LU87134A1 - STABILIZED AQUEOUS THIXOTROPIC LIQUID COMPOSITIONS AND METHODS OF USE THEREOF FOR AUTOMATIC DISHWASHING - Google Patents

Description

88 / B 52 725

_ * * 0 7 1 Tl Λ GRAND-DUCHÉ DE LUXEMBOURG

Patent N ° ^ l · V ^,.

Minister of February 12. 1388. JlpyC for Economy and the Middle Classes „, 3¾¾ Intellectual Property Service

_Z_ LUXEMBOURG

s s s i, 'Application for Patent of invention q ...

7 ------------------------------------------------- ---------------------------------------------------------- ------------------- ------------------------------- -------------------—.............................. ......................... (1) I. Request

The so-called company: COLGATE-PALMOLIVE COMPANY, 300 Park Avenue, -.................................... .................................................- ...................................... — ..... — ..... ..................................... —......------ ---------------------------------------------------------- --------------- (2) NEWYORK, NY10022 (United States of America), represented ______ ________ by Monsieur Jacques de Muyser acting as _________ agent______________________________________________________________________________________________________________________________________________________________________________________________ (3) deposits (s) this .. ..... twelve February 1900 eighty-eight___________ ____________ (at DD? hours, at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent for an invention concerning : ____ "Stabilized aqueous thixotropic liquid compositions ^ ______ and ...... their methods of use for washing automatic________ ............ from ... go out ___.____________________ · ______________________________ ..

2. the description in language f ruPG ai s e ------------------------------- of the invention in triplicate; 3 ............... Z ................................. ................... drawing boards, three copies; 4. the receipt of the taxes paid to the Registration Office in Luxembourg, 1 J — Éier 1988.

5. the delegation of power, dated_____________________________________________________________________________ on__________________________________; 6. the successor document (authorization); declares (s) assuming responsibility for this declaration, that the inventor (s) is (are): (6) _-Julien ..... DRAPIER, rue deTavier, 192 (B-4100 SERAING ( Belgium) ............. Daniel ...... VAN DE ..... GAER. Place ...... E. Vinck 2/1, B-4110 FLEMALLE______. ..........................(Belgium)________________________________________________________________________________________________________________________________________________________________

.............-...... Chantal GALLANT, Allée ..... de ...... la Belle Fleur, 19fB-4521 CHERATTE

..........................(Belgium)..................... .................................................. .................................................. .................................................. ...........................................

claim) for the above patent application the priority of one (or more) application (s) of (...) ............. patent ............ .................................................. ......................................... filed in (8) in United States of America (9) ...... 1.2 ....... February ....... 1987 .................. .................................................. .................................................. .................................................. .................................................. ................

under N ° (10) .0..1.3.9 96 ................................... .................................................. .................................................. .................................................. .................................................. .....................

on behalf of (he) s ........ inventor s ................................. .................................................. .................................................. ......................._.......................... .............._......................

elect (elect) domicile for him / her and, if designated, for his / her representative, in Luxembourg___________________________________________________________________ .............. 35 ...... boulevard ...... Royal ...... in Luxembourg .......................................... .................................................. ................................... (12) requests (s) the issue of a patent for invention for the subject described and represented in the abovementioned appendices, with postponement of this delivery to .................... 8 .......... .................................................. .................................................. .................................................. ........month. (13)

The representative / representative: .............................................. .................................................. .................................................. .................................................. ............................................._... ( 14) riuxmiM. Π. Deposit Report The above! patent application has been filed with the Ministry of the Economy and the Middle Classes, Department of Intellectual Property ^ é ^ le ^ | rtuxembourg, dated: February 12, 1988 .....-: - K \, t? ” \ Pr. The Minister of Economy and the Middle Classes, tf at ..................... 15 .......... hours \ 1¾! Λ>. d. /; '\ / The head of the intellectual property department, A68007_- _j / __ EXPLANATIONS RELATING TO THE FORM OF BÖOT. 'Λ AA (1) if applicable "Application for certificate of addition to the main patent, to the main patent application No ...........% of ....... ..... "- (2) enter the surname, first name, profession.

88 / B 52 725

. , *; CLAIM OF PRIORITY

of the patent application / utility model EiX IN THE UNITED STATES OF AMERICA of 12 FEBRUARY 1987 (No. 013.996) · Brief Description filed in support of an application for

PATENT

at

Luxembourg

in the name of: COLGATE-PALMOLIVE COMPANY

NEW YORK, N.Y. 10022 (United States of America) for: "Stabilized aqueous thixotropic liquid compositions and methods of using them for automatic dishwashing." 'ν'Ή; χ; * "

COMPOSITIONS LI QJIDES THIXOTROPES 05 AQUEOUS STABILIZED AND THEIR

METHODS OF USE FOR THE AUTOMATIC WASHING OF THE DISHWASHER.

10

The present invention relates to an aqueous suspension of thixotropic clay whose physical stability is improved. More particularly, the invention relates to the use of potassium polyphosphates and metal salts of long chain fatty acids as physical stabilizers for aqueous suspensions of thixotropic clays.

The addition of small effective amounts of potassium polyphosphates and small effective amounts of polyvalent metal salts of long chain fatty acids improves physical stability and the stability against variations in rheological properties over time of detergent-based compositions. aqueous suspensions of thixotropic clay. The thixotropic properties can be preserved or improved by using lower proportions, for example from 0.25 to 0.50%, of thixotropic clay thickener than in the absence of the stabilizing potassium polyphosphates.

The present invention relates, in particular, to detergent compositions for automatic dishwashing which are endowed with thixotropic properties, with improved physical and chemical stability and with improved stability against variations in rheological properties. over time, of which 2 the apparent viscosity is increased and which are easily dispersible in the washing medium to ensure effective cleaning of dishes / glassware, porcelain, etc.

05 Commercial detergent products for household dishwashers supplied in powder form have various drawbacks, for example a non-uniform composition; costly operations necessary for their manufacture; a tendency to agglomerate during storage in a very humid environment, resulting in the formation of pieces which are difficult to disperse; a dusty state which is a particular source of irritation for users suffering from allergies; and a tendency to clump together in the dishwasher dispenser.

