FI83430C - Tixotropic liquid detergent composition for automatic dishwashers with improved physical stability - Google Patents

Description

1 83430

Thixotropic liquid detergent composition for use in an automatic dishwasher with improved physical stability

The present invention relates to a detergent composition for use in an automatic dishwasher having thixotropic properties, improved chemical and physical stability, and which can be easily dispersed in a washing liquid for dishes, glassware, porcelain, etc. for efficient cleaning.

Commercially available household dishwashing detergents, supplied in powder form, have several drawbacks, for example, an uneven composition; expensive manufacturing costs; a tendency to form lumps when stored in a very humid place, resulting in the formation of sparsely dispersible lumps; dusting which is a particular irritation for washing machine users with allergies; and a tendency to harden in the dispensing tank in the dishwasher. Also, liquid forms of such compositions cannot usually be used in automatic dishwashers due to excessive foaming, inappropriately low viscosities, and excessive alkalinity.

Recent research and development has focused on the gel or "thixotropic" form of such compositions, such as stain removers and products for automatic dishwashers that can be characterized as thixotropic pastes. Dishwashing products supplied in this form are worth recalling firstly because they are not viscous enough to remain "anchored" in the dispenser of the dishwasher and leave spots on dishes, glassware, porcelain, etc. Thixotropic detergent compositions should ideally be very , and should have relatively high flow limits. However, when subjected to shear stress, 2 83430, for example when shaken in a container or squeezed through a nozzle, they should rapidly become fluid and quickly return to a high viscosity / Bingham plastic state when the shear stress ceases. Stability is also of paramount importance, i.e. no significant phase separation or leakage should be visible after long standing.

The preparation of automatic dishwasher detergent compositions in the form of a gel having the above properties has thus proved problematic, especially with regard to compositions used in household dishwashers. For efficient use, it is generally recommended that an automatic dishwasher detergent, hereinafter also referred to as ADD, contain 1) sodium tripolyphosphate (NaTPP) to soften or bind hard water minerals and emulsify and / or pepticize stains; 2) sodium silicate to provide the alkalinity required for effective washing and to protect the glazing and patterns of fine porcelain; 3) sodium carbonate, which is usually considered optional, to improve alkalinity; 4) a chlorine-releasing agent to help remove dirt stains caused by water stains; and 5) a suds suppressant / surfactant to reduce foaming, which improves the efficiency of the machine and provides the necessary washing power. See, e.g., SDA Detergents in Depth, "Formulations Aspects of Machine Dishwashing," Thomas Oberle (1974). The detergents of the compositions described above are mostly liquids or powders. Combining such ingredients into a gel form that would be effective for use in household appliances has proven difficult. In such compositions, hypochlorite bleaching is generally avoided because it tends to react with other chemically active ingredients, especially the surfactant, which degrades the suspending or thixotropic agent and impairs its effectiveness. U.S. Patent 4,115,308 discloses thixotropic automatic dishwasher detergent pastes containing a suspending agent, e.g., CMC, synthetic clay, and the like.

II 3 83430 inorganic salts such as silicates, phosphates and polyphosphates; a small amount of surfactant and antifoaming agent. Bleach is not reported. U.S. Patent 4,147,650 is almost identical and optionally includes a Cl (hypochlorite) bleach, but no organic surfactant or defoamer. The product is even more described as a detergent solution without clear thixotropic properties.

U.S. Patent 3,985,668 discloses abrasive detergents having a gel-like consistency and containing 1) a suspending agent primarily of clay grades of the smectite and attapulgite type; 2) an abrasive such as silica sand or perlite; and 3) a filler which is a low density powdered polymer, foamed perlite, etc., which has a bouyancy and thus a stabilizing effect on the composition and which further serves as a filler and thus replaces water that would otherwise be available to the harmful floating layer, which consists of leakage and phase instability. The above are the main ingredients. Optional ingredients include hypochlorite bleach, bleach-resistant surfactant, and buffer such as silicates, carbonates, and monophosphates. Enhancers such as NaTPP may also be included as optional additives to provide or compensate for an enhancer effect not provided by the buffer, and the amount of such enhancer does not exceed 5% of the total composition according to the patent. Maintaining a desired pH above 10 is accomplished with buffer / enhancer components. A high pH is said to minimize the degradation of the chlorine bleach and the detrimental reaction of the surfactant and the bleach. When NaTPP is present, its amount is limited to 5%, as stated in the patent. Antifoam is not reported.

