EP1141212B1 - Pasty washing agent - Google Patents

Abstract

The invention relates to a pasty washing agent for use in commercial laundering which contains a non-ionic surfactant, an organic and/or inorganic builder, a bleaching agent based on peroxygen, and optionally contains other common constituents. The inventive pasty washing agent is characterized in that it contains 30 wt. % to 60 wt. % of non-ionic surfactant, 0.5 wt. % to 5 wt. % of a fatty acid and/or fatty acid alkaline-salt, 5 wt. % to 15 wt. % of citrate and/or citric acid and 15 wt. % to 35 wt. % of an inorganic peroxygen compound. In addition, the pasty washing agent does not contain alkali metasilicate nor a bleach activator. In addition to exhibiting a good cleaning efficiency, the inventive agent has a disinfecting action.

Description

The present invention relates to paste detergents for use in commercial laundry, a process for producing such compositions, and a disinfecting laundry process in commercial laundry.

Detergents used in the household are tailored to the needs that occur there; they are usually powdery or sufficiently liquid to be easily poured out and dosed. Since such liquid detergents are to be storage-stable within relatively wide temperature ranges, additions of organic solvents and / or hydrotropes are frequently added, but these themselves do not contribute to the washing or cleaning result and are undesirable for this reason. One way to circumvent any dosing problems with insufficiently liquid agents is in the European patent application EP 253 151 A2 proposed. From this document liquid, sometimes highly viscous detergents based on nonionic and anionic surfactants are known which contain polyethylene glycol as a hydrotrope and which do not have to be metered by the user in liquid form, but are portioned into bags of water-soluble material, for example polyvinyl alcohol.

That in the European patent specification EP 295 525 B1 described pasty detergent consists of a liquid in the temperature range below 10 ° C phase, which is formed from nonionic surfactant, and dispersed therein a solid phase of certain grain size, which is formed from wash alkalis, sequestering agents and optionally anionic surfactants. For surfactants or their mixtures are used, the pour point (solidification point) must be below 5 ° C in order to avoid solidification of the paste at low transport and storage temperatures. This detergent paste is intended for commercial laundries and is so flowable that it can be conveyed via a suction line by means of a conventional feed pump. It has been found, however, that such pastes during their preparation can not always ensure satisfactory homogeneity of their ingredients and also often tend to segregate during storage. The segregation not only affects the separation of the solid from the liquid components, but also the phase separation of the liquid ingredients.

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

From the international patent application WO 98/10049 a paste-type detergent for use in commercial laundry is known, the nonionic surfactant, organic and / or inorganic builder, alkalizing, and optionally bleach, enzyme, graying inhibiting polymer and / or other conventional ingredients and is characterized in that it contains 5 wt .-% to 30 wt .-% of an ethoxylated alcohol of the general formula R ¹ - (OC ₂ H ₄ ) _m -OH (I) in which R ^{1 is} an alkyl or alkenyl radical having 9 to 15 carbon atoms and the mean degree of ethoxylation m can assume values of 1 to 8, 1 wt .-% to 20 wt .-% of an ethoxylated alcohol of the general formula R ² - (OC ₂ H ₄ ) _n -OH (II), in the R ^{2 is} an alkyl or alkenyl radical having 12 to 22 carbon atoms and the average degree of ethoxylation n can assume values of 3 to 14, with the proviso that n is at least 1.0 greater than m, 20% by weight to 80% by weight Alkalizing agent, in particular alkali metal silicate, 1 wt .-% to 2 0 wt .-% medium to long-chain alcohol or alkyl ethers of the general formula R ³ -OR ⁴ (III) in which R ^{3 is} an alkyl or alkenyl radical having 6 to 22 carbon atoms, in particular 8 to 22 carbon atoms and R ⁴ hydrogen or an alkyl radical having 1 to 6 carbon atoms, and containing up to 15 wt .-% organic builder of the type of polymeric polycarboxylates, where polymeric polycarboxylates polymerization products of unsaturated mono- and / or dicarboxylic acids are understood that except carboxyl groups no have further functionalities.

The commercial washing methods differ from household laundry, inter alia, that although also incurred different types of textiles and variously soiled textiles, but within the same time for washing upcoming material largely uniform mass wash occurs, which allows a specific cleaning task on the specific washing technology. However, in commercial laundries, there is a demand for efficient cleaning methods to a greater extent than household linen, since extremely soiled laundry and hospitalized laundry may be incurred. In order to keep the consumption of detergent as low as possible, commercial laundries are almost always washed with water free of hardness ions. For a detailed overview, please refer to the publication of H. Krüßmann and HG Hloch, "Washing Methods in Commercial Laundry", Surfactants Surfactants Detergents 24 (1987), 341-349 , and referenced the literature cited there.

The agents known from the above-mentioned documents have a high cleaning performance and are very well suited for commercial washing of soiled laundry. If incurred with possibly even pathogenic microorganisms scrubbed laundry, but they can not meet the demand for a simultaneous disinfection, so that in their use, the additional use of disinfecting agents is necessary.

There is thus a need for a cleaning agent composed as simply as possible which, in addition to a good cleaning performance, has a disinfecting effect when used in the wash cycle of conventional commercial washing devices.

