EP1119604B1 - Foaming system and detergent compositions containing the same - Google Patents

Foaming system and detergent compositions containing the same Download PDF

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Publication number
EP1119604B1
EP1119604B1 EP98949783A EP98949783A EP1119604B1 EP 1119604 B1 EP1119604 B1 EP 1119604B1 EP 98949783 A EP98949783 A EP 98949783A EP 98949783 A EP98949783 A EP 98949783A EP 1119604 B1 EP1119604 B1 EP 1119604B1
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EP
European Patent Office
Prior art keywords
acid
component
foaming
alkyl
silicone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP98949783A
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German (de)
English (en)
French (fr)
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EP1119604A1 (en
Inventor
Rinko Kobe Park City C507 KATSUDA
Kevin Todd Norwood
Susumu Murata
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of EP1119604A1 publication Critical patent/EP1119604A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/162—Organic compounds containing Si
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • This invention relates to a novel foaming system useful in a detergent composition. More particularly, the present invention relates to granular detergent compositions intended for cleaning fabrics containing novel foaming components.
  • Foam or suds formation is desired in various applications, such as during the wash process.
  • specific surfactants are known to provide sudsing in the wash water. Not only is the formation of foaming or sudsing desirable, but there is also a desire to readily create foam as well as maintaining the foam for a desired duration. For example, it may be desired that the foam occurs immediately upon contact of a detergent composition with water. Although there are various reasons as to why foam formation is desired, one known reason is that consumers who use detergent compositions directly associate the formation of foam with the cleaning ability of the detergent composition.
  • foam may also pose problems during the washing process. For example, drainage of the suds or foam during the washing process may be difficult. Particularly for a machine wash process, the suds or foam may hamper the drainage of the wash solution from the machine before the rinse stage. Therefore, it is desired to gradually suppress the formation of foam over time.
  • WO 93/01269 describes antifoam particles comprising a porous particulate organic carrier material , a specific silicone antifoam and a coating layer.
  • the present invention is directed to a controlled foaming system especially adapted for use in detergent compositions containing a foaming component capable of providing foaming or sudsing without agitation, and a delayed-release foam suppressing component according to claim 1.
  • the present invention also relates to detergent compositions containing the controlled foaming system.
  • alkyl means a hydrocarbyl moiety which is straight or branched, saturated or unsaturated. Unless otherwise specified, alkyl moieties are preferably saturated or unsaturated with double bonds, preferably with one or two double bonds. Included in the term “alkyl” is the alkyl portion of acyl groups.
  • the present invention is directed to a controlled foaming system especially adapted for use in detergent compositions containing a foaming component capable of providing foaming or sudsing without agitation, and a delayed-release foam suppressing component.
  • the delayed-release foam suppressing component is a silicone foam suppressing agent which is releasably incorporated in a carrier, thereby delaying the release of the silicone foam suppressing agent.
  • the foaming component When the controlled foaming system first comes into contact with water, the foaming component generates rapid and stable foaming without agitation.
  • the term "foaming" means any form of formation of gas bubbles, including sudsing and effervescing. Agitation is not necessary, but may enhance the generation of foam, and thus, may be preferred.
  • the foaming component produces upon contact with water, gas bubbles having an average bubble particle size of 400 microns or less, preferably 200 microns or less, and more preferably 100 microns or less.
  • the delayed-release foam suppressing component is released over time and the foaming is suppressed or otherwise controlled by decreasing the amount of foam.
  • the time delay may be adjusted by choosing the appropriate type of foam suppressing component. For example, for some machine wash conditions, the foam suppressing component reduces the water gas bubbles as early as upon agitation, so that preferably after 120 seconds, the bubbles have been reduced at least 30%. Also for example in some other machine wash conditions, after from 360 seconds to 600 seconds, the bubbles have been reduced to from 40 to 70% percentage, or otherwise become substantially suppressed before the rinse stage.
  • the foam suppressing component may not reduce the water gas bubbles at the initial stages in the wash, since it may be preferable to maintain the amount of foam for a longer period of time.
  • the foaming component and the delayed-release foam suppressing component are independent dry particles.
  • dry is to be understood that the particles of the raw materials are substantially free of water, i.e., that no water has been added other than the moisture of the raw materials themselves.
  • the level of water is below 5% by weight of the total particle, preferably below 3% and more preferably below 1.5%.
  • the final composition contains a mixture of the two types of particles in addition to other conventional detersive components.
  • one of the particles is present as a part of an other conventional detersive component. Having separate particles is particularly useful because one can control the different levels and thus provide controlled delivery of the foaming component and the suppressing component to the washing process, e.g., both a more efficient and a time delivery can be achieved, to provide optimum performance.
  • a detergent composition having a controlled foaming system especially in the early phases of the wash cycle, has cleaning benefits.
  • the foam helps transfer the surfactant in the detergent composition onto the soil to be removed and/or on to the fabric.
  • the foam helps further wetting and dissolution of the detergent composition.
  • the foam is believed to provide an early reservoir of unprecipitated surfactant to wet fabrics and helps suspend the soil in the wash solution.
  • the controlled foaming system also is storage stable. For example, the components do not degrade during storage while being exposed to moisture from the air.
  • the foaming component contains an effervescent granule, the incorporation of the controlled foaming system in a detergent composition improves the dissolution characteristics of the active ingredients present in the detergent composition.
  • Another advantage of the present invention is the improved dispensing characteristics associated to the detergent compositions of the present invention, e.g., the detergent compositions intended for use in a drum-type fabric washing machine.
