EP0413616B1 - Non-aqueous, nonionic heavy duty laundry detergent - Google Patents

Non-aqueous, nonionic heavy duty laundry detergent Download PDF

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Publication number
EP0413616B1
EP0413616B1 EP90400897A EP90400897A EP0413616B1 EP 0413616 B1 EP0413616 B1 EP 0413616B1 EP 90400897 A EP90400897 A EP 90400897A EP 90400897 A EP90400897 A EP 90400897A EP 0413616 B1 EP0413616 B1 EP 0413616B1
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EP
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Prior art keywords
composition
polymer
weight
acid
builder
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EP90400897A
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German (de)
English (en)
French (fr)
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EP0413616A1 (en
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Nicole Antheunis
Christine Toussaint
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Colgate Palmolive Co
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Colgate Palmolive Co
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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/38618—Protease or amylase in liquid compositions only
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • This invention relates to stabilization of non-aqueous liquid suspensions, especially non-aqueous liquid fabric-treating compositions. More particularly, this invention relates to non-aqueous liquid laundry detergent compositions which are made stable against phase separation under both static and dynamic conditions and are easily pourable, to the method of preparing these compositions and to the use of these compositions for cleaning soiled fabrics.
  • compositions of this type may comprise a liquid nonionic surfactant in which are dispersed particles of a builder, as shown for instance in U.S. Patents No. 4,316,812; 3,630,929; 4,264,466; and 4,661,280.
  • Liquid detergents are often considered to be more convenient to employ than dry powdered or particulate products and, therefore, have found substantial favor with consumers. They are readily measurable, speedily dissolved in the wash water, capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments to be laundered and are non-dusting, and they usually occupy less storage space. Additionally, the liquid detergents may have incorporated in their formulations materials which can not stand drying operations without deterioration, which materials are often desirably employed in the manufacture of particulate detergent products.
  • liquid detergents Although they are possessed of many advantages over unitary or particulate solid products, liquid detergents often have certain inherent disadvantages too, which have to be overcome to produce acceptable commercial detergent products. Thus, some such products separate out on storage and others separate out on cooling and are not readily redispersed. In some cases the product viscosity changes and it becomes either too thick to pour or so thin as to appear watery. Some clear products become cloudy and others gell on standing.
  • suspensions can be stabilized against settling by adding inorganic or organic thickening agents or dispersants, such as, for example, very high surface area inorganic materials, e.g. finely divided silica, clays etc., organic thickeners, such as the cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc.
  • inorganic or organic thickening agents or dispersants such as, for example, very high surface area inorganic materials, e.g. finely divided silica, clays etc., organic thickeners, such as the cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc.
  • inorganic or organic thickening agents or dispersants such as, for example, very high surface area inorganic materials, e.g. finely divided silica, clays etc., organic thickeners, such as the cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc.
  • these additives do not contribute to tie
  • an aqueous false body fluid abrasive scouring composition is prepared from an aqueous liquid and an appropriate colloid-forming materials, such as clay or other inorganic or organic thickening or suspending agent, especially smectite clays, and a relatively light, water-insoluble particulate filler material, which, like the abrasive materials, is suspended throughout the false body fluid phase.
  • the lighweight filler has particle size diameters ranging from 1 to 250 »m and a specific gravity less than that of the false body fluid phase. It is suggested by Hartman that inclusion of the relatively light, insoluble filler in the false body fluid phase helps to minimize phase separation, i.e.
  • the filler material acts as a bulking agent replacing a portion of the water which would normally he used in the absence of the filler material, thereby resulting in less aqueous liquid available to cause clear layer formation and separation.
  • British Application GB 2,168,377A published June 18, 1986, discloses aqueous liquid dishwashing detergent compositions with abrasive, colloidal clay thickener and low density particulate filler having particle sizes ranging from about 1 to about 250 »m and densities ranging from about 0.01 to about 0.5 g/cc, used at a level of from about 0.07% to about 1% by weight of the composition. It is suggested that the filler material improves stability by lowering the specific gravity of the clay mass so that it floats in the liquid phase of the composition. The type and amount of filler is selected such that the specific gravity of the final composition is adjusted to match that of the clear fluid (i.e. the compositon without clay or abrasive materials).
