CA2069770A1 - Phosphate-free, gel-like automatic dishwasher detergent compositions - Google Patents

Abstract

Abstract of the Disclosure An aqueous thixotropic liquid composition comprising water, a thixotropic thickener, a means to increase the physical stability of the composition, chlorine bleach and detergent builder, said composition containing alkali metal and alkaline earth metal components in amount sufficient to provide a pH of at least 11.2, when 10 grams of the composition is added to one liter of water, wherein the composition provides improved rheological behavior and physical stability with low residue left in the bottle and a new aesthetic effect in a translucent appearance.

Description

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PHOSPHATE-FREE, GEL-~IKE AUTO~TIC
DISHWASHER DET~RGENT COMPOSITIONS

BACKGROUND OF INVENTION
The present invention relates to gel-like aqueous liquid automatic dishwasher detergent compo,sitions which are phosphate-free with equivalent cleaning performance and physical stability with improved characteristics as compared to phosphate containing compositions.
Commercially available household-machine dishwasher detergents pro~ided in powder form have several disadvantages, e.g. non-uniform composition; costly operations necessary in their manufacture; tendency to cake in storage at high humidities resulting in the formation of lumps which are difficult to disperse; dllstiness, a source of particular irritation to users who suffer allergies; and tendency to cake in the dishwasher machine dispenser. Liquid forms of such compositions, however, generally cannot be used in automatic dishwashers.
Recent research and development activity has focused on the gel or "thixotropic" form of such compositions, e.g.
scouring cleansers and automatic-dishwasher products characterized as thixotropic pastes. Dishwasher products so provided are primarily objectionable in that they are insufficiently viscous to remain ~'anchored" in the dispenser cup of the dishwasher. Ideally, thixotropic cleaning compositions should be highly viscous in a quiescent state, ~ t~ S) ~
~up of the dishwasher. Ideally, thixotropic cleaning compositions should be highl~ viscous in a quiescent state, singham plastic in nature, and have relatively high yield values. When subjected to shear stresses, however, such as ~ein~ shaken in a container or squeezed through an orifice, they should quickly fluidize and, upon cessation of th~
applied shear stress, quickly revert to the high viscosity or Bingham plastic state. Stability is likewi~e of prim~ry importance, i.e. there should be no signiEicant evidence of 10 phase separation or leaking after lollg standing.
The provision of automatic dishwasher compositions in gel form having the afore-described properties has thus far proven problematical, particularly with regard to compositions for use in home dishwasher machines. For effective use, it i9 15 generally recommended that the automatic dishwashing detergent, hereinafter also designated ADD, contain (1) sodium tripolyphosphate (NaTPP) to soften or tie up hard water minerals and to emulsify and/or peptide soi.1; (2) sodium silicate to supply the alkalinity necessary for effective 20 detergency and to pro~ide protection for fine china glaze and pattern; (3) sodium carbonate, generally considered to be optional, to enhance alkalinity; (4) a chlorine-releasing agent to aid in the elimination of soil specks which lead to water spotting and filming; and (5) defoamer/surfactant to 25 reduce foam, thereby enhancing machine efficiency and supplying requisite detergency. See, for example, SDA
Detergents in Depth, "Formulations Aspects of Machine Dishwashing", Thomas Oberle (1974). Cleansers approximating r3 ~o the afore-described compositions are mostly liquids or powders. Combining such ingredients in a gel form effective for home-machine use has proved difficult. Generally, such compositions omit hypochlorite bleach, since it tends to react ~ith other chemically active ingredients, particularly surfactant. Thus, U.S. Patent 4,115,308 discloses thixotropic automatic dishwasher pastes containing a suspending agent, e.g. CMC, synthetic clays or the like; inorganic salts including silicates, phosphates and polyphosphates; a small amount of surfactant and a suds depressor. Bleach is not disclosed. U.S. Patent 4,147,650 is somewhat similar, optionally including Cl-(hypochlorite) bleach but no organic surfactant or foam depressant. The product is described, moreover, as a detergent slurry with no apparent thixotropic properties.
U.S. Patent 3,g85,66~ describes abrasive scouring cleaners of gel-like consistency containing (1) suspending agent, preferably the smectite and attapulgite types of clay;

(2) abrasive, e.g. silica sand or perlite; and (3) filler comprising light density powdered polymers, expanded perlite and the like, which has a buoyancy and thus stabilizirlg effect on the composition in addition to serving as a bulking agent, thereby replacing water otherwise available for undesired supernatant layer formation due to leaking and phase destabilization. The foregoing are the essential ingredients.
Optional ingredients include hypochlorite bleach, bleach stable surfactant and buffer, e.g. silicates, carbonates, and monophosphates. Builders, such as NaTPP, can be included as r~d) ~ r3 (h) sodlum hydroxide, AS necessary, to adjust pH; and (i) water, balance.
~DD compositions so formulated are low-foaming; are readily soluble in the washing medium and most effective at pH
~alues best conducive to improved cleaning performance, viz, pH 10.5-14. The compositions are normally of gel consistency, i.e. a highly viscous, opaque jelly-like material having Bingham plastic character and thus relatively high yield values. Accordingly, a definite shear force is necessary to initiate or increase flow. Under such conditions, the composition is quickly fluidized and easily dispersed. When the shear force is discontinued, the fluid composition quickly reverts to a hi~h viscosity, Bingham plastic state closely approximating its prior con~istency.
U.S. Patent 4,511,~87, dated April 16, 1985, describes a low-foaming detergent paste for dishwashers. The patented thixotropic cleaning agent has a viscosity of at least 30 Pa.s at 20C as determined with rotational viscometer at a spindle speed of 5 revolutions per minute. The composition is based on a mixture of finely divided hydrated sodium metasilicate, an active chlorine compound and a thickening agent which is a foliated silicate of the hectorite type. Small amounts of nonionic tensides and alkali metal carbonates and/or hydroxides may be used.
The compositions of the instant in~ention overcome many of the aforementioned deficiencies, while providing compositions which are phosphate-free and consequently environmentally safe.

