SE459660B - A WATER-TIXOTROP PREPARATION FOR AUTOMATIC DISHWASHERS AND PROCEDURES FOR PREPARING PREPARATION - Google Patents

Description

459 660 10 15 20 25 30 35 shaking in a container or when squeezing through an opening, however, they need to become liquid rapidly, at the end of the shear force quickly returning to the viscous / Bingham plastic state. Stability is also of paramount importance, i.e. mën hög- is there should be no significant signs of phase separation or sweating long-term storage. In the manufacture of dishwashing detergents in gel form for automatic dishwashers, which agents have the properties described above, have so far proved to be problematic, especially with regard to preparations intended for use in dishwashers in the home. It is generally recommended that effective automatic dishwashing detergents, ADMs, hereinafter also referred to as contain (1) sodium tripolyphosphate (NaTPP) to soften or bind minerals in hard water and to emulsify and / or peptize soil; (2) sodium silicate to provide the alkali needed for efficient cleaning and to provide protection for fine porcelain glaze and pattern; (3) sodium carbonate, generally considered optional, to enhance the alkalinity; (4) a chlorine-releasing agent that helps to remove soil stains that cause water staining; and (5) defoamers / surfactants to reduce foaming and thereby improve the efficiency of the machine and provide the required cleaning ability. See, for example, SDA Detergents in Depth, "Formulations Aspects of Machine Dishwashing", Thomas Oberle (1974). Polishing agents of the type just described are in most cases liquids or powders. Such preparations generally do not contain hypochlorite bleach, as this tends to react with other chemically active ingredients, especially surfactants, thereby degrading the suspending or thixotropic agent and impairing its effectiveness. Thus, U.S. Patent No. 4,115,308 discloses thixotropic pastes for automatic dishwashers which contain a suspending agent, for example CMC, synthetic clays or the like: inorganic salts such as silicates, phosphates, polyphosphates, etc .; surfactant and a defoamer, no bleach is mentioned, U.S. Patent No. 4,147,65O is similar, and includes faculty vt chlorine bleach but not any organic surfactant or defoamer. The product is also described as consisting of a detergent sludge without any clear thixotropic properties. see U.S. Pat. No. 3,985,668 discloses abrasive gels having a gel consistency containing (1) suspending agents, preferably a smectite and atta- pulgite clay; (2) abrasives, for example silica sand or perlite; and (3) fillers consisting of low density powdered polymers, expanded perlite and the like, which have buoyancy and thus have a stabilizing effect on the formulation, in addition to serving as bulking agents and thereby replacing water which would otherwise be available for undesired formation of an overlying layers due to sweating and phase destabilization. The above are essential ingredients. Optional ingredients include hypochlorite bleach, surfactant that is stable to bleach, such as silicates, carbonates, monophosphates, etc. Enhancers such as NaTPP may be included as an additional optional ingredient to provide or enhance the enhancer function not provided by the buffer, the amount of such amplifier according to the patent shall not exceed 5% of the entire preparation.

Maintaining a desired pH greater than 10 is accomplished through the buffer / enhancer components. High pH is claimed to minimize the decomposition of the chlorine bleach and minimize unwanted interaction between the surfactant and the bleach. When NaTPP is included, this is limited to 5%, as previously mentioned. No defoamer is described. 10 15 20 25 30 459 660 is described.

A main object of the invention is thus to provide a detergent preparation with thixotropic properties and which is adapted to be used to advantage in an automatic dishwasher, and which lacks one or more of the above-mentioned limitations.

A further object of the invention is to provide a preparation with good physical stability and which does not show any appreciable phase separation even after long storage. Yet another object of the invention is to provide a formulation in which the problems associated with undesirable interactions between chemically active ingredients are eliminated or at least mitigated to a considerable extent. Yet another object of the invention is to provide a formulation which has the above-mentioned stability under the highly alkaline conditions necessary for effective cleaning properties.

Yet another object of the invention is to provide a preparation with improved rheological properties and which has higher viscosity at low shear rate, and lower viscosity at high shear rate, and thus is suitably adapted for use in detergent cups in automatic dishwashers. Yet another object of the invention is to provide a preparation with low foaming properties, improved cleaning ability, and which is easily dissolved in the dishwasher.

Other objects and advantages of the invention will become apparent in the following.