The present invention, which is intended to remedy this need, is a paste-type laundry detergent for use in commercial laundry, according to claim 1.

It must be surprising that despite the absence of bleach activators, which is to be understood here under perhydrolysis precursor compounds such as esters and amides forming percarboxylic, a disinfecting agent is obtained.

Another object of the invention is a method for washing and disinfecting laundry in commercial laundry, using a corresponding pasty agent. It is preferably used in the 60 ° C wash program, ie at a washing temperature of about 60 ° C, used. In a preferred embodiment of the method according to the invention, it is also possible not to use all the ingredients of the paste-like composition according to the invention together in a detergent paste, but to use one or more of the ingredients, in particular the inorganic peroxygen compound, separately, wherein additionally a pasty agent is used, which corresponds to an agent according to the invention except for the missing ingredient or the wrong ingredients. With this procedure, it is possible with the use of a multi-chamber washing system to meter in the separately used ingredient, in particular the inorganic peroxygen compound, in the same or a different chamber than the pasty agent. The term "separately" used above is to be understood merely as the property "separate from the pasty agent", that is to say that the ingredient to be added separately can also be combined or blended with further substances customary in detergents which do not interact undesirably with it. be used.

The liquid phase of the pasty agent according to the invention is essentially formed by nonionic surfactants. An agent according to the invention contains from 32% by weight to 55% by weight, in particular from 35% by weight to 50% by weight. nonionic surfactant in the form of one or more ethoxylated and / or propoxylated alcohols, preferably those which correspond to the abovementioned formulas I or II. Particularly preferred is the use of mixtures of these. Alcohols or ethers of the formula III given above and, if appropriate, additional surfactants according to the general formula IV,

R ⁵ - (OC ₂ H ₄ ) _x - (OC ₃ H ₆ ) _y -OH (IV)

in which R ⁵ denotes an alkyl or alkenyl radical having 9 to 15 C atoms, in particular 12 to 15 C atoms, and the average degree of ethoxylation x can assume values of 3 to 7 and the average degree of propoxylation y values of 2 to 8 can be described in agents according to the invention also be present. The viscosity of the agent according to the invention can be adjusted by the combination of ethoxylated alcohols of the formulas I and II. In the case of the compounds of the formulas I, II and IV, the radicals R ¹ , R ² and R ^{5 may 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 a mean degree of ethoxylation m of 1 to 8, in particular 1 to 5. The nonionic surfactant according to formula II has a broader carbon chain length distribution towards longer chains having 12 to 22, in particular 12 to 18 and particularly preferably 16 to 18 carbon atoms and a higher average degree of ethoxylation n of 3 to 14, in particular 6 to 12. The ethoxylated alcohols of the formula I and the ethoxylated alcohols of the formula II are preferably present in weight ratios of from 2: 1 to 1: 1.8. The composition according to the invention may comprise further nonionic surfactants commonly used in detergents and cleaners, for example alkylpolyglycosides and / or fatty acid polyhydroxyamides. However, the surfactant component is preferably free of exclusively propoxylated alcohols.

For the alcohols or ethers of the general formula III, which contribute to the particularly good low-temperature stability of the compositions according to the invention, for the foaming and Reduce the surfactant deposition on the washed laundry provide and also contribute to the washing performance, applies with respect to the radical R ³ substantially the above for the radicals R ¹ and R ² executed. In addition to hydrogen, R ⁴ is preferably a methyl, ethyl, propyl or butyl group, with hydrogen and the methyl group, in particular hydrogen, being particularly preferred. In a preferred embodiment of the invention, the compositions contain up to 15% by weight, preferably 2% by weight to 10% by weight, of substances according to general formula III.

Fatty acids or their alkali metal salts, the so-called soaps, or mixtures of fatty acids and soaps are preferably present in compositions according to the invention in amounts of from 0.75% by weight to 2.5% by weight, in particular from 1% by weight to 2% by weight. -%, contain. Suitable soaps are in particular the alkali metal salts of saturated and / or unsaturated C ₁₂ come -18 fatty acids, for example coconut, palm kernel or tallow fatty acid in question, the corresponding acids can be used as such. Particularly preferred is the use of an optionally saponified carboxylic acid mixture, in each case based on the total carboxylic acid mixture, 2 wt .-% to 8 wt .-% C ₁₄ -, up to 1 wt .-% C ₁₅ -, 18 wt .-% to 24 Wt% C ₁₆ -, up to 3 wt% C ₁₇ -, 20 wt% - 42 wt% C ₁₈ - and 30 wt% - 44 wt% C _20-22 - carboxylic acid. In fatty acid soap mixtures, the weight ratio of fatty acid to fatty acid alkali salt is preferably in the range of 1:99 to 50:50, more preferably 5:95 to 25:75.