UK Patent Applications GB-2,116,199 A and GB-2,140,450 A disclose liquid ADD compositions having properties characteristic of a thixotropic, gel-type structure and containing a variety of 4,83430 ingredients necessary for efficient washing in an automatic dishwasher. A normally gel-like, aqueous aqueous dishwasher detergent composition having thixotropic properties contains the following ingredients by weight: a) 5-3% alkali metal tripolyphosphate; b) 2.5-20% sodium silicate; c) 0-9% alkali metal carbonate; d) 0.1-5% chlorine bleach stable, water dispersible organic active detergent; e) 0-5% chlorine bleach stable antifoaming agent; f) a chlorine bleaching compound in an amount such that about 0.2-4% free chlorine is generated; and g) a sufficient amount of a thixotropic thickener such that the thixotropic index of the composition is about 2.5-10.

ADD compositions formulated in this way are low foaming; they are readily soluble in the washing solution and are most effective at pH values that result in improved washing performance, i. pH 10.5-13.5. The compositions normally have a gel-like consistency, i. they are a very viscous, opaque jelly-like substance with the character of Bingham plastic and thus relatively high flow limits. Therefore, a certain shear force is required to initiate or increase runoff, such as in a shaken dispensing tank of an automatic dishwasher. Under such conditions, the composition becomes rapidly flowable and easily dispersed. When the shear force ceases, the liquid composition quickly returns to high viscosity, and the state of the Bingham plastic corresponds very close to its previous consistency.

Although these previously known liquid ADD formulations do not have the disadvantages described above, nor are they of a lesser degree, it has been found that

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5 83430 practice requires further improvements in physical stability so as to increase the storage stability of the product and thus make it more acceptable to the consumer.

It is an object of the invention to provide liquid ADD compositions having thixotropic properties and thus improved physical stability and improved rheological properties.

It is also an object of the invention to provide thixotropic liquid ADD compositions having lower concentrations of thixotropic thickener without adversely affecting high viscosities at low shear rates in general and lower viscosities at high shear rates characteristic of the desired thixotropic agents.

These and other objects of the invention, which will be more readily understood from the following detailed description of the invention and its preferred embodiments, are accomplished by adding to a normally gel-like aqueous automatic dishwasher detergent composition an amount of a long chain fatty acid polyvalent

In a broader sense, the present invention normally provides a gel-like aqueous automatic dishwasher detergent composition having thixotropic properties and comprising by weight: a) 5-35% alkali metal tripolyphosphate; b) 2.5-20% sodium silicate; c) 0-9% alkali metal carbonate; d) 0.1-5% chlorine bleach stable water-dispersible organic active detergent; e) 0-5% chlorine bleach stable foam suppressant; f) a chlorine bleaching compound in an amount such that about 0.2-4% free chlorine is generated; g) a sufficient amount of thixotropic thickener so that the thixotropic index of the composition becomes n.

2.0 to 10; h) 0-3% sodium hydroxide; (i) an effective amount of a polyvalent metal salt of a long chain fatty acid that increases the physical stability of the composition; and j) the remainder of the water.

In another aspect, the invention provides a method of washing dishes in an automatic dishwasher in an aqueous washing solution containing an effective amount of the liquid automatic dishwasher detergent composition (LADD) set forth above. According to this aspect of the invention, the LADD composition can be easily poured into the dispenser of an automatic dishwasher and in just a few seconds it rapidly thickens to its normal gel-like state and remains inside the dispenser until it is again subjected to shear forces such as water jet from the dishwasher.