  • a difficulty with conventional high density granular detergent compositions is that they are not easily flushed from the dispenser drawer of a washing machine: i.e. when the granular composition is wetted by the water flowing through the dispenser, the detergent ingredients may become stuck together resulting in considerable residues of wetted and adhering powder left behind the drawer. Similar problems are encountered when using such granular detergent compositions in a dosing device in the washing drum.
  • the presence of the effervescent granule in the granular detergent compositions provides improved dispensing typically when used in a washing machine and good storage stability in respect of the dispensing potential.
  • the detergent compositions containing the controlled foaming system are preferably solid laundry or dish washing compositions, preferably in the form of granules, extrudates, or tablets.
  • granular detergent compositions have a density of at least 500 g/l, more preferably at least 700 g/l.
  • the detergent compositions as well as the foaming component and the delayed-release foam suppressing component may also comprise additional ingredients, as described herein. The precise nature of these additional ingredients, and levels of incorporation thereof will depend on the application of the component or composition and the physical form of the component and composition.
  • the foaming component preferably contains an effervescent granule. Any effervescent granule capable of forming gas upon contact with water, known in the art, can be used.
  • a preferred effervescent granule comprises an acid source, capable of reacting with an alkali source in the presence of water to produce a gas.
  • the acid source may be any organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof.
  • the acid source comprises an organic acid.
  • the acid source is preferably substantially anhydrous or non-hydroscopic and the acid is preferably water-soluble. It may be preferred that the acid source is overdried.
  • Suitable acids source components include an acid or salt form of a mono or polycarboxylic acid. Such preferred acids include those selected from the group consisting of citric, malic, maleic, fumaric, aspartic, glutaric, tartaric, malonic, succinic or adipic acid, monosodium phosphate, boric acid, 3 ketoglutaric acid acid, citramalic acid, and mixtures thereof. Citric acid, maleic or malic acid are especially preferred.
  • the acid source provides acidic compounds which have an average particle size in the range of from 75 microns to 1180 microns, more preferably from 150 microns to 710 microns, calculated by sieving a sample of the source of acidity on a series of Tyler sieves.
  • the effervescent granule preferably comprises an alkali source.
  • Any alkali source which has the capacity to react with the acid source to produce a gas may be present in the particle, including sources capable of producing nitrogen, oxygen or carbon dioxide gas.
  • sources capable of producing nitrogen, oxygen or carbon dioxide gas Preferred can be perhydrate bleaches and silicate material
  • the alkali source is preferably substantial anhydrous or non-hydroscopic. It may be preferred that the alkali source is overdried.
  • the produced gas is carbon dioxide, and therefore the alkali source is preferably a source of carbonate; and in particular, a carbonate salt.
  • preferred carbonates are the alkaline earth and alkali metal carbonates, including sodium or potassium carbonate, bicarbonate and sesquicarbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Alkali metal percarbonate salts are also suitable sources of carbonate species, which may be present combined with one or more other carbonate sources.
  • the carbonate and bicarbonate preferably have an amorphous structure.
  • the carbonate and/ or bicarbonates may be coated with coating materials.
  • the particles of carbonate and bicarbonate can have a mean particle size of 75 microns or greater, preferably 150 ⁇ m or greater, more preferably of 250 ⁇ m or greater, preferably 500 ⁇ m or greater. It may be preferred that the carbonate salt is such that fewer than 20% (by weight) of the particles have a particle size below 500 ⁇ m, calculated by sieving a sample of the carbonate or bicarbonate on a series of Tyler sieves.
  • fewer than 60% or even 25% of the particles have a particle size below 150 ⁇ m, whilst fewer than 5% has a particle size of more than 1.18 mm, more preferably fewer than 20% have a particle size of more than 212 ⁇ m, calculated by sieving a sample of the carbonate or bicarbonate on a series of Tyler sieves.
  • the molecular ratio of the acid source to the alkali source present in the particle core is preferably from 60;1 to 1:60, more preferably from 20:1 to 1:20, more preferably from 10:1 to 1:10, more preferably from 5:1 to 1:3, more preferably from 3:1 to 1:2, more preferably from 2:1 to 1:2.
  • the effervescent granule optionally contains a binder which binds the acid source with the alkali source.
  • the effervescent granule comprises up to 50 % by weight of the total granule of a binder or a mixture thereof, preferably up to 35% and more preferably up to 20%.
  • Suitable binders to use herein are those known to those skilled in the art and include anionic surfactants like C6-C20 alkyl or alkylaryl sulphonates or sulphates, preferably C8-C20 alkylbenzene sulphonates, cellulose derivatives such as carboxymethylcellulose and homo- or co- polymeric polycarboxylic acid or their salts, nonionic surfactants, preferably C10-C20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 primary alcohol ethoxylates containing from 20-100 moles of ethylene oxide per mole of alcohol.
  • anionic surfactants like C6-C20 alkyl or alkylaryl sulphonates or sulphates, preferably C8-C20 alkylbenzene sulphonates, cellulose derivatives such as carboxymethylcellulose and homo- or co- polymeric polycarboxylic acid or their salts
  • binders include the polymeric materials like polyvinylpyrrolidones with an average molecular weight of from 12 000 to 700 000 and polyethylene glycols with an average weight of from 600 to 10 000. Copolymers of maleic anhydride with ethylene, methylvinyl ether, methacrylic acid or acrylic acid are other examples of polymeric binders. Others binders further include C10-C20 mono and diglycerol ethers as well as C10-C20 fatty acids. In the embodiment of the present invention where a binder is desired C8-C20 alkylbenzene sulphonates are particularly preferred.
  • the foaming component may-also contain a surface active component which reduces the water-air surface tension.
  • the preferred surface active component has a melting point above 45°C, and is preferably selected from the group consisting of nonionic alkoxylated amides, alkyl esters of fatty acids, or alkoxylated alcohols.
