EP0721498A1

EP0721498A1 - Pasty washing agent

Info

Publication number: EP0721498A1
Application number: EP94928372A
Authority: EP
Inventors: Hans-Josef Beaujean; Thomas Merz; Erich Holz; Thomas Holderbaum; Günther Amberg; Khalil Shamayeli; Michael Marschner; Hubert Harth
Original assignee: Henkel AG and Co KGaA
Current assignee: Ecolab GmbH and Co oHG
Priority date: 1993-09-27
Filing date: 1994-09-19
Publication date: 1996-07-17
Anticipated expiration: 2014-09-19
Also published as: WO1995009229A1; NO960252L; US5929014A; DK0721498T3; DE4332849A1; ES2126149T3; CA2172602C; NO5830A; NO20005830D0; HUT73750A; FI961357A; FI961357A0; FI113277B; NO314665B1; HU9600749D0; NO960252D0; EP0721498B1; CA2172602A1; DE59407315D1; NO310568B1

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

"Paste detergent"

The invention relates to structurally viscous pasty detergents, in particular for automatic dosing in commercial laundries, a method for dosing such structurally viscous agents, a method for their production and stable, flowable surfactant mixtures which are specially adapted to the production method, the nonionic surfactant, long-chain carboxylic acid or 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 the needs of the household, so that they usually have to be sufficiently liquid to be poured and dosed without problems. Since such liquid detergents are also said to be stable in storage within relatively wide temperature ranges without losing their liquid properties, it is often not possible to do without additions of organic solvents and / or hydrotropes which themselves do not contribute to the washing or cleaning result and are therefore undesirable are. European patent application EP 253 151 A2 proposes a way of circumventing possible metering problems with insufficiently liquid agents. Liquid, partly highly viscous detergents based on nonionic and anionic surfactants are known from this document, which contain polyethylene glycol as hydrotrope and are packaged in portions in bags made of water-soluble material.

The pasty detergent presented in German Offenlegungsschrift DE 37 19906 AI consists of a phase which is liquid in the temperature range below 10 ° C. and which is formed from nonionic surfactant, and a solid phase of a certain grain size dispersed therein, which consists of detergents, sequestering agents and optionally anionic surfactants is formed. For this purpose tensides or their mixture are used, the pour point (solidification point) of which is below 5 ° C, in order to avoid solidification of the paste 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, which is undoubtedly an advantage. However, it has now been found that such pastes cannot always ensure the homogeneity of their mixed ingredients satisfactorily during their production and often also tend to separate during storage. This negative property affects not only the separation of the solid from the liquid components, but also the phase separation of the liquid ingredients. This disadvantage is particularly evident when the pastes stored in storage containers are exposed to shear effects. Although the viscosity of the known pastes can be reduced by scissors and thus the conveyability and metering can be made even easier, phase separation of the paste which has already been sheared but not yet conveyed cannot generally be avoided in the storage container. The object was therefore to prevent the paste constituents from segregating even more during production and during shear under removal conditions from the transport or storage container and to further increase the storage stability of the detergent paste.

Surprisingly, this was achieved essentially by changing the viscosity and the intrinsic viscosity of the paste. The paste-like compositions according to the invention have such a high viscosity at room temperature (20 ° C. to 25 ° C.) without the action of shear forces that they can neither flow out of a container nor be conveyed by simple suction. The shear effect of a movable plate or even a pressure stamp, as provided in the metering system according to German Offenlegungsschrift DE 37 19906 AI, is by no means sufficient to reduce the viscosity of the paste-like compositions according to the invention to such an extent that they are conveyed by a suction pump can. Only higher shear forces, such as can be achieved, for example, with the aid of the paste container with removal device according to the unpublished German patent application P 4332850.4 from Henkel Ecolab GmbH & Co. OHG, are in this position, 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, the entire contents of the storage container should not be dosed into the commercial washing machine at once, such as which largely have the same properties as before the start of the action of shear forces.

Such pastes can advantageously be produced using a flowable, storage-stable surfactant mixture of certain nonionic surfactant and long-chain carboxylic acid and / or soap, which does not have the aforementioned structural viscosity or only in a significantly reduced form.

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,

Rl- (0C ₂ H ₄ ) _n -0H (I)

in which R * 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 of nonionic surfactant of the general formula (II) which is liquid at room temperature,

R2- (0C ₂ H4) _r - (0C ₃ H6) p-0H (II)

in which R ² denotes an alkyl or alkenyl radical with 9 to 20 C atoms, the average degree of ethoxylation r can take on values from 2 to 8 and the average degree of propoxylation p can take on values from 1 to 6, and 1% by weight to 10 % By weight of a C 1 -C 22 -carboxylic acid and / or its alkali salt.

