EP0721498B1 - Pasty washing agent - Google Patents

Abstract

PCT No. PCT/EP94/03122 Sec. 371 Date Apr. 18, 1996 Sec. 102(e) Date Apr. 18, 1996 PCT Filed Sep. 19, 1994 PCT Pub. No. WO95/09229 PCT Pub. Date Apr. 6, 1995A storable, substantially water-free flowable surfactant mixture containing 40% by weight to 70% by weight of a nonionic surfactant of the formula R1-(OC2H4)n-OH wherein R1 is an alkyl or alkenyl group containing 10 to 20 carbon atoms and an average degree of ethoxylation n of from 1 to 8; 20% by weight to 50% by weight of a nonionic surfactant, liquid at room temperature, of the formula: R2-(OC2H4)r-(OC3H6)p-OH wherein R2 is an alkyl or alkenyl group containing 10 to 20 carbon atoms, an average degree of ethoxylation r of from 2 to 8 and an average degree of propoxylation p of from 1 to 6; and 1% by weight to 10% by weight of a C10 to C22 carboxylic acid and/or alkali metal salts thereof. The flowable surfactant mixture provides a base for forming a pseudo-plastic detergent formulation. The pseudoplastic detergent formulation is formed by introducing solid materials such as an anionic surfactants, solid foam regulators, detergent builders and the like. When the solid materials are introduced into the substantially water-free, flowable surfactant mixture, a paste-form detergent is formed. The paste-form detergent does not flow under the action of gravity but upon introducing shear energy into the mixture, the viscosity is reduced and the composition flows under the force of gravity. Upon removing the shearing forces, the composition returns to its pseudoplastic form.

Description

The invention relates to pseudoplastic detergent, in particular for automatic detergents Dosing in commercial laundries, a method for dosing such pseudoplastic Means, a process for their preparation and stable specially adapted to the production process flowable surfactant mixtures, the nonionic surfactant, long-chain carboxylic acid respectively their salt and optionally contain synthetic anionic surfactant.

Liquid to pasty detergents have become known in large numbers in particular recently. They are usually tailored to household needs, so that they usually have to be sufficiently liquid to pour and dose easily to let. Since such liquid detergents also have a long shelf life within relatively wide temperature ranges should be without losing their liquid properties, one often does not come without additives from organic solvents and / or hydrotropes, which themselves do not contribute to washing or Deliver cleaning results and are therefore undesirable. A way to get around Possible dosing problems with insufficiently liquid agents is in the European Patent application EP253 151 A2 proposed. From this document are fluid, partially highly viscous detergents based on nonionic and anionic surfactants known, which are polyethylene glycol Contained as a hydrotrope and packed in portions in bags made of water-soluble material will.

A pasty detergent is known from European patent application EP 0 356 707 A1, which is essentially free of water and organic solvents and from a liquid Phase from nonionic surfactants of the class of polyglycol ether compounds and one therein dispersed finely divided solid phase from washing alkalis, sequestering agents and optionally other detergent ingredients. That too in the German patent application DE 37 19 906 A1 presented pasty detergent consists of one in the temperature range below 10 ° C liquid phase, which is formed from nonionic surfactant, and a dispersed therein solid phase of certain grain size, which consists of washing alkalis, sequestering agents and optionally anionic surfactants is formed. For this purpose surfactants or their mixtures used, whose pour point (solidification point) is below 5 ° C to solidify the paste to avoid at low transport and storage temperatures. This detergent paste for commercial Laundries is so flowable that it can be conveyed via a suction line by means of a conventional feed pump, what is undoubtedly an advantage. Now, however, it has been found that such pastes during their manufacture does not always ensure satisfactory homogeneity of their mixed ingredients can and often tend to separate during storage. This negative quality concerns not only the separation of the solid from the liquid components, but also that Phase separation of the liquid ingredients. This disadvantage is particularly evident when the pastes stored in storage containers are exposed to shear effects. So the viscosity can be lower the known pastes by scissors and thus the conveyability and meterability make it even easier, but a phase separation of the already can be in the reservoir usually do not avoid sheared but not yet promoted paste. So there was Task, a segregation of the paste ingredients both in the production and in shear even better under removal conditions from the transport or storage container prevent and further increase the storage stability of the detergent paste.

Surprisingly, this was achieved essentially by changing the viscosity and the Structural viscosity of the paste. The paste-like compositions according to the invention exhibit at room temperature (20 ° C to 25 ° C) without the action of shear forces such a high viscosity that they neither flowing out of a container can still be conveyed by simple suction. Also the Shear effect of a movable plate or even a pressure stamp, as in the dosing system according to the German patent application DE 37 19 906 A1 provided, the viscosity is in no way sufficient to reduce the paste-like compositions according to the invention so far that they are by a suction pump can be promoted. Only higher shear forces, such as those with the help of the paste container with removal device according to the unpublished German patent application DE 43 32 850 A1 (published on March 30, 1995) = WO-A-95/09263 by Henkel Ecolab GmbH & Co. OHG are able to do so, with the agents according to the invention being a very significant advantage do not separate during shearing and after the shearing process has ended, for example if As a rule, not all of the contents of the storage container are put into the commercial washing machine at once should be dosed again largely have the same properties as before the start of Exposure to shear forces.

Such pastes can advantageously be made using a flowable, Storage-stable surfactant mixture from certain nonionic surfactant and long chain carboxylic acid and / or soap, which the aforementioned structural viscosity is not or only significantly reduced Has shape.