Recent research and development activities have focused on the "gel" or "thixotropic" form of such compositions, for example scouring cleaners and dishwasher products which are characterized by the fact that are in the form of thixotropic pastes. The main criticism that can be made of the dishwashing products so presented is that they are not viscous enough to remain "hooked" in the dishwasher dispenser cup. Ideally, the Thixotropic cleaning compositions are very viscous at rest, have a plastic nature according to Bin-gham and have relatively high flow limits. However, when they are subjected to shear stresses, for example by being shaken in a container or expressed by an orifice, they should become fluid, quickly and, when the shear stress ceases to be applied, quickly return to the state of high viscosity / plasticity 35 Bingham. The stability is also of iraportan- 3

* AT

γ Λ. 'Jh this primordial, that is to say that there should be no sign of phase separation or oozing after a long rest.

French patent application 86.082 87 05 filed on June 9, 1986, by the Applicant relates to detergent compositions for the automatic washing of dishes based on aqueous suspensions of thixotropic clay, containing aluminum stearate as physical stabilizing agent . These compositions exhibit an improvement in physical stability and an improvement in stability against phase separation compared to clay compositions which do not contain aluminum stearate. The compositions of this application N ° 86.082 87 15 however gave rise in certain cases to some difficulty in achieving stability against variations in rheological properties over time and with large variations in temperature and they generally required relatively high clay contents. 20 high, such as 0.5 to 2.0%.

Apart from the improvements described in the aforementioned application ftf ° 86.082 87, it has therefore proven to be very difficult to obtain gel-like compositions for automatic dishwashers having the properties described above, in particular as regards relates to compositions for use in household dishwashers. For effective use, it is generally recommended that the detergent composition for automatic dishwasher, hereinafter referred to as 30 DLVA, contain: (1) sodium tripolyphosphate (NaTPP) to soften water or retain minerals hard water and for emulsifying and / or peptising soiling; (2) sodium silicate to provide the alka-35 linearity necessary for an effective detergent action and 4 .. 9- Jk *,. H, to protect the patterns and varnishes of fine porcelain; (3) sodium carbonate, generally considered optional, to increase alkalinity; 05 (4) a chlorine releasing agent to facilitate the removal of small dirt stains which lead to the formation of water stains; and (5) an antifoam / surfactant to reduce the foam and thereby increase the efficiency of the machine while producing the required detergent action.

See, for example, SDA Detergents in Depth, "Formulations Aspects of Machine Dishwashing", Thomas Oberle (1974). The cleaning products, the composition of which approaches that which has just been described, are for the most part liquids or powders. It has proven difficult to combine these ingredients in the form of an effective gel for use in household machines.

In general, these compositions do not contain a hypochlorite-type bleach, as this tends to react with other chemically active ingredients, in particular with the surfactant. Thus, U.S. Patent No. 4,115,308 describes thixotropic pastes for automatic dishwashers which contain a suspending agent, for example CMC, synthetic clays or the like; mineral salts, including silicates, phosphates and poly-phosphates; a small amount of surfactant and a foam inhibitor. There is no mention of a bleaching agent. U.S. Patent No. 4,147,650 is somewhat similar, a chlorine bleach (hypochlorite) being optionally included, but no organic surfactant or foam inhibitor. The product is further described as a detergent suspension, apparently devoid of thixotropic properties.

"- A 4 Λ 5

EUA Patent No. 3,985,668 describes abrasive scourers having the consistency of a gel, which contain: "(1) a suspending agent, preferably smectite and attapulgite-type clays; (2) an abrasive, for example silica sand or perlite; and (3) a filler made of low density polymers, expanded perlite or the like, which has a certain buoyancy and thus exerts a stabilizing effect on the composition, in addition to the fact that it serves as a bulking agent and thus replaces water which would otherwise be available for the undesirable formation of a supernatant layer due to oozing and phase destabilization. essential ingredients Optional ingredients include a hypochlorite-type bleach, a surfactant stable to the bleach and a buffer, for example silicates, carbonates and monophosphates. as NaTPP, can be included as other optional ingredients to provide an adjuvant function that does not provide the buffer or complete its action, the proportion of such a detergency builder 25 not exceeding 5% of the total composition, depending this patent. Maintaining the desired pH values (greater than 10) is achieved by the buffer / detergency builder components. These high pHs are said to minimize the decomposition of the chlorine bleaching agent and the undesirable interaction between the surfactant and the bleaching agent, If present, NaTPP is limited to 5 %, as indicated.

There is no mention of a foam suppressant.

In UK patent applications 35 GB-2 116 199 A and GB-2 140 450 A in the name of Application - 'Kl ^ 4- 6 resse, it describes liquid DLVA compositions ·· having the properties which advantageously characterize a thixotropic structure of the gel type and containing each of the various ingredients necessary for effective detergent action with an automatic dishwasher. The aqueous detergent composition, normally in the gel state, for automatic dishwashers, having thixotropic properties, contains the following ingredients on a weight basis: 10 (a) 5 to 35% of metal tripolyphosphate alca lin; (b) 2.5 to 20% sodium silicate; (c) 0 to 9% alkali metal carbonate; (d) 0.1 to 5% of organic detersive substance, dispersible in water and stable towards the chlorine bleach; (e) 0 to 5% of foam inhibitor stable against the chlorine bleach; (f) a chlorine bleach in a proportion capable of providing about 0.2 to 4% of active chlorine; (g) a thixotropy thickening agent in a proportion sufficient to give the composition a thixotropy index of about 2.5 to 10; (H) sodium hydroxide, as necessary, to adjust the pH; and (i) additional water.

The DLVA compositions, thus formulated, are not very foaming, are easily soluble in the washing medium and are most effective at the pH values most conducive to the best cleaning performance, that is to say at pH 10.5. -14.0. These compositions normally have a gel consistency, that is to say that they are very viscous products resembling opaque jelly, having the nature of a plastic. Bingham and therefore having relatively high flow limits. Under these conditions, the composition fluidizes quickly and disperses easily. When the shear force ceases to be applied, the flowable composition quickly returns to a state of high viscosity Bingham plasticity, which closely approximates its previous consistency.

U.S. Patent No. 4,511,487 describes a low foaming detergent paste for dishwashers. The thixotropic cleaning product of this patent has a viscosity of at least 30 Pa.s at 20 ° C, as determined by means of a rotational viscometer at a spindle speed of 5 revolutions per minute. The composition is based on a mixture of finely divided hydrated sodium metasilicate, a compound with active chlorine and a thickening agent which is a lamellar silicate of the hectorite type. Small amounts of nonionic surfactants and alkali metal carbonates and / or hydroxides can be used.

In addition, the formation of organic clays by the interaction of clays (such as bentonite and hectorite) with organic compounds such as quaternary ammonium salts has been described (W. S, 25 Mardis, JAOCS, Vol. 61, No. 2, page 382 (1984)).

