US3816320A - Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate - Google Patents

Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate Download PDF

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US3816320A
US3816320A US35991573A US3816320A US 3816320 A US3816320 A US 3816320A US 35991573 A US35991573 A US 35991573A US 3816320 A US3816320 A US 3816320A
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percent
sodium
alkali metal
dichloroisocyanurate dihydrate
sodium dichloroisocyanurate
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D Corliss
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OLIN Corp 120 LONG RIDGE ROAD STAMFORD CT 06904 A CORP OF VA
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
    • C11D3/395Bleaching agents
    • C11D3/3958Bleaching agents combined with phosphates

Abstract

A dishwashing composition having high stability against loss of available chlorine is formulated to contain 0.5 to 10 percent by weight of sodium dichloroisocyanurate dihydrate, 5 to 65 percent of an alkali metal silicate, 20 to 60 percent of a compound having water softening and detergent building properties, usually sodium tripolyphosphate, 0.5 to 10 percent of a low-foaming chlorine-compatible nonionic surface active agent, and 0 to 50 percent of filler, usually sodium carbonate.

Description

United States Patent [191 Corliss STABLE DISHWASI-IING COMPOSITIONS CONTAINING SODIUM DICHLOROISOCYANURATE DII'IYDRATE Related US. Application Data Continuation-in-part of Ser. No. 309,277, Nov. 24, 1972, abandoned.

Inventor:

U.S. Cl 252/99, 252/95, 252/187 C Int. Cl Clld 7/56 Field of Search 252/99, 95, 187 C References Cited UNITED STATES PATENTS 12/1970 Kitchen et a1. 252/99 June 11, 1974 3,575,865 4/1971 Burke et al. 252/99 Primary Examiner-Mayer Weinblatt [57] ABSTRACT A dishwashing composition having high stability against loss of available chlorine is formulated to contain 0.5 to 10 percent by weight of sodium dichloroisocyanurate dihydrate, 5 to 65 percent of an alkali metal silicate, 20 to 60 percent of a compound having water softening and detergent building properties, usually sodium tripolyphosphate, 0.5 to 10 percent of a low-foaming chlorine-compatible nonionic surface active agent, and 0 to 50 percent of filler, usually sodium carbonate.

5 Claims, No Drawings STABLE DISHWASHING COMPOSITIONS CONTAINING SODIUM DICHLOROISOCYANURATE DIHYDRATE CROSS-REFERENCE TO RELATED APPLICATIONS This is a continuation-in-part of Ser. No. 309,277, filed Nov. 24, 1972, now abandoned.

This invention relates to detergent compositions use ful as cleaners and, more specifically, to those compositions containing sodium dichloroisocyanurate dihydrate which are useful in household automatic dishwashing machines.

In the formulation of household automatic dishwashing compositions, the usual practice is to incorporate chlorinating agents, such as chlorinated isocyanurates, alkaline silicates, known detergent builders such as sodium tripolyphosphate, low-foaming chlorinecompatible nonionic surfactants, and, optionally, fillers such as sodium carbonate.

A serious problem with these compositions is their rather poor stability as manifested by loss of available chlorine during storage. A number of solutions to this problem have been put forward, as for example US. Pat. No. 3,390,092 to Keast et al. wherein the chlorine stability of automatic dishwashing fonnulations was enhanced by incorporation of a white paraffin oil.

But despite these marked advances, chlorine losses in automatic dishwashing compositions have not been reduced to the desired minimum. As a consequence, considerable effort is being expended in an effort to develop even more stable formulations.

It has now been found that dishwashing compositions having improved stability against loss of available chlorine contain by weight the following essential ingredients:

1. Sodium dichloroisocyanurate dihydrate. From about 0.5 to about 10 percent, preferably about 1 to about 5 percent.

2. An alkali metal silicate having a M to SiO weight ratio of about 1:3.3 to 1:1, M being either sodium or potassium. From about to about 65 percent, preferably about 20 to about 65 percent.

3. A compound having water-softening and detergent building properties, preferably a polyphosphate having an R 0 to P 0 mol ratio of 1:1 to 2:1, R being either sodium or potassium. From about 20 to about 60 percent, preferably about 30 to about 50 percent.

4. A low-foaming nonionic surface active agent compatible with chlorinated isocyanurates. From about 0.5 to about percent, preferably about 1 to about 5 percent.

