EP0929630B1 - Paste-like washing and cleaning agent - Google Patents

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

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; so they are usually powdery or sufficiently liquid to be themselves pour and dispense easily. Because such liquid detergents should be stable in storage within relatively wide temperature ranges are common Additions of organic solvents and / or hydrotropes added, however itself make no contribution to the washing or cleaning result are undesirable for this reason. A way to circumvent any Dosing problems with insufficiently liquid agents are in the European Patent application EP 253 151 A2 proposed. From this document, liquid, some highly viscous detergents based on non-ionic and anionic surfactants known which contain polyethylene glycol as hydrotrope and which the user does not must be dosed in liquid form, but portioned into bags water-soluble material, for example polyvinyl alcohol.

The paste-like detergent described in European patent EP 295 525 B1 consists of a liquid phase in the temperature range below 10 ° C nonionic surfactant is formed, and a solid phase dispersed therein Grain size, which consists of washing alkalis, sequestrants and optionally Anionic surfactants is formed. For this purpose surfactants or their mixtures used, the pour point (solidification point) must be below 5 ° C to solidify avoid 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. However, it has been found that such pastes are not during their manufacture always and satisfactorily ensure the homogeneity of their ingredients often tend to separate 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.

From French patent application FR 2 254 632 it is known that mixtures are nonionic Surfactants with different degrees of ethoxylation give good washing performance. The European Patent application EP 0 356 707 describes storage-stable and well-effective paste-like Detergent, the 15-36 wt .-% of a nonionic surfactant mixture, 35-70 wt .-% one Alkalinity component and up to 4 wt .-% sulfonate surfactant. Another pasty Detergent, which is a nonionic surfactant 40 to 70 wt .-% liquid at room temperature ethoxylated fatty alcohol with 10 to 20 carbon atoms and an average degree of ethoxylation from 1 to 8 and 20 to 50% by weight of ethoxylated and liquid at room temperature propoxylated fatty alcohol with 10 to 20 carbon atoms and a medium Degree of ethoxylation from 2 to 8 and an average degree of propoxylation from 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 Room temperature is not flowable under the influence of gravity, but one under shear has significantly lower viscosity and is then flowable under the influence of gravity. The dosage of this pasty detergent or cleaning agent is preferably carried out in that the agent for lowering the viscosity is subjected to shear and that then flowable agents can be metered by means of feed pumps.

In more recent times, the demand for the waiver of as is also in the commercial laundry detergent ingredients that are not sufficiently biodegradable. This Demand is particularly difficult to meet because of the cleaning performance of the detergent in the Compared to the conditions for household laundry, much higher demands are made have to. This applies in particular to those that make a significant contribution to cleaning performance surfactant ingredients in which synthetic anionic surfactants, in particular of the type sulfonated alkylbenzenes play an outstanding role in this regard.

The present invention was therefore based on the object of a pasty detergent for to provide use in commercial laundries with good storage stability has a good washing performance, although it is based on the synthetic materials normally required for this Anionic surfactants of the alkylbenzenesulfonate type are dispensed with.

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 present invention relates to a pasty detergent for use in commercial laundries, containing nonionic surfactant, organic and / or inorganic builders, alkalizing agents and optionally bleaching agent, enzyme, graying-inhibiting polymer and / or other conventional ingredients, which is characterized in 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 - (OC ₂ H ₄ ) _m -OH in which R ¹ denotes an alkyl or alkenyl radical with 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 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 in which R ^{3 is} an alkyl or alkenyl radical with 8 to 22 C atoms and R ^{4 is} hydrogen or an alkyl radical with 1 to 6 C atoms, and contains up to 5% by weight of organic builders of the polymeric polycarboxylate type. 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 agent according to the invention can be adjusted by combining ethoxylated alcohols with the formulas I and II. In the case of 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, 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 polyhydroxyamides. 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 11 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 derived saturated C ₁₂ to C ₁₈ fatty acids and lower alcohols, such as methanol, ethanol and propanol, and olefin sulfonates, as are formed, for example, by sulfonation of terminal C ₁₂ to C ₁₈ 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 reaction of the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization 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 the saturated and / or unsaturated C _12-18 fatty acids, for example coconut, palm kernel or tallow fatty acid. 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 _14- , up to 1% by weight of C _15- , 18% by weight to 24 is particularly preferred % By weight C ₁₆ -, up to 3% by weight C ₁₇ -, 20% by weight to 42% by weight C ₁₈ - and 30% by weight to 44% by weight C _20-22 - Carboxylic acid.