The invention accordingly relates to a storage-stable, essentially water-free, flowable surfactant mixture containing nonionic surfactant in the form of alkoxylation products of alcohols and soap, which in this case means long-chain carboxylic acid and / or its salt, which is characterized in that it is 40 wt % to 70% by weight of nonionic surfactant of the general formula (I) which is liquid at room temperature, R ¹ - (OC ₂ H ₄ ) _n -OH in which R ¹ denotes an alkyl or alkenyl radical with 9 to 20 C atoms and the average degree of ethoxylation n can assume values from 1 to 8, in particular from 1 to 6, 20% by weight to 50% by weight liquid at room temperature nonionic surfactant of the general formula (II), R ² - (OC ₂ H ₄ ) _r - (OC ₃ H ₆ ) _p -OH in which R ² denotes an alkyl or alkenyl radical having 9 to 20 carbon atoms, the average degree of ethoxylation r can take on values from 2 to 8 and the average degree of propoxylation can take on values from 1 to 6, and 1% by weight to 10% by weight -% of a C ₁₀ - to C ₂₂ carboxylic acid and / or its alkali salt.

Another object of the invention is a structurally viscous pasty Detergent or cleaning agent which contains a surfactant mixture described above, in particular using the mentioned surfactant mixture has been produced and without the action of Shear forces have such a viscosity that it is at room temperature is not flowable under the influence of gravity, but under shear has a significantly lower viscosity and under the influence of Gravity is flowable. This property can be experimentally determined check that the paste viscosity under different shear conditions measures. A conventional rotary viscometer offers one possibility for this at different speeds of rotation of the spindle. Pastes according to the invention preferably have at 25 ° C. using a Brookfield (R) DV-II or DV-II plus rotary viscometer with spindle No. 7 at 5 revolutions per minute a viscosity above 100,000 mPa · s, in particular from 150,000 mPa · s to 500,000 mPa · s, and at 50 revolutions per minute a viscosity below 100,000 mPa · s, in particular of 10,000 mPas to 90,000 mPas and particularly preferably from 50,000 mPas to 80,000 mPas. The numerical values mentioned refer to possible Thixotropy effects of the paste to be taken into account on the reading after a Measuring time of 3 minutes and should only be seen as a guide, because comparatively small changes in the measurement conditions with regard to Temperature or the viscometer, as indicated below, to others Results of the viscosity measurement can lead.

Another object of the invention is a method for loading a washing machine, especially a commercial washing machine, with liquid and solid detergent components, which is characterized in that a flowable surfactant mixture containing 40 wt .-% to 70 wt .-% liquid at room temperature nonionic surfactant of the general formula (I) as indicated above, 20% by weight to 50% by weight liquid nonionic surfactant of the general formula (II) as indicated above at room temperature, and 1% by weight to 10% by weight a C ₁₀ - to C ₂₂ -carboxylic acid and / or its alkali salt, produced, dispersed therein finely divided solid, the resulting stable storage, non-flowable preparation directly before use with mechanical energy, especially by stirring, makes the flowable preparation flowable diluted a predetermined amount of water and dosed into the washing machine.

In the compounds of the formulas I and II, the radicals R ¹ and R ^{2 can be} linear or branched, for example methyl-branched in the 2-position (oxo alcohols). The nonionic surfactant according to formula (I) preferably has an average degree of ethoxylation n of 2 to 4 and / or the nonionic surfactant according to formula (II) has an average degree of ethoxylation r of 3 to 7 and / or an average degree of propoxylation p of 3 to 5. Examples of suitable nonionic surfactants are C _9-11 oxo alcohols with 2 to 10 EO, such as C _9-11 + 3 EO, C _9-11 + 5 EO, C _9-11 + 7 EO, C _9-11 + 9 EO ; C _11-13 oxo alcohols with 2 to 8 EO, such as C _11-13 + 2 EO, C _11-13 + 5 EO, C _11-13 + 6 EO, C _11-13 + 7 EO; C _12-15 oxo alcohols with 3 to 6 EO, such as C _12-15 + 3 EO, C _12-15 + 5 EO; Isotridecanol with 3 to 8 EO; partially unsaturated linear C _10-16 fatty alcohols with 8 EO; linear fatty alcohols with 10 to 14 carbon atoms and 2.5 to 5 EO; linear saturated and unsaturated C _12-18 fatty alcohols or C _9-15 -0xoalcohols with 1 to 3 PO and 4 to 8 EO, such as C _12-18 coco alcohol + (EO) _4-7 (PO) _1-2 , oley alcohol or 1: 1 mixture of cetyl oleyl alcohol + (EO) _5-7 (PO) _1-2 , C _11-15 -oxo alcohol + (EO) _4-6 (PO) _1-2 .

Among the surfactants liquid at room temperature according to formulas (I) and (II) are particularly preferred those at temperatures below 10 ° C. melt. If desired, small amounts of similarly constructed non-ionic surfactants are present as long as it is ensured that the nonionic component of the surfactant mixture at room temperature and is preferably liquid at 10 ° C.

The surfactant mixture according to the invention preferably contains 48% by weight to 64% by weight nonionic surfactant of the general formula (I), 28% by weight to 40% by weight of nonionic surfactant of the general formula (II) and 2% by weight up to 6% by weight of carboxylic acid and / or its alkali salt.

In addition, up to 10% by weight, in particular 0.5% by weight to 8% by weight of synthetic solid at room temperature Anionic surfactant and / or up to 5 wt .-%, in particular 0.1 wt .-% to 4% by weight more solid, alkali-stable and shear-stable at room temperature Foam regulator can be included.