The foregoing objects are achieved according to the invention, which in its broader aspects relates to an aqueous thixotropic preparation for automatic dishwashers and which has thixotropic properties, and which contains (by weight): (a) 8 to 35% alkali metal tripolyphosphate; (b) 2.5 to 20% sodium silicate; (c) 2 to 9% alkali metal carbonate; (d) 0.1 to 5% of water-dispersible organic active detergent which is stable to chlorine bleach; (e) 0 to 5% defoamer which is stable to chlorine bleach; (f) sodium hypochlorite in an amount of about 0.2 to 4% available chlorine: and. (g) 1.5 to 10% thixotropic smectite and / or attapulgite clay thickener in an amount sufficient to give the preparation a thixotropic index of about 2.5 to 10, and (h) sodium hydroxide in an amount sufficient to give the preparation a pH of about 10.5 to 13.5.

ADM preparations with such a composition are low foaming; both chemically and physically stable, readily soluble in the detergent medium and are most effective at those pH values which provide the best washability, i.e. pH 10.5 - 13.5. The formulations have a normal gel consistency, i.e. they are highly viscous, opaque gel-like materials with Bingham plastic character, and thus have a high yield strength. Consequently, a certain shear force is necessary to initiate or increase the flow, such as is obtained, for example, inside a dispensing cup equipped with a stirrer in a switched on automatic dishwasher. Under these conditions, the preparation becomes rapidly fluidized and easily dispersed. When the shear force ceases, the liquid preparation quickly returns to a highly viscous, Bingham plastic state that closely resembles the preparation's previous consistency. 10 15 20 25 30 35 459 660 In general, the ADM ability is directly related to (a) prevailing chlorine content; (b) alkalinity; (c) solubility in the detergent; (d) defoaming. Preferably, the pH of the ADM formulation should be at least about 9.5, more preferably from about 10.5 - 13.5, and most preferably at least about 11.5. At relatively lower pH values, the ADM product becomes too viscous, i.e. it resembles a solid and is not easily fluidized at the shear force levels obtained inside the dispensing cup during normal operation of the machine. In summary, the preparation loses much or all of its thixotropic character. Addition of NaOH is therefore often necessary to increase the pH to within the above-mentioned ranges, and to increase the flowability properties. The presence of carbonate is also often necessary, as it acts as a buffer and maintains the desired pH. Excess carbonate should be avoided, however, as this may cause the formation of needle-like carbonate crystals and thus impair the stability, thixotropic properties and / or washability of the ADM product. Caustic soda (NaOH) provides an additional effect by neutralizing phosphoric acid or phosphonic acid ester defoamers, when present. About 0.5 to 3% by weight of NaOH and about 2 to 9% by weight of sodium carbonate in the formulation are normal, although it should be noted that sufficient alkalinity can be obtained by NaTPP and sodium silicate.

The NaTPP used in the formulation at a level of about 8 to 35% by weight, preferably about 20 to 30% by weight, should preferably be free of heavy metals which tend to decompose or inactivate the preferred sodium hypochlorite and other chlorine-based bleaches.

To improve and accelerate the hydration and solubilization of NaTPP, and to avoid undesired thickening of the preparation, the NaTPP used should not be completely anhydrous but should preferably be moistened or hydrated so that it contains up to about 15% water, which corresponds to an average degree of hydration of about 5 (pentahydrate). Humidification to an average of about 0.3 to 1% water is in fact highly effective, as it produces seed crystals of stable hexahydrate that accelerate the hydration and solubilization of the remaining NaTPP particles. Foam damping is important to increase the efficiency of the dishwasher and to minimize destabilizing effects, which could occur due to excess foam inside the dishwasher during its use. The foam cushioning can be sufficient by a suitable choice of type and / or amount of active detergent material, which is the main foam-producing component.

The degree of foaming is opkså to some extent depends on the hardness of the washing water in the machine, in which case appropriate adjustment of the amount of NaTPP, which has a softening effect on water, can help to provide the desired foam attenuation. However, it is generally preferred to include a defoamer or foam inhibitor that is stable to chlorine bleach. Alkylphosphonic acid esters of the formula II: ao -__ P-- R OR available, for example, from BAS? -Wyandotte (PCUK-PAE) are particularly effective, and especially alkyl acid phosphate esters of the formula 109 459 660 ÄOI) HO-- P- OR in OR available for example from Hooker (SAP) and Knapsack (LPKn-158), in which formulas either or both of the R groups in each type of ester are independently C12-20 alkyl. Mixtures of these two types, or any other type that is stable to chlorine bleaching, or mixtures of mono- and diesters of the same type, can be used. Particularly preferred is a mixture of mono- and di-C 16 -C 18 alkyl acid phosphate esters such as monostearyl distearyl acid phosphates 1.2 / 1 (Knapsack). When defoamer is included, it is typically present in a content of 0.1 to 5% by weight, preferably about 0.1 to 0.5% by weight, the weight ratio of active detergent (d) to defoamer (e) generally being in the range of about 10: 1 to 1: 1 and preferably about 4: 1 to 1: 1.