ADD efficiency is usually directly related to a) free chlorine concentrations; (b) alkalinity; c) solubility in the washing medium; and d) foaming prevention. It is preferred that the pH of the ADD composition be at least about 9.5, preferably about 10, ΞΙ 3, 5, and most preferably at least about 11.5. At relatively low pH values, the ADD product is too viscous, i.e. like a solid and thus does not become easily flowable at the shear rates generated in the dispensing tank under normal machine operating conditions. The composition loses much of what is essential, if not completely, in its thixotropic nature. Therefore, it is often necessary to add NaOH to raise the pH to the above limits and to increase the flow properties. The presence of carbonate is also often necessary because it acts as a buffer, helping to maintain the desired pH level. However, excess carbonate should be avoided

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7 83430 because it can cause the formation of carbonate needle-like crystals and thus impair the stability, thixotropy and / or washability of the ADD product. Caustic soda (NaOH) further helps to neutralize the anti-foaming phosphoric or phosphonic acid ester, when present. The composition contains about 0.5-3% by weight of NaOH and about 2-9% by weight of sodium carbonate. About 0.5-3% by weight of NaOH and about 2-9% by weight of sodium carbonate in the composition are typical, although it should be noted that sufficient alkalinity may come from NaTPP and sodium silicate.

The NaTPPrn used in the composition is about 8-35% by weight, preferably about 20-30% by weight, should preferably be a free heavy metal that tends to decompose or inactivate the preferred sodium hypochlorite and other chlorine bleach compounds. The degree of hydration of NaTPP is on average less than about 1 or greater than about 5, for example 0-2.7% by weight or at least 16.5% of water, taking into account a stable hexahydrate with a degree of hydration of 6, which corresponds to n. 18% by weight of water or more. Wetting with an average of about 0.3-1% water is very effective and is thought to form stable hexahydrate grains, which accelerates the hydration and dissolution of the remaining NaTPP particles. NaTPP contains on average about 5-15% by weight of water, which corresponds to an average degree of hydration of about 1-5. If only hexahydrate is used, the detergent product is a liquid and has little or no thixotropic character. If only anhydrous NaTPP is used, the product is too thick and therefore unsuitable. Effective compositions are obtained, for example, by using a weight ratio of anhydrous to hexahydrate-NaTPPr of 0.5: 1 to 2: 1, and values of about 1: 1 are considered particularly good.

Preventing foaming is important as it increases the efficiency of the dishwasher and minimizes the instability that could occur due to excess foam in the washing machine during use. Foaming can be sufficiently reduced by appropriately selecting the active detergent, which is the main foam-generating component, type and / or amount. The amount of foam also depends somewhat on the hardness of the wash water in the machine, and 8,83430

Appropriate control of the proportion of NaTPP having a water softening effect may help to provide the desired antifoaming effect. However, it is generally preferred to add an anti-foaming agent stable to chlorine bleach. Alkylphosphonic acid esters of the formula 0 are particularly effective

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HO P R

OR

available, for example, from BASF-Wyandotte (PCUK-PAE), and in particular acidic alkyl phosphate esters of formula 0

II

HO-P OR

OR

obtained, for example, from Hooker (SAP) and Knapsack (LPKn-158), in which one or both R groups in each ester type may independently represent a C 1-2 alkyl group. Mixtures of these two types or mixtures of any type of chlorine bleach stable or mixtures of mono- and di-esters of the same type may be used. Particularly preferred is a 1.2 / 1 mixture of acidic mono- and di-C 1-6 alkyl phosphate esters such as acidic monostearyl / distearyl phosphates (Knapsack). When an antifoaming agent is used in the composition, the amounts are 0.1 to 5% by weight, preferably about 0.1 to 0.5% by weight, and the weight ratio of the active detergent component d) to the antifoaming agent e) is usually about 10% by weight. : 1 to 1: 1 and primarily about 4: 1 to 1: 1. Other antifoaming agents that can be used include, for example, known silicones.

Although any chlorine bleaching compound can be used in the compositions of this invention, such as dichloro-

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9,83430 isocyanurate, dichlorodimethylhydantoin or chlorinated TSP, an alkali metal such as potassium, lithium, magnesium and especially sodium hypochlorite is preferred. The composition should contain sufficient chlorine bleach compound to provide about 0.2-4.0% by weight of free chlorine, as determined, for example, by acidifying 100 parts of the composition with excess hydrochloric acid. A solution containing about 0.2-4% by weight of sodium hypochlorite contains or releases approximately the same percentage of free chlorine. 0.8-1.6% by weight of free chlorine is particularly preferred. For example, sodium hypochlorite solution (NaOCl) can be preferably used, which can give off 11-13% chlorine, about 3-20%, mainly 7-12%.

