EP0929630A1

EP0929630A1 - Paste-like washing and cleaning agent

Info

Publication number: EP0929630A1
Application number: EP97944804A
Authority: EP
Inventors: Thomas Merz; Khalil Shamayeli
Original assignee: Henkel Ecolab GmbH and Co KG
Current assignee: Ecolab GmbH and Co OHG
Priority date: 1996-09-05
Filing date: 1997-08-28
Publication date: 1999-07-21
Anticipated expiration: 2017-08-28
Also published as: WO1998010049A1; NO991069L; PL331858A1; DE19636035A1; ATE210717T1; US6248708B1; EP0929630B1; DE59705800D1; CA2264838A1; NO991069D0; DK0929630T3; NO319284B1

Abstract

A paste-form detergent for use in institutional laundries free from synthetic anionic surfactant of the alkyl benzenesulfonate type containing 5% to 30% by weight of an ethoxylated alcohol corresponding to formula (I):in which R1 is an alkyl or alkenyl group containing 12 to 14 carbon atoms and m has a value of 1 to 8, 1% to 20% by weight of an ethoxylated alcohol corresponding to formula (II):in which R2 is an alkyl or alkenyl group containing 12 to 22 carbon atoms and n has a value of 3 to 14, with proviso that n is greater than m by at least 1.0, 20% to 80% by weight of alkalizing agent, 1% to 20% by weight of long-chain alcohol or alkyl ether corresponding to formula (III):in which R3 is an alkyl or alkenyl group containing 8-22 carbon atoms and R4 is hydrogen or an alkyl group containing 1 to 6 carbon atoms, and up to 5% by weight of organic builder of the polymeric polycarboxylate type.

Description

Paste-like detergent and cleaning agent

The present invention relates to pasty detergents and cleaning agents and a process for their production.

Detergents used in the household are tailored to the needs 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 the 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 is formed from washing alkalis, sequestering agents and optionally anionic surfactants becomes. 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 flowable 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 does not only concern the separation 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 with 10 to 20 carbon atoms which is liquid at room temperature and an average degree of ethoxylation of 1 to 8 and 20 to 50% by weight of ethoxylated and propoxylated fatty alcohols which are liquid at room temperature Contains 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% by weight of 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.

More recently, the demand for the waiver of detergent ingredients that are not sufficiently biodegradable has also been raised in commercial laundries. This requirement is particularly difficult to meet, since the cleaning performance of the detergents has to be subject to much higher demands than the conditions for household washing. This applies in particular to the surfactant ingredients which make a significant contribution to cleaning performance, in which synthetic anionic surfactants, in particular of the sulfonated alkylbenzenes type, play an outstanding role in this regard.

The present invention was therefore based on the object of providing a pasty detergent for use in commercial laundries which has good washing performance with good storage stability, although it does without the synthetic anionic surfactants of the alkylbenzenesulfonate type which are normally required for this purpose.

This could essentially be solved by optimizing the nonionic Surfactant component and the use of long-chain alcohols and or long-chain alkyl ethers.

The subject of the present invention is a pasty detergent for use in commercial laundries, containing nonionic surfactant, organic and / or inorganic builders, alkalizing agents, and, if appropriate, bleaching agent, enzyme, graying-inhibiting polymer and / or other conventional ingredients, which are characterized in that is that it is free from synthetic anionic surfactant of the alkylbenzenesulfonate type and 5% by weight to 30% by weight, in particular 10% by weight to 25% by weight, of an ethoxylated alcohol of the general formula I,

R ¹ - (OCΛVOH (I) in which R ¹ denotes an alkyl or alkenyl radical having 8 to 14 carbon atoms and the average degree of ethoxylation m can assume values from 1 to 8, 1% by weight to 20% by weight, in particular 5% by weight to 15% by weight of an ethoxylated alcohol of the general formula II,

R ² - (OC ₂ H ₄ ) _n -OH (II) in which R ² denotes an alkyl or alkenyl radical having 12 to 22 carbon atoms and the average degree of ethoxylation n can assume values from 3 to 14 with the proviso that n is at least 1.0, in particular at least 2.0, greater than m, 20% by weight to 80% by weight of alkalizing agent, 1% by weight to 20% by weight, in particular 3% by weight to 15 % By weight of long-chain alcohol or alkyl ether of the general formula III,

R ³ -OR ⁴ (III), in which R ^{3 is} an alkyl or alkenyl radical having 8 to 22 carbon atoms and R ^{4 is} hydrogen or an alkyl radical having 1 to 6 carbon atoms, and up to 5% by weight of organic Containers of the type of polymeric polycarboxylates contains. In the context of the invention, polymeric polycarboxylates are to be understood as meaning polymerization products of unsaturated mono- and / or dicarboxylic acids which, apart from carboxyl groups, have no further functionalities.

