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Publication numberUS3816320 A
Publication typeGrant
Publication dateJun 11, 1974
Filing dateMay 14, 1973
Priority dateNov 24, 1972
Also published asCA1004947A1, DE2358249A1, DE2358249C2, US3936386
Publication numberUS 3816320 A, US 3816320A, US-A-3816320, US3816320 A, US3816320A
InventorsCorliss D
Original AssigneeFmc Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate
US 3816320 A
Abstract
An agglomerated dishwashing composition containing the following components: }Sodium dichloroisocyanurate 0.5-10% }dihydrate }A polyphosphate having an 25-60% }Na2O or K2O to P2O5 ratio (anhydrous basis) }of about 1:1 to 2:1 }Sodium carbonate 0-60% } (anhydrous basis) }A sodium silicate having 10-15% }a SiO2 to Na2O ratio of (total silicate }from about 2.40 to about solids) }3.22 }Low-foaming chlorine- 1-10% }compatible nonionic }surfactant }Water 5-20% } The compositions exhibit lower chlorine loss than similar formulations containing commercial anhydrous sodium dichloroisocyanurate as the dry bleach component.
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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.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4169806 *Aug 9, 1978Oct 2, 1979The Procter & Gamble CompanyAgglomeration process for making granular detergents
US4279764 *Jun 30, 1980Jul 21, 1981Fmc CorporationEncapsulated bleaches and methods of preparing them
US4324677 *Dec 29, 1980Apr 13, 1982Henkel Kommanditgesellschaft Auf AktienVery pure trichloroisocyanuric acid
US4389325 *Jan 25, 1982Jun 21, 1983Monsanto CompanyChloroisocyanurate compositions
US4690770 *May 29, 1986Sep 1, 1987Henkel Kommanditgesellschaft Auf AktienMixture of sodium metasilicate, pentasodiumtriphosphates and chlorine donor
US4729845 *May 29, 1986Mar 8, 1988Henkel Kommanditgesellschaft Auf AktienStorage stable
US5089162 *May 8, 1989Feb 18, 1992Lever Brothers Company, Division Of Conopco, Inc.Liquid or grains, lemon scent, yellow color; automatic dishwasher detergent
US5096609 *Feb 1, 1991Mar 17, 1992Hoechst AktiengesellschaftAmorphous; anionic, nonionic or zwitterionic surfactant
US5112518 *Dec 8, 1989May 12, 1992Lever Brothers Company, Division Of Conopco, Inc.Enzymatic dishwashing composition containing a chlorine-type bleaching agent
US6150324 *Jan 13, 1997Nov 21, 2000Ecolab, Inc.Alkali metal carbonate detergent, soil removing surfactant, sequestrant comprising an organic phosphonate and an inorganic condensed phosphate; dishwasher detergents
US6156715 *Jun 2, 1998Dec 5, 2000Ecolab Inc.Stable solid block metal protecting warewashing detergent composition
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US6258765Dec 12, 1997Jul 10, 2001Ecolab Inc.Binding agent for solid block functional material
US6350726 *Aug 27, 2001Feb 26, 2002Colgate Palmolive CompanyNoncolored particles comprising alkali metal disilicate, sulfate, and phosphate and ethoxylated nonionic surfactant; colored particles include alkali metal carbonate and green and yellow pigments
US6410495Oct 19, 2000Jun 25, 2002Ecolab Inc.Solidified mixture of sodium carbonate and alklai metal silicate
US6436893Oct 18, 2000Aug 20, 2002Ecolab Inc.Detergent comprising alkali metal carbonate, surfactant, sequestrant comprising organic phosphonate and inorganic condensed phosphate
US6503879Mar 15, 2001Jan 7, 2003Ecolab Inc.Containing organic phosphonate and inorganic phosphate
US6583094Nov 8, 2000Jun 24, 2003Ecolab Inc.Stable solid block detergent composition
US6632291Mar 23, 2001Oct 14, 2003Ecolab Inc.Methods and compositions for cleaning, rinsing, and antimicrobial treatment of medical equipment
US6638902Feb 1, 2001Oct 28, 2003Ecolab Inc.Stable solid enzyme compositions and methods employing them
US6653266Dec 13, 2000Nov 25, 2003Ecolab Inc.An organic sequestrant that can cooperate in the formation of the binding agent containing an organo phosphonate or an organoamino acetate and water and alkali metal carbonate hydrate as binding agent; solid alkaline detergent
US6660707Jun 24, 2002Dec 9, 2003Ecolab Inc.Stable solid block metal protecting warewashing detergent composition
US6831054May 8, 2003Dec 14, 2004Ecolab Inc.Stable solid block detergent composition
US6835706Jan 7, 2003Dec 28, 2004Ecolab Inc.Alkaline detergent containing mixed organic and inorganic sequestrants resulting in improved soil removal
US7087569Nov 14, 2003Aug 8, 2006Ecolab Inc.Stable solid block metal protecting warewashing detergent composition
US7094746Dec 10, 2004Aug 22, 2006Ecolab Inc.dimensionally stable alkaline solid block warewashing detergent uses an E-form binder comprising a nonhydrated alkali metal carbonate, an organic sequestrant, and a mono-hydrated alkali metal carbonate binder
US7341987Nov 14, 2003Mar 11, 2008Ecolab Inc.Binding agent for solid block functional material
US7517846Oct 20, 2005Apr 14, 2009Ecolab Inc.Inwardly curved bar having an inner opening with an insert interlocking with the bar by insertion into the opening; each part contains a hardener and a source of alkalinity, a surfactant, an enzyme, or an antimicrobial agent; covered with a water soluble or dispersable polymeric film; cleaning detergents
DE3123680A1 *Jun 15, 1981May 6, 1982Fuji Photo Film Co Ltd"verpackungsmaterialien"
Classifications
U.S. Classification510/232, 510/233, 510/381, 252/187.34, 252/186.35
International ClassificationC11D11/00, C11D3/395, C11D3/26, C11D3/24
Cooperative ClassificationC11D3/3958
European ClassificationC11D3/395J
Legal Events
DateCodeEventDescription
Oct 11, 1985AS02Assignment of assignor's interest
Owner name: FMC CORPORATION, 2000 MARKET STREET, PHILADELPHIA,
Owner name: OLIN CORPORATION, 120 LONG RIDGE ROAD, STAMFORD, C
Effective date: 19850816
Oct 11, 1985ASAssignment
Owner name: OLIN CORPORATION, 120 LONG RIDGE ROAD, STAMFORD, C
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:FMC CORPORATION, 2000 MARKET STREET, PHILADELPHIA, PA., A CORP. OF DE.;REEL/FRAME:004467/0590
Effective date: 19850816