US3255117A - Low-foaming dishwashing composition - Google Patents

Low-foaming dishwashing composition Download PDF

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US3255117A
US3255117A US31462663A US3255117A US 3255117 A US3255117 A US 3255117A US 31462663 A US31462663 A US 31462663A US 3255117 A US3255117 A US 3255117A
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sodium
alkali
dishwashing
compositions
composition
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Kenneth W Knapp
John S Thompson
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FMC Corp
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FMC Corp
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D19/00Degasification of liquids
    • B01D19/02Foam dispersion or prevention
    • B01D19/04Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0409Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • C11D1/721End blocked ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0026Low foaming or foam regulating compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • C11D3/3958Bleaching agents combined with phosphates

Description

United States Patent 3,255,117 LOW-FOAMING DISHWASHING COMPOSITION Kenneth W. Knapp, Pennington, and John S. Thompson,

Princeton Junction, N.J., assignors to FMC Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Oct. 8, 1963, Ser. No. 314,626 8 Claims. (Cl. 252-99) This invention relates to low-foaming detergent compositions for use in automatic dishwashers and is directed particularly to detergent compositions which do not attack overglaze colors and decorations of fine china and .the aluminum of pots and pans, and do not tarnish stainless steel used in cutlery and on the surfaces of dishwashers which are exposed to them.

The dishwashing compounds used in automatic dishwashers preferably are characterized by their low-forming properties, since the washing action of such equipment relies largely on the scrubbing effect of vigorous jets or sprays of liquid which would be rendered relatively ineffective if cushioned by the action of large amounts of foam. However, the low-foaming compositions heretofore used in automatic dishwashers have sometimes been relatively strong or harsh in their action on the surface or decorations carried by the articles being washed. For example, most dishwashing compounds contain polyphosphates as soil emulsifiers and water softeners; such phosphates tend to attack aluminum articles such as pots and pans and are injurious to overglaze decorations on dinnerware. The injury to decorations on fine china is particularly objectionable and is believed to be due to weakening or destruction of the bonding material by which the decoration is secured to the glaze on the china. The bond generally consists of a glass-like lead bore silicate flux containing about 60 to 65% lead and minor proportions of boric oxide and silica. The detergents used in the usual dishwashing compounds are believed to attack the flux constituents, weakening the bond to such an extent that the decorative material may be washed or rubbed off of the glaze.

It is known that sodium silicate serves to reduce the attack of polyphosphates on glazing and decorative material. It also has been suggested that the action of alkalicarbonates, -orthophosphates and -sulfates, also common ingredients in dishwashing compounds can be inhibited in their attack upon vitreous and ceramic surfaces by the use of water-soluble zinc, beryllium or aluminum compounds. However, when soluble silicate and aluminate compounds have both been used in dishwashing compounds heretofore, an undesirable precipitate has been formed which tends to deposit on the dishes, cutlery and exposed surfaces of the dishwasher leaving them tarished or unclean in appearance. While such an objectionable precipitate can be emulsified or suspended if a suitable surfactant composition is employed, the surfactants heretofore considered suitable for this purpose have been employed in such large amounts as to render the compositions unacceptable for use in automatic dishwashers due to the excessive amount of foam produced.

Accordingly, the principal objects of the present invention are to reduce the injury or attack upon decorated china by dishwashing compositions, to limit the formation of undesired precipitates in dishwashing solutions, and to assure the effective cleaning and protection of articles subjected to the action of low foaming detergent materials in automatic dishwashers.

These and other objects and features of the present invention will appear from the following description therepresent invention by suitably combining and relating the character and proportions of the ingredients of the herein dishwashing compounds. In particular, it has now been found possible to provide excellent dishwashing compounds in which the formation of objectionable amounts of the undesired precipitate heretofore produced upon dissolving polyphosphate, orthophosphate, carbonate, sulfate and other alkaline and detergent agents in the presence of aluminate and silicate are prevented without resorting to the use of large, foaming amounts of surfactants. This advantage is attained by providing a dry composition containing as essential ingredients an alkali salt of an amphoteric metal, particularly an alkali aluminate, zincate or berylliate, in the amount of about 0.5 to 5%, and preferably 1 to 3%, by weight, an alkali silicate having an Me O to SiO ratio of 1:1 to 1:3 in the amount of about 10 to 30%, and preferably 15 to 20%, by weight, a dry agent which yields available chlorine in aqueous solution, preferably a chlorinated cyanuric compound from the group consisting of trichlorocyanuric, dichlorocyanuric acid or an alkali salt of dichlorocyanuric acid, in the amount of about 1 to 5%, and preferably 2 to 3%, by weight, a sodium polyphosphate in the amount of about 20 to 50%, and preferably 30 to 45%, by weight, a nonionic surfactant resistant to the action of available chlorine, particularly such a surfactant having the formula in which R is an alkaryl group in which the alkyl group has 6 to 13 carbon atoms or an alkyl group having. 8 to 18 carbon atoms, x is 10 to 18, and R is an alkyl, aryl, alkaryl or aralkyl group having 3 to 12 carbon atoms, in the amount of about 1 to 5%, and preferably 1 to 3%, by weight, and the balance an alkali sulfate, orthophosphate, carbonate or chloride.

