PT100538A - Phosphate-free gel type detergent compositions for automatic dishwashers containing a low molecular weight polyacrylate - Google Patents

Abstract

This invention relates to an aqueous thixotropic liquid comprising water, a thixotropic thickener, means to increase the physical stability of the composition, a chlorine-based bleach and a detergent structuring agent, the said composition containing alkali metal and alkaline earth metal components in sufficient quantity to obtain a pH of at least 11.2 when 10 grams of the composition are added to one litre of water, in which the composition provides improved rheological behaviour and physical stability with little residue remaining in the vessel and a new aesthetic effect with a translucent appearance.

Description

FUMMING OF THE INVENTION The present invention relates to non-aqueous liquid gel dishwasher detergent compositions which are phosphate-free with equivalent cleaning performance and physical stability with improved characteristics when compared to phosphate-containing compositions.

Commercially available household dishwashing detergents provided in the form of powder have several disadvantages, eg non-uniform composition, expensive operations required to manufacture them, tendency to agglomerate in high humidity storage resulting in the formation of agglomerates which are difficult to disperse, formation of dust which is a source of irritation, in particular for users suffering from allergies, and tendency to form cakes in the dishwasher dispenser. The liquid forms of such compositions, however, can generally not be used in automatic dishwashers.

Recent research and development activities have directed your attention to the gel form or " thixotropic " of such compositions, e.g. by looking for cleaning agents and automatic dishwashing products characterized as thixotropic pastes. The automatic dishwasher products thus provided are primarily subject to objections because they are insufficiently viscous to remain " anchored "in the dishwasher dispenser cavity. Ideally, the thixotropic cleaning compositions should be highly viscous in a quiescent state, of a Bingham plastic nature and have relatively high yield values. When subjected to shear stresses, however, such as shaking in a container or compression vessel to pass through an orifice,

should rapidly fluidize and, upon cessation of applied shear stress, revert rapidly to the high viscosity Bingham plastic state. Stability is likewise of prime importance, that is, there should be no significant evidence of phase separation or leakage after long rest. The provision of automatic dishwasher compositions in gel form having the above-described properties has hitherto been problematic, particularly with respect to the compositions for use in household dishwashers. For effective use, it is generally recommended that the automatic dishwasher detergent contains (1) sodium tripolyphosphate (NaTPP) to soften or bond the hard water minerals and to emulsify and / or decompose peptides; (2) sodium silicate to provide the alkalinity required for effective detergency and to provide protection to the glazed fine porcelain and with decorations; (3) sodium carbonate, generally considered optional, to increase alkalinity; (4) a chlorine-releasing agent to assist in the elimination of soil spots leading to water staining and film formation; and (5) antifoams / surfactants to reduce the foam, thereby increasing the effectiveness of the machine and providing the necessary detergency. See, for example, SDA Detergents in Depth, " Formulations Aspects of Machine Dishwashing ", Thomas Oberle (1974). Cleaning agents approaching the compositions described above are mostly liquids or powders. The combination of such gel ingredients effective for use in home machines has experienced difficulties. Generally, such compositions omit the hypochlorite bleach, as it tends to react with other chemically active ingredients, particularly the surfactant. Thus, U.S. Patent 4,158,308 discloses thixotropic automatic dishwashers containing a suspending agent, and 4

e.g. CMC, synthetic clays or the like; inorganic salts including silicates, phosphates and polyphosphates; a small amount of surfactant and a foam suppressant. The bleach is not disclosed. U.S. Patent No. 4,147,650 is somewhat similar, optionally including Cl- bleach (hypochlorite) but no surfactant or antifoam agent. The product is further described as a detergent sludge with no apparent thixotropic properties. U.S. Patent No. 3,985,668 discloses abrasive polish cleaners of gel-like consistency which contain (1) suspending agent, preferably types of tackifying clay and attapulgite; (2) abrasive, e.g. silica sand or perlite; and (3) filler comprising low density, expanded perlite powder polymers and the like having buoyancy and, therefore, stabilizing effect on the composition, in addition to serving as bulking agents, substituting therefor otherwise available water for the formation of the undesired supernatant layer due to leakage and phase destabilization. The essential ingredients are the foregoing.

Optional ingredients include chlorine bleach, surfactant and bleach-stable buffer, e.g., silicates, carbonates and monophosphates. Structurers, such as NaTPP, may be included as other optional ingredients to provide or supplement the non-structuring function provided by the buffer, not exceeding the amount of such a builder 5% of the total composition, according to the patent. The maintenance of the desired (higher) pH levels is achieved by the buffer / builder components. High pH is reported as being able to minimize the decomposition of chlorine bleach and the undesired interaction between the surfactant and the surfactant.

bleach. When present, NaTPP is limited to 5%, as stated. The foaming agent is not disclosed.

In UK Patent Application GB 2 116 199A and GB 2 140 450A, both assigned to Colgate-Palmolive, there are disclosed automatic automatic dishwasher detergent compositions having desirable properties characterizing the gel type thixotropic structure and including each of the various ingredients needed for effective detergency inside an automatic dishwasher. The aqueous automatic dishwashing detergent composition, usually of the gel type, having thixotropic properties includes the following ingredients, on a weight basis: (a) 5 to 35% alkali metal tripolyphosphate; (b) 2.5 to 20% sodium silicate; (c) 0 to 9% alkali metal carbonate; (d) 0.1 to 5% stable chlorine bleach, water dispersible organic detergent active material; (e) 0 to 5% chlorine bleach stable antifoam agent; (f) chlorine bleach compound in an amount to provide 0.2 to 4% available chlorine; (g) thixotropic thickening agent in an amount sufficient to yield the composition having a thixotropy content of 2.5 to 10; (h) sodium hydroxide, as necessary, to adjust the pH; and (i) equilibrium water.

The automatic dishwasher detergent compositions thus formulated are of low foaming; are readily soluble in a washing medium and more effective at 6

pH values better conducive to improved cleaning performance, namely, pH = 10.5-14. The compositions usually have gel consistency, ie, of highly viscous, opaque jelly material having a plastic character of Bingham and, therefore, relatively high yield values. Accordingly, a defined shear force is required to initiate or increase the flow. Under such conditions, the composition is readily fluidized and readily dispersed. When the shear force is discontinuous, the flow composition returns rapidly to a high viscosity, very close to the Bingham plastic state approaching its previous consistency. U.S. Patent No. 4,511,487, issued April 16, 1985, describes a low foaming detergent paste for dishwashers. The patented tixo-tropic cleaning agent has a viscosity of at least 30 Pa * s at 20 ° C as determined with a rotary viscometer at a spindle speed of 5 revolutions per minute. The composition is based on a mixture of finely divided sodium metasilicate hydrate, an active chlorine compound and a thickening agent which is a hectorite-type veneer silicate. Small amounts of nonionic surfactants and alkali metal carbonates and / or hydroxides may be used.

