NL8601532A - LIQUID THIXOTROPE DETERGENT COMPOSITION WITH IMPROVED PHYSICAL STABILITY FOR AUTOMATIC DISHWASHERS. - Google Patents

Description

• i VO 8227

Liquid thixotropic detargent composition with improved physical stability for automatic dishwashers.

The invention relates to detergent compositions for automatic dishwashers which exhibit thixotropic properties and improved chemical and physical stability and which are readily dispersible in the washing medium to provide effective cleaning of dishes, glassware, china and the like.

Commercially available household dishwashing detergents, which come in powder form, have several drawbacks, for example, a non-uniform composition, an expensive preparation, a tendency to coagulate on storage at high humidity, leading to the formation of lumps that are difficult to disperse, dusting, which is a source of particular irritation for allergy sufferers, and a tendency to stick in the dishwasher dispenser. Liquid forms of such compositions generally cannot be used in automatic dishwashers because of the high foaming, unacceptably low viscosity and excessively high alkalinity.

Recent research and development activity has focused on the gel or "thixotropic" form of such compositions, for example, abrasives and automatic dishwashing machine products, which are characterized as thixotropic pastes.

Products for dishwashers supplied in this form are objectionable in the first place because they are insufficiently viscous to remain "anchored" to the dishwasher's dosing cup and further because they form stain residues on crockery, glassware, porcelain and the like. Ideally In this case, thixotropic cleaning compositions are highly viscous in the quiescent state, Bingham is plastic in nature and exhibit relatively high flow values. However, if they are subjected to shear stresses, for example if they are shaken in a vessel or squeezed through a nozzle, they should become fluid quickly and quickly return to the highly viscous / Bingham when the applied shear stress disappears. plastic condition. Stability is also of primary importance, ie no significant separation or leakage occurs after a long time.

Providing gel form compositions with the aforementioned properties for automatic dishwashers has hitherto been problematic, particularly as regards compositions for use in household dishwashers. For effective use, it is generally recommended that the automatic dishwasher detergent, further referred to as AVD, contain (1) sodium tripolyphosphate (NaTPP) for softening or binding minerals in hard water and for emulsifying and / or peptizing soil; (2) sodium silicate to provide the alkalinity necessary for effective detergency and to protect the fine china glaze and pattern, (3) sodium carbonate, which is generally considered optional to enhance the alkalinity; (4) a chlorine-releasing agent for promoting the elimination of dirt speckles leading to water stains; and (5) a defoamer / surfactant to reduce foam and thereby increase machine efficiency and provide the required detergent (see, for example: SDA Detergents in Depth, "Formulations Aspects of Machine Dishwashing", Thomas Oberle (1974). Cleansers having approximately the compositions described are largely liquids or powders. Combination of such ingredients in a gel form suitable for use in household machines has been found to be difficult. In general, hypochlorite bleach is omitted in such compositions as this can react with other chemically active ingredients, especially surfactant, thereby degrading the suspending agent or thixotropic agent and impairing its effectiveness, for example, thixotropic pastes for automatic dishwashers are disclosed in U.S. Pat. No. 4,115,308 a sweetener, for example, CMC, synthetic clay and the similar inorganic salts such as silicates, phosphates and polyphosphates, a small amount of surfactant and a suds suppressor. A bleaching agent is not mentioned. U.S. Patent 4,147,650 describes an analog, optionally containing a chlorine bleach (hypochlorite), but no organic surfactant or suds suppressor. The product is furthermore described as a detergent suspension 86 0 1 5 3 2 -3- i apparently without thixotropic properties.

U.S. Patent 3,985,668 describes abrasive abrasive cleaners of gel-like consistency containing (1) a suspending agent, preferably smectite and attapulgite type 5 clay (2), an abrasive agent, e.g. silica sand or perlite; and (3) a filler comprising powdered polymers, expanded perlite and the like of low specific gravity, which filler has buoyancy and thereby a stabilizing effect on the composition, as well as serving as a bulk agent, thereby replacing water otherwise available for undesirable formation of an above layer due to leakage and phase destabilization. The substances mentioned are the essential ingredients. Optional ingredients include hypochlorite bleach, bleach stable surfactant and buffer, e.g. silicates, carbonates and monophosphates. As further optional ingredients, builders, such as NaTPP, can be included in the composition to provide or supplement the building function, which is not provided by the buffer, the amount of builder shown in the patent not exceeding 5% of the total composition. Maintenance of the desired pH of {more than) 10 is achieved by the buffer / builder components. High pH is said to minimize decomposition of the chlorine bleach and unwanted interaction between surfactant and bleach. If present, the amount of NaTPP is limited to 5% as stated. A suds suppressor is not mentioned.