As further surfactants, the agent may optionally be up to 10 wt .-%, preferably up to 5 wt .-% and in particular 0.5 wt .-% to 3 wt .-% of synthetic anionic surfactants, in particular selected from the alkylbenzylsulfonates, alkyl or Alkenyl sulfates and / or ether sulfates. Suitable synthetic anionic surfactants which may preferably be incorporated into the composition according to the invention in solid, finely divided, substantially anhydrous form include in particular those of the sulphonate or sulphate type which are normally present as alkali metal salts, preferably as sodium salts. However, in particular the said surfactants of the sulfonate type can also be used in the form of their free acids. Suitable anionic surfactants of the sulfonate type are, in addition to the C _9-13 -alkylbenzenesulfonates, linear alkanesulfonates with 11 to 15 C atoms, as obtainable by sulfochlorination or sulfoxidation of alkanes and subsequent saponification or neutralization, Salts of sulfo fatty acids and their esters derived from saturated in particular α-position saturated C ₁₂ - to C ₁₈ fatty acids and lower alcohols such as methanol, ethanol and propanol, and Olefinsulfonate, as for example by sulfonation of terminal C ₁₂ - to form 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 C atoms, which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as a counter cation. Particularly suitable are the derivatives of linear alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. Accordingly, in particular the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl or octadecyl radicals and mixtures thereof are useful. Particularly preferred alkyl sulfates contain a tallow alkyl radical, that is to say mixtures having essentially hexadecyl and octadecyl radicals. The alkyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. In addition, the sulfated alkoxylation products of such alcohols, so-called ether sulfates, may be included in the compositions. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.

The solid phase of the composition according to the invention is essentially formed by the alkalizing agents, the inorganic peroxygen compounds and the builders, it being possible for further particulate auxiliaries to be present if appropriate. The solid phase should be dispersed as homogeneously as possible in the liquid surfactant phase. The components of the pasty agent contained as a solid phase should be finely divided and have a mean particle size in the range of 5 microns to 200 microns, with at most 15% of the particles have a particle size of more than 200 microns. Surprisingly, it is possible to incorporate relatively coarse-grained solids, for example those containing 20% to 50% of particles with particle sizes greater than 100 μm, into the pasty compositions without any disadvantage. Preferably the mean particle size of the particles forming the solid phase is 10 μm to 80 μm and in particular 10 μm to 60 μm, the maximum particle size being less than 300 μm, in particular less than 250 μm. Preferably, 90% by weight of the solid powdery constituents are smaller than 200 μm, in particular smaller than 150 μm. The average particle size can be determined by known methods (for example by means of laser diffraction or Coulter Counter).

The alkalizing agents contained as another component are often referred to as Waschalkalien. They are predominantly assigned to the fixed phase. Under conditions of use, they provide for a pH in the alkaline range, which is normally in the range from 9.5 to 11.5, in particular from 10 to 11 (measured in 1% by weight solution of the agent in ion-exchanged water). Preferred alkalizing agent is alkali metal carbonate, which may optionally also be used in admixture with alkali metal bicarbonate. Alkali metal silicates as strong alkalizing agents are not included in the pasty compositions of the invention. The proportion of agents in alkalizing agents is generally from 20% by weight to 80% by weight, preferably from 30% by weight to 70% by weight and in particular from 40% by weight to 60% by weight. In particular, when a phosphate content is ecologically harmless when using agents according to the invention (for example in a wastewater treatment which eliminates the phosphates), pasty agents according to the invention may optionally also contain polymeric alkali metal phosphates, such as sodium tripolyphosphate. Their proportion is preferably up to 70 wt .-%, in particular 15 wt .-% to 40 wt .-%, based on the total agent, wherein the proportion of other solids, for example, the alkali metal carbonate and / or aluminosilicate, if appropriate, accordingly can be reduced. In a preferred embodiment of the invention, these agents contain from 5% by weight to 15% by weight, in particular from 6% by weight to 10% by weight, of alkali metal carbonate and / or alkali metal bicarbonate.

As an organic builder substance, an agent according to the invention contains citric acid, alkali citrate or mixtures thereof. In addition, other monomeric polycarboxylic acids or hydroxycarboxylic acids such as gluconic acid or salts thereof and customary co-builders or complexing agents from the class of aminopolycarboxylic acids and polyphosphonic acids are suitable. To the aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues, with N, N-bis (carboxymethyl) aspartic acid being preferably used. Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and their higher homologs, such as diethylenetetramine tetra (methylenephosphonic acid). The abovementioned acids are usually used in the form of their alkali metal salts, in particular the sodium or potassium salts. The builders which can also be used include homopolymeric and / or copolymeric carboxylic acids or their alkali metal salts, the sodium or potassium salts being particularly preferred here as well. Particularly suitable are polymeric carboxylates or polymeric carboxylic acids having a molecular weight of at least 350, in the form of their water-soluble salts, in particular in the form of sodium and / or potassium salts, as oxidized polysaccharides according to the international patent application WO 93/08251 , Polyacrylates, polymethacrylates, polymaleinates and in particular copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those of 50 to 70% of acrylic acid and 50 to 10% of maleic acid, as described, for example, in European Pat EP 022 551 are characterized. The molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. 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 may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical. Such polymers can be prepared in particular by methods which are described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1,000 and 200,000. Other preferred copolymers are those described in the German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate. Polyacetalcarboxylic acids, as used, for example, in US Pat US Pat. No. 4,144,226 and US 4,146,495 are obtained by polymerization of esters of glycolic acid, introduction of stable terminal end groups and saponification to the sodium or potassium salts. Also suitable are polymeric acids which are obtained by polymerization of acrolein and disproportionation of the polymer to Canizzaro by means of strong alkalis. They are composed essentially of acrylic acid units and vinyl alcohol units or acrolein units. A Mitttel invention preferably contains 8 wt .-% to 12.5 wt .-% citrate and / or citric acid. In addition to citrate and / or citric acid, it preferably contains from 2% by weight to 12% by weight, in particular from 5% by weight to 10% by weight, of further organic builder in the form of polymeric polycarboxylate.