The compositions of the present invention have overcome many of the aforementioned deficiencies while providing compositions which are phosphate free and hence environmentally safe.

Very surprisingly, it has been found that the phosphate-free compositions of the present invention while providing compositions which are environmentally safe also produce the

desired cleaning performance. They also provide remarkable stabilization against changes over time in rheological properties.

Accordingly, it is an object of the present invention to provide liquid automatic dishwasher detergent compositions having excellent cleaning performance, improved physical stability and improved rheological properties and having a density of 1.20 to 1.44 g / L while being phosphate free and environmentally safe. It is yet another object of the present invention to provide compositions having satisfactory levels of chlorine with satisfactory stability.

More specifically, it is an object of this invention to provide excellent cleaning performance and improved physical stability of aqueous liquid automatic dishwasher detergent pastes or gels which are phosphate-free.

SUMMARY OF THE INVENTION

These and other objects of the invention, which will become more readily understood from the following summary and the detailed description of the invention and its preferred embodiments, are achieved by a phosphate-free structured aqueous liquid automatic dishwashing detergent composition which contains a stabilizing agent such that when the composition is added to an aqueous wash bath at a concentration of 10 grams per liter the bath has a pH of at least 11.2. 8

According to a particularly preferred embodiment, the present invention provides a gel-type viscoelastic aqueous automatic dishwashing detergent composition having a three-dimensional structure and comprising, in a weight ratio: (a) 1 to 20% of at least one polyacrylate of non-cross-linked low molecular weight; (b) 0 to 20% alkali metal silicate; (c) 1 to 15% of at least one phosphate-free detergent builder salt, such as an alkali metal carbonate; (d) 0 to 8% of alkali metal hydroxide; (e) 0 to 5% of organic detergent active material stable to chlorine bleach; (f) 0 to 1.5% stable foam dimer; (g) chlorine bleach compound in an amount to provide 0.2 to 4% available chlorine; (h) 0.1 to 5% of a polymeric thickening agent having a molecular weight of at least 500,000; (i) up to 2% of a metal salt of a long chain fatty acid or a fatty acid in an amount effective to increase the physical stability of the composition; (j) 0 to 8% sodium sulfate; (k) equilibrium water, wherein the water is substantially bound by hydration to the polymeric thickening agent, so that the composition is substantially free of unbound water and the total amount of alkali metal silicate (b), alkali metal carbonate (c ) and alkali metal hydroxide (d) produces a sufficiently high pH such that when the composition is diluted in a 9

aqueous wash to produce a concentration of 10 grams per liter, the pH of the aqueous water bath becomes at least 11.2 and the concentration of the alkali metal, alkali metal hydroxide and alkali metal hydroxide builder salt is preferably less than which is 25% by weight, more preferably less than 22% by weight, and still more preferably by less than 20% by weight, and the residual amount of the composition remaining in a polyolefin container vessel after the polyolefin composition is drained from the The composition is less than 5% by weight of the original amount of the composition in the container and more preferably less than 2% by weight. The invention also provides a method for cleaning crockery in an automatic dishwasher with an aqueous wash bath containing an effective amount of the above described automatic automatic dishwasher detergent composition. According to this aspect of the invention the liquid automatic dishwasher detergent composition can be readily poured into the dispenser cavity of the automatic dishwasher and will be sufficiently viscous to remain securely inside the dispenser cavity until it is again Cutting forces are applied, such as by spraying water from the dishwasher. It is known that the effectiveness of the automatic dishwasher detergent liquid is directly related to (a) levels of available chlorine; (b) alkalinity; (c) solubility of the washing medium; and (d) foam inhibition. According to the present invention, the types and amounts of the alkali components which are phosphate-free are selected such that when the composition is added to an aqueous washing bath 10

to produce a concentration of 10 grams of composition per liter of wash bath, the pH of the wash bath becomes at least 11.2, preferably at least 11.5, such as from 11.5 to 13.5, preferably from 11.5 to 12.5.

GENERAL DESCRIPTION OF THE INVENTION

The viscoelastic gel-like compositions of the present invention having a three-dimensional structure can generally be described as follows:

0 to 20% 0 to 20% 1 to 20% 0 to 8% 0 to 20% 0 to 20% 0 to 20% 0 to 20% 0 to 20%

Ingredient Sodium Sulphate Alkali Metal Silicate Anti Foam

Low molecular weight polyacrylate Phosphate free builder salt Alkali metal hydroxide Metal hypochlorite solution (13%) Fatty acid or fatty acid metal salt

Polymeric thickening agent Water

An organic detergent active material wherein the water in the composition is hydration-bonded to the polymeric thickening agent, so that the composition is substantially free of free water.

Accordingly, according to a particularly preferred embodiment of this invention, high alkalinity is achieved in a liquid automatic dishwasher detergent composition containing chlorine bleach, stabilized by 11 11

phosphate-free fatty acid salt, wherein the alkaline compounds include, on an active basis, based on the total composition, from 0 to 20 percent by weight of alkali metal silicate, from 0 to 8 percent by weight of alkali metal hydroxide, from 0 to 20 percent by weight of phosphate free builder salt, from 1 to 8% by weight of at least one low molecular weight uncrosslinked polyacrylate, from 0.1 to 5 percent by weight of polymeric thickening agent and optionally a metal hypochlorite, an antifoam agent and a detergent active material, wherein the pH of 1 liter of aqueous wash bath containing 10 grams of the composition is at least 11.2. The alkali metal silicate, such as sodium silicate, which provides alkalinity and protection of hard surfaces, such as glazes and porcelain decorations, is employed in an amount ranging from 1.0 to 20.0 percent by weight in a basis weight, preferably from 2.5 to 20 weight percent, in the composition. Sodium silicate is generally added in the form of an aqueous solution, preferably having a Na2 O: SiC ratio of from 1: 1.3 to 1: 2.8, especially preferably from 1: 2.0 to 1: 2.6 . At this point, it should be mentioned, especially sodium hydroxide and sodium hypochlorite, are also often added in the form of a preliminarily prepared aqueous dispersion or solution. The automatic automatic dishwasher composition contains from 1 to 20% by weight of a builder salt of alkali metal phosphate free detergent builder, more preferably from 2 to 20% by weight, and even more preferably from 3 to 20% on a weight basis, wherein the builder is usually an alkali metal carbonate, such as sodium carbonate or potassium carbonate.