The conjoint presence of the amphoteric metal ions and the silicate in this composition effectively inhibits attack of aqueous solutions of the composition on overglaze decorations by alkaline agents present in the dishwashing solution. In this way, destruction of the bond by which the decorative material is secured to the underlying glaze is reduced or eliminated. The relationship or ratio of the amphoteric ion material with respect to the silicate as well as to the other ingredients in these compositions is critical, and whereas heretofore it was considered necessary to employ large amounts of surfactant materials in order to provide effective cleaning in compositions containing the amphoteric metal ions and silicate, the present compositions are extremely effective cleansing agents despite the small amount of surfactant, a nonionic available chlorine-resistant surfactant, employed in them. It is believed that the joint action of the nonionic surfactant with the polyphosphate and the chlorinated compound is responsible for the effective cleaning. In any event, the ability of the composition to clean dishware effectively without requiring excessive and foam-producing amounts of surfactant is most important in utilization of this composition.

The dishwashing compositions of this invention contain a major part, about 20 to 50%, and preferably 30 to 45%, by weight of a sodium salt of a polyphosphoric acid having from 2 to 20 phosphorus atoms, particularly sodium tripolyphosphate and tetrasodium pyrophosphate.

This ingredient serves as detergency builder, soil emulsifier and a water softener. Use of more than the indicated maximum amount of the polyphosphate is apt to result in attack on china, while use of less than the indicated minimum provides ineffective dishwashing.

The chlorinated compound, preferably trichlorocyanuric acid, dichlorocyanuric acid or an alkali salt of dichlorocyanuric acid, and particularly the sodium and potassium salts, is employed in the amount of about 1 to and preferably 2 to 3%, by weight in the dishwashing composition. Other chlorinated compounds available in dry form and cap-able of yielding available chlorine in aqueous solution may be used. Such other compounds include chlorinated trisodiurn orthophosphate and dichlorodimethyl hydantoin. Likewise, other alkaline salts of dichlorocyanuric acid can be used, for example the magnesium and calcium salts.

This chlorinated compound coacts with the polyphosphate and the nonionic surfactant to provide effective cleansing of the dishware and cutlery. It not only serves to oxidize and aid in the removal and emulsification of proteinaceous soil, but at the same time acts as a bleach through its available chlorine, thereby removing coffee, tea and the like stains. Use of this ingredient in the amount of 1 to 5%, and preferably 2 to 3%, by Weight makes it possible to employ amounts of the herein nonionic surfactant which are sufficiently small to avoid excessive foaming, while at the same time providing effective cleaning of dishware and cutlery.

The nonionic surfactants useful in the herein compositions are the nonionic surfactants resistant to the action of available chlorine, particularly those having the following formula:

in which R is an alkaryl group in which the alkyl group has 6 to 13 carbon atoms or an alkyl group having 8 to 18 carbon atoms, x is 10 to 18, and R is an alkyl, aryl, alkaryl or aralkyl group having 3 to 12 carbon atoms. The preferred agents are those in which R is an alkyl phenylene group in which the alkyl group has 8 to 9 carbon atoms, x is 10 to 18 and R is an alkyl group having 3 to 7 carbon atoms or is a benzyl group. These agents are used in the present composition in the amount of only about 1 to 5%, and preferably 1 to 3%, by weight. It is interesting to note by way of contrast that the anionic surfactants are ineffective in the compositions of this invention, serving to create excessive amounts of foam, even when they are used in small amounts. The foam binds pumps and prevents the necessary strong mechanical action which results from impingement of water on the surface of dishes in a dishwasher. Likewise, the cationic surfactants are ineffective since they are incompatible with alkaline systems. Accordingly, the kind and amount of surfactant employed in the dishwashing compositions of this invention are quite specific; the specified minimum amount is required to provide effective cleansing, while use of more is uneconomical and is not needed for effective cleaning.

The compositions of the present invention also contain both amphoteric metal compounds, such as sodium aluminate, and a sodium silicate. The amounts of these agents employed and the ratio of one to the other, as well as the form in which they are present in the dishwashing composition and solution, is important. Thus, when the polyphosphate sodium tripolyphosphate is empolyed in the amount of about 20 to 50% by weight of the composition, the alkali aluminate is employed in the amount of about 0.5 to 5% of the weight of the total dishwashing composition. The sodium silicate or other alkali silicate is employed under these circumstances in the amount of about 10 to 30% by weight. Preferred compositions contain about 1 to 3% by weight of sodium aluminate or other amphoteric metal compound and about 15 to by weight of sodium silicate or other alkali silicate.

