LU86473A1 - THIXOTROPE LIQUID DETERGENT COMPOSITION WITH IMPROVED PHYSICAL STABILITY FOR WASHING DISHWASHER IN A MACHINE, AND METHOD OF USING SAME - Google Patents

Description

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The present invention relates to detergent compositions for washing dishes in the machine, endowed with thixotropic properties, having better chemical and physical stability and which are easily dispersed in a washing medium to ensure effective cleaning of dishes, glasses. , porcelain, etc.

Detergents presented in the form of powder which are commercially available for household dishwashing machines have several drawbacks, for example a non-uniform composition; costly operations necessary for their manufacture; the tendency to solidify during high humidity storage, resulting in the formation of lumps which are difficult to disperse; dust generation, which is a particular source of irritation for users with allergies; and the tendency to solidify in the dispenser of the dishwasher.

In addition, the liquid forms of such compositions cannot generally be used in automatic dishwashing machines due to the high degrees of foaming, unacceptably low viscosities and too high alkalinity.

Recent research and development activity has focused on the gel or "thixotropic" form of such compositions, for example degreasing agents and products for automatic dishwashing machines characterized as thi-xotropic fads. The main drawback of the products for dishwashing machines thus obtained is that they are not viscous enough to remain in the machine's dispenser tank and, moreover, they form spots on the plates, glasses, porcelain, etc. Ideally, thixotropic cleaning compositions should be very viscous at rest, have Bingham plasticity, and have 2 relatively high flow indices. When subjected to shear stresses #, however, as occurs during their shaking in a container or compression through an orifice, 05 they must become fluid quickly and, when the shear stresses are relaxed, they should quickly return to their high viscosity / Bingham plasticity state. Stability is also of paramount importance, that is, there should be no obvious sign of phase separation or leakage after prolonged storage.

* t

The presentation of the compositions for automatic dishwashing machines in gel form having the properties described above has therefore been my problematic, in particular with regard to the compositions to be used in household dishwashing machines. . For effective use, it is generally recommended that the detergent for automatic dishwashing, hereinafter also referred to as DAV below, contains: (1) sodium tripolyphosphate (NaTPP) to soften water or fix substances minerals responsible for the hardness of the water and for emulsifying and / or peptising soiling; (2) sodium silicate to provide the alkalinity necessary for effective detergent action and to protect the varnish and designs of fine porcelain; (3) sodium carbonate, generally considered optional, to improve alkalinity? (4) a chlorine-releasing agent to assist in the removal of dirt stains that soil water; and (5) an antifoam / surfactant to reduce the foam, so as to improve the efficiency of the machine and provide the necessary detergent action. See for example SDA Detergents in Depth, "Formulations Aspects i 3 of Machine Dishwashing", Thomas Oberle (1974). Detergents approaching the compositions described above are mostly liquids or powders.

Combining such ingredients as an effective 05 gel for a home machine has proven difficult. Generally, these compositions do not contain hypochlorite as a bleaching agent, as it tends to react with the other chemically active ingredients, in particular the surfactant, thereby degrading the suspending or thixotropic agent and altering its effectiveness. Thus, the patent of E. ü. A. No. 4,115,308 describes thixotropic pastes for automatic dishwashing machines, containing a suspending agent, for example 15 CMC, synthetic clays, etc. ; mineral salts including silicates, phosphates and polyphosphates; a small amount of surfactant and a foam reducer. The bleach is not described. The E. ü patent. A. N® 4 147 650 is somewhat similar, and optionally includes a chlorine bleach (hypochlorite) but no organic surfactant or foam reducer. In addition, the product is described as a detergent suspension with no apparent thixotropic properties.

US Pat. No. 3,985,668 describes abrasive cleaning agents having the consistency of a gel, containing: (1) a suspending agent, preferably types of smectite and attapulgite clays? (2) an abrasive, for example silica sand or perlite? and (3) a filler comprising low density powdered polymers, expanded perlite, etc., which exhibits buoyancy and thus has a stabilizing effect on the composition in addition to its role of increasing agent. , thereby replacing otherwise available water to form an undesirable supernatant liquid phase 4 due to leakage and phase destabilization. The above ingredients are the essential ingredients. Optional ingredients include bleach hypochlorite, surfactant and tam-05 pon stable to bleach, e.g. silicates, carbonates of monophosphates. Detergency builders, such as NaTPP, may be included as other optional ingredients to provide or enhance the adjuvant function not provided by the buffer, the amount of this detergency builder not exceeding 5% of the total composition. »Sition, according to the patent. Maintaining the pH at desired values of 10 or more is obtained by the buffer / detergency builder component. A high pH is believed to minimize the breakdown of bleach chlorine and an undesirable interaction between the surfactant and the bleach. NaTPP, when present, is limited to 5%, as indicated. There is no description of a foam destroyer.