Suitable inorganic builders for use in compositions according to the invention are, in addition to the abovementioned phosphate, crystalline alkali metal silicates and finely divided alkali metal aluminosilicates, in particular zeolites of the NaA, X and / or P type. Suitable zeolites normally have a calcium binding capacity in the range of 100 to 200 mg CaO / g, which is as described in US Pat German patent DE 24 12 837 can be determined. Their particle size is usually in the range of 1 .mu.m to 10 .mu.m. They are used in dry form. The water contained in bound form in the zeolites does not interfere in the present case. Crystalline silicates which may be present alone or in a mixture with the said aluminosilicates are preferably crystalline phyllosilicates of the formula NaMSi _x O _{2 +} x.yH ₂ O in which M is hydrogen or sodium, x is a number of 1.9 to 4 and y is a number from 0 to 20. Preferred values for x are 2, 3 and 4. Such crystalline sheet silicates are For example, in the European patent application EP 164 514 described. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ · yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the process described in International Patent Application WO 91/08171 is described. Useful crystalline silicates are commercially available under the names SKS-6 (manufacturer Hoechst) and Nabion® 15 (manufacturer Rhone-Poulenc). The content of such inorganic builder material in the paste may be up to 35% by weight, preferably up to 25% by weight and especially 10% by weight to 25% by weight.

In addition, a paste-form agent according to the invention contains oxygen-containing oxidizing agent in the form of inorganic peroxygen compounds, which are preferably selected from the group consisting of alkali metal perborate, alkali metal percarbonate and mixtures thereof and wherein sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important in addition to sodium percarbonate. Further suitable oxidizing agents are, for example, persulfates and peroxypyrophosphates. Inorganic peroxygen compounds may preferably be present in agents according to the invention in amounts of from 20% by weight to 30% by weight, in particular from 22.5% by weight to 27.5% by weight. The disinfecting power of the compositions according to the invention at temperatures around 60 ° C is given without the presence of bleach activators, so that the agents according to the invention are free from such usually the oxidizing power of such oxidizing agents improving bleach activators.

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

The paste detergent according to the invention are preferably substantially free from water. By "essentially free of water" is meant a state in which the content of free water, that is not in the form of water of hydration and water of constitution, is up to 5% by weight, preferably below 3% by weight. It is noteworthy that, despite the presence of the pers oxygen-containing bleach certainly higher water contents than conventional pasty substantially anhydrous detergents are possible. Organic solvents, which include the low molecular weight and low boiling alcohols and ether alcohols commonly used in liquid concentrates, as well as hydrotropic compounds may optionally be included in amounts up to 6 wt .-%, but are preferably not present.

Suitable enzymes in the compositions according to the invention are, in particular, those from the class of proteases, lipases, cutinases, amylases, pullulanases, 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 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner to carriers and / or be embedded in encasing substances or incorporated into the pastes as concentrated, preferably anhydrous liquid formulations. Useful proteases 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 known. Enzymes stabilized against oxidative damage, for example the proteases or amylases known under the trade names Durazym® or Purafect® OxP or Duramyl® or Purafect® OxAm, are preferably used.

Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preferably, sodium carboxymethylcellulose and their mixtures are used with methylcellulose. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Dirt-releasing copolyesters of the type mentioned as well as their use in detergents have been known for a long time. For example, this describes the German patent application DE 16 17 141 a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. The German patent application DE 22 00 911 relates to detergents containing nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. In the German Offenlegungsschrift DE 22 53 063 are called acidic textile finishing agents containing 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 compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From the European patent EP 185 427 For example, methyl or ethyl group-end capped polyesters having 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 grayness inhibitors and / or soil-release active ingredients in compositions according to the invention is generally not more than 2% by weight and is preferably from 0.5% by weight to 1.5% by weight.

Suitable color transfer inhibitors for use in compositions according to the invention include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole, and mixtures thereof. The proportion of color transfer inhibitors in compositions according to the invention is preferably 0.1% by weight to 2% by weight, in particular 0.2% by weight to 1% by weight.

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

The customary foam regulators which can be used in the compositions 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 as well as crosslinked polysiloxane resins and mixtures thereof. Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Among these, preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C ₁₆ - to C ₁₈ -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight. In many cases, the additional use of defoaming agents can be completely dispensed with.

Dehydrating agents, for example in the form of water-crystal-binding salts such as anhydrous sodium acetate, calcium sulfate, calcium chloride, sodium hydroxide, magnesium silicate, or metal oxides such as CaO, MgO, P ₄ O ₁₀ or Al may also be used to increase the physical stability and chemical stability of the optionally present enzymes ₂ O ₃ , are used. Such dehydrating agents, with which the water content of inventive agents can be reduced to particularly low levels if desired, are present in amounts of preferably 1 wt .-% to 10 wt.% And in particular 2 wt.% To 8 wt.% In the compositions according to the invention.