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further optional ingredients to supply or supplement building function not provided by the buffer, the amount of such builder not exceeding 5~ of the total composition, according to the patent. Maintenance of the desired (greater than~ Ph lo levels is achieved by the buffer/builder components. High Ph is said to minimize decomposition of chlorine bleach and undesired interaction between surfactant and blèach. When present, NaTPP is limited to 5%, as stated. Foam killer is not disclosed.
In U.K. Yatent Application G~ 2,116,199A and G~
2,140,450A, both of which are assigned to Colgate-Palmolive, liquid ADD compositions are disclosed which have properties desirably characterizing thixotropic, gel-type structure and which include each of the various ingredient~ necessaxy for effective detergency within an automatic dishwasher. The normally gel-like aqueous automatic dishwasher detergent composition having thixotropic properties includes the ~ollowing ingredients, on a weight basis:
(a) 5 to 35~ alkali metal tripol~pho phate;
(b) 2.5 to 20~ sodium silicate;
(c) 0 to 9% alkali metal carbonate;
(d) 0.1 to 5~ chlorine bleach stable, water dispersible organic detergent active material;
(e) 0 to 5% chlorine bleach stable foam depressant;
(f) chlorine bleach compound in an amount to provide 0.2 to 4~ of available chlorine;
(g) thixotropic thickener in an amount sufficient to provide the composition with thixotropy index of 2.5 to 10;

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Quite surprisingly, it was ~iscovered that the phosp~ate-free compositions of the instant invention while providing compositions which are environmentally safe also provide the desired cleaning performance. They also provided remarkable stabilization against change with time of the rheological properties.
Accordingly, it is an object of the invention to provide liquid ADD compositions having excellent cleaning performance, improved physical stability and improved rheological 10 properties and having a density of 1.20 to 1.44 grams/li~er while being phosphate-free and environmentally safe.
It i9 still another object of the instant invention to provide compositions which have satisfactory chlorine levels 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 detailed description of the invention and preferred embodiments thereof, are achieved by a phosphate-free built 25 aqueous liquid automatic dishwasher detergent composition containing a stabilization system such that when the composition is added to an aqueous wash bath, at a ~r~3J~7~

concentration of 10 grams per liter, the wa.sh bath has a pH of at least 11.2.
In accordance with an especially preferred embodiment, the present invention provides a gel-like viscoelastic aqueou.s automatic dishwasher detergent composition which has a three-dimensional structure and includes, on a weight basis:
(a) 1 to 20~ of at least one low molecular weight non crosslinked polyacrylate;
(b) 0 to 20~ alkali metal sil:icate;
(c) 1 to 15~ of at least one phosphate free detergent builder salt such as alkali metal carbonate;
(d) 0 to 8~ alkali metal hydroxide;
(e) 0 to 5~ chlorine bleach stable organic detergent active material;
(f) 0 to 1.5~ stable foam depressant;
(g) chlorine bleach compound in an amount to provide 0.2 to 4~ of available chlorine;
(h) 0.1 to 5~ of a polymeric thickener having a molecular weight of at least 500,000;
(i) 0 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 a~ sodium sulfate;
(k) balance water, wherein the water is substantially bound by hydration to the polymeric thickener so that the composition is substantially free of unbound water and the total amount of (b) alkali silicate, (c) alkali metal carbonate and (d) alkali metal hydroxide provides a pH

sufficiently high such that when the composition is diluted in an aqueous wash bath to provide a concentration of 10 grams per liter the pH of the aqueous wash bath becomes at least 11.2 and the concentration of the alkali metal builder salt, alkali metal hydroxide and alkali metal hydroxide is preferably less than 25 wt.~, more preferably less than 22 wt.~, and most preferably less than 20 wt.~ and the residual amount of the composition remaining in a poly olefinic container after the poly olefinic composition is drained o~
the composition is less 5 wt.~ of the original amount of the composition in the container and more preferably less than 2 wt.%.
The invention also provides a method for cleaning dishware in an automatic dishwashing machine with an aqueous wash bath containing an eEfective amount of th~ liquid automatic dishwasher detergent ~LADD) composition as described above. According to this aspect of the invention, the LADD
composition can be readily poured into the dispensing cup of the automatic dishwashing machine and will be sufficiently viscous to remain securely within the dispensing cup until shear forces are again applied thereto, such as by the water spray from the dishwashing machine.
It is known that LADD effectiveness i9 directly related to (a) available chlorine levels; (b) alkalinity; (c) solubility in washing medium; and (d) foam inhibition. In accordance with the present invention, the types and amounts of the alkaline components which are phosphate-free are chosen so that when the composition is added to an aqueous wash bath 3~
to provide 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 11.5 to 12.5.
~ENERAL DESCRIPTION OF THE INVENTION
The viscoelastic gel compositions of the in~tant invention which have a three dimens:ional structure can be generally descrlbed as follows:

Ingredient Amount (A._I.) Wt Sodlum Sulfate 0 to 8 Alkali Metal Sllicate 0 to 20 Foam Depressant 0 to 1.5 Low Molecular Weight Polyacrylate ]. to 20~
Phosphate-free Bullder Salt 1 to 20%
Alkali Metal Hydroxide 0 to 8%
Metal Hypochlorite Solution (13~) 1 to 15%
Fatty Acid or Metal Salt of Fatty Acid 0 to 2~
Polymeric Thickener 0.1 to 2.5%
Water Balance Organic Detergent Active Material 0 to 5~