Although these liquid DLVA compositions previously described are not subject, or are subject to a lesser degree, to the deficiencies mentioned above, it has been found that new improvements in physical stability and stability against variations in rheological properties over time are desirable in order to increase the shelf life of the product and thus promote its acceptance by the consumer.

35 At the same time, it would be very advantageous f -4 *.

8 d1 increase the physical stability and the stability against variations in rheological properties over time of other thixotropic liquid compositions based on clay, such as cleaning agents for re-cleaning, dental pastes, "liquid" soaps , etc.

Therefore, an object of the present invention is to provide anti-sedimentation additives for aqueous suspensions of thixotropic clays. Another object of the invention is to provide liquid DLVA compositions having thixotropic properties as well as better physical stability and better stability against variations in rheological properties over time.

Yet another object of the invention is to provide thixotropic liquid DL.VA compositions whose thixotropic thickener contents are reduced without adversely affecting the generally high viscosities at high levels of salience and the viscosities lower at the low shear rates which are characteristic of the desired thixotropic properties.

Yet another object of the invention is to improve the stability of aqueous compositions based on thixotropic clay, in particular of liquid detergent pastes or gels for automatic dishwashers, by incorporating in the aqueous suspension of clay a proportion minor potassium polyphosphates and a minor proportion of a metal salt of fatty acid to inhibit sedimentation of suspended particles and to prevent phase separation.

Yet another object of the invention is to improve the stability against variations in rheological properties over time of compositions based on thixotropic clay, in particular pastes or gels * AA, 9 liquid washing tergents - automatic dishes, incorporating into the aqueous clay suspension a small effective proportion of potassium polyphosphates and a small effective proportion of a metal salt · '·' 05 fatty acid liquid as stabilizing agents.

These and other objects of the invention will become more apparent from the following detailed description of the present invention and its preferred embodiments and are achieved by incorporating, in a small but effective proportion, into a composition. aqueous liquid normally in the form of gels, physical stabilizers which are potassium polyphosphates and a metal salt of long chain fatty acid. More particularly, according to a particular and preferred embodiment of the invention, there is provided a detergent composition normally in the gel state for automatic dishwashing, in which a certain amount is incorporated. amount of potassium polyphosphates and some amount of a metal salt of a long chain fatty acid, which are effective in inhibiting variations in rheological properties over time and in inhibiting the sedimentation of suspended particles # such as the particles of thixotropy agent and sodium tripolyphosphate used as the detergency builder salt.

In these particular aspects, the present invention provides an aqueous detergent composition, normally in the gel state, with thi-xotropic properties, for an automatic dishwasher, which comprises, on a weight basis: (a) 5 to 35% sodium tripolyphosphate? (b) 2.5 to 20% sodium silicate; (c) 0 to 9% alkali metal carbonate; (D) 0.1 to 5% detersiye organic substance.

* AT

10 dispersible in water, stable towards chlorine bleach j.

(e) 0 to 5% of foam inhibitor stable against the chlorine bleach; 05 (f) a chlorine bleach in a proportion capable of supplying approximately 0.2 to 4% of active chlorine? (g) a thixotropic thickener in an amount sufficient to give the composition a thixotropy index of about 2.5 to 10; and (h) 0 to 8% sodium hydroxide? (i) potassium polyphosphates and a polyvalent metal salt of a long chain fatty acid, in amounts effective to increase the physical stability of the composition and the stability of the composition against variations in rheological properties in the weather ; and (j) additional water.

Related also to this particular aspect, the invention provides a method for cleaning dishes in an automatic dishwasher with an aqueous washing bath containing an effective proportion of the liquid detergent composition for automatic dishwasher (DLLVA). ) as described above. In this aspect of the invention, the DLLVA composition can be easily poured into the dispensing cup of the automatic dishwasher and, within a matter of seconds, thickens rapidly to return to its normal pasty state or the like to a gel.

In general, the effectiveness of a DLLVA composition is directly linked to: (a) the contents of active chlorine; (b) alkalinity? (C) solubility in the washing medium; and r * * 11 (d) inhibition of. foam.

It is preferable here that the pH of the DLLVA composition is at least 9.5, more preferably about 10.5 to 14.0, and at best about 11.5 at least. carbonate is also often needed here since it acts as a buffer helping to maintain the desired pH. However, an excess of carbonate should be avoided, as this may result in the formation of needle-like carbonate crystals, which would alter the stability, thixotropy and / or detergency of the DLLVA product, and also reduce the ability of the product. to be poured, for example from bottles with compressible tubes. Another function of caustic soda (NaOH) is to neutralize the foam inhibitor of the phosphoric ester or acid phosphonic ester type, if present. Typical proportions of NaOH and sodium carbonate in the DLLAV composition are, respectively, from about 0.5 to 6 percent by weight and from about 2 to 9 percent by weight, although it should be noted that Sufficient alkalinity can be provided by NaTPP and sodium silicate.

The NaTPP used in the DLLVA composition in an amount of about 8 to 35 percent by weight, preferably about 20 to 30 percent by weight, should preferably be free of heavy metals which tend to decompose or inactivating chlorine bleaches such as sodium hypochlorite which is preferred. The NaTPP can be anhydrous or hydrated, including the stable hexahydrate whose hydrata-'30 tion of 6 corresponds to about 18% by weight of water or more. Particularly preferred DLLVA compositions are obtained, for example, using a ratio of 0.5: 1 to 2: 1 by weight of anhydrous NaTPP to NaTPP hexahydrate, with ratios in the region of 1: 1 being particularly preferred.

