is proposed in the European patent application EP 253 151 A2. From this document, liquid, partly highly viscous detergents based on nonionic and anionic surfactants are known, which contain polyethylene glycol as hydrotrope and which do not have to be dosed by the user in liquid form, but rather are packed in portions in bags made of water-soluble material, for example polyvinyl alcohol.

The paste-like detergent described in European patent EP 295 525 B1 consists of a phase which is liquid in the temperature range below 10 ° C. and which is formed from nonionic surfactant, and a solid phase of a certain particle size dispersed therein, which consists of washing alkalis, sequestering agents and optionally anionic surfactants is formed. For this purpose, surfactants or their mixtures are used, the pour point (solidification point) of which 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 fluid that it can be conveyed via a suction line using a conventional feed pump. It has been found, however, that such pastes cannot always ensure the homogeneity of their ingredients satisfactorily during their production and often tend to separate even during storage. The segregation affects not only the sepa- - 2 -

ration of the solid from the liquid components, but also the phase separation of the liquid ingredients.

Another paste-like detergent which, as a nonionic surfactant, comprises 40 to 70% by weight of ethoxylated fatty alcohol which is liquid at room temperature and has 10 to 20 carbon atoms and an average degree of ethoxylation of 1 to 8 and 20 to 50% by weight of ethoxylated and propoxylated fatty alcohol with 10 to 20 carbon atoms and an average degree of ethoxylation of 2 to 8 and an average degree of propoxylation of 1 to 6 and 1 to 10 wt .-% soap is described in international patent application WO 95/09229. This pasty detergent is so structurally viscous that it is not flowable at room temperature under the influence of gravity, but has a significantly lower viscosity when sheared and is then flowable under the influence of gravity. The metering of this pasty detergent or cleaning agent is preferably carried out by subjecting the agent to lowering the viscosity to shear and then metering the flowable agent by means of feed pumps.

From European patent EP 0 448 581 B1 a liquid to pasty, bleach-containing detergent is known, each based on the detergent, (A) 20 to 35% by weight of a surfactant component of the composition (AI) 1 to 4% by weight. % anionic surfactants from the class of the sulfonates and the soaps, which are present as alkali salts, (A2) 16 to 34% by weight of nonionic surfactants with a pour point of at most 10 ° C., the alkoxylated linear alcohols or in 2- Methyl-branched alcohols with 10 to 18 carbon atoms or mixtures thereof, (B) 10 to 35% by weight of complexing or alkaline earth metal ion-binding builder salts, (C) 15 to 40% by weight sodium metasilicate, (D) 8 to 25% by weight of bleaching persalts, (E) up to 15% by weight of other detergent constituents and (F) less than 3% by weight of water, with the proviso that the sum of the components (B + C) = 30 is up to 60% by weight.

The washing and cleaning agents described in the aforementioned publication are highly viscous and have thixotropic properties. Even if the status stability of the incorporated oxidizing agents is said to be sufficient, it has been found, however, that their cleaning action is unsatisfactory, particularly with regard to bleachable soiling. Particularly with detergents and cleaning agents that are used as full detergents, a particularly good bleaching effect is required in order to be able to completely remove even bleachable dirt, such as food residues and food dyes.

The present invention was based on the object of providing a pasty washing and cleaning agent which has good storage stability and contains both oxidizing agents and bleach activators which increase the oxidizing power, so that it has an excellent bleaching action against bleachable dirt.

The present invention relates to a pasty washing or cleaning agent containing 20% by weight to 58% by weight of a surfactant component (A) which at least partially consists of nonionic surfactant, 2% by weight to 40% by weight. % Builder substances (B), and 2% by weight to 40% by weight of bleaching component (C), which is characterized in that component (C) contains peroxygen-containing oxidizing agent and bleach activator.

The surfactants of component (A) or their nonionic subcomponent are preferably selected from ethoxylated and optionally propoxylated alcohols of the general formula I,

R ¹ - (OC ₂ H ₄ ) _rn - (OC ₃ H ₆ ) _π -OH (I) in which R ¹ denotes an alkyl or alkenyl radical with 6 to 11 carbon atoms, m values from 3 to 15 and n values can assume from 0 to 6, and / or of the general formula II,

R ² - (OC ₂ H ₄ ) ₀ - (OC ₃ H ₆ ) _p -OH (II) in which R ² denotes an alkyl or alkenyl radical with 12 to 22 C atoms, and o values from 3 to 15 and p Can assume values from 0 to 6.