Another object of the invention is a structurally viscous pasty washing or cleaning agent, which has been produced in particular using the surfactant mixture mentioned and has such a viscosity without the action of shear forces that it is at room temperature is not flowable under the influence of gravity, but has a significantly lower viscosity when sheared and is flowable under the influence of gravity. This property can be checked experimentally by measuring the paste viscosity under different shear conditions. One way of doing this is to use a conventional rotary viscometer at different speeds of rotation of the spindle. Pastes according to the invention preferably have a viscosity above 100,000 mPa-s, in particular from 150,000 mPa-s to at 25 ° C. using a Brookfield ( ^R ) rotary viscometer DV-II or DV-II plus with spindle No. 7 at 5 revolutions per minute 500,000 mPa-s, and at 50 revolutions per minute a viscosity below 100000 mPa-s, in particular from 10000 mPa ^« s to 90,000 mPa * s and particularly preferably from 50,000 mPa-s to 80,000 mPa-s. In order to take into account possible thixotropy effects of the paste, the numerical values mentioned refer to the reading after a measuring time of 3 minutes and are only to be regarded as indicative, since comparatively small changes in the measuring conditions with regard to the temperature or the viscometer, as indicated below , can lead to other results of the viscosity measurement.

Another object of the invention is a method for loading a washing machine, in particular a commercial washing machine, with liquid and solid detergent components, which is characterized in that a flowable surfactant mixture, in particular containing 40% by weight to 70% by weight. % nonionic surfactant of the general formula (I) liquid at room temperature as stated above, 20% by weight to 50% by weight nonionic surfactant of the general formula (II) liquid at room temperature as stated above, and 1 to 10% by weight % By weight of a Cχo to C22 "carboxylic acid and / or its alkali salt, produced, dispersed therein finely divided solid, which makes the storage-stable, non-flowable preparation thus obtained flowable directly before use with the input of mechanical energy, in particular by stirring, the flowable preparation is diluted with a predetermined amount of water and metered into the washing machine.

In the compounds of the formulas I and II, the radicals R * and R ^{2 can be} linear or branched, for example methyl-branched in the 2-position (oxo alcohols). Preferably, the nonionic surfactant has Formula (I) 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 Cg_n-0xoalcohols with 2 to 10 EO, such as Cg_n + 3 EO, Cg.n + 5 EO, Cg_n + 7 EO, Cg.n + 9 EO; Cιi-13-oxo alcohols with 2 to 8 EO, such as Cπ_i3 + 2 EO, Cn_i3 + 5 EO, Cll-13 ⁺ 6 EO, Cn_i3 ⁺ 7 EO; Cχ2-15-0xoalcohols with 3 to 6 EO, such as Cχ2-15 + 3 EO, C12-15 + 5 EO; Isotridecanol with 3 to 8 EO; partially unsaturated linear Cιo-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 Ci2-i8 ~ Eett alcohols or Cg_i5-0xo alcohols with 1 to 3 PO and 4 to 8 EO, such as Ci2-18 ~ coco alcohol + (E0) 4_7 (P0) ι_2, Oley alcohol or 1: 1 mixture of cetyl -Oleyl alcohol + (E0) 5_7 (P0) ι_2, Cπ_i5-0xo alcohol + (E0) 4_6 (P0) ι_2-

Among the surfactants of the formulas (I) and (II) which are liquid at room temperature, those which melt at temperatures below 10 ° C. are particularly preferred. If desired, small amounts of nonionic surfactants of the same structure can be present as long as it is ensured that the nonionic component of the surfactant mixture is liquid at room temperature and preferably at 10 ° C.

The surfactant mixture according to the invention preferably contains 48% by weight to 64% by weight of 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, in such a surfactant premix, up to 10% by weight, in particular 0.5% by weight to 8% by weight, of solid anionic surfactant at room temperature and / or up to 5% by weight, in particular 0.1 % By weight to 4% by weight of foam regulator which is solid, alkali-stable and shear-stable at room temperature.

Suitable synthetic anionic surfactants which can be incorporated into the surfactant mixture according to the invention in solid, fine, largely anhydrous form include, in particular, those of the sulfonate or sulfate type, which are normally used as alkali metal salts, preferably as sodium salts are present. 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 Cg_i3-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 their esters, which are derived from lower alcohols such as methanol, ethanol and propanol, in particular in the α-position sulfonated saturated ^c 12-18 " ^{fatty acids} ""d, and olefin sulfonates, such as those obtained by SO3 sulfonation Ententiger Ci2_i8-01efine 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 is an alkali, ammonium or alkyl or hydroxy-alkyl substituted The ammonium ion has a counter cation, and the deri are particularly suitable vate of linear alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. 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, that is to say mixtures with essentially hexadecyl and octadecyl radicals. The alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. In addition, the sulfated alkoxylation products of 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 alkylsulfates.