12 * * * Inhibition of foam is important to increase the efficiency of the dishwasher and minimize the destabilizing effects that may occur due to the presence of excess foam in water during use, the foam can be reduced sufficiently by an appropriate choice of the type and / or the proportion of the deter-sive substance which is the main component producing foam. The degree of foaming also depends to some extent on the hardness of the washing water contained in the machine, so that a suitable adjustment of the proportions of NaTPP, which exerts a water softening effect, can help achieve the desired degree of foam inhibition. However, it is generally preferable to include a foam reducer or inhibitor stable against the chlorine bleach. Particularly effective compounds for this purpose are the acidic alkyl phosphonates corresponding to the formula: 20 0

II

HO - P - R

'25 available for example from BASF-Wyandotte (PCUK-PAE), and in particular the acidic alkyl phosphates corresponding to the formula: 30 0

II

HO - P - OR

GOLD

35 * · 4 13 available for example from Hooker (SAP) and Knapsack (LPKn-158), in which one of the R groups or the two R groups of each type of ester can independently represent a C 12 alkyl group ^ 20 '05 can use mixtures of these two types, or any other types stable with respect to the chlorine bleach, or mixtures of mono- and di-esters of the same type. A particularly preferred foam inhibitor is a mixture of 10 acid mono- and di phosphates (C 1 -C 4 alkyl) ^ 13 or 3 acid monostearyl / distearyl phosphates in the ratio of 1.2: 1 (from firms Knapsack or Ugine Kuhl-mann). If used, typical proportions of foam inhibitor in the composition are 0.1 to 5 percent by weight, preferably about 0.1 to 0.5 percent by weight, the ratio by weight of the detergent component (d) to the foam inhibitor (e) generally ranging from about 10: 1 to 1: 1, and preferably from about 5: 1 to 1: 1. Other anti-foaming agents which can be used include, for example, known silicones. Furthermore, an advantageous feature of the present invention is that many of the stabilizing agents, such as stearic acid salts such as aluminum stearate, are also effective as foam suppressants. Although any chlorine bleach can be used in the compositions of the present invention, for example a dichlo-ro-isocyanurate, dichloro-dimethylhydantoin or chlorinated trisodium phosphate, hypochlorites are preferred , for example potassium, lithium, magnesium and, in particular, sodium · The composition must contain sufficient chlorine bleach to provide about 0.2 to 4.0% by weight of active chlorine, as determined, for example, by acidifying 100 14 * * · parts of the composition with an excess of hydrochloric acid. A solution containing about 0.2 to 4.0% by weight of sodium hypochlorite contains or provides about the same percentage of active chlorine. A content of 0.8 to 16% by weight of active chlorine is particularly preferred. For example, it is advantageous to use a sodium hypochlorite solution (NaOCl) containing approximately 11 to approximately 13% of active chlorine in proportions of approximately 3 to 20%, preferably of approximately 7 to 12%. .

Sodium silicate, which provides alkalinity and provides protection for hard surfaces, such as varnishes and patterns from fine porcelain, is used in the composition in an amount ranging from about 2.5 to 20 percent. by weight, preferably from about 5 to 15 percent by weight. The sodium silicate is generally added in the form of an aqueous solution, preferably having an Na 2 O: SiO 2 ratio of about 1: 2 to 1: 2.8.

The detersive substance useful here must be stable in the presence of the chlorine bleach, especially a bleach hypochlorite, and those which are preferred are water dispersible anionic organic surfactants of the amine oxide type. , phosphine oxide, sulfoxide or betaine. They are used in proportions of from about 0.1 to 5%, preferably from about 0.3 to 2.0%. Surfactants which are particularly preferred here are the mono- and / or di (linear or branched c14 'c14 alkyl) - (diphenyl oxide) -mono- and / or disulfates or di-sulfonates of alkali metals , commercially available, for example under the designation DOWFAX (registered trademark) 3B-2 and DOWFAX 2A-1. In addition, the surfactant must be compatible with the other ift-35 ingredients of the composition. Other suitable surfactants include the primary alkyl sulfates, alkyl sulfonates and alkylarylsulfonates and the sec. Alkyl sulfates. Examples are the sodium alkyl sulfates Cjo ~ Ci8 such as Ie sodium dodecyl sulfate and 05 (tallow alkyl) sodium sulfate; C 2 -C 18 sodium alkanesulfonates such as sodium hexadecyl-1-sulfonate; and sodium (C1-C2 alkyl) benzenesulfonates such as sodium dodecylbenzenesulfonates. The corresponding potassium salts can also be used.

As other suitable surfactants or detergents, surfactants of the amine oxide type typically have the structure R <3R ^ N = 0, where each R represents

^ 1 a lower alkyl group, for example methyl, and R

15 represents a long chain alkyl group having 8 to 22 carbon atoms, for example a lauryl, myristyle, palmityl or cetyl group. Instead of an amine oxide, a corresponding surfactant of the phosphine oxide R2R1P0 or sulfoxide RR1S0 type can be used.

Betaine surfactants typically have the structure R2R1N-R'C00 "', where R' represents a lower al-kylene group having 1 to 5 carbon atoms. Particular examples of these surfactants are lauryl oxide dimethyl-amine, myristyl-dimé-thyl-amine oxide, the corresponding phosphine and sulfoxide oxides, and the corresponding betaines, including dodecyl dimethyl ammonium acetate, tetradecyl diethyl ammonium pentanoate , hexadecyl-dimethyl-ammonium hexanoate, etc. To ensure biodegradability, the alkyl groups of these surfactants must be linear, and such compounds are preferred.

Surfactants of the above type, all being well known in the art, are described for example ~ 35 pie in the patents of E. ü. A. No. 3 985 668 and. · "T", * * 16 4 271 030.

Thixotropic thickeners, i.e. thickeners or suspending agents which impart thixotropic properties to an aqueous medium, are known in the art and can be organic or mineral, water soluble, dispersible in water. 'water or colloidogens, and monomers or polymers, and they must of course be stable in the present compositions, for example stable towards high alkalinity' and chlorine bleaches such as hypochlorite sodium. Those which are particularly preferred generally comprise colloidogenic mineral clays of the smectite and / or attapulgite types. These materials have generally been used in proportions of about 1.5 to 10, preferably 2 to 5, percent by weight to impart the desired thixotropic properties and Bingham plasticity to the DLLVA compositions previously described in the Above-mentioned applications of Deman-20 deresse G3-2 116 199 A and GB-2 140 450 A. One of the advantages of the DLLVA compositions of the present invention resides in that the desired thixotropic properties and the Bingham plasticity character can be obtained, in the presence of the polyphosphates of potassium-25 and the metal salts of fatty acids used as stabilizers in the present invention, with lower proportions of thixotropic thickeners. For example, proportions of colloidogenic mineral clays of the smectite and / or attapulgite types included in the range of approximately 0.1 to 0.5%, preferably 0.2 to 0.4%, and in particular 0.25 to 0.30% are generally sufficient to obtain the desired thixotropic properties and Bingham plasticity when used in combination with potassium polyphosphates and metal salts of fatty acids serving as physical stabilizers.