In British patent application GB-A-2 116 199 and G3-A-2 140 450, both assigned to Colgate-Palmolive, there are described DAV compositions which exhibit properties advantageously characterizing the thixotropic structure, of the type gel, and 25 which each include the various ingredients necessary for effective detergent action with an automatic dishwashing machine. The aqueous detergent composition, normally in gel, for an automatic dishwashing machine having thixotropic properties, comprises the following ingredients, on a weight basis: (a) 5 to 3% of: alkali metal tripolyphosphate, (b ) 2.5 to 20% sodium silicate, 35 (c) 0 to 9% alkali metal carbonate, (d) 0.1 to 5% active, detergent, organic material, dispersible in water and stable to bleach chlorine 5, (e) 0 to 5% bleach reducer stable to bleach, (f) a bleach chlorine compound in an amount capable of providing about 0.2 to 4% chlorine available; and (g) a thixotropic thickener in an amount sufficient to impart a thixotropy index of about 2.5 to 10 to the composition. The DAV compositions thus formulated have low foaming; they are easily soluble in the '· washing medium and show their maximum efficiency - quoted at pH values best ensuring the improved cleaning action, namely a pH of 10.5 to 13.5.

The compositions normally have the consistency of a gel, i.e. a very viscous, opaque, jelly-like material having Bingham plasticity and thus relatively high flow limits. Consequently, a determined shear force 20 is necessary to initiate or increase the flow, such as that obtained in the tank of a dispenser with stirring of an automatic dishwashing machine in operation. Under these conditions, the composition fluidizes quickly and disperses easily. When the shear force is interrupted, the fluid composition quickly returns to a state of high viscosity, of Bingham plasticity, very close to its initial consistency.

Although these previously described liquid VAD formulations are not subject to or are to a lesser extent subject to one or more of the disadvantages described above, it has been found that in actual practice, physical stability needs to be further improved. to increase the shelf life of the product and thus improve the acceptability on the part of the consumer.

Therefore, the present invention proposes to provide liquid VAD compositions having thixotropic properties as well as better physical stability and improved rheological properties.

Another object of the invention is to provide liquid thixotropic DAY compositions having reduced rates of thixotropic thickener without adversely affecting the generally high viscosities at low shear rates and the lower visio cosities at high shear rates which are characteristic of the desired thixotropic properties.

These objects of the invention / as well as others, which will emerge more clearly from the detailed description which follows, are achieved by the incorporation, in an aqueous detergent composition, normally analogous to a gel, for an automatic machine. for washing dishes, an amount of a polyvalent metal salt of a long chain fatty acid which effectively inhibits the deposition of suspended particles, for example a thixotropic agent.

Therefore, in a broad aspect, the present invention provides an aqueous detergent composition, normally gel-like, for washing dishes in an automatic machine, having thixotropic properties, which comprises, on a weight basis; (a) 5 to 35% of alkali metal tripolyphosphate, (b) 2.5 to 20% of sodium silicate, 30 (c) 0 to 9% of alkali metal carbonate, (d) 0.1 to 5% of an organic detergent active ingredient dispersible in water and stable to bleaching chlorine, (e) 0 to 5% of foam reducer stable to bleaching chlorine, (f) a chlorinated bleaching compound in an amount suitable for provide about 0.2 to 4% of available chlorine 7, (g) a thixotropic thickener in an amount sufficient to give the composition a thixotropy index of about 2.0 to 10.05 (h) 0 to 3% d sodium hydroxide, (i) a polyvalent metal salt of a long chain fatty acid in an amount effective to increase the physical stability of the composition, and (j) the balance being water.

According to another aspect, the invention provides a method for cleaning the dishes in an automatic washing machine with an aqueous washing bath containing an effective amount of the detergent composition for an automatic dish washing machine (DMALV) as described above. above. According to this aspect of the invention, the dmalv composition can be easily poured into the dispenser of the machine and, in just a few seconds, it thickens quickly to return to its normal gel state to maintain itself. Firmly screw into the tank until shear forces are applied to it again, for example by the jet of water from the dishwasher.