Other defoamers include, for example, the known silicones, etc. Although any chlorine bleach can be used in the formulations of the invention, such as dichloroisocyanurate, dichloro-dimethylhydantoin, chlorinated TSP and the like, it is preferred to use alkali metal, for example potassium, lithium, magnesium, and especially sodium hypochlorite. . The formulation should contain (i.e., sufficient chlorine bleach to give) about 0.2 to 4% by weight of available chlorine, for example, as measured by acidifying 100 parts of the formulation with excess hydrochloric acid. A solution containing about 0.2 to 4% by weight of sodium hypochlorite contains or gives approximately the same percentage of available chlorine. About 0.8 to 1.6% by weight of available chlorine is especially preferred.

The sodium silicate, which provides alkalinity and protection for hard surfaces such as fine porcelain glaze and patterning, is used in amounts ranging from about 2.5 to 20% by weight, preferably about 5 to 15% by weight, in the formulation.

The sodium silicate is generally added in the form of an aqueous solution, which preferably has a Na 2 O: SiO 2 ratio of about 1: 2.2 to 1: 2.8. In this context, it should be mentioned that most of the other components of the preparation, especially NaOH, sodium hypochlorite, defoamers and thixotropic thickeners, are often also added in the form of pre-prepared water dispersions or aqueous solutions.

The active detergent material used herein must be stable in the presence of chlorine bleaches, especially hypochlorite chlorine bleaches, and preferably be water-dispersible surfactants containing organic anions, amine oxide, phosphine oxide, sulfoxide or betaine, wherein organic anions are most preferred. They are used in amounts ranging from about 0.1 to 5% and preferably about 0.3 to 0.8%. Particularly preferred surfactants are straight or branched alkali metal mono- and / or di-C 8-14 alkyldiphenyl oxide mono- and / or disulfonates, commercially available as DOWFAX 3B-2 and DOWFAX 2A-1. In general, paraffin sulfonates tend to deteriorate or even destroy thixotropin, and have been shown to increase viscosity to an undesirable level which causes severe shear problems. In addition, the surfactant should be compatible with the other ingredients of the formulation. Other suitable surfactants include primary alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates and sec-alkyl sulfates. Examples of such are sodium C10-C alkyl sulphates such as sodium dodecyl sulphate and sodium tallow alkyl sulphate; sodium C10-C18 alkane sulfonates such as sodium hexadecyl-1-sulfonate; and sodium C 2 -C 18 alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate.

Corresponding potassium salts can also be used.

As examples of other suitable surfactants or detergents may be mentioned amine oxide surfactants having the characteristic structure R 2 R 1 NO, in which each R is a lower alkyl group. for example methyl, and R 1 is a long chain alkyl group having from 8 to 22 carbon atoms, for example a lauryl, myristyl example. palmityl or cetyl group.

Instead of amine oxide, the corresponding surfactant phosphine oxide R2R1PO or sulfoxide RR1SO can be used. Surfactant betaines have the characteristic structure R 2 R 1 N + R 2 COO 2 in which each R is a lower alkylene group having from 1 to 5 carbon atoms.

Specific examples of such surfactants are lauryl dimethylamine oxide, myristyldimethylamine oxide, cocodimethylamine oxide, cured tallow dimethylamine oxide, corresponding phosphine oxides and sulfoxides, and corresponding betaines including dodecyl dimethylammonium acetonetylmethane methetone methetone methanoethyldimethonate methatone methate decetonate. In order to obtain biodegradability, the alkyl groups in these surfactants should be straight, and thus this is preferred.

Surfactants of the above kind are all well known in the art, and are described, for example, in U.S. Patents 3,98556B and 4,271D30.