The liquid phase of the paste-like composition according to the invention is essentially formed by the nonionic surfactants of the formulas I and II, which have different carbon chain lengths and different degrees of ethoxylation, and the alcohols or ethers of the formula III. The viscosity of the invention Can be adjusted by combining ethoxylated alcohols with the formulas I and II. In the compounds of the formulas I and II, the radicals R ¹ and R can be linear or branched, for example methyl-branched in the 2-position, linear radicals having primary etherified alcohol functions being preferred. The nonionic surfactant according to formula I preferably has a carbon chain length of 8 to 14, in particular 12 to 14, carbon atoms and an average degree of alkoxylation m of 1 to 8. The nonionic surfactant according to formula II has a broader carbon chain length distribution towards longer chains with 12 to 22, in particular 12 to 18, carbon atoms and a higher average degree of alkoxylation n of 3 to 14. The ethoxylated alcohols of the formula I and the ethoxylated alcohols of the formula II are preferably in weight ratios of 2: 1 to 1.1.8. The agent according to the invention can contain further nonionic surfactants commonly used in washing and cleaning agents, such as, for example, alkyl polyglycosides and / or fatty acid polyhydroxy ide. However, the surfactant component is preferably free from propoxylated alcohols, since poorer biodegradability is expected from these.

For the alcohols or ethers of the general formula III, which contribute to the particularly good low-temperature stability of the agents according to the invention and can additionally contribute to the washing performance, the above applies essentially to the radicals R ³ for the radicals R ¹ and R ² . In addition to hydrogen, R ⁴ 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 agents contain up to 10% by weight, preferably 2% by weight to 6% by weight, of substances according to general formula III.

The agent can contain up to 5% by weight, in particular 0.5% by weight to 3% by weight, of natural or synthetic anionic surfactants as further surfactants. Suitable synthetic anionic surfactants, which can preferably be incorporated into the agent 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 metal 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 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 sulfo fatty acids and their esters, which are particularly found in α- Position derived sulfonated Cι ₂ - to Cig fatty acids and lower alcohols, such as methanol, ethanol and propanol, and olefin sulfonates, such as those formed by sulfonation of terminal Cj ₂ - to cis olefins and subsequent alkaline hydrolysis. Suitable surfactants of the sulfate type are 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 countercation. 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, that is to say 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 conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. In addition, the sulfated alkoxylation products of such alcohols, so-called ether sulfates, can be contained in the compositions. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Synthetic anionic surfactants of the alkylbenzenesulfonate type are completely absent in the agents according to the invention. In a preferred embodiment of the invention, the agent is completely free from synthetic anionic surfactants. The naturally occurring anionic surfactants include, in particular, the soaps, which can be present in the agents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.5% by weight to 2% by weight. Suitable soaps are in particular the alkali metal salts of saturated and / or unsaturated Ci2-i come ₈ fatty acids, for example coconut, palm kernel or tallow fatty acid in question. The use of salts of a carboxylic acid mixture of, based in each case on the total carboxylic acid mixture, from 2% by weight to 8% by weight is particularly preferred. CM-, up to 1 wt .-% Cι ₅ -, 18 wt .-% to 24 wt .-% C, ₆ -, up to 3 wt .-% C, ₇ -, 20 wt .-% to 42 wt .-% C | ₈ % and 30% by weight to 44% by weight of C ₂₀ . ₂₂ carboxylic acid.

The solid phase of the agent according to the invention is essentially formed by the alkalizing agents and builder substances, it being possible for further particulate 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 using known methods (for example by means of laser diffraction or a Coulter Counter).

The alkalizing agents contained as a further component are often also referred to as washing alkalis. They are mainly assigned to the fixed phase. Under the conditions of use of agents according to the invention, they ensure a pH in the alkaline range which is normally in the range from 9 to 13, in particular from 10 to 12 (in each case measured in a 1% strength by weight solution of the agent in ion-exchanged water). The preferred alkalizing agent 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 alkali silicate, anhydrous alkali carbonate or alkali hydrogen carbonate are also suitable, which, however, requires larger proportions of the liquid phase due to absorption processes and is therefore less preferred. The proportion of alkalizing agents in the agents is 20% by weight to 80% by weight, preferably 30% by weight to 70% by weight and in particular 40% by weight to 60% by weight. The alkali agent component of the agent according to the invention can consist solely of silicate. Alkali carbonate or alkali hydrogen Carbonate is preferably present at most up to 20% by weight, in particular below 10% by weight. In particular, if a phosphate content is ecologically harmless when using agents according to the invention (for example in the case of wastewater treatment which eliminates the phosphates), polymeric alkali phosphates, such as sodium tripolyphosphate, may also be present in paste-like agents according to the invention. Their proportion is preferably up to 70% by weight, in particular 15% by weight to 25% by weight, based on the total composition, the proportion of the other solids, for example the alkali silicate and / or optionally contained aluminosilicate, accordingly can be reduced.

