EP0929630A1 - Paste-like washing and cleaning agent - Google Patents

Paste-like washing and cleaning agent

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Publication number
EP0929630A1
EP0929630A1 EP19970944804 EP97944804A EP0929630A1 EP 0929630 A1 EP0929630 A1 EP 0929630A1 EP 19970944804 EP19970944804 EP 19970944804 EP 97944804 A EP97944804 A EP 97944804A EP 0929630 A1 EP0929630 A1 EP 0929630A1
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EP
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wt
alkyl
characterized
composition according
contains
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EP19970944804
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German (de)
French (fr)
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EP0929630B1 (en )
Inventor
Thomas Merz
Khalil Shamayeli
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Ecolab GmbH and Co oHG
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Ecolab GmbH and Co oHG
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2068Ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0004Non aqueous liquid compositions comprising insoluble particles
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0008Detergent materials characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions; Pastes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Abstract

A paste-like washing and cleaning agent contains non-ionic surfactants, organic and/or inorganic builders, alkalising agents and if required bleaching agents, enzymes, greying-inhibiting polymers and/or other usual ingredients and is characterised in that it is free from synthetic anionic surfactants of the alkyl benzene sulphonate type and in that it contains 5 to 30 wt % of an ethoxylated alcohol of general formula (I): R1-(OC2H4)m-OH, in which R1 stands for an alkyl or alkenyl radical with 12 to 14 C atoms and can take a mean ethoxylation value m from 1 to 8; 1 to 20 wt % of an ethoxylated alcohol of general formula (II): R2-(OC2H4)n-OH, in which R2 stands for an alkyl or alkenyl radical with 12 to 22 C atoms and can take a mean ethoxylation value n from 3 to 14, provided that n be higher than m by at least 1.0; 20 to 80 wt % alkalising agents; 1 to 20 wt %, in particular 3 to 15 wt % of a long-chain alcohol or alkyl ether of general formula (III): R3-O-R4, in which R3 is an alkyl or alkenyl radical with 8 to 22 C atoms and R4 is hydrogen or an alkyl radical with 1 to 6 C atoms; and up to 5 wt % organic builders of the polymer polycarboxylate type.

Description

A paste detergents and cleaners

The present invention relates pastenformige detergents and cleaning agents and a process for their preparation.

Detergents used in the home are adapted to the occurring there Bedürfhisse; so they are usually in powder form or sufficiently fluid to be poured easily and can be metered. Since such liquid detergent should be stable in storage over relatively broad temperature ranges, additions of organic solvents and / or hydrotropes are often added, which however themselves provide no contribution to the washing or cleaning result and are undesirable for this reason. One way of avoiding possible dosing problems with insufficiently liquid means is proposed in the European patent application EP 253 151 A2. From this document liquid, partially highly viscous detergents are known on the basis of nonionic and anionic surfactants which contain polyethylene glycol as hydrotrope and which do not have to be dosed in liquid form by the user, but in portions in bags of water-soluble material, for example polyvinyl alcohol, packaged.

The pastenformige detergent described in European Patent EP 295 525 B 1 comprises a liquid in the temperature range below 10 ° C phase, which is formed from non-ionic surfactant, and dispersed therein a solid phase certain grain size, formed from washing alkalis, sequestering agents and optionally anionic surfactants becomes. Thereof are surfactants or surfactant mixtures used whose pour point must (solidification point) is below 5 ° C, to avoid solidification of the paste at low transportation and storage temperatures. This detergent paste is intended for institutional laundries and has such a flowability that it can be conveyed via a suction line by a conventional delivery pump. However, it was found that such pastes can not always satisfactorily ensure the homogeneity of their ingredients during their production and during storage often tend to separate. The separation involves not only the separation of the solid from the liquid components, but also the phase separation of the liquid ingredients.

Another paste-form detergent which contains ethoxylated liquid nonionic surfactant 40 to 70 wt .-% at room temperature liquid ethoxylated fatty alcohol having 10 to 20 carbon atoms and an average degree of ethoxylation of 1 to 8 and 20 to 50 wt .-% at room temperature and propoxylated Fettalkohoi with contains 10 to 20 carbon atoms and an average degree of ethoxylation of 2 to 8 and an average degree of propoxylation of 1 to 6 and 1 to 10 wt .-% of soap, is described in the international patent application WO 95/09229. This paste-form detergent or cleaning agent is so pseudoplastic that it is at room temperature under the action of gravity can not flow, but has a distinctly lower viscosity on shearing and then flows under the influence of gravity. The dosage of this paste-form detergent or cleaning agent is preferably characterized in that the means for lowering the viscosity of the shear is subjected and then flowable means may be metered by feed pumps.