  • Especially preferred surface active components are selected from the group consisting of polyhydroxy fatty acid amides and condensation products of aliphatic alcohols with from 1 to 15 moles of alkylene oxide. If a surface active component is used, the weight ratio of the surface active component to the effervescent granule is preferably from 20:1 to 1:10.
  • the foaming component may further include the addition of suds boosters.
  • the suds boosters may enhance the formation of suds in conjunction with the effervescent granule.
  • the suds booster may be part of the same particle or component as the foaming component, or the suds booster may be a separate independent particle or component.
  • Preferred suds boosters include amine oxide, polyethylene glycol, monoethanol amine, diethanol amine, fatty alcohol, sugar, protein, betaine, and mixtures thereof.
  • Suitable amine oxides include those compounds having the formula R 3 (OR 4 ) x N 0 (R 5 ) 2 wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are C 10 -C 18 alkyl dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide.
  • Suitable betaines are those compounds having the formula R(R') 2 N + R 2 COO - wherein R is a C 6 -C 18 hydrocarbyl group, each R 1 is typically C 1 -C 3 alkyl, and R 2 is a C 1 -C 5 hydrocarbyl group.
  • Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • the foaming component may be made my conventional methods, including as part of a tabletting process, extrusion process, and/or an agglomeration process.
  • the foaming component is preferably such that 80% by weight of the particles have a particle size of more than 75 microns (more than 80% by weight of the particles on Tyler sieve mesh 200) and less than 10% by weight of the particles have a particle size of more than 2 cm; preferably 80% by weight of the particles have a particle size of more than 150 microns (80% by weight on Tyler sieve mesh 100) and Less than 10% by weight of the particles have a particle size of more than 1 cm; or more preferably 80% by weight of the particles have a particle size of more than 300 microns (80% by weight on Tyler sieve mesh 48) and less than 10% by weight of the particles have a particle size of more than 0.5 cm; or even more preferably the particles have an average particle size of from 500 microns (on Tyler sieve mesh 32) to 3
  • the foaming component and the delayed-release foam suppressing component are independent dry particles, wherein the foaming component has an average particle size of from 75 microns to 2 cm.
  • a suds suppressing amount of the delayed-release foam suppressing component is used in the present invention.
  • the term "delayed-release foam suppressing component” means that the foam suppressing component begins to suppress foam over time. Depending on when the foam should be suppressed, the time delay may be adjusted by choosing the appropriate type of foam suppressing component.
  • the term “suds suppressing amount” is meant that the formulator of the detergent composition selected an amount of this component which will control the suds to the extent desired. The amount of suppressing component will vary with the detergent component selected.
  • the delayed-release foam suppressing component is a silicone foam suppressing component.
  • Said silicone foam suppressing component contains a silicone suds controlling agent having an average droplet diameter of from 1 to 50 microns, releasably incorporated in a water-soluble or water dispersible, substantially non-surface active, detergent-impermeable, and non-hydroscopic carrier, the silicone foam suppressing component being substantially free of water-soluble relatively hydroscopic inorganic salts and in the form of an irregularly shaped particle having a minimum dimension of not less than 0.05 cm and the maximum dimension being at least 20% greater than the minimum dimension.
  • the preferred suppressing component contains a silicone suds controlling agent which is substantially isolated from the other detersive components of the detergent composition.
  • This "isolation" is achieved by incorporating the controlling agent in a water-soluble or water-dispersible organic carrier matrix.
  • the matrix is a substantially non-surface active, non-hydroscopic material which does not interact with the controlling agent.
  • the carrier must be substantially impenetrable by the detersive components to prevent undesirable silicone/detergent and/or silicone/alkalinity interactions.
  • the carrier matrix herein preferably does not contain added surface active agents, other than the silicone.
  • the carrier is selected such that, upon admixture with water, the carrier matrix dissolves or disperses to release the silicone suds controlling agent to perform its suds or foam controlling function.
  • the silicone materials employed as the preferred silicone suds controlling agents herein can be alkylated polysiloxane materials of several types, either singly or in combination with various solid materials such as silica aerogels and xerogels and hydrophobic silicas of various types.
  • silica aerogels and xerogels and hydrophobic silicas of various types.
  • the term "silicone” has become a generic term which encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl groups of various types.
  • the silicone suds controllers can be described as siloxanes having the general structure backbone. wherein x is from 20 to 2,000 and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl or phenyl.
  • the polydimethylsiloxanes (R and R' are methyl) having a molecular weight within the range of from 200 to 200,000, and higher, are all useful as suds controlling agents. Silicone materials are commercially available from the Dow Coming Corporation under the trade name Silicone 200 Fluids®. Suitable polydimethylsiloxanes have a viscosity of from 2 ⁇ 10 -5 to 1.5 ⁇ 10 -3 m 2 s -1 (20-1500cs), at 25°C when used with silica and/or siloxane resin.
  • silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl and aryl hydrocarbyl groups exhibit useful suds controlling properties.
  • These materials are readily prepared by the hydrolysis of the appropriate alkyl, aryl or mixed alkylaryl or aralkyl silicone dichlorides with water in the manner well known in the art.
  • silicone suds controlling agents useful herein there can be mentioned, for example, diethyl polysiloxanes; dipropyl polysiloxanes; dibutyl polysiloxanes; methylethyl polysiloxanes; phenylmethyl polysiloxanes.
  • the dimethyl polysiloxanes are particularly useful herein due to their low cost and ready availability.