5. Filler, usually sodium carbonate or sodium sulfate, or mixtures of these; essentially the balance of the compositions, usually from about 0 to about 50 percent.

Since the presence of moisture tends to accelerate loss of available chlorine in automatic dishwashing compositions containing chlorinated isocyanurate, it is indeed surprising that higher stability against chlorine loss is realized by replacing sodium dichloroisocyanurate with the dihydrate form which contains about 14 percent water. As yet no explanation is known which would account for such enhanced stability.

Sodium dichloroisocyanurate dihydrate is a known chemical entity which is documented extensively in the 2 patent literature. Its description and preparation is disclosed in US. Pat. No. 3,035,056.

In the present formulations the sodium dichloroisocyanurate dihydrate component: provides available chlorine which aids in the cleaning action and acts as an excellent destainer and germicide. The particle size of the sodium dichloroisocyanurate dihydrate has not been found critical; in general, any granular product can be used with good effect.

The nonionic surfactant components result in a preparation high in food soil defoaming power, i.e., a preparation which has little or no tendency to foam by itself or in the presence of a foam-producing food soil. The nonionic surfactant employed must have a combination of three properties: (1) it must be a low-foaming material; (2) it must be capable of defoaming food soils such as milk; and (3) it must be compatible with chlorinated isocyanurates, that is, it must not decompose these chlorinated compounds markedly in the formulation.

Nonionic surfactants which meet these requirements include the lower alkyl ethers of polyoxyethylated octylphenols such as those sold under the Triton CF trade name, for example Triton CF-54l which is the butyl ether of polyoxyethylated octylphenol; an alkylether of polyoxyethylated alkanol such as Triton DF12"; polyoxyalkylene glycols having a plurality of alternating hydrophobic and hydrophilic polyoxyalkylene chains, the hydrophilic chains consisting of linked oxyethylene radicals and the hydrophobic chains consisting of linked oxypropylene radicals, said product having three hydrophobic chains linked by two hydrophilic chains, the central hydrophobic chain constituting 3O to 34 percent by weight of the product, the terminal hydrophobic chains together constituting 31 to 39 percent by weight of the product, the linking hydrophilic chains together constituting 31 to 35 percent by weight of the product, the intrinsic viscosity of the product being from about 0.06 to 0.09 and the molecular weight of the product being from about 3,000 to 5,000, all as described in US. Pat. No. 3,048,548; the alkyl polyoxyalkylene ether alcohols based on straight chain -biodegradable hydrophobic segments, for example Tretolite H-0307-S"; and the water soluble benzyl ether of octylphenol condensed with ethylene oxide. Other nonionic surfactants are suitable for use in the herein dishwashing preparations and it is not intended to exclude any surfactant possessing the above properties.

The builder component functions as a water softener and a detergent builder. Polyphosphates of commerce, having an Na O or K 0 to P 0 mol ratio of about 1:1 to 2:1 can be used. Typical polyphosphates of this kind are the preferred sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate as well as the corresponding potassium polyphosphates. The particle size of the polyphosphate is not considered critical and any finely divided commercially available product can be employed. Non-phosphate builders and water softeners are suitable also such as for instances nitrilotriacetic acid (NTA); Polycarboxlic acids formed from the polymerization of polycarboxylic monomers and described in US. Pat. No. 3,308,067 and related polyelectrolytes.

In the present formulation the alkali metal silicate acts as a detergent builder and enhances the cleaning action. The silicate also acts as a corrosion inhibitor for metal parts of the dishwashing machine.

7 Typical alkali metal silicates which can be used in the formulation are those having an M to SiO ratio of about 1:33 to 1:1 and containing about 0 to about percent of water. These include sodium metasilicate anhydrous and sodium metasilicate S-hydrate, GD Silicate also called disilicate, which is a product having an Na O to Si0 ratio of 1:2 and typically available in the form containing bound water in the amount of 18.5 percent, and G Silicate, which has an Na O to SiO ratio of 123.22 and a typical water content of about 19 percent.

While the above constitutes the essential ingredients of the composition it is to be understood that additional ingredients such as fillers, e.g., sodium chloride, sodium sulfate, etc., coloring agents and perfumes may also be added without departing from the basic formulation. All components are by weight based on the composition.