In UK patent applications GB 2.116.199A and GB 2.140.450A, liquid AVD compositions are described which have properties which desirably characterize a thixotropic gel-type structure, and which contain each of the various ingredients necessary for effective detergent in an automatic dishwasher.

The normally gel-like aqueous detergent composition with thixotropic properties for automatic dishwashers contains the following ingredients: (a) 5-3 wt% alkali metal tripolyphosphate; (b) 2.5-20 wt% sodium silicate; ^ (c) 0-9 wt% alkali metal carbonate; 3 6 0 1 5 3 2 * -4- (d) 0.1-5 wt% chlorine bleach stable water-dispersible organic detergent active material; (e) 0-5 wt% chlorine proved to be stable suds suppressor; (f) chlorine bleach in an amount to provide about 0.2-4 wt% available chlorine; and (g) thixotropic thickener in an amount sufficient to provide a composition with a thixotropy index of about 2.5-10

AVD compositions thus composed show little foaming, are easily soluble in the washing medium and are most effective at pH values which best lead to improved cleaning, namely a pH of 10.5-13.5. The compositions normally have a bile consistency, and consist of highly viscous, opaque jelly-like materials with a Bingham plastic character and therefore relatively high flow values. Therefore, a certain shear force is required to initiate or increase flow, such as is obtained in the stirring dosing cup of an operating automatic dishwasher. Under such conditions, the composition is quickly liquefied and easily dispersed. When the shear force is lost, the liquid composition returns to a high viscosity, in which the Bingham plastic state closely approximates the previous consistency.

Although this previously described liquid AVI; Compositions are not, or to a lesser extent subject to one or more of the shortcomings described above, it has been found that in practice further improvements in physical stability are required to improve the shelf life of the product and thereby increase consumer acceptance.

An object of the invention is therefore to provide liquid AVD compositions with thixotropic properties, with improved physical stability and rheological properties.

Another object of the invention is to provide thixotropic liquid AVD compositions with reduced levels of thixotropic thickener without the generally high viscosities at low shear values and low viscosities at higher shear values characteristic for the desired thixotropic properties. 2 -5- * ι are adversely affected.

These and other objects of the invention are prepared by incorporation in a normally gel-like aqueous dishwashing detergent composition for automatic dishwashers of an amount of a multivalent metal salt of a long chain fatty acid which effectively inhibits settling of the suspended particles, such as a thixotropic pic medium.

In an embodiment, the invention provides a normally gel-like aqueous detergent composition with thixotropic properties for automatic dishwashers containing (a) 5-35 wt% alkali metal tripolyphosphate; (b) 2.5-20 wt% sodium silicate; (c) 0-9 wt% alkali metal carbonate; (d) 0.1-5 wt% chlorine was found to be stable, water-dispersible organic detergent active material; (e) 0-5 wt% chlorine was found to be stable suds suppressor; (f) a chlorine bleach in an amount providing about 0.2-4% by weight of available chlorine; (g) a thixotropic thickener in an amount sufficient to impart a thixotropy index of about 2.0-10 to the composition; (h) 0-3 wt% sodium hydroxide; (i) a multivalent long chain fatty acid metal salt in an amount that effectively increases the physical stability of the composition; and (j) for the rest water.

In another embodiment, the invention provides a method of cleaning dishes in an automatic dishwashing machine with an aqueous washing bath containing an effective amount of the above described liquid detergent composition for automatic dishwashing machines (VAVD). In this embodiment of the invention, the VAVD composition can easily be poured into the automatic dishwashing dosing bowl, in which the composition promptly thickens to its normal gel-like state within a few seconds, and remains securely in the dosing bowl in that state until again · '<1 «» “f Λ -6- ♦ ♦ shear forces are exerted on it, for example by the water sprayed from the dishwasher.

In general, there is a direct relationship between the effectiveness of the AVD with (a) the available chlorine content; (b) the alkalini-5 text; (c) the solubility in the wash medium and (d) the foam suppression. Preferably, the pH of the AVD composition is at least about 9.5, especially between about 10.5 and 13.5, and most preferably at least about 11.5. At relatively lower pH values, the AVD product is too viscous, so that it does not readily liquefy below the shear force levels created in the dosing cup under normal machine operating conditions.