  • inorganic insoluble thickening agent or dispersant of very high surface area such as finely divided silica of extremely fine particle size (e.g. of 5-100 10 ⁇ 9 m diameter such as sold under the name Aerosil) or the other highly voluminous inorganic carrier materials as disclosed in U.S. Patent 3,630,929.
  • aqueous swelling colloidal clays such as bentonite and montmorillonite clays
  • organophilic clays as gel-forming clays has been described in U.S. Patent 2,531,427 to E.A. Hauser. Improvements and modifications of the organophilic gel-forming clays are described, for example, in the following U.S.
  • Patents 2,966,506 - Jordan; 4,105,578 - Finlayson, et al.; 4,208,218 - Finlayson; 4,287,086 - Finlayson; 4,434,075 - Mardis, et al.; 4,434,076 - Mardis, et al.; all assigned to NL Industries, Inc., formerly National Lead Company.
  • these organophilic clay gellants are useful in lubricating greases, oil based muds, oil base packer fluids, paints, paint-varnish-lacquer removers, adhesives, sealants, inks, polyester gel coats and the like,
  • use as a stabilizer in a non-aqueous liquid detergent composition for laundering fabrics has not been suggested.
  • the physical stability of a dispersion of the particulate materials, such as detergent builders, in a non-aquoeus liquid phase is improved by using as a primary suspending agent an impalpable chain structure type clay, including sepiolite, attapulgite, and palygorskite clays.
  • an impalpable chain structure type clay including sepiolite, attapulgite, and palygorskite clays.
  • the patentees state the comparative examples in this patent show that other types of clays, such as montmorillonite clay, e.g. Bentolite L. hectorite clay (e.g. Veegum T) and kaolinite clay (e.g.
  • Hydrite PX even when used in conjunction with an auxiliary suspension aid, including cationic surfactants, inclusive of QA compounds, are only poor suspending agents.
  • Carleton, et al. also refer to use of other clays as suspension aids and mention, as examples, U.S. Patents 4,049,034 and 4,005,027 (both aqueous systems); and U.S. Patents 4,166,039; 3,259,574; 3,557,037 and 3,549,542; and U.K. Patent Application 2,017,072.
  • organophilic clay improves stability of the suspension, still further improvements are desired especially for particulate suspensions having relatively low yield values for optimizing dispensing and dispersion during use.
  • the non-aqueous liquid laundry detergents based on liquid nonionic surfactants suffer from the drawback that the nonionics tend to gell when added to cold water.
  • This is a particularly important problem in the ordinary use of European household automatic washing machines where the user places the laundry detergent composition in a dispensing unit (e.g. a dispensing drawer) of the machine.
  • the detergent in the dispenser is subjected to a stream of cold water to transfer it to the main body of wash solution.
  • the detergent viscosity increases markedly and a gel forms.
  • some of the composition is not flushed completely off the dispenser during operation of the machine, and a deposit of the composition builds up with repeated wash cycles, eventually requiring the user to flush the dispenser with hot water.
  • the gelling phenomenon can also be a problem whenever it is desired to carry out washing using cold water as may be recommended for certain synthetic and delicate fabrics or fabrics which can shrink in warm or hot water.
  • Partial solutions to the gelling problem in aqueous, substantially builder-free compositions have been proposed and include, for example, diluting the liquid non-ionic with certain viscosity controlling solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol (see U.S. Patent No. 3,953,380), alkali metal formates and adipates (see U.S. Patent No. 4,363,147), hexylene glycol, polyethylene glycol, etc. and nonionic structure modification and organization.