The amphoteric metal compound employed preferably is sodium aluminate, although other alkali aluminates and alkali zincates and berylliates are also useful. The type of silicate employed is important; the silicates having an Me O to SiO ratio of 1:1 to 1:3 in which the Me is an alkali metal, and preferably sodium or potassium, are the useful silicates. The silicates not falling within the above class have been found to be substantially less effective in the compositions of this invention.

The alkali carbonates, orthophosphates, sulfates and chlorides employed in compositions of this invention are employed for their usual purpose, principally as fillers. The preferred agents from this class are sodium sulfate, sodium orthophosphate, sodium chloride and sodium carbonate, although other alkali metal salts from this group have been found useful.

The pH of dishwashing solutions containing the compositions of the present invention may vary considerably, as for example, from about 10 to 12. The preferred pH of aqueous dishwashing solutions containing 0.3% of the dishwashing composition is about 10.5, or, from about 10.0 to 11.0. The pH in any case depends primarily upon the amount and character of the alkali polyphosphate and the alkali sulfates, orthophosphates, carbonates or chlorides used in producing the composition. In general, the amount of the sodium aluminate or other alkali compound of an amphoteric metal employed may be increased as the pH of the dishwashing solution is increased; but undesired amounts of precipitate may be formed if the amount of sodium aluminate used substantially exceeds about 5% by weight of the composition.

When the various ingredients used in producing dishwashing compositions in accordance with the present invention are employed in amounts and proportions substantially as indicated above, it is found that a chemical, or perhaps physical, balance is maintained which assures the continued presence of aluminate or other amphoteric metal ions in the dishwashing solution. Moreover, the formation of objectionable deposits or unsightly films on the surfaces of the articles being washed is prevented. Overglaze decorations on fine china are thereby protected and tarnishing of stainless steel, aluminum and other metallic surfaces or articles exposed to the dishwashing solution does not occur. Furthermore, undesirable foaming of the dishwashing solution is avoided even under the severe conditions encountered in automatic dishwashers.

In order to illustrate typical dishwashing compositions embodying the present invention, the following examples are cited wherein the percentages indicate percent by weight of the mixture, and the compositions were blended in a twin shell liquids-solids blender.

Nonionic Surfactant A in the examples is:

(O C2134) m0 CH1 Nonionic Surfactant B is:

(OC2H4)10OC4H9 Cs n Example 1 Percent Sodium tripolyphosphate 20 Sodium hexametaphosphate l0 Disodium phosphate 10 Sodium chloride 41 Sodium silicate (Na O:2SiO 13 Sodium aluminate Nonionic Surfactant B 1.5 Potassium dichlorocyanurate 2.5

Example 2 Percent Tetrasodium pyrophosphate 30 Sodium carbonate 39 Sodium metasilicate, anhydrous 25 Sodium zincate 2 Nonionic Surfactant A 1.5 Sodium dichlorocyanurate 2.5

Example 3 Percent Sodium tripolyphosphate 40 Sodium sulfate 37 Sodium silicate (N21 O:2SiO 17 Sodium aluminate 2 Nonionic Surfactant B 1.5 Sodium dichlorocyanurate 2.5

Example A Percent Sodium tripolyphosphate 20 Sodium hex-ametaphosphate Disodium phosphate 10 Sodium chloride 43 Sodium silicate (Na O:2SiO 13 Nonionic Surfactant B 1.5 Potassium dichlorocyanurate 2.5

The formulation cited above (Example A) is identical to that presented in Example 1 with the exception that the sodium aluminate has been replaced with sodium chloride.

Example B Percent Sodium tripolyphosphate 40 Sodium sulfate 39 Sodium silicate (Na O:2SiO 17 Nonionic Surfactant B 1.5 Sodium dichlorocyanurate 2.5

The formulation of this Example B is identical to that presented in Example 3 with the exception that the sodium aluminate'has been replaced with sodium sulfate.

Example 6.China-attack test Wedge shaped sections (five different patterns) of overglaze chinaware dinner plates, containing a wide variety of different colored pigments, were immersed in 0.3% solutions of the compositions of Examples 1, 2, 3, A and B for 3 hours at boiling. Upon completion of the test, the sections were removed from the solution, wiped with adry cloth and examined for irridescence, dulling and pattern erosion. The chinaware patterns were noticeably dulled and eroded by the compositions given in Examples A and B while patterns tested with the aluminate-containing compositions given in Examples 1, 2 and 3 remained bright and unalfected.

The formulas for dishwashing compositions set forth in Examples 1 through 3 are, of course, merely illustrative and other compositions and amounts and ratios of the ingredients may be employed Within the herein limits. Although the chlorinated compounds shown by way of example are dichlorocyanurates, other chlorinated compounds, e.g. trichlorocyanuric acid, chlorinated trisodium phosphate and dichlorodimethyl hydantoin serve as effective replacements for them in the formulations of the above examples. Likewise, other salts of the amphoteric metals are effective replacements for sodium aluminate and zincate.