In general, the effectiveness of DAV is directly associated with: (a) available chlorine levels, (b) alkalinity, (c) solubility in the wash medium, and (d) l foam inhibition. It is preferable that in this case the pH of the composition of DAV is * at least about 9.5, preferably about 10.5 to 13.5, and more preferably at least about 11 , 5. At relatively lower pH values, the DAV product is too viscous, i.e. it looks like a solid, and is therefore not easily fluidized under the shear forces created in the dispenser in normal machine operating conditions 8. In principle, the composition loses most, if not all, of its thixotropic character. The addition of NaOH is therefore often necessary to increase the pH within the above limits, and to increase the flowability properties. The presence of carbonate is also often necessary in this case, as it acts as a tam-pon helping to maintain the desired level of pH. However, an excess of carbonate should be avoided, as it may cause the formation of needle-like carbonate crystals, which impairs the stability, thixotropy and / or detergent action of the DAY product. The caustic soda (NaOH) has the other function of neutralizing the foam reducer of the ester type of phosphoric or phosphonic acid, if present.

The composition contains about 0.5 to 3% by weight of NaOH and about 2 to 9% by weight of sodium carbonate. In general, the composition contains about 0.5 to 3% by weight of NaOH and about 2 to 9% by weight of sodium carbonate although it has been observed that sufficient alkalinity can be provided by NaTPP and silicate sodium.

The NaTPP used in the composition in the range of about 8 to 35% by weight, preferably about 20 to 30% by weight, should preferably be free of heavy metal which tends to decompose or inactivate 1 preferred sodium hypochlorite and other chlorine bleaching compounds. NaTPP can have an average degree of hydration of less than about 1 or more than about 5, for example 0 to 2.7% by weight or at least 16.5% water, including 1 ' A stable hexahydrate having a hydration level of 6 corresponding to about 18% by weight of water or more. In reality, humidification to an average of about 0.3 to 1% water is very effective and apparently serves to form seeds of the stable hexahydrate which accelerate hydration and solubilization of remaining NaTPP particles. On average, NaTPP contains approximately 5 to 15% by weight of water, which corresponds to an average degree of hydration of approximately 1 to 5. If only hexahydrate is used, the detergent product is liquid. and has a weak or zero thixotropic character. If only anhydrous NaTPP is used, the product is too thick and therefore not suitable. Effective compositions are obtained, for example, using a weight ratio of 0.5: 1 to 10 2: 1 of anhydrous NaTPP to NaTPP hexahydrate, values of about 1: 1 being particularly preferred.

<* Inhibition of foam is important to increase the efficiency of the dishwasher and minimize destabilizing effects which may occur as a result of the presence of excess foam in the machine during use.

The foam can be sufficiently reduced by an appropriate choice of the type and / or amount of the active detergent material, the main foam-producing component. The degree of foaming is also a function, to some extent, of the hardness of the washing water contained in the machine, so that an appropriate adjustment of the proportions of NaTPP which has a water softening effect can assist in obtaining the desired degree of foam inhibition. However, it is generally preferable to include a reducing agent or a foam inhibitor which is stable against the chlorine bleach. The alkyl acid phosphonates of formula: 30 0

II

HO— P —R

GOLD

available for example from BASF-Wyandotte 35 (pcuk-pea) and in particular the alkyl acid phosphates of formula: 10 ο

II

HO — P — OR

GOLD

05 available for example from Hooker (SAP) and Knapsack (LPKn-158), formulas in which one or both R groups of each type of ester can independently represent a alkyl group at ^ 20 'are particularly effective. Mixtures of both types, or any other types stable to chlorine bleaching agents, or mixtures of mono- and di-esters of the same type can be used. Particular preference is given to a mixture of acid phosphates of mono- and di (C 1 -C 4 alkyl) - such as acid monostearyl / distearyl 1,2 / 1 phosphates (Knapsack). When used, the typical proportions are 0.1 to 5% by weight, preferably about 0.1 to 0.5% by weight, of foam reducing agent in the composition, the weight ratio of active detergent component (d) in the foam reducer (e) generally lying between approximately, 10: 1 and 1: 1, and preferably between approximately 4: 1 and 1: 1. Other foam reducers that can be used include, for example, known silicones.

Although any chlorine bleaching compound can be used in the compositions of the present invention, for example dichloroisocya-nurate, dichlorodimethyl-hydantoin or chlorinated TSP, an alkali metal hypochlorite, for example potassium, is preferred , lithium, magnesium and especially sodium. The composition should contain enough chlorine bleach to provide about 0.2-4.0% by weight of available chlorine, as determined for example by acidifying 100 parts of the composition with excess chlor-35 acid water. A solution containing about 0.2 to 4.0% by weight of sodium hypochlorite contains or provides about the same percentage of available chlorine.