Suitable synthetic anionic surfactants which can be incorporated into the surfactant mixture according to the invention in solid, finely divided, largely anhydrous form include, in particular, those of the sulfonate or sulfate type, which are normally present as alkali metal salts, preferably as sodium salts. In particular, the surfactants of the sulfonate type mentioned can also be used in the form of their free acids. Suitable anionic surfactants of the sulfonate type are alkylbenzenesulfonates with linear C _9-13 alkyl chains, in particular dodecylbenzenesulfonate, linear alkanesulfonates with 11 to 15 C atoms, as can be obtained by sulfochlorination or sulfoxidation of alkanes and subsequent saponification or neutralization, salts of sulfofatty acids and esters thereof, the sulfonated from particular in α-position of saturated _C12-18 fatty acids and lower alcohols such as methanol, ethanol and propanol derived, and olefin sulfonates, such as, for example, by SO ₃ sulphonation entständiger C _12-18 - Olefins and subsequent alkaline hydrolysis are formed. 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, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. The derivatives of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are particularly suitable. Accordingly, the sulfation products of primary fatty alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl sulfates contain a tallow alkyl radical, ie mixtures with essentially hexadecyl and octadecyl radicals. The alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. In addition, the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates, can be present in the compositions. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.

Preferred synthetic anionic surfactants are alkylbenzenesulfonates and / or Alkyl sulfates.

Among the carboxylic acids or their salts contained in the surfactant mixtures according to the invention, preference is given to saturated and / or unsaturated C _12-22 fatty acids, for example coconut, palm kernel or tallow fatty acid, or their alkali metal salts (soaps), although their branched-chain isomers can also be used . It is particularly preferred to use a carboxylic acid mixture of, based in each case on the total carboxylic acid mixture, 2% by weight to 8% by weight of C _14- , up to 1% by weight of C _15- , 18% by weight to 24% by weight. -% C ₁₆ -, up to 3% by weight C ₁₇ -, 20% by weight to 42% by weight C ₁₈ - and 30% by weight to 44% by weight C ₂₀ - to C ₂₂ - Carboxylic acid or its alkali salts.

The foam regulator which is solid, stable at room temperature and stable to shear can be selected, for example, from polysiloxane-silica mixtures, the fine-particle silica contained therein preferably being silanated. The polysiloxanes can consist of both linear compounds and crosslinked polysiloxane resins and mixtures thereof. Further defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, whose melting point is above 40 ° C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, for example sodium behenate, and alkali metal salts of phosphoric acid mono- and / or dialkyl esters, in which the alkyl chains each have 12 to 22 carbon atoms. Sodium monoalkyl phosphate and / or dialkyl phosphate with C ₁₆ to C ₁₈ alkyl groups is particularly preferably used. The proportion of the foam regulators, based on the surfactant mixture according to the invention, can preferably be 0.2% by weight to 2% by weight. In many cases, a suitable selection of the nonionic surfactants can reduce the tendency to foam, so that the use of defoaming foam regulators can be dispensed with entirely.

When producing the surfactant mixtures according to the invention, it is important that the solid components at room temperature, including the carboxylic acid or their salt and, if appropriate, the synthetic anionic surfactant and the foam regulator should be as homogeneous as possible with the nonionic Surfactants are mixed. The preferred way to do this is that at least one of the nonionic surfactants of the formula (I) or (II) to temperatures in the range from 60 ° C to 120 ° C, especially from 70 ° C to 100 ° C heated, the solid components at these temperatures dissolves or disperses in the nonionic surfactant and the resulting mixture, optionally after adding the second nonionic surfactant, to temperatures cools from 60 ° C to room temperature.

With this method, the energy consumption is lower due to the lower energy requirements when heating preferably the nonionic surfactant according to Formula (I) or (II) to be used in a smaller amount, warmed, if necessary mixes the foam regulation, then gives the carboxylic acid or its alkali salt, then optionally that synthetic anionic surfactant and finally the non-ionic one not presented Surfactant according to formula (II) or (I).

The surfactant mixture according to the invention is largely stable on storage and at temperatures flowable from room temperature to 40 ° C, even if at this Temperature of the solids contained in the mixture is not always complete are dissolved in the nonionic surfactant.

The surfactant mixture can be used to produce liquid to pasty detergents Cleaning agents are used, which are known in principle prepared by admixing other ingredients customary in such agents can be. It is preferably used for the production of pasty Detergents or cleaning agents are used, which consist of a liquid Phase and a finely divided solid phase dispersed therein. The liquid phase of such agents is essentially from the in the nonionic surfactants contained in the surfactant mixture according to the invention formed according to formulas (I) and (II).

The use of the surfactant mixture according to the invention has the advantage that in this all substances, which the viscosity of the finished product significantly affect, especially the carboxylic acid or its Salt. This ensures the homogeneous incorporation of these Substances in finished detergents or cleaning agents are much easier, what about constant product quality, especially regarding its Viscosity contributes. In addition, the result of the invention Premix also advantages in the manufacture of pasty finished products, since when the carboxylic acid or its salts are incorporated in powder form prior grinding is required. It happens in everything Rule for loss of soap active substance for reasons that are not fully clarified, what completely when using the surfactant mixture according to the invention can be avoided. In addition, it was found that when used of the surfactant mixture according to the invention for the production of pasty Means whose final viscosity is advantageously much faster sets as when the individual components of the surfactant mixture are used separately.