Suitable organic builder substances are, in particular, monomeric polycarboxylic acids or hydroxycarboxylic acids such as citric acid or gluconic acid or their salts and, in addition, 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 polyphosphonic acids are l-hydroxyethane-l, l-diphosphonic acid, amino-tri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and their higher homologues, such as, for example, ylenteframintetra (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 also being particularly preferred here. Polymeric 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 the copolymers between 2,000 and 200,000, 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. Terpolymers which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as monomers can also be used as polymeric carboxylates or carboxylic acids. 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 -monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C -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 C 1 -C 8 -carboxylic acids, with vinyl alcohol. Preferred terpolymers 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. Terpolymers in which the weight ratio (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 are very particularly preferred. 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, in the 2-position, has an alkyl radical, preferably 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% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight, preferably 15 % By weight to 25% by weight of methallylsulfonic acid preferably methallylsulfonate and, as the third monomer, 15% by weight to 40% by weight, preferably 20% by weight 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. Sucrose 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. Polymers which are either completely or at least partially, in particular to more than 50%, based on the carboxyl groups present, are also preferably used. Particularly preferred polymeric polycarboxylates are produced by processes which are 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 form 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 agents according to the invention, the proportion of organic, carboxyl group-containing builder materials in the paste-like agents according to the invention can be up to 10% by weight, preferably 1% by weight to 7.5% by weight and in particular 2% by weight to less than 5% by weight, the proportion of polymeric polycarboxylate being as small as possible and being less than 5% by weight. These substances mentioned are also used in anhydrous form.

In addition to the abovementioned phosphate, crystalline alkali silicates and finely divided alkali alumosilicates, in particular zeolites of the NaA, X and / or P type, are suitable as inorganic builders for use in agents according to the 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. That contained in bound form in the zeolites In the present case, water is not a problem. 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 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 β- and δ-sodium disilicate Na ₂ Si ₂ θ ₅ yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method 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 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 present, the amount of polymeric polycarboxylates not more than 5% by weight, in particular 0% by weight, and the amount of phosphonates is not more than 0.5% by weight, in particular not more than 0.2% by weight.

In addition, a paste-like agent according to the invention can contain an oxygen-containing oxidizing agent and optionally a bleach activator. Inorganic peroxygen compounds in particular are used as oxidizing agents, 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. Oxidizing agents can be present in the agents according to the invention preferably in amounts of up to 25% by weight and in particular from 10% by weight to 20% by weight.

The oxidizing power of such oxidizing agents can be tors are improved, which form peroxocarboxylic acids under perhydrolysis conditions. There are numerous proposals for such bleach activators, especially from the substance classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, drazoles - Piperazines, sulfurylamides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzene-sulfonate, sodium isononanoyl-oxybenzenesulfonate and triacetin (glycerol triacetate), and acylated sugar derivatives, known as pentaacetyl glucose, have become known as pentaacetyl glucose. A bleach activator is preferably 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 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 the European patent applications EP 0 392 592, EP 0 443 651, EP 0 458 397, EP 0 544490, EP 0 549 271, EP 0 630 964 or EP 0 693 550 proposed that, as so-called bleaching catalysts, in addition to or instead of the conventional bleaching activators, they result in 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, in particular with the center atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are present in the inventive agents in amounts of preferably not more than 1% by weight, in particular 0.0025% by weight. % to 0.25 wt .-% contain.

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. Enzymes, graying inhibitors, soil-release active substances, optical brighteners, foam regulators, for example, can be used as washing aids of this type and / or dyes and fragrances are used. If fragrances are contained which are generally liquid, these pass into the liquid phase of agents according to the invention. Because of their small amount, however, they have no significant influence on the flow behavior of the pastes.