More recently, the demand for the renunciation as not sufficiently biodegradable perceived detergent ingredients is charged in commercial laundries. This requirement is particularly difficult to comply with because much higher demands must be imposed on the cleaning performance of detergent compared to the conditions in the household. This is especially true for very much contributing to the cleaning performance surfactant components in which synthetic anionic surfactants, in particular, play the type of sulfonated alkyl benzenes, in this regard a major role.

The present invention was therefore based on the object to provide a paste-form detergent for use in commercial laundry facility, which has a good washing performance with good storage stability, though it usually omitted required for this synthetic anionic surfactants of the alkylbenzenesulfonate type.

This could be substantially achieved by an optimization of the nonionic surfactant component and the use of long-chain alcohols or long-chain alkyl ethers and.

Gegenst.and of the present invention is a paste-form detergent for use in institutional laundries, contains tend nonionic surfactant, organic and / or inorganic builder, alkalizing agent and optionally bleaching agent, enzyme, redeposition-inhibiting polymer and / or other customary ingredients, which is characterized is that it is free from synthetic anionic surfactant of the alkyl benzenesulfonate type and 5 wt .-% to 30 wt .-%, especially 10 wt .-% to 25 wt .-% of an ethoxylated alcohol of the general formula I,

R 1 - (OCΛVOH (I) in which R 1 is an alkyl or alkenyl radical having 8 to 14 carbon atoms and the average degree of ethoxylation m values 1-8 can accept, 1 wt .-% to 20 wt .-%, particularly 5 wt .-% to 15 wt .-% of an ethoxylated alcohol of the general formula II,

R 2 - (OC 2 H 4) n -OH (II) in which R 2 is an alkyl or alkenyl group 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 20 wt .-% is greater by at least 1.0, in particular by at least 2.0 than m, to 80% by weight of alkalizing agent, 1 wt .-% to 20 wt .-%, more preferably 3 wt .-% to 15 % by weight of long-chain alcohol or alkyl ether of the general formula III,

R 3 -O-R 4 (III), an alkyl or alkenyl radical having 8 to 22 carbon atoms and R 4 is hydrogen or an alkyl radical having 1 to 6 carbon atoms in the R 3, and up to 5 wt .-% organic Builder contains the type of polymeric polycarboxylates. Polymeric polycarboxylates are to be understood in the context of the invention, polymerization products of unsaturated mono- and / or dicarboxylic acids which have no additional functionalities other than carboxyl groups.

The liquid phase of the inventive paste-form detergent is essentially formed of the nonionic surfactants of formulas I and II, having chain lengths different carbon and having different degrees of ethoxylation, and the alcohols or ethers of the formula III. The viscosity of the composition of the invention can be adjusted by combining ethoxylated alcohols having the formulas I and II. In the compounds of formulas I and II the radicals R 1 and R may be linear or branched, for example methyl-branched in the 2-position, with linear radicals containing primary etherified alcohol functions being preferred. Preferably, the nonionic surfactant according to formula I to a carbon chain length of 8 to 14, in particular 12 to 14 carbon atoms and an average degree of alkoxylation m 1 to 8 The nonionic surfactant corresponding to formula II has a broader carbon chain length distribution towards longer chains with 12 to 22, especially 12 to 18 carbon atoms and a higher average degree of alkoxylation n is from 3 to 14.. The ethoxylated alcohols of the formula I and the ethoxylated alcohols of the formula II are preferably present in weight ratios of 2: 1 to 1 before 1.8. The inventive composition may contain further non-ionic, normally used in detergents and cleaning agents surfactants, such as alkyl polyglycosides and / or Fettsäurepolyhydroxya ide. However, the surfactant component is preferably free of propoxylated alcohols, as you would expect a worse biodegradability of these.

For the alcohols or ethers of the general formula III, which contribute to the particularly good low-temperature stability of the compositions of the invention and may additionally provide a contribution to the washing performance, is considered in relation to the group R 3 is substantially the executed above for the radicals R 1 and R 2. R 4 is preferably in addition to hydrogen, methyl, ethyl, propyl or butyl, with hydrogen and methyl group are particularly preferred. In a preferred embodiment of the invention in the compositions up to 10 wt .-%, preferably 2 wt .-% to 6 wt .-% of substances according to general formula III.