  • the silicone "droplets" in the carrier matrix preferably have an average diameter of 1 to 50 ⁇ m, preferably from 5 to 40 ⁇ m, more preferably from 5 to 30 ⁇ m for maximum effectiveness. Droplets below 5 ⁇ m in diameter are not very effective and above 30 ⁇ m in diameter are increasingly less effective. Similar sizes are required for the other silicone suds controlling agents disclosed hereinafter.
  • a second highly preferred type of silicone suds controlling agent useful herein comprises a mixture of an alkylated siloxane of the type hereinabove disclosed and solid silica.
  • Such mixtures of silicone and silica can be prepared by affixing the silicone to the surface of silica (SiO 2 ), for example by means of the catalytic reaction disclosed in U.S. Pat. No. 3,235,509.
  • Suds controlling agents comprising mixtures of silicone and silica prepared in this manner preferably comprise silicone and silica in a silicone:silica ratio of from 19:1 to 1:2, preferably from 10:1 to 1:1.
  • the silica can be chemically and/or physically bound to the silicone in an amount which is preferably 5% to 20%, preferably from 10 to 15%, by weight, based on the silicone.
  • the particle size of the silica employed in such silica/silicone suds controlling agents should preferably be not more than about 1000, preferably not more than 100 nm, preferably from 5 nm to 50 nm, more preferably from 10 to 20 nm, and the specific surface area of the silica should exceed 5 m 2 /g, preferably more than 50 m 2 /g.
  • suds controlling agents containing silicone and silica can be prepared by admixing a silicone fluid of the type hereinabove disclosed with a hydrophobic silica having a particle size and surface area in the range disclosed above.
  • a hydrophobic silica which can be employed herein in combination with a silicone as the suds controlling agent.
  • a fumed silica can be reacted with a trialkyl chlorosilane (i.e., "silanated") to affix hydrophobic trialkylsilane groups on the surface of the silica.
  • fumed silica is contacted with trimethylchlorosilane and a preferred hydrophobic silanated silica useful in the present compositions is prepared.
  • a hydrophobic silica useful in the present compositions is obtained by contacting silica with any of the following compounds: metal, ammonium and substituted ammonium salts of long chain fatty acids, such as sodium stearate, aluminum stearate; silylhalides, such as ethyltrichlorosilane, butyltrichlorosilane, tricyclohexylchlorosilane; and long chain alkyl amines or ammonium salts, such as cetyl trimethyl amine, cetyl trimethyl ammonium chloride.
  • metal, ammonium and substituted ammonium salts of long chain fatty acids such as sodium stearate, aluminum stearate
  • silylhalides such as ethyltrichlorosilane, butyltrichlorosilane, tricyclohexylchlorosilane
  • long chain alkyl amines or ammonium salts such as cetyl trimethyl amine, cety
  • a preferred suds controlling agent herein comprises a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from 10 nm to 20 nm and a specific surface area above 50 m 2 /g intimately admixed with a dimethyl silicone fluid having a molecular weight in the range of from 500 to 200,000, at a weight ratio of silicone to silanated silica of from 10:1 to 1:2.
  • Such suds controlling agents preferably comprise silicone and the silanated silica in a weight ratio of silicone:silanated silica of from 10:1 to 1:1.
  • the mixed hydrophobic silanated (especially trimethylsilanated) silica-silicone suds controlling agents provide suds control over a broad range of temperatures, presumably due to the controlled release of the silicone from the surface of the silanated silica.
  • Another type of suds control agent herein comprises a silicone material of the type hereinabove disclosed sorbed onto and into a solid.
  • Such suds controlling agents comprise the silicone and solid in a silicone:solid ratio of from 20:1 to 1:20, preferably from 5:1 to 1:1.
  • suitable solid sorbents for the silicones herein include clay, starch, kieselguhr, Fuller's Earth. The alkalinity of the solid sorbents is of no consequence to the compositions herein, inasmuch as it has been discovered that the silicones are stable when admixed therewith.
  • the sorbent-plus-silicone suds controlling agent must be coated or otherwise incorporated into a carrier material of the type hereinafter disclosed to effectively isolate the silicone from the detergent component of the instant compositions.
  • silicone suds controlling agent herein comprises a silicone fluid, a silicone resin and silica.
  • the silicone fluids useful in such suds controlling mixtures are any of the types hereinabove disclosed, but are preferably dimethyl silicones.
  • the silicone "resins” used in such compositions can be any alkylated silicone resins, but are usually those prepared from methylsilanes. Silicone resins are commonly described as "three-dimensional" polymers arising from the hydrolysis of alkyl trichlorosilanes, whereas the silicone fluids are "two-dimensionat" polymers prepared by the hydrolysis of dichlorosilanes.
  • the silica components of such compositions are microporous materials such as the fumed silica aerogels and xerogels having the particle sizes and surface areas hereinabove disclosed.
  • the mixed silicone fluid/silicone resin/silica materials useful in the present compositions can be prepared in the manner disclosed in U.S. Pat. No. 3,455,839. These mixed materials are commercially available from the Dow Coming Corporation. According to U.S. Pat. No. 3,455,839, such materials can be described as mixtures consisting essentially of: for each 100 parts by weight of a polydimethylsiloxane fluid having a viscosity in the range from 2 ⁇ 10 -5 to 1.5 ⁇ 10 -3 m 2 s -1 (20cs.
  • the silicone suds controlling agents of the aforementioned type is preferably incorporated within (i.e., coated, encapsulated, covered by, internalized. or otherwise substantially contained within) a substantially water-soluble, or water-dispersible, and non-hydroscopic carrier material which must be impermeable to detergents and alkalinity and which, itself, must be substantially nonsurface active.