Sodium silicate, which makes alkaline and protects hard surfaces such as fine porcelain glaze and patterns, is used in an amount of between about 2.5 and 20% by weight, mainly about.

5-15% by weight of the composition. Sodium silicate is usually added in the form of an aqueous solution in which the ratio of Na 2 <3: SiO 2 is preferably between about 1: 2.2 and 1: 2.8. In this connection, it should be noted that most of the other components of this invention, especially NaOH, sodium hypochlorite, an antifoaming agent and a thixotropic thickener, are often added in the form of a preformed aqueous dispersion or solution.

The active detergent used herein should be stable to a chlorine bleach, especially sodium hypochlorite, and is primarily an organic, anionic, amine oxide, phosphine oxide, sulfoxide or betaine type water-dispersible surfactant, with the former being considered the best. They are used in an amount of about 0.1-5%, preferably about 0.5-2.0%, most preferably about 0.3-0.8%. Particularly preferred surfactants in this context are straight-chain or branched alkali metal mono- and / or di- (C 1-4) -alkyl-diphenyloxide mono- and / or disulfates, which are commercially available, for example, under the name DOWFAX (registered trademark). 3 B-2 and DOWFAX 2 Al. Paraffin sulfonates generally tend to deteriorate unless thixotropy is completely destroyed and have been found to inappropriately increase viscosity, causing severe shear problems. In addition, the surfactant should be compatible with the other ingredients of the composition. Other suitable surfactants include primary alkyl sulfonates, alkyl sulfonates, alkyl aryl sulfonates and secondary alkyl sulfates. Examples include sodium C ^ Q-C ^ g alkyl sulfates such as sodium dodecyl sulfate, and sodium tallow alcohol sulphate, sodium q C ^ C ^ g-alkanesulfonates such as natriumheksadekyyli - 1-sulfonate and sodium C ^ 2-CI8 alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate . Corresponding potassium salts can also be used.

Of other suitable surfactants or detergents, amine oxide surfactants typically have the structure R 2 R NO, wherein each R represents a lower alkyl group, for example methyl, and R represents a long chain alkyl group having 8 to 22 carbon atoms, for example lauryl, myrrh. a style, palmityl or ketyl group. Instead of the amine oxide, the corresponding surfactant phosphine-11 oxide R ~ R PO or sulfoxide RR SO can also be used. Betaine surfactants typically follow the structure R 2 R N 1 -R "COO, wherein each R represents a lower alkylene group having 1 to 5 carbon atoms. Specific examples of these surfactants include lauryl dimethylamine oxide, myristyl. dimethylamine oxide, the corresponding phosphine oxides and sulfoxides and the corresponding betaines such as dodecyldimethylammonium acetate, tetradecyldiethylammonium pentanoate, hexa-decyldimethylammoniumhexanoate and the like.

Surfactants of the above type are all known in the art, as described, for example, in U.S. Patents 3,985,668 and 4,271,030.

ιι 8 3430

Thixotropic thickeners, i.e. thickeners or suspending agents which impart thixotropic properties to the aqueous medium are known in the art and may be organic or inorganic water-soluble, water-dispersible or colloidal and monomers or polymers and should, of course, be stable in these compositions, e.g. chlorine bleaching compounds such as sodium hypochlorite. Particularly preferred are usually inorganic, colloid-forming clays of the smectite and / or attapulgite type. These substances have usually been used in an amount of about 1.5-10%, mainly 2-5% by weight, to give the desired thixotropic properties and the nature of Bingham plastic in the previously reported ADD formulations in the above-mentioned patents GB-2 116 199 A and GB-2 140 45 A. An advantage of the ADD formulations of the present invention is that the desired thixotropic properties and the nature of the Bingham plastic can be obtained with lower amounts of thixotropic thickeners in the presence of a stabilizing polyvalent fatty acid metal salt. For example, amounts of about 0.1-3%, preferably 0.2-2.5%, especially 0.5-2.2%, of inorganic colloid-forming smectite and / or attapulgite-type clays are usually sufficient to provide the desired thixotropic properties and nature of Bingham plastic when used in combination with a physical stability enhancer.