The liquid phase of the agent according to the invention is formed by component (A), the nonionic surfactants according to the invention, preferably ethoxylated and optionally propoxylated alcohols with the general formulas I and / or II, which may have different carbon chain lengths. The viscosity of the agent according to the invention can be adjusted by combining ethoxylated / propoxylated alcohols with the formulas (I) and (II). In the compounds of the formulas I and II, the radicals R ¹ and R ^{2 can be} linear or branched, for example methyl-branched in the 2-position (oxo alcohols). The nonionic surfactant according to formula (I) preferably has a carbon chain length of 6 to 11 carbon atoms and an average degree of alkoxylation m of 3 to 15. The nonionic surfactant according to formula (II) preferably has a carbon chain length with 12 to 22 carbon atoms, in particular 12 to 15 carbon atoms, and an average degree of alkoxylation o of 3 to 15, in particular 5 to 15. The short-chain ethoxylated / propoxylated alcohols of the formula (I) and the long-chain ethoxylated / propoxylated alcohols of the formula (II) are preferably in weight ratios of 2: 1 to 1: 2. In a preferred embodiment, component (A) contains 20 to 40% by weight, based on component (A), surfactants with the formula I and / or II and from 60 to 80% by weight, based on component ( A), further anionic or nonionic surfactants usually used in washing and cleaning agents.

As further surfactants, component (A) can contain up to 10% by weight, preferably 0.5% by weight to 8% by weight, based on component (A), of synthetic anionic surfactants. Suitable synthetic anionic surfactants, which can preferably be incorporated into the composition according to the invention in solid, finely divided, largely anhydrous form, include, in particular, those of the sulfonate or sulfate type which are normally present as alkali salts, preferably as sodium salts. In particular, the surfactants of the sulfonate type mentioned can also be used in the form of their free acids. Suitable anionic surfactants of the sulfonate type are alkylbenzenesulfonates with linear C ₉ . ₁₃ -alkyl chains, especially dodecylbenzenesulfonate, linear alkanesulfonates with 1 1 to 15 carbon atoms, as can be obtained by sulfochlorination or sulfoxidation of alkanes and subsequent saponification or neutralization, salts of sulfofatty acids and their esters, which are sulfonated, in particular in the α-position saturated C ₁₂ to C ₁₈ fatty acids and lower alcohols, such as methanol, ethanol and pro derive panol, and olefin sulfonates, such as are formed, for example, by sulfonation of terminal C ₁₂ to C ₈ olefins and subsequent alkaline hydrolysis. Suitable surfactants of the sulfate type are, however, in particular the primary alkyl sulfates with preferably linear alkyl radicals having 10 to 20 carbon atoms, which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as the counter cation. The derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are particularly suitable. Accordingly, the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl sulfates contain a tallow alkyl radical, ie mixtures with essentially hexadecyl and octadecyl radicals. The alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. The agents can also contain the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.

Furthermore, up to 20% by weight, preferably 0.5% by weight to 8% by weight, in each case based on the total composition, can be present in the composition according to the invention as part of component (A). In particular, the alkali salts of saturated and / or unsaturated C ₁₂ come as soaps. ₁₈ fatty acids, for example coconut, palm kernel or tallow fatty acid, in question. The use of salts of a carboxylic acid mixture of, in each case based on the total carboxylic acid mixture, from 2% by weight to 8% by weight of C ₄ to up to 1% by weight of C ₅ to 18% is particularly preferred. -% to 24% by weight C ₁₆ -, up to 3% by weight C, ₇ -, 20% by weight to 42% by weight C ₁₈ - and 30% by weight to 44% by weight C ₂ or ₂₂ carboxylic acid.

Suitable cold stabilizers are branched alcohols having 6 to 15 carbon atoms, preferably 10 to 13 carbon atoms. The paste-like detergents according to the invention are essentially free of water and organic solvents. Under "in essentially free of water "is understood to mean a state in which the content of free water, that is to say which is not in the form of hydrate water and water of constitution, is preferably below 3% by weight, particularly preferably below 2% by weight and in particular below Higher water contents are disadvantageous because they disproportionately increase the viscosity of the agent and, in particular, reduce its stability. Organic solvents, which include the low molecular weight and low-boiling alcohols and ether alcohols commonly used in liquid concentrates, and hydrotropic compounds are excluded traces that can be introduced with individual active substances are preferably also not present.