Other builder salts that can be mixed with sodium carbonate are gluconates, phosphonates and nitriloacetic acid salts. In conjunction with the structuring salts, non-crosslinked polyacrylates of low molecular weight having a molecular weight of 1000 to 10000, more preferably of 2000 to 80,000, are optionally used. A polyacrylate. . Preferred low molecular weight is Sokalan PA30CL manufactured by BASF and having a molecular weight of 8000. Another sodium salt of a low molecular weight polyacrylate is Norasol LMW45ND which is also known as Acusol 445N and is manufactured by Noroshaas and has a molecular mass of 4500. Other useful low molecular mass non-crosslinked polymers are: Acusol 640D supplied by Rohm &Hass; Norosol QR1014 from Noroshaas which has a molecular weight GPC of 10,000; Norasol Al has a molar mass of 60,000. BASF's Sokalan PA30CL is most preferred because of its extremely high bleach stability of at least six months compared to the other listed low molecular mass polymers having all bleach stabilities less than six months. Sokalan PA30CL is a polyacrylate of a chemical structure similar to Norasol LMW45 which has been modified to have improved bleach stability believed to be by the elimination of heavy metals used in the synthesis of Sokalan PA30CL. Acusol 445N is an excellent dispersant for calcium carbonate which is formed during the washing process, where Acusol 445N controls the growth of the calcium carbonate crystal and helps to suspend the calcium carbonate in the wash bath. Another low mass polyacrylate polymer 13

I. . . Especially useful molecular weight is Good-Rite K-7058N which is a 90-100% neutralized sodium salt of a polyacrylate polymer having a molecular weight of 5800. K-7058N is a good dispersing agent for the calcium carbonate and an excellent structuring or sequestration agent for heavy metal ions, such as calcium or magnesium. A combination of Acusol 445N and K-7058N produces maximum accent to the non-structuring salt.

alkali metal phosphate, such as sodium carbonate. The chlorine stability of a composition made with a combination of Acusol 445 and Good-Rite K7058N is improved over those compositions made with either Acusol 445 or Good-Rite K7058N alone.

Another class of builders useful herein are the water insoluble aluminosilicates, both of the crystalline type and of the amorphous type. Various crystalline zeolites (ie, aluminosilicates) are described in U.S. Patent Nos. 1 504 168, U.S. Patent No. 4,409,136 and U.S. Patent Nos. 1,072,835 and 1 087 477. An example of useful amorphous zeolites here can be found in Belgian Patent No. 835,351. Zeolites generally have the formula: <20> x <A1203> y <SI02> x-WH2 ° where x is 1, y ranges from 0.8 to 1.2, and preferably is 1, z ranges from 1.5 to 3.5 or more, and preferably from 2 to 3, and w ranges from 0 to 9, preferably from 2.5 to 6, and M is sodium. A typical zeolite is type A or similar structure, type 4A being particularly preferred. Preferred aluminosilicates have calcium ion exchange capacities of 200 milliequivalents per gram or greater, i.e. 400 meq / g. Foam inhibition is important to increase the efficiency of the dishwasher and minimize the destabilizing effects that may occur due to the presence of excess

of foam into the washing tub during use. The foam may be sufficiently reduced by the appropriate selection of the type and / or amount of detergent active material, the main foam producing component. The degree of foam also depends in some way on the hardness of the washing water in the machine, whereby a suitable adjustment of the proportions of the organic or inorganic structure-pain salt having a water softening effect can assist in obtaining the desired degree of inhibition of foam. However, it is generally preferred to include a stable antifoam agent (decrease or inhibitor) to the chlorine bleach. Particularly effective alkyl esters of phosphoric acid of the formula:

HO-P-R

I

OR and especially the alkyl acid phosphate ethers of the formula:

II

HO-P-R

I

OR

In the above formulas, one or both of the R groups in each ester type may independently represent a C 12 -C 20 alkyl group or an ethoxylated &lt; 3 &gt;. The ethoxylated derivatives of each ester type, for example the condensation products of an ester moiety of from 1 to 10 moles, preferably from 2 to 6 moles, more preferably 3 or 4 moles, of ethylene oxide may also be used . Some examples of the foregoing compounds are commercially available, such as SAP products from Hooker and LPKN-158 from Knapsack. Mixtures of the two types, or any other types stable to chlorine bleach, or mixtures of mono- and diesters of the same type, may be employed. Particularly preferred is a mixture of acid phosphate esters of ethoxylated mono- and dialkyl alkyl or ethoxylated alkyl phosphate such as monostearyl / distearyl acid phosphate 1.2 / 1 and their condensates of 3 to 4 moles of ethylene oxide. When employed, proportions of 0 to 5 percent by weight, preferably 0.1 to 1.5 percent by weight, of antifoam agent in the composition are typical. Other antifoam agents which may be used include, for example, known silicones, such as those available from Dow Chemical. In addition, it is an advantageous aspect of this invention that many of the stabilizing salts, such as the stearate salts, for example sodium stearate, are also effective as antifoam agents.

While any chlorine bleach compound may be employed in the compositions of this invention, such as dichloroiso-cyanurate, dichloro-dimethyl-handantoin or chlorinated TSP, alkali metal or alkaline earth metal hypochlorite, eg potassium, lithium, magnesium, and especially sodium. The composition should contain sufficient chlorine bleach compound to provide 1.5 to 3.1% by weight of available chlorine as determined, for example, by acidifying 100 parts of the composition with excess hydrochloric acid. A solution containing 0.2 to 4.0% by weight of sodium hypochlorite (13% available chlorine) contains or provides roughly the same percentage of available chlorine. 0.8 to 1.6% of available chlorine is especially preferred. The detergent active material which may be useful herein should be stable in the presence of chlorine bleach, especially hypochlorite bleach, and organic anionic, amine oxide, phosphine oxide, sulfoxide or betaine water. Those of the dispersible surfactant type are preferred; the most preferred being the anionic ones mentioned above. They are used in amounts ranging from 0 to 16

5%, preferably from 0.1 to 5.0%. Particularly preferred surfactants herein are commercially available straight or branched chain alkali metal mono- and / or di (C 1 -C 14) -diphenyl oxide mono and / or disulfates, for example as DOWFAX 3B-2 and DOWFAX 2A-1. C 12 -C 12 -alkyl ether sulfates are suitable surface active agents. In addition, the surfactant should be compatible with the other ingredients of the composition. Other suitable surfactants include primary alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates and s-alkyl sulfates. Examples include sodium C alquilo-C sulf alkyl sulphates, such as sodium dodecyl sulfate and sodium tallow alcohol sulfate; sodium alkane (Cin-C) -sulfonates, such as sodium hexadecyl-1-sulfonate and sodium C.-C --benzenesulfonates, such as sodium dodecylbenzenesulfonates. The corresponding potassium salts may also be employed.