In essence, the composition then loses its thixotropic character to a large extent, if not entirely. Addition of NaOH is therefore often required to bring the pH within the ranges mentioned and to improve the fluidity properties. The presence of carbonate is also often necessary as it acts as a buffer and thereby helps maintain the desired pH level.However, an excess of carbonate should be avoided as this can cause the formation of needle-like carbonate crystals, which can reduce stability, thixotropy and / or may damage detergent of the AVD product. A NaOH further functions as a neutralizing agent for the phosphorus or phosphonic acid ester suds suppressor, if any. The composition typically contains about 0.5-3 wt% NaOH and about 2-9 wt% sodium carbonate, however, it is noted that sufficient alkalinity is provided by the NaTPP and sodium silicate channel.

The NaTPP used in the composition in an amount of 8-35% by weight, preferably 20-30% by weight, is preferably free of heavy metals, which can decompose or inactivate the preferred sodium hypochlorite and other chlorine bleaching compounds.

The NaTPP may have an average degree of hydration of less than about 1 or more than about 5, for example, 0-2.7 wt% or at least 16.5 wt% water, including the stable hexahydrate having a hydration degree of 6, correspondingly with about 18% by weight of water or more. Humidification to an average of about 0.3-1% water is in fact very effective and is believed to form germs of the stable hexahydrate, which is believed to form λ λ aa τ * a ύου1 ewe -7- w «. accelerates hydration and solubilization of the remaining NaTPP particles. On average, the NaTPP contains about 5-15 wt% water, corresponding to an average degree of hydration of about 1 to 5. If only the 2 hexahydrate is used, the detergent product is liquid and has little or no thixotropic character. If only the anhydrous NaTPP is used, the product is too thick and therefore unsuitable.

Effective compositions are obtained, for example, using a weight ratio of 0.5: 1 to 2: 1 of anhydrous NaTPP to NaTPP hexahydrate, with values of about 1: 1 being particularly preferred.

The inhibition of foam is important to increase the efficiency of the dishwasher and to minimize the destabilizing effects which may occur during use due to the presence of excess foam within the machine.

The foaming can be sufficiently reduced by an appropriate choice of the type and / or amount of the detergent active material, the main foaming component. The degree of foaming is also somewhat dependent on the hardness of the washing water in the machine, whereby an appropriate adjustment of the amount of NaTPP, which has a water softening effect, can assist in providing the desired degree of foam inhibition.

However, it is generally preferable to include a chlorine-bleachable foam suppressant or inhibitor in the composition.

Particularly useful are the alkyl phosphonic acid esters of the formula 1 of the formula sheet sold by, for example, BASF-Wyandotte (PCUK-PAE), and in particular the alkyl acid phosphate esters of the formula 2, which are produced, for example, by Hooker (SAP) and Knapsack (LPKn-158) are marketed, in which one or both groups R in each 2Q ester type can independently represent a C 1-20 group. Mixtures of the two types or other chlorine-bleach stable types or mixtures of mono- and diesters of the same type can be used. Particular preference is given to a mixture of mono and di-C 1 -G-C 8 alkyl acid phosphate esters, such as monostearyl / distearyl acid phosphates 1.2 / 1 (Knapsack). If used, typical how- ·.>; ·* seven pounds ? .. ·. * -% j L ·> fc -8- quantities 0.1-5 wt.%, Preferably 0.1-0.5 wt.%, Foam suppressor in the composition, the weight ratio of the detergent- active component (d) to the suds suppressor (e) are generally between about 10: 1 and 1: 1, and preferably about 5: 1 to 1: 1. Examples of other suds suppressors that can be used are e.g. the well-known silicone.

Although any chlorine bleach compound, for example dichloroisocyanurate, dichlorodimethylhydantoin or chlorinated TSP, may be used in the compositions of the invention, alkali metal-1Θ e.g. potassium, lithium, magnesium and especially sodium hypochlorite are preferred. Most preferably, the composition contains sufficient chlorine bleaching compound to provide about 0.2-4.0 wt% available chlorine, as determined, for example, by acidifying 100 parts of the composition with excess hydrochloric acid. A solution containing about 0.2-4.0 wt% sodium hypochlorite provides or contains about the same percentage of available chlorine. Particular preference is given to about 0.8-1.6% by weight of available chlorine. For example, e.g. a sodium hypochlorite solution with 11-13% available chlorine is advantageously used in amounts of about 3-20%, preferably about 7-12%.