The solid phase of the preferred agent is essentially formed by components (B) and (C), that is to say by the builder substances and the bleach component, it being possible for washing alkalis and optionally other auxiliaries to be present. The solid phase should be dispersed as homogeneously as possible in the liquid surfactant phase. The constituents of the paste-like composition contained as a solid phase should be finely divided and have an average grain size in the range from 5 μm to 200 μm, with at most 10% of the particles having a grain size of more than 200 μm. Surprisingly, it is possible to incorporate relatively coarse-grained solids, for example those which contain 20% to 50% particles with particle sizes above 100 μm, without disadvantage into the paste-like compositions. The mean grain size of the particles forming the solid phase is preferably 10 μm to 80 μm and in particular 10 μm to 60 μm, the maximum grain size being below 300 μm, in particular below 250 μm. 90% by weight of the solid powdery constituents are preferably less than 200 μm, in particular less than 140 μm. The average grain size can be determined by known methods (for example by means of laser diffraction or a Coulter Counter).

In addition to monomeric polycarboxylic acids such as citric acid or its salts, suitable builders are those from the class of the aminopolycarboxylic acids and polyphosphonic acids. The aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues, preference being given to using N, N-bis (carboxymethyl) aspartic acid. Suitable poly Phosphonic acids are l-hydroxyethane-l, l-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and their higher homologs, such as, for example, diethylenetetraminetetra (methylenephosphonic acid). The abovementioned acids are usually used in the form of their alkali metal salts, in particular the sodium or potassium salts. Sodium nitrilotriacetate is preferably used in proportions of up to 10% by weight, in particular 2% by weight to 6% by weight. Suitable builders also include monomeric polycarboxylic acids or hydroxypolycarboxylic acids, in particular in the form of the alkali salts, for example sodium citrate and / or sodium gluconate. The preferred builders include homopolymeric and / or copolymeric carboxylic acids or their alkali metal salts, with the sodium or potassium salts being particularly preferred. Polymer carboxylates or polymeric carboxylic acids with a relative molecular weight of at least 350, in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, have proven to be particularly suitable, such 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% acrylic acid and 50 to 10% maleic acid, as are characterized, for example, in European patent EP 022 551. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit 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% by weight. As polymeric carboxylates or carboxylic acids, it is also possible to use polymers which contain two unsaturated acids and / or their salts 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 mono-ethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ mono- carboxylic acid, especially from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, vinyl alcohol derivatives are preferred which are an ester of short-chain carboxylic acids, for example of C 1 -C ₄ -carboxylic acids, with vinyl alcohol. Preferred polymers contain 60 to 95% by weight, in particular 70 to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleinate and 5 to 40% by weight, preferably 10 to 30 wt .-% vinyl alcohol and / or vinyl acetate. Tepolymers in which the weight ratio (meth) acrylic acid to maleic acid or maleinate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2.5: 1, are very particularly preferred. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt may also be a derivative of an allyl sulfonic acid in the 2-abutment condition with an alkyl group, preferably with a C _r C ₄ - alkyl group, or an aromatic radical which is preferably benzene or derived benzene derivatives is substituted. Preferred polymers contain 40 to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 to 30% by weight, preferably 15 up to 25% by weight of methallylsulfonic acid or methyl sulfonate and as the third monomer 15 to 40% by weight, preferably 20 to 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Saccharose is particularly preferred. By using the third monomer, predetermined breaking points are built into the polymer, which are probably responsible for the good biodegradability of such polymers. The polymers used can be prepared by any of the known and customary processes. Those polymers which are neutralized either completely or at least partially, in particular to more than 50%, based on the carboxyl groups present, are also preferably used. Particularly preferred Teφoly Mers are produced by the processes described in German patent application DE 43 00 772 and German patent DE 42 21 381. Also useful are polyacetal carboxylic acids, as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups and saponifying to give the sodium or potassium salts. Also suitable are polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.