What is claimed is:

1. A low-foaming dishwashing composition which does not attack overglaze colors and decorations of fine china consisting essentially of the following ingredients in the indicated weight percentages: 20 to 50% of a sodium polyphosphate, 1 to 5% of an alkali metal salt of dichlorocyanuric acid, 10 to 30% of a sodium silicate having an Na O:SiO ratio of 1:1 to 1:3, 0.5 to 5% of an amphoteric metal compound from the group consisting of alkali aluminates and alkali zincates, 1 to 5% of a nonionic surfactant having the following formula:

in which R is an alkylphenyl group in which the alkyl group has 6 to 13 carbon atoms or an alkyl group having 8 to 18 carbon atoms, x is 10 to 18, and R is an alkyl, phenyl, alkylphenyl or phenylalkyl group, said R having 3 to 12 carbon atoms, and the balance an alkali metal salt from the group consisting of sulfates, orthophosphates, carbonates and chlorides.

2. A low-foaming dishwashing composition which does not attack overglaze colors and decorations of fine china consisting essentially of the following ingredients in the indicated weight percentages: 30 to 45% of a sodium polyphosphate, 2 to 3% of an alkali metal salt of dichlorocyanuric acid, 15 to 20% of a sodium silicate having an Na O to Si0 ratio of 1:1 to 1:3, 1 to 3% of an amphoteric metal compound from the group consisting of alkali aluminates and alkali zincates, 1 to 3% of a nonionic surfactant having the following formula:

moc np on' in which R is an alkylphenyl group in which the alkyl group has 6 to 13 carbon atoms or an alkyl group having 8 to 18 carbon atoms, x is 10 to 18, and R is an alkyl, phenyl, alkylphenyl, or phenylalkyl group, said R having 3 to 12 carbon atoms, and the balance an alkali metal salt from the group consisting of sulfates, orthophosphates, carbonates and chlorides.

3. A low-foaming dishwashing composition which does not attack overglaze colors and decorations of fine china consisting essentially of the following ingredients in the indicated weight percentages: 20 to 50% of sodium tripolyphosphate, 1 to 5% of an alkali metal dichlorocyanurate, 10 to 30% of a sodium silicate having an Na O to SiO ratio of 1:2, 0.5 to 5% of sodium aluminate, 1 to 5% of a nonionic surfactant having the following formula:

C aHuOwCzHO reOCHzO and the balance sodium sulfate.

4. A low-foaming dishwashing composition which does not attack overglaze colors and decorations of fine china consisting essentially of the following ingredients in the indicated weight percentages: 30 to 45 of sodium tripolyphosphate, 2 to 3% of an alkali metal dichlorocyanurate, 15 to 20% of a sodium silicate having an Na O to S10 ratio of 1:2, 1 to 3% of sodium aluminate, 1 to 3 of a nonionic surfactant having thefollowing formula:

and the balance sodium sulfate.

5. The composition of claim 4 in which the alkali metal dichlorocyanurate is sodium dichlorocyanurate.

6. The composition of claim 8 in which the alkali metal dichlorocyanurate is potassium dichlorocyanurate.

7 8 7. The composition of claim 3 in which the nonionic References Cited by the Examiner surfactant has the following formula: UNITED STATES PATENTS 2,431,946 12/1947 Lurie 252135 5 2,447,297 8/1948 Wegst et a1 252135 2,455,648 12/1948 Bennett 252135 08H" (OCZHDWOCQHg 2,608,496 8/1952 Tuttle et al 252-135 XR 3,110,677 11/1963 Karablnos 252--99 3,128,250 4/1964 Lintner 252- 99 8. The composition of claim 4 in which the nonionic 10 FOREIGN PATENTS surfactant has the following formula: 559,029 7/1958 Canada 922,252 3/1963 Great Britain.

JULIUS GREENWALD, Primary Examiner.

c 1 (00,134) oo 3, M. WEINBLATT, Assistant Examiner.

Claims (1)