The solid phase of the agent according to the invention is essentially from the Alkalizing agents and builder substances are formed, optionally further particulate auxiliaries may be present. The solid phase should be in the liquid Be dispersed as homogeneously as possible. The contained as a solid phase Components of the paste-like agent should be finely divided and an average grain size have in the range of 5 microns to 200 microns, with at most 10% of the particles Have grain size of more than 200 microns. Surprisingly, it is possible to be relative coarse-grained solids, for example those containing 20% to 50% particles Grain sizes over 100 microns included, without disadvantage in the pasty agents to incorporate. The average grain size is preferably that of the solid phase Particles 10 microns to 80 microns and especially 10 microns to 60 microns, the maximum Grain size is less than 300 microns, especially less than 250 microns. Are preferred 90 wt .-% of the solid powdery components smaller than 200 microns, in particular smaller than 140 µm. The average grain size can be determined by known methods (for example using 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 alkalizing 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 metal 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 1-hydroxyethane-1,1-diphosphonic acid, amino-tri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and their higher homologs, such as, for example, diethylene tetramine 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 also being particularly preferred here. Polymer carboxylates or polymer 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. 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 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 ₄ monocarboxylic acid, in particular 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. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ -carboxylic acids, with vinyl alcohol are particularly preferred. 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 or 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, such as are 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 at all in the paste-like compositions according to the invention are contained, the proportion of organic, carboxyl group-containing builder materials in the paste-like composition according to the invention 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 is as low as possible and less than 5% by weight lies. 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. 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 aluminosilicates 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 β- and δ-sodium disilicate Na ₂ Si ₂ O 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, the Amount of polymeric polycarboxylates not more than 5% by weight, in particular 0% by weight, and the amount of phosphonates not more than 0.5% by weight, especially 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 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. Oxidizing agents can be present in 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 achieved by using bleach activators be improved, which form peroxocarboxylic acids under perhydrolysis conditions. There are numerous proposals for such bleach activators, especially from the substance classes the N- or O-acyl compounds, for example multiple acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, Sulfurylamides and cyanurates, also carboxylic anhydrides, in particular 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 in the literature. A bleach activator is preferably used which contains peracetic acid under the washing conditions forms, with tetraacetylethylenediamine being particularly preferred. Agents according to the invention preferably contain up to 10% by weight, in particular of 3% to 8% bleach activator by weight. The addition of bleach activators can the bleaching effect of aqueous peroxide liquors can be increased so far that already at Temperatures around 60 ° C essentially the same effects as with the peroxide liquor enter at 95 ° C alone. Especially at even lower temperatures through the use of transition metal salts and complexes, such as 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 proposed as so-called bleach catalysts in addition to or instead of the conventional bleach activators, result in an increase in bleaching performance. Are also particularly suitable from the 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 known transition metal complexes. Bleach-activating transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in the invention Averages in amounts of preferably not more than 1% by weight, contain in particular from 0.0025% by weight to 0.25% by weight.

In addition, an agent according to the invention can contain further washing auxiliaries which normally in amounts up to about 15% by weight, based on the finished product, can be present. Enzymes, graying inhibitors, soil release agents, optical brighteners, foam regulators and / or colors and fragrances are used. As far as fragrances are contained in the are generally liquid, they go into the liquid phase of agents according to the invention about. Because of their small amount, however, they have an impact on the flow behavior of the pastes no noteworthy influence.

The paste-like detergents according to the invention are essentially free of Water and organic solvents. Under "essentially free of water" is a To understand state in which the content of free, that is, not in the form of Water of hydration and constitutional water less than 3% by weight, preferably is 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 especially its Reduce stability. Organic solvents, which are commonly found in liquid concentrates used low molecular weight and low boiling alcohols and ether alcohols count, as well as hydrotropic compounds are apart from traces associated with individual active ingredients can also be introduced, also not available.