A pasty detergent or cleaning agent in the context of the invention is preferably so structurally viscous that it has a viscosity in the range from 10,000 mPa · s to 500,000 mPa · s at 20 ° C. and a shear rate of 0.025 s ^-1 Plate viscometer Carrimed ^(R) CS 100 with grooved 2 cm plate (Cross Hatch Flat Plate), plate distance 1.5 mm. When sufficient shear forces are applied, an agent according to the invention has a viscosity which is considerably lower, as a rule 2 to 15 times lower, at a shear rate of 0.2 s ^-1 and otherwise identical measuring conditions in the range from 5,000 mPa · s to 130 000 mPas, in particular from 5,000 mPas to 13,000 mPas, and at a shear rate of 2 s ^-1 and otherwise identical measuring conditions in the range from 400 mPas to 100,000 mPas, in particular from 400 mPas · S to 1,600 mPa · s. To take account of possible thixotropy effects of the paste, these numerical values also refer to the reading after a measuring time of 3 minutes. The reduction in viscosity is largely reversible, that is to say after the shear has ended, the agent returns to its original physical state without segregation occurring. In this context, it should be noted that the viscosities mentioned do not refer to measurements directly after the paste has been made, but to stored pastes that are, so to speak, in equilibrium, since the shear forces acting in the course of the manufacturing process lead to a lower paste viscosity, which only occurs in the Increased over time to the definitive final viscosity. Storage periods of 1 month are usually completely sufficient for this.

In one embodiment, a pasty according to the invention contains Means in particular 20% by weight to 80% by weight of the surfactant mixture according to the invention and 20% to 80% by weight of additional solid powdery particulate Components. The components of the paste-like agents should be finely divided and have an average grain size have in the range of 5 microns to 120 microns, with at most 10% of the particles have a grain size of more than 150 microns. Surprisingly it is it is possible to use relatively coarse-grained solids, for example those that Contain 20% to 50% particles with grain sizes over 80 µm, without disadvantage to incorporate into the pasty agents. The mean is preferably Grain size of the particles forming the solid phase 10 microns to 80 microns and in particular 10 µm to 60 µm, the maximum grain size below 200 microns, especially less than 150 microns. 90% by weight are preferably the solid powdery components smaller than 140 microns, in particular smaller than 100 µm. The average grain size relates to the volume distribution of the particles, which are produced by known methods (for example by means of laser diffraction or Coulter Counter) can be determined.

As part of the optimization of the pastes according to the invention, it was found that that particularly stable paste-like agents are obtained when in for their preparation used the inventive surfactant premix Anionic surfactant in its acid form, for example as free alkylbenzenesulfonic acid, is used, and / or the carboxylic acid as alkali salt is used. Although the resulting paste-like means the surprisingly had the same gross composition, they were still more stable than such agents, with the help of surfactant mixtures were prepared in which free carboxylic acid and synthetic anionic surfactant had been incorporated in alkali salt form.

The paste-like detergent as well as that, if necessary, for its production serving surfactant mixture is essentially free of water and organic solvents. Under is essentially "free of water" to understand a state in which the content of liquid, that is, not in the form of water of hydration and constitutional water 5% by weight, preferably below 2% by weight and in particular below 1% by weight lies. Higher water contents are disadvantageous because they affect the viscosity of the Increase disproportionately and especially reduce its stability. Organic solvents, which are commonly found in liquid concentrates used low molecular weight and low boiling alcohols and ether alcohols, as well as hydrotropic compounds, are apart of traces that can be introduced with individual active ingredients, too absent.

The agent contains a solid phase that is homogeneous in the liquid surfactant phase is dispersed and which the other detergent ingredients have a cleaning effect and optionally contains auxiliaries. To this other cleaning ingredients primarily include washing alkalis and sequestering connections.

The liquid phase of the paste-like composition according to the invention consists in essentially from the nonionic surfactants according to formulas (I) and (II) from the surfactant mixture according to the invention and from where appropriate synthetic anionic surfactant contained in this surfactant mixture essentially distributed in the liquid phase. If the invention Surfactant mixture stored or transported at lower temperatures nonionic surfactants are expediently used, whose pour point (solidification point) is below 5 ° C for solidification avoid the surfactant mixture if possible. For those using of the surfactant mixture according to the invention produced according to the invention pasty agents this problem does not matter because the agents already have such a high viscosity at room temperature that a any further solidification at lower temperatures is of no importance owns.

The preferred washing alkali contained in the solid phase of the agent according to the invention is amorphous and / or crystalline alkali silicate, in particular sodium metasilicate of the composition Na ₂ O: SiO ₂ from 1: 0.8 to 1: 1.3, preferably 1: 1, in anhydrous Form is used. In addition to the metasilicate, anhydrous alkali carbonate is also suitable, which, however, requires larger proportions of the liquid phase due to absorption processes and is therefore less preferred. The proportion of the agents in silicate can be 35% by weight to 70% by weight, preferably 40% by weight to 65% by weight and in particular 45% by weight to 55% by weight. Alkali carbonate is preferably present at most up to 20% by weight, in particular below 10% by weight.

Suitable sequestrants are those from the class of the aminopolycarboxylic acids and polyphosphonic acids. The aminopolycarboxylic acids include Nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid as well as their higher homologues. Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri- (methylenephosphonic acid), Ethylenediaminetetra- (methylenephosphonic acid) and their higher homologues, such as for example diethylene tetramine tetra (methylenephosphonic acid). The aforementioned Acids usually come in the form of their alkali salts, especially the sodium or potassium salts for use. Prefers sodium nitrilotriacetate is used in proportions of up to 10% by weight, preferably 2 wt .-% to 6 wt .-% used.

Suitable sequestrants also include monomeric polycarboxylic acids or hydroxypolycarboxylic acids, especially in the form the alkali salts, for example sodium citrate and / or sodium gluconate.