wherein the water of the composition is bound by hydration to the polymeric thickener so that the composition has substantially no free water.
Therefore, in accordance with an especially preferred embodiment of this invention, the high alkalinity is achieved in a phosphate-free, fatty acid salt stabilized, chlorine-bleach containing li~uid automatic dishwasher detergent composition, wherein the alkaline compounds include, on an active basis, based on the total composition, from 0 to 20 weight alkali metal silicate, from 0 to 8 wt ~ alkali metal hydroxide, from 1 to 20 wt ~ phosphate-free builder salt, from 1 to 8~ of at least low molecular weight noncrosslinked polyacrylate, from 0.1 to 5 weight percent polymeric thickener and optionally a metal hypochlorite, a foam depressant, and a detergent active material, wherein the pH of 1 li.ter of aqueous wash bath containing 10 grams of the composition being at least 11.2.
The alkali metal silicate such as sodium silicate, which provides alkalinity and protection of hard surfaces, such as fine china glaze and pattern, is employed in an amount ranging from 1.0 to 20.0 weight percent, preferably 2.5 to 20 weight percent, in the composition. The sodium silicate is generally added in the form of an aqueous solution, preferab].y having Na2O:SiO2 ratio of 1:1.3 to 1:2.~, especially preferably 1:2.0 to 1:2.6. At this point, it should be mentioned, especially NaOH and sodium hypochlorite, are also o~ten added in the form of a preliminary prepared aqueous dispersion or solution.
The liquid automatic dishwashing detergent composition contains 1 to 20~ by weight of an akali metal phosphate free detergency builder salt, more preferably 2 to 20~ by weight, and most preferably 3 to 20~ by weight, wherein the detergency builder is usually an alkali metal carbonate such as sodium carbonate or potassium carbonate.
Other builder salts which can be mixed with the sodium carbonate are gluconates and nitriloacetic acid salts. In conjunction with the builder salts are optionally used a low ~ dJ ~r3 molecular weigh~ noncrosslinked polyacrylates having a molecular weight of 1,000 to 100,000, more preferably 2,000 to 80,000. A preferred low molecular weight polyacrylate is Sokalan~n PA30CL manufactured by BASF and having a molecular weight of 8,000. Another preferred low molecular weight sodium salt of a polyacrylate is Norasol LMW45~ which is also know as Acusol 445N manufactured by Norsoshaas and having a molecular weight of 4,500.
Other useful low molecular weight noncrosslinked polymers are: Acusol~ 640D provided by Rohm & Haas; Norasol QR1014 from Norsohaas having a GPC molecular weiyht of 10,000.
Norasol A-l has a molecular weight of 60,000. SokalanPA30CL
from BASF is the most preferred because of its extremely high bleach stability of at least six months as compared to the other listed low molecular polymers which all have bleach stabilities of less than six months. Sokalan PA30CL is a polyacrylate of a chemical structure similar to Norasol LMW45 which has been modified to have increased bleach stability it is believed by the elimination of heavy metals used in the synthesis of the Sokalan PA30CL.
Acusol 445N is an excellent dispersant for calcium carbonate which i9 formed during the washing process, wherein the Acusol 445N controls crystal growth of the calcium carbonate and helps suspends the calcium carbonate in the wash bath. Another especially useful low molecular weight polyacrylate polymer is Good-Rite3 K-7058N which is a 90 -100~ neutralized sodium salt of a polyacrylate polymer having a molecular weight of 5,800. K-70s8N is a good dispersant for Jr~

calciu~l carbonate and excellent builder or sequestering agent for heavy metal ions such as calcium or magnesium. A
combination of Acusol 445N and K-7058N provides maximum enhancement for the alkali metal non phosphate builder salt such as sodium carbonate. The chlorine stability of a composition made with a combination of Acusol 445 and Good-Rite3 K7058N is improved over 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 and amorphous type. Various crystalline zeolites (i.e. alumino-silicates) are described in British Patent No. 1,504,168, U.S.
Patent No. 4,409,13~ and Canadian Patent Nos. 1,072,835 and 1,087,477. ~1 example of amorphous zeolites useful herein can be found in Belgium Patent No. 835,351. The zeolites generally have the formula:
(M2O)~(Al2O3~y(SiO2)~ wH~O
wherein x i9 1, y iS from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0 to 9, preferably 2.5 to ~ and M is preferably sodium. A
typical zeolite is type A or similar structure, with type 4A
particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of 200 millie~uivalents per gram or greater, e.g. 400 meq/g.
Foam inhibition is important to increase dishwasher machine efficiency and minimize destabilizing effects which might occur due to the presence of excess foam within the washer during use. Foam may be sufficiently reduced by suitable selection of the type and/or amount of detergent actlve material, the main foam-producing component. The degree of foam is also somewhat dependent on the hardness of the wash water in the machine whereby suitable adjustment of ~he proportions of the inorganic or organic builder salt ~Ihich has a water softening effect may aid in providing the desired degree of foam inhibition. However, it is generally preferred to include a chlorine bleach stable foam depressant ox inhibitor. Particularly effective are the alkyl phosphoric acid esters of the formula:
O
HO--P--R
OR

and especially the alkyl acid phosphate esters of the formula:

HO--P--R
OR
In the above formulas, one or both R groups in each type of ester may represent independently a C,2-C20 alkyl or ethoxylated alkyl group. The ethoxylated derivative of each type of ester, for example, the condensation products of one mole of ester with from 1 to 10 moles, preferably 2 to Ç moles, more preferably 3 or 4 moles, ethylene oxide can also be used~
Some examples of the foregoing are commercially available, such as the products SAP from Hooker and LPKN-158 from Knapsack. Mixtures of the two types, or any other chlorine bleach stable types, or mixtures of mono- and diesters of the ~ t~ ,J~