11

In particular, a proportion of about 0.8 to 1.6% by weight of available chlorine is preferred. For example, one can advantageously use a sodium hypochlorite solution (NaOCl) of 11 or 13% of chloride 05 available in proportions of about 3 to 20%, preferably about 7 to 12%.

Sodium silicate, which provides alkalinity and protection for hard surfaces such as varnish and designs of porcelain is used in an amount of about 2.5 to 20% by weight, preferably about 5 to 15% by weight in the composition. The sodium silicate is generally added in the form of an aqueous solution, preferably having an Na 2 O: SiO 2 ratio of from about 1: 2.2 to 1: 2.8. In this regard, it should be mentioned that most of the other components of this composition, in particular NaOH, sodium hypochlorite, the foam reducer and the thixotropic thickener, are also often added in the form of a dispersion or so -20 aqueous lution prepared beforehand.

The active detergent material useful here must be stable in the presence of bleaching chlorine, in particular hypochlorite, and it preferably comprises materials of the anionic organic surfactant types, amine oxide, phosphine oxide, sulfoxide or beta water dispersible, the first anionic types mentioned being preferred. They are used in amounts of between about 0.1 and 5%, preferably about 0.5 and 2.0%, and more preferably between about 0.3 and 0.8%. Particularly preferred surfactants here are the mono- and / or disulphates mono- and / or di (Cg-Cl4 alkyl) of linear or branched alkali metal, commercially available, for example under the designation 35 DOWFAX (trademark) 3B-2 and DOWFAX 2A-1. In general, paraffin sulfonates tend to disrupt if not destroy thixotropy, and have been found to excessively over-viscose viscosity causing severe problems of shear forces. In addition, the surfactant must be compatible with the other ingredients of the composition. Other suitable surfactants include primary alkyl sulfonates, alkyl sulfonates, alkylarylsulfonates and sec.alkyl sulfates. Examples are sodium (C1-10Cl8) alkyl such as sodium dodecylsulfate and sodium tallow (tallow alcohol), sodium sulfonates such as C1-C18 alkane sodium hexadecyl-1-sulfonate and sodium (C 1 -C 4 -alkylbenzenesulfonates) such as sodium do-decylbenzenesulfonates. The corresponding potassium salts can also be used.

Like other suitable surfactants or detergents, amine oxide type surfactants generally have the structure I ^ R ^ NO in which each R represents a lower alkyl group, for example methyl, and R1 represents a long chain alkyl group from 8 to 22 carbon atoms, for example a lauryl, myristyle, palmityl or cetyl group. In place of an amine oxide, a phosphine oxide R0R1PO or a corresponding sulfine 1 ^ of phosphine RR SO can be used as a surfactant. Betaine surfactants generally have the structure RjR1N "- R" C00 "where each R represents a lower alkylene group having 1 to 5 carbon atoms. Particular examples of these surfactants are lauryl-dimethylamine oxide, myristyldimethylamine oxide, the corresponding phosphine oxides and sulfoxides, and the corresponding betaines comprising dodecyldimethylammonium acetate, tetradecyl-diethylammonium pentanoate, hexadecyldimethylammonium hexanoate, etc. For biodegradability, the group The alkyl of these surfactants should be linear, and these compounds are preferable.

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

Thixotropic thickeners, i.e. thickeners or suspending agents which impart thixotropic properties to the aqueous medium, are known in the art and can be organic or inorganic, water-soluble, water-dispersible or forming a colloid, and monomers or polymers, and they must naturally be stable in these compositions, for example stable towards a high alkalinity and chlorinated bleaching compounds such as sodium hypochlorite. Those which are particularly preferred in general comprise the mineral clays of the smectite and / or attapulgite types forming a colloid. These materials have generally been used in amounts of about 1.5 to 10, preferably 2 to 5% by weight, to impart the desired thixotropic properties and Bingham plasticity to earlier DAV formulations of the aforementioned patent applications GB- A-2 116 199A and GB-A-2 140 450. One of the advantages of the DAV formulations of the present invention is that the desired thixotropic properties and Bingham plasticity can be obtained in the presence of polyvalent metal salts stabilizing fatty acids with lesser amounts of thixotropic thickeners. For example, amounts of mineral clays forming a colloid of the smectite and / or attapulgite types of between approximately 0.1 and 3%, preferably between 0.2 and 2.5%, and better still between 0.5 and 2.2% is generally sufficient to obtain the desired thixotropic properties and Bingham plasticity when used in combination with the physical stabilizer.