The carboxylic acids or salts thereof contained in the surfactant mixtures according to the invention preferably include saturated and / or unsaturated Ci2-22-- ^ret '- ^{: s,} = i ^uren ' for example coconut, palm kernel or Taig¬ fatty acid, or their alkali salts (soaps) in question, although their branched chain isomers are also useful. 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 C14-, up to 1% by weight of C15-, 18% by weight to 24% by weight. % Ciss, up to 3% by weight of C17, 20% by weight to 42% by weight of Ci8 ~ and 30% by weight to 44% by weight of C20 to C22 carboxylic acid or its alkali metal 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 both of linear compounds and of crosslinked polysiloxane resins and of their mixtures. Other defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, the melting point of which 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 which the alkyl chains each have 12 to 22 carbon atoms. Sodium monoalkyl phosphate and / or dialkyl phosphate with Ci6 to Ci8 ~ alkyl groups is particularly preferably used. The proportion of 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.

In the course of the preparation of the surfactant mixtures according to the invention, it is important that the constituents which are solid at room temperature, which include the carboxylic acid or its salt and optionally the synthetic anionic surfactant and the foam regulator, are mixed as homogeneously as possible with the non-ionic surfactants . This is preferably done by heating at least one of the nonionic surfactants of the formula (I) or (II) to temperatures in the range from 60 ° C. to 120 ° C., in particular from 70 ° C. to 100 ° C., at these temperatures dissolves or disperses the solid components in the non-ionic surfactant and the resulting mixture, optionally after addition of the second nonionic surfactant, cooled to temperatures from 60 ° C. to room temperature.

In this process, the nonionic surfactant according to formula (I) or (II) which is to be used in a smaller amount is preferably heated, heated, mixed if necessary with the foam control, then the carboxylic acid is added or their alkali salt, then optionally the synthetic anionic surfactant and finally the non-ionic surfactant according to formula (II) or (I) which is not initially introduced.

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

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

The use of the surfactant mixture according to the invention has the advantage that all substances which have a substantial influence on the viscosity of the finished product, in particular the carboxylic acid or its salt, are incorporated into it. The homogeneous incorporation of these substances into finished washing or cleaning agents is thereby considerably facilitated, which contributes to the constant product quality, in particular with regard to its viscosity. In addition, the premix according to the invention also has advantages in the production of pasty finished products, since prior incorporation of the carboxylic acid or its salts in powder form is necessary. It happens in everything As a rule, for reasons that are not completely clarified, there is a loss of soap active substance, which can be completely avoided when using the surfactant mixture according to the invention. In addition, it was found that when the surfactant mixture according to the invention is used to produce pasty compositions, its final viscosity advantageously sets up much more rapidly than when the individual components of the surfactant mixture are used separately.

A paste-form detergent or cleaning agent in the invention is preferably so pseudoplastic that it has a viscosity in the range of 10,000 mPa ^'s to 500,000 ^mPa' s at 20 ° C and a shear rate of 0.025 s ^"1, to determine with a plate viscometer Carrimed ( ^R ) CS 100 with a grooved 2 cm plate (Cross Hatch Fiat Plate), plate spacing 1.5 mm .. When exposed to sufficient shear forces, an agent according to the invention has a considerable amount, as a rule 2 to 15 times never Third viscosity, which at a shear rate of 0.2 s " ¹ and otherwise identical measuring conditions in the range from 5000 mPa-s to 130 000 mPa-s, in particular from 5000 mPa-s to 13000 mPa-s, and at a shear rate of 2 s " ¹ and otherwise the same measuring conditions are in the range from 400 mPa-s to 100000 mPa-s, in particular from 400 mPa-s to 1 600 mPa-s. These numerical values also refer to possible thixotropy effects of the paste take into account 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 relate to measurements directly after the paste has been produced, but to stored pastes which are, so to speak, in equilibrium, since the shear forces acting in the course of the production process lead to a lower paste viscosity, which results only increased over time to the definitive final viscosity. Storage periods of 1 month are usually completely sufficient for this.