1. A LOW-FOAMING DISHWASHING COMPOSITION WHICH DOES NOT ATTACK OVERGLAZE COLORS AND DECORATIONS OF FINE CHINA CONSISTING ESSENTIALLY OF THE FOLLOWING INGREDIENTS IN THE INDICATED WIEGHT PERCENTAGES: 20 TO 50% OF A SODIUM POLYPHOSPHATE, 1 TO 5% OF AN ALKALI METAL SALT OF DICHLOROCYANURIC ACID, 10 TO 30% OF A SODIUM SILICATE HAVING AN NA2O:SIO2 RATIO OF 1:1 TO 1:3, 0.5 TO 5% OF AN AMPHOTERIC METAL COMPOUND FROM THE GROUP CONSISTING OF ALKALI ALUMINATES AND ALKALI ZINCATES, 1 TO 5% OF A NONIONIC SURFACTANT HAVING THE FOLLOWING FORMULA:
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Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3350318A (en) * 1964-02-18 1967-10-31 Fmc Corp Method of producing detergent composition
US3352785A (en) * 1965-06-18 1967-11-14 Fmc Corp Stable dishwashing compositions containing sodium dichloroisocyanurate
US3356612A (en) * 1965-02-01 1967-12-05 Petrolite Corp Stable detergent compositions
US3361675A (en) * 1965-08-23 1968-01-02 Fmc Corp Dry-mixed detergent compositions
US3390092A (en) * 1965-03-30 1968-06-25 Fmc Corp Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate
US3429822A (en) * 1964-10-09 1969-02-25 Mo Och Domsjoe Ab Detergent compositions
US3468803A (en) * 1966-04-14 1969-09-23 Fmc Corp Dishwashing compositions
US3494868A (en) * 1966-02-15 1970-02-10 Frederick William Gray Dishwashing composition and method of using same
US3755180A (en) * 1972-02-25 1973-08-28 Colgate Palmolive Co Means to inhibit overglaze damage by automatic dishwashing detergents
US4299739A (en) * 1976-03-25 1981-11-10 Lever Brothers Company Use of aluminum salts in laundry detergent formulations
US4443270A (en) * 1981-07-17 1984-04-17 The Procter & Gamble Company Rinse aid composition
EP0197434A2 (en) * 1985-04-03 1986-10-15 Henkel Kommanditgesellschaft auf Aktien Rinsing agents for use in mechanical dish washing
EP0224167A2 (en) * 1985-11-25 1987-06-03 Henkel Kommanditgesellschaft auf Aktien Use of polyglycol dialkyl ethers as viscosity regulators for aqueous solutions containing anionic surface-active agents
US4859358A (en) * 1988-06-09 1989-08-22 The Procter & Gamble Company Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection
EP0337760A2 (en) * 1988-04-14 1989-10-18 Unilever Plc Detergent compositions
US4908148A (en) * 1989-02-13 1990-03-13 The Procter & Gamble Company Rinse additive compositions providing glassware protection comprising insoluble zinc compounds
US4933101A (en) * 1989-02-13 1990-06-12 The Procter & Gamble Company Liquid automatic dishwashing compositions compounds providing glassware protection
EP0383482A2 (en) * 1989-02-13 1990-08-22 THE PROCTER & GAMBLE COMPANY Granular automatic dishwasher detergent composition providing glassware protection
US4988452A (en) * 1988-06-09 1991-01-29 The Procter & Gamble Company Liquid automatic dishwashing detergent compositions containing bleach-stable nonionic surfactant
US5130043A (en) * 1988-06-09 1992-07-14 The Procter & Gamble Company Liquid automatic dishwashing compositions having enhanced stability
US5180511A (en) * 1989-09-14 1993-01-19 J.M. Huber Corporation Flotation aid and process for removal of impurities from silicate minerals
US5624892A (en) * 1995-05-19 1997-04-29 Lever Brothers Company, Division Of Conopco, Inc. Process for incorporating aluminum salts into an automatic dishwashing composition
US5698506A (en) * 1995-05-19 1997-12-16 Lever Brothers Company, Division Of Conopco, Inc. Automatic dishwashing compositions containing aluminum salts
US5703027A (en) * 1994-11-29 1997-12-30 The Procter & Gamble Company Monomeric rich silicate system in automatic dishwashing composition with improved glass etching
US5731277A (en) * 1996-06-21 1998-03-24 Lever Brothers Company, Division Of Conopco, Inc. Automatic dishwashing compositions containing aluminum tetrahydroxide
US6083894A (en) * 1999-03-19 2000-07-04 S. C. Johnson Commercial Markets, Inc. Liquid automatic dishwashing composition with glassware protection
WO2001042410A1 (en) * 1999-12-08 2001-06-14 The Procter & Gamble Company Compositions including ether-capped poly(oxyalkylated) alcohol surfactants
GB2361708A (en) * 2000-03-02 2001-10-31 Reckitt Benckiser Nv Dishwashing compositions comprising ceramics
US6448210B1 (en) 1999-03-19 2002-09-10 Johnsondiversey, Inc. Liquid automatic dishwashing composition with glassware protection
US6506945B2 (en) 1999-12-08 2003-01-14 The Procter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
DE10225116A1 (en) * 2002-06-06 2003-12-24 Henkel Kgaa Dishwasher detergent with improved glass corrosion protection II
US6686330B2 (en) 1999-12-08 2004-02-03 The Procter & Gamble Company Compositions including ether-capped poly (oxyalkylated) alcohol wetting agents
US20040147427A1 (en) * 2002-11-14 2004-07-29 The Procter & Gamble Company Rinse aid containing encapsulated glasscare active salt
US20040176264A1 (en) * 2002-12-30 2004-09-09 The Procter & Gamble Company Rinse aid composition containing water-soluble metal salt for use in automatic dishwashing for glassware corrosion protection
US20040176269A1 (en) * 2002-12-30 2004-09-09 The Procter & Gamble Company Process of preparing in-situ water-soluble zinc salt for use in automatic dishwashing compositions
US20050003979A1 (en) * 2003-07-02 2005-01-06 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
US6844309B1 (en) 1999-12-08 2005-01-18 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
US20050020464A1 (en) * 2003-07-02 2005-01-27 Smith Kim R. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US20050039781A1 (en) * 2002-11-01 2005-02-24 The Procter & Gamble Company Dispensing device for liquid detergent compositions
US20050090417A1 (en) * 2002-02-09 2005-04-28 Hahn Karlheinz U.G. Glassware corrosion inhibitor
US20050087213A1 (en) * 2001-02-22 2005-04-28 Hahn Karlheinz U.G. Water-soluble glass as corrosion protector in dishwashing machines
US20050130863A1 (en) * 2002-01-18 2005-06-16 Adrian Blagg Dilutable cleaning compositions and their uses
US20070054824A1 (en) * 2003-05-28 2007-03-08 Rackitt Benckiser N.V. Composition for the protection of glassware in a dishwashing process
US20070054826A1 (en) * 2003-10-17 2007-03-08 Reckitt Benckiser N.V. Water-soluble glass composition
US20070054825A1 (en) * 2003-10-17 2007-03-08 Reckitt Benckiser N.V. Composition for protection of glassware in dishwashers
US20080020960A1 (en) * 2006-07-24 2008-01-24 Smith Kim R Warewashing composition for use in automatic dishwashing machines, and method for using
WO2012153143A2 (en) 2011-05-12 2012-11-15 Reckitt Benckiser N.V. Improved composition