same type, may be employed. Especially preferred is a mixture of mono- and di- Cl6-C~8 alkyl acid or ethoxylated alkyl phosphate esters such as monostearyl/distearyl acid phosphate 1.2/1, and the 3 to 4 mole ethylene oxide condensates thereof.
~hen employed, proportions of O to 5 weight percent, preferably 0.1 to 1.5 weight percent, of foam depressant in the composition is typical. Other defoamers which may be used include, for example, the known silicones, such as available from Dow Chemicals. In addition, it is an advantageous feature of this invention that many of the stabilizing salts, such as the stearate salts, for example, sodium stearate, are also effective as foam killers.
Although any chlorine bleach compound may be employed in the compositions of this invention, such as dichloroisocyanurate, dichloro-dimethyl handantoin, or chlorinated TSP, alkali metal or alkaline earth metal, e.g.
potassium, lithium, magnesium and especially sodium, hypochlorite is preferred. 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 acidification of 100 parts of the composition with excess hydrochloric acid. A solution containing 0.2 to 4.0% by weight of sodium hypochlorite (13~ of available chlorine) contains or provides roughly the same percentage of available chlorine. 0.8 to 1.6% by weight of available chlorine is especially preferred.
~etergent active material which may be, useful herein must be stable in the presence of chlorine bleach, especially ypochlorite bleach, and those of the organic anionic, aMine oxide, phosphine oxide, sulphoxide or betaine water.
Dispersible surfactant types are preferred; the first mentioned anionics being most preferred. They are used in amounts ranging from O to 5~, preferably 0.1 to 5.0%.
Particularly preferred surfactants herein are the linear or branched alkali metal mono- and/or di-(C8-CI4) alkyl diphenyl oxide mono- and/or disulphates, commercially available for example as DOWE'~X~ 3B-2 and DOWFAX~ 2A-1. Alkyl ether sulfates (Ct2-C~ 3EO-SO3-NaL) are suitable surfactants. In addition, the surfactant should be compatible with the other ingredients of the composition. Other suitable surfactants include the primary alkylsulphates, alkylsulphonates, alkylarylsulphonates and sec.-alkylsulphates. E~amples include sodium ClO-Cl8 alkylsulphates such as sodium dodecylsulphate and sodium tallow alcoholsulphate; sodium ClO-Cl8 alkanesulphonates such as sodium hexadecyl-1-sulphonate and sodium C12-C~8 alkylbenzenesulphonates such as sodium dodecylbenzenesulphonates. The corresponding potassium salts may also be employed.
As other suitable surfactants or detergents, the amine oxide surfactants are typically of the structure R2RIN~O, in which each R represents a lower alkyl group, for instance, methyl, and Rl represents a long chain alkyl group having from 8 to 22 carbon atoms, for instance a lauryl, myristyl, palmityl or cetyl group. Instead of an amine oxide, a corresponding surfactant phosphine oxide R2RIPO or sulphoxide RRISO can be employed. Betaine surfactants are typically of t~J,~

~he structure R~RI~R''CO~-, in which each R represents a lower alkylene group having from 1 to 5 carbon atoms. Specific exa~lples of these surfactants include lauryl-dimethylamine oxide, myristyl-dimethylamine oxide, the corresponding ~hosphine oxides and sulphoxides, and the corresponding betaines, including 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. Patents 3,985,663 and 4,271,030.
Other useful surfactants are Akypos from Chemy which is a nonionic. surfactant terminated by one functional carboxylate;
C-l230 3EO ether sulfates; and C, 12-18 alcohol sulEates.
Thixotropic thickeners, i.e. thickeners for suspending agents which provide an aqueous medium with thixotropic properties, are known in the art and may be organic or inorganic water soluble, water dispersible or colloid-forming, and monomeric or polymeric, and should, of course, be stable in these compositions, e.g. stable to high alkalinity and chlorine bleach compounds, such as sodium hypochlorite. These materials are generally used in amounts of 0.1 to 4.0 percent by weight, preferably 0.2 to 3.5 weight percent, more preferably 0.3 to 3 welght percent, to confer the desired thixotropic properties and Bingham plastic character.
However, in the presence of the metal salt fatty acid i 3 stablllzers, the desired t~ixotropic properties and Bingham plastic character can be obtained ln the presence of lesser amounts of the thixotropic thickeners. Those especially preferred generally comprise the inorganic, colloid-forming ~clays of smectite and/or attapulgite types.For example, amounts of the inorganic colloid-forming clays of the smectite and/or attapulgite types in the range of from 0.1 to 3~, preferably 0.1 to 2.5~, especially 0.1 to 2~, are generally sufficient to achieve the desired thixotropic properties and Bingham plastic character when used in combination with the physical stabilizer.
Smectite clays include montmorillonite (bentonite), hectorite, attapulgite smectite, saponite and the like.
Montmorillonite clays are preferred and are available under the tradenames such as Thixogel (registered trademark) No. 1 and Gelwhite (registered trademark) GP, H, etc., from Georgia Kaolin Company; and ECCAGUM (registered trademark) GP, H, etc., from Luthern Clay Products. Attapulgite clays include the materials commercially available under the tradename Attagel (registered trademar~), i.e. Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporation. Mixtures of smectite and attapulgite types in weight ratios of 4:1 to 1:5 are also useful herein. Abrasives or polishing agents should be avoided in the LADD compositions as they may mar the surface of fine dishware, crystal and the like.

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The polymeric thixotropic thickeners are usually polyacrylate resins such as Carbopol 614 or Carbopol 940 or 624.
Exemplary of the polycarboxylate type thickening agents are cross-linked polyacrylic acid type thickening agents are cross-linked polyacrylic acid-type thickening agents sold by B.F. Goodrich under their Carbopol trademark, including both the 900 series resins, especially Carbopol 941, which i9 the most ion-insensitive of this class of polymers, and Carbopol 940 and Carbopol 934, and the 600 series resins, especially Carbopol 614. The Carbopol 600 and 900 series resins are hydrophilic high molecular weight, cross-linked linear acrylic acid polymers having an average equivalent weight of 76, and the general structure illustrated by the following formulas:
R

/ \\
OH O n.
wherein R can be hydrogen or an alkyl chain. Carbopol 941 has a molecular weight of 1,250,000; Carbopol 940 has a molecular weight of approximately 3,000,000. The Carbopol 900 series resins are highly branched chained and highly cross-linked with polyalkenyl polyether, e.g. 1~ of a polyalkyl ether of sucrose having an average of 5.8 allyl groups for each molecule of sucrose. The preparation of this class of cross-linked carboxylic polymers is described in U.S. Patent 2,798,053, the disclosure of which is incorporated by il2~ 3~