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 in question, 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 found in be adsorbed onto carrier substances and / or embedded in coating substances in the usual way or as concentrated, water-free liquid formulations in the pastes be incorporated. Proteases that can be used are, for example, from the 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 95/0204/1, 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 are known. Prefers enzymes are stabilized against oxidative damage, for example those under the trade names Durazym® or Purafect® Oxp or Duramyl® or Purafect® OxAm known proteases or amylases.

Suitable graying inhibitors or soil release agents are Cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Preferably are sodium carboxymethyl cellulose and their mixtures with methyl cellulose used. Soil release agents commonly used include Copolyester, the dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units contain. Soil-removing copolyesters of the type mentioned as well their use in detergents has been known for a long time. For example, the German Offenlegungsschrift DT 16 17 141 a washing process using Polyethylene terephthalate-polyoxyethylene glycol copolymers. The German published application DT 22 00 911 relates to detergents made from nonionic surfactant and a copolymer Contain polyoxyethylene glycol and polyethylene terephthalate. In the German patent application DT 22 53 063 are acidic textile finishing agents called a copolymer from a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally contain 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 contained in certain molar ratios. From the European patent EP 185 427 are methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and Detergents containing such soil release polymer are known. The 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 ingredients in Agents according to the invention are generally not more than 2% by weight and are preferably 0.5% to 1.5% by weight. In a preferred embodiment of the Invention is the agent free of such active ingredients.

As an optical brightener for in particular textiles made of cellulose fibers (for example Cotton) can, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts may be included. 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 that replace the morpholino group a diethanolamino group, a methylamino group or a 2-methoxyethylamino group wear. Furthermore, brighteners of the type of substituted 4,4'-distyryl diphenyl may be present, for example 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of brighteners can also be used. For Polyamide fibers are particularly suitable for brighteners of the 1,3-diaryl-2-pyrazoline type, for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similar connections. The content of the agent in optical brighteners or brightener mixtures 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 that is Agents free from 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 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, the propensity to foam can be reduced by a suitable selection of the nonionic surfactants, so that the use of defoaming active substances can be completely dispensed with in a preferred embodiment of the invention.

To increase the physical stability as well as the chemical stability, in particular of the bleach component and enzymes which may be present, dehydrating agents can also be used, 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 the production of pasty detergents and cleaning agents according to the invention expediently the surfactant components, that is the nonionic Surfactants of the formulas I and II and the alcohols or ethers of the formula III and optionally soap and synthetic anionic surfactants to a homogeneous The premix is mixed and the solids and optionally in this premix other components can be incorporated. If the particulate solids are not are sufficiently finely divided, one or more grinding steps can be inserted.

A paste-like agent according to the invention preferably has a viscosity at 25 ° C. in the range from 80,000 mPas to 250,000 mPas, in particular 100,000 mPas to 250,000 mPas, 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 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 action of gravity. It is then preferably particularly pseudoplastic, that is to say it has a significantly lower viscosity when sheared and is flowable under the action 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 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, which is 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 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 during 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 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 of 1.3 kg / l up to 1.6 kg / l. The agent according to the invention can be used with conventional devices Dosing of pastes can be dosed, as for example in the international Patent application WO 95/29282, German patent application DE 196 05 906, the German patent specification DE 44 30 418 or the European patent specifications EP 0 295 525 and EP 0 356 707 have been described. One for them Dosage of structurally viscous pasty detergents is particularly suitable The device is, for example, from international patent application WO 95/09263 is known and is preferred for metering pseudoplastic pastes according to the invention used. The detergents and cleaning agents according to the invention can optionally can also be filled pre-portioned into water-soluble films in particular. Such films are, for example, in European patent application EP 253 151 described.