  • substantially nonsurface active is meant that the carrier material, itself, does not interact with the silicone material in such fashion that the silicone material is emulsified or otherwise excessively dispersed prior to its release in the wash water. I.e., the particle size of the silicone droplet should be maintained above 1, more preferably above 5 mm.
  • the silicone suds controlling component thereof when preparing a dry powder or granulated detergent composition, it is preferable that the silicone suds controlling component thereof also be substantially dry and nontacky at ambient temperatures. Accordingly, it is preferred herein to use as the carrier material, or vehicle, plastic, organic compounds which can be conveniently melted, admixed with the silicone suds controlling agent, and thereafter cooled to form solid flakes.
  • the carrier material or vehicle, plastic, organic compounds which can be conveniently melted, admixed with the silicone suds controlling agent, and thereafter cooled to form solid flakes.
  • the carrier material be water soluble.
  • water-dispersible materials are also useful, inasmuch as they will also release the silicone upon addition to an aqueous bath.
  • PEG polyethylene glycol
  • highly ethoxylated fatty alcohols such as tallow alcohol condensed with at least 25 molar proportions of ethylene oxide are also useful herein.
  • Other alcohol condensates containing extremely high ethoxylate proportions are also useful herein.
  • Such high ethoxylates apparently lack sufficient surface active characteristics to interact or otherwise interfere with the desired suds control properties of the silicone agents herein.
  • a variety of other materials useful as the carrier agents herein can also be used, e.g., gelatin; agar; gum arabic; and various algae-derived gels.
  • a very preferred carrier material is a mixture of from 0.2% to 15%, preferably from 0.25% to 5%, more preferably from 0.25% to 2% of fatty acids containing from 12 to 30, preferably from 14 to 20, more preferably from 14 to 16, carbon atoms and the balance PEG.
  • fatty acids containing from 12 to 30, preferably from 14 to 20, more preferably from 14 to 16, carbon atoms and the balance PEG.
  • Such a carrier material gives a more desirable suds pattern over the duration of the washing process, providing more suds at the start and less suds at the end than PEG alone.
  • the fatty acid delays the solubility of the suds suppressor particle and thereby delays the release of the silicone. Soap and/or wax may also be used in place of the fatty acid.
  • the preferred irregularly shaped particulate silicone suds controlling component can be conveniently prepared in a highly preferred flake form by admixing the silicone suds controlling agent with a molten carrier material, mixing to form the appropriate silicone droplet size, and flaking, e.g., by milling or extruding to form a thin sheet, cooling to solidify the carrier material, and breaking the sheet into particles of the right size.
  • thin films can be formed by cooling molten carrier material with the suds suppressor dispersed therein on, e.g., a chill roll or belt cooler and then breaking said film into appropriate sized flakes.
  • the thickness of the flake should be from 0.05 to 0.15 cm, preferably from 0.05 to 0.1 cm.
  • the flake of the silicone suds controlling agent and carrier material should be substantially solidified. This can be achieved by use of belt coolers and which quickly cool the sheets or flakes such that the carrier melt is hardened. Extrusion techniques can also be used.
  • the amount of carrier used to isolate the silicone suds controlling agent herein from the detergent component of the compositions herein is not critical. It is only necessary that enough carrier be used to provide sufficient volume that substantially all the silicone can be incorporated therein. Likewise, it is preferred to have sufficient carrier material to provide for sufficient strength of the resultant granule to resist premature breakage. Generally, above a 2:1, preferably from 5:1 to 100:1, more preferably from 20:1 to 40:1, weight ratio of carrier to silicone suds controlling agent is employed.
  • the size of the particles of the suds controlling component used in the present compositions is selected to be compatible with the remainder of the detergent composition.
  • the suds controlling components herein do not segregate unacceptably within the detergent composition.
  • particles with a maximum dimension of from 600 to 2000, preferably from 800 to 1600 ⁇ m are compatible with spray-dried detergent granules. Therefore, the majority of the particles should have these maximum dimensions.
  • the majority of the particles should have a ratio of the maximum to the minimum diameter of from 1.5:1 to 5:1, preferably from 1.5:1 to 4:1.
  • suds controlling components which can be releasably incorporated in a carrier material besides silicone, include monocarboxylic fatty acids and soluble salts thereof. These typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Other suitable suds controlling components include high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g.
  • N-alkylated amino triazines such as tri- to hexaalkylmelamines or di- to tetraalkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • a primary or secondary amine containing 1 to 24 carbon atoms
  • propylene oxide bis stearic acid amide
  • monostearyl di-alkali metal e.g. sodium, potassium, lithium
  • an encapsulated antifoam composition having a suds controlling agent and the reaction product of (i) an alkylalkoxysilane; and (ii) a silicone condensation cure catalyst wherein the suds controlling agent is encapsulated by the reaction product may be used.
  • the method of making such preferred encapsulated antifoam compositions are described in GB 2 318 355, published on April 22, 1998, by General Electric Co.
  • a homogenous rosin/silicone mixture made from a mixture of liquid polydimethyl siloxane with aqueous caustic soda solution and melted rosin can also be used as a delayed-release foam suppressing component. Because the rosin/silicone mixture becomes soluble at higher temperatures, such foam suppressing is especially useful for the delayed-release in washing conditions in which the wash water is heated over time. See also GB 1340043, published December 5, 1978, by Griffiths et. al.
  • the carrier for the suds controlling agent can be a solid particulate structure of modified cellulose which is soluble in water, but dissolves at a relatively slow rate due to the swelling of the surface of the cellulose.
  • a suds controlling agent can be enclosed in a microcapsule composed of a core and a shell of a polymer, so that there is a controlled release of the core material (suds controlling agent) by destruction of the polymer shell by the action of bases.
  • microcapsules can be used as a delayed-release foam suppressing component.