While the above ingredients may be mixed in any desired order, best results are obtained when the nonionic surfactant is added to the alkali metal silicate and the alkali metal carbonate (if used) with good mixing. This is also desirable because the nonionic surfactant is a liquid and is readily absorbed by the particulate alkali metal silicate and alkali metal carbonate. In preparing the formulation, the alkali metal silicate and alkali metal carbonate are mixed with the nonionic surfactant followed by the addition of sodium tripolyphosphate and sodium dichloroisocyanurate dihydrate. Each of these ingredients is added with vigorous mixing so that the particulate formulation is substantially homogeneous with a minimum of segregation of any given ingredients. Normally it is advisable to use ingredients having approximately the same particle size in order to prevent segregation on storage.

The following examples are given to illustrate the present invention and are not deemed to be limiting thereof. All components are given in terms of percentage by weight and add up to 100 percent.

EXAMPLE 1 Formulation Component 1 11 111 Available chlorine as chlorinated isocyanurate 1 1.5 1.5 1.5 Sodium tripolyphosphate 30.0 30.0 30.0 Nonionic surfactant (Plurafac RA 43) 3.5 3.5 5.0

Sodium carbonate 0.0 25.0 15.0 Sodium merasilicate S-hydrate Balance 0.0 0.0 Sodium metasilicate anhydrous 0.0 Balance 0.0 Sodium disilicate (18.5% water) 0.0 0.0 Balance A condensation product of an aliphatic, straight chain primary alcohol with ethylene oxide sold by the BASF-Wyandotre Co.

Available chlorine analyses before and after the storage period gave the following results.

TABLE 1 Available Chlorine As the results of Table I show, incorporation of sodium dichloroisocyanurate dihydrate (NaDCC-211 0), instead of anhydrous sodium dichloroisocyanurate (NaDCC) or potassium dichloroisocyanurate (KDCC), in household automatic dishwashing detergents gives markedly improved storage stability.

What is claimed is;

l. A dishwashing detergent composition having good stability against loss of available chlorine and consisting essentially of on a percent weight basis:

1. sodium dichloroisocyanurate dihydrate; from about 0.5 to about 10 percent;

2. an alkali metal silicate having 21 M 0 to SiO mol ratio of 1:3.3 to 1:1, M being either sodium or potassium; from about 5 to about 65 percent;

3. detergent builder and water softener from about 20 to about 60 percent;

4. a low-foaming nonionic surface active agent compatible with chlorinated isocyanurates; from about 0.5 to about 10 percent; and

5. a filler; from about 0 to about 50 percent.

2. The composition of claim 1 in which the alkali metal silicate is sodium disilicate.

3. The composition according to claim 1 wherein (3) is a polyphosphate having an R 0 to P 0 mol ratio of 1:1 to 2:1, R being either sodium or potassium.

4. The composition according to claim 3 wherein (3) is sodium tripolyphosphate.

5. The composition according to claim 1 wherein (5) is selected from the class consisting of sodium carbonate and sodium sulfate or mixtures thereof.

Claims (8)

  1. 2. The composition of claim 1 in which the alkali metal silicate is sodium disilicate.
  2. 2. an alkali metal silicate having a M2O to SiO2 mol ratio of 1: 3.3 to 1:1, M being either sodium or potassium; from about 5 to about 65 percent;
  3. 3. The composition according to claim 1 wherein (3) is a polyphosphate having an R2O to P2O5 mol ratio of 1:1 to 2:1, R being either sodium or potassium.
  4. 3. detergent builder and water softener from about 20 to about 60 percent;
  5. 4. a low-foaming nonionic surface active agent compatible with chlorinated isocyanurates; from about 0.5 to about 10 percent; and
  6. 4. The composition according to claim 3 wherein (3) is sodium tripolyphosphate.
  7. 5. The composition according to claim 1 wherein (5) is selected from the class consisting of sodium carbonate and sodium sulfate or mixtures thereof.
  8. 5. a filler; from about 0 to about 50 percent.
US3816320A 1972-11-24 1973-05-14 Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate Expired - Lifetime US3816320A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US30927772 true 1972-11-24 1972-11-24
US3816320A US3816320A (en) 1972-11-24 1973-05-14 Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate
US05385843 US3936386A (en) 1972-11-24 1973-08-06 Dishwashing compositions containing chlorinated isocyanurate