The sodium silicate, which provides alkalinity and protects hard surfaces, such as the fine porcelain glaze and decoration, is used in the composition in an amount of 2.5-20 wt%, preferably 5-15 wt%. The sodium silicate is generally added in the form of an aqueous solution, preferably with a Na 2 O: SiO 2 ratio of about 1: 2.2 to 1: 2.8. It is to be noted that most other components of the composition, especially NaOH, sodium hypochlorite, suds suppressor and thixotropic thickener, are also often added in the form of a previously prepared aqueous dispersion or solution.

The detergent active material to be used should be stable in the presence of a chlorine bleach, in particular hypochlorite, and preferably consists of the water-dispersible organic anionic, amine oxide, phosphine oxide, sulfoxide or betaine surfactant types the former anionic types being most preferred. They are used in amounts from 0.1-5%, preferably from 0.5-2.0% and especially from 0.3-0.8%.

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Particularly preferred surfactants are the linear or branched alkali metal, mono- and / or di- (Cg ~ C14) alkyl diphenyl oxide mono- and / or disulfates, commercially available, for example, under the trade name DOWFAX 3B-2 and DOWFAX 2A-1. Generally, the paraffin nesulphonates tend to be harmful if not destructive to thixotropy as they undesirably increase viscosity and thereby cause serious shear problems. In addition, the surfactant must be compatible with the other ingredients of the composition. Examples of other suitable surfactants are the primary alkyl sulfonates, alkyl sulfonates, alkyl aryl sulfonates and secondary alkyl sulfates, such as sodium C 1 -C-C 2 g alkyl sulfates, e.g. sodium dodecyl sulfate and sodium tallow alcohol sulfate; sodium C10 -C18 alkane sulfonates such as sodium hexadecyl-1-sulfonate, and sodium C1 -C18 alkylbenzene sulfonates, such as sodium dodecylbenzene sulfonates. The corresponding potassium salts can also be used.

Other suitable surfactants or detergents are the amine oxide surfactants, typically of the structure R ^ R ^ NO, wherein each R is a lower alkyl group, for example methyl, and R1 is a long chain alkyl group with 8-20 carbon atoms, for example a lauryl, myristyl -, 20 palmityl or cetyl group. Instead of an amine oxide, a corresponding surfactant phosphine oxide R2R * PO or suipoxide RR ^ SO can also be used. Betaine surfactants typically have the structure R 1, R 3 N 1 - R "COO", where each R represents a lower alkylene group of 1 to 5 carbon atoms. Specific examples of these surfactants are lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, the corresponding phosphine oxides and sulf oxides, and the corresponding betaines, including dodecyldirnethylammonium acetate, tetradecyldiethyl ammonium pentanoate, hexadecyldirnethylammonium hexanoate and the like.

For the biodegradability, the alkyl groups in these surfactants are preferably linear, such compounds are preferred.

Surfactants of the said type are well known and described, for example, in U.S. Pat. Nos. 3,985,668 and 4,271,030.

Thixotropic thickeners, i.e. thickeners Λ \ 1 ï * Λ. T Λ Λ / i * -lh or suspending agents which impart thixotropic properties to an aqueous medium are well known and may be organic or inorganic water-soluble water-dispersible or colloid-forming monomeric or polymeric compounds, and are most preferably stable in the present compositions, e.g. resistant to high alkalinity and chlorine bleaching compounds, such as sodium hypochlorite. Particular preference is given to the inorganic, colloid-forming clays of the smeetite and / or attapulgite types. These materials were generally used in amounts of 1.5-10 wt%, preferably 2-5 wt%, to impart the desired thixotropic properties and Bingham plastic character to the U.K. previously mentioned. patent applications GB 2,116,199A and GB 2,140,450A disclose AVD compositions. One of the advantages of the AVD compositions of the invention is that the desired thixotropic properties and the desired Bingham plastic character in the presence of the polyvalent metal salts. of fatty acids with smaller amounts of the thixotropic thickeners can be obtained. For example, e.g. amounts of the inorganic colloid-forming clays of smectite and / or attapulgite type of 0.1-3%, preferably 0.2-2.5%, in particular 0.5-2.2%, generally sufficient for obtaining the desired thixotropic properties and the Bingham plastic character when used in combination with the physical stabilizer.

Smectite clays are montmorillonite (bentonite), hectorite, saponite and the like. Materials of this type are available under brand names such as Thixogel No. 1 and Gelwhite GP, H and the like (both montmorillonites) from Georgia Kaolin Company. Examples of attapulgite clays are the materials available commercially under the trade name Attagel, for example Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporation. Also mixtures of smectite and attapulgite types can be used in weight ratios from 4: 1 to 1: 5. Thickening or suspending agents of the types described are generally known and are described, for example, in the aforementioned U.S. Pat. No. 3,985,668. Abrasive materials or polishes are preferably avoided.