If such substances are contained at all in the paste-like compositions according to the invention, the proportion of organic, carboxyl group-containing builder materials in the paste-like compositions according to the invention can be up to 10% by weight, preferably 1% to 7.5% by weight and in particular 2% by weight to less than 5% by weight, the polyphosphonic acids up to 3% by weight, preferably 0.05% by weight to 1.5% by weight and in particular 0.1% by weight amount to 1% by weight. These substances mentioned are also used in anhydrous form.

Crystalline alkali silicates and finely divided alkali alumosilicates, in particular zeolites of the NaA, X and / or P type, can also be regarded as further useful builders within the meaning of the present invention. Suitable zeolites normally have a calcium binding capacity in the range from 100 to 200 mg CaO / g, which can be determined according to the information in German patent DE 24 12 837. Their particle size is usually in the range from 1 μm to 10 μm. They are used in dry form. The water contained in bound form in the zeolites does not interfere in the present case. Crystalline sheet silicates of the formula NaMSi _x O _{2 + x} yH ₂ O, in which M represents hydrogen or sodium, x is a number from 1.9 to, are preferably used as crystalline silicates, which may be present alone or in a mixture with the alumosilicates mentioned 4 and y is a number from 0 to 20. Preferred values for x are 2, 3 and 4. Such crystalline layered silicates are described, for example, in European patent application EP 164 514. In particular, both ß- and δ- Sodium disilicates Na ₂ Si ₂ 0 ₅ yH ₂ O are preferred, β-sodium disilicate being able to be obtained, for example, by the process described in international patent application WO 91/08171. Usable 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 can be up to 35% by weight, preferably up to 25% by weight and in particular 10% by weight to 25% by weight.

In particular, if a phosphate content is ecologically harmless when using agents according to the invention (for example in the case of waste water purification eliminating the phosphates), polymeric alkali metal phosphates, such as sodium tripolyphosphate, may also be present in paste-like agents according to the invention. Their proportion is preferably up to 20% by weight, based on the total agent, the proportion of the other solids, for example the alkali silicate and / or aluminosilicate, being reduced accordingly.

In a preferred embodiment of agents according to the invention, 5% by weight to 25% by weight, in particular 10% by weight to 20% by weight, of builder substances are contained.

The bleaching agent component (C) is a mixture of oxygen-containing oxidizing agent and bleach activator. Inorganic peroxygen compounds in particular are used as the oxidizing agent, the sodium perborate tetrahydrate and the sodium perborate monohydrate being of particular importance in addition to sodium percarbonate. Other suitable oxidizing agents are, for example, persulfates, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid. Sodium percarbonate, sodium persulfate and / or sodium perborate monohydrate are preferably used.

The oxidizing power of the oxidizing agents mentioned is improved by using bleach activators which form peroxocarboxylic acids under perhydrolysis conditions. There are numerous proposals for such bleach activators, especially from the N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines. Sulfurylamides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, sodium isononanoyl-oxybenzenesulfonate and triacetin (glycerol triacetate), and acylated sugar derivatives, such as pentaacetyl glucose, have become known. A bleach activator is preferably used which forms peracetic acid under the washing conditions, with tetraacetylethylenediamine being particularly preferred. By adding bleach activators, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C.

In particular at even lower temperatures, the use of transition metal salts and complexes, as for example in European patent applications EP 0 392 592, EP 0443 651, EP 0 458 397, EP 0 544 490, EP 0 549 271, EP 0 630 964 or EP 0 693 550 suggests that, as so-called bleach catalysts, in addition to or instead of the conventional bleach activators, there is an increase in the bleaching performance. The transition metal complexes known as bleach activating catalysts from German patent applications DE 195 29 905, DE 195 36 082, DE 196 05 688, DE 196 20 41 1 and DE 196 20 267 are also particularly suitable. Bleach-activating transition metal complexes, especially with the central atoms Mn, Fe. Co, Cu, Mo, V, Ti and / or Ru are contained in agents according to the invention in amounts of preferably up to 1% by weight, in particular 0.0025% by weight to 0.25% by weight.