Like other suitable surfactants or detergents, the amine oxide surfactants are typically of the structure R2RN-> 0, wherein each R represents a lower alkyl group, for example methyl, and R3 represents a group long chain alkyl having from 8 to 22 carbon atoms, for example a lauryl, myristyl, palmityl or cetyl group. Instead of an amine oxide, a surfactant 1. 1 phosphor oxide R2R PO or RR sulphoxide SO2 may be employed. Betaine surfactants are typically of the structure R2R1N &lt; -R &quot; C00-, wherein each R represents a lower alkylene group having from 1 to 5 carbon atoms. Specific examples of such surfactants include lauryl dimethylamine oxide, myristyl dimethylamine oxide, the corresponding phosphine oxides and sulfoxides and the corresponding betaines, which include dodecyldimethylammonium acetate, tetradecyldiethylammonium pentanoate, hexadecyldimethylammonium hexanoate and the like. For biodegradability, the alkyl groups in these surfactants should be linear and such compounds are preferred.

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

Other useful surfactants are Chemy's Akipos which is a functional carboxylate terminated non-ionic surfactant; C12-C30-3EO ether sulfates; and alcohol sulphates

Thixotropic thickening agents, ie thickening agents for suspending agents which provide an aqueous medium with thixotropic properties, are known in the art and may be organic or inorganic, water soluble, dispersible or colloid forming in water, and monomeric or polymeric and should certainly be stable in such compositions, eg stable at high alkalinity and chlorine bleach compounds, such as sodium hypochlorite. These materials are generally used in amounts of from 0.1 to 4.0 percent by weight, preferably from 0.2 to 3.5 percent by weight, more preferably from 0.3 to 3 percent by weight, to confer the desired thixotropic properties and plastic character of Bingham. However, in the presence of the fatty acid metal salt stabilizers, the desired thixotropic and plastic Bingham properties can be obtained in the presence of lower amounts of the thixotropic thickening agents. Especially preferred are clays which form inorganic colloids of the estic and / or attapulgite types. For example, amounts of clays forming inorganic colloids of the ointment types and / or

attapulgite in a range from Ofl to 3%, preferably from 0.1 to 2.5%, especially from 0.1 to 2%, are generally sufficient to achieve the desired thixotropic properties and Bingham's plastic character when used in combination with the physical stabilizer.

Estic clays include montmorillonite (bento-nite), hectorite, esophageal attapulgite, saponite, and the like. Montemorilonite clays are preferred and are available under trademarks such as Thixogel (trade mark) N 1 and Gelwhite (trade mark) GP, H, etc., from Georgia Kaolin Company; and ECCAGUM (trade mark) GP, H, etc., from Luthern Clay Products. Atapulgite clays include materials commercially available under the tradenames Attagel (trade mark), i.e. Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporation. Mixtures of the types esmético and atapulgite in proportions weighing from 4: 1 to 1: 5 are also useful here. Abrasives or polishing agents should be avoided in liquid automatic dishwasher detergent compositions as they may disfigure the surface of fine porcelains, crystals and the like.

Thixotropic polymeric thickening agents are usually polyacrylate resins, such as Carbopol 614 or Carbopol 940 or 624.

Examples of thickeners of the polycarboxylate type are thickeners of the cross-linked acrylic acid type are thickeners of the cross-linked polyacrylic acid type sold by BF Goodrich under the trade mark Carbopol which includes not only 900 series resins, in particular Carbopol 941, which is the most insensitive to ions of this class of polymers, and Carbopol 940 and Carbopol 934, but also χ 600 resins, especially Carbopol 614; Carbopol 600 and 900 series resins are crosslinked linear, high molecular weight, hydrophilic acrylic acid polymers having an average equivalent mass of 76 and the overall structure shown by the following formulas:

R 1 is hydrogen; -W--

C-I / wherein R may be hydrogen or an alkyl chain. Carbopol 941 has a molecular mass of 1 250 000; Carbopol 940 has a molecular mass of approximately 3,000,000. The Carbopol 900 series resins are highly branched chain and highly crosslinked in nature with polyalkenyl polyether, eg 1% of a polyalkyl sucrose ether having a mean of 5, 8 allyl groups per sucrose molecule. The preparation of this class of carboxylic polymers of crosslinked nature is described in U.S. Patent No. 2,798,053, the disclosure of which is hereby incorporated by reference. Further detailed information on the resins of Serine 900 is available from B.F. Goodrich, see for example, GC-67 catalog by B. F. Goodrich, &quot; Carbopol® Water Soluble Resins.

In general, these thickening resins are preferably water dispersible copolymers of an α-β-monoethylenically unsaturated lower aliphatic carboxylic acid crosslinked with a polyether or polyol selected from oligosaccharides, their reduced derivatives wherein the carbonyl group is converted to an alcohol group and pentaerythritol, the hydroxyl groups of the polyol being 20

are modified, esterified with allyl groups, preferably with at least two of these allyl groups per molecule.

These water dispersible crosslinked thickening resins as described in the aforementioned U.S. Patent No. 2,798,053 and which have been marketed by R. F. Goodrich as Carbopol 900 series resins are prepared from essentially linear copolymers. More recently, B.F. Goodrich introduced the 600 series Carbopol resins. These are non-linear, moderately branched, high molecular weight non-linear polyacrylic acid cross-linked polyalkylene ether polymers. In addition to the non-linear or branched nature of these resins, they are also believed to be more highly crosslinked than the 900 series resins and have molecular weights between 1,000,000 and 4,000,000.

The most particularly useful of Carbopol 600 series resins are Carbopol 614 and Carbopol 624 which are the most stable to the chlorine bleach of this class of thickening resins. Carbopol 614 and Carbopol 624 are also highly stable in the highly alkaline environment of the preferred liquid automatic dishwasher detergent compositions and are also highly stable under any anticipated storage temperature conditions from below freezing to temperatures as high as 48.9 120øF, preferably 60.0øC (140øF), and especially 71.1øC (160øF), for periods as long as from several days to several weeks or months or longer.

While the more favorable results have now been achieved with the Carbopol 614 moderately branched chain polyacrylic resin, other crosslinked branched polycarboxylate type thickening agents may also be used in the compositions of this invention. As used herein, the term &quot; polycarboxylate type &quot; refers to water soluble carboxyvinyl polymers of α, β-monoethylenically unsaturated lower carboxylic acids, which may be linear or non-linear, and are exemplified by homopolymers of acrylic acid or methacrylic acid or its salts, esters or amides dispersible in water-soluble or water-soluble copolymers or water-soluble copolymers of these acids or their salts, esters or amides with one another or with one or more other ethylenically unsaturated monomers such as, for example, styrene, maleic acid, maleic anhydride, 2-hydroxyethyl, acrylonitrile, vinyl acetate, ethylene, propylene, and the like, and which have molecular weights of from 500,000 to 10,000,000 and are crosslinked in nature or interpolymerized with a multivinyl or multivalylated functionalized crosslinking agent, especially with a compound polyhydric.