35 Smectite clays include montmorillonite (bentonite), hectorite, saponite, etc. Materials of this type are available under t 14 trademarks such as Thixogel (registered trademark) No. 1 and Gelwhite (registered trademark) GP, H, etc., from Georgia Kaolin Company (both being montmorillonites). Clays of the attapulgite 05 type include the materials available in the beginning under the trade name Attagel (registered trademark), that is to say Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerais and Chemicals Corporation. Mixtures of smectite and attapulgite in weight ratios of 4: 1 to 1: 5 are also useful here. Thickeners or suspending agents of the above types are well known in the art and are described, for example, in U.S. Patent No. 3,985,668 cited above. Abrasives or polishing agents should be avoided.

The amount of water contained in these compositions must naturally neither be high enough to produce too low a viscosity and a fluidity, nor low enough to produce a too high viscosity and a too low flowability, the thixotropic properties. being in each case diminished or suppressed. This amount is easy to determine by routine experimentation in any particular case, and is generally between about 45 and 75% by weight, preferably between about 55 and 65% by weight. The water should also preferably be deionized or softened.

So far, the description of the DAV product, unless otherwise specified, corresponds to the compositions as described in the abovementioned British patent applications GB-A-2 116 199 and GB-A-2 140 450.

The DAV products of these previous descriptions have better rheological properties as evidenced by a test of the viscosity of the products as a function of the shear rate. The compositions have a viscosity greater than a low shear rate and a viscosity lower than a high shear rate, the results indicating effective fluidization and gelation being in the ranges of shear rates than we meet in the dishwasher. In practice, this means improved flow and treatment characteristics as well as a reduction in leaks in the machine's distribution tank, compared to the liquid or gel ADD products of the prior art, for shear speeds corresponding to 3 to 30 rpm *, the viscosities (Brookfield) are correspondingly between approximately 15,000 and 30,000 mPa.s and approximately 3000 and 5,000 mPa.s, as measured at room temperature. using a Brookfield LVT viscometer after 3 minutes using a No. 4 spindle. A shear speed of 7.4 s ~ 1 corresponds to a number of spindle revolutions of approximately 3. An increase in the shear rate of a factor of 10 20 produces a reduction in viscosity of a factor of 6 to .7. With prior art DAV gels, the corresponding decrease in viscosity was only about a factor of 2. In addition, with such compositions, the initial viscosity measured at about 3 rpm / 25 min. Was only about 2,500 to 2,700 mPa.s. The compositions of the aforementioned applications therefore exhibit threshold fluidizations at lower shear rates and to a much greater extent in terms of incremental increase in shear rate as a function of the incremental decrease in viscosity. This property of the DAV products of the previous invention is summarized in terms of a thixotropy index (IT) which is the ratio of the apparent viscosity at 3 rpm and 30 rpm. The prior compositions have an IT of 2.5 to 10. The VAD compositions tested exhibit a large and rapid return to their former consistency in the quiescent state when the shear force is interrupted.

The present invention is based on the discovery that the physical stability, i.e. resistance to phase separation, deposition, etc., of these aqueous liquid compositions of prior DAV can be greatly improved, It does not adversely affect, and in some cases, advantageously affects their rheological properties, by adding to the composition a small but effective amount of a polyvalent metal salt of a long chain fatty acid.

As an example of improving the rheological properties, it has been found that at low shear speeds, for example at a number of spindle revolutions of about 3, the apparent viscosities can often be increased by a factor of two to three, by incorporating as little as 0.2% or less of the metal salt type fatty acid stabilizer. At the same time, physical stability can be improved to the point that even after six weeks or more, in temperature ranges from freezing temperatures to 40 ° C and above, the compositions containing the metal salts stabilizers do not undergo visible phase separation.

Preferred long chain fatty acids are higher fatty aliphatic acids having about 8 to about 22 carbon atoms, preferably about 10 to 20 carbon atoms, and most preferably about 12 to 18 carbon atoms, including including the carbon atom of the carboxyl group of the fatty acid. The aliphatic radical can be saturated or unsaturated or it can be straight or branched chain. Mixtures of fatty acids can be used, such as those derived from natural sources such as tallow fatty acid, coconut fatty acid, soy fatty acid, etc.

17

So examples of fatty acids in. from which the polyvalent metal salts used as stabilizers can be formed include decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid , tallow fatty acid, coconut fatty acid, soy fatty acid, mixtures of these acids, etc. Stearic acid, because of both its commercial availability and the results it provides, is preferable.