Other suitable surfactants are natural or synthetic anionic surfactants, the agent up to 5 wt .-%, particularly 0.5 wt .-% to 3 wt .-% by weight. Suitable synthetic anionic surfactants that can be incorporated in solid, finely divided, substantially anhydrous form in the present invention means, preferably, include in particular those of the sulfonate or sulfate type which are normally present as alkali salts preferably as sodium salts. However in particular the above-mentioned surfactants of the sulfonate type can also be used in form of their free acids. Suitable anionic surfactants of the sulfonate type are linear alkane sulfonates having from 1 1 to 15 C atoms, such as are obtainable by sulfochlorination or sulfoxidation of alkanes and subsequent saponification or neutralization, fofettsäuren salts of sulfonic and esters thereof which are derived from particular in α position sulfonated saturated Cι 2 - to Cig fatty acids and lower alcohols such as methanol, ethanol and propanol derived, and olefin sulfonates, such as, for example, by sulfonation of terminal Cj 2 - are formed to C-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 metal, Ammomum- or alkyl- or hydroxyalkyl-substituted ammonium ion as a counter cation. Particularly suitable are the derivatives of linear alcohols containing in particular 12 to 18 carbon atoms and branched-chain analogs, are so-called oxoalcohols. accordingly, are useful in particular the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl or octadecyl groups and mixtures thereof. Particularly preferred alkyl sulfates contain a tallow alkyl group, i.e. mixtures essentially containing hexadecyl and octadecyl groups. The alkyl sulfates may be prepared by reaction of the corresponding alcohol component with a typical sulfating agent, more particularly sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium bases in known manner. In addition, the sulfated alkoxylation such alcohols, so-called ether, may be included in the media. Preferably, such ether sulphates 2 to 30, especially 4 to 10 ethylene glycol groups per molecule. Synthetic anionic surfactants of the type of alkyl benzene entirely absent in the agents. In a preferred Ausftihrungsform the invention, the composition is completely free of synthetic anionic surfactants. To the naturally occurring anionic surfactants include, in particular soaps, which in the invention in quantities of preferably up to 5 wt .-%, particularly from 0.5 wt .-% to 2 wt .-%, may be included. Suitable soaps are in particular the alkali metal salts of saturated and / or unsaturated Ci2-i come 8 fatty acids, for example coconut, palm kernel or tallow fatty acid in question. Especially preferred is the use of salts of a carboxylic acid mixture is made, in each case based on the total carboxylic acid mixture, 2 wt .-% to 8 wt .-% CM-, up to 1 wt .-% Cι 5 - wt, 18 wt .-% to 24 .-% C, 6 - up to 3 wt .-% C, 7 - 20 wt .-% to 42 wt .-% C |8 - and 30 wt .-% to 44 wt .-% C twentieth 22 carboxylic acid.

The solid phase of the composition according to the invention is essentially formed by the alkalizing agents and builders, which further teilchenfbrmige auxiliaries may optionally be present. The solid phase should be homogeneously dispersed in the liquid surfactant phase. The ingredients of the paste-form detergent present as solid phase should be very finely divided and have an average grain size in the range of 5 microns to 200 microns, at most 10% of the particles have a particle size greater than 200 microns. Surprisingly, it is possible to relatively coarse-grained solids, for example, those containing 20% ​​to 50% of particles with grain sizes over 100 microns, incorporated into the paste-like agent without disadvantage. Preferably, the mean grain size of the solid phase particles 10 microns to 80 microns and most preferably 10 microns to 60 microns, wherein the maximum grain size below 300 microns, especially less than 250 microns. Preferably, 90 are smaller than 200 microns wt .-% of the solid powdered ingredients, in particular less than 140 microns. The average grain size (for example, by laser diffraction or Coulter Counter) may be determined by known methods.