,eEerence. Further detailed information on the Carbopol 900 series resins is available from ~.F. Goodrich, see, for example, the B.F. Goodrich cataloy GC-67, CarbopolR Water Soluble Resins.
' In general, these thickening resins are preferably water dispersible copo].ymers of an alpha-beta monoethylenically unsaturated lower aliphatic carboxylic acid cross-l.inked with a polyether of a polyol selected from oligo saccharides, reduced derivatives thereof in which the carbonyl group i9 converted to an alcohol group and pentaerythritol, the hydroxyl groups of the polyol which are modified being etherified with allyl groups, there being preferably at lease two such allyl groups per molecule.
These water-dispersible cross-linked thickening resins as described in the aforementioned U.S. Patent 2,798,053 and which have been commercialized by B.F. Goodrich as the Carbopol 900 series resins are prepared from essentially linear copolymers. More recently, ~.F. Goodrich has introduced the Carbopol 600 series resin. These are high molecular weight, non-linear moderate branched chain polyacrylic acid cross-linked with polyalkenyl ether. In addition to the non-linear or branched nature of these re~ins, they are also believed to he more highly cross-linked than the 900 series resins and have molecular weights between 1,000,000 and 4,000,000.
Most especially useful of the Carbopol 600 series resins are Carbopol 614 and Carbopol 624 which are the most chlorine bleach stable of this class of thickening resins. Carbopol 3~ r3 i ~14 and 624 are also highly stable in the high alkalinity environment of the pxeferred liquid automatic dishwasher detergent compositions and is also highly stable to any anticipated storage temperature conditions from below freezing ~o elevated temperatures as high as 120F, preferably 1~0F, and especially 160F, for periods of as long as several days to several weeks or months or longer.
While the most favorable results have now been achieved with Carbopol 614 moderate branched chain polyacrylic resin, other branched cross-linked polycarboxylate-type thickening agents can also be used in the compositions of this invention.
As used herein "polycarboxylate-type" refers to water-soluble carboxyvinyl polymers of alpha, beta monoethylenically unsaturated lower aliphatic carboxylic acids, which may be linear or non-linear, and are exemplified by homopolymers of acrylic acid or methacrylic acid or water-dispersible or water-soluble salts, esters or amides thereof, or water-soluble copolymers of these acids or their salts, esters or amides with each other or with one or more other ethylenically unsaturated monomers, such as, for example, styrene, maleic acid, maleic anhydride, 2-hydroxethylacrylate, acrylonitrile, vinyl acetate, ethylene, propylene, and the like, and which have molecular weights of from 500,000 to 10,000,000 and are cross-linked or interpolymerized with a multi-vinyl or multi-allylic functionalized cross-linking agent, especially with a polyhydric compound.
These homopolymers or copolymers are characterized by their high molecular weight, in the range of from f~'l~i~33~7'~

JOO ~ 0001000 ~ especially from 1,ooo,Ooo,000 to 4,000,000, and by their water solubility, generally at least to an extent of up to 5~ by weight, or more, in water at 25C.
The th;ckening agents are used in their cross-linked ~orm, wherein the cross-linking may be accomplished by means known in the polymer arts, as by irradiation, or, preferably, by the incorporation into the monomer mixture to be polymerized of known chemical cross-linking monomer mixture to be polymerized of known chemical cross-linking monomeric agents, typically polyunsaturated (e.g. diethylenically unsaturated) monomers, s~ch as, for example, divinylbenzene, divinylether of diethylent glycol, N,N'-methylene bisacrylamide, polyalkenylpolyethers (such as described above), and the like. Typically, amounts of cross-linking agent to be incorporated in the final polymer may range from 0.01 to 5 percent, preferably from 0.05 to 2 percent, and especially, preferably form 0.1 to 1.5 percent, by weight of cross-linking agent to weight of total polymer. Generally, those skilled in the art will recognize that the degree of cross-linking should be sufficient to impart some coiling of the otherwise generally linear or non-linear polymeric compound while maintaining the cross-linked polymer at least water dispersible and highly water-swellable in an ionic aqueous medium.
2~ The amount of the high molecular weight, branched chained cross-linked polymeric acid or other high molecular weight, hydrophilic cross-linked polycarboxylate thickening agent to impart the desired rheological property of linear 7~
vlscoelasticity to the instarlt compositions will generally be in the range of from 0.1 to 4.0~, based on the weight of the composition, although the amount will depend on the particular cross-linking agent, ionic strength of the composition, ~ydroxyl donors and the like, wherein mixtures of two or more polymerlc thickening agents can be employed.
The bleach stability of the compositions can be improved by employing in the composition a cross-linked linear polyacrylate homopolymer type thickening agent which i9 substantially formed in non aromatic solvents in place oE the Carbopol polymer which are branched chained, crosslinked polyacrylic acid type thickening agents. These crosslinked linear polyacrylate homopolymer type thickening agents are sold by 3-V Chemical corporation under the names Polygel DB~, Polygel DK~ and are manufactured by polymerization in a trichloroethan non aromatic solvent such that they are free of aromatic solvents. The Polygel DB~ and Polygel DK~ have an Mw of 2,000,000 to 4,000,000.
The amount of the high molecular weight, cross-linked polyacrylic acid or other high molecular weight, hydrophilic cfross-linked polyacrylic acid-type thickening agent to impart the desired rheological property of linear viscoelasticity will generally be in the range of from 0.1 to 2~, preferably from 0.2 to 1.4~ by weight, based on the weight of the composition, although the amount will depend on the particular cross-linking agent, ionic strength of the composition, hydroxyl donors and the like.

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Another class of polymers useful in the instant composition are based on methyl vinyl either/maleic anhydride copolymers and terpolymers. Examples of useful polymers are:
methyl vinyl ether, maleic anhydride, acrylic acid, cross-linked; methyl vinyl ether, maleic anhydride, vinyl pyrrolidone, cross-linked; and methyl vinyl ether, maleic anhydride, isobutene, cross-linked. The cross-linking agent is essential to establish the kind of polymer network useful in this invention. The cross-linking agent can be any hydrocarbon with a chain length of four or more carbon atoms containing at least two carbon-carbon double bonds. The cross-linking ayent is mainly a hydrocarbon with optional halogen and oxygen-containing substituents and linkages such as ester, ether and OH groups. These cross-linking agents can vary in amount from 0.01 to 30% by weight of the total ~uantity of polymer used. examples of cross-linking agents are 1,7-Octadiene, 1,9 Decadiene, non-terminal dienes, Divinyl Glycol, Butane Divinylether, polyallyl pentaerythritol and polyally sucrose. Cross-linking can also be achieved through the maleic anhydride after the polymer is formed, via ester or amide formation using polyols and polyamines such as 1,4 butane diol and polyethylene glycols.
The most useful polymers of these inventions are the Gantrez AN cross-]inked with aliphatic dienes such as 1,7 oc~adiene and 1,9 decadiene.
Gantrez AN polymers cross-linked from .01 to 10~ by weight of 1,7 octadiene were shaken overnight in order to ~r3~7~