Component (C) preferably contains from 60 to 95% by weight, based on component (C), oxidizing agent and from 5 to 40% by weight, based on component (C), bleach activator. The amounts of the constituents of the component are preferably adjusted so that the agent according to the invention comprises 5 to 25% by weight and in particular 10 to 20% by weight of oxidizing agent and from 1 to 10% by weight, in particular 3 to 8% by weight .-% bleach activator contains. The detergents according to the invention can contain washing alkalis as further components. The washing alkalis are mainly assigned to the solid phase. Preferred washing alkali is amorphous alkali silicate, in particular sodium metasilicate of the composition Na ₂ O: SiO ₂ from 1: 0.8 to 1: 1.3, preferably 1: 1, which is used in anhydrous form. In addition to the metasilicate, anhydrous alkali carbonate or alkali hydrogen carbonate are also suitable, which, however, requires larger portions of the liquid phase due to absorption processes and is therefore less preferred. The proportion of detergents in washing alkalis, in particular silicate, can be 10% by weight to 70% by weight, preferably 15% by weight to 50% by weight and in particular 25% by weight to 45% by weight . Alkali carbonate or alkali hydrogen carbonate is preferably present at most up to 20% by weight, in particular below 10% by weight.

To increase the physical stability as well as the chemical stability, in particular of the bleach activator components and the enzymes which may be present, dehydrating agents, for example in the form of salts which bind water of crystallization, such as anhydrous sodium acetate, calcium sulfate, calcium chloride, sodium hydroxide, magnesium silicate, or metal oxides such as CaO, MgO, P ₄ O ₁₀ or Al ₂ O ₃ can be used. Such dehydrating agents, with which the water content of agents according to the invention can be reduced to particularly low values, are present in the agents in amounts of preferably 1% by weight to 10% by weight and in particular 2% by weight to 8% by weight of the invention.

In addition, an agent according to the invention can contain further washing aids, which can normally be present in amounts of up to about 15% by weight, based on the finished agent. Graying inhibitors, soil-release agents, optical brighteners, enzymes, foam regulators and / or colorants and fragrances can be used, for example, as washing auxiliaries of this type. If fragrances are contained which are generally liquid, these pass into the liquid phase of agents according to the invention. Due to their small amount, however, they have no significant influence on the flow behavior of the pastes. Suitable graying inhibitors or soil release active ingredients are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and cellulose ether, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Sodium carboxymethyl cellulose and mixtures thereof with methyl cellulose are preferably used. The soil release agents normally used include copolyesters, the dicarboxylic acid units,

Contain alkylene glycol units and polyalkylene glycol units. Dirt-releasing copolyesters of the type mentioned and 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 91 1 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 finishing agents which contain 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 agents which contain 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 with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain 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 glycerol units. The proportion of graying inhibitors and / or soil release active substances in agents according to the invention is generally not more than 2% by weight and is preferably 0.5% to 1.5% by weight.

Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts, for example, can be present as optical brighteners for, in particular, textiles made of cellulose fibers (for example cotton). For example, salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or the like are suitable built-up compounds that carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group instead of the Moφholino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of brighteners can also be used. Brighteners of the 1,3-diaryl-2-pyrazoline type, for example 1 - (p-sulfoamoylphenyl) -3- (p-chloro-phenyl) -2-pyrazoline, and compounds of the same structure are particularly suitable for polyamide fibers. The content of optical brighteners or brightener mixtures in the agent is generally not more than 1% by weight, preferably 0.05% by weight to 0.5% by weight.

Enzymes which may be present in the agents according to the invention are in particular those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or their mixtures, the use of protease, Amylase and / or lipase is particularly preferred. The proportion is preferably 0.2% by weight to 1.5% by weight, in particular 0.5% by weight to 1% by weight. The enzymes can be adsorbed onto carriers in a conventional manner and / or embedded in coating substances or incorporated into the pastes as concentrated liquid formulations which are as anhydrous as possible. Proteases that can be used are, for example, from 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 are preferably used, for example the proteases or amylases known under the trade names Durazym® or Purafect® OxP or Duramyl® or Purafect® OxAm.