Smectite clays include montmorillonite (bentonite), hectorite, attapulgi-05 te, smectite, saponite ,. etc. Montmorilloni-tes are preferred and are available under trademarks such as Thixogel (registered trademark) No. 1 and Gelwhite (registered trademark) GP, H, etc., from Georgia Kaolin Company; and 10 ECCAGUM (registered trademark) GP, H, etc., from Luthern Clay Products. Attapulgites include materials available commercially under the trademarks Attagel (registered trademark), i.e., Attagel 40, Attagel 50 and Attagel 150, 15 from Engelhard Minerais and Chemicals Corporation. Mixtures of the smectite and attapulgite types in weight ratios of 4: 1 to 1: 5 are also useful here. Thickening or suspending agents of the foregoing types are well known in the art, for example, being described in the U.S. patent. A. No. 3,985,668 mentioned above. Abrasives or polishing agents should be avoided in DLLVA compositions as they can damage the surface of fine dishes, crystal and the like.

It is evidently necessary that the water is contained in the present compositions in a proportion neither too high so as not to cause an excessively low viscosity and excessive fluidity, nor too low as not to cause an excessively high viscosity and poor capacity. at flow, the thixotropic properties being reduced or destroyed in both cases. It is easy to determine this proportion by routine experimentation in any particular case, and it generally ranges from about 30 to 55 percent by weight, preferably about 3%. *> -x 18 ron 30 to 65 percent by weight, The water should also preferably be deionized or softened.

So far, the description of the DLLVA product is, unless otherwise indicated, in accordance with that of the 05 compositions disclosed by the abovementioned United Kingdom patent applications GB-2 116 199 A and GB-2 140 450, which are dedicated to the Applicant .

The DLLVA products of UK patent applications GB-2 116 199 A and GB-2 140 450 show improved rheological properties, as assessed by determining the viscosity of the product as a function of the shear rate . These compositions had a viscosity higher than a low shear rate and a viscosity lower than a high shear rate, the results showing that effective fluidization and gelling occur largely between the limits of the shear rates encountered in dishwashers. currents. In practical terms, this means that, compared to the liquid or gel DLVA products of the prior art, the pouring and processing characteristics are better and that there are also less losses in the cup. machine vending machine. For applied shear rates corresponding to 3 to 30 rpm, the viscosities (Brook-field) range correspondingly from approximately 10 to 30 Pa.s to approximately 2 to 6 Pa.s, as measured at room temperature using a Brookfield LVT viscometer after 3 minutes using a No. 4 softcover one day after manufacture. A shear rate of 7.4 s-1 corresponds to a spindle speed of approximately 3 rpm. An increase in shear rate of about ten times causes a reduction in viscosity of about 3 to 9 times. With 35 DLVA gels of the prior art, the corresponding reduction in viscosity was only about twice. In addition, with these compositions, the initial viscosity noted at approximately 3 rpm was only approximately 2.5 to 2.7 Pa.s. The compositions of the prior invention of the Applicant therefore have fluidification thresholds at lower shear rates and with significantly greater amplitudes in terms of additional increase in the shear rate as a function of the further reduction in viscosity. This property of the DLLVA products of the prior invention is expressed by a thixotropy index (IT) which is the ratio between the apparent viscosities at 3 rpm and 30 rpm. The prior compositions have an IT of 2 to 10. The tested DLLVA compositions exhibited a rapid and massive return to the consistency of the previous quiescent state when the shear force ceased to be applied.

The present invention is based on the discovery that the physical stability, i.e. resistance to phase separation, sedimentation, etc., of aqueous liquid DLVA compositions from UK patent applications Uni GB-2 116 199 A and GB-2 140 450 A and French patent application 86.082 87, can be significantly improved, or at least not be adversely affected while the stability against variations in rheological properties over time and with temperature, adding to the composition of potassium polyphosphates in a small but effective proportion and a metal salt of a long chain fatty acid in small but effective proportions.

To illustrate, by way of example, the improvement in the rheological properties, it has been observed that at low shear rates, for example at a spindle speed of approximately 3 rpm, the bulk viscosities can often be increased two to three times by incorporating potassium polyphosphates in an amount as small as 1 to 2% or less and the metal salt of fatty acid in an amount as small as 0.25% at 0.50% or less, as stabilizers. At the same time, physical stability can be improved to such an extent that even after twelve weeks or more, over temperature intervals ranging from near freezing to 40 ° C and above, the compositions containing the potassium polyphosphates and the metal salt of stabilizing fatty acids remain stable against variations in rheological properties over time and with temperature, and undergo no observable phase separation.

The potassium polyphosphates which can be used are generally commercially available. Particular examples of potassium polyphosphates are potassium tripolyphosphate (TPP), potassium pyrophosphate and potassium hexametaphos-phate. Potassium tripolyphosphate (TPP) is preferred.

The proportion of potassium polyphosphates which must be used to obtain the desired improvement in physical stability is a function of factors such as the nature of the fatty acid salt, the nature and the proportion of the thixotropy agent, detergent detergent, mineral salts, TPP sodium and other ingredients of the DLLVA product, as well as the planned storage and transport conditions.

The proportions of stabilizing potassium polyphosphates (50% active ingredient) that can be used are in the range of about 0.5 to 3.0%, preferably '' about 0.80 to 2.0%, and better still about 1.0 to 1.8%,

Preferred long chain fatty acids are higher aliphatic fatty acids having about 8 to about 22 carbon atoms preferably about 10 to 20 carbon atoms, and more preferably about 12 to 18 carbon atoms, including the carbon atom of the carboxyl group of the fatty acid. The aliphatic radical can be saturated or unsaturated and it can be straight or branched. Straight chain saturated fatty acids are preferred. Mixtures of fatty acids, such as those from natural sources, such as tallow fatty acid, coconut fatty acid, soy fatty acid, etc., or sour sourced, may be used. synthetics that are available from industrial manufacturing processes.

Thus, examples of the fatty acids from which the polyvalent metal salts can be prepared include, for example, decanox-20 acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid , oleic acid, eicosanoxque acid, tallow fatty acid, coconut fatty acid, soy fatty acid, mixtures of these acids, etc. Stearic acid and mixed fatty acids are preferred.

Preferred metals are the polyvalent metals of Groups lla, Ilb and Illb, such as magnesium, calcium, aluminum and zinc, although other polyvalent metals can be used, including those of Groups Ilia , Va, VEa, Via, Vlla, Ib, IVb, Vb, VIb and VIII of the Periodic Table of the Elements, Particular examples of these other polyvalent metals include Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cd , Sn, Sb, Bi, etc. In general, the metals can be present in the divalent or pentavalent state. Preferably, the metal salts are used in their states of highest oxidation. Obviously, for the DLLVA compositions, as well as for all other applications where the composition of the invention comes into contact with or can come into contact with articles used for handling, preserving or serving food products or can come into contact with human beings or of animals or to be consumed by them, the metal salt must be chosen taking into account the toxicity of the metal. From this point of view, the calcium and magnesium salts are very especially preferred in that they. are generally harmless food additives.