nydrolyze the maleic anhydride ring. The polymer solutions were neutralized to pH 7 to fully ionize the carboxyl yroup~.
The results show that 5~ by weight of cross-linking agent is necessary before a gel is formed. If Gantrez AN is cross-Iinked with 1,0 decadiene then a gel is formed at 3-4~ cross-linking.
The cross-linking causes the formation of a polymer that disperses in water to form a gel with a yield point. Table II
gives typical yield points for the polymer cross-linked with 1,9 decadiene.

Table II. Yield Point~ as a Function of Polymer Concentration in Water for Cross-linked Gantrez (Gantrez ACV-4006 Cross-linked with 1,9 Decadiene).

Polymer Concentration PH Yield Point, Pa _ (Weight_-O) __ 0.125 7 37 0.250 7 64 ~easurements were made using the Haake Rotoviscometer RV12 with MV IP sensor system. Shear rate was varied from 0 to 10 sec~~.

srookfield viscosity measurements were made using cross-linked Gantrez polymers, and results are summarized in ~able III. Results show that even at very low concentrations, cross-linked Gantrez yield highly viscous polymer solutions.

These viscosities characterize the degree of polymerization of the polymers.
Table III. Brookfield Viscosityn of 0.5~ Cross-linked Gantrez (ACV-4006) in water at pH 7.

1 0 .. ---~
Spindle #RPMBrookfield Viscosity ~,cps l T-C 2.5 180 X 103 ~The measurements were taken with a Brookfield Model DV II.

__ The copolymer of methyl vinyl ether/maleic anhydride is illustrated by the following formula:
--(C~ ~(C~ C)y 1 ~
j O===C\ ; ~O

Me wherein x is 50 mole~.

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The copolymer is cross-linked with 0.5 to 20.0 wt~ of a diene monomer having 6 to 20 carbon atoms, more preferably 7 to 16 and most preferably 8 to 12, wherein preferred diene monomers are 1,7 Octadiene and 1,9 decadiene. These water-~dispersible, cross-linked thickening resins were obtained from the GAF corporation. The amount of the cross-linked polymeric thickening agent or other high molecular weight, hydrophilic cross-linked polycarboxylate thickening agent to impart the desired rheological property of linear viscoelasticity will generally be in the range of from 1.5 to 5~, preferably from .5 to 2.5, by weight, based on the weight of the composition, although the amount will depend on the particular cross-linking a~ent, ionic strength of the composition, hydroxyl donors and the like.
The preferred long chain fatty acids are the higher aliphatic fatty acids having from 8 to 22 carbon atoms, more preferably from 10 to 20 carbon atoms, and especially preferably from 12 to 18 carbon atoms, inclusive of the carbon atom of the carbox~l group of the fatty acid. The aliphatic radical may be saturated or unsaturated and may be straight or branched. Straight chain saturated fatty acids are preferred. Mixtures of fatty acids may be used, such as those derived from natural sources such as tallow fatty acid, coco fatty acid, soya fatty acid, etc., or from synthetic sources available from industrial manufacturing processes.
Thus, examples of the fatty acids from which the polyvalent metal salt stabilizers can be formed include, for example, decanoic acid, dodecanoic acid, palmitic acid, 2~
myristic acid, stearic acid, oleic acid, eicosanoi.c acid, tallow acid, coco fatty acid, soya fatty acid, 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 can also be used. A key requirement is that the metal salt of the fatty acid must be dispersible in the aqueous medium containing the Carbopol within the composition. The most preferred metal cations are selected from Group lA. Naturally, for ~ADD compositions, as well as any other applications where the invention composition will or may come into contact with articles used for the handling, storage or serving of food products or which otherwise may come into contact with or be consumed by people or animals, the metal salt should be selected by taking into consideration the toxicity of the metal. For this purpose, the calcium and magne3ium and sodium salts are especially higher preferred as generally safe food additives. Sodium stearate i9 the most preferred species of the instant invention.
The amount of the fatty acid salt stabilizer to achieve the desired enhancement of physical stability and viscosity enhancement will depend on such factors as the nature of the fatty acid salt, the nature and amount oE the thixotropic agent, detergent active compound, inorganic salts, other LADD
ingredients, as well as the anticipated storage and shipping conditions.

Generally, however, amounts of the metal fatty acid salt or fatty acid stabilizing agents in the range of from 0 to 0.4 wt.~, preferably from 0.005 to 0.6 wt.~, especially preferably from 0.04 to 0.50 wt.~, and most preferably 0.02 ~o 0.4 wt.~, provide a long-te~ stability and absence of phase separation upon standing or during transport at both low and elevated temperatures as are required for a commercially acceptable product. To obtain the ~laximum benefit of the fatty acid or the metal salt of the fatty acid it is critical that they must be properly dispersed in the medium containing the polymeric thickener.
Depending on the amounts, proportions and types of physical stabilizers and thixotropic agents, the addition of the fatty acid salt or fatty acid not only increases physical stability, but alRo provides a simultaneous increase in apparent viscosityO Ratios of fatty acid salt or fatty acid to thixotropic agent in the range of from 0.02-0.4 weight percent fatty acid salt and from 0.1 - 2.5 wei~ht percent thixotropic agent are usually sufficient to provide these simultaneous benefits and, therefore, the use of these ingredients in these ratios is most preferred.
Other conventional ingredients may be included in these compositions in small amounts, generally less than 3 weight percent, such as perfume, preservatives, dyestuffs and pigments and the like, all of course being stable to chlorine bleach compound and high alkalinity (properties of all components). Especially preferred for coloring are the chlorinated phthalocyanines and polysulphides of 7 ~

~luminosllicate which provide, respectively, pleasing green and blue tints. Tio~ may be employed for whitening or neutralizing off-shades.
The liquid ADD compositions of this invention are readily employed in known manner for washing dishes, other kitchen utensils and the like in an automatic dishwasher, provided with a suitable detergent dispenser, in an aqueous wash bath containing an effective amount of the composition, generally sufficient to fill or partially fill the automatic dispenser cup of the particular machine being used.
DETAILED DESCRIPTION OF THE_INVENTION
The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples.
All amounts of proportions referred to herein are by weight of the composition unless otherwise indicated.