These homopolymers or copolymers are characterized by their high molecular mass, in the range of from 500,000, especially from 1,000,000 to 4,000,000 and by their solubility in water, generally at least to an extent of 5% by weight or more, in water at 25 ° C.

Thickening agents are used in their crosslinked form, where crosslinking can be achieved by means known in the art of polymer, such as by irradiation or, preferably, by the incorporation into the monomer mixture to be polymerized of known monomeric chemical crosslinking agents , typically polyunsaturated (eg diethylenically unsaturated) monomers, such as, for example, divinylbenzene, divinyl ether and diethyleneglycol, N, N'-methylene-bis-acrylamide, polyalkylene polyethers (such as those described above), and the like. Typically, the amounts of agent of 22

crosslinking to be incorporated into the final polymer may range from 0.01 to 5 percent, preferably from 0.05 to 2 percent, and especially preferably from 0.1 to 1.5 percent, by weight of the agent of crosslinking to the total weight of the polymer. Generally, those skilled in the art will recognize that the degree of cross-linking should be sufficient to provide some winding to the polymer compound in another generally linear or non-linear manner while maintaining the crosslinked polymer at least water dispersible and highly water swellable in an aqueous aqueous medium. The amount of high molecular weight branched chain crosslinked polymeric acid or other hydrophilic crosslinked polycarboxylate thickening agent to provide the desired rheological property of viscoelastocity to the present compositions will generally range from 0.1 to 4.0% based on the weight of the composition, although the amount depends on the particular cross-linking agent, the ionic strength of the composition, the hydroxyl donors and the like, wherein mixtures of two or more polymeric thickening agents may be employed. The bleach stability of the compositions may be improved by employing in the composition a crosslinked linear polyacrylate homopolymer type thickening agent which is substantially formed in non-aromatic solvents, rather than the Carbopol polymers which are thickeners of the branched chain crosslinked polyacrylic acid type . These crosslinked linear polyacrylate homopolymer type thickeners are sold by 3-V Chemical Corporation under the names Polygel DB and a. .

Polygel DK and are manufactured by polymerization in a non-aromatic solvent of trichloroethane so that it is free of solids. &amp; aromatic compounds. Polygel DB and Polygel DK have a molecular weight of 2,000,000 to 4,000,000.

The amount of the high molecular weight crosslinked polyacrylic acid or other high molecular weight crosslinked polyhydrocrylic acid type thickening agent to give the desired linear viscoelastic rheological property will generally range from 0.1 up to 2%, preferably from 0.2 to 1.4%, on a weight basis based on the weight of the composition, although the amount depends on the particular crosslinking agent, the ionic strength of the composition, the hydroxyl donors and the like.

Another class of polymers useful in the present invention is based on copolymers and thermopolymers of methyl vinyl ether / maleic anhydride. Examples of useful polymers are: methyl vinyl ether, maleic anhydride, acrylic acid, crosslinked; methyl vinyl ether, maleic anhydride, vinylpyrrolidone, crosslinked; and methyl vinyl ether, maleic anhydride, isobutene, crosslinked. The crosslinking agent is essential for establishing the type of polymer network useful in this invention. The crosslinking agent may be any hydrocarbon having a chain length of four or more carbon atoms containing at least two carbon-carbon double bonds. The crosslinking agent is primarily a hydrocarbon optionally having halogen and oxygen containing substituents and linkages such as ester, ether and OH groups. These crosslinking agents may be varied in an amount of from 0.01 to 30% by weight based on the total amount of the polymer used. Examples of crosslinking agents are 1,7-octa-diene, 1,9-decadiene, non-terminal dienes, divinyl glycol, butanediyl ether, polyalylpentaerythritol and polyalylsucrose. Crosslinking can also be achieved through maleic anhydride after the polymer is formed via ester or amide formation using polyols and polyamines such as 1,4-butanediol and polyethylene glycols. 24

The most useful polymers of this invention are Gantrez AN crosslinked with aliphatic dienes, such as 1,7-octadiene and 1,9-decadiene.

Gantrez AN crosslinked polymers from 0.01 to 10% by weight of 1,7-octadiene were shaken overnight in order to hydrolyse the maleic anhydride ring. The polymer solutions were neutralized to pH = 7 to completely ionize the carboxyl groups. The results show that 5% by weight of cross-linking agent is necessary before a gel is formed. If Gantrez AN is cross-linked with 1,9-decadiene then a 3-4% crosslinking gel is formed. Crosslinking causes the formation of a polymer which disperses in water to form a gel with an elastic limit. Table II gives typical elastic limits for the 1,9-decadiene cross-linked polymer. TABLE II - Elastic Limit as Function of Polymer Concentration in Water for Gantrez Reticulated (Gantrez ACV-4006 Crosslinked with 1,9-Decadiene)

Polymer Concentration pH Elastic Limit, Pa (%) 0.125 7 37 0.250 7 64 0.500 7 176 - Measurements were made using the Haake RV12 Rotovisosimeter with the IP MV sensor system. The cutting ratio ranged from 0 to 10 s

Brookfield viscosity measurements were made using crosslinked Grantrez polymers and the results are summarized in Table III. The results show that even at very low concentrations, the highly viscous polymer solutions produce cross-linked Grantrez.

These viscosities characterize the degree of polymerization of the polymers. TABLE III - Brookfielda Viscosity 0.5% Cross-linked Gantrez (ACV-4006) in water at pH 7

F2 N2 rpm Brookfield Viscosity (cPs) T-C 1 376 X 103 T-C 2.5 180 X 103 T-C 5 105 X 103 T-C 10 59 X 103

- Measurements were made with a Brookfield Model DV II The methyl vinyl ether / maleic anhydride copolymer is illustrated by the following formula: x (C-C) (C-C). o == c c = o o / o o

Me where x is 50 mol%. 26

The copolymer is crosslinked with 0.5 to 20.0% by weight of a diene monomer having 6 to 20 carbon atoms, more preferably 7 to 16 and more preferably 8 to 12 carbon atoms, wherein the Preferred diene monomers are 1,7-octadiene and 1,9-decadiene. These water dispersible crosslinked thickening resins were obtained from GAF Corporation. The amount of the crosslinked polymeric thickening agent or other high molecular weight crosslinked polycarboxylate thickening agent to give the desired linear viscoelastecity rheological property will generally range from 1.5 to 5%, preferably from 0 , 5 to 2.5% by weight based on the weight of the composition, although the amount depends on the particular crosslinking agent, the ionic strength of the composition, the hydroxyl donors and the like.