In one embodiment, a paste-like composition according to the invention contains in particular 20% by weight to 80% by weight of the surfactant mixture according to the invention and 20% by weight to 80% by weight of additional solid powdery fine partial components. The constituents of the paste-like composition contained as a solid phase should be finely divided and have an average grain size in the range from 5 μm to 120 μm, with at most 10% of the particles having a grain size of more than 150 μm. Surprisingly, it is possible to incorporate relatively coarse-grained solids, for example those which contain 20% to 50% of particles with particle sizes above 80 μm, without disadvantage into the paste-like compositions. The mean grain size of the particles forming the solid phase is preferably 10 μm to 80 μm and in particular 10 μm to 60 μm, the maximum grain size being below 200 μm, in particular below 150 μm. 90% by weight of the solid powdery constituents are preferably less than 140 μm, in particular less than 100 μm. The mean grain size relates to the volume distribution of the particles, which can be determined by known methods (for example by means of laser diffraction or a Coulter Counter).

In the course of the optimization of the pastes according to the invention, it was found that particularly stable paste-like agents are obtained if the synthetic anionic surfactant is used in its acid form, for example as free alkylbenzenesulfonic acid, and / or the carboxylic acid in the surfactant premix used for its preparation is used as alkali salt. Although the resulting paste-like compositions had the same gross composition, they were surprisingly even more stable than compositions which were prepared with the aid of surfactant mixtures into which free carboxylic acid and synthetic anionic surfactant in alkali salt form had been incorporated.

The pasty detergent and also the surfactant mixture which may be used to produce it are essentially free of water and organic solvents. "Substantially free of water" is understood to mean a state in which the content of liquid water, ie water not in the form of water of hydration and constitutional water, is below 5% by weight, preferably below 2% by weight and in particular below 1 % By weight. Higher water contents are disadvantageous since they increase the viscosity of the agent disproportionately and in particular reduce its stability. Organic solvents, to which the low-molecular and low-boiling alcohols usually used in liquid concentrates and counting ether alcohols, as well as hydrotropic compounds, are also absent, apart from traces that can be introduced with individual active ingredients.

The agent contains a solid phase which is homogeneously dispersed in the liquid surfactant phase and which contains the other detergent constituents which have a cleaning action and optionally auxiliaries. These other cleaning ingredients primarily include washing alkalis and sequestering compounds.

The liquid phase of the paste-like composition according to the invention essentially consists of the nonionic surfactants according to formulas (I) and (II) from the surfactant mixture according to the invention and from the synthetic anionic surfactant which may be present in this surfactant mixture and which is essentially distributed in the liquid phase. If the surfactant mixture according to the invention is to be stored or transported at lower temperatures, nonionic surfactants whose pour point (solidification point) is below 5 ° C. are expediently used in order to avoid solidification of the surfactant mixture as far as possible. This problem plays no role for the paste-like compositions according to the invention produced using the surfactant mixture according to the invention, since the compositions already have such a high viscosity at room temperature that any further solidification at lower temperatures has no significance.

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: Si O 2 of 1: 0.8 to 1: 1.3, preferably 1: 1, which is used in anhydrous form . In addition to the metasilicate, anhydrous alkali carbonate is also suitable, but because of absorption processes it requires larger proportions of the liquid phase 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 aminopolycarboxylic acids and polyphosphonic acids. The aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues. Suitable polyphosphonic acids are l-hydroxyethane-l, l-diphosphonic acid, aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and their higher homologs, such as, for example, diethylenetetraminetetra- (methylenephosphonic acid). The aforementioned acids are usually used in the form of their alkali metal salts, in particular the sodium or potassium salts. Sodium nitrilotriacetate is preferably used in proportions of up to 10% by weight, preferably 2% by weight to 6% by weight.

Suitable sequestering agents also include monomeric polycarboxylic acids or hydroxypolycarboxylic acids, in particular in the form of 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, polyethacrylates, 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 022551 . 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. As polymeric carboxylates respectively Carboxylic acids can also be used in 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 the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-Cs carboxylic acid and preferably from a C3-C4 monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C4-C8-dicarboxylic acid, preferably a C4-C8 ~ dicarboxylic acid, maleic acid being preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, vinyl alcohol derivatives are preferred which are an ester of short-chain carboxylic acids, for example C 1 -C 4 -carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60 to 95% by weight, in particular 70 to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 to 40% by weight .-%, preferably 10 to 30 wt .-% vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio (meth) acrylic acid 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 are particularly preferred 2.1 and 2.5: 1. 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 methylsulfonic acid or methallyl sulfonate 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 01-iosaccharides 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 prepared by any of the known and customary processes. Terpolymers are also preferably used, which are either completely or at least partially, in particular more than 50%, based on the carboxyl groups present, neutralized. Particularly preferred terpolymers are produced by a process which is described in German patent applications DE 4221 381 and DE 4300772.

Also useful are polyacetal carboxylic acids, as described, for example, in US Pat. Nos. 4144226 and 4146495, and obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups and saponification to give the sodium or potassium salts. Also suitable are polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.