The preferred polyvalent metals are aluminum, minium and zinc, although other polyvalent metals, in particular those of Groups IIA, IIIA, IVA, VA, VIIA, IIB, IIIB, can also be used. , IVB, 15 VB and VIII of the Periodic Table of the Elements. Particular examples of such other polyvalent metals include Mg, Co, Ti, Zr, V, Nb, Mn, Fef Co,

Ni, Cd, Sn, Sb, Bi, etc. Preferably, the metal salts are used in their higher oxidation states.

Many of these metal salts are commercially available. For example, aluminum salts are available as a triacid, e.g. aluminum stearate as aluminum tristate-arate, AKC ^ yH ^^ COO) ^ · Monoacid salts, e.g. aluminum monosterate,

Al (OH) 2 (Ci7H35C ° 0) and the salts of diacids, for example aluminum distearate, Al (OH) (C ^ H ^ COO) 2, and mixtures of two or three of the salts of mono-, Di- and tri-acids can be used with these metals, for example Al, with valences of +3, and mixtures of the salts of mono- and di-acids can be used with these metals, for example Zn, with valences of +2. It is very advantageous that the diacids of the valence metals +2 and the triacids of the valence metals +3, and that the tetraacids of the valence metals +4 are used in predominant amounts. For example, at least 30%, preferably at least 50%, more preferably 80 to 100% of the total metal salt is in the highest possible oxidation state, i.e., each of the 05 Possible valence sites is occupied by a fatty acid residue.

Metal salts, as mentioned above, are generally commercially available, but they can be readily produced, for example by saponification of a fatty acid, for example animal fat, stearic acid, etc., or of the corresponding fatty acid ester, followed by treatment with an oxide or hydroxide of the polyvalent metal, for example in the case of the aluminum salt, with a-15 lun, alumina, etc. .

Aluminum stearate, i.e. aluminum tristëarate, and zinc stearate, i.e. zinc distearate, are the preferred polyvalent fatty acid salts as sta-20 bilisants.

The amount of stabilizing fatty acid salts to achieve the desired improvement in physical stability depends on factors such as the nature of the fatty acid salt, the nature and quantity of the thixotropic agent. , the active detergent compound, mineral salts, in particular TPP, other ingredients of DAV, as well as envisaged conditions of storage and transport.

In general, however, the amounts of polyvalent metal fatty acid salts serving as stabilizers of about 0.02 to 1%, preferably about 0.06 to 0.8%, and most preferably d '' about 0.08 to 0.4% provide long term stability and absence of phase separation during storage or transport both at low and high temperatures, as required by a industrially acceptable product.

19

According to a preferred method of manufacturing these compositions, all of the mineral salts must be dissolved or dispersed first, that is to say carbonate (when it is used), silicate and tripolyphosphate, in the aqueous medium. The thickening agent is added last. The foam reducer (when used) is first presented as an aqueous solution, as the thickening agent. The foam reducer dispersion, caustic sou-10 (when used) and mineral salts are first mixed at high temperatures in aqueous solution (deionized water) and then cooled, with continuous stirring. The bleach, the surfactant, the fatty acid salt, the stabilizer and the thickener dispersion at room temperature are then added to the cooled solution (25-35 ° C). Excluding the chlorine bleach, the total salt concentration (NaTPP, sodium silicate carbonate is generally about 20 to 50% by weight, preferably about 30 to 40% by weight of the composition.

Other conventional ingredients can be incorporated into these compositions in small amounts, generally less than about 3% by weight, for example a perfume, hydrotropic agents such as benzene-, toluene-, xylene- and sodium cumene sulfonates , preservatives, dyes and pigments, etc., all of which are naturally stable with respect to the chlorinated bleaching compound and of high alkalinity (properties of all the components); Particularly preferred dyes are chlorinated phthalocyanines and aluminosilicate polysulfides which provide, respectively, pleasant green and blue hues. TiO2 can be used for bleaching or neutralizing past tints.

The liquid DAV compositions of the present invention are readily used in known manner for washing plates, or other cooking utensils, etc., in an automatic dishwashing machine, equipped with a suitable dispenser. of detergent, in an aqueous wash bath containing an effective amount of the composition.

The following nonlimiting examples illustrate the invention. All quantities and proportions are expressed relative to the weight of the composition, unless otherwise specified.