For the preparation of inventive paste-form detergents and cleaning agents, preference is given to initially introducing the nonionic surfactant or nonionic surfactants, optionally admixing the alcohol or ether of formula III with the mixture of fatty acid alkali metal salt and fatty acid and optionally the foam regulator and the synthetic anionic Surfactant mixed into a homogeneous premix. Such a premix is largely storage-stable and flowable at temperatures ranging from room temperature to 40 ° C, even if at these temperatures, the components of the premix are not always completely liquid or dissolved. To this premix, preferably after heating to temperatures in the range of about 80 ° C, the powdery ingredients including the citric acid / citrate of the pasting agent are mixed, which are dispersed in particular by stirring in the premix. After that, the premix. Subsequently, the mixture thus obtained is preferably subjected to a wet grinding operation. This gives the product the desired consistency and homogeneity. The admixture of further, especially temperature or shear-sensitive ingredients such as perfume oils and enzymes is then carried out, their homogeneous incorporation should be done as gently as possible, so as not to destroy the structure of the paste. The resulting detergents or cleaners according to the invention are flowable and pumpable directly after production by the applied shear forces and can thus be filled into conventional sales containers.

A paste-like composition according to the invention preferably has a viscosity at 25 ° C. in the range from 60,000 mPa.s to 100,000 mPa.s, in particular 70,000 mPa.s to 90,000 mPa.s, measured with a Brookfield rotary viscometer (Spindel.Nr 7) at 5 revolutions per minute. These viscosity values refer to the reading after a measuring time of 3 minutes to take into account any possible thixotropic effect of the paste. The pasty washing and cleaning agent has in one special embodiment of the invention preferably at room temperature such a viscosity that it is not flowable under the action of gravity. Preferably, it is then particularly thixotropic and structurally viscous, that is, it has a significantly lower viscosity in shear and is flowable under the action of gravity, with it particularly preferred an apparent viscosity of about 80,000 to 120,000 Pas at 25 ° C and a shear rate from 0.0001 s ^-1 - to be determined with a CS-Rheometer from Bohlin with measuring system plate / plate, plate distance 4 mm - has. When exposed to sufficient shear forces, for example, a shear rate of 0.1 s ^-1 and otherwise the same measurement conditions, an agent according to the invention preferably has a considerable, typically 100 to 1000 times lower viscosity. The reduction in viscosity under shear is largely reversible, that is, after completion of the shear, the agent goes back to its original physical state without the occurrence of segregation. In this context, it should be noted that the viscosities mentioned refer not to measurements directly after preparation of the paste, but to stored, so to speak in equilibrium pastes, since the shear forces acting in the context of the manufacturing process lead to a lower paste viscosity, which only in Course of time increased to the relevant final viscosity. Storage periods of 1 month are generally sufficient.

An agent according to the invention normally has a density in the range of 1.3 kg / l to 1.6 kg / l. The composition according to the invention can be dosed with conventional devices for metering pastes, as described, for example, in the international patent application WO 95/29282 , of the German patent application DE 196 05 906 , of the German patent DE 44 30 418 or the European patents EP 0 295 525 respectively EP 0 356 707 have been described. A particularly suitable for the dosage pseudoplastic paste-form detergent is suitable for example from the European patent EP 0 721 521 is known and is preferably used for the dosage pseudoplastic viscosity pastes. If appropriate, the detergents and cleaners according to the invention can also be filled in pre-portioned form into, in particular, water-soluble films. Such films are for example in the European Patent Application EP 0 253 151 described. A paste-form agent according to the invention is preferably used in commercial laundry for washing and disinfecting dirty laundry. It is used in concentrations of preferably 2 g / l to 5 g / l in the wash.

example example 1

The substances indicated in the table below were mixed together and ground in a mill (roller mill, continuous flow rate). Directly after production, flowable paste-form detergents M1 to M6 were obtained. The agents had a density of about 1.4 g / cm ³ and a viscosity (measured at 25 ° C with a Brookfield viscometer DV-II with spindle no. 7, at 5 revolutions per minute, after a measuring time of 3 minutes) of about 80 000 mPa.s on. The viscosity of the pastes did not change significantly when stored for 3 months. <u> Table 1: Composition of paste detergent (% by weight) </ u> M1 M2 M3 M4 M5 M6 Nonionic surfactant ^a) 20 19 19 - - 9 Nonionic surfactant ^b) 10 9 7 7 7 9 Nonionic surfactant ^c) - - - - 16 - Nonionic surfactant ^d) - - - 16 - - Nonionic surfactant ^e) - - - 3 3 - Nonionic surfactant ^f) 8th 7 9 9 11 19 alkylbenzenesulfonate 0.8 0.7 0.7 0.7 0.7 0.7 Fatty acid / soap ^g) 1.2 1.6 1.6 1.6 2 2 isotridecanol - 3 3 3 3 3 Na citrate 10 10 - 5 10 - citric acid - - 10 5 - 10 Na perborate 25 25 25 25 25 25 Polymeric polycarboxylate 4 6 6 6 6 6 phosphonate 0.5 1.6 1.6 1.6 1.6 1.6 Na bicarbonate - 7 - - - - Foam inhibitor ^h) 1 1 1 1 1 1 opt. brighteners 0.2 0.5 0.5 0.5 0.5 0.5 enzymes 0.6 0.8 0.8 0.8 0.8 0.8 Na carbonate on 100 a) C _12-14 fatty alcohol + 3 EO (Dehydol® LS 3, manufacturer Henkel KGaA)
b) C _12-18 fatty alcohol + 7 EO (Dehydol® LT 7, manufacturer Henkel KGaA)
c) C _9-11 oxo alcohol + 3 EO (Lutensol® ON 30, manufacturer BASF AG)
d) C _9-11 oxo alcohol + 7 EO (Lutensol® ON 70, manufacturer BASF AG)
e) Oleyl Cetyl Alcohol + 2 EO (Foryl® 502, Manufacturer Henkel KGaA)
f) C _12-14 fatty alcohol + 4 EO + 5 PO (Dehypon® LS 54, manufacturer Henkel KGaA)
g) C _16/22 fatty acid present as Na salt (Edenor® W 35, manufactured by Henkel KGaA)
h) mono- / distearyl phosphate