The paste-like detergents according to the invention are essentially free of water and organic solvents. "Substantially 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 water of hydration and constitutional water, is below 3% by weight, preferably below 2% by weight and in particular below 1 % By weight. Higher water contents are disadvantageous because they increase the viscosity of the agent disproportionately and in particular reduce its stability. Organic solvents, which include the low-molecular and low-boiling alcohols and ether alcohols commonly used in liquid concentrates, as well as hydrotropic compounds are also not present, apart from traces that can be introduced with individual active ingredients.

Enzymes which may be present in the agents according to the invention are, in particular, those from the class of proteases, lipases, cutinases, amylases, pullulases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, Lipase and / or cellulase 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 95/3001 1, 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. Suitable graying inhibitors or soil release active substances are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, 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 active ingredients commonly used include copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil-removing 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 00 911 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 finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol. The 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. In a preferred embodiment of the invention, the agent is free from such active ingredients.

Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts, for example, can be present as optical brighteners for textiles made in particular from cellulose fibers (for example cotton). For example, are suitable Salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the morpho- lino group carry a diethanolamino group, a methyl.amino group or a 2-methoxyethylamino 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 l- (-Sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of the same structure are particularly suitable for polyamide fibers. The optical brightener or brightener mixture content of the agent is generally not more than 1% by weight, preferably 0.05% by weight to 0.5% by weight. In a preferred embodiment of the invention, the agent is free of such active ingredients.

The usual foam regulators which can be used in the agents according to the invention include, for example, polysiloxane / silica mixtures, the finely divided silica contained therein preferably being silanated. The polysiloxanes can consist of both linear compounds and crosslinked polysiloxane resins and mixtures thereof. Further defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, whose melting point is above 40 ° C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, for example sodium behenate, and alkali metal 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 ₆ to C 12 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 substances in a preferred embodiment of the invention can be dispensed with entirely.

To increase the physical stability as well as the chemical stability, in particular of the bleaching agent component and 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, PO | ₀ or Al ₂ O 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 the preparation of paste-like detergents and cleaning agents according to the invention, the surfactant components, that is to say the nonionic surfactants of the formulas I and II and the alcohols or ethers of the formula III and, if appropriate, soap and synthetic anionic surfactants are advantageously mixed to form a homogeneous premix and the solids in this premix and, if necessary, further constituents can be incorporated. If the particulate solids are not sufficiently fine, one or more grinding steps can be inserted.

A paste-like agent according to the invention preferably has a viscosity in the range from 80,000 mPas to 250,000 mPas, in particular 100,000 mPas to 250,000 mPas, measured at 25 ° 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 20,000 mPa s to 80,000 mPa s. In a special 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 viscous, i.e. it has a significantly lower viscosity when sheared and is flowable under the influence of gravity, it being particularly preferred to have a viscosity in the range from 8,000 mPas to 45,000 mPas at 25 ° C. and a shear rate of 0.01 s ^"1 , to be determined using a CVO CS rheometer from Bohlin with a 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 considerable, usually 100- up to 2000 times lower viscosity, which is at a shear rate of 10 s ^"1 and otherwise the same measurement conditions, in particular in the range from 40 mPas to 60 mPas. 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 at shear is largely reversible, i.e. after shearing 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 refer to measurements directly after the paste has been made, but to stored pastes that are, so to speak, in equilibrium, since the shear forces acting in the course of the manufacturing process lead to a lower paste viscosity, which only occurs in the Increased over time to the definitive final viscosity. Storage times of 1 month are usually completely sufficient for this.

An agent according to the invention normally has a density in the range from 1.3 kg / 1 to 1.6 kg / 1. The agent according to the invention can be metered using conventional devices 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 30418 or European patent EP 0 295 525 EP 0356 707 have been described. A device which is particularly well suited for the dosing of viscous pasty detergents is known, for example, from international patent application WO 95/09263 and is preferably used for dosing pastes according to the invention which are structurally viscous. The detergents and cleaning agents according to the invention can, if appropriate, also be filled in portions, in particular in water-soluble films. Films of this type are described, for example, in European patent application EP 253 151.