EXAMPLE 1

In order to demonstrate the effect of metal salts as a stabilizer, liquid formulations of DAV are prepared by varying the amounts of stabilizer and thixotropic thickener. The following ingredients are first mixed in a Guisti mixer at 50-609C:% 20 Deionized water 41.10 + y-x

Caustic soda solution (50% NaOH) 1.00

Sodium carbonate, anhydrous 5.00

Sodium silicate, 47.5% solution of Na2O: SiO2 in a ratio of 1: 2.4 15.74 TPP of sodium (substantially anhydrous, i.e. 0 to 5% moisture, in particular 3% 30, humidity) (Thermphos NW) 12.00 TPP sodium (hexahydrate) (Thermphos N hexa) 12.00

The mixture is cooled to 25-30 ° C and continued stirring, then the following ingredients are added thereto at room temperature: 21. · \ \

Sodium hypochlorite solution (11% available chlorine) 9.00

DOWFAX 3B-2 monostëaryl phosphate 0.16 (05% aqueous solution 45% monodecyl / didecyl) (diphenyl oxide) -disulfona-te sodium 0.80

Al tristearate or Zn distearate x 10 Gel White H 2.00-y »»

Monostëaryl phosphate used as a foam reducer and Dowfax 3B2 which is the active detergent compound are added to the mixture immediately before the aluminum tristearate or zinc distearate used as stabilizers or just before the thickener Gel White H.

Determine the apparent density, the VDC (Capillary Drainage Speed), the apparent viscosity at 3 and 30 rpm, and the physical stability (phase separation) of each of the resulting liquid VAD formulations, as indicated on the Table I, at rest and in a transport trial. The results are also shown in Table I.

25 From the results indicated in Table I, the following conclusions are drawn: The incorporation of 0.2% Al stearate into a formula containing 1.5% or 1% of Gel White H as well as the incorporation of 0.1% Al stea-30 rate or 0.1% ziuc stearate into a formula containing 2% Gel White H results in a simultaneous increase in physical stability and apparent viscosity (Table I , tests I (control), 2, 3, 6 and S) - 35 The incorporation of 0.1% of stearate

Al in a formula containing 1% Gel White H, and 0.3 or 0.4% Al stearate in a form Λ '.

22 mule containing 0.25% Gel White H results in. an increase in physical stability without significant increase in viscosity (Table II, tests 1 (control), 4, 7, 10 and 11).

05 For the combination of 0.1% stearate

Al and 0.5% of Gel White H (Test 8), the apparent viscosities remain acceptable, but it is not possible to. a significant improvement in physical stability.

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m ° Ξ en il I_s - ^^ - 1 26

Notes containing Table X

(1) Filter paper No. 1 (Whatman) on which a 6.4 cm circle is drawn is placed on a flat glass plate, 10 cm x 10 cm. A plastic tube 05, 6.4 cm long, 3.4 cm in diameter, is placed vertically in the center of the circle. The tube is filled with the composition of DAV sampling liquid (after standing for one day). The time required for the solvent to exit the tube and reach the drawn circle is measured. Time is measured at three points in the circle and averaged. Faster times mean that the gel does not properly retain the solvent (water) which can then leak into the pa-15 pier-flitre. Times longer than 5 minutes are considered satisfactory. Times between 4 and 5 minutes are considered unstable but acceptable.

(2) Measured with a No. 4 pin after 3 20 minutes on 24 hour samples.

(3) In height.

(4) By weight.

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

25 (6) Liquid separation measured after 6 weeks and 3000 km in a private car (by weight in a plastic container).

EXAMPLE 2 Using the same composition and the same preparation process as in Example 1, except that instead of Gel White H used as thixotropic thickener, 2% of Attagel 50 is used (one attapulgite clay) or 0.4% Bentone EW (a hectorite clay specially treated with (tests 2 and 4) or without (control tests 1 and 3) aluminum tristearate. The apparent viscosities and physical stability are measured in the same manner as described in 1 * Example 1. The results are shown in Table II.

It can be seen from the results indicated in Table II that small amounts of aluminum stearate are also effective in increasing the physical stability of liquid thixotropic detergent compositions for automatic dishwashing. base of attapulgite clay and ar-10 hectorite gile.

28

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29 EXAMPLE 3

This example shows that the mineral aluminum and zinc salts, including A ^ O ^, ZnSO ^ and Al ^ (SO ^) 2 and the slow monova-05 metal fatty acid salts do not confer an improvement in physical stability to thixotropic liquid DAV compositions. Using the same formulation as in Test 6 of Example 1, 0.1% Al 2 O 3, ZnSO 4, A12 (SO 4) 3 and sodium stearate are used in place of 0.1% aluminum sterate. The results of the measurements of the apparent viscosity and of the physical stability are indicated in Table III. * 1 "30

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<'û en en II ω * 32 c EXAMPLE 4

The following gel-like thixotropic liquid DAV is prepared by following the same general procedures as in Example 1.