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
US3816320A US3816320A (en) 1972-11-24 1973-05-14 Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate
US05385843 US3936386A (en) 1972-11-24 1973-08-06 Dishwashing compositions containing chlorinated isocyanurate
CA 183849 CA1004947A (en) 1972-11-24 1973-10-19 Dishwashing compositions containing chlorinated isocyanurate and method of manufacture
NL7315130A NL178427C (en) 1972-11-24 1973-11-05 A process for the preparation of a detergent.
JP12407573A JPS5521798B2 (en) 1972-11-24 1973-11-06
FR7341490A FR2207982B1 (en) 1972-11-24 1973-11-21
FI358873A FI57126C (en) 1972-11-24 1973-11-21 Diskmedelkompositioner innehaollande klorerat isocyanurat samt foerfarande Foer framstaellning daerav
GB5393173A GB1415070A (en) 1972-11-24 1973-11-21 Dishwashing compositions containing chlorinated isocyanurate
DE19732358249 DE2358249C2 (en) 1972-11-24 1973-11-22
BE138142A BE807770A (en) 1972-11-24 1973-11-23 detergent compositions for dishwashing in automatic dishwashers
DK634373A DK140023C (en) 1972-11-24 1973-11-23

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US3816320A Expired - Lifetime US3816320A (en) 1972-11-24 1973-05-14 Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate
US05385843 Expired - Lifetime US3936386A (en) 1972-11-24 1973-08-06 Dishwashing compositions containing chlorinated isocyanurate

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US05385843 Expired - Lifetime US3936386A (en) 1972-11-24 1973-08-06 Dishwashing compositions containing chlorinated isocyanurate

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JP (1) JPS5521798B2 (en)
BE (1) BE807770A (en)
CA (1) CA1004947A (en)
DE (1) DE2358249C2 (en)
DK (1) DK140023C (en)
FI (1) FI57126C (en)
FR (1) FR2207982B1 (en)
GB (1) GB1415070A (en)
NL (1) NL178427C (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4169806A (en) * 1978-08-09 1979-10-02 The Procter & Gamble Company Agglomeration process for making granular detergents
US4279764A (en) * 1980-06-30 1981-07-21 Fmc Corporation Encapsulated bleaches and methods of preparing them
US4324677A (en) * 1980-01-12 1982-04-13 Henkel Kommanditgesellschaft Auf Aktien Stable dishwashing agent compositions containing active chlorine
DE3123680A1 (en) * 1980-06-17 1982-05-06 Fuji Photo Film Co Ltd "Packaging materials"
US4389325A (en) * 1982-01-25 1983-06-21 Monsanto Company Chloroisocyanurate compositions
US4690770A (en) * 1985-05-30 1987-09-01 Henkel Kommanditgesellschaft Auf Aktien Block-form detergent free from alkali hydroxides for use in dishwashing machines and a process for its production
US4729845A (en) * 1985-05-30 1988-03-08 Henkel Kommanditgesellschaft Auf Aktien Detergents for dishwashing machines in the form of fused blocks containing alkali hydroxides and active chlorine and a process for their production
US5089162A (en) * 1989-05-08 1992-02-18 Lever Brothers Company, Division Of Conopco, Inc. Cleaning compositions with bleach-stable colorant
US5096609A (en) * 1990-02-15 1992-03-17 Hoechst Aktiengesellschaft Detergent containing sodium disilicate having a water content of 0.3 to 6% by weight
US5112518A (en) * 1988-06-09 1992-05-12 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic dishwashing composition containing a chlorine-type bleaching agent
US6150324A (en) * 1997-01-13 2000-11-21 Ecolab, Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US6156715A (en) * 1997-01-13 2000-12-05 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6177392B1 (en) 1997-01-13 2001-01-23 Ecolab Inc. Stable solid block detergent composition
US6258765B1 (en) 1997-01-13 2001-07-10 Ecolab Inc. Binding agent for solid block functional material
US6350726B1 (en) * 2001-08-27 2002-02-26 Colgate Palmolive Company Speckled powdered automatic dishwashing composition
US6632291B2 (en) 2001-03-23 2003-10-14 Ecolab Inc. Methods and compositions for cleaning, rinsing, and antimicrobial treatment of medical equipment
US6638902B2 (en) 2001-02-01 2003-10-28 Ecolab Inc. Stable solid enzyme compositions and methods employing them
US20040259757A1 (en) * 1991-05-14 2004-12-23 Ecolab Inc. Two part chemical concentrate