The sequestering agents used with preference include homopolymeric and / or copolymeric carboxylic acids or their alkali metal salts, the sodium or potassium salts being preferred. Polymeric carboxylates or polymeric carboxylic acids with a relative molecular weight of at least 350, in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, have proven to be particularly suitable, such as oxidized polysaccharides according to international patent application WO 93/08251, polyacrylates , Polyhydroxyacrylates, polymethacrylates, polymaleates and in particular copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those composed of 50 to 70% acrylic acid and 50 to 10% maleic acid, as are characterized, for example, in European patent EP 022 551. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as monomers can also be used as polymeric carboxylates or carboxylic acids. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, preferably a C ₄ -C ₈ dicarboxylic acid, maleic acid being preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ -carboxylic acids, with vinyl alcohol are particularly preferred. Preferred terpolymers contain 60 to 95% by weight, in particular 70 to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 to 40% by weight. %, preferably 10 to 30% by weight of vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2.1 and 2, are very particularly preferred. 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives derives, is substituted. Preferred terpolymers contain 40 to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 to 30% by weight, preferably 15 to 25 % By weight of methallylsulfonic acid or methallylsulfonate and, as the third monomer, 15 to 40% by weight, preferably 20 to 40% by weight, of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. By using the third monomer, predetermined breaking points are built into the polymer, which are responsible for the degradability of the polymer. The terpolymers used can be produced by any of the known and customary processes. Terpolymers which are neutralized either completely or at least partially, in particular to more than 50%, based on the carboxyl groups present, are also preferably used. Particularly preferred terpolymers are produced by a process which is described in German patent applications DE 42 21 381 and DE 43 00 772.

Polyacetal carboxylic acids, as described, for example, in US Pat U.S. Patent Nos. 4,144,226 and 4,146,495; and by polymerization of esters of glycolic acid, introduction of stable terminal End groups and saponification to obtain the sodium or potassium salts will. Also suitable are polymeric acids by polymerization of acrolein and disproportionation of the polymer by Canizzaro using strong alkalis can be obtained. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units built up.

The proportion of organic, carboxyl group-containing builder materials in the Pasty agent according to the invention can preferably up to 10 wt .-% 1% by weight to 7.5% by weight and in particular 2% by weight to 5% by weight of the Polyphosphonic acids "up to 3% by weight, preferably 0.05% by weight to 1.5% by weight and in particular 0.1% to 1% by weight. These also mentioned Substances are used in an anhydrous form.

Crystalline alkali silicates and finely divided alkali alumosilicates, in particular zeolites of the NaA type, can also be regarded as useful sequestering agents in the context of the present invention. Suitable zeolites have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in German patent DE 24 12 837 C2). Their particle size is usually in the range from 1 µm to 10 µm. They are used in dry form. The water contained in bound form in the zeolites does not interfere in the present case. Crystalline layered silicates of the formula NaMSi _x O _{2x + 1} + _y H ₂ O, in which M represents sodium, x a number from 1.9 to, are preferably used as crystalline silicates, which may be present alone or in a mixture with the aluminosilicates mentioned 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO91 / 08171. Usable crystalline silicates are commercially available under the names SKS-6 (manufacturer Hoechst) and Nabion ^(R) 15 (manufacturer Rhone-Poulenc). The content of inorganic builder material in the paste can be up to 35% by weight, preferably up to 25% by weight and in particular 10% by weight to 25% by weight.

The washing pastes according to the invention are preferably phosphate-free. Provided a phosphate content is ecologically harmless (for example with a Waste water treatment eliminating phosphates), polymeric alkali phosphates, such as sodium tripolyphosphate. Your share can go up to 20 wt .-%, based on the total agent, the proportion the other solids, for example the alkali silicate and / or aluminosilicate, is reduced accordingly. The proportion is preferably Tripolyphosphate at most 10 wt .-%.

As further components, which are also predominantly assigned to the solid phase washing aids are possible. These include graying inhibitors, optical brighteners, bleaches and dyes. So much fragrance are used, which are generally liquid, go into the liquid phase. Because of their small amount, however, they are on the flow behavior of the pastes without any notable influence.

Suitable graying inhibitors or soil release agents are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose as well (Poly) alkylene glycol esters of dicarboxylic acids, such as ethylene terephthalate-polyoxyethylene terephthalate copolyesters. Sodium carboxymethyl cellulose is preferred and mixtures thereof with methyl cellulose. Of the The proportion of graying inhibitors is generally up to 2% by weight. and is preferably 0.5% to 1.5% by weight.

In particular as an optical brightener for textiles made of cellulose fibers (cotton) Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts contain. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or similarly structured compounds that replace the morpholino group a diethanolamino group, a methylamino group or a 2-methoxyethylamino group carry. Furthermore, brighteners of the type des substituted 4,4'-distyryl diphenyl may be present, for example 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of brighteners can also be used. Brighteners of the 1,3-diaryl-2-pyrazoline type are suitable for polyamide fibers, for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline as well as connections constructed in the same way. The content of the agent of optical brighteners or brightener mixtures in general up to 1% by weight, preferably 0.05% by weight to 0.5% by weight.

Another component of the solid phase can be finely divided bleaches to be present. Peroxygen compounds, such as sodium perborate monohydrate, can be used. -tetrahydrate, sodium percarbonate, persilicates, caroates and organic peracids, such as perbenzoates or peroxyphthalates. This Peroxygen compounds are in the agents according to the invention the extensive absence of water has a long shelf life. If necessary, you can also known bleach activators may be present when water is added hydrolyze with the peroxygen compounds to form peracids, for example N-acyl or O-acyl compounds, preferably N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine, further Carboxylic anhydrides such as benzoic anhydride and phthalic anhydride, and Esters of polyols such as glucose pentaacetate. Because in commercial laundries the bleaching component is often added to the wash liquor separately and in Usually applied only when special needs can be applied to a salary the paste of bleaching agents can be dispensed with in such cases.

Another advantage of the invention is that the addition of Low molecular weight polyethylene glycols from about 200 to 800, which usually results in a flow of up to 15% the pastes are to be improved, can be dispensed with entirely. This Additives do not contribute to the detergency and are therefore undesirable.