35 The amount of water in the compositions according to the invention may be 8 Λ Λ .-. 1 - »« 7 f?

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Obviously, they are not so large as to produce an undesirably low viscosity and high fluidity, nor so small that the viscosity is undesirably high and the fluidity undesirably low, since in either case the thixotropic properties are reduced or destroyed.

The amount of water can be easily determined in any particular case by routine testing and is generally 45-75 wt%, preferably about 55-65 wt%. Preferably, the water is deionized or softened.

Heretofore, the composition of the AVD product, except as otherwise noted, corresponds to the compositions described in the aforementioned UK patent applications GB 2,116,199A and GB 2,140,450A.

These previously described AVD products exhibit improved rheological properties, evaluated by measuring product viscosity as a function of shear. The compositions exhibited higher viscosity at low shear and lower viscosity at higher shear, the data indicating efficient fluidity or gel formation within the shear values that occur in the dishwasher. In practice, this meant improved casting and processing properties, as well as less leakage in the dosing cup of the machine, compared to the earlier liquid or gelled AVD products. For shear corresponding to 3-30 r.p.m., the viscosities (Brookfield) ranged from about 15000-30000 cP to about 3000-5000 cP, measured at room temperature using an LVT Brookfield viscometer after 3 minutes with a spindle no. 4. A shear of 7.4 sec. Corresponds to a spindle speed of about 3 revolutions per minute. At about a 10-fold increase in shear yields a six- to seven-fold decrease in viscosity. With the earlier AVD gels, the corresponding viscosity reduction was only about two-fold. In addition, in such compositions, the initial viscosity at about 3 rpm was only about 2500-2700 cP. Thus, the previously described compositions exhibited threshold fluidizations at iag® 5 shears and to a significantly greater extent in terms of stepwise shear increase versus stepwise viscosity reduction. This property A, i ^ ^ Λ>: - t \ / J «4 ^ ii -μ; -12- of the previously described AVD products are summarized in terms of a thixotropy index (TI), which is the ratio of the apparent viscosity at 3 rpm and at 30 rpm.

The compositions previously described have a TI of 2.5-10. The tested AVD compositions exhibited marked and rapid return to the previous resting state consistency when the shear was lost.

The invention is based on the discovery that the physical stability, ie the resistance to phase separation, settling and the like of these previously described liquid aqueous AVD compositions can be significantly improved without adversely affecting, and in some cases beneficially influencing their rheological properties by adding to the composition a small, yet effective amount of a polyvalent metal salt of a long chain fatty acid.

As an example of the improvement in rheological properties, it has been found that the low shear viscosities, for example, at a spindle speed of about 3 rpm, can often be increased two to three fold by incorporating as little as 0.2% or less of the fatty acid metal salt stabilizer.

At the same time, physical stability can be improved such that the compositions containing the metal salt stabilizers, even after 6 weeks or longer over temperature ranges, extending from near freezing point to 40 ° C and above, do not undergo visible phase separation.

The preferred long chain fatty acids are the higher aliphatic fatty acids having 8-22 carbon atoms, preferably 10-20 carbon atoms, especially 12-18 carbon atoms, including the carbon atom of the carboxyl group of the fatty acid. The aliphatic group can be saturated or unsaturated and branched or unbranched. Mixtures of fatty acids can also be used, such as the fatty acids from natural sources, for example tallow fatty acid, coco fatty acid, soy fatty acid, and the like.

Examples of the fatty acids from which the polyvalent metal salt stabilizers can be formed are decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, o λ «ï - 7 r * Λ · Λ i: V 'v J -J ·· “Λ» • <-13- tallow fatty acid, coco fatty acid, soy fatty acid, mixtures of these acids, and the like. Stearic acid is preferred for commercial availability and results.

The preferred polyvalent metals are. aluminum and zinc, although other polyvalent metals can also be used, especially metals from groups IIA, IIIA, IVA, VA, VIA, VIIA, IIB, III3, IVB, VB and VIII of the periodic table. Specific examples of such other polyvalent metals are magnesium, cobalt, titanium, zirconium, vanadium, niobium, manganese, iron, cobalt, nickel, cadmium, tin, antimony, bismuth, and the like.