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. Composition of pasty detergents (% by weight) component 1 2nd 3rd 4th Nonionic surfactant I 18th 18th 18th 11 Nonionic surfactant II 11 11 11 18th Isotridecanol 5 5 5 5 Soap 1 1 1 1 Builder I 5 5 5 5 Builder II 0.2 0.2 0.2 0.2 Sodium silicate 47 57 - - Sodium tripolyphosphate 20th - 20th 20th Sodium percarbonate - - 20th 20th TAED - - 4th 4th enzyme - - 1 1 CMC / MC 1 1 1 1 Foam inhibitor 1 1 1 1 sodium to 100

Claims (14)

1. A paste-form detergent for use in institutional laundries containing nonionic surfactant, organic and/or inorganic builder, alkalizing agent and optionally bleaching agent, enzyme, redeposition-inhibiting polymer and/or other typical ingredients, characterized in that it is free from synthetic anionic surfactant of the alkyl benzenesulfonate type and contains 5% by weight to 30% by weight of an ethoxylated alcohol corresponding to general formula (I): R¹-(OC₂H₄)_m-OH in R¹ is an alkyl or alkenyl group containing 12 to 14 carbon atoms and the average degree of ethoxylation m may assume values of 1 to 8,
   1% by weight to 20% by weight of an ethoxylated alcohol corresponding to general formula (II): R²-(OC₂H₄)_n-OH in which R² is an alkyl or alkenyl group containing 12 to 22 carbon atoms and the average degree of ethoxylation n may assume values of 3 to 14, with the proviso that n is greater than m by at least 1.0,
   20% by weight to 80% by weight of alkalizing agent, 1% by weight to 20% by weight and, more particularly, 3% by weight to 15% by weight of long-chain alcohol or alkyl ether corresponding to general formula (III): R³-O-R⁴ in which R³ is an alkyl or alkenyl group containing 8 to 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.
2. A detergent as claimed in claim 1, characterized in that it contains 10% by weight to 25% by weight of the ethoxylated alcohol corresponding to general formula I.
3. A detergent as claimed in claim 1 or 2, characterized in that it contains 5% by weight to 15% by weight of the ethoxylated alcohol corresponding to general formula II.
4. A detergent as claimed in claim 3, characterized in that the average degree of ethoxylation n of the surfactant corresponding to formula II is higher by at least 2.0 than the average degree of ethoxylation m of the surfactant corresponding to formula 1.
5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains 3% by weight to 15% by weight of long-chain alcohol or alkyl ether corresponding to general formula III.
6. A detergent as claimed in any of claims 1 to 5, characterized in that it contains up to 5% by weight and, more particularly, from 0.5% by weight to 2% by weight of soap.
7. A detergent as claimed in any of claims 1 to 5, characterized in that it contains up to 5% by weight and, more particularly, from 0.5% by weight to 3% by weight of synthetic anionic surfactant selected from alkyl or alkenyl sulfates and/or ether sulfates.
8. A detergent as claimed in any of claims 1 to 7, characterized in that it contains 30% by weight to 70% by weight and, more particularly, 40% by weight to 60% by weight of alkalizing agent.
9. A detergent as claimed in any of claims 1 to 8, characterized in that it contains 5% by weight to 25% by weight and, more particularly, 10% by weight to 20% by weight of builders.
10. A detergent as claimed in any of claims 1 to 9, characterized in that the constituents of the paste-form detergent present as solid phase are in the form of fine particles with an average particle size of 5 µm to 200 µm and, more particularly, 10 µm to 80 µm.
11. A detergent as claimed in any of claims 1 to 10, characterized in that at most 10% of the particles of the constituents present as the solid phase have a particle size of more than 200 µm.
12. A detergent as claimed in any of claims 1 to 11, characterized in that it contains 0.2% by weight to 1.5% by weight and, more particularly, 0.5% by weight to 1% by weight of enzyme, more particularly protease, amylase, lipase and/or cellulase.
13. A detergent as claimed in any of claims 1 to 12, characterized in that it contains 1% by weight to 10% by weight and, more particularly, 2% by weight to 8% by weight dehydrating agent.
14. A detergent as claimed in any of claims 1 to 13, characterized in that it has a viscosity at 25°C of 80,000 mPa·s to 250,000 mPa·s, as measured with a Brookfield rotational viscosimeter (spindle No. 7) at 5 r.p.m., and a viscosity of 20,000 mPa·s to 80,000 mPa·s at 50 r.p.m. under otherwise the same conditions.