The proportion of organic, carboxyl group-containing builder materials in the pasty composition according to the invention can be up to 10% by weight, preferably 1% to 7.5% by weight and in particular 2% to 5% by weight, of the of polyphosphonic acids up to 3% by weight, preferably 0.05% by weight to 1.5% by weight and in particular 0.1% by weight to 1% by weight. These substances mentioned are also used in anhydrous form.

Crystalline alkali silicates and finely divided alkali alumosilicates, in particular zeolites of the NaA type, are also to be regarded as useful sequestering agents for the purposes 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 2412837 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 Na Si _x θ2χ + ι + yH2θ, in which M represents sodium, x is a number from 1.9 to 4, are preferably used as crystalline silicas, which may be present alone or in a mixture with the aluminosilicates mentioned and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are, for example described in European patent application 164514. In particular, ^'sodium disilicates Na2Sι'2θ5 * yH2θ are both .beta.- and δ preferred, with .beta.-sodium disilicate being obtainable, for example, by the method described in International Patent Application W091 / 08,171th Crystalline silicates that can be used 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. If a phosphate content is ecologically harmless (for example in the case of waste water purification which eliminates phosphates), polymeric alkali phosphates, such as sodium tripolyphosphate, can also be present. Their proportion can be up to 20% by weight, based on the total composition, the proportion of the other solids, for example the alkali silicate and / or aluminosilicate, being reduced accordingly. The proportion of tripolyphosphate is preferably at most 10% by weight.

Washing aids can be considered as further constituents, which are also predominantly assigned to the solid phase. These include graying inhibitors, optical brighteners, bleaches and dyes. Insofar as fragrances that are generally liquid are also used, these pass into the liquid phase. Because of their small amount, however, they have no appreciable influence on the flow behavior of the pastes.

Suitable graying inhibitors or soil release active substances are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose, and (poly) alkylene glycol esters of dicarboxylic acids, such as ethylene terephthalate polyoxyethylene terephthalate polyoxyethylene terephthalate. Sodium carboxymethyl cellulose and mixtures thereof with methyl cellulose are preferably used. The proportion of graying inhibitors is generally up to 2% by weight and is preferably from 0.5% by weight to 1.5% by weight. In particular, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts are contained as optical brighteners for textiles made of cellulose fibers (cotton). Are suitable for. B. salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of Morpholino group, a diethanola ino group, a methylamino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type of the substituted 4,4'-distyryl-diphenyl can be present, for example 4,4 * -bis (4-chloro-3-sulfostyryl) -diphenyl. Mixtures of brighteners can also be used. Brighteners of the 1,3-diaryl-2-pyrazoline type, for example l- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of the same structure are suitable for polyamide fibers. The content of optical brighteners or brightener mixtures in the agent is generally up to 1% by weight, preferably 0.05% by weight to 0.5% by weight.

Fine-particle bleaches can also be present as a further component of the solid phase. Peroxygen compounds such as sodium perborate monohydrate, tetrahydrate, sodium percarbonate, persilicates, caroates and organic peracids such as perbenzoates or peroxyphthalates can be used. These peroxygen compounds are in the agents according to the invention due to the substantial absence of water storage rod l. If appropriate, known bleach activators can also be present, which hydrolyze with the peroxygen compounds to form peracids when water is added, for example N-acyl or O-acyl compounds, preferably N, N'-tetraacylated diamines, such as NNN ' jN'-tetraacetylethylene diamine, also carboxylic anhydrides such as benzoic anhydride and phthalic anhydride, and esters of polyols such as glucose pentaacetate. Since the bleaching component is often added separately to the wash liquor in commercial laundries and is generally used only when there is a particular need, bleaching agents in the paste can be dispensed with in such cases.

A further advantage of the invention is the fact that the addition of polyethylene glycols with a low molecular weight of about 200 to 800, which is usually intended to improve the flow properties of the pastes at levels of up to 15%, can be dispensed with entirely. These additives do not contribute to the detergency and are therefore undesirable. For the same reason, paraffin oils or liquid paraffin mixtures are preferably completely absent in the pasty compositions according to the invention. However, small amounts of such substances, since they normally bring about a certain reduction in foam under the conditions of use, which can be particularly noticeable in the rinse cycle, can be present to support the foam regulator which is solid at room temperature. The proportion of such liquid foam-reducing active ingredients, which include not only the paraffin oils mentioned but also liquid long-chain ethers, in the paste-like compositions according to the invention is preferably not more than 5% by weight, in particular from 0.1% by weight to 2% by weight.