Preferably, the metal salts are used in their higher oxidation states.

Many of these metal salts are commercially available.

The aluminum salts are available, for example, in the triacid form, for example aluminum stearate such as aluminum tristearate, AKC ^ H ^ COO)

The monoacid salts, e.g. aluminum monostearate Al (OH) 2 (C ^ H ^ COO) and diacid salts, e.g. aluminum distearate Al (OH) (C 1 -H-R COO), and mixtures of two or three of the mono-, di- and tri-acid salts can be used for such metals, e.g. aluminum, with valencies of +3, and mixtures of the mono and di-acid salts can be used for such metals, e.g. zinc, with valencies of +2. It is most preferred that the diacids of the divalent metals and the triacids of the trivalent metals and the tetraacids of the tetravalent metals are used in predominant amounts. For example, at least 30%, preferably at least 50% and in particular 80-100% of the total metal salt is in the highest possible oxidation state, ie each of the possible valence sites is occupied by a fatty acid residue .

As mentioned, the metal salts are generally commercially available, but they can also be easily prepared, for example, by saponification of a fatty acid, for example, animal fat, stearic acid and the like, or the corresponding fatty acid ester, followed by treatment with a hydroxide or oxide of the polyvalent metal, in the case of the aluminum salt, for example with alum, alumina, and the like.

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Aluminum stearate, especially aluminum tristearate, and zinc stearate, especially zinc distearate, are preferred as polyvalent fatty acid salt stabilizers.

The amount of the fatty acid salt stabilizers needed to achieve the desired increase in physical stability depends on various factors, such as the nature of the fatty acid salt, the nature and amount of the thixotropic agent, the detergent active compound, inorganic salts, in particular TPP, other components of the AVD, as well as the intended storage and transport conditions.

In general, however, the polyvalent metal salts of the fatty acids to be used as stabilizers in amounts of 0.02-1%, preferably 0.06-0.8%, in particular 0.08-0.4%, give the long-term stability and absence of phase separation in storage or transport at both low and high temperatures, which are required for a commercially acceptable product.

According to a preferred method for the preparation of the present compositions, all inorganic salts, in particular carbonate (if used), silicate and tripolyphosphate, are first dissolved or dispersed in the aqueous medium. The thickener is added last. The suds suppressor (if used) is pre-placed in aqueous dispersion, as is the thickener. The dispersion of the suds suppressor, NaOH (if used), and inorganic salts are first mixed in aqueous solution (deionized water) with stirring at elevated temperature and then cooled also with stirring. Bleach, surfactant, fatty acid salt, stabilizer and thickener dispersion are then added to the cooled (25-35 ° C) solution at room temperature. With the exception of the chlorine bleach, the total salt concentration (NaTPP, sodium silicate and carbonate) in the composition is generally 20-50 wt%, preferably 30-40 wt%.

In these compositions, other conventional ingredients may be included in minor amounts, generally less than about 3% by weight, such as perfume, hydrotropic agents such as the sodium 35 benzene, toluene, xylene and cumene sulfonates, preservatives, dyes and pigments and the like, all of which naturally resist λ V a ·.

* W -X - ·· i ✓ *. > / & W j 'V ^ -15- are against the chlorine bleach and high alkalinity (properties of all components). Particularly preferred coloring agents are the chlorinated phthalocyanines and polysulfides of alumino-silicate, which give pleasant green and blue tones, respectively.

TiO2 are used as a whitener or for neutralizing color deviations.

The liquid AVD compositions according to the invention can be used in a known manner for washing dishes, other kitchen utensils and the like in an automatic dishwasher, provided with a suitable detergent dosing vessel, in an aqueous washing bath containing an effective amount of the composition. .

The invention can be practiced in various ways. In the examples, the invention is further elucidated on the basis of a number of specific embodiments.

Example I

To demonstrate the effect of the metal salt stabilizer, liquid AVD compositions are prepared with varying amounts of stabilizer and thixotropic thickener. First, the following 20 ingredients are mixed in a Guisti mixer at 50-60 ° C: wt%

Deionized water 41.10fy-x

NaOH solution (50 wt% NaOH) 1.00

Sodium carbonate, anhydrous 5.00 Sodium silicate, 47.5% by weight solution. Na2O: SiO2 ratio 1: 2.4 15.74

Sodium TPP (virtually anhydrous, i.e.