05 Ingredient Amount of active substance,% by Weight

Sodium silicate (47.5% Na20 solution: Si02 - 1: 2.4) 7.48 10 Monostearyl phosphate 0.16

Dowfax 3B-2 0.37 M

Thermphos NW 12.0

Thermphos N hexa 12.0

Aluminum tristearate 0.1 15 Sodium carbonate, anhydrous 4.9

Caustic soda solution (38% NaOH) 3.0

Pharmagel Ex Uroclay (Mg / Al silicate clay) 1.25 20 Sodium hypochlorite solution (11%) 1.0

Water the rest pH - 12.5 to 12.9.

It is also possible to add minor amounts of perfume, color, etc. to the formulation.

i *

Claims (22)

33 1. An aqueous thixotropic composition for washing the dishes in an automatic machine, characterized in that it comprises approximately, by weight 05 (d) 5 to 35 I of alkali metal tripolyphosphate; (b) 2.5 to 20% sodium silicate î (c) 0 to 9% alkali metal carbonate? 10 (d) 0.1 to 5% of active detergent material or- *. ganic, dispersible in water and stable to chlorine% bleaching; (e) 0 to 5% of foam reducer stable with respect to bleaching chlorine; (F) a bleaching chlorine compound in an amount capable of providing about 0.2 to 4% of available chlorine? (g) a thixotropic thickener in an amount sufficient to provide the composition with a thixotropy index of about 2 to 10; (h) 0 to 3% sodium hydroxide; (i) a polyvalent metal salt of a long chain fatty acid as a physical stabilizer in an amount effective to increase the physical stability of the composition; and (j) the rest being water. 2. Composition according to claim 1, characterized in that the physical stabilizer (i) is a polyvalent metal salt of an aliphatic fatty acid of about 8 to 22 carbon atoms. 3. Composition according to claim 2, characterized in that the acid has about 12 to 18 carbon atoms. 4. Composition according to claim 2, characterized in that the polyvalent metal is a metal chosen from any one of Groups IIA, IIIA, IVA, VA, VIIA, IIB, IIIB, IVB, V3 and VIII of Table II · K 34 Periodical of the Elements. 05 Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi, Al and Zn. 5. Composition according to claim 4, characterized in that the polyvalent metal is chosen from the group consisting of Mg, Ca, Ti, Zr, V, Nb, 6. Composition according to claim 2, characterized in that the physical stabilizer (i) is the aluminum salt or the zinc salt of said fatty acid. 7. Composition according to claim 1, characterized in that the physical stabilizer (i) »% is aluminum tristearate · 8. Composition according to claim 1, characterized in that the physical stabilizer (i) is zinc distearate. 9. Composition according to claim 1 / characterized in that the physical stabilizer (i) is present in an amount of about 0.02 to 1%. 10. Composition according to claim 1, characterized in that the physical stabilizer (i) is present in an amount of about 0.06 to 0.8%. 11. Composition according to claim 1, characterized in that the physical stabilizer (i) is present in an amount of about 0.08 to 0.4%. 12. Composition according to claim 1, characterized in that the thixotropic thickener (g) is a mineral clay forming a colloid. 13. Composition according to claim 12, characterized in that the clay is a clay of montmorillonite type, an attapulgite-type clay, a hectorite-type clay or a smectite-type clay. 14. Composition according to claim 12, characterized in that the amount of the clay-type thickener is approximately 0.1 to 3%. 15. Composition according to claim 12, characterized in that the amount of thick clay t i 35 sissant is about 0.5 to 2.2%. 16. Composition according to claim 6, characterized in that it contains approximately 0.1 to 0.2% of the physical stabilizer (i) and approximately 0.5 to 05 2% by weight of a mineral clay forming a loid neck , as a thixotropic thickener (g). 17. Composition according to claim 6, characterized in that it contains approximately 0.3 to 0.4% of the physical stabilizer (i) and approximately 0.25% of a mineral clay forming a colloid as thixotropic thickener (g) . ", 18. Composition according to claim 1, characterized in that the bleaching chlorine compound (f) is sodium hypochlorite. 19. Composition according to claim 1, characterized in that it contains at least about 0.1% by weight of the foam reducer (e). 20. Composition according to claim 19, characterized in that the foam reducer is an alkyl acid phosphate or an al-kyle acid phosphate containing one or two C12 "C20 'alkyl groups or a mixture thereof. 21. Composition according to claim 1, characterized in that it has a pH of 10.5 to approximately 25 13.5. 22. Method for cleaning soiled dishes in an automatic dishwashing machine, characterized in that it consists in bringing the soiled dishes in a dishwashing machine in contact with an aqueous washing bath in which an effective amount of the composition according to claim 1 is dispersed.