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

Thus, examples of fatty acids from which the polyvalent metal salt stabilizers may be formed include, for example, decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, icosanoic acid, tallow acids , coconut fatty acid, fatty acid of 27

soybeans, mixtures of these acids, etc. Stearic acid and mixed fatty acids are preferred.

The polyvalent metals of groups IA, IIA, IIB and IIIB and groups IIIA, IVA, VA, IB, IIB, IVB, VB, VIIB and VIII of the Periodic Table of the Elements may also be used. A key requirement is that the metal salt of the fatty acid should be dispersible in the aqueous medium containing Carbopol in its composition. The most preferred metal cations are selected from group IA. Of course, for liquid automatic dishwasher detergent compositions, as well as any other applications where the composition of the invention will or may come into contact with articles used for handling, storage or serving food or otherwise to be in contact with or to be consumed by persons or animals, - the metal salt should be chosen taking into account the toxicity of the metal. For this purpose, the calcium, magnesium and sodium salts are in particular the most highly preferred because they are generally safe food additives. Sodium stearate is the most preferred species of the present invention. The amount of fatty acid salt stabilizer to achieve the desired improvement in physical stability and viscosity enhancement will depend upon factors such as the nature of the fatty acid salt, the nature and amount of the thixotropic agent, detergent active compound, inorganic salts, other ingredients of the dishwasher automatic liquid detergent, as well as the anticipated storage and transport conditions.

Generally, however, the amounts of the fatty acid metal salt or fatty acid stabilizing agents are in the range of 0 to 0.4% by weight,

preferably from 0.005 to 0.6% by weight, especially from 0.04 to 0.50% by weight, and more preferably from 0.02 to 0.4% by weight, provide a long-term stability and absence of phase separation during standing or during transport at either high or low temperatures as required for a commercially acceptable product. To obtain the maximum benefit of the fatty acid or metal salt of the fatty acid it is critical that they be suitably dispersed in the medium containing the polymeric thickening agent.

Depending on the amounts, proportions and types of physical stabilizers and thixotropic agents, addition of the fatty acid salt or the fatty acid not only increases the physical stability, but also produces a simultaneous increase in apparent viscosity. The proportions of the fatty acid or fatty acid salt for the thixotropic agent in the range of from 0.02 to 0.4 percent by weight of the fatty acid salt and from 0.1 to 2.5 percent by weight of the agent thixotropic agents are usually sufficient to provide these simultaneous benefits, and therefore the use of these ingredients in these proportions is most preferred.

Other conventional ingredients may be included in these compositions in small amounts, generally less than 3 percent by weight, such as perfumes, preservatives, paint materials and pigments, and the like, all of which are certainly stable to the chlorine bleach compound and in high alkalinity (properties of all components). Especially preferred for staining are the chlorinated phthalocyanines and chlorinated aluminosilicate polysulfides which respectively produce pleasant green and blue colorations. Ti02 may be employed for whitening or shadow neutralization. 29

The liquid automatic dishwasher detergent compositions of this invention are readily employed in a manner known for washing dishes and other cookware and the like in an automatic dishwasher provided with a suitable detergent dispenser in an aqueous lavage bath which contains an effective amount of the composition, generally sufficient to fill or partially fill the cavity of the automatic dispenser of the particular machine to be used.

DETAILED DESCRIPTION OF THE INVENTION The invention may be practiced in various manners and numerous specific embodiments will be described to illustrate the invention with reference to the following examples.

All amounts of ratios referred to herein are in a weightless form of the composition, unless otherwise noted.

Example 1

The following formulas have been formulated: TABLE 1

Anhydrous sodium sulphate A 6.0 B 6.10% Hypochlorite solution 1.3 1.3 1.3 to 13 X sodium (13 X available chlorine) Sodium / disilicate 13.1 13.1 17.2 Ether disulfonate of 0.46 0.46 0.46 dodecyldiphenyl ether phosphate Monodi 0.16 - - ethoxroero Stearic acid 0.15 0.15 0.15 Potassium carbonate - - - Anhydrous sodium carbonate 4.0 4.0 4.0 Sodium hydroxide (38%) 4.92 4, 92 3.42 Carbopol 614 0.75 0.75 0.75 Norasol LMU-45NX (4.5 4.5 4.5 dispersion in water at 45% concentration of polyacrylic builder) Water softened &lt; ......... ...

Sokatan PA 30CL Norasol LMW-45NX Norasol QR1014 Norasol A-1

Serdet DCK 30 C -C4 / 3E0 SO-a 12 12 + 3 SLS C-30E SO-Na

Akypo MB 1 & 21 DEFGHI J oTo o7o 0.0 oTo oo 0.0 o7o 1.3 1.3 1.3 1.3 1.3 1.3 1.3 17.2 17.2 17.2 17.2 13.7 13.7 17.2 0.46 0.46 0.46 0.46 0 , 46 0.46 0.46 0.15 0.15 0.25 0.15 0.15 8.0 0.15 0.15 4.0 4.0 4.0 4.0 2.0 10.0 4, 0 3.42 3.55 3.28 3.28 3.42 3.42 3.42 0.75 1.0 0.5 0.5 0.75 0.75 0.75 2.25 a 5. 3.6 3.6.5 4,5-Fluoro-benzyl- &lt; / RTI &gt; The process for forming the formulations (AO) comprises forming a first aqueous solution A 'by adding at room temperature under conditions of firstly mixing the water of the Norasol LMW-45NX dispersion, secondly of Carbopol 61 'and thirdly a sufficient amount of caustic soda (sodium hydroxide) to precisely neutralize the polycarboxylate polymer. A second aqueous solution (B7) is formed by adding at room temperature under mixing conditions to the water, first the structuring salt, second the sodium sulfate, third the sodium disilicate and, finally, the equilibrium of caustic soda. A third aqueous solution (C ') which is entitled premixture is formed at 60-70 ° C by addition to water (3 parts) of dodecyldiphenylsulfonate (0.46 parts) and , second, stearic acid (0.15 parts). Solution B 'is added at room temperature under mixing conditions to Solution A'. To the mixed solutions A 'and B' at room temperature under mixing conditions is added the third Solution C '. The combined A ', B' and C 'solutions are added a 13% hypochlorite solution to form final formulations A-0.

Example III

A-0 solutions were tested for soiling on cymbals in a standard multi-soils test using a Bosch SMS521 (dishwasher) at 65øC where 3 ml of Galaxi rinse aid sold by Colgate-Palmolive Co. were used. A rating system from 1 to 10 was used, with 10 representing a maximum soil removal.