The preparation of the paste-like compositions according to the invention can directly follow the preparation of the surfactant premix according to the invention, but the surfactant mixture according to the invention can also be intermediately stored over a longer period of time without any problems after its preparation. In the preparation of the agents according to the invention, the procedure is preferably such that the other solid constituents, which are individually present, are added to the surfactant mixture according to the invention, which has been reheated after storage and has been presented at temperatures from room temperature to 120 ° C., in a conventional stirred kettle, while avoiding excessive air intake or may be present as mixtures containing two or more powder components. It was found that the process leads to particularly stable paste-like compositions if one works in the temperature range from room temperature to 45 ° C., in particular up to 40 ° C., or in the temperature range from 80 ° C. to 120 ° C. Temperatures in the latter higher temperature range also facilitate wetting of the solid phase, which leads to faster homogenization of the ingredients. The mixing order of the finely divided solid components is largely arbitrary, but the alkali silicate is preferably added last as the constituent that makes up the largest proportion of the solid phase. It is also possible to add the finely divided main component in cycles, that is to say to add a portion of the alkali silicate in alternation with the solid secondary components. After the solids have been mixed with the surfactant premix, the resulting paste is preferably applied to a grinding device, for example a colloid mill, for the solid phase Grind the specified grain size if the finely divided solids used did not already have the desired grain sizes. It is then expedient to subsequently carry out a homogenizing mixing of the ground solid constituents with the liquid phase in a further stirred tank, thermally sensitive minor components in particular, for example bleaching agents, dyes and / or fragrances and enzymes, in particular protease, amylase, lipase and / or Cellulase and, where appropriate, enzyme stabilizers, in particular lower carboxylic acids or calcium compounds, can be incorporated into the paste. In particular if acicular or platelet-shaped alkali metal silicate has been used, a further grinding step can be carried out after the homogenization if the particle size range specified for the solid phase has not yet been reached.

A preferred embodiment of the method according to the invention consists of 20 parts by weight to 45 parts by weight of a flowable surfactant premix according to the invention with 40 parts by weight to 65 parts by weight of solid, powdered alkali silicate and 2 parts by weight up to 10 parts by weight of solid polymeric polycarboxylate and up to 5 parts by weight, especially if this is absent in the surfactant premix, 1 part by weight to 3.5 parts by weight, synthetic anionic surfactant, up to 10 parts by weight. Parts, in particular 1.5 parts by weight to 8 parts by weight of 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, in particular 0.1 part by weight to 0.5 part by weight of powdered optical brightener.

The pastes according to the invention are flowable and pumpable immediately after their production by the shear forces acting on them and can be filled into storage containers without problems. These storage containers are that the pastes according to the invention become so viscous relatively quickly without the action of shear forces that they lose their flowability and can no longer be pumped, preferably shipping containers, in particular those with rigid outer walls , for example barrels or barrels in which the product is delivered to the commercial washing machine and from which it is loaded into the washing machine with the aid of a removal device which is capable of developing sufficient shear forces. or their base liquor container can be dosed. A device suitable for this purpose is described in German patent application P 4332850.4, "paste container with removal device" from Henkel Ecolab GmbH & Co. OHG.

Examples

example 1

Ethoxylated Ci2 / 14 fatty alcohol (average degree of ethoxylation 3; manufacturer Henkel) and ethoxylated and then propoxylated Ci2 / i4 fatty alcohol (average degree of ethoxylation degree 5, average degree of propoxylation 4; manufacturer Henkel) were in the following in a table in a heated stirred kettle 1 specified proportions heated to 80 ° C. While stirring, phosphoric acid mono / stearate (manufacturer Hoechst) and then fatty acid sodium salt (Edenor ( ^R ) HT; manufacturer Henkel) and sodium Cg / ιι-alkylbenzenesulfonate were added and 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.

Table 1: surfactant mixture Gl (parts by weight)

ethoxylated fatty alcohol 20 ethoxylated / propoxylated fatty alcohol 10

Phosphoric acid mono / stearate 1.5

Fatty acid sodium salt 1.5

Alkylbenzenesulfonate 2 Example 2

The amounts of sodium nitrilotriacetate, polymeric polycarboxylate Na salt (Sokalan ( ^R ) CP 5; manufacturer BASF), sodium hydroxyethane given in Table 2 were added to 35 parts by weight of the surfactant mixture Gl from Example 1 at 55 ° C. l, l-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, added, after each added component was stirred for about 1 minute before the next component was incorporated. The resulting mixture was then ground in a grinding 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 Wl which flowed directly after production was obtained and was filled into 280 kg barrels. After a storage period of 10 days, the agent had a viscosity (measured at 25 ° C. using a Brookfield ( ^R ) - rotary viscometer DV-II with spindle No. 7 at 5 revolutions per minute) of 200,000 mPa * s, otherwise the same Conditions at 50 revolutions per minute from 70000 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 in the course of the paste removal or dosing in a commercial washing machine.