Thixotropic thickeners, i.e. thickeners or suspending agents which impart thixotropic properties to an aqueous medium, are known in the art and may be organic or inorganic water soluble, fermentable or colloidal, water dispersing and monomeric or polymeric, and should, of course, be stable in these formulations. For example, stable against high alkalinity and chlorine bleaches such as sodium hypochlorite. Those of these which are particularly preferred generally consist of inorganic, colloidal clays of the smectite and / or attapulgite type. These materials are generally used in amounts of about 2 to 5% by weight, but in all conditions in an amount sufficient to impart the desired thixotropic properties or Bingham plastic character.

Smectite clays include montmorillonite (bentonite), hectorite, saponite and the like. Materials of this kind are available under trade names such as Thixogel Nr. 1 and Gelwhite GP from Georgia Kaolin Company (both are montmorillonites). Attapulgite clays include materials commercially available under the trade name Attagel, such as Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporation. Mixtures of smectite and attapulgite types in weight ratios of 4: 1 to 1: 5 are also useful. Thickeners or suspending agents of the above-mentioned types are well known in the art and are described, for example, in the aforementioned U.S. Pat. 3,985,668. Abrasives or polishes should be avoided.

The amount of water in these preparations should, of course, not be so high as to give an inappropriately low viscosity and flowability, or so low as to give an inappropriately high viscosity and low flowability, since the thixotropic properties in these two cases can be reduced or destroyed.

The appropriate amount of water can be readily determined by routine experimentation, and is generally in the range of about 45 to 75% by weight, preferably about 55 to 65% by weight. The water should preferably be deionized or softened.

The ADM product of this invention exhibits improved rheological properties, evaluated by testing the viscosity as a function of shear rate. Studies confirm that the formulations exhibit higher viscosity at low shear rate and lower viscosity at high shear rate, and data indicate effective fluidization and gelation well within the shear rate ranges present within the dishwasher. in practical use, this provides improved pouring and process characteristics as well as less light "sweating" in the machine's dispensing cup, compared with currently used liquid or gel ADM products. At applied shear speeds corresponding to 3 - 30 rpm, the corresponding viscosities (Brookfield) are in the range from about 15,000 - 30,000 cps. to about 3,000 - 5,000 eps., measured at room temperature with an LVT Brookfield viscometer after 3 minutes and using a 5: 4 spindle. A shear rate of 7, sek sec_1 ns corresponds to a rotation of the spindle of about 3 rpm. An approximately 10-fold increase in shear rate results in a 6- to 7-fold decrease in viscosity. With ADM gels now used, the corresponding reduction in viscosity is only about 2-fold. In addition, the initial viscosity of such formulations is only about 2,500 - 2,700 cps, measured at about 3 rpm. Thus, the present formulations have a threshold for fluidization at lower shear rates, and which fluidization is significantly higher, measured as an increase in shear rate relative to a decrease in viscosity. This property of the present ADM products is summarized in the form of a thixotropic index (TI) which measures the ratio of measured viscosity (a) at 3 rpm to measured viscosity (b) at 30 rpm. The present formulations have a TI of from 2.5 to 10 and preferably from 6 to 8. each of the ADM formulations tested showed substantial and rapid return to the previously immobile consistency when the shear force ceases. 10 15 20 25 30 459 660 13 According to a preferred method of making these preparations, all the inorganic salts are first dissolved or dispersed, i.e. carbonate (if used), silicate and tripolyphosphate, in the aqueous medium. Thickeners are added last. Defoamer (if used) is first provided in the form of an aqueous dispersion, in the same way as the thickener. The dispersion of defoamer, caustic soda (if used) and inorganic salts are first mixed at elevated temperature in aqueous solution (deionized water) and then cooled, stirring constantly. Bleach, surfactant and the dispersant of thickener are then added at room temperature: in the cooling (2s-3s ° c) solution. The tea eal concentration (NaTPP, sodium silicate and carbonate) in the preparation is generally about 20 to 50% by weight, preferably about 30 to 40% by weight, excluding the chlorine bleach.

Other conventional ingredients may be incorporated in small amounts into these formulations, generally less than about 3% by weight, such as perfume, hydrotropic agents such as sodium benzene, sodium toluene, sodium xylene, and sodium cumene sulfonates, preservatives, dyes and pigments and the like, all of which must, of course, be stable to chlorine bleach and high alkalinity (properties of all constituents). For dyeing, it is particularly preferred to use chlorinated phthalocyanines and polysulphides of aluminum silicate which respectively give a pleasant green and blue color. TiO2 can be used for white coloring or to neutralize shades.