For the same reason, paraffin oils or liquid paraffin mixtures are missing preferably in the paste-like compositions according to the invention all. Small amounts of such substances can, however, since they are normally a certain foam reduction under application conditions cause what can be particularly noticeable in the rinse cycle, for Support of the foam regulator, which is fixed at room temperature, is included be. The proportion of such liquid foam-reducing agents is preferably Active ingredients, in addition to the above-mentioned paraffin oils Liquid long-chain ethers belong in the paste-like form according to the invention Average not more than 5 wt .-%, in particular from 0.1 wt .-% to 2% by weight.

The preparation of the paste-like compositions according to the invention can be carried out directly connect to the preparation of the surfactant premix according to the invention, however, the surfactant mixture according to the invention can also be produced after it can be stored temporarily without any problems. In the The preparation of the agents according to the invention is preferably carried out in such a way that one to the, if necessary, reheated after storage, at temperatures from room temperature to 120 ° C submitted surfactant mixture according to the invention in a conventional stirred kettle, avoiding excessive Air entry the other solid components, which individually or as mixtures containing two or more powder components may be present, mixes. It was found that the process is particularly stable paste-like agents results when one is in the temperature range from room temperature up to 45 ° C, in particular up to 40 ° C, or in the temperature range works from 80 ° C to 120 ° C. Temperatures in the latter higher temperature range also facilitate the wetting of the solid phase, what leads to faster homogenization of the ingredients. The admixing order the finely divided solid components are largely arbitrary, however, the alkali silicate is preferred as the largest proportion of the solid phase constituent added last. Likewise it is possible to add the finely divided main component in cycles, that is the addition of part of the alkali silicate alternating with the fixed secondary components. After mixing the solids with the surfactant premix the resulting paste is preferably in a grinding device, for example a colloid mill, on the for the solid phase Grind the specified grain size if the fine-particle solids used did not already have the desired grain sizes. Conveniently is then a homogenizing in a further stirred kettle Mixing the ground solid components with the liquid Phase carried out, in particular also thermally sensitive minimum components, for example bleach, dyes and / or fragrances and Enzymes, especially protease, amylase, lipase and / or cellulase and optionally Enzyme stabilizers, especially lower carboxylic acids or Calcium compounds in which paste can be incorporated. Especially if needle-like or platelet-shaped alkali metal silicate has been used a further grinding step can be carried out after the homogenization if the grain spectrum specified for the solid phase has not yet been reached was.

There is a preferred embodiment of the method according to the invention therein, 20 parts by weight to 45 parts by weight of a flowable according to the invention Premix of surfactant with 40 parts by weight to 65 parts by weight of solid, powdery Alkali silicate and 2 parts by weight to 10 parts by weight of solid polymer Polycarboxylate and up to 5 parts by weight, especially if this is Surfactant premix is missing, 1 part by weight to 3.5 parts by weight, synthetic anionic surfactant, up to 10 parts by weight, in particular 1.5 parts by weight up to 8 parts by weight complexing agent for heavy metals, up to 5 parts by weight, in particular 0.5 parts by weight to 3 parts by weight of solid powder Cellulose ether and up to 1 part by weight, especially 0.1 part by weight Mix 0.5 parts by weight of powdered optical brightener.

The pastes according to the invention are produced directly by the the shear forces acting are flowable and pumpable and can be done without problems be filled into storage containers. These storage containers are trading it because the pastes according to the invention without the action of shear forces become so viscous relatively quickly that they lose their fluidity and can no longer be pumped, preferably around shipping containers, especially those with rigid outer walls, for example barrels or tons in which the product is delivered to the commercial washing machine and from which it is removed with the help of a removal device, which in the Is able to develop sufficient shear forces in the washing machine respectively whose stock container can be dosed. A good one for that suitable device is in the German patent application P 43 32 850.4 = WO-A-95/09263, "paste container with removal device" from Henkel Ecolab GmbH & Co. OHG.

Examples example 1

In a heated stirred kettle, ethoxylated C _12/14 fatty alcohol (average degree of ethoxylation 3; manufacturer Henkel) and ethoxylated and then propoxylated C _12/14 fatty alcohol (average degree of ethoxylation 5, average degree of propoxylation 4; manufacturer Henkel) were given in Table 1 below Quantity ratios heated to 80 ° C. While stirring, phosphoric acid monostearate (manufacturer Hoechst) and then fatty acid sodium salt (Edenor ^(R) HT; manufacturer Henkel) and sodium C _9/11 alkylbenzenesulfonate were added and the mixture was then stirred at 80 ° C. for a few minutes. A surfactant mixture ( G1 ) according to the invention was obtained which was flowable and pumpable at room temperature and could be stored for several months without changing its properties, in particular its flowability. G1 surfactant mixture (parts by weight) ethoxylated fatty alcohol 20th ethoxylated / propoxylated fatty alcohol 10th Phosphoric acid mono / di-stearate 1.5 Fatty acid sodium salt 1.5 Alkyl benzene sulfonate 2nd