0-5 wt%, especially 3 wt% moisture) (Thermphos NW) 12.00 30 Sodium TPP (hexahydrate) (Thermphos N hexa) 12.00

The mixture is cooled to 25-30 ° C while maintaining stirring, and the following ingredients are added to the mixture at room temperature:. - / * ": t v 'J v" V j J * -16- wt. %

Sodium hypochlorite solution (11 wt% available chlorine) 9.00

Monostearyl Phosphate 0.16 DOWFAX 3B-2 (45% by weight Na 5 monodecyl / didecyldiphenyloxydedisulfonate aqueous solution) 0.80

Al tristearate or Zn distearate x

Gel White H 2.00-y

The monostearyl phosphate suds suppressor and Dowfax 3B2 detergent active compound are added to the mixture just before the aluminum tristearate or zinc distearate stabilizer or just before the Gel White H thickener.

For each of the obtained liquid AVD products as shown in Table A, the density, the CAS (capillary run-off rate), the apparent viscosity at 3 rpm and 30 rpm, and the physical stability (phase separation) were determined and measured in a transport test. The results are shown in Table A.

From the data listed in Table A, the following conclusions can be drawn: The inclusion of 0.2 wt% aluminum stearate in a composition containing 1.5 wt% or 1 wt% Gel White H, as well as the incorporation of 0 1 wt% aluminum stearate or 0.1 wt% zinc stearate in a composition containing 2 wt% Gel White H leads to a simultaneous increase in physical stability and apparent viscosity (Table A, 25 Runs 1 (Control ) 2,3,6 and 9.

The inclusion of 0.1 wt% aluminum stearate in a composition containing 1 wt% Gel White H, or of 0.2 wt% aluminum stearate in a composition containing 0.5 wt% Gel White H, and of 0.3 or 0.4 wt% aluminum stearate in a composition containing 0.25 wt% Gel White H results in an increase in physical stability without any drastic increase in viscosity (Table B, Trials 1 (control), 4,7,10 and 11).

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In the combination of 0.1 wt% aluminum stearate and 0.5 wt% Gel White H (Run 8), the apparent viscosity values remain acceptable, but no significant improvement in physical stability is obtained.

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Fat notes at Table A

(1) Filter paper No. 1 (Whatman) with a circle with a diameter of 6.4 cm drawn on it is placed on a flat glass plate of 10 x 10 cm. A crust tube with a length of 6.4 cm and a diameter of 3.4 cm is Your standing position is placed in the center of the circle. The tube is filled with the sample of the liquid AVD composition (after standing for 1 day). The time it takes for the solvent to seep out of the tube and reach the drawn circle is measured. Time is measured on three sides of the circle and averaged. A shorter time means that the gel cannot successfully hold the solvent (water), so it leaks into the filter paper. A time longer than 5 minutes is considered good. A time between 4 and 5 min is considered unstable, but acceptable.

2.5 (2) Measured with spindle 4 after 3 min on 24 hour old samples.

(3) In height.

(4) By weight.

(5) At 4 ° C, room temperature (kt = 20 + 2 ° C), 35 ° C and 43 ° C in a glass bottle.

20 (6) Fluid separation measured after 6 weeks and 3000 km in a car (by weight in a plastic bottle).

Example II

This example was carried out with the same composition and preparation method as in Example I, except that instead of Gel White H 25 as thixotropic thickener 2 wt% Attagel 50 (an attapulgite clay) or 0.4 wt% Bentone EW (a specially treated Hectorite clay) was used with (Trials 2 and 4) or without (Controls 1 and 3) Aluminum Tristearate. The apparent viscosity-physical stabilities were measured in the same manner as described in Example 1. The results are shown in Table B.

The results reported in Table B show that small amounts of aluminum stearate are equally effective in increasing the physical stability of liquid thixotropic detergent compositions based on attapulgite clay and hectorite clay in an automatic dishwashing machine.

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Example III

This example shows that inorganic aluminum and zinc salts, such as zinc sulfate and aluminum sulfate, and the monovalent metal salts of fatty acids do not impart the improved physical stability to the liquid thixotropic AVD compositions. In the same composition as in Run 6 of Example I, 0.1 wt% Al 2 O 3, 0.1 wt% zinc sulfate, 0.1 wt% aluminum sulfate, or 0.1 wt% sodium stearate was used instead of 0 1 wt% aluminum stearate. The results of the apparent viscosity and physical stability measurements 10 are shown in Table C.