Table 2: Composition of the paste Wl (parts by weight)

Eq 35

Sodium nitrilotriacetate 4

Sokalan ( ^R ) CP 5 5

Hydroxyethane diphosphonate 1

Relatin ( ^R ) DM 4050 1.5

Tinopal ( ^R ) CBS 0.2

Sodium metasilicate 53.3

Claims

claims

1. Storage-stable, essentially water-free, flowable surfactant mixture containing nonionic surfactant in the form of alkoxylation products of alcohols and soap, characterized in that it

40% by weight to 70% by weight of nonionic surfactant of the general formula (I) which is liquid at room temperature,

R ¹ - (0C ₂ H ₄ ) _n -0H (I)

in which R ¹ denotes an alkyl or alkenyl radical having 10 to 20 carbon atoms and the average degree of ethoxylation n can assume values from 1 to 8,

R2- (0C2H ₄ ) _r - (0C ₃ H ₆ ) p-0H (II)

in which R ^{2 means} an alkyl or alkenyl radical having 10 to 20 carbon atoms, the average degree of ethoxylation r can assume values from 2 to 8 and the average degree of propoxylation p can assume values from 1 to 6, and 1% by weight contains up to 10 wt .-% of a Cχo- to C22 ~ carboxylic acid and / or its alkali salt.

2. surfactant mixture according to claim 1, characterized in that it additionally Lich up to 10 wt .-%, in particular 0.5 wt .-% to 8 wt .-% at room temperature synthetic anionic surfactant, in particular alkylbenzenesulfonic acid, Contains alkali alkyl benzene sulfonate and / or alkali alkyl or alkenyl sulfate.

3. surfactant mixture according to claim 1 or 2, characterized in that it additionally contains up to 5 wt .-%, in particular 0.1 wt .-% to 4 wt .-% at room temperature solid, alkali-stable and shear-stable foam regulator.

4. Surfactant mixture according to one of claims 1 to 3, characterized gekennzeich¬ net that it 48 wt .-% to 64 wt .-% nonionic surfactant of the general formula (I), 28 wt .-% to 40 wt .-% % nonionic surfactant of the general formula (II) and 2 wt .-% to 6 wt .-% carboxylic acid and / or its alkali salt.

5. surfactant mixture according to one of claims 1 to 4, characterized gekennzeich¬ net that it consists of a carboxylic acid mixture, based in each case on the total carboxylic acid mixture, 2 wt .-% to 8 wt .-% C14-, up to 1 wt .-% C15 -, 18% by weight to 24% by weight Ciss-, up to 3% by weight Ci7-, 20% by weight to 42% by weight Ci8 ~ and 30% by weight to 44% by weight % Contains C20- to C22 ~ carboxylic acid or its alkali metal salts.

6. A surfactant mixture according to one of claims 1 to 5, characterized in that the nonionic surfactant according to formula (I) has an average degree of ethoxylation n from 1 to 6, in particular from 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.

7. A process for the preparation of the surfactant mixture as claimed in one of claims 1 to 6, characterized in that at least one of the nonionic surfactants of the formula (I) or (II) is heated to temperatures in the range from 60 ° C to 120 ° C, at these temperatures the solid constituents dissolve or disperse in the nonionic surfactant and the resulting mixture, optionally after addition of the second non-ionic surfactant, cools to temperatures from 60 ° C. to room temperature.

8. The method according to claim 7, characterized in that the constituents which are solid at room temperature are mixed at temperatures in the range from 70 ° C to 100 ° C with the nonionic surfactant or the nonionic surfactants.

9. The method according to claim 7 or 8, characterized in that das¬ that nonionic surfactant according to formula (I) or (II) is submitted, which in a smaller amount is to be used, heated, optionally admixed with the foam regulation, then admixing the carboxylic acid or its alkali salt, then optionally the synthetic anionic surfactant and finally the non-ionic surfactant of the formula (II) or (I) not initially introduced.

10. Use of a surfactant mixture according to one of claims 1 to 6 or of a surfactant mixture prepared by the process according to one of claims 6 to 9 for the production of paste-like detergents or cleaners.

11. Structurally viscous pasty washing or cleaning agent which has been produced in particular using the surfactant mixture according to one of claims 1 to 6 and which, without the action of shear forces, has a viscosity such that it does not act at room temperature under the action of gravity is flowable, but has a significantly lower viscosity when sheared and is flowable under the influence of gravity.