  • certain viscosity controlling solvents and gel-inhibiting agents such as lower alkanols, e.g. ethyl alcohol (see U.S. Patent No. 3,953,380), alkali metal formates and adipates (see U.S. Patent No. 4,363,147), hexylene glycol, polyethylene glycol, etc. and nonionic structure modification and organization.
  • non-aqueous nonionic detergent compositions containing builders suspended therein with the aid of certain dispersants for the builder such as finely divided silica and/or polyether group containing compounds having molecular weights of at least 500
  • the former is exemplified by C12 - C15 fatty alcohols with 5 to 15 moles of etylene and/or propylene oxide per mole.
  • the other surfactant is exemplified by linear C6 - C8 or branched C8 - C11 fatty alcohols with 2 to 8 moles ethylene and/or propylene oxide per mole. Again, there is no teaching that these low carbon chain compounds could control the viscosity and prevent gelation of the heavy duty non-aqueous liquid nonionic surfactant compositions with builder suspended in the nonionic liquid surfactant.
  • Us 4,326,979 is directed to a non-aqueous built liquid detergent composition consisting essentially of a non-ionic surface active detergent, an at least partially hydrolyzed copolymer of maleic anhydride with ethylene or vinylmethylether in the presence of a strongly alkaline material.
  • liquid fabric treating compositions which are suspensions of insoluble fabric-treating particles in a non-aqueous liquid and which are storage and transportation stable, easily pourable and dispersible in cold, warm or hot water.
  • Another object of this invention is to formulate highly built heavy duty non-aqueous liquid nonionic surfactant laundry detergent compositions which resist settling of the suspended solid particles or separation of the liquid phase.
  • a still further object of this invention is to provide nonionic liquids compositions which are readily dispersible in water, particularly laundry bath water.
  • a heterogenous system of solids in a liquid medium which is structured to act as a solid during states of rest and under the ordinary stresses of vibrations, oscillations, shear forces and the like which occur during the handling (e.g. transportation etc.) of the packaged product.
  • the system acts as a conventional solids suspension in a liquid vehicle or matrix, i.e. it is flowable, pourable, and of course in this state, Stokes Law takes over and the solid suspended matter may settle and the liquid solid phases stratify. It has been determined that several rheological parameters are meaningful indications of the stability of a solids suspension in a liquid phase system.
  • G'' storage modulus or loss modulus
  • relaxation time critical strain (i.e. structure not destroyed below the strain)
  • critical strain i.e. structure not destroyed below the strain
  • targets to reach for optimized stability are a long relaxation time (G'>G''), a critical strain above 0.1 and a recovery time shorter than 1 minute.
  • the polymers are derived from ⁇ , ⁇ -monethylenically unsaturated carboxy-containing monomers which also contain at least one other chalcogen-containing group substituted with at least one group of at least 2 carbon atoms.
  • the polymers may be cross-linked homopolymers, copolymers, ter-polymers (i.e. interpolymers) or cross-linked block interpolymers (e.g. block copolymers) obtained by using a difunctional reagent such as a diol, dithiol or the like.
  • a difunctional reagent such as a diol, dithiol or the like.
  • the amount of polymer in the composition may vary from about 0.01% to about 10% by weight, and preferably from about 0.05% to about 5% by weight. Typical amounts are 0.10; 0.20 and 0.25.
  • An object of the invention is to provide a stable, non aqueous liquid detergent composition
  • a stable, non aqueous liquid detergent composition comprising a non-ionic surfactant suspended particles including builder, and from about 0.01 to about 10% by weight of the composition an amphiphilic cross-linked carboxy-containing polymer.
  • the polymer in addition to the carboxy group contains (preferably in the same monomer moiety) a further chalecogen group, i.e. oxygen, nitrogen or sulfur, which is substituted by a grouping of at least 2 carbon atoms.
  • a further chalecogen group i.e. oxygen, nitrogen or sulfur, which is substituted by a grouping of at least 2 carbon atoms.
  • Illustrative groups are carboxy, carboxamido, sulfonate, etc. Specific groups include carboethoxy, carbobutoxy, N-ethyl carboxamido, N,N-diethyl carboxamido, N-n-butyl-carboxamido, etc.