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Example IV

Using the same general procedures as described in Example I, the following liquid gel-like thixotropic AVD composition was prepared: 5 Ingredient Amount, wt%

Sodium Slicate (47.5 wt% solution,

Na2O / SiO2 = 1 / 2.4) 7.48

Monostearyl Phosphate 0.16

Dowfax 3B-2 0.37 10 Thermphos NW 12.0

Thermphos N hexa 12.0

Aluminum tristearate 0.1

Sodium carbonate, anhydrous 4.9

NaOH solution (38 wt%) 3.0 15 Pharmagel Ex Uroclay 1.25 (Mg / Al silicate clay)

Sodium hypochlorite solution (11 wt%) 1.0

Water to 100 wt% pH = 12.5 - 12.9 20

Minor amounts of perfume, colorant, and the like can also be added to the composition.

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Claims (22)

Aqueous thixotropic composition for automatic dishwashers, characterized by: (a) 5-35 wt% alkali metal tripolyphosphate; (b) 2.5-20 wt% sodium silicate; (C) 0-9 wt% alkali metal carbonate; (d) 0.1-5 wt% chlorine bleach stable water-dispersible organic detergent active material; (e) 0-5 wt% chlorine bleach stable suds suppressor; (f) chlorine bleach in an amount providing 0.2-4% by weight of available chlorine; (g) thixotropic thickener in an amount sufficient to impart a thixotropy index of 2-10 to the composition; (h) 0-3 wt% sodium hydroxide; (i) a polyvalent long chain fatty acid metal salt as a physical stabilizer in sufficient amount to increase the physical stability of the composition, and (j) water to 100% by weight. 2. Composition according to claim 1, characterized in that the physical stabilizer (i) is a polyvalent metal salt of an aliphatic fatty acid with 8-22 carbon atoms. Composition according to claim 2, characterized in that the acid contains 12-18 carbon atoms. Composition according to claim 2, characterized in that the polyvalent metal is selected from the groups IIA, UIA, IVA, VA, 25 VIIA, IIB, IIIB, IVB, VB and VIII of the periodic table. Composition according to claim 4, characterized in that the polyvalent metal is selected from magnesium, calcium, titanium, zirconium, vanadium, niobium, manganese, iron, cobalt, nickel, cadmium, tin, antimony, bismuth, aluminum and zinc. Composition according to claim 2, characterized in that the physical stabilizer (i) is the aluminum or zinc salt of the fatty acid. Composition according to claim 1, characterized in that the physical stabilizer (i) is aluminum tristearate. ï- ¾ 1 1 νΛ Λ / V. · V i Ha / ia ^ "V -28- Composition according to claim 1, characterized in that the physical stabilizer (i) is zinc distearate. Composition according to claim 1, characterized in that the physical stabilizer (i) is present in an amount of 0.02-1.5% by weight. Composition according to claim 1, characterized in that the physical stabilizer (i) is present in an amount of 0.06-0.8% by weight. 11. Composition according to claim 1, characterized in that the physical stabilizer (i) is present in an amount of 0.08-0.4% by weight. Composition according to claim 1, characterized in that the thixotropic thickener (g) is an inorganic colloid of the clay. 13. A composition according to claim 12, characterized in that the clay is a montomorillonite clay, an attapulgite clay, a hectorite clay or a smectite clay. Composition according to claim 12, characterized in that the amount of clay thickener is 0.1-3% by weight. 15. Composition according to claim 12, characterized in that the amount of clay thickener is 0.5-2.2% by weight. A composition according to claim 6, characterized by 0.1-0.2 wt% of the physical stabilizer (i) and 0.5-2 wt% of an inorganic colloid-forming clay as the thixotropic thickener (g). 17. The composition of claim 6, characterized by 0.3-0.4 wt% of the physical stabilizer (i) and about 0.25 wt% of an inorganic colloid-forming clay as the thixotropic thickener (g). The composition according to claim 1, characterized in that the chlorine bleach (f) is sodium hypochlorite. Composition according to claim 1, characterized by at least 0.1% by weight of the foam suppressor (e). Composition according to claim 19, characterized in that the foam suppressor comprises an alkyl acid phosphate ester and / or an alkyl phosphonic acid ester with one or two C 2 - C 2 alkyl groups. 21. Composition according to claim 1, characterized by a pH of 10.5-10-13.5. 8601532 -29- A method for cleaning dirty dishes in an automatic dishwashing machine, wherein the dishes in the machine are contacted with an aqueous washing liquid, in which an effective amount of the composition according to claim 1 is dispersed. 5 8 (M 5 3 f o 4 ^ Y - W W CM 0 II HO —P —R OR 2 0 II HO — P — OR OR 8681532