Smectite clays include montmorillonite (bentonite), hecto-rite, saponite, etc. These types of substances are available under the trademarks Thixogel (registered trademark) No. 1 and Gelwhite (registered trademark) GP, H, etc. from Georgia Kaolin Company (both are montmorillonites). . Attapulgite pigs are commercially available under the trademark Attagel (registered trademark), for example, 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 in this context. Thickening or suspending agents of the type 12,83430 above are well known in the art and are described, for example, in U.S. Patent 3,985,668, which is incorporated herein by reference. Abrasives and polishes should be avoided.

The amount of water in these compositions should, of course, not be so high as to cause inappropriately low viscosity and fluidity, nor so low as to cause inappropriately high viscosity and poor fluidity, and the thixotropic properties would instead be impaired or lost in either case. This amount is readily determined by routine experimentation in each special case and is usually in the range of about 45-75% by weight, preferably about 55-65% by weight. The water should also preferably be deionized or softened.

The description of the ADD product is hereby consistent, unless otherwise noted, with the description of the compositions disclosed in the aforementioned UK patent applications GB-2 116 199 A and GB-2 140 450 A.

The ADD products described in these prior inventions have improved Theological properties which have been evaluated by testing the viscosity of the product as a function of shear force. The compositions had a higher viscosity at a low shear rate and a lower viscosity at a higher shear rate, which data indicate efficient flowability and gelation, within the shear rates within the dishwasher. In practical terms, this meant improved pouring and manufacturing properties as well as less leakage from the machine's distribution tank compared to previous liquid and gel-like ADD products. The shear rates used, corresponding to 3-30 rpm, had corresponding (Brookfield) viscosities ranging from about 15,000-30,000 cp to about 3,000-5,000 cp measured at room temperature on an LVT Brookfield viscometer after 3 min using No. 4 rounds. The cutting speed of 7.4 s "* corresponds to a rotation speed of 3 rpm.

li 13 83430

An approximately ten-fold increase in shear rate results in a six- or seven-fold decrease in viscosity. Previous ADD gels had only a roughly twofold decrease in viscosity. In addition, these compositions initially had a viscosity of only about 2,500-2,700 cp at about 3 rpm. Thus, the compositions of the prior invention have a flow rate threshold at lower shear rates and, to a much greater extent, expressed as an increase in shear rate against a decrease in viscosity. This property of the ADD products of the previous invention can be represented by a thixotropic index (TI), which is the ratio of the apparent viscosity at shear rates of 3 rpm and 30 rpm. Previous compositions have a TI of 2.5-10. The ADD compositions tested showed complete and rapid recovery to previous resting consistency when shear force was interrupted.

The present invention is based on the finding that physical stability, i. the resistance to phase separation, settling, etc. with these prior aqueous aqueous ADD compositions can be clearly improved without adversely affecting and in some cases even beneficially affecting their Theological properties by adding a small but effective amount of a long chain fatty acid polyvalent metal salt to the composition.

As an example of an improvement in theological properties, it has been found that viscosities at low shear rates, e.g. at about 3 rpm, can often double or triple the apparent viscosities when added as little as 0.2% or less of a fatty acid metal salt stabilizer. At the same time, the physical stability can be improved to such an extent that even after six weeks or more at a temperature close to the freezing point to 40 ° C and above, compositions containing the metal salt as a stabilizer do not show phase separation.

Preferred fatty acids are the higher aliphatic 14,83430 fatty acids having from about 8 to about 22 carbon atoms, preferably from about 10 to 20 carbon atoms, and particularly preferably from about 12 to 18 carbon atoms, including the carbon atom of the carboxyl group of the fatty acid. The aliphatic radical may be saturated or unsaturated and may be straight or branched. Mixtures of fatty acids can be used, for example, mixtures of natural sources such as tallow fatty acids, coconut fatty acids, soybean fatty acids, etc.

Examples of fatty acids that can be formed into polyvalent metal salt stabilizers include: decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanic acid, tallow fatty acid, and acid fatty acid, coconut fatty acid, soybean fatty acid, soybean fatty acid, soybean fatty acid, soybean fatty acid. therefore given priority.