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The procedure ~o~ ~4rm~ng ~o~ulation~ (A~O) comprise~ ~onming a ~ir~t a~ueou~ ~olution A' by ~ddin~ a~
room temperatur~ urder mixin~ conditio~ fir~t the di~per~ion o~ the Nora~ol LMW-45~ into tha wa~er, seco~dly, th~ Carbopol S 614 and thirdly, a sufficlent amount of caustic ~oda to j~st neutrali7e ~he ~olyc~rboxylate pol~mer. A 3econd agueou~
solutio~ (B') i~ ~ormed by ~ddin~ at room tempex~ture under conditions of mixing to the water, ~ir~t the builde~ ~lt, secondly, the ~oqium eulfate, thir~ly, the ~odium ~l~ilicate an~ lastly, the bala~c~ o~ the cau~tic ~oda. A third a~ou8 ~olution (C') whlch is s~titled the premi~ i~ ~ormed ~t 60-70C
by adding to wate~ (3 ~arka~ fi~st ~e did~cyldiphenyl ethe~
disulfonate (0.4~ part~) and secondly, the ætearic acld (O.lS
part~). Solution ~ a~ded under condiCiong o~ mixins a~
room tem~erature to Solutio~ A'~ The mixed ~olu~ion~ o~ A' ~
B' a~ room ~emperature under conditions o~ mixin~ i~ a~ded the third solution (C'). The combined solutions of A', B' and C' are added to the 13% hypochlorite solution to form the final formulations A-O.
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Formulatio~ 0 we~e te~to~ ~or ~oil removal on di~he~ in a ~tandard multl-~oil ~e~e u~ing a Bo~ch SMS5~1 (di~hw~ah~r) at 65C wherein 3 ml. of Galax~ ~in~e ald ~old ~y Colya~e Palmoli~e Co. wa~ u~ed. A rating ~y~tem of l-10 wa~
~5 u~ed with lO rep~e~en~ln~ maximum ~oil removal.

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~G971~ ~ 62301-1767 ~ULTI-$0IL TEST
This method allows to evaluate the removal of critical soils on several representative items of dishes as well the performance on soiled glasses.
ETHODOLOGY:
. Dishwasher: Bosch SMS 5021 . Rinse Aid: 3 ml Galaxy . Recommended Dosage: Gel emerald 55 g Galaxy 55 g . Dishwasher Load:
Lower Basket: . 6 Plates with Porridge Soils . A Stainless Steel Plate with Rice Soils . A Stainless Steel Plate with White Sauce (mixture made from milk, flour, butter) . Cutleries in the Cutlery Basket:
with Rice (2 spoons, 2 knives, 2 forks) with Porridge (2 spoons ~ 2 knives) Upper Basket: . 8 Glasses Soiled with Tomato Juice . 8 Glasses Soiled with Cocoa Beverage . 8 Glasses Soiled with Milk 4 products are ~ested simultaneously in 4 dishwashers according to the statistical procedure made in "Latin Square".
A wash cycle with 4 replicates per product.
. pH value is measured during wash cycle . Washing Program: .Prewash .Main Wash at 65 C
.Rin~qe Cycle .Drying ~ 62301-1767 Water hardness during wash: 100-150 ppm CaCoz.
EVALUATION:
. Each piece of dishes is evaluated according to a scale from 0 (no removal) to 10 (complete soil removal).
' . The glasses are evaluated in a viewing box in . overall performance (from 0 to 10) . p~r item of performance as .Filming (on a scale from 0 to 4 (no filming) .Spotting (0 to 4 (no spotting) .Soil Redeposition (0 to 4) Example of Results shown in the preceeding Table.

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2~ 62301-1767 RHEOLOGICAL DETERMINATION
CARRIMED (model:_ CSL 100): This apparatus is equipped to operate in oscillating mode ln order to fully assess the viscoelastic behavior of Carbopol-based No P gels. This ~e~hod is attractive for its "in depth" characterization of gel structures because several experiments can be carried out to test completely one sample.
One experiment usually done on gels is "The Structure Recovery~': This one allows to characterize how the gel structure is recovered after breakage by an high steady stress:
STRUCI~RE RECOVERY MEASURING CON ITIONS:
. The samples are studied Eirst after 1 week aging (i.e. when the structure is obtained) and on aging. (1 month, 2 months, 3 months) at different storage temperatures.
The Carbopol NOP Gels are observed to be rheologically stabilized within 2 weeks - 1 month period.
. Cell for measuring: Cone-Plate (gap: 53 Mm - cone angle: 4 degrees - (cone diameter: 2 cm) . The gel structure is broken, first by a steady stress of 400N/m2 during 1'. After an equilibrium time of 10 sec, storage modulus (G'~ representative of ~he alastic component and loss modulus ~G") representative of the viscous component are determined versus recovery time. In oscillating mode:
Measuring Conditions: Torque: 100 micro N.m Oscillation Frequency: 1 Hz Thermostatisation Temp.: 20 C

~ 31 J~ 3 ~ 2301-1767 The moduli are observed to be stabilized around 20' (1200 sec).