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US4105573A (en) * 1976-10-01 1978-08-08 The Procter & Gamble Company Dishwasher detergent composition
USRE32818E (en) * 1978-02-07 1989-01-03 Ecolab Inc. Cast detergent-containing article and method of using
US4569780A (en) * 1978-02-07 1986-02-11 Economics Laboratory, Inc. Cast detergent-containing article and method of making and using
USRE32763E (en) * 1978-02-07 1988-10-11 Ecolab Inc. Cast detergent-containing article and method of making and using
JPS5598356U (en) * 1978-12-27 1980-07-08
US4259199A (en) * 1979-06-29 1981-03-31 The Procter & Gamble Company Alkaline dishwasher detergent
DE3315950A1 (en) * 1983-05-02 1984-11-15 Henkel Kgaa A process for the production of detergent tablets
US4690305A (en) * 1985-11-06 1987-09-01 Ecolab Inc. Solid block chemical dispenser for cleaning systems
US4687121A (en) * 1986-01-09 1987-08-18 Ecolab Inc. Solid block chemical dispenser for cleaning systems
US5080819A (en) * 1988-05-27 1992-01-14 Ecolab Inc. Low temperature cast detergent-containing article and method of making and using
JPH02206482A (en) * 1989-02-06 1990-08-16 Mizuno Corp Mitt for soft ball-baseball game
JPH0315584U (en) * 1989-06-27 1991-02-15
US5209864A (en) * 1991-07-03 1993-05-11 Winbro Group, Ltd. Cake-like detergent and method of manufacture
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
DE19627809A1 (en) * 1996-07-11 1998-01-15 Henkel Kgaa A process for the production of oxidation-stable detergent components, detergents thus obtained and the use thereof
JP2010280796A (en) * 2009-06-04 2010-12-16 Kao Corp Detergent composition for dishwasher
JP5837362B2 (en) * 2011-08-24 2015-12-24 花王株式会社 Automatic dishwashing solid compositions

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US3035056A (en) * 1962-05-15 Potassium dichloroisocyanurate
US2607738A (en) * 1948-06-25 1952-08-19 Monsanto Chemicals Bleaching, sterilizing, disinfecting, and deterging compositions
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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
US3410804A (en) * 1966-01-03 1968-11-12 Stauffer Chemical Co Cleaning compositions and method of using the same
US3431206A (en) * 1966-04-18 1969-03-04 Monsanto Co Compositions for and processes of bleaching treated textiles
US3549539A (en) * 1967-10-23 1970-12-22 Lever Brothers Ltd Dishwashing powders
BE755475A (en) * 1968-11-19 1971-02-01 Fmc Corp Compositions to clean and disinfect utensils for serving food and drinks
US3491028A (en) * 1969-06-03 1970-01-20 Grace W R & Co Chlorine stable machine dishwashing composition
US3682829A (en) * 1970-09-10 1972-08-08 Desoto Inc Production of low silica content dry,granular automatic dish washing detergent
US3701735A (en) * 1971-04-12 1972-10-31 Colgate Palmolive Co Automatic dishwashing compositions