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2431946A (en) * 1944-03-22 1947-12-02 American Cyanamid Co Sodium phosphate aluminates
US2447297A (en) * 1942-01-06 1948-08-17 Wyandotte Chemicals Corp Protection of glass surfaces against alkali attack
US2455648A (en) * 1948-12-07 Method of producing an alkaline
US2608496A (en) * 1950-04-01 1952-08-26 J N Tuttle Inc Composition for producing protective coatings
CA559029A (en) * 1958-06-17 Monsanto Chemical Company Mechanical washing of dishes utilizing a detergent containing organic chlorine compounds
GB922252A (en) * 1959-12-21 1963-03-27 Henkel & Cie Gmbh Low foaming washing agents
US3110677A (en) * 1959-04-23 1963-11-12 Olin Mathieson Chlorinated trisodium phosphate
US3128250A (en) * 1959-07-01 1964-04-07 Calgon Corp Corrosion and china pattern fading inhibitor

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2455648A (en) * 1948-12-07 Method of producing an alkaline
CA559029A (en) * 1958-06-17 Monsanto Chemical Company Mechanical washing of dishes utilizing a detergent containing organic chlorine compounds
US2447297A (en) * 1942-01-06 1948-08-17 Wyandotte Chemicals Corp Protection of glass surfaces against alkali attack
US2431946A (en) * 1944-03-22 1947-12-02 American Cyanamid Co Sodium phosphate aluminates
US2608496A (en) * 1950-04-01 1952-08-26 J N Tuttle Inc Composition for producing protective coatings
US3110677A (en) * 1959-04-23 1963-11-12 Olin Mathieson Chlorinated trisodium phosphate
US3128250A (en) * 1959-07-01 1964-04-07 Calgon Corp Corrosion and china pattern fading inhibitor
GB922252A (en) * 1959-12-21 1963-03-27 Henkel & Cie Gmbh Low foaming washing agents