The alkalizing agents present as an additional component are often also referred to as washing alkalis. They are mainly attributable to the solid phase. They ensure under conditions of use of inventive compositions for a pH value in the alkaline range which is normally in the range of 9 to 13, especially from 10 to 12 (in each case measured in 1 -gewichtsprozentiger solution of the agent in ion-exchanged water). The preferred alkalizing agent is amorphous alkali silicate, especially sodium metasilicate of the composition Na 2 O: SiO 2 of 1: 0.8 to 1: 1.3, preferably 1: 1, which is used in anhydrous form. In addition to the alkali silicate and anhydrous alkali carbonate or alkali are suitable, which, however, due to absorption processes requires larger amounts of liquid phase and is therefore less preferred. The proportion of the resources of alkalizing agents is 20 wt .-% to 80 wt .-%, preferably 30 wt .-% to 70 wt .-% and in particular 40 wt .-% to 60 wt .-%. The alkali sierungsmittelkomponente of the agent may consist solely of silicate. Alkali metal carbonate or alkali metal hydrogen carbonate is preferably at most up to 20 wt .-%, in particular less than 10 wt .-%, yet. Specifically, when a phosphate is ecologically acceptable in the use of inventive compositions (for example, a phosphates-eliminating waste water treatment) may be used in the inventive paste compositions also optionally contain polymeric alkali metal phosphates such as sodium tripolyphosphate, to be present. Their percentage content is preferably up to 70 wt .-%, in particular 15 wt .-% to 25 wt .-%, based on the total composition, wherein the proportion of other solids, for example, the alkali metal silicate and / or optionally contained aluminosilicate according can be reduced.

As organic builders, in particular, monomeric polycarboxylic acids or hydroxy carboxylic acids such as citric acid or gluconic acid or salts and next to those from the class of aminopolycarboxylic acids and polyphosphonic own. The aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and higher homologs thereof, wherein N, is N-bis (carboxymethyl) aspartic acid are preferably used. Suitable polyphosphonic acids are l-hydroxyethane-l, l-diphosphonic acid, amino tri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and higher homologs thereof, such as the ylenteframintetra (methylenephosphonic acid). The acids mentioned above are normally used in the form of their alkali metal salts, especially the sodium or potassium salts. To also usable builders include homopolymers and copolymers or carboxylic acids or alkali salts, the sodium or potassium salts are particularly preferred here. Particularly suitable are polymeric carboxylates and polymeric carboxylic acids with a relative molecular mass of at least 350, proven in the form of their water-soluble salts, in particular in the form of sodium and / or potassium salts, 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% of maleic acid, as characterized, for example, in European patent EP 022,551. The relative molecular mass of the homopolymers is generally 1000 to 100,000, of the copolymers between 2,000 and 200,000 and preferably between 50,000 and 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, but less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl, Vinylester, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-% by weight. As polymeric carboxylates or carboxylic acids are terpolymers used which contain as monomers two unsaturated acids and / or salts thereof and, as third monomer, vinyl alcohol and or a vinyl alcohol derivative or a carbohydrate. 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 - from monocarboxylic acid, in particular of the (meth) acrylic acid. The second acidic monomer or its salt may be a derivative of a dicarboxylic acid 8 C -C, maleic acid being preferred. The third monomeric unit is in this case formed of vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives are preferred which represent an ester of short-chain carboxylic acids, for example, Cι-C carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60 to 95 wt .-%, in particular 70 to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, more preferably acrylic acid or acrylate, and maleic acid or maleate and 5 to 40 wt .-%, preferably 10 to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particularly preferred are terpolymers in which the weight ratio of (meth) acrylic acid to maleic acid or maleate is between 1: 1 and 4: 1., preferably between 2: 1 and 3: 1 and especially 2: 1 to 2.5: 1. Here, both the quantities and the weight ratios are based on the acids. The second acidic monomer or its salt may be sulfonic acid and a derivative of an allyl group, the 2-position with an alkyl group, preferably a Cι-C - alkyl group, or an aromatic radical which is derived preferably from benzene or benzene derivatives is substituted. Preferred terpolymers contain 40 to 60 wt .-%, in particular 45 to 55 wt .-% of (meth) acrylic acid or (meth) acrylate, more preferably acrylic acid or acrylate, 10 wt .-% to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic loading relationship as methallyl sulfonate and, as the third monomer, 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose. Through the use of the third monomer predetermined breaking points are incorporated in the polymer, which are probably responsible for the good biodegradability of such polymers. also, such polymers are preferably used, which are either completely or at least partially, in particular more than 50%, based on the carboxyl groups present neutralized. Particularly preferred polymeric polycarboxylates are prepared according to methods described 43 00 772 and German Patent DE 42 21 381 in the German patent application DE. Also suitable are polyacetal carboxylic acids, such as are described 4,144,226 and US 4,146,495, for example, in U.S. Patents US and are obtained by polymerization of esters of glycolic acid, introduction of stable terminal groups and saponification to the sodium or potassium salts. Also suitable are polymeric acids obtained by polymerization of acrolein and disproportionation of the polymer with strong alkalis Canizzaro. They are composed of acrylic acid units and vinyl alcohol units or acrolein units substantially.