The preferred polyvalent metals are Aluminum and Zinc, although other polyvalent metals may be used, especially metals from Groups HA, IIIA, IVA, VA, VIIA, IIB, IIIB, IVB, VB and VIII of the Periodic Table of the Elements. Specific examples of these other polyvalent metals are Mg, Co, Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cd,

Sn, Sb, Bi, etc. Metal salts are preferably used at their higher oxidation states.

Several of these metal salts are commercially available. For example, aluminum salts are available in the form of triacid, for example aluminum stearate as aluminum tristearate,

Al (C ^ H ^^ COO) 2. Monoacid salts, for example aluminum monostearate, Al (OH) 2 (C 1 H 2 Cl 2) and diacid salts, for example aluminum distearate, Al (OH) (C 1 H 2 Cl 2) and two or three mono-, di- and tri mixtures of the acid salts can be used from these metals, for example with valences of Al +3 and mixtures of these metals, for example mono- and diacid salts of Zn with valences of +2. It is preferred that +2 valence diacids and +3 valence triacids and +4 valence tetrahydric acids be used as the main

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1S 83430 amounts. For example, at least 30%, preferably at least 50%, particularly preferably 80-100% of the total metal salt has the highest possible degree of oxidation, i. all possible valence sites are bound by fatty acid residues.

Metal salts, as mentioned above, are usually commercially available, but can be easily prepared, for example, by saponification of a fatty acid, e.g. animal fat, stearic acid, etc. or a corresponding fatty acid ester, followed by treatment with a polyvalent metal hydroxide or oxide, e.g. alum, alumina, etc.

Aluminum stearate, i.e., aluminum tristearate and zinc stearate, i.e. zinc distearate are the preferred stabilizing salts of a polyvalent fatty acid.

The amount of stabilizing fatty acid salt which provides the desired improvement in physical stability depends on factors such as the nature of the fatty acid salt, the nature and amount of the thixotropic agent, the active detergent compound, inorganic salts, especially TPP, and other excipients. laivausolosuhteista.

In general, however, amounts of stabilizing polyvalent metal fatty acid salts in the range of about 0.02-1%, more preferably about 0.06-0.8%, and most preferably about 0.08-0.4% provide long-term stability and prevent phase separation during standing or transport at both low and elevated temperatures as required for a commercially acceptable product.

According to a preferred method of preparing these compositions, all inorganic salts should first be dissolved or dispersed, i. carbonate (when used), silicate and tripolyphosphate in an aqueous medium. The thickener ie 83430 is added last. The antifoam agent is initially (when used) initially dispersed in water as a thickener. The antifoam dispersion, caustic soda (when used) and inorganic salts are first mixed together at elevated temperatures in aqueous solution (deionized water) and then cooled with constant stirring. The bleach, surfactant, fatty acid salt, stabilizer and thickener dispersion at room temperature are then added to the cooled (25-35 ° C) solution. Excluding the bleaching agent, the total salt concentration (NaTPP, sodium silicate and carbonate) is usually n.

20-50% by weight, preferably about 30-40% by weight of the composition.

Other conventional ingredients may be included in these compositions in small amounts, usually less than about 3% by weight such as perfume, hydrotropic agents such as sodium benzene, toluene. xylene and cumene sulfonates, preservatives, dyes and pigments, etc., all of which are, of course, stable to chlorine bleach and high alkalinity (properties of all components). Chlorinated phthalocyanines and aluminosilicate polysulfides are considered to be particularly suitable for dyeing, giving a pleasant green and blue color, respectively. TiCl 2 and can be used to whiten or neutralize nuances.

The liquid ADD compositions of this invention can be readily used in a known manner to wash dishes, other kitchen utensils, etc. in an automatic dishwasher equipped with a suitable detergent dispensing tank in an aqueous washing solution containing an effective amount of the composition.

The invention may be practiced in a number of different ways, and several specific embodiments 17 83430 for illustrating the invention will now be described in the accompanying examples.

All amounts and proportions used herein are by weight of the composition unless otherwise indicated.