Cited By (86)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3350318A (en) * 1964-02-18 1967-10-31 Fmc Corp Method of producing detergent composition
US3429822A (en) * 1964-10-09 1969-02-25 Mo Och Domsjoe Ab Detergent compositions
US3356612A (en) * 1965-02-01 1967-12-05 Petrolite Corp Stable detergent compositions
US3390092A (en) * 1965-03-30 1968-06-25 Fmc Corp Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate
US3352785A (en) * 1965-06-18 1967-11-14 Fmc Corp Stable dishwashing compositions containing sodium dichloroisocyanurate
US3361675A (en) * 1965-08-23 1968-01-02 Fmc Corp Dry-mixed detergent compositions
US3494868A (en) * 1966-02-15 1970-02-10 Frederick William Gray Dishwashing composition and method of using same
US3468803A (en) * 1966-04-14 1969-09-23 Fmc Corp Dishwashing compositions
US3755180A (en) * 1972-02-25 1973-08-28 Colgate Palmolive Co Means to inhibit overglaze damage by automatic dishwashing detergents
US4299739A (en) * 1976-03-25 1981-11-10 Lever Brothers Company Use of aluminum salts in laundry detergent formulations
US4443270A (en) * 1981-07-17 1984-04-17 The Procter & Gamble Company Rinse aid composition
EP0197434A2 (en) * 1985-04-03 1986-10-15 Henkel Kommanditgesellschaft auf Aktien Rinsing agents for use in mechanical dish washing
EP0197434A3 (en) * 1985-04-03 1987-03-18 Henkel Kommanditgesellschaft Auf Aktien Rinsing agents for use in mechanical dish washing
EP0224167A2 (en) * 1985-11-25 1987-06-03 Henkel Kommanditgesellschaft auf Aktien Use of polyglycol dialkyl ethers as viscosity regulators for aqueous solutions containing anionic surface-active agents
EP0224167A3 (en) * 1985-11-25 1987-11-25 Henkel Kommanditgesellschaft auf Aktien Use of polyglycol dialkyl ethers as viscosity regulators for aqueous solutions containing anionic surface-active agents
EP0337760A2 (en) * 1988-04-14 1989-10-18 Unilever Plc Detergent compositions
EP0337760A3 (en) * 1988-04-14 1992-04-29 Unilever N.V. Detergent compositions
US4859358A (en) * 1988-06-09 1989-08-22 The Procter & Gamble Company Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection
US5130043A (en) * 1988-06-09 1992-07-14 The Procter & Gamble Company Liquid automatic dishwashing compositions having enhanced stability
US4988452A (en) * 1988-06-09 1991-01-29 The Procter & Gamble Company Liquid automatic dishwashing detergent compositions containing bleach-stable nonionic surfactant
EP0383482A3 (en) * 1989-02-13 1992-03-18 THE PROCTER & GAMBLE COMPANY Granular automatic dishwasher detergent composition providing glassware protection
US4933101A (en) * 1989-02-13 1990-06-12 The Procter & Gamble Company Liquid automatic dishwashing compositions compounds providing glassware protection
US4908148A (en) * 1989-02-13 1990-03-13 The Procter & Gamble Company Rinse additive compositions providing glassware protection comprising insoluble zinc compounds
EP0383482A2 (en) * 1989-02-13 1990-08-22 THE PROCTER & GAMBLE COMPANY Granular automatic dishwasher detergent composition providing glassware protection
US5180511A (en) * 1989-09-14 1993-01-19 J.M. Huber Corporation Flotation aid and process for removal of impurities from silicate minerals
US5703027A (en) * 1994-11-29 1997-12-30 The Procter & Gamble Company Monomeric rich silicate system in automatic dishwashing composition with improved glass etching
US5698506A (en) * 1995-05-19 1997-12-16 Lever Brothers Company, Division Of Conopco, Inc. Automatic dishwashing compositions containing aluminum salts
US5624892A (en) * 1995-05-19 1997-04-29 Lever Brothers Company, Division Of Conopco, Inc. Process for incorporating aluminum salts into an automatic dishwashing composition
US5731277A (en) * 1996-06-21 1998-03-24 Lever Brothers Company, Division Of Conopco, Inc. Automatic dishwashing compositions containing aluminum tetrahydroxide
US6448210B1 (en) 1999-03-19 2002-09-10 Johnsondiversey, Inc. Liquid automatic dishwashing composition with glassware protection
US6083894A (en) * 1999-03-19 2000-07-04 S. C. Johnson Commercial Markets, Inc. Liquid automatic dishwashing composition with glassware protection
US6593287B1 (en) 1999-12-08 2003-07-15 The Procter & Gamble Company Compositions including ether-capped poly(oxyalkylated) alcohol surfactants
US6844309B1 (en) 1999-12-08 2005-01-18 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
US6506945B2 (en) 1999-12-08 2003-01-14 The Procter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
US6686330B2 (en) 1999-12-08 2004-02-03 The Procter & Gamble Company Compositions including ether-capped poly (oxyalkylated) alcohol wetting agents
WO2001042410A1 (en) * 1999-12-08 2001-06-14 The Procter & Gamble Company Compositions including ether-capped poly(oxyalkylated) alcohol surfactants
US6806245B2 (en) 2000-03-02 2004-10-19 Reckitt Benckiser N.V. Ceramic dishwashing composition and method for inhibiting corrosion of glassware
US7179776B2 (en) 2000-03-02 2007-02-20 Reckitt Benckiser, N.V. Ceramic dishwashing composition for inhibiting corrosion of glassware
US20030050205A1 (en) * 2000-03-02 2003-03-13 Reckitt Benckiser N.V. Ceramic dishwashing composition and method for inhibiting corrosion of glassware
GB2361708A (en) * 2000-03-02 2001-10-31 Reckitt Benckiser Nv Dishwashing compositions comprising ceramics