  • One preferred microcapsule is made by polymerizing (i) more than 40% by weight of maleic anhydride, (ii) 0-99% by weight of at least one monoethylenically unsaturated monomer which is oil-soluble and which is different from the monomers of maleic anhydride, (iii) 0-80% by weight of crosslinking monomers which are oil soluble and different from maleic anhydride which have at least two monoethylenically unsaturated non-conjugated double bonds in the molecule, and (iv) 0-20% by weight of water-soluble monoethylenically unsaturated monomers, the percentages relating to the total amount of monomers (i) to (iv), in the oil phase of a stable oil-in-water emulsion in the presence of polymerization initiators which form free radicals, where the temperature of the polymerizing reaction mixture may be continuously or periodically increased during the polymerization.
  • the detergent composition of the invention can comprise additional detersive components known in the art.
  • the foaming component and/or the delayed-release foam suppressing component may further contain detersive components.
  • the precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used.
  • the detergent compositions preferably contains one or more additional detersive components selected from the group consisting of surfactants, bleaches, alkali metal salt of silicate, builders, chelating agents, enzymes, fillers, soil suspending agents, optical brighteners, dispersants, soil release agents, photoactivated bleaches, dyes, dye transfer inhibitors, pigments, perfumes, clay softening system, cationic fabric softening agents, and mixtures thereof.
  • additional detersive components selected from the group consisting of surfactants, bleaches, alkali metal salt of silicate, builders, chelating agents, enzymes, fillers, soil suspending agents, optical brighteners, dispersants, soil release agents, photoactivated bleaches, dyes, dye transfer inhibitors, pigments, perfumes, clay softening system, cationic fabric softening agents, and mixtures thereof.
  • the particles comprises at least one or more anionic surfactants and preferably one or more cationic surfactants, as described herein. It can also be preferred that the particles also, or alternatively comprise builder material and bleaching species, as described herein
  • the detergent compositions may contain one or more surfactants selected from anionic, cationic, ampholytic, amphoteric and zwitterionic surfactants or nonionic surfactants as described above, and mixtures thereof.
  • surfactants selected from anionic, cationic, ampholytic, amphoteric and zwitterionic surfactants or nonionic surfactants as described above, and mixtures thereof.
  • a typical listing of these surfactants is given in U.S. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
  • a list of suitable cationic surfactants is given in U.S. 4,259,217 issued to Murphy on March 31, 1981.
  • anionic surfactant useful for detersive purposes is suitable.
  • examples include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
  • Anionic sulfate surfactants are preferred.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • the anionic surfactant can be present at a level of 0.5% to 80%, preferably at a level of from 3% to 60%, more preferably of from 5% to 35% by weight of the composition or the particle.
  • the ratio of the stabilising agent to the anionic surfactant is preferably from 1:20 to 20:1, more preferably from 1:6 to 6:1.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C 5 -C 17 acyl-N-(C 1 -C 4 alkyl) and -N-(C 1 -C 2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C 9 -C 22 alkyl sulfates, more preferably the C 11 -C 15 branched chain alkyl sulfates and the C 12 -C 14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C 10 -C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 50 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 11 -C 18 , most preferably C 11 -C 15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic sulfonate surfactants suitable for use herein include the salts of C 5 -C 20 linear or branched alkylbenzene sulfonates, alkyl ester sulfonates, in particular methyl ester sulfonates, C 6 -C 22 primary or secondary alkane sulfonates, C 6 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH 2 CH 2 0) x CH 2 C00 - M + wherein R is a C 6 to C 18 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR 1 -CHR 2 -O) X -R 3 wherein R is a C 6 to C 18 alkyl group, x is from 1 to 25, R 1 and R 2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R-CON (R 1 ) CH 2 COOM, wherein R is a C 5 -C 17 linear or branched alkyl or alkenyl group, R 1 is a C 1 -C 4 alkyl group and M is an alkali metal ion.
  • R is a C 5 -C 17 linear or branched alkyl or alkenyl group
  • R 1 is a C 1 -C 4 alkyl group
  • M is an alkali metal ion.
  • Another preferred surfactant is a cationic surfactant, which may preferably be present at a level of from 0.1% to 60% by weight of the composition or particle, more preferably from 0.4% to 20%, most preferably from 0.5% to 5% by weight of the composition.
  • the ratio of the anionic surfactant to the cationic surfactant is preferably from 25:1 to 1:3, more preferably from 15:1 to 1:1. most preferably from 10:1 to 1:1
  • the ratio of cationic surfactant to the stabilising agent is preferably from 1:30 to 20: 1, more preferably from 1:20 to 10:1.
  • the cationic surfactant is selected from the group consisting of cationic ester surfactants, cationic mono-alkoxylated amine surfactants, cationic bis-alkoxylated amine surfactants and mixtures thereof.
  • the optional cationic mono-alkoxylated amine surfactant for use herein has the general formula: wherein R 1 is an alkyl or alkenyl moiety containing from 6 to 18 carbon atoms, preferably 6 to 16 carbon atoms, most preferably from 6 to 11 carbon atoms; R 2 and R 3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl; R 4 is selected from hydrogen (preferred), methyl and ethyl, X - is an anion such as chloride, bromide, methylsulfate, or sulfate, to provide electrical neutrality; A is selected from C 1 -C 4 alkoxy, especially ethoxy (i.e., -CH 2 CH 2 O-), propoxy, butoxy and mixtures thereof: and p is from 1 to 30, preferably 1 to 15, most preferably 1 to 8.
  • Highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula wherein R 1 is C 6 -C 18 hydrocarbyl and mixtures thereof, preferably C 6 -C 14 , especially C 6 -C 11 alkyl, preferably C 8 and C 10 alkyl, and X - is any convenient anion to provide charge balance, preferably chloride or bromide.
  • compounds of the foregoing type include those wherein the ethoxy (CH 2 CH 2 O) units (EO) are replaced by butoxy, isopropoxy [CH(CH 3 )CH 2 O] and [CH 2 CH(CH 3 O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
  • EO ethoxy
  • i-Pr isopropoxy units
  • Pr n-propoxy units
  • the cationic bis-alkoxylated amine surfactant for use herein has the general formula: wherein R 1 is an alkyl or alkenyl moiety containing from 6 to 18 carbon atoms, preferably 6 to 16 carbon atoms, more preferably 6 to 11, most preferably from 8 to 10 carbon atoms; R 2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R 3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X - is an anion such as chloride, bromide, methylsulfate, or sulfate, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C 1 -C 4 alkoxy, especially ethoxy, (i.e., -CH 2 CH 2 O-), propoxy, butoxy and mixtures thereof; p is from 1 to 30, preferably 1 to 4 and q is from 1 to 30, preferably 1 to 4, and most preferably both p and q are 1.
  • Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula wherein R 1 is C 6 -C 18 hydrocarbyl and mixtures thereof, preferably C 6 , C 8 , C 10 , C 12 , C 14 alkyl and mixtures thereof.
  • X - is any convenient anion to provide charge balance, preferably chloride.
  • cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula: wherein R 1 is C 6 -C 18 hydrocarbyl, preferably C 6 -C 14 alkyl, independently p is 1 to 3 and q is 1 to 3, R 2 is C 1 -C 3 alkyl, preferably methyl, and X - is an anion, especially chloride or bromide.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R 3 (OR 4 ) x N 0 (R 5 ) 2 wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • C 10 -C 18 alkyl dimethylamine oxide Preferred are C 10 -C 18 alkyl dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be incorporated into the particle of the invention or the compositions containing the particle of the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R') 2 N + R 2 COO - wherein R is a C 6 -C 18 hydrocarbyl group, each R 1 is typically C 1 -C 3 alkyl, and R 2 is a C 1 -C 5 hydrocarbyl group.
  • Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10 - 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • compositions preferably contain a water-soluble builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition or particle.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from 6 to 21, and salts of phytic acid.
  • the composition may contain a partially soluble or insoluble builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition or particle.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z[ (AlO 2 ) z (SiO 2 )y]. xH 2 O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 [AlO 2 ) 12 (SiO 2 ) 12 ]. xH 2 O wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ]. 276 H 2 O.
  • Preferred crystalline layered silicates for use herein have the general formula NaMSi x O 2x+1 .yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2.
  • the most preferred material is ⁇ -Na 2 Si 2 0 5 , available from Hoechst AG as NaSKS-6.
  • An preferred additional components of the composition is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts.
  • Perborate can be mono or tetra hydrated.
  • Sodium percarbonate has the formula corresponding to 2Na 2 CO 3 .3H 2 O 2 , and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate is another optional inorganic perhydrate salt of use in the detergent compositions herein.
  • compositions are an organic peroxyacid bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 80% by weight of the particle, more preferably from 5% to 45% by weight, most preferably from 3% to 15% by weight of the compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiency reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of: and mixtures thereof, wherein R 1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group.
  • R 1 , R 3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
  • the preferred solubilizing groups are -SO 3 - M + , -CO 2 - M + , -SO 4 - M + , -N + (R 3 ) 4 X - and O ⁇ --N(R 3 ) 3 and most preferably -SO 3 - M + and -CO 2 - M + wherein R 3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N 1 N 1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
  • Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • the TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae: wherein R 1 is an alkyl group with from 1 to 14 carbon atoms, R 2 is an alkylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoytating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole.
  • Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyi pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: wherein R 1 is H, alkyl, alkaryl, aryl, or arylalkyl.
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: wherein R 1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • compositions optionally contain a transition metal containing bleach catalyst.
  • a transition metal containing bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • ethylenediaminetetraacetic acid ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(ClO 4 ) 2 , Mn lV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 -(ClO 4 ) 2 , Mn III Mn lV 4 (u-O) 1 (u-OAc) 2 -(1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(ClO 4 ) 3 , and mixtures thereof.
  • ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.
  • bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH 3 ) 3- (PF 6 ).
  • Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands including N 4 Mn III (u-O) 2 Mn IV N 4 ) + and [Bipy 2 Mn III (u-O) 2 Mn IV bipy 2 ]-(ClO 4 ) 3 .
  • bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat.
  • the composition preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions or particle.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • diethylene triamine penta methylene phosphonate
  • ethylene diamine tri methylene phosphonate
  • hexamethylene diamine tetra methylene phosphonate
  • hydroxy-ethylene 1,1 diphosphonate nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable.
  • Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
  • Another preferred ingredient useful in the composition is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 10% by weight of the particle, preferably 0.001% to 3% by weight of the composition, most preferably from 0.001% to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • Organic polymeric compounds are preferred in compositions.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 50% by weight of the particle, preferably from 0.5% to 25%, most preferably from 1% to 15% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1,596,756.
  • salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
  • the polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • X is a nonionic group selected from the group consisting of H, C 1 -C 4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof
  • a is from 0 to 20, preferably from
  • compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
  • the clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
  • the particles or compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
  • Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula : wherein P is a polymerisable unit, and A is - O-, -S-, -N-; x is O or 1; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures : wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • a preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • the polyamine N-oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000.
  • Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
  • the preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
  • compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • PVP K-15 is also available from ISP Corporation.
  • Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
  • Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
  • compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
  • compositions herein also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having the structural formula: wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • R 1 is anilino
  • R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R 1 is anilino
  • R 2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2 -hydroxyethyl-N-methylamino )-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R 1 is anilino
  • R 2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention.
  • Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
  • Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.
  • the detergent compositions preferably can have an acidic or an alkaline pH, depending on the application or the additional ingredients. It may be preferred that the particles or the compositions have a pH, measured as a 1% solution in distilled water, of at least 3.0, preferably from 4.0 to 12.5.
  • the method typically comprises contacting and/or treating soiled fabric with an aqueous wash solution containing detergent composition in a bucket or a container with a solid bar.
  • the consumer contacts the solid bar with the soiled fabric by scrubbing. After all the fabric has been scrubbed, fresh water is added to the container and the fabrics are rinsed. This rinsing process may be repeated.
  • a cleaning or scrubbing implement may also be used.
  • the method typically comprises treating soiled laundry with an aqueous wash solution having dissolved or dispensed therein an effective amount of detergent composition.
  • an effective amount is from 10g to 300 g or product dissolved or dispersed in a wash solution of volume from 5 to 65 litres.
  • soiled fabrics are immersed in an aqueous soaking solution containing the detergent composition for an effective period of time. Then, the fabrics are removed from the soaking solution.
  • the controlled foaming system of the present invention can be made by any method known in the art for formation of particles, as described above.
  • the foaming component and the delayed-release foam suppressing component may be combined.
  • the foaming component and the foam suppressing component may be agglomerated or otherwise mixed together with other optional components to form one solid particle.
  • the foaming component and the foam suppressing component may be two separate particles. Either the one solid particle or the two separate particles making up the foaming system may be used in detergent compositions.
  • Component 1 1.0 3.0 - - 10.0 - 10.0 - - 5.0 Foam supp.
  • Foaming systems A-J produces upon contact with water gas bubbles having an average bubble particle size of 400 microns or less, and the foam suppressing components reduces the water gas bubbles as soon as the mixture is agitated.
  • the bubbles have been reduced at least 40% to 70% after 6 to 10 minutes after the mixture is first agitated.
  • high density and bleach-containing detergent formulations can be for either granular form or tablet form: a b c Blown Powder Zeolite A 5.0 5.0 15.0 Sodium sulfate 0.0 5.0 0.0 LAS 20.0 30.0 20.0 C45AS 3.0 5.0 20.0 QAS - - 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Foaming System A 20.0 Foaming System B - 15.0 - Foaming System G - - 10.0 Spray On (on particles) Encapsulated Perfume 0.3 0.3 0.3 C25E3 - - 2.0 Dry additives QEA - - 0.5 Citrate 5.0 - 2.0 Bicarbonate - 3.0 - Carbonate 8.0 10.0 5.0 NAC OBS 6.0 - - Manganese catalyst - - 0.3 NOBS - 2.0 - PB1 14.0 7.0 - Polyethylene oxide of MW 5,000,000 - - 0.2

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EP98949783A 1998-10-05 1998-10-05 Foaming system and detergent compositions containing the same Expired - Lifetime EP1119604B1 (en)

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US6491947B2 (en) * 2000-11-03 2002-12-10 Chemlink Laboratories, Llc Expanded perborate salt, use, and method of production
US6440906B1 (en) * 2000-11-03 2002-08-27 Chemlink Laboratories, Llc Solvent for liquid ingredients to be used in effervescent products
EP1470210A1 (en) * 2002-01-31 2004-10-27 Givaudan SA Effervescent granulated composition
DE60302883T2 (de) * 2002-04-19 2006-08-17 Dow Corning S.A. Schaumregulierungsmittel
KR100598863B1 (ko) 2004-09-24 2006-07-10 한국화학연구원 캡슐화된 자기유화형 실리콘 컴파운드를 포함하는 입자형실리콘 소포제 조성물 및 이의 제조방법
KR100728474B1 (ko) * 2005-11-24 2007-06-13 주식회사 엘지생활건강 발포성 정제형 야채 및 과일 세제 조성물
GB0818025D0 (en) * 2008-10-02 2008-11-05 Dow Corning Granular composition
JP6238451B2 (ja) * 2014-04-16 2017-11-29 ライオン株式会社 繊維製品用液体洗浄剤
CN106422427A (zh) * 2016-09-28 2017-02-22 佛山慧创正元新材料科技有限公司 一种1‑环己烯乙胺/纳米二氧化硅复合消泡剂其制备方法
US10851331B2 (en) 2017-04-27 2020-12-01 Ecolab Usa Inc. Solid controlled release carbonate detergent compositions
JP7091454B2 (ja) 2017-11-14 2022-06-27 エコラボ ユーエスエー インコーポレイティド 固形制御放出苛性洗剤組成物
KR101989597B1 (ko) * 2018-06-12 2019-06-14 주식회사 아이엠 탈염 및 이염 방지용 세탁세제 조성물
EP3636733B1 (en) * 2018-10-12 2022-09-21 Wacker Metroark Chemicals Pvt. Ltd. Silicone composition and its application as an additive in detergent composition to enhance foamability and cleaning effect
EP4007803A1 (en) 2019-09-27 2022-06-08 Ecolab USA Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid
CN113501951A (zh) * 2021-06-09 2021-10-15 内蒙古科学技术研究院 一种聚醚消泡剂及其制备方法与应用

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GB8513074D0 (en) * 1985-05-23 1985-06-26 Unilever Plc Antifoam ingredient
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ATE286963T1 (de) 2005-01-15
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AU9602998A (en) 2000-04-26
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CA2345581A1 (en) 2000-04-13
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