Example 1

To demonstrate the effect of the stabilizing metal salt, liquid ADD formulations are prepared with varying amounts of stabilizer and thixotropic thickener. First, mix the following ingredients in a Guisti mixer at 50-60 ° C:%

Deionized water 41.10 + y-x

Caustic soda solution (50% NaOH) 1.00

Anhydrous sodium carbonate 5.00 47.5% sodium silicate solution with a ratio of Na 2 O: SiO 2 = 1: 2.4 15.74

Sodium TPP (almost anhydrous, ie contains 0-5%, especially 3% moisture (Thermphos NW) 12.00

Sodium TPP (hexahydrate) (Thermphos N hexa) 12.00

The mixture is cooled to 25-30 ° C and stirred at all times and the following ingredients are added at room temperature:

Sodium hypochlorite solution (11% chlorine released) 9.00

Monostearyl phosphate 0.16 DOWFAX 3B-2 (45% Na-monodecyl / dodecyl diphenyloxide - aqueous disulfonate solution 0.80

Al tristearate or Zn distearate x

Gel White H 2.00-y 18 83430

The antifoam monostearyl phosphate and active detergent Dowfax 3B-2 are added to the mixture just before the addition of aluminum tristearate or zinc distearate as stabilizers or just before the thickener Gel White H.

For each of the resulting liquid ADD formulations shown in Table I, density, CDR (capillary flow rate), apparent viscosity at 3 and 30 rpm, and physical stability (phase separation) at stand and in the shipping test are measured. The results are also shown in Table 1. The following conclusions can be drawn from the data reported in Table 1:

When 0.2% Al stearate is added to a formulation containing 1.5% or 1% Gel White H, as well as when 0.1% Al stearate or 0.1% zinc stearate is added to a formulation containing 2 % Gel White H, results in a simultaneous increase in physical stability and apparent viscosity (Table 1, Experiments 1 (Comparative) 2, 3, 6 and 9).

When 0.1 t of Al stearate is added to a formulation containing 1 μl of Gel White H, 0.2% of Al stearate to a formulation containing 0.5% of Gel White H, and 0.3% or 0 .4% Al stearate in a formulation containing 0.25% Gel White H results in an increase in physical stability without a sharp increase in viscosity (Table 2, Experiments 1 (Comparative) 4, 7, 10 and 11).

With the combination of 0.1% Al stearate and 0.5% Gel White H, the apparent viscosity values remain acceptable, but no significant improvement in physical stability is achieved.

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Notes to Table 1 1) A No. 1 filter paper (Whatman) with a 6.4 cm ring drawn on it is placed on a flat glass plate, size 10 cm x 10 cm. A plastic tube, 6.4 cm long, 3.4 cm in diameter, is placed in a standing position in the center of the tire. The tubes are filled with a liquid sample of the ADD composition (after standing for one day). Measure the time it takes for the solvent to seep out of the tube and reach the drawn ring.

Time is measured on three sides of the tire and averaged. Faster times mean that the gel does not retain solvent (water) well, which can then leak into the filter paper. Times longer than 5 minutes are considered good. Times of 4-5 minutes are considered unstable but acceptable.

2) Measured with a rotator 4 three minutes after 24 h samples.

3) In length measurements 4) In weight measurements 5) At 4 ° C, room temperature (RT = 20 ° - 2 ° C), 35 ° C and 43 ° C in a glass bottle.

6) Liquid separation was measured after 6 weeks and after the sample had traveled 3000 km in a private car (in a weighted plastic bottle).

Example 2 The same composition and method of preparation were used as in Example 1 except that 2% Attagel 50 (attapulgite clay) or 0.4% Bentone EW (specially prepared hectorite clay) with either aluminum tristearate was used as the thixotropic thickener instead of Gel White H. experiments 2 and 4) or without it (comparative experiments 1 and 3). Apparent viscosities and physical stability were measured in the same manner as described in Example 1. The results are shown in Table 2.

From the results shown in Table 2, it can be seen that small amounts of aluminum stearate are equally effective in increasing the physical stability of a liquid thixotropic detergent composition for an automatic dishwasher based on attapulgite clay or hectorite clay.