12. A composition according to claim 11, characterized in that it is at 25 ° C using a Brookfield ( ^R ) rotary viscometer DV-II or DV-II plus 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 has a viscosity below 100,000 mPa-s, in particular from 10,000 mPa-s to 90,000 mPa-s.

13. A paste-like, essentially water-free, structurally viscous washing or cleaning agent containing 20% by weight to 80% by weight of the surfactant mixture according to one of claims 1 to 6, characterized in that it is 20% by weight to 80 % By weight of solid powdery constituents with an average grain size of 5 μm to 120 μm, preferably 10 μm to 100 μm and in particular 10 μm to 80 μm and at 20 ° C. a viscosity in the range from 10000 mPa-s to 500000 mPa- s at a shear rate of 0.025 s "and at a shear rate of 0.2 s" l a viscosity in the range from 5000 mPa-s to 130,000 mPa ^« s, in particular from 5000 mPa-s to 13000 mPa-s, and at a shear rate of 2 s "* has a viscosity in the range from 400 mPa-s to 10000 mPa-s, in particular from 400 mPa-s to 1 600 mPa-s.

14. Paste-like composition according to claim 13, characterized in that 90% by weight of the solid powdery constituents have a grain size below 140 μm, in particular below 100 μm.

15. A process for the preparation of the paste-like composition according to any one of claims 11 to 14, characterized in that the surfactant mixture according to any one of claims 1 to 1 which has been reheated after storage, if any, at a temperature in the range from room temperature to 120 ° C. 6 in a conventional stirred kettle, if possible avoiding excessive air entry, admixing the other solid constituents, which may be present individually or as mixtures containing two or more powder components.

16. The method according to claim 15, characterized in that one works at a temperature in the range from room temperature to 45 ° C, in particular up to 40 ° C.

17. The method according to claim 15, characterized in that one works at a temperature in the range of 80 ° C to 120 ° C.

18. The method according to any one of claims 15 to 17, characterized in that the Be¬ constituent, which makes up the largest proportion of the solid phase, in particular the alkali silicate, is added last.

19. The method according to any one of claims 15 to 18, characterized in that the finely divided main component is added in cycles.

20. The method according to any one of claims 15 to 19, characterized in that, after mixing the solids with the surfactant premix, the resulting paste is ground in a grinding device to the grain size specified for the solid phase and then a continuous mixes the ground solid components with the liquid phase.

21. The method according to any one of claims 15 to 20, characterized in that

20 parts by weight to 45 parts by weight of a flowable surfactant premix containing 40% by weight to 70% by weight of nonionic surfactant of the general formula (I) which is liquid at room temperature,

^Rl - (0C ₂ H ₄ ) _n -0H (I)

in which R ^{1 is} an alkyl or alkenyl radical having 10 to 20 carbon atoms and the average degree of ethoxylation n can assume values from 1 to 8, 20% by weight to 50% by weight of nonionic surfactant which is liquid at room temperature of the general formula (II),

R - (0C2H ₄ ) _r - (0C ₃ H6) p-0H (II)

in which R ^{2 means} an alkyl or alkenyl radical having 10 to 20 carbon atoms, the average degree of ethoxylation r can assume values from 2 to 8 and the average degree of propoxylation p can assume values from 1 to 6, 1% by weight to 10% by weight of a C 1 -C 20 "carboxylic acid and / or its alkali salt, up to 10% by weight of synthetic anionic surfactant which is solid at room temperature and up to 5% by weight of an alkali-stable and shear-stable foam regulator which is stable at room temperature , With

40 parts by weight to 65 parts by weight of solid, powdered alkali silicate and

2 parts by weight to 10 parts by weight of solid polymeric polycarboxylate, and up to 5 parts by weight, in particular if this is absent in the surfactant premix, 1 part by weight to 3.5 parts by weight of synthetic anionic surfactant , up to 10 parts by weight, in particular 1.5 parts by weight to 8 parts by weight of 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 powdered cellulose ether and up to 1 part by weight, in particular 0.1 part by weight to 0.5 part by weight of powdered optical brightener.

22. A process for loading a washing machine, in particular a commercial washing machine, with liquid and solid detergent constituents, characterized in that a flowable surfactant mixture, in particular comprising 40% by weight to 70% by weight of nonionic surfactant which is liquid at room temperature of the general formula (I), 20% by weight to 50% by weight of nonionic surfactant of the general formula (II) which is liquid at room temperature and 1% by weight to 10% by weight of a C 1 -C 22 -carboxylic acid and / or whose alkali salt, produced, dispersed therein finely divided solid, the storage-stable, non-flowable preparation thus obtained directly before use with the input of mechanical

I.

Make energy flowable, in particular by stirring, dilute the flowable preparation with a predetermined amount of water and meter it into the washing machine.