Example 2: Determination of the disinfecting effect of M1 Material and methodology:

4.2 Chemothermic laundry disinfection - disinfectant commission of the Hygiene and Microbiology, Hyg. Med 1998, 23, 127-129 ,

Test germs:

S. aureus ATCC 6538 E. faecium ATCC 6057 E. coli NCTC 10538 C. albicans ATCC 10231

1. Determination of bacteriostatic and fungistatic efficacy as well as suitable inactivating substances (according to "Guidelines" I / 2.1)

Growth inhibition after 72 hours incubation at 37 ° C Final concentrations of M1 10 g / liter - further dilutions 1: 1 No inactivation additive S. aureus - - + + + + E. faecium - + + + + + E. coli - + + + + + C. albicans - + + + + + 3% Tween 80 + 0.3% Lecithin + 0.1% Cysteine S. aureus - + + + + + E. faecium - + + + + + E. coli - - - + + + C. albicans - + + + + + 3% Tween 80 + 3% saponin + 0.1% histidine + 0.1% cysteine S. aureus - - + + + + E. faecium - + + + + + E. coli - + + + + + C. albicans - + + + + + 3% Tween 80 + 0.3% Lecithin + 0.1% Histidine + 0.5% Na thiosulfate S. aureus + + + + + + E. faecium + + + + + + E. coli - + + + + + C. albicans + + + + + + Inactivation combination in the further experiments: 3% Tween 80 + 0.3% lecithin + 0.1% histidine + 0.5% sodium thiosulfate
Explanations:
+ = Turbidity due to germ multiplication
- = lack of turbidity due to germ multiplication

2. Bactericidal action in the quantitative suspension test (mod. according to "Guidelines" I / 2.3) Process temperature : 60 ° C Seed content of the starting suspension:

E. faecium ATCC 6057: 9.34 log./ml (preculture on Brain Heart infusion agar, 48 h at 36 ± 1 ° C) Concentrations of Reduction factors (log.) After M1 Exposure time in minutes (g per liter) 5 10 15 30 Without albumin load (I / 2.3.1) 6 5.07 ≥ 5.27 ≥ 5.26 ≥ 5.26 3 3.50 ≥ 5.27 ≥ 5.26 ≥ 5.26 1.5 3.05 ≥ 5.27 ≥ 5.26 ≥ 5.26 0.75 3.02 ≥ 5.27 ≥ 5.26 ≥ 5.26 passphrase (Log./20°C) 6.27 6.27 6.27 6.26 6.26 passphrase (log./60 ° C) 6,24 6,17 6.17 6.16 6.10 With 0.2% albumin load (I / 2.3.2) 6 4.90 ≥ 5.29 ≥ 5.24 ≥ 5.10 3 4.51 ≥ 5.29 ≥ 5.24 ≥ 5.10 1.5 3.62 ≥ 5.29 ≥ 5.24 ≥ 5.10 0.75 3.09 ≥ 5.29 ≥ 5.24 ≥ 5.10 passphrase (log./20 ° C) 6.31 6.29 6.24 6.10 passphrase (log./60 ° C) 6.30 6.19 6.16 6.11

3. Examination of the chemothermal laundry disinfection Test germ: Enterococcus faecium ATCC 6057

Incultured on Brain Heart Infusion Agar (BHI, Becton-Dickinson 11065) for 48 hours at 36 ± 1 ° C. After washing with physiological saline solution, after centrifuging and pouring off the supernatant, the germs were taken up in concentrated shaking blood (Oxoid) and homogenized.

Contamination of the germ carriers

The standard cotton cloth lobules (1 × 1 cm, DIN 53919) were immersed in the germ-blood suspension and dried in open Petri dishes for 3 hours at 36 ± 1 ° C.