  • Specific monomer moieties of particular advantage are the ⁇ , ⁇ -unsaturated dicarboxylic anhydride and especially those of the formula wherein R1 and R2 are independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, aralkyl, (and substituted alkyl, aryl or aralkyl), or --SO3H.
  • Example of these compounds are: maleic anhydride chloromaleic anhydride citraconic anhydride (methylmaleic) fumaric anhydride mesaconic anhydride phenylmaleic anhydride benzyl maleic anhydride sulfomaleic anhydride aconitic anhydride itaconic anhydride methylene malonic anhydride alkyl succinic anhydride and the like It is preferred to provide the carboxy monomer moieties in conjunction with other copolymerizable ⁇ , ⁇ - ethylenically unsaturated monomers.
  • vinyl ethers e.g., vinyl methyl ether vinyl ethyl ether vinyl n-propyl ether vinyl iso-proply ether vinyl n-butyl ether vinyl iso-butyl ether vinyl iso-octyl ether vinyl phenyl ether a-chlorovinyl phenyl ether vinyl B-naphthyl ether vinyl esters, e.g., vinyl acetate vinyl propionate vinyl butyrate vinyl caproate vinyl stearate, etc.
  • vinyl ethers e.g., vinyl methyl ether vinyl ethyl ether vinyl n-propyl ether vinyl iso-proply ether vinyl n-butyl ether vinyl iso-butyl ether vinyl iso-octyl ether vinyl phenyl ether a-chlorovinyl phenyl ether vinyl B-naphthyl ether vinyl esters, e.g., vinyl
  • vinyl halides e.g., vinyl chloride vinyl fluoride vinyl bromide acrylic acid and esters, e.g., methyl acrylate ethyl acrylate propyl acrylate acrylic acid derivatives, e.g., methacrylic acid and esters a-haloacrylic acid and esters acrylonitrile methacrylonitrile acrylamide methacrylamide N-alkyl acrylamides N-aryl acrylamides N-vinyl heterocycles, e.g., N-vinyl pyrrolidone N-vinyl 3-morpholinones N-vinyl oxazolidone N-vinyl imidazole styrene alkyl styrenes, e.g., a-methyl styrene vinylidene chloride vinyl ketones, e.g., methyl vinyl ketone olefins such as ethylene propylene isobutylene butene-1 2,4,4-tri
  • the anhydride-ethylenically unsaturated interpolymers preferably contain the two moieties in equimolar amount whereby the repeating unit in the interpolymer contains 1 anhydride and 1 comonomer moiety.
  • Other ratios are feasible 3.t. 5:4, 4:5, 3:2, 2:3, 2:1, 1:2 etc.
  • Examples of specific interpolymers which may be employed are: vinyl methyl ether-maleic anhydride vinyl ethyl ether-maleic anhydride styrene-maleic anhydride a-methyl styrene-maleic anhydride ethylene-maleic anhydride vinyl methyl ether-citraconic anhydride vinyl methyl ether-itaconic anhydride vinyl methyl ether-chlormaleic anhydride vinyl chloride-maleic anhydride vinyl acetate-maleic anhydride vinyl chloride-vinyl acetate-maleic anhydride styrene-vinyl acetate-maleic anhydride
  • An especially useful type of polymer (Z) is one based on an ⁇ , ⁇ -- ethylenically-unsaturated dicarboxylic acid or arhydride (e.g.
  • a further particularly useful sub-group covers the mono ester's (e.g. 1/2-butyl, 1/2-ethyl, 1/2-isohexyl) of these polymers.
  • Another useful subgroup involves the cross-linked (or reaction products) of the interpolymers of the type Z.