Multi-Suite Cleaning Test

(Grades 1 to 10) ABCDEF 6 HIJ Oatmeal (cutlery and crockery) 8.0 8.1 7.4 6.8 Rice (cutlery and containers) 8.5 9.25 7.5 6.6 7 , 25 White sauce 9.25 8.8 8.25 8.25 9.25 (cooking containers) 32

Multi-Suit Cleaning Test (continued) Removing Suits (ranged from 1 to 10)

KLMN 0 Galaxy Oatmeal (cutlery and crockery) 7.6 7.4 6.2 Rice (cutlery and containers) 6.5 6.6 7.5 White sauce 8.5 7.2 8.8 (cooking containers) CLEANING TEST OF MULTI-SUBJECTS

This method allows to evaluate the removal of critical soils on various items representative of kitchen containers as well as performance in dirty cups.

METHODOLOGY. Mq. Dishwasher: Bosch SMS 5021

. Rinse Aid: Galaxy 3 mL. Recommended Dosage: Emerald Gel 55 g

Galaxy 55 g. load of the machine:

Bottom basket: 6 dishes with oatmeal stains 1 stainless steel dish with rice soils 1 stainless steel dish with white sauce (mixture made with milk, flour and butter)

Cutlery basket: with rice (2 tablespoons, 2 knives and 2 forks) 33 33

with oatmeal potatoes (2 tablespoons and 2 knives)

Top basket: 8 cups dirty with tomato sauce 8 cups dirty with coconut drink 8 cups dirty with milk.

4 products were simultaneously tested on 4 dishwashers according to the statistical process done in &quot; Latin square &quot;. One wash cycle with 4 replicates per product. . The pH value is measured during the wash cycle. Washing Program:. pre-wash . main wash at 65 ° C. rinse cycle. drying

. Water hardness during washing: 100-150 ppm CaCoz. EVALUATION . Each kitchen container is rated according to a scale from 0 (no removal) to 10 (complete removal of dirt). . The glasses are evaluated in a display box:. overall performance (from 0 to 10). per performance item like. film formation [on a scale from 0 to 4 (no film)]. formation of spots [0 to 4 (absence of spots)]. (0 to 4) Examples of results are shown in the previous table. A B C REOLOGICAL DATA AT TA 2 1. G '(Pa) 57 56 21 2. G &quot; (Pa) 24 27 13, 3 3. H (Pa-S) APPEARANCE 1.5 - 1.6 1 STABILITY OF CHLORINE AT TA 61% 59% 63% (chlorine remaining after 3 months) PHYSICAL STABILITY OK OK 4 OK phase separation at 3 months of age, presence of syneresis)

D E G G H i J 13 3 56 25 very 8.5 4.5 27 15 thick 1.4 0.9 translucent-- trans lucid lightness of 72% 59% 52% 75% O o OK OK OK OK OK

(A) and (b), and (b), the chlorophyll content of the chlorophyll is determined by the following equation: (a) TA 78% 77% (chlorine remaining after 3 months) OK οκ4 phase separation PHYSICAL STABILITY (at 3 months of age, presence of syneresis)

As measured in CARRIHED Model CSL (cell: cone-plate-aperture: 53 micron - cone angle: 4 degrees - cone diameter: 2 cm) oscillation mode operation under "structure recovery" (recorded 11 84 seconds after destruction of the structure - frequency: 1 Hz - time: 100 MN-m.

Registered in Rheomat 108 at 17.7 s. Tested after two weeks. Presence of phase separation at 35 ° C after one month of age.

For dispersion of stearic acid. i 36

CARRIMED REOLOLOGICAL DETERMINATION (model: CSL 100): This apparatus is equipped to operate in oscillation mode in order to fully evaluate the viscoelastic behavior of Carbopol - based on gels in P. This method is attractive by its in-depth characterization &quot; of the gel structures because many experiments can be carried out to thoroughly test a sample.

An experiment normally performed on gels is the &quot; Structure Recurrence &quot;: this allows characterizing the way in which the gel structure is recovered after breakage by a high constant stress: STRUCTURE RECOVERY MEASUREMENT CONDITIONS:

Samples are first studied after one week of age (i.e. when the structure is obtained) and then after aging (1 month, 2 months, 3 months) at different storage temperatures.

It is observed that Carbopol NOP gels are rheologically stabilized within 2 weeks - one month period. . Measuring cell: Cone-Plate (aperture: 53 μια, cone angle: 4 °, cone diameter: 2 cm). . The gel structure is broken first by a constant stress of 400 N / m2 for 1 '. After a 10 sec equilibrium time, the storage modulus (GM representative of the elastic component and the loss modulus (G &quot;) representative of the viscous component are determined in relation to the recovery time.) In oscillation mode:

Measurement Conditions: Moment: 100 μΝ · η

Frequency of oscillation: 1 Hz

Temp. of thermostating: 20 ° C It is observed that the modules are stabilized at about 20 '(1200 s). This apparatus observes the principle of the rotary viscometer operating in continuous mode to determine apparent viscosities over a wide range of cutting rates (30-32 values). PRINCIPLE; The concentric measuring cell is based on the measuring head and a measuring tube rigidly coupled together, the measurement shafts being driven by a DC motor. The moment of rupture exerted by the sample results in a change in the motor armature current. Translated into viscosity, shear stress and shear rate from the measurements. The data are then analyzed in terms of Casson's Law (VG (Pa) = Go + μVS)

OR

Binqham's Law (G = Go + μδ) where: G = shear stress; δ = cut-off ratio gradient; μ = viscosity. (Cell type: regulation B) (Measuring temperature: 25 ° C). rheomat 108 (CONTRAVES): Uses the same principle of

Rheomat 30. But it only operates at a chosen cut-off ratio suitable for conditions and sample tested. Viscosity measurement is performed after a 30 second disturbance. REGULATION FOR FORMULAS BASED ON CARBOPOL: Cell: 2 Ratio: 1 (5 = 17.7 s ~ ^) (Minimum value detected: 0.8 Po s)

REGULATION FOR EMERALD SOLUTIONS: -1 Cell: 2 Reason: 4 (δ = 64 s) (Minimum value detected: 0.2 Po s) CELL 2: Slit diameter measurement: 32.54 mm

Measure of shaking: 24 mm. PHYSICAL STABILITY: Samples are stored in small glass containers (brown to avoid the influence of UV) and physical stability is visually determined after aging at 3 storage temperatures: 4 ° C, 35 ° C and ambient temperature (RT). The sample is considered to be physically stable when there is no presence of syneresis during aging (syneresis: separation of liquid from the gel at the bottom of the glass container for emerald structures). 39