Carrying out the tests

All tests were carried out on a Miele WS 5080 automatic washer-extractor. Per kilogram of laundry, 12.5 ml of shaking blood (Oxoid) were added to the wash before the water inlet. After completion of the disinfection phase, ie before rinsing, the 10 germ carriers were removed and immediately introduced individually into 5 ml each of casein peptone-soybean meal peptone solution (CSL) with inactivating substances + glass beads. The germ detection was carried out after homogenizing the enrichment cultures by shaking (10 min, 300 min ^-1 ) in the casting process. To this was added 1 ml directly and 1 ml after dilution (0.5 ml in 4.5 ml CSL) in 20 ml each of liquid CSA (casein peptone-soybean meal peptone agar). In addition, the individual lobules were introduced into cast plates. These plates as well as the above were incubated at 36 ± 1 ° C for 3 weeks.
For the detection of propagatable test germs in the liquor, 100 ml of liquor were taken after completion of the disinfection phase and immediately mixed with 100 ml of doubly concentrated CSL + double-concentrated inactivating substances.
After 3, 7 and 21 days of incubation at 36 ± 1 ° C, subcultures were grown on SLANETZ BARTLEY agar (Oxoid / CM 377) to detect the test germs, incubation for 48 hours at 44 ° C. Test series : M1: 3.0 g / l liquor - added to Start of the washing process disinfection temperature 60 ° C Reaction time: 15 minutes Liquor ratio: 1: 4 1st test series 2nd test series 3rd test series Linen (sheets): 4.72 kg 4.72 kg 4.72 kg Additional blood: 59.0 ml 59.0 ml 59.0 ml Amount of M1: 57.0 g 57.0 g 57.0 g Heating time: 10 min 54 s 11 min 10 s 11 min 07 s measured temp .: Beginning : 60.3 ° C 60.0 ° C 60.2 ° C End : 62.1 ° C 60.4 ° C 60.1 ° C Area: 59.9 - 64.2 ° C 59.8 - 64.1 ° C 60.0 - 64.1 ° C Starting blood germ suspension log / CFU / ml: 10.70 10.70 10.70 per germ carrier log KBE: 9.70 9.70 9.70 9.60 9.60 9.60 9.65 9.65 9.65 x: 9.65 9.65 9.65 Recoverable CFU after exposure: 1 ml of CSA Cast plate RF 1 ml of CSA Cast plate RF 1 ml of CSA Cast plate RF Germ carrier 1 0 + > 8.95 0 + > 8.95 0 + > 8.95 Germ carrier 2 0 + > 8.95 2 + 8.65 0 + > 8.95 Germ carrier 3 2 + 8.65 0 + > 8.95 0 + > 8.95 Germ carrier 4 1 + 8.95 3 + 8.47 0 + > 8.95 Germ carrier 5 1 + 8.95 0 + > 8.95 0 + > 8.95 Germ carrier 6 1 + 8.95 0 + > 8.95 0 + > 8.95 Germ carrier 7 0 + > 8.95 0 + > 8.95 0 + > 8.95 Germ carrier 8 1 + 8.95 0 + > 8.95 1 + 8.95 Germ carrier 9 0 + > 8.95 1 + 8.95 0 + > 8.95 Germ carrier 10 0 + > 8.95 3 + 8.47 0 + > 8.95 + = Growth of the test germ (germ carrier in cast plates)
- = no growth of the test germ (germ carrier in cast plates)

Testreihe:

Ohne Waschmittel
Waschschleuderautomat Miele WS 5080
Flottenverhältnis: 1 : 4

No proof of the test germ in the enrichments of 100 ml liquor. Sterile 6 lobes exposed in the 1st test series showed no evidence of the test organisms in the enrichment culture.

Test series :

Without detergent
Washer-extractor Miele WS 5080
Fleet ratio: 1: 4

1st test series

Laundry: Bed linen 4.72 kg Blood supplement : 59.0 ml Heating time : 12 min 44 s Disinfection temperature : 60 ° C Disinfection time : 15 minutes measured temp .: Beginning : 60.1 ° C End : 63.6 ° C Area : 60.0 - 64.2 ° C Starting blood germ suspension log.KBE / ml : 10,70 E. faecium per germ carrier log. KBE: 9.70 9.60 9.60 x : 9.65 recoverable KBE (log) on 1 ml of CSA cast iron plate RF Germ carrier 1 398 + 6.35 Germ carrier 2 578 + 6.19 Germ carrier 3 714 + 6.10 Germ carrier 4 178 + 6.70 Germ carrier 5 156 + 6.76 Germ carrier 6 44 + 7.31 Germ carrier 7 311 + 6.46 Germ carrier 8 262 + 6.53 Germ carrier 9 436 + 6.31 Germ carrier 10 360 + 6.40 + = Proof of the test germ (lobes in cast plates)
- = no proof of the test germ (lobes in cast plates) Detection test germ in the liquor (enrichment).

4. Assessment of the results

The tests were carried out according to the requirements "4.2 Chemothermic laundry disinfection" (as of April 1998) of the German Society for Hygiene and Microbiology. According to the current state of knowledge, it can be assumed that in chemothermic laundry disinfection processes at temperatures of 60 ° C. and above, the test germ Enterococcus faecium is more resistant than tuberculosis pathogens and the previously used further test bacteria Staphylococcus aureus, Candida alibicans and Escherichia coli.
The results of the quantitative suspension experiments at 60 ° C show that reduction factors of ≥ 5 log ₁₀ units were achieved within 10 minutes with the addition of the detergent M1 (3.0 g / liter) of interest for the method in the washing machine.