The usual foam regulators which can be used in the agents according to the invention include, for example, polysiloxane-silica mixtures, the fine-particle silica contained therein preferably being silanated. The polysiloxanes can be made from both consist of linear compounds as well as cross-linked polysiloxane resins and their mixtures. Further defoamers are paraffin hydrocarbons, in particular micro-paraffins and paraffin waxes, the melting point of which is above 40 ° C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, for example sodium behenate, and alkali salts of phosphoric acid mono- and / or dialkyl esters, in which the alkyl chains each have 12 to 22 carbon atoms. Sodium monoalkyl phosphate and / or dialkyl phosphate with C ₁₆ to C ₁₈ alkyl groups is particularly preferably used. The proportion of foam regulators can preferably be 0.2% by weight to 2% by weight. In many cases, a suitable selection of the nonionic surfactants can reduce the tendency to foam, so that the use of defoaming active ingredients can be dispensed with entirely.

The present invention further relates to a process for the preparation of the pasty detergent and cleaning agent according to the invention, in which the components of component (A), ie the nonionic surfactants and, if appropriate, the synthetic anionic surfactants and soap, are mixed to form a homogeneous premix are mixed and the components of components (B), (C) and optionally further components are incorporated into this premix.

The washing and cleaning agent of the present invention thus produced is pasty and usually consists of a liquid phase and a finely divided solid phase dispersed therein. The liquid phase of such agents is essentially formed from the, in particular nonionic, surfactants contained in the agent according to the invention. An agent according to the invention preferably has a viscosity of 70,000 mPas to HO OOO mPas at 20 ° C., measured with a Brookfield rotary viscometer (spindle no. 7) at 5 revolutions per minute. Under otherwise identical conditions, the viscosity at 50 revolutions per minute is preferably 18,000 mPa s to 25,000 mPa s. In a particular embodiment of the invention, the paste-like detergent and cleaning agent preferably has a viscosity at room temperature such that it is not flowable under the influence of gravity. It is then preferably particularly pseudoplastic that it is said to have a significantly lower viscosity when sheared and is flowable under the influence of gravity, it being particularly preferred to determine a viscosity in the range from 8 OOO mPas to 45 OOO mPas at 25 ° C. and a shear rate of 0.01 s ^{' 1} with a CS rheometer CVO from Bohlin with plate / plate measuring system, plate spacing 1 to 3 mm. When sufficient shear forces are applied, an agent according to the invention preferably has a viscosity which is considerably lower, as a rule 100 to 2000 times lower, at a shear rate of 10 s ^-1 and otherwise identical measuring conditions, in particular in the range from 40 mPas to 60 mPas lies. The numerical values for viscosity refer to the reading after a measuring time of 3 minutes, in order to take into account any thixotropy effect of the paste. The reduction in viscosity in the case of shear is largely reversible, that is to say after the shear has ended, the agent returns to its original physical state without segregation occurring. In this context, it should be noted that the viscosities mentioned do not relate to measurements directly after the paste has been produced, but rather to pastes which are stored, so to speak, in equilibrium, since the shear forces acting in the course of the production process lead to a lower paste viscosity, which leads to a lower viscosity only increased over time to the definitive final viscosity. Storage times of 1 month are usually completely sufficient for this.

The agent according to the invention can be metered using conventional devices for metering pastes, such as are described, for example, in international patent application WO 95/29282, German patent application DE 196 05 906, German patent DE 44 30418 or European patent EP 0 295 525 and EP 0 356 707 have been described. A device which is particularly well suited for metering structurally viscous pasty detergents is known, for example, from international patent application WO 95/09263 and is preferably used for metering structurally viscous pastes according to the invention. The detergents and cleaners according to the invention can optionally also be filled pre-portioned into water-soluble films in particular. Films of this type are described, for example, in European patent application EP 253 151. Examples

The following table gives some examples of detergents according to the invention.

a) C | _2nd , _g -fatty alcohol + 7 EO (Dehydol® LT 7; manufacturer Henkel KGaA) b) C ₉ . , - fatty alcohol + 3 EO (Dehydol® D3; manufacturer Henkel KGaA) c) C ₁₂ . ₁₄ -Fatty alcohol + 4 EO d) Cι _2. , ₄ -Fatty alcohol + 3 EO + 4 PO e) Cι ₃ .ι ₅ -Fatty alcohol + 7 EO (Lutensol® AO 7; manufacturer BASF AG) f) Isotridecyl alcohol + 3 EO ( Lutensol® TO 3; manufacturer BASF AG) g) isodecyl alcohol + 3 EO (Lutensol® ON 30; manufacturer BASF AG h) C | _4. , ₅ - alcohol + 4 EO (Dobanol® 45/4; manufacturer Shell AG)