GB2361708B (en) * 2000-03-02 2003-04-23 Reckitt Benckiser Nv Ceramic dishwashing composition
US20040220068A1 (en) * 2000-03-02 2004-11-04 Reckitt Benckiser N.V. Ceramic dishwashing composition for inhibiting corrosion of glassware
US20050253116A1 (en) * 2001-02-22 2005-11-17 Reckitt Benckiser N.V. Water soluble glass as corrosion protector in dishwashing machines
US20100186451A1 (en) * 2001-02-22 2010-07-29 Reckitt Benckiser N.V. Water-soluble glass as corrosion protector in dishwashing machines
US7456142B2 (en) * 2001-02-22 2008-11-25 Reckitt Benckiser N.V. Water-soluble glass as corrosion protector in dishwashing machines
US7361632B2 (en) * 2001-02-22 2008-04-22 Reckitt Benckiser N.V. Water soluble glass as corrosion protector in dishwashing machines
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US20080015101A1 (en) * 2001-02-22 2008-01-17 Hahn Karlheinz U G Water-Soluble Glass as Corrosion Protector in Dishwashing Machines
US20050087213A1 (en) * 2001-02-22 2005-04-28 Hahn Karlheinz U.G. Water-soluble glass as corrosion protector in dishwashing machines
US20050130863A1 (en) * 2002-01-18 2005-06-16 Adrian Blagg Dilutable cleaning compositions and their uses
US7378380B2 (en) 2002-01-18 2008-05-27 Reckitt Benckiser (Uk) Limited Dilutable cleaning compositions and their uses
US20050090417A1 (en) * 2002-02-09 2005-04-28 Hahn Karlheinz U.G. Glassware corrosion inhibitor
US7276470B2 (en) 2002-02-09 2007-10-02 Reckitt Benckiser N.V. Glassware corrosion inhibitor
DE10225116A1 (en) * 2002-06-06 2003-12-24 Henkel Kgaa Dishwasher detergent with improved glass corrosion protection II
US20050039781A1 (en) * 2002-11-01 2005-02-24 The Procter & Gamble Company Dispensing device for liquid detergent compositions
US20040147427A1 (en) * 2002-11-14 2004-07-29 The Procter & Gamble Company Rinse aid containing encapsulated glasscare active salt
US6992052B2 (en) 2002-12-30 2006-01-31 The Procter & Gamble Company Process of preparing in-situ water-soluble zinc salt for use in automatic dishwashing compositions
US20060100118A1 (en) * 2002-12-30 2006-05-11 Song Brian X Process of preparing in-situ water-soluble zinc salt for use in automatic dishwashing compositions
US20040176264A1 (en) * 2002-12-30 2004-09-09 The Procter & Gamble Company Rinse aid composition containing water-soluble metal salt for use in automatic dishwashing for glassware corrosion protection
US20040176269A1 (en) * 2002-12-30 2004-09-09 The Procter & Gamble Company Process of preparing in-situ water-soluble zinc salt for use in automatic dishwashing compositions
US20070054824A1 (en) * 2003-05-28 2007-03-08 Rackitt Benckiser N.V. Composition for the protection of glassware in a dishwashing process
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US20070149431A1 (en) * 2003-07-02 2007-06-28 Lentsch Steven E Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US7196045B2 (en) 2003-07-02 2007-03-27 Ecolab Inc. Warewashing composition comprising a corrosion inhibitor with Al and Zn ions
US7196044B2 (en) 2003-07-02 2007-03-27 Ecolab, Inc. Warewashing composition for use in automatic dishwashing machines, comprising a zinc ion and aluminum ion corrosion inhibitor
US20060270580A1 (en) * 2003-07-02 2006-11-30 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US7135448B2 (en) * 2003-07-02 2006-11-14 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
US20050020464A1 (en) * 2003-07-02 2005-01-27 Smith Kim R. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US20050003979A1 (en) * 2003-07-02 2005-01-06 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, comprising a mixture of aluminum and zinc ions
US20090038649A1 (en) * 2003-07-02 2009-02-12 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US7524803B2 (en) 2003-07-02 2009-04-28 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines comprising an aluminum/zinc ion mixture
US7638473B2 (en) 2003-07-02 2009-12-29 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines, and methods for manufacturing and using
US7452853B2 (en) 2003-07-02 2008-11-18 Ecolab Inc. Warewashing composition comprising zinc and aluminum ions for use in automatic dishwashing machines
US7829516B2 (en) 2003-07-02 2010-11-09 Ecolab Usa Inc. Warewashing composition comprising a Zn/Al corrosion inhibitor for use in automatic dishwashing machines
US7741236B2 (en) * 2003-10-17 2010-06-22 Reckitt Benckiser N.V. Water-soluble glass composition
US20090239731A1 (en) * 2003-10-17 2009-09-24 Reckitt Benckiser N.V. Water-soluble glass composition
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US20070054826A1 (en) * 2003-10-17 2007-03-08 Reckitt Benckiser N.V. Water-soluble glass composition
US20080020960A1 (en) * 2006-07-24 2008-01-24 Smith Kim R Warewashing composition for use in automatic dishwashing machines, and method for using
US7759299B2 (en) 2006-07-24 2010-07-20 Ecolab Inc. Warewashing composition for use in automatic dishwashing machines
US7858574B2 (en) 2006-07-24 2010-12-28 Ecolab Usa Inc. Method for using warewashing composition comprising AI and Ca or Mg IONS in automatic dishwashing machines
US20100242997A1 (en) * 2006-07-24 2010-09-30 Ecolab Usa Inc. Method for using warewashing composition in automatic dishwashing machines
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