Example 2

The amounts of sodium nitrilotriacetate, polymeric polycarboxylate Na salt (Sokalan ^(R) CP 5; manufacturer BASF), sodium hydroxyethane-1, given in Table 2, were added to 35 parts by weight of the surfactant mixture G1 from Example 1 at 55 ° C. 1-diphosphonate, cellulose ether (Relatin ^(R) DM 4050; manufacturer Aqualon), optical brightener (Tinopal ^(R) CBS; manufacturer Ciba-Geigy) and as the last sodium metasilicate, each as an anhydrous powder, with about 1 added after each added component Minute was stirred before the next ingredient was incorporated. The resulting mixture was then ground in a milling device (roller mill, continuous throughput), transferred to a stirred kettle and stirred for a further 10 minutes at its own temperature (approx. 40 ° C.) without external heating. A paste-like detergent W1 which was flowable immediately after production and was filled into 280 kg drums was obtained. After a storage period of 10 days, the agent had a viscosity (measured at 25 ° C. with a Brookfield ^(R) rotary viscometer DV-II with spindle No. 7 at 5 revolutions per minute) of 200,000 mPa · s, under otherwise identical conditions at 50 revolutions per minute from 70,000 mPa · s. These viscosity values of the paste did not change significantly when stored for 3 months. Likewise, no separation or phase separation was observed during this period, even if part of the paste in the barrel was subjected to shear forces as part of the paste removal or dosing in a commercial washing machine. Composition of paste W1 (parts by weight) G1 35 Sodium nitrilotriacetate 4th Sokalan ^(R) CP 5 5 Hydroxyethane diphosphonate 1 Relatin ^(R) DM 4050 1.5 Tinopal ^(R) CBS 0.2 Sodium metasilicate 53.3

Claims (20)