0 C _{| 2/18} fatty acid Na salt (Edenor® NAK 90; manufacturer Henkel KGaA) k) C, _6/22 fatty acid Na salt (Edenor® HT 35; manufacturer Henkel KGaA)

1) C ₁₂ fatty acid, 92 - 94% saponified (Edenor® C12 92/94; manufacturer Henkel KGaA) m) From palm kernel oil (Edenor® PK 1805; manufacturer Henkel KGaA) n) phosphonate (Tuφinal® 2 NZ; manufacturer Henkel KGaA) o) Polymeric polycarboxylate (Sokalan® CP 5; manufacturer BASF AG) p) Na citrate, anhydrous q) Protease granules (BLAP® S200; manufacturer Biozym)

The paste-like detergents showed despite their content of oxidizing agents and Bleach activator has a very good storage stability. For example, the active oxygen content after storage at 30 ° C. and 40% relative atmospheric humidity only decreased to 95% of the initial value within 8 weeks.

Claims

Patgntansprϋςhg

1. Paste-form washing or cleaning agent containing 20% by weight to 58% by weight of a surfactant component (A), which at least partially consists of nonionic surfactant, 2% by weight to 40% by weight of builder substances (B ), and 2% by weight to 40% by weight of a bleaching agent component (C), characterized in that component (C) contains an oxidizing agent and bleach activator containing peroxygen.

2. Composition according to claim 1, characterized in that the surfactants of component (A) or their nonionic partial component are selected from ethoxylated and optionally propoxylated alcohols of the general formula I,

R ¹ - (OC ₂ H ₄ ) _m - (OC ₃ H ₆ ) _n -OH (I) in which R ¹ denotes an alkyl or alkenyl radical with 6 to 11 carbon atoms, m values from 3 to 15 and n values can assume from 0 to 6, and / or of the general formula II,

R ² - (OC ₂ H ₄ ) ₀ - (OC ₃ H ₆ ) _p -OH (II) in which R denotes an alkyl or alkenyl radical with 12 to 22 C atoms, and o values from 3 to 15 and p values can assume from 0 to 6.

3. Composition according to claim 1 or 2, characterized in that component (A) contains up to 10% by weight, based on component (A), of synthetic anionic surfactants selected from alkylbenzenesulfonate and / or alkyl or alkenyl sulfate.

4. Agent according to one of claims 1 to 3, characterized in that component (A) contains up to 20 wt .-%, based on the agent, soap.

5. Agent according to one of claims 1 to 4, characterized in that the bleaching agent component (C) 60 to 95 wt .-%, based on the bleaching agent component, oxidizing agent and 5 to 40 wt .-%, based on the bleaching agent component, Bleach activator that forms percarboxylic acid under perhydrolysis conditions.

6. Agent according to one of claims 1 to 5, characterized in that the bleaching agent component (C) bleach-activating transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru. in amounts up to 1% by weight, in particular 0.0025% by weight to 0.25% by weight, in each case based on the composition.

7. Composition according to one of claims 1 to 6, characterized in that it contains 10 wt .-% to 70 wt .-%, in particular 15 wt .-% to 50 wt .-% washing alkalis.

8. Composition according to claim 7, characterized in that it contains 5 wt .-% to 25 wt .-%, in particular 10 wt .-% to 20 wt .-% builder substances.

9. Composition according to one of claims 1 to 8, characterized in that the constituents of the paste-like composition contained as a solid phase are finely divided and have an average grain size in the range from 5 μm to 200 μm, in particular 10 μm to 80 μm.

10. Agent according to one of claims 1 to 9, characterized in that at most 10% of the particles of the constituents contained as a solid phase have a grain size of more than 200 microns.

1 1. Agent according to one of claims 1 to 10, characterized in that it contains 0.2% by weight to 1.5% by weight, in particular 0.5% by weight to 1% by weight, of enzyme Protease, amylase and / or lipase contains.

12. Composition according to one of claims 1 to 11, characterized in that it contains 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, of dehydrating agent.

13. A process for the preparation of detergents and cleaning agents according to one of claims 1 to 12, characterized in that the constituents of component (A) are mixed to form a homogeneous premix and the constituents of components (B) are mixed in this premix. and (C) and optionally further constituents can be incorporated.