RHEOM~T 30 (CONTR~VES~: This apparatus observes the ~otational viscometer principle operating in steady mode to determine the apparent viscosities on a large range of shear rates (30-32 values).
PRINCIPLE:
The concentric measuring cell i8 based on a measuring head and measuring tube rigidly coupled together, the measuring bob being driven by a DC motor. The braking torque exerted by the sample results in a change in the motor's armature current.
Translated in viscosity, shear stress and shear rate from measuring conditions. The data are then analyzed in terms of Casson Law ( ~ (Pa) = Go or Bingham Law ( G = Go +~ ~ ) G = shear stress ~ = shear rate gradient ~ = Viscosity (Type of Cello Setting B) Measurement Temp.: 25 C).
RHEOMAT 108 (CONTRAVES): Uses the ~ame principle as Rheomat 30. But only operates at selected shear rate appropriate to conditions and tested sample.
Viscosity measurement is done after perturbation 30 sec.
SETT NG FOR CARBOPOL-BASED FORMULAE:
Cell: 2 Rate: 1 ( ~= 17.7 sec~) (Minimum value detectable: 0.3 Po sec) SETTING FOR_EMERALD SOLUTIONS.

~ 37 -~ 62301-1767 Cell: 2 Rate: 4 ( ~ = 64 sec-l) tMinimum value detectable: 0.2 Po sec).
CEL~ 2: Measuring cup diameter: 32.54 mm Measuring bob: 24 mm.
PHYSICAL STABILITY. The samples are stored in small glasswares (brown to avoid W influence) and the physical stability is visually determined on aging at 3 te~lperatures of storage 4C, 35C, RT.
The sample is considered a~ physically stable when no presence of syneresis is observed on ageing ~syneresis: liquid separation from gel in bottom of gla~sware for emerald structures.) 7~

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3xample IV 62301-1767 Forrnulas F-I were formulated according to the following procedure.
F G H
, _ _ I
ICarbopol 1.0 1.0 1.0 1.0 l ... 1614 l ¦Polygel DX b 0 0 0 I ._ ._ _, IGantrez O 0 0 0 ¦Sodïum ~~~~ 25-.b-- 25.025.0 25.0 ¦Silicate 1~47.S%) ¦NaOH (S0%) 4.s 4.5 4.5 ~

¦Good-Rite_~ ___ 7.75 7 75i--75 1¦
¦K-¦7058N(45%) .. .. _ _I
Acusol 445N 9.25 7.75 7.75 7.75 . . _ _ ~
l Sodlurn 0 5 5 5 ~ Carbonate Sodium -~ o --- - 6 -- 6 -- ~
Fluoride Dowfax 3B2 0.8 0.8 0.8 0 8 ------(45O
_... ... _ ...... _ .. ___ ~ 62301-1767 Fatty Acid' ~ 0.1 - 0.1 NaOCï (12%) 10.0 9.2 9.2 10.0 Colorant -- .0-0-3 .00-3 .b0:1 .003 ~-Fragrance .03 ~ 03 .03 .03 Sodium- 0.i 0 0.1 0 Stearate _ ._ _ _ _~_ Water Balance ~alance Balance BalanCe Sodium _ _ 1.5 ~
l Ben~oate Density1.23 1.32 1.32 _ Spottin-g-~-- 1 0~~--- 1-`---- ~ --- 2 _ Filming~ 2.6 2.0 2 _ Viscosity~ ~800 ~- 3980 3620----- 6500 --C1 Avg~ 1.04 0.93 0.94 1.05 - _ -~Fatty acid is a mixture of stearic acid and palmatic acid -ratio 1:1 2Te~ted according to ASTMD-3566 79 3Tested according to ASTM2-3566-79 ~Brookfield HATD Model Spindle #4 20 rpms, R.T. reading taken after 90 seconds of shear on example.

~r~q 5~ 3~7~

- The above formulas were made by first making an aqueous solution of the cro~s-linked polymer such as Carbopol 614 at room temperature amd subsequently neutralizing the polymer under mild agitation at room temperature first with ~he sodium silicate and then the sodium hydroxide. The 7058 polymer was then added with ~lurring followed by the 44 SN
polymer. To the resultant solution was added with slurring the sodium carbonate then an aqueous solution of the NaF (if present), then an emulsion of the Dowfax 3~2 and the fatty acid or sodium st~arate, then the bleach was added with slutting and finally the fragrance was added with slurring if A~203 or so~ium benzoate were added, they were post added to the composition with ~tirring.
The emulsion of the Dowfax 3B2 and fatty acid or sodium stearate was formed by fir~t heating the Dowfax 3~2 to a temperature of 70-80C and the powdered fatty acid or sodium stearate was added to the heated Dowfax 3B2 with stirring.
The formed heated emul~ion was then added to the batch.

Claims (9)

1. An aqueous automatic dishwasher composition comprising approximately by weight:
(a) 0 to 20% of at least one phosphate free builder salt;
(b) 1 to 20% alkali-metal silicate;
(c) 0 to 8% alkali metal hydroxide;
(d) 0 to 5% organic detergent active material;
(e) 0 to 5% foam depressant;
(f) chlorine bleach compound in an amount to provide 0.2 to 4% of available chlorine;
(g) 1 to 20% of at least onelow molecular weight polyacrylate;
(h) 0 to 2.0% of a metal salt 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 thickener; and (k) water, wherein said water is bound to said other ingredients in said composition.

2. The composition of Claim 1, wherein the detergent builder salt is sodium carbonate.

3. The composition of Claim 2 wherein the foam depressant is in the range of from 0.1 to 1.5%.

4. The composition of Claim 1 wherein the detergent active material is in the range of 0.1 to 5.0%.

5. The composition of Claim 2 in which the chlorine bleach compound is sodium hypochlorite.

6. The composition of claim 2 in which the foam depressant is an alkyl acid phosphate ester, an alkyl phosphoric acid ester containing one or two C12-20 alkyl or ethoxylated alkyl groups.

7. The composition of claim 2 wherein the amount of components is such that when the composition is diluted to 10 g/l the pH of the diluted composition is from 11.2 to 13.5.

8. The composition of Claim 1, wherein the concentration of said fatty acid is .005 to 2.0 wt.%

9. A method for cleaning soiled dishware in an automatic dishwashing machine which comprises contacting the soiled dishware in an automatic dishwashing machine in an aqueous washbath having dispersed therein an effective amount of the composition of claim 2 in an amount sufficient to provide a pH of the washbath of at least 11.2.