Also in the tests of the suitability of the chemothermal wash disinfection process under severe conditions with 12.5 ml blood supplement per kilogram of wash, reduction procedures greater than 8.5 log ₁₀ units were detected.

When agents M2 to M6 from Example 1 were used, similarly good disinfection results were obtained.

Claims (19)

1. A pasty detergent with a disinfecting effect for use in commercial laundries, said detergent including non-ionic surfactant, organic and/or inorganic builder, peroxygen-based bleaching agent, and optionally other usual ingredients, characterized in that it includes 30 wt.-% to 60 wt.-% of non-ionic surfactant, with 32 wt.-% to 55 wt.-% of non-ionic surfactant being included in the form of one or more ethoxylated and/or propoxylated alcohols, 0.5 wt.% to 5 wt.-% of fatty acid and/or fatty acid alkali salt, 5 wt.-% to 15 wt.-% of citrate and/or citric acid and 15 wt.-% to 35 wt,-% of inorganic peroxygen compound, and is free of alkali metasilicate and bleach activator.
2. The detergent according to claim 1, characterized in that it includes 35 wt.-% to 50 wt.-% of non-ionic surfactant in the form of one or more ethoxylated and/or propoxylated alcohols.
3. The detergent according to claim 1 or 2, characterized in that it includes 0.75 wt.-% to 2.5 wt.-%, particularly 1 wt.-% to 2 wt.%, of the fatty acid and/or fatty acid alkali salt.
4. The detergent according to any of claims 1 to 3, characterized in that it includes a mixture of fatty acid and fatty acid alkali salt with a weight ratio ranging from 1:99 to 50:50, particularly from 5:95 to 25:75.
5. The detergent according to any of claims 1 to 4, characterized in that it includes 8 wt.-% to 12.5 wt.-% of citrate and/or citric acid.
6. The detergent according to any of claims 1 to 5, characterized in that it includes, in addition to citrate and/or citric acid, 2 wt.% to 12 wt.-%, particularly 5 wt.-% to 10 wt.-%, of further organic builder in the form of polymeric polycarboxylate.
7. The detergent according to any of claims 1 to 6, characterized in that it includes 20 wt.-% to 30 wt.-%, particularly 22.5 wt.-% to 27.5 wt.-%, of inorganic peroxygen compound.
8. The detergent according to any of claims 1 to 7, characterized in that the inorganic peroxygen compound is selected from the group comprising alkali perborate, alkali percarbonate and mixtures thereof.
9. The detergent according to any of claims 1 to 8, characterized in that it includes up to 5 wt.-%, particularly 0.5 wt.-% to 3 wt.-%, of alkyl benzenesulfonate.
10. The detergent according to any of claims 1 to 3, characterized in that a 1% by weight aqueous solution thereof has a pH value ranging from 9.5 to 11.5, particularly from 10 to 11.
11. The detergent according to any of claims 1 to 10, characterized in that it has a viscosity at 25°C in a range of from 60,000 mPas to 100,000 mPas, particularly from 70,000 mPas to 90,000 mPas (Brookfield rotary viscosimeter, spindle No. 7, 5 rpm).
12. The detergent according to any of claims 1 to 11, characterized in that it includes 5 wt.-% to 15 wt.-%, particularly 6 wt.-% to 10 wt.%, of alkali carbonate and/or alkali hydrogen carbonate.
13. The detergent according to any of claims 1 to 12, characterized in that the ingredients of the pasty detergent included in the form of a solid phase are fine particles, having a mean grain size ranging from 5 µm to 200 µm, particularly from 10 µm to 80 µm.
14. The detergent according to any of claims 1 to 13, characterized in that at most 15% of the particles of the ingredients included in the form of a solid phase have a grain size of more than 200 µm.
15. The detergent according to any of claims 1 to 14, characterized in that it includes 0.2 wt.-% to 1.5 wt.-%, particularly 0.5 wt.% to 1 wt.%, of enzyme, particularly protease, amylase, lipase and/or cellulase.
16. A process for the production of the pasty detergent according to any of claims 1 to 15, characterized in that the non-ionic surfactant is introduced, the mixture of fatty acid and fatty acid alkali salt and optional foam regulator and synthetic anionic surfactant is mixed into a homogeneous premix, said premix, optionally following heating at temperatures in a range of about 80°C, the powdered components, including citric acid/citrate, of the pasty detergent are added with mixing, which components are dispersed in the premix particularly by stirring, followed by optional cooling to temperatures in a range of about 45°C, and the peroxygen compound is metered thereto, the resulting mixture is subsequently subjected to a wet grinding process, so that the product obtains the desired consistency and homogeneity, followed by preferably careful homogeneous incorporation of additional, particularly temperature-sensitive or shear-sensitive, ingredients.
17. Use of the detergent according to any of claims 1 to 15 in commercial laundries for washing and disinfecting soiled laundry.
18. A method of washing and disinfecting laundry in commercial laundries, characterized in that a detergent according to any of claims 1 to 15 is used.
19. A method of washing and disinfecting laundry in commercial laundries, characterized in that a detergent according to any of claims 1 to 15 is used, in which detergent one ingredient, particularly the inorganic peroxygen compound, is absent, and that said ingredient is employed separately.