If such substances are in general contained in the inventive paste compositions, the proportion of organic carboxyl Builderma- can terialien in the inventive pasty agent up to 10 wt .-%, preferably 1 wt .-% to 7.5 wt .-% and in particular 2 wt .-% to less than 5 wt .-%, respectively, wherein the content of polymeric polycarboxylate is minimized and is less than 5 wt .-%. These aforementioned substances are used in anhydrous form.

Suitable inorganic builder are used in the inventive compositions in addition to the above-mentioned phosphate come crystalline alkali metal silicates and fine-particle alkali metal alumosilicates, more particularly zeolites of the NaA type X and / or P, in question. Suitable zeolites normally have a calcium binding capacity in the range of 100 to 200 mg CaO / g, which may be determined as described in the German patent DE 24 12 837, on. Their particle size is normally in the range from 1 .mu.m to 10 .mu.m. They come in dry form used. The water contained in the zeolite in bound form does not interfere in this case. The crystalline silicates which may be present alone or in admixture with the aforementioned aluminosilicates, crystalline layered silicates of the formula NaMSi x O 2 + x are preferably used yH 2 O, in which M is hydrogen or sodium, x is a number from 1.9 to is 4 and y is a number from 0 to 20th Preferred values ​​for x are 2, 3 and 4. Corresponding crystalline layer silicates are described, for example in the European patent application EP 164 514.. In particular, both .beta.- and δ-sodium Na 2 Si 2 θ 5 yH 2 O are preferred, with beta-sodium disilicate being obtainable, for example, by the method described in International Patent Application WO 91/08171. Suitable crystalline silicates are under the names SKS-6 (manufactured by Hoechst) and Nabion® 15 (manufacturer Rhone-Poulenc). The content of inorganic Buil- dermaterial in the paste may be up to 35 wt .-%, preferably up to 25 wt .-% and in particular 10 wt .-% to 25 wt .-%.

In a preferred embodiment according to the invention means are 5 wt .-% to 25 wt .-%, especially 10 wt .-% to 20 wt .-% builder substances contained, wherein the amount of polymeric polycarboxylates not more than 5 wt .-%, in particular 0% by weight, and the amount of phosphonates not more than 0.5 wt .-%, particularly not more than 0.2 wt .-% is.

Furthermore, an inventive pasty agent oxygen-containing oxidising agent and optionally bleach activator. As an oxidizing agent in particular, inorganic peroxygen compounds are used, the Natriumper- borattetrahydrat and sodium perborate monohydrate are of particular importance in addition to sodium. Other suitable oxidizing agents are, for example, persulfates, peroxypyrophosphates, citrate perhydrates and H2 O2 -yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic Diperoxy- or dodecanedioic acid. Sodium percarbonate, sodium persulfate and / or sodium perborate monohydrate are preferably used. Oxidizing agents may be included in the inventive compositions preferably wt .-%, in amounts up to 25 wt .-% and particularly 10 wt .-% to 20th

The oxidizing power of such oxidants, may be improved by the use of Bleichaktiva- factors which form peroxocarboxylic acids under perhydrolysis conditions. Numerous proposals, especially from the classes of N- or O-acyl compounds, for example, multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetyl are glycoluril for such bleach activators, N-acylated hydantoins, hydrazides, triazoles, Hydrotriazine, urazols, diketo - piperazine, sulfuryl amides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, Carbonsäureester, in particular, sodium nonanoyloxy-benzene sulfonate, sodium isononanoylsarcosine-oxybenzenesulfonate, and triacetin (glycerol triacetate), and acylated sugar derivatives, such as pentaacetylglucose, known in the literature. Preferably, a bleach activator is used, which forms peracetic acid under washing conditions, wherein tetraacetyl ethylenediamine is particularly preferable. Agents of the invention preferably contain up to 10 wt .-%, particularly from 3 wt .-% to 8 wt .-% bleach activator. By the addition of bleach activators of the bleaching action of aqueous peroxide can be increased to the extent that even at temperatures around 60 ° C is substantially the same effects occur as with the peroxide liquor alone at 95 ° C. In particular, at even lower temperatures may be increased by the use of transition metal salts and complexes, such as, for example, in European patent applications EP 0392592, EP 0443651, EP 0458397, EP 0 544 490, EP 0549271, EP 0 630 proposed 964 or EP 0693550, arising as so-called bleach catalysts in addition to or instead of the conventional bleach activators, to increase the bleaching power. Particularly suitable are also known from German patent applications DE 195 29 905 DE 195 36 082 DE 196 05 688, DE 196 20 41 1 196 20 267 and DE known as bleach-activating transition metal catalysts complexes. Bleach-activating transition metal complexes, in particular with the Central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in accordance with the invention in quantities of preferably not more than 1 wt .-%, in particular 0.0025 wt % to 0.25 wt .-% by weight.