1. A storable, substantially water-free, flowable surfactant mixture containing nonionic surfactant in the form of alkoxylation products of alcohol and soap, characterized in that it contains 40% by weight to 70% by weight of nonionic surfactant - liquid at room temperature - corresponding to general formula (I): R¹-(OC₂H₄)_n-OH in which R¹ is an alkyl or alkenyl radical containing 10 to 20 carbon atoms and the average degree of ethoxylation n may assume a value of 1 to 8, 20% by weight to 50% by weight of nonionic surfactant - liquid at room temperature - corresponding to general formula (II): R²-(OC₂H₄)_r-(OC₃H₆)_p-OH in which R² is an alkyl or alkenyl radical containing 10 to 20 carbon atoms, the average degree of ethoxylation r may assume a value of 2 to 8 and the average degree of propoxylation p may assume a value of 1 to 6, and 1% by weight to 10% by weight of a C₁₀ to C₂₂ carboxylic acid and/or an alkali metal salt thereof.
2. A surfactant mixture as claimed in claim 1, characterized in that it additionally contains up to 10% by weight and, more particularly, 0.5% by weight to 8% by weight, of synthetic anionic surfactant solid at room temperature, more particularly alkyl benzene sulfonic acid, alkali metal alkyl benzene sulfonate and/or alkali metal alkyl or alkenyl sulfate.
3. A surfactant mixture as claimed in claim 1 or 2, characterized in that it additionally contains up to 5% by weight and, more particularly, 0.1% by weight to 4% by weight of alkali-stable and shear-stable foam regulator solid at room temperature.
4. A surfactant mixture as claimed in any of claims 1 to 3, characterized in that it contains 48% by weight to 64% by weight of nonionic surfactant corresponding to general formula (1), 28% by weight to 40% by weight of nonionic surfactant corresponding to general formula (II) and 2% by weight to 6% by weight of carboxylic acid and/or an alkali metal salt thereof.
5. A surfactant mixture as claimed in any of claims 1 to 4, characterized in that it contains a carboxylic acid mixture of - based on the carboxylic acid mixture as a whole - 2% by weight to 8% by weight of C₁₄, up to 1% by weight of C₁₅, 18% by weight to 24% by weight of C₁₆, up to 3% by weight of C₁₇, 20% by weight to 42% by weight of C₁₈ and 30% by weight to 44% by weight of C₂₀ to C₂₂ carboxylic acid or alkali metal salts thereof.
6. A surfactant mixture as claimed in any of claims 1 to 5, characterized in that the nonionic surfactant corresponding to formula (I) has an average degree of ethoxylation n of 1 to 6 and, more particularly, 2 to 4 and/or the nonionic surfactant corresponding to formula (II) has an average degree of ethoxylation r of 3 to 7 and/or an average degree of propoxylation p of 3 to 5.
7. A process for the production of the surfactant mixture claimed in any of claims 1 to 6, characterized in that at least one of the nonionic surfactants corresponding to formula (I) or (II) is heated to temperatures of 60°C to 120°C, the solid constituents are dissolved or dispersed in the nonionic surfactant at those temperatures and the mixture formed is heated to temperatures of 60°C to room temperature, optionally after addition of the second nonionic surfactant.
8. A process as claimed in claim 7, characterized in that the constituents solid at room temperature are mixed with the nonionic surfactant or the nonionic surfactants at temperatures in the range from 70°C to 100°C.
9. A process as claimed in claim 7 or 8, characterized in that the nonionic surfactant corresponding to formula (I) or (II) which is to be used in the smaller quantity is introduced first and heated, the foam regulator, if any, is added, the carboxylic acid or alkali metal salt is then introduced, the synthetic anionic surfactant is optionally added and the nonionic surfactant corresponding to formula (II) or (I) which was not added first is introduced last of all.
10. The use of the surfactant mixture claimed in any of claims 1 to 6 or of a surfactant mixture produced by the process claimed in any of claims 6 to 9 for the production of paste-form detergents or cleaning compositions.
11. A pseudoplastic paste-form detergent or cleaning composition containing fine-particle constituents which has been produced in particular using the surfactant mixture claimed in any of claims 1 to 6 and which has such a viscosity in the absence of shear forces that it does not flow under the effect of gravity at room temperature, but has a distinctly lower viscosity and flows under the effect of gravity on exposure to shearing, characterized in that it contains a surfactant mixture which contains 40% by weight to 70% by weight of nonionic surfactant liquid at room temperature corresponding to general formula (I): R¹-(OC₂H₄)_n-OH in which R¹ is an alkyl or alkenyl radical containing 10 to 20 carbon atoms and the average degree of ethoxylation n may assume a value of 1 to 8, 20% by weight to 50% by weight of nonionic surfactant liquid at room temperature corresponding to general formula (II): R²-(OC₂H₄)_r-(OC₃H₆)_p-OH in which R² is an alkyl or alkenyl radical containing 10 to 20 carbon atoms, the average degree of ethoxylation r may assume a value of 2 to 8 and the average degree of propoxylation p may assume a value of 1 to 6, and 1% by weight to 10% by weight of a C₁₀ to C₂₂ carboxylic acid and/or an alkali metal salt thereof,
    and in that 20% to 50% of the solid particles have particle sizes above 80 µm.
12. A detergent or cleaning composition as claimed in claim 11, characterized in that, using a Brookfield® DV-II or DV-II plus rotational viscosimeter with a No. 7 spindle, it has a viscosity at 25°C of more than 100,000 mPa·s, more particularly in the range from 150,000 mPa·s to 500,000 mPa·s, at 5 revolutions per minute and a viscosity below 100,000 mPa·s, more particularly in the range from 10,000 mPa·s to 90,000 mPa·s, at 50 revolutions per minute.
13. A paste-form, substantially water-free pseudoplastic detergent or cleaning composition containing 20% by weight to 80% by weight of the surfactant mixture claimed in any of claims 1 to 6, characterized in that it contains 20% by weight to 80% by weight of solid powder-form constituents with an average particle size of 5 µm to 120 µm, preferably 10 µm to 100 µm and, more preferably, 10 µm to 80 µm and a viscosity at 20°C in the range from 10,000 mPa·s to 500.000 mPa·s at a shear rate of 0.025 s^-1, in the range from 5,000 mPa·s to 130,000 mPa·s and more particularly in the range from 5,000 mPa·s to 13,000 mPa·s at a shear rate of 0.2 s^-1 and in the range from 400 mPa·s to 10,000 mPa·s and more particularly in the range from 400 mPa·s to 1,600 mPa·s at a shear rate of 2 s^-1.
14. A paste-form detergent or cleaning composition as claimed in claim 13, characterized in that 90% by weight of the solid powder-form constituents have a particle size below 140 µm and, more particularly, below 100 µm.
15. A process for the production of the paste-form detergent or cleaning composition claimed in any of claims 11 to 14, characterized in that the other solid constituents, which may be present individually or in the form of mixtures containing two or more powder components, are added to the surfactant mixture claimed in any of claims 1 to 6 optionally reheated after storage and introduced into a standard stirred tank reactor at temperatures of 80°C to 120°C, care being taken to avoid any excessive introduction of air.
16. A process as claimed in claim 15, characterized in that the constituent which makes up the largest component by weight of the solid phase, more particularly the alkali metal silicate, is added last.
17. A process as claimed in claim 15 or 16, characterized in that the fine-particle main component is added in portions.
18. A process as claimed in any of claims 15 to 17, characterized in that, after mixing of the solids with the surfactant compound, the paste formed is ground in a mill to the particle size indicated for the solid phase and the ground solid constituents are subsequently mixed with the liquid phase.
19. A process as claimed in any of claims 15 to 18, characterized in that 20 parts by weight to 45 parts by weight of a flowable surfactant compound containing 40% by weight to 70% by weight of nonionic surfactant liquid at room temperature corresponding to general formula (I): R¹-(OC₂H₄)_n-OH in which R¹ is an alkyl or alkenyl radical containing 10 to 20 carbon atoms and the average degree of ethoxylation n may assume a value of 1 to 8, 20% by weight to 50% by weight of nonionic surfactant liquid at room temperature corresponding to general formula (II): R²-(OC₂H₄)_r-(OC₃H₆)_p-OH in which R² is an alkyl or alkenyl radical containing 10 to 20 carbon atoms, the average degree of ethoxylation r may assume a value of 2 to 8 and the average degree of propoxylation p may assume a value of 1 to 6, 1% by weight to 10% by weight of a C₁₀ to C₂₀ carboxylic acid and/or an alkali metal salt thereof, up to 10% by weight of synthetic anionic surfactant solid at room temperature and up to 5% by weight of alkali-stable and shear-stable foam regulator solid at room temperature are mixed with
    40 parts by weight to 65 parts by weight of solid powder-form alkali metal silicate and 2 parts by weight to 10 parts by weight of solid polymeric polycarboxylate and up to 5 parts by weight - particularly where it is missing from the surfactant compound - 1 part by weight to 3.5 parts by weight of synthetic anionic surfactant, up to 10 parts by weight and, more particularly, 1.5 parts by weight to 8 parts by weight of a heavy-metal complexing agent, up to 5 parts by weight and, more particularly, 0.5 part by weight to 3 parts by weight of solid powder-form cellulose ether and up to 1 part by weight and, more particularly, 0.1 part by weight to 0.5 part by weight of powder-form optical brightener.
20. A process for charging a washing machine, more particularly an institutional washing machine, with liquid and solid detergent constituents, characterized in that a flowable surfactant mixture, more particularly containing 40% by weight to 70% by weight of a nonionic surfactant liquid at room temperature corresponding to general formula (I) above, 20% by weight to 50% by weight of a nonionic surfactant liquid at room temperature corresponding to general formula (II) above and 1% by weight to 10% by weight of a C_10-22 carboxylic acid and/or an alkali metal salt thereof is produced, a fine-particle solid (20% to 50% of the solid particles having particle sizes above 80 µm) is dispersed therein, the non-flowable preparation thus obtained is made flowable immediately before use by application of mechanical energy, more particularly in the form of stirring, the flowable preparation is diluted with a predetermined quantity of water and is introduced into the washing machine.