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4169806A (en) * 1978-08-09 1979-10-02 The Procter & Gamble Company Agglomeration process for making granular detergents
US4324677A (en) * 1980-01-12 1982-04-13 Henkel Kommanditgesellschaft Auf Aktien Stable dishwashing agent compositions containing active chlorine
DE3123680A1 (en) * 1980-06-17 1982-05-06 Fuji Photo Film Co Ltd "Packaging materials"
US4279764A (en) * 1980-06-30 1981-07-21 Fmc Corporation Encapsulated bleaches and methods of preparing them
US4389325A (en) * 1982-01-25 1983-06-21 Monsanto Company Chloroisocyanurate compositions
US4690770A (en) * 1985-05-30 1987-09-01 Henkel Kommanditgesellschaft Auf Aktien Block-form detergent free from alkali hydroxides for use in dishwashing machines and a process for its production
US4729845A (en) * 1985-05-30 1988-03-08 Henkel Kommanditgesellschaft Auf Aktien Detergents for dishwashing machines in the form of fused blocks containing alkali hydroxides and active chlorine and a process for their production
US5112518A (en) * 1988-06-09 1992-05-12 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic dishwashing composition containing a chlorine-type bleaching agent
US5089162A (en) * 1989-05-08 1992-02-18 Lever Brothers Company, Division Of Conopco, Inc. Cleaning compositions with bleach-stable colorant
US5096609A (en) * 1990-02-15 1992-03-17 Hoechst Aktiengesellschaft Detergent containing sodium disilicate having a water content of 0.3 to 6% by weight
US20060040845A1 (en) * 1991-05-14 2006-02-23 Ecolab Inc. Two part chemical concentrate
US20040259757A1 (en) * 1991-05-14 2004-12-23 Ecolab Inc. Two part chemical concentrate
US7517846B2 (en) 1991-05-14 2009-04-14 Ecolab Inc. Solid, two part chemical concentrate
US6436893B1 (en) 1997-01-13 2002-08-20 Ecolab Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US20100323940A1 (en) * 1997-01-13 2010-12-23 Ecolab Inc. Alkaline detergent containing mixing organic and inorganic sequestrants resulting in improved soil removal
US6410495B1 (en) 1997-01-13 2002-06-25 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US6258765B1 (en) 1997-01-13 2001-07-10 Ecolab Inc. Binding agent for solid block functional material
US6503879B2 (en) 1997-01-13 2003-01-07 Ecolab Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US6583094B1 (en) 1997-01-13 2003-06-24 Ecolab Inc. Stable solid block detergent composition
US6177392B1 (en) 1997-01-13 2001-01-23 Ecolab Inc. Stable solid block detergent composition
US6156715A (en) * 1997-01-13 2000-12-05 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US20030216279A1 (en) * 1997-01-13 2003-11-20 Ecolab Inc. Stable solid block detergent composition
US6653266B2 (en) 1997-01-13 2003-11-25 Ecolab Inc. Binding agent for solid block functional material
US6660707B2 (en) 1997-01-13 2003-12-09 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US20080287338A1 (en) * 1997-01-13 2008-11-20 Ecolab Inc. Binding agent for solid block functional material
US7341987B2 (en) 1997-01-13 2008-03-11 Ecolab Inc. Binding agent for solid block functional material
US20040102353A1 (en) * 1997-01-13 2004-05-27 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US20040106535A1 (en) * 1997-01-13 2004-06-03 Ecolab Inc. Binding agent for solid block functional material
US6831054B2 (en) 1997-01-13 2004-12-14 Ecolab Inc. Stable solid block detergent composition
US6150324A (en) * 1997-01-13 2000-11-21 Ecolab, Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US6835706B2 (en) 1997-01-13 2004-12-28 Ecolab Inc. Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US20050119149A1 (en) * 1997-01-13 2005-06-02 Ecolab Inc. Stable solid block detergent composition
US7087569B2 (en) 1997-01-13 2006-08-08 Ecolab Inc. Stable solid block metal protecting warewashing detergent composition
US8906839B2 (en) 1997-01-13 2014-12-09 Ecolab Usa Inc. Alkaline detergent containing mixing organic and inorganic sequestrants resulting in improved soil removal
US7094746B2 (en) 1997-01-13 2006-08-22 Ecolab Inc. Stable solid block detergent composition
US20040072714A1 (en) * 2001-02-01 2004-04-15 Ecolab Inc. Stable solid enzyme compositions and methods employing them
US6638902B2 (en) 2001-02-01 2003-10-28 Ecolab Inc. Stable solid enzyme compositions and methods employing them
US20040048760A1 (en) * 2001-03-23 2004-03-11 Ecolab Inc. Methods and compositions for cleaning, rinsing, and antimicrobial treatment of medical equipment
US6632291B2 (en) 2001-03-23 2003-10-14 Ecolab Inc. Methods and compositions for cleaning, rinsing, and antimicrobial treatment of medical equipment
US6350726B1 (en) * 2001-08-27 2002-02-26 Colgate Palmolive Company Speckled powdered automatic dishwashing composition

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Publication number Publication date Type
FI57126C (en) 1980-06-10 grant
DE2358249C2 (en) 1982-03-11 grant
DK140023C (en) 1979-11-26 grant
JPS5521798B2 (en) 1980-06-12 grant
CA1004947A (en) 1977-02-08 grant
BE807770A (en) 1974-05-24 grant
FI57126B (en) 1980-02-29 application
FR2207982A1 (en) 1974-06-21 application
CA1004947A1 (en) grant
GB1415070A (en) 1975-11-26 application
US3936386A (en) 1976-02-03 grant
DK140023B (en) 1979-06-05 grant
DE2358249A1 (en) 1974-05-30 application
NL178427B (en) 1985-10-16 application
BE807770A1 (en) grant
FR2207982B1 (en) 1977-06-10 grant
NL178427C (en) 1986-03-17 grant
NL7315130A (en) 1974-05-28 application
JPS4982712A (en) 1974-08-09 application

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