In addition, an agent of the invention contain other washing aids which are normally to wt .-%, based on the finished composition, may be present in amounts to about 15 °. As such washing aids, for example, enzymes, supply grauungsinhibitoren, soil-release agents, optical brighteners, foam regulators and / or dyes and fragrances are used. As far as perfumes are included, which are generally liquid, this invention in the liquid phase means go over. However, due to their small amount they have on the flow behavior of the pastes no appreciable effect.

The inventive pasty washing agent are substantially free of water and organic solvents. By "substantially free of water" is a condition to be understood, wherein the content of free, i.e. not in the form of water of hydration and water of constitution lying water below 3 wt .-%, preferably below 2 wt .-% and in particular less than 1 is wt .-%. Higher water contents are a disadvantage, because they increase the viscosity of the composition disproportionately and in particular reduce its stability. Organic solvents, for which the low molecular weight and low-boiling alcohols and ether alcohols normally used in liquid concentrates include, and hydrotropes are, apart from traces which may be incorporated with various ingredients, is not also present.

When optionally present in the inventive compositions enzymes particular, those from the class of proteases, lipases, cutinases, amylases, Pullulana- sen, xylanases, hemicellulases, cellulases, peroxidases and oxidases, or mixtures thereof, in question, the use of protease, amylase, lipase and / or cellulase is particularly preferred. The proportion is preferably 0.2 wt .-% to 1.5 wt .-%, particularly 0.5 wt .-% to 1 wt .-%. The enzymes may be adsorbed in a conventional manner onto supports and / or encapsulated in membrane or incorporated as concentrated water-free liquid formulations in the pastes. Suitable proteases are known 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 95/02044, WO 95/05477, WO 95/07350, WO 95/10592, WO 95/10615, WO 95/20039, WO 95/20663, WO 95/23211, WO 95 / 27049, WO 95/30010, WO 95/3001 1, WO 95/30743 and WO 95/34627 known. Preference is given to oxidative damage stabilized enzymes, such as those known under the trade name Durazym® or Purafect® OxP or Duramyl® or Purafect® OxAm proteases or amylases used. Suitable redeposition inhibitors or soil release agents are cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose,

Methylhydroxypropylcellulose and methyl carboxymethyl cellulose. Preferably sodium carboxymethyl cellulose and mixtures thereof are used with methylcellulose. The customarily used soil release agents are copolyesters, the dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units contained. Soil-release copolyesters of the type mentioned and their use in detergents have been known for a long time. For example, the German OS 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. The German OS 22 00 911 relates to detergents containing nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate included. In the German Offenlegungsschrift DT 22 53 063 acidic textile finishes are known which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene and optionally an alkylene or cycloalkylene glycol. The European patent EP 066 944 relates to textile treatment compositions containing a copolyester of Ethyien- glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From the European patent EP 185 427 discloses methyl or ethyl-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such a soil-release polymer are known. The European patent EP 241 984 relates to a polyester acid units, also contains substituted ethylene units and glycerol units in addition to oxyethylene groups and terephthalic. The percentage content of redeposition inhibitors and soil-release or active ingredients in the inventive compositions is generally not more than 2 wt .-% and preferably 0.5 wt .-% to 1.5 wt .-%. In a preferred embodiment of the invention, the agent is free of such agents.

As optical brighteners, in particular for textiles of cellulose fibers (for example cotton) may be included, for example, derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, which instead of Morpho- linogruppe a diethanolamino, a Methyl.aminogruppe or a 2-methoxyethylamino carry. Brighteners of the substituted 4,4'-be distyryl-diphenyl styryl type, for example 4,4'-bis- (4-chloro-3- sulfostyryl) -diphenyl. Mixtures of brighteners may be used. For polyamide fibers particularly suitable brighteners are of the type of 1, 3-diaryl-2-pyrazolines, for example l- (-Sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and compounds of similar structure. The content of the agent to optical brighteners or Aufhellergemischen is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%. In a preferred embodiment of the invention, the agent is free of such agents.