Many of these metal salts are commercially available. For example, aluminum salts are available in the form of three acid residues, for example aluminum stearate in the form of aluminum tristearate Al (C ^ H ^ COO) 3. Salts with a single residue acid, for example aluminum monostearate Al (OH) _ (Cn_H_cC00) and salts with two acid residues, for example aluminum distearate

Al (OH) _H _,. C00) n, and mixtures of two or three 1 / JD 2 of these salts with one, two or three acid residues can be used for metals which, such as Al, have the value Lence +3, and mixtures of salts with one and two acid residues can be used for metals which, like Zn, have the valence +2. What is most preferable is to use in predominant proportions the salts with two acid residues of metals with valence +2, the salts with three acid residues of metals with valence +3, the salts with four residues d +4 valence metals acid and the five-residue salts of +5 valence metals. For example, at least 30%, preferably at least 50%, and more preferably 80 to 100%, of the total metal salt should be in the highest possible oxidation state, that is, where each of the potential valence sites is occupied by a fatty acid residue.

As mentioned above, the metal salts are generally commercially available, but can be produced easily, for example by saponifying a fatty acid, for example animal fat, stearic acid, etc., or the ester corresponding fatty acid, then treating with a hydroxide or oxide of the polyvalent metal, for example, in the case of an aluminum salt, with alum, alumina, etc.

Preferred stabilizers of the polyvalent metal fatty acid salt type are calcium stearate, i.e. calcium distearate, magnesium stearate, i.e. magnesium distearate, aluminum stearate, that is to say aluminum trestarate, and zinc stearate, that is to say zinc distearate. It is also advantageous to use metal salts of mixed fatty acids, such as naturally occurring acids such as copra acid as well as mixed fatty acids from industrial manufacturing processes, as these are important sources and inexpensive long chain fatty acids.

The proportion of potassium-25 polyphosphates and stabilizing fatty acid salts to be employed to achieve the desired improvement in physical stability is also a function of factors such as the nature of the fatty acid salt, the nature and the proportion of thixotropic agent, detersive compound, mineral salts, NaTPP and other ingredients of the DLLVA product, as well as the planned storage and transport conditions.

In general, however, the proportions of the polyvalent metal fatty acid salt stabilizers are in the range of about 0.10 t * 24 to 0.5%, preferably about 0. 2 to 0.4%, and better still about 0.25 to 0.30%. The use of potassium po-lyphosphates in combination with the metal salts of stabilizing fatty acids ensures long-term physical stability, stability against variations in rheological properties over time and with temperature, and absence of phase separation at rest or during transport, both at low temperatures and at high temperatures, as is necessary for a commercially acceptable product.

In another embodiment of the invention, the fatty acids themselves can be used as stabilizers in place of the metal salts of fatty acids described above.

For example, long chain fatty acids which can be used are higher aliphatic fatty acids having about 8 to about 22 carbon atoms, preferably about 10 to 20 carbon atoms, and more preferably about 12 to 18 atoms of carbon, including the carbon atom of the carboxyl group of the fatty acid. The aliphatic radical can be saturated or unsaturated and it can be straight or branched. Straight chain saturated fatty acids are preferred. Mixtures of fatty acids, such as those from natural sources, such as tallow fatty acid, coconut fatty acid, tallow fatty acid, etc., or synthetic sources can be used. from industrial manufacturing processes.

Examples of fatty acids which can be used as stabilizers include, for example, decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, behenic acid, oleic acid, ei-35 cosanoic acid, tallow fatty acid, co-* * 25 prah fatty acid, soy fatty acid, mixtures of these acids etc. Behenic acid, stearic acid and mixed fatty acids are preferred.

Many of these fatty acids are commercially available. For example, stearic acid and behenic acid are readily available. It is also advantageous to use mixed fatty acids, such as naturally occurring acids such as coconut fatty acid, as well as fatty acids from industrial manufacturing processes, as these are important and inexpensive sources long chain fatty acids. The sodium and potassium salts of fatty acids can also be used as stabilizers.

The proportion of stabilizing fatty acids, and / or their sodium or potassium salts, which can be used is within the same range as that mentioned above with respect to the metal salts of fatty acids.

From the examples which are given below, it will be seen that, depending on the proportions and types of physical stabilizers and thixotropy agents, the addition of potassium polyphosphates and fatty acid salt not only increases physical stability, but also, in some cases, produces a simultaneous increase in apparent viscosity and provides stability against variations in rheological properties over time and / or with temperature, 30 Physical stabilizers are added just before adding the thickening clay. Excluding the chlorine bleach, the total concentration of the salts (NaTPP, sodium silicate and carbonate) in the composition is generally about 20 to 50 percent by weight, 3 to 3%. preferably about 30 to 40 percent by weight,

A preferred method for mixing the ingredients of the DLLVA compositions consists in first of all forming a mixture with the water, the suppressor of soft-rv 05 se, the detergent, the physical stabilizing agents (potassium tripolyphosphate and fatty acid salt ) and the thixotropy agent, for example a clay. These ingredients are mixed together under high shear conditions, preferably starting at room temperature, to produce a uniform dispersion. The remaining ingredients are introduced into this premixed portion under low shear mixing conditions. For example, place the required amount of premix in a low shear mixer, then add the remaining ingredients, while mixing, either one at a time or all at the same time. Preferably, the ingredients are added one after the other, although it is not necessary to complete the addition of all of an ingredient before starting to add the next ingredient. In addition, one or more of the ingredients can be divided into portions and added at different times. Good results are obtained by adding the remaining ingredients in the following order of success: sodium hydroxide, alkali metal carbonate, sodium silicate, sodium tripolyphosphate (hydrated), sodium tripolyphosphate (anhydrous or limited to 5% water), bleaching agent (preferably sodium hypochlorite) and sodium hydroxide -> - dium · Other conventional ingredients may be included in these compositions in small proportions, in generally less than about 3 percent by weight, such as perfume, hydrotropes such as sodium benzene, toluene, xylene and cumene sulfonates, preservatives, dyes and pigments, etc., all of which must of course be stable against the bleaching agent and the high alkalinity (properties common to all the ingredients). Particularly preferred coloring materials are chlorinated phthalocyanines and aluminum polysulfides. minosilicates which give, respectively nt, pleasant green and blue hues. Ti02 can be used to whiten or neutralize degraded shades.