Example IV

Formulas A-I were formulated according to the following procedure. AB c DE Carbopol 614 1.0 1.0 0 0 0 Poligel DK 0 0 1.0 1.2 0 Gantrez (13%) 0 0 0 0 21.34 Sodium silicate (47.5%) 25.0 25 , 0 25.0 25.0 25.0 NaOH (50%) 4.5 4.5 4.5 4.5 7.0 Good-Rite K-7058N (45%) 18.5 7.75 7.75 7.75 13.9 Acusol 445 N (45%) 0 7.75 7.75 7.75 - Sodium carbonate 6.0 6.0 6.0 0 Sodium fluoride 0 0 0 0 0 Dowfax 3B2 (45 %) 0.8 0.8 0.8 0.8 0.8 Fatty acid (1) 0.1 0.1 0.1 0.1 0 NaOCl (12%) 9.2 10.0 12.0 12 , 0 10.0 Dye 0.003 0.003 0.003 0.003 0.003 Fragrance 0.03 0.03 0.03 0.03 0.03 Sodium stearate 0 0 0 0 0.1 40 AB c DE Water balance balance balance balance balance Sodium benzoate Density 1.28 1.27 1.26 1.27 1.22 Stain (2) 1.6 1.25 1.20 - 1.0 Film (3) 3.0 2.1 2.1 - 3.0 Viscosity 6750 3700 4700 5750 3400 Cl Mean% sodium 0.99 1.01 1.33 1.10 1.05 (1) Fatty acid is a mixture of stearic acid and palmitic acid - a ratio of 1: 1 (2) Tested according to ASTMD-3566-79 (3) Tested according to ASTM2-3566-79 (4) Brookfield HATD Model Spindle N2 4 20 rpm; reading to TA made after 90 seconds of cutting in the example.

Example IV (contd)

Formulas A-I were formulated according to the following procedure. FGHI Carbopol 614 1/0 1.0 1.0 1.0 Poligel DK 0 0 0 0 Gantrez (13%) 0 0 0 0 Sodium silicate (47.5%) 25.0 25.0 25.0 25, NaOH (50%) 4.5 4.5 4.5 4.5 Good-Rite K-7058N (45%) 9.25 7.75 7.75 7.75 Acusol 445 N (45%) 9.25 7.75 7.75 7.75 Sodium carbonate 0 5 5 Sodium fluoride 0 6 6 0 Dowfax 3B2 (45%) 0.8 0.8 0.8 0.8 Fatty acid (1) 0 0.1 0.1 NaOCl (12%) 10.0 9/2 9.2 10.0 Dye 0.003 0.003 0.003 0.003 Fragrance 0.03 0.03 0.03 0.03 Sodium stearate 0.1 0 0.1 0 - 42 - 3 * FGHI Water balance balance balance balance Sodium benzoate 1/5 Density 1.23 1.32 1.32 Stain (2) 1.0 1 2 Film (3) 2.6 2.0 2 Viscosity 2800 3980 3620 6500 Cl Mean% sodium 1.04 0 , 93 0.94 1.05 (1) Fatty acid is a mixture of stearic acid and palmitic acid - 1: 1 ratio (2) Tested according to ASTMD-3566-79 (3) Tested according to ASTM2 -3566-79 (4) Brookfield HATD Model Spindle N2 4 20 rpm; reading to TA made after 90 seconds of cutting in the example.

The above formulas were made by making a first aqueous solution of the crosslinked polymer, such as Carbopol 614, at ambient temperature and subsequently neutralizing the polymer under gentle stirring at ambient temperature first with the sodium silicate and then with sodium hydroxide. The 7058 polymer was then added in mud formation followed by the SN polymer. To the resulting solution was added slurrying the sodium carbonate, then an aqueous NaF solution (if present), then an emulsion of Dowfax 3B2 and the fatty acid or sodium stearate, then the bleach was added with formation of mud and finally the fragrance was added with mud formation and, if A / 203 or sodium benzoate were added, they are added after the composition with stirring. The emulsion of Dowfax 3B2 and fatty acid or sodium stearate was formed by first heating Dowfax 3B2 to a temperature of 70-80 ° C and the fatty acid or sodium boron stearate powder was added to Dowfax 3B2 with stirring. The heated emulsion formed was then added to the mixture.

Lisbon, May 29, 1992

J. PEREIRA DA CROZ

Official Agent of Industrial Property RUA VKJTOR CORDON, 10-A 3. &quot; 1200 LISBOA

Claims (4)

I. An automatic dishwashing aqueous composition, comprising approximately on a weight basis: (a) 0 to 20% of at least one phosphate free builder salt; (b) 1 to 20% alkali metal silicate; (c) 0 to 8% of alkali metal hydroxide; (d) 0 to 5% of organic detergent active material; (e) 0 to 5% foam dimer; (f) chlorine bleach compound in an amount to provide 0.2 to 4% available chlorine; (g) 1 to 20% of at least one low molecular weight polyacrylate; (h) 0 up to 2.0% of a long chain fatty acid or a metal salt thereof; (i) 0 to 8% sodium sulfate; (j) 0.1 to 2.5% of at least one polymeric thickening agent; and (k) water, wherein said water is bonded to other ingredients referred to in said composition. 2β. Composition according to Claim 1, characterized in that the detergent builder salt is sodium carbonate. 2 '. Composition according to Claim 2, characterized in that the foam dimmer is in the range of from 0.1 to 1.5%. 4s. Composition according to Claim 1, characterized in that the detergent active material is in the range of from 0.1 to 5.0%. 5 '. Composition according to Claim 2, characterized in that the chlorine bleach compound is sodium hypochlorite. A composition according to claim 2, characterized in that the foam dimer is an acid alkyl phosphate ester or an alkylphosphoric acid ester containing one or two C 12-20 alkyl or C 20-20 ethoxylated alkyl groups. Composition according to Claim 2, characterized in that the amount of the components is such that when the composition is diluted to 10 g / l, the pH of the diluted composition is in the range of from 11.2 to 13.5. The composition according to claim 1, wherein the concentration of said fatty acid is in the range of from 0.005 to 2.0% by weight. A method of cleaning dirty containers and cooking utensils in an automatic dishwasher comprising contacting the dirty containers and cooking utensils in an automatic dishwasher with an aqueous washing bath which disperses therein an effective amount of the composition of claim 2 in an amount sufficient to provide a wash bath pH of at least 11.2. Lisbon, May 29, 1992 J. PEREIRA DA CRUZ Official Agent for Industrial Property RUA VtCTOR CORDON, 10-A 3 "1200 LISBOA