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Example 3 This example demonstrates that inorganic aluminum and zinc salts such as Al 2 O 3 / ZnSO 4 and monovalent metal salts of a fatty acid do not provide improved physical stability in liquid thixotropic ADD compositions. The same formulation was used as in Experiment 6 of Example 1, and instead of 0.1%, aluminum stearate was used in 0.1% of each of Al 2 O 2, ZnSO 4, Al 2 O 2) and sodium stearate. The results of the apparent viscosity and physical stability measurements are shown in Table 3.

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Example 4

The following gel-like thixotropic liquid ADD composition was prepared following the same general preparation methods as in Example 1.

Ingredient Amount (Active ingredient) Weight -% _

Sodium silicate (47.5% solution with a ratio of

Na 2 O: SiO 2 = 1: 2.4) 7.48

Monostearyl phosphate 0.16

Dov / fax 3li-2 0.37

Thormphos NW 12.0

Thermphos N hexa 12.0

Aluminum tristearate 0.1

Anhydrous sodium carbonate 4.9

Caustic soda, in solution 38% NaOH 3.0

Pharmagel Ex Uroclay (Mg / Al-silicate clay) 1.25

Sodium hypochlorite (11% solution) 1.0

Water remaining pH = 12.5-12.9

Smaller amounts of perfume, color, etc. can also be added to the composition.

Claims (15)

An aqueous thixotropic composition for automatic dishwashers, which composition in parts by weight contains approximately: a) 5-35% alkali metal tripolyphosphate; b) 2.5-20% sodium silicate; c) 0-9% of alkali metal carbonate; d) 0.1-5% chlorine bleach stable, water dispersible organic active detergent; e) 0.1-5% chlorine bleach stable antifoam; f) chlorine bleaching compound in an amount which forms about 0.2-4% free chlorine; g) 0.1-10.0% thixotropic thickener in an amount such that the thixotropic index of the composition becomes about 2.0-10; h) 0-3% sodium hydroxide; and i) water; characterized in that the composition further contains j) 0.08-0.40% of a polyvalent metal salt of a long-chain fatty acid of 8-22 carbon atoms as a physical stabilizer, the ether being water. Composition according to claim 1, characterized in that the physical stabilizer (j) is the Mg, Ca, AI or Zn salt of an aliphatic fatty acid having 10-20 carbon atoms. Composition according to claim 1 or 2, characterized in that the physical stabilizer (j) is a polyvalent metal salt of an aliphatic fatty acid having 12-18 carbon atoms. Composition according to any of the preceding claims, characterized in that the physical stabilizer (j) is a polyvalent metal salt of stearic acid, myristic acid, palmitic acid, oleic acid, tallow fatty acid or soya fatty acid or a mixture thereof. 32 8 3 430 Composition according to any of the preceding claims, characterized in that the physical stabilizer (j) is aluminum tristearate or zinc distearate. Composition according to claim 1, characterized in that the thixotropic thickener (g) is inorganic colloid-forming clay. 7. Composition according to claim 6, characterized in that the clay consists of attapulgitizing or smectic clay. Composition according to claim 6, characterized in that the amount of the clay thickener is about 0.1-3%. Composition according to Claim 1, characterized in that it contains about 0.5-2% inorganic colloid-forming clay such as thixotropic thickening agent (g). Composition according to claim 1, characterized in that its pH is 10.5 - about 13.5. 11. A composition according to claim 1, characterized in that the antifoaming agent (s) is an acidic alkyl phosphate ester or an alkylphosphonic acid ester containing one or two C or branched alkali metal mono- and / or di- (C8-C14) -alkyl di-phenyloxide mono- and / or disulfate. Composition according to claim 1, characterized in that the amount of alkali metal carbonate (c) is about 2-9%. Composition according to claim 1, characterized in that the amount of sodium hydroxide (h) is about 0.5-3%. Composition according to claim 1, characterized in that its density is about 1.29 g / cm 3. li 33 83 430 Method for cleaning dirty dishes in an automatic dishwasher, characterized in that the dirty dishes are brought into contact with an aqueous washing solution in an automatic dishwasher, where an effective amount of the composition according to claim 1 is dispersed by pouring this composition. in the dispenser of the automatic dishwasher, leave this composition thickened in the dispenser and then subject this composition to shear forces, such as a water jet, in the dishwasher.