The liquid DLVA compositions of the present invention are readily employed in a known manner for washing dishes, kitchen utensils and the like in an automatic dishwasher fitted with a suitable detergent dispenser, in an aqueous bath. washing containing an effective amount of the composition.

Although the invention has been described particularly in relation to its application to liquid detergent products for automatic dishwashers, it will be obvious to any person normally versed in the subject that the advantages which one obtains by addition of potassium tripolyphosphate and metal salt of long chain fatty acid, namely better physical stability of the thixotropic suspension based on clay and better stability against variations in rheological properties over time, s apply equally well to other thixotropic clay suspensions, such as the scouring paste compositions which are described in the patent of E, ü. A, cited above No. 3,985,668, The invention can be practiced in various ways and a number of particular embodiments will be described by way of illustration in the following examples where all the amounts and proportions indicated are expressed by weight * * * 28 relative to the weight of the composition, unless otherwise indicated.

EXAMPLE 1

In order to demonstrate the effect of tripolyphospha-05 te of potassium and metal salts as stabilizers, liquid DLVA compositions are prepared. with various proportions of potassium tripolyphosphate (TPP) and stabilizing fatty acid salt, and various proportions of thickening thixotropic clay, as follows:

Thixotropic clay compositions

Percent "_ Deionized water (adjusted to 100%) 33.06 to 42.55 15 Monostearyl phosphate 0.16

Dowfax 3B2 (0.8 45% aqueous solution of monodecyl - / <3idecyl- (diphenyl oxide) - Na disulfonate) potassium TPP (50% active ingredient 0-1.6 20)

Aluminum stearate 0-0.4

Pharmagel H 0.25-2.0

These products are mixed under strong shear at room temperature and then the following ingredients are added at room temperature.

Caustic soda solution (50% 2.2 to 10.2 NaOH) 30 Anhydrous sodium carbonate 5.00

Sodium silicate, 15.74 solution 47.5% Na20 ratio; Si02 = 1: 2.4 TPP sodium hexahydrate (The.rm- 12.00 35 phos N hexa) * »29 TPP sodium (substantially anhy - '12.00 dre, that is to say 5%, and in particular 3%, of humidity) (Thermphos NW) 05 Sodium hypochlorite solution 9.00 (Il% of active chlorine)

Liquid DLVA compositions are prepared l to 9 and their density, their apparent viscosity at 3 to 30 rpm and their physical stability (phase separation) are determined at rest and in a transport test. The results obtained are presented in the following Tables I and II.

From the results reported in Tables I and II, the following conclusions are reached.

The incorporation of 0.1% aluminum stearate into a formula containing 1.25% of Pharma-gel H, Test 2 (control), leads to an increase in physical stability without altering the apparent viscosity, as is sees it by comparison with Test 1 (witness).

The incorporation of 0.4% aluminum stearate into a formula containing 0.25% of Pharma-25 gel H, Test 3 (control), leads, compared to Tests 1 (control) and 2 (control), to an increase in physical stability and apparent viscosity. The use of a higher content, of 0.4% f in aluminum stera-te, Test 3 (control), also makes it possible to reduce the clay content which goes from 1.25% for the Test 2 (control) at 0.25% for Test 3 (control), while maintaining the physical stability of the composition.

The results in Table I also show that the simultaneous use of about 1.6% TPP of 4 p potassium in a formula containing 0.5% or 0.3% of Pharmagel H, Tests 4 and 6 , does not adversely affect the physical stability of the compositions while ensuring stabilization against variations in 05 rheological properties over time.

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(1) Measured with a pin N ° 4 bare end of 3 ιηΐ ^ nutes on samples aged 24 hours, (2) By weight (TA = 5 room temperature ^ 20 05 Î2 ° C), (3) By weight ( TA = ambient temperature - 20 -2PC), (4) Liquid separation measured after 6 weeks and 2000 km in a private automobile (by weight, 10 in a plastic bottle), EXAMPLE 2

In order to determine the variations in the rheological properties over time, the learned viscosities of the compositions of Tests 2 to 7 of Example 1 are measured at 3 rpm and 30 rpm after 1 day, 2 weeks, 4 weeks, 6 weeks and 12 weeks. The results obtained are reported in Table II below.

The results of Table II show that the addition of 1.6% (Tests 4, 6 and 7) leads to a powerful stabilization against variations in rheological properties over time, without altering the physical stability of the compositions at contents of 25 Pharmagel H clay from 0.3 to 0.5%, in comparison with Tests 3 (control) and 5 (control) which manifest significant variations in apparent viscosity over time.

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* i - w 34 EXAMPLE 3

Following the same general procedures as in Example 1, the thixotropic liquid DLVA composition with the following gel appearance is prepared; 05 ingredient Proportion (¾ by weight)

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

Dowfax 3B-2 0.36

Thermphos NW 12.0 "... Thermphos N hexa 12.0 TPP potassium (50% AI) 1.6 15 Aluminum stearate 0.25

Anhydrous sodium carbonate 4.9

Caustic soda solution (50% NaOH) 6.2

Pharmagel H 1.25 20 Sodium hypochlorite solution (11%) 1.0

Water the rest pH s 13 to 13.4 1 2 3 4 5 6 7 8 9 10 11

We can also add to the formula 2 minor proportions of perfume / color, etc.

3

It is found that the composition has 4 good thixotropic properties, good stability 5 against phase separation and good stability 6 against variations in rheological properties over time.

8 EXAMPLE 4 9

A thixotropic liquid DLVA composition with gel appearance is prepared as in Example 3, with the difference that the potassium TPP is replaced by 1 tsp.

35 1.6% potassium pyrophosphate (50% AI). Results similar to those of Example 3, Example 5 are obtained. Following the same general procedures as in Example 1, the thixotropic liquid DLVA composition with the appearance of next gel;

Ingredient Proportion (% by weight) 10 Sodium silicate (solution with 47.5 S ratio

Na20: Si02 - 1: 2.4) 7.48

0.16 monostearyl phosphate

Dowfax 3B-2 0.36 - 15 Thermphos NW 12.0

Thermphos N hexa 12.0 TPP potassium (50% AI) 1/6

Stearic acid 0.4

Anhydrous sodium carbonate 5.0 20 Caustic soda solution (50% NaOH) 3.1

Pharmagel H 0.5

Sodium hypochloçite solution (11%) 1.0 25 Water the rest

It is also possible to add to the formula minor proportions of perfume, dye, etc., 1 EXAMPLE 6

By following the same general procedures as in Example 1, the thixotropic liquid DLVA composition is prepared with the following gel appearance; ί β * 36

Ingredient Proportion (% by weight)

Sodium silicate (47.5% solution 05 ratio Na20: Si02 = 1: 2.4) 7.48

0.16 monostearyl phosphate

Dowfax 3B-2 0.36

Thermphos NW 12.0

Thermphos N hexa 12.0 10 TPP potassium (50% AI) 1.6

Behenic acid 0, 2

Anhydrous sodium carbonate 5.0

Caustic soda solution (50% NaOH) 6.2 15 Pharmagel H 0.5

Sodium hypochlorite solution (11%) 1.0

Water the rest. 1

Minor proportions of perfume, color, etc. can also be added to the formula.