Examples

The following table gives some examples of the composition of detergents according to the invention. The paste-like detergents had a very good storage stability and, despite the absence of synthetic anionic surfactant, had an excellent cleaning performance. Table 1: Composition of pasty detergents (% by weight)

Component 1 2 3 4 5 6

Nonionic surfactant I ^a) 19 19 18 18 18 11

Nonionic surfactant II ^b) 1 1 1 1 1 1 11 11 18

Isotridecanol - - 5 5 5 5

Soap ^c) 1 1 1 1 1 1

Builder I ^d) 5 5 5 5 5 5

Builder II ^e) 0.2 0.2 0.2 0.2 0.2 0.2

Sodium silicate 60 40 47 57 - -

Sodium tripolyphosphate - 20 20 - 20 20

Sodium percarbonate - - - - 20 20

TAED - - - - 4 4

Enzyme - - - - 1 1

CMC / MC ⁰ 1 1 1 1 1 1

Foam inhibitor ^ε) 1 1 1 1 1 1

Sodium carbonate to 100

a) Ci ₂ -ι ₄ fatty alcohol + 3 EO (Dehydol® LS 3; manufacturer Henkel KGaA) b) C, ₂ .i ₈ fatty alcohol + 5 EO (Dehydol® LT 5; manufacturer Henkel KGaA) c) Ci6 / 2 ₂ -Fatty acid Na salt (Edenor® HT 35; manufacturer Henkel KGaA) d) polymeric polycarboxylate (Sokalan® CP 5; manufacturer BASF AG) e) phosphonate (Turpinal® 2 NZ; manufacturer Henkel KGaA) f) carboxymethyl cellulose-methyl cellulose- Mixture (2.5: 1) g) mono / distearyl phosphate

Claims

claims

1. paste detergent for use in commercial laundry, containing nonionic surfactant, organic and / or inorganic builders, alkalizing agents, and optionally bleach, enzyme, graying-inhibiting polymer and / or other conventional ingredients, characterized in that it is free of synthetic anionic surfactant Is alkylbenzenesulfonate type and 5% by weight to 30% by weight of an ethoxylated alcohol of the general formula I, in which R ¹ denotes an alkyl or alkenyl radical with 12 to 14 carbon atoms and the average degree of ethoxylation m can assume values from 1 to 8, 1% by weight to 20% by weight of an ethoxylated alcohol of the general formula II,

R ² - (OC ₂ H ₄ ) _n -OH (II) in which R ² denotes an alkyl or alkenyl radical having 12 to 22 carbon atoms and the average degree of ethoxylation n can assume values from 3 to 14 with the proviso that n is at least 1.0 greater than m, 20% by weight to 80% by weight of alkalizing agent, 1% by weight to 20% by weight, in particular 3% by weight to 15% by weight of long-chain alcohol or Alkyl ethers of the general formula III,

R ³ -OR ⁴ (III), in which R ^{3 is} an alkyl or alkenyl radical having 8 to 22 carbon atoms and R ^{4 is} hydrogen or an alkyl radical having 1 to 6 carbon atoms, and up to 5% by weight of organic Containers of the type of polymeric polycarboxylates contains.

2. Composition according to claim 1, characterized in that it contains 10 wt .-% to 25 wt .-% of the ethoxylated alcohol of the general formula I.

3. Composition according to claim 1 or 2, characterized in that it contains 5 wt .-% to 15 wt .-% of the ethoxylated alcohol of the general formula II.

4. Agent according to 3, characterized in that the average degree of ethoxylation n of the surfactant according to formula II is at least 2.0 greater than the average degree of ethoxylation m of the surfactant according to formula I.

5. Agent according to one of claims 1 to 4, characterized in that it contains 3% by weight to 15% by weight of long-chain alcohol or alkyl ether of the general formula III.

6. Composition according to one of claims 1 to 5, characterized in that it contains up to 5 wt .-%, in particular 0.5 wt .-% to 2 wt .-%, soap.

7. Composition according to one of claims 1 to 5, characterized in that it is up to 5 wt .-%, in particular 0.5 wt .-% to 3 wt .-% synthetic anionic surfactant selected from the alkyl or alkenyl sulfates and or Contains ether sulfates.

8. Composition according to one of claims 1 to 7, characterized in that it contains 30 wt .-% to 70 wt .-%, in particular 40 wt .-% to 60 wt .-% alkalizing agent.

9. Composition according to one of claims 1 to 8, characterized in that it contains 5 wt .-% to 25 wt .-%, in particular 10 wt .-% to 20 wt .-% builder substances.

10. Composition according to one of claims 1 to 9, 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.

11. Agent according to one of claims 1 to 10, 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.

12. Composition according to one of claims 1 to 1 1, 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, lipase and / or cellulase contains.

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

14. Composition according to one of claims 1 to 13, characterized in that it has a viscosity of 80,000 mPa s to 250,000 mPas at 25 ° C, measured with a Brookfield rotary viscometer (spindle No. 7) at 5 revolutions per minute and under otherwise identical conditions at 50 revolutions per minute it has a viscosity of 20,000 mPa s to 80,000 mPa s.