The liquid ADM preparations of this invention can be readily used in a known manner for washing dishes, other utensils and the like in an automatic dishwasher, provided with a suitable detergent dispenser, in an aqueous washing liquid containing an effective detergent. amount of the preparation.

The following examples are intended only to illustrate preferred embodiments and are not to be construed as limiting the invention. All amounts and proportions mentioned below are by weight unless otherwise indicated.

Example 1 A first dispersion of defoamers, consisting of a 2: 1 mixture of mono * and di- (C16-C18) alkyl esters of phosphoric acid (0.16g) in 6g of water, was prepared by mixing at 60 ° C for 30 minutes and using a lamella stirrer. This dispersion is called Part I.

A first dispersion of GELWHITE GP (water) thickener (39) in 17 g of water was prepared by mixing at 70 ° C for 10 minutes and using a Z-blade stirrer. This dispersion is called Part 2.

The following components are mixed in a Giusti mixer at so-eo ° c =% AI% 2 Deionized water 16.9 Part I 6.16 0.16 Caustic soda solution 49% NaOH 2.40 1.2 Sodium carbonate 7.00 7.0 Sodium silicate, _47, s% 1solution3 13.74 6.5 Sodium TPP (essentially water: enfr1) 4 12.00 11.54 Sodium TPP (hexahydrate) - 12.00 9.36 The mixture is cooled to 25-3o ° c , with stirring being maintained, after which the following ingredients are added at room temperature return: 10 15 20 25 30 459 660 15% AI åz Sodium hypochlorite solution113% available chlorine 7,615 1.0 Part 2 (dispersed with high speed turbine) 20.00 3.0 Dowfax 3B- 25 0.80 0.36 1. Knapsack LPKn1S8 2. Active ingredient 3. Na20: SiO2- 1: 2.4 4. ie. 0-5%, especially 3%, humidity 5. 45% Na-monodecyl / didecyl diphenyloxide disulfonates, aqueous solution An opaque preparation (about 40% AI) with gel-like consistency was obtained. According to the previously described method, the TI value of the formulation was measured to be about 7, based on a measured viscosity of 28,000 cps. and 4,000 cps. at 3 rpm and 30 rpm respectively. When tested in an automatic dishwasher equipped with a suitable dispensing cup, the above preparation provided excellent cleaning, and was easy and quick to dispense. The preparation had satisfactory non-foaming properties. Little or no phase separation was observed even after prolonged storage in a closed container.

The pH of the preparation, measured as a 1% solution in water, was 11.6. When carrying out the shear tests, it was noted that the preparation quickly returned to its previously immobile consistency, which indicates that the yield strength did not decrease to any great extent when tested within the previously described limits, i.e. with values of shear force of at least approximately within the limits prevailing inside a switched-on automatic dishwasher. No noticeable differences were obtained when dispensing the ADM product through a clamping tube instead of in a dispensing cup. Example 2 Example 1, which illustrates a combined polyphosphate carbonate-silicate concentration of about 37%, is repeated but with varying total content of such salts within the aforementioned limits. The best results were obtained with a total salt content of at least 30%, especially when the sodium tripolyphosphate content is at least about 20%.

Higher silicate levels, which are desired to protect porcelain glaze and patterning, also give higher alkalinity, which can be compensated by a suitable reduction of the level of caustic soda and / or adjustment of the level of sodium carbonate (buffet). The preparation appears to be most sensitive to variations in the NaTPP content (the higher concentration range is more effective) as well as to the degree of hydration. Variations in the level of surfactant generally require corresponding and immediate variation in the level of defoamer, in order to achieve the desired low level of foaming.

A decrease in the pH of the formulation of Example 1 to below about 10.5 is accompanied by a marked decrease in the effectiveness of the formulation, as well as a corresponding decrease in flowability.

Example 3 Similar results are obtained when the procedure of Example 1 is repeated by replacing the surfactant with surfactant based on alkyl sulphate, for example sodium coconut alkyl sulphate, attapulgite clay, for example Attagel SO; and 2: 1 mixture of montmorillonite and Attagel 50. Addition of small amounts, for example 0.002-0.05% chlorinated phthalocyanine and aluminosilicate dyes to the preparation according to example 1 (includes in the first dispersion 17 459 660 sion of thickener or added afterwards to the cooled solution) gives pleasantly colored green and blue formulations, respectively.