Claims (26)

1. An aqueous thixotropic liquid composition comprising a clay thixotropy agent, potassium polyphosphate and at least one long chain fatty acid or a metal salt of a long chain fatty acid, said potassium polyphosphate and said acid. fatty or metallic salt of fatty acid being present in an amount effective to increase the physical stability of the composition and the stability of the composition against variations in rheological properties over time, also comprising water and at least one ingredient selected from organic detergents, pH modifiers, chlorine bleaches, detergency builders, sequestering agents, foam inhibitors, abrasive particles and mixtures thereof. 2. Composition according to claim 1, characterized in that it comprises at least one of potassium tripolyphosphate, potassium pyrophosphate and potassium hexametaphosphate. 3. Composition according to claim 1 / characterized in that the metal salt comprises a polyvalent metal salt from Group II, III or IV of the 25 Periodic Table of the Elements of a long chain fatty acid having about 8 to 22 carbon atoms or of a mixture of two or more such fatty acids, 4. Composition according to claim 1, characterized in that the polyvalent metal is aluminum, zinc, calcium or magnesium. 5. Composition according to claim 1, characterized in that the metal salt of fatty acid is aluminum stearate, calcium stearate or magnesium stearate. 6. Aqueous thixotropic composition for automatic dishwashers ^ comprenant 38, comprising approximately by weight: (a) 5 to 35% sodium tripolyphosphate; (b) 2.5 to 20% sodium silicate; 05 (c) o 9% alkali metal carbonate; (d) 0.1 to 5% of organic detergent dispersible in water, stable with respect to the chlorine bleach; (e) 0 to 5% stable foam inhibitor against the chlorine bleach; (f) a chlorine bleach in a proportion capable of providing approximately 0.2 to 4% of active chlorine; (g) a thixotropic thickener in an amount sufficient to give the composition a thixotropy index of about 2 to 10; (h) 0 to 8% sodium hydroxide? (i) an agent for stabilizing physical and rheological properties comprising at least one of potassium tripolyphosphate, potassium pyrophosphate and potassium hexametaphosphate, and a polyvalent metal salt of a fatty acid containing long chain; and (j) additional water. 7. Composition according to claim 6, characterized in that the stabilizing agent comprises potassium tripolyphosphate. 8, Composition according to claim 6, characterized in that the stabilizing agent comprises potassium pyrophosphate. 9. Composition according to claim 6, characterized in that the stabilizing agent comprises potassium hexametaphosphate. 10. Composition according to claim 6, characterized in that the stabilizing metal salt 35 is a polyvalent metal salt of an alipha- * "39 *" ç> tick fatty acid having about 8 to 22 carbon atoms, il. Composition according to Claim 6f, characterized in that the acid has approximately 12 to 18 carbon atoms, 12. Composition according to claim 6f characterized in that the stabilizing metal salt is an aluminum salt or a zinc salt of said fatty acid. 13. Composition according to claim 6, 10 characterized in that the stabilizing metal salt is aluminum stearate. 14. Composition according to claim 6, characterized in that the stabilizing metal salt is zinc stearate. 15. Composition according to claim 6, characterized in that it contains 0.1 to 0.5 percent by weight of clay, 0.5 to 3.0 percent by weight of potassium polyphosphate and 0.1 to 0.5 percent by weight of metal salt of fatty acid. 16. Composition according to claim 6, characterized in that the thixotropic thickener (g) is a colloidogenic mineral clay. 17, An aqueous thixotropic composition for an automatic dishwasher, comprising approximately by weight: (a) 5 to 35% of tripolyphosphate; (b) 2.5 to 20% sodium silicate; (c) 0 to 9% alkali metal carbonate; (d) 0.1 to 5% organic detersive material dispersible in water, stable with respect to the chlorine bleach; (e) 0 to 5% of foam inhibitor stable against the chlorine bleach; (f) a chlorine bleach in a pro ~ -35 portion capable of supplying approximately 0.2 to 4% of chlorine ac- 40 3 *.>. "" · Ç, tif; (g) a thixotropic thickener in a proportion sufficient to give the composition nn thixotropy index of approximately 2 to 10; 05 (h) 0 to 8% sodium hydroxide j (i) a stabilizing agent for physical and rheological properties comprising potassium polyphosphate and a polyvalent metal salt of an aliphatic fatty acid containing 12 to 18 carbon atoms; 10 and (j) additional water. 18. Composition according to claim 17, characterized in that it comprises potassium tripolyphospha-te. 19. Composition according to claim 17, characterized in that it comprises potassium pyrophosphate. 20. Composition according to claim 17 / characterized in that the stabilizing metal salt 20 is an aluminum salt or a zinc salt of said fatty acid. 21. Composition according to Claim 17 / characterized in that the stabilizing metal salt is aluminum stearate · 22. Composition according to claim 17, ^ _ characterized in that the stabilizing metal salt is zinc stearate. 23. Composition according to claim 17, characterized in that it contains 0.2 to 0.4 per cent by weight of clay, 0.8 to 2.0 per cent by weight of potassium polyphosphate, and 0, 2 to 0.4 percent by weight of metal salt of fatty acid, 24. Composition according to claim 17, characterized in that the thixotropic thickener (gj) is a colloidogenic mineral clay. 41 1 'Λ * 1, * * * 25, A method for cleaning dishes soiled in an automatic dishwasher, characterized in that it consists in bringing the soiled dishes in contact, in an automatic dishwasher, with an aqueous washing bath in which is dispersed an effective amount of the composition of claim 6. 26. Method for cleaning soiled dishes in an automatic dishwasher, characterized in that it consists in bringing the soiled dishes in contact, in an automatic dishwasher, with an aqueous washing bath in which is dispersed a effective amount of the composition of claim 17.