  • Illustrative crosslinking agents are glycols such as diethylene glycol, triethylene glycol, 1,6 hezanediol, polyethylene glycols with molecular weights ranging from several hundred (e.g. 200, 300, 400, etc.) to several hundred thousand (100,000; 150,000; 200,000; 250,000; 350,000; 500,00 etc.) and especially those in the range of about 400 to about 40,000
  • the amount of cross-linking agent may vary from 1% by weight based on the weight of the polymer to 10 times the weight of the polymer, preferably the ratio of polymer to cross-linker should range from about 10:1 to 1:5 and most preferably 5:1 to 1:2.
  • liquid phase of the composition of this invention is comprised predominantly or totally of liquid nonionic synthetic organic detergent.
  • a portion of the liquid phase may be composed, however, of organic solvents which may enter the composition as solvent, vehicles or carriers for one or more of the solid particulate ingredients, such as in enzyme slurries, perfumes, and the like.
  • organic solvents such as alcohols and ethers, may be added as further viscosity control and anti-gelling agents.
  • noniomic synthetic organic detergents employed in the practice of the invention nay be any of a wide variety of such compounds, which are well known and, for example, are described at length in the text Surface Active Agents , Vol. II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, and in McCutcheon's Detergents and Emulsifiers , 1969 Annual, the relevant disclosures of which are hereby incorporated by reference.
  • the nonionic detergents are poly-lower alkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety.
  • a preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher alkanol wherein the alkanol is of 10 to 22 carbon atoms and wherein the number of mols of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 20.
  • the higher alkanol is a higher fatty alcohol of about 12 to 18 carbon atoms and which contain from 3 to 14, preferably 3 to 12 lower alkoxy groups per mol.
  • the lower alkoxy is often just ethoxy but in some instances, it may be desirably mixed with propoxy, the latter, if present, often being in a minor (less than 50% proportion).
  • Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mol, e.g., Neodol 25-7 and Neodol 23-6.5, which products are made by Shell Chemical Company, Inc.
  • the former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 mols of ethylene oxide and the latter is a corresponding mixture wherein the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6.5.
  • the higher alcohols are primary alkanols.
  • Tergitol 15-S-7 and Tergitol 15-S-9 are linear secondary alcohol ethoxylates made by Union Carbide Corp.
  • the former is mixed ethoxylation product of 11 to 15 carbon atoms linear secondary alkanol with seven mols of ethylene oxide and the latter is a similar product but with nine mols of ethylene oxide being reacted.
  • nonionic detergent also useful in the present compositions as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mol being about 11. Such products are also made by Shell Chemical Company.
  • Another preferred class of useful nonionics are represented by the commercially well know class of nonionics which are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group.
  • Examples include the nonionics sold under the Plurafac trademark of BASF, such as Plurafac RA30, Plurafac RA40 (a C13-C15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide), Plurafac D25 (a C13-C15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide), Plurafac B26, and Plurafac RA50 (a mixture of equal parts Plurafac D25 and Plurafac RA40).
  • Plurafac RA30 Plurafac RA40
  • Plurafac D25 a C13-C15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide
  • Plurafac B26 and Plurafac RA50 (a mixture of equal parts Plurafac D25 and Plurafac RA40).
  • the mixed ethylene oxide-propylene oxide fatty alcohol condensation products represented by the general formula RO(C3H6O) p (C2H4O) q H, wherein R is a straight or branched primary or secondary aliphatic hydrocarbon, preferably alkyl or alkenyl, especially preferably alkyl, of from 60 to 20, preferably 10 to 18, especially preferably 12 to 18 carbon atoms, p is a number of up to 14, preferably 3 to 8, and q is a number of up to 14, preferably 3 to 12, can be advantageously used where low foaming characteristics are desired.
  • these surfactants have the advantage of low gelling temperatures.
  • Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol with an average of 5 moles ethylene oxide
  • Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles ethylene oxide; etc.
  • the number of lower alkoxies will usually be from 40% to 100% of the number of carbon atoms in the higher alcohol, such as 40 to 60% thereof and the nonionic detergent will often contain at least 50% of such preferred poly-lower alkoxy higher alkanol.