The usable in the inventive compositions usual foam regulators include, for example polysiloxane-silica mixtures in which the fine-particle silica present therein preferably being silanized is. The polysiloxanes may consist both of linear compounds of crosslinked polysiloxane resins and from mixtures thereof. Other defoamers are paraffin hydrocarbons, in particular micro-paraffins and paraffin waxes whose melting point is above 40 ° C, saturated fatty acids or soaps containing in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali salts of phosphoric acid mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Is particularly preferred and Natriummonoalkylphosphat or -dialkylphosphat with Cι 6 - used to Cig alkyl groups. The proportion of foam regulators may be preferably wt .-% to 2 wt% 0.2. In many cases, the tendency to foam can be reduced by an appropriate selection of the nonionic surfactants, so that it is possible to dispense with the use of defoaming agents in a preferred embodiment of the invention altogether.

In order to increase the physical stability as well as the chemical stability in particular of the bleach component and enzymes optionally present can also dehydrating agent, for example in the form of water of crystallization of salts which bind such as anhydrous sodium acetate, calcium sulfate, calcium chloride, sodium hydroxide, magnesium silicate, or metal oxides such as CaO, MgO, PO |0 or Al 2 O can be used. Such a dehydrating agent, with which the water content of inventive compositions can be reduced to particularly low values, are in accordance in amounts of preferably 1 wt .-% to 10 wt .-%, and particularly 2 wt .-% to 8 wt .-% in the compositions of the invention exist.

In the preparation according to the invention paste-like detergent and cleaning agent are conveniently the surfactant components, that is, the nonionic surfactants of formulas I and II and mixed the alcohols or ethers of formula III and optionally soap and synthetic anionic surfactants to form a homogeneous premix and this premix the solids and optionally further ingredients are incorporated. If the particulate solids are not sufficiently finely divided form, one or more grinding steps can be inserted.

An inventive pasty agent preferably has at 25 ° C has a viscosity of from 80,000 mPas to 250,000 mPas, in particular 100 000 mPas to 250 000 mPas, measured with a Brookfield rotational viscometer (spindle no. 7) at 5 revolutions per minute. Under otherwise identical conditions, the viscosity at 50 revolutions per minute, preferably 20 000; mPa s to 80 000 mPa s. The pastenformige detergents and cleaning agents, in one particular embodiment of the invention at room temperature, preferably at a viscosity such that it is not fließfahig under the effect of gravity. it is then particularly pseudoplastic, preferably that is, it has in shear a distinctly lower viscosity and is fließfahig under the effect of gravity, and it particularly preferably has a viscosity in the range of 8,000 mPas to 45,000 mPas at 25 ° C and a shear rate of 0.01 s "1, to determine a CS rheometer CVO Bohlin comprising a measuring system plate / plate, plate interval 1 to 3 mm. on exposure to adequate shear forces, an inventive agent is preferably a substantially, typically 100- to 2000-fold lower viscosity, the s "is located at a shear rate of 10 1 and otherwise the same measuring conditions, in particular in the range from 40 mPas to 60 mPas. , The numerical values ​​of viscosity relate to allow for any thixotropic effect the paste to the reading after a measuring time of 3 minutes. The reduction in viscosity on shearing is largely reversible, that is, after the end of the shear is d.as means without occurrence of separation again to its original physical state. In this context it should be noted that the viscosities mentioned are not related to measurements immediately after preparation of the paste, but since the acting as part of the manufacturing process shear forces lead to stored, so to speak in equilibrium pastes to a lower paste viscosity which only in the Over time the relevant final viscosity increased. Storage times of 1 month is it perfectly adequate as a rule.

An agent of the invention normally has a density in the range of 1, 3 kg / 1 to 1.6 kg /. 1 The inventive agent can be dosed with conventional devices for dosing of pastes, as for example in international patent application WO 95/29282, German patent application DE 196 05 906 German patent DE 44 30 418 or European patents EP 0,295,525 or EP have been described in 0356 707th A stnikturviskoser for dosing paste-like detergent particularly suitable device is for example known from the international patent application WO 95/09263 and is preferably used for dosing pseudoplastic pastes according to the invention. The washing and cleaning compositions may optionally also already pre-portioned be bottled in particular water-soluble films. Such films are described, for example in the European patent application EP 253,151.