Example 4 In this example, the ingredients are added with stirring to the mixing vessel in the order given below, and with final homogenization: Deionized water 2% green color solution Atuææl 50-clay thickener1 Titanium dioxide-Anatase Na5TPP-0.5% moisture (1/2 total) Knapsack LPKn1582 13% sodium hypochlorite solution3 Sodium carbonate 47, s% sodium silicate solution4 49% sodium hydroxide solution Na5TPP-0.5% moisture Dowfax 3B-2 Measurement results Total moisture Available chlorine Silicates pH Specific gravity Viscosity, 20 Brookfield (20 Brookfield) 20 rev. 6 2s ° c 1. Actapulgite 2. Defoamer Parts (weight) 39.436 0.173 3.375 0.375 11.558 0.160 9.230 3,000 17.895 2.600 11.558 0.800 59.5% 1.2% +/- 0.1% 8.5% 12.8 +/- 0.3 1.35 min. 9.250 +/- 3.250 cps. _ 1 459 660 18 3. 13% available chlorine, approx. 4. Na2O: SiO2 - 1: 2.4 5. Detergent surfactant The invention has described with respect to preferred embodiments, and it is to be understood that related modifications and va Variations of the invention are included in the application and within the scope of the appended claims.

Claims (14)

10 15 20 25 30 459 660 19 P a t e n t k r a v An aqueous thixotropic preparation for automatic dishwashers, characterized in that it contains by weight: (a) 8 to 35% sodium tripolyphosphate, (b) 2.5 to 20% sodium silicate, (c) 2 to 9% sodium carbonate, (d) 0.1 to 5% organic, water-dispersible active cleaning material which is stable against chlorine bleach, (e) 0 to 5% defoamer which is stable against chlorine bleach, (f) sodium hypochlorite in an amount which gives about 0.2 to 2% available chlorine, (g) 1.5 to 10% thixotropic smectite and / or attapulgite clay thickener sufficient to give the preparation a thixotropic index of about 2.5 to 10; and (h) sodium hydroxide in an amount sufficient to give the formulation a pH of about 10.5 to 13.5. Preparation according to Claim 1, characterized in that it contains 0.5 to 2% of the active detergent which is a mixture of mono- and di-C 3-14 alkyl-diphenyloxide sodium sulfonates. 3. A formulation according to claim 1 or 2, characterized in that it contains 0.1 to 0.5% of the defoamer which is a mixture of mono- and di-C 1-6 alkyl acid phosphate esters. Preparation according to one of Claims 1 to 3, characterized in that it contains 20 to 30% of sodium tripolyphosphate. 10 15 20 25 459 660 20 Preparation according to one of Claims 1 to 4, characterized in that it contains 2 to 5% of thixotropic montmorillonite clay thickeners. Preparation according to one of Claims 1 to 4, characterized in that it contains 2 to 5% of thixotropic attapulgite clay thickeners. Preparation according to claim 1, characterized in that the active cleaning material is selected from the group consisting of surfactants based on organic anions, amine oxide, phosphine oxide, sulfoxide or betaine, and any mixture thereof. 1 Preparation according to claim 1, characterized in that the active cleaning material is an organic anionic alkali metal sulphate or sulphonate. Preparation according to Claim 1 or 8, characterized in that the active cleaning material is an alkali metal C8-14 alkyl diphenyl oxide sulfonate. Preparation according to Claim 1, characterized in that the chlorine bleach is sodium hypochlorite. Formulation according to claim 1, characterized in that the defoamer is selected from a group consisting of alkyl acid phosphate esters and alkyl phosphonic acid esters containing one or two C12-20 alkyl groups and mixtures thereof. The formulation of claim 4, wherein it has a thixotropic index of about 6 to 8. A process for preparing a preparation according to claim 1, characterized by first preparing an aqueous dispersion of any used component (e), mixing the dispersion with the aqueous components (a), (b) and optionally used (c), followed by mixing the resulting mixture with the components (d), (f) and a pre-prepared aqueous dispersion of the component (g). Process for the preparation of a preparation according to claim 1, characterized by mixing in water in the following order of the ingredients (9). half of the component (a), eventnell (e), (f), possibly (c), (b), the other half of the component (a), and finally (d). I 'U