Examples

The following table shows some examples of the composition according to the invention are given detergent. The pasty detergent had a very good storage stability and had despite the absence of synthetic anionic surfactant of an excellent cleaning performance. Table 1: Composition of paste-form detergent (wt .-%)

Component 1 2 3 4 5 6

Nonionic surfactant I a) 19 19 18 18 18 11

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

Isotridecanol - - 5 5 5 5

Soap c) 1 1 1 1 1 1

Builder I d) 5 5 5 5 5 5

Builder II e) 0.2 0.2 0.2 0.2 0.2 0.2

Sodium silicate 60 40 47 57 - -

Sodium - 20 20 - 20 20

Sodium - - - - 20 20

TAED - - - - 4 4

Enzyme - - - - 1 1

CMC / MC 0 1 1 1 1 1 1

Foam inhibitor ε) 1 1 1 1 1 1

Sodium carbonate in 100

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

Claims

claims
1. A paste 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 conventional ingredients, characterized, in that it is free from synthetic anionic surfactant of the is alkylbenzene sulfonate type and 5 wt .-% to 30 wt .-% of an ethoxylated alcohol of the general formula I, in which R 1 is an alkyl or alkenyl radical containing 12 to 14 carbon atoms and the average degree of ethoxylation m is from 1 to 8 may assume 1 wt .-% to 20 wt .-% of an ethoxylated alcohol of the general formula II,
R 2 - (OC 2 H 4) n -OH (II) in which R 2 is an alkyl or alkenyl group 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 20 wt .-% wt .-% 1 is greater than at least 1.0 m, to 80 wt .-% alkalizing to 20 wt .-%, more preferably 3 wt .-% to 15% by weight long-chain alcohol or alkyl ethers of the general formula III,
R 3 -O-R 4 (III), an alkyl or alkenyl radical having 8 to 22 carbon atoms and R 4 is hydrogen or an alkyl radical having 1 to 6 carbon atoms in the R 3, and up to 5 wt .-% organic Builder contains the type of polymeric polycarboxylates.
2. The composition according to claim 1, characterized in that it contains .-% to 25 wt .-% contains the ethoxylated alcohol of the general formula I 10th
3. Composition according to claim 1 or 2, characterized in that it includes 5 wt .-% to 15 wt .-% of the ethoxylated alcohol of the general formula II.
4. A composition according to 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 according to formula I.
5. A composition according to any one of claims 1 to 4, characterized in that eb3 includes wt .-% to 15 wt .-% long-chain alcohol or alkyl ether of the general formula III.
6. A composition according to any one of claims 1 to 5, characterized in that it contains up to 5 wt .-%, particularly 0.5 wt .-% to 2 wt .-%, of soap.
7. Composition according to one of claims 1 to 5, characterized in that it contains up to 5 wt .-%, particularly 0.5 wt .-% to 3 wt .-% of synthetic anionic surfactant selected from alkyl or alkenyl sulfates and or containing ether sulfates.
8. A composition according to any one of claims 1 to 7, characterized in that it contains 30 wt .-% to 70 wt .-%, in particular 40 wt .-% to 60 wt .-% alkalizing agent.
9. A composition according to any one of claims 1 to 8, characterized in that it contains .-% to 25 wt .-%, especially 10 wt .-% contains 5 to 20 wt .-% builder substances.
10. A composition according to any one of claims 1 to 9, characterized in that the constituents of the paste-form detergent present as solid phase are finely divided and have an average grain size in the range of 5 .mu.m to 200 .mu.m, in particular 10 microns to 80 microns.
11. A composition according to any one of claims 1 to 10, characterized in that at most 10% of the particles of the ingredients present as solid phase have a grain size of more than 200 microns.
12. Composition according to one of claims 1 to 1 1, characterized in that it contains 0.2 wt% to 1.5 wt .-%, particularly 0.5 wt .-% to 1 wt .-% enzyme, especially protease, amylase, lipase and / or cellulase contains.
13. Composition according to one of claims 1 to 12, characterized in that it contains .-% to 10 wt .-%, especially 2 wt .- includes wt .-% to 8% dehydrating agent. 1
14. Composition according to one of claims 1 to 13, characterized in that it at 25 ° C a viscosity of 80,000 mPa s to 250,000 mPas, measured with a Brookfield rotational viscometer (spindle no. 7) at 5 revolutions per minute and .Otherwise at the same conditions at 50 revolutions per minute s has a viscosity of 20 000 mPa to 80000 mPa.
EP19970944804 1996-09-05 1997-08-28 Paste-like washing and cleaning agent Expired - Lifetime EP0929630B1 (en)

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DE1996136035 DE19636035A1 (en) 1996-09-05 1996-09-05 A paste detergents and cleaners
DE19636035 1996-09-05
PCT/EP1997/004690 WO1998010049A1 (en) 1996-09-05 1997-08-28 Paste-like washing and cleaning agent

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