  • alkyl groups present therein are generally linear although branching may be tolerated, such as at a carbon next to or two carbons removed from the terminal carbon of the straight chain and away from the alkoxy chain, if such branched alkyl is not more than three carbons in length. Normally, the proportion of carbon atoms in such a branched configuration will be minor rarely exceeding 20% of the total carbon atom content of the alkyl.
  • linear alkyls which are terminally joined to the alkylene oxide chains are highly preferred and are considered to result in the best combination of detergency, biodegradability and non-gelling characteristics, medial or secondary joinder to the alkylene oxide in the chain may occur. It is usually in only a minor proportion of such alkyls, generally less than 20% but, as is the case of the mentioned Tergitols, may be greater. Also, when propylene oxide is present in the lower alkylene oxide chain, it will usually be less than 20% thereof and preferably less than 10% thereof.
  • non-terminally alkoxylated alkanols propylene oxide-containing poly-lower alkoxylated alkanols and less hydrophile-lipophile balanced nonionic detergent than mentioned above are employed and when other nonionic detergents are used instead of the preferred nonionics recited herein, the product resulting may not have as good detergency, stability, viscosity and non-gelling properties as the preferred compositions but use of viscosity and gel controlling compounds can also improve the properties of the detergents based on such nonionics.
  • another preferred class of nonionic surfactants includes the C12-C13 secondary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 7 to 9 moles, especially about 8 moles ethylene oxide per molecule and the C9-C11, especially C10 fatty alcohols ethoxylated with about 6 moles ethylene oxide.
  • compositions of this invention it may be advantageous to include an organic solvent or diluent which can function as a viscosity control and gel-inhibiting agent for the liquid nonionic surface active agents.
  • organic solvent or diluent which can function as a viscosity control and gel-inhibiting agent for the liquid nonionic surface active agents.
  • Lower (C1-C6) aliphatic alcohols and glycols, such as ethonol, isopropanol, ethylene glycol, hexylene glycol and the like have been used for this purpose.
  • Polyethylene glycols, such as PEG 400 are also useful diluients.
  • Alkylene glycol ethers such as the compounds sold under the trademarks, Carbopol and Carbitol which have relatively short hydrocarbon chain lengths (C2-C8) and a low content of ethylene oxide (about 2 to 6 EO units per molecule) are especially useful viscosity control and anti-gelling solvents in the compositions of this invention.
  • This use of the alkylene glycol ethers is disclosed in U.S. Patent No. 4,753,750 filed December 31, 1984, to T. Ouhadi, et al. the disclosure of which is incorporated herein by reference.
  • Suitable glycol ethers can be represented by the following general formula RO(CH2CH2O) n H where R is a C2-C8, preferably C2-C8 alkyl group, and n is a number of from about 1 to 6, preferably 1 to 4, on average.
  • suitable solvents include ethylene glycol monoethyl ether (C2H5-O-CH2CH2OH), diethylene glycol monobutyl ether (C4H9-O-(CH2CH2O)2H), tetraethylene glycol monooctyl ether (C8H17-O-(CH2CG2O)4H), etc.
  • Diethylene glycol monobutyl ether is especially preferred.
  • Another useful antigelling agent which can be included as a minor component of the liquid phase is an aliphatic linear or aliphatic monocyclic dicarboxylic acid, such as the C6 to C12 alkyl and alkenyl derivatives of succinic acid or maleic acid, and the corresponding anhydrides or an aliphatic monocyclic dicarboxylic acid compound.
  • an aliphatic linear or aliphatic monocyclic dicarboxylic acid such as the C6 to C12 alkyl and alkenyl derivatives of succinic acid or maleic acid, and the corresponding anhydrides or an aliphatic monocyclic dicarboxylic acid compound.
  • these gel-inhibiting compounds are aliphatic linear or aliphatic monocyclic dicarboxyllc acid compounds.
  • the aliphatic portion of the molecule may be saturated or ethylenically unsaturated and the aliphatic linear portion may be straight of branched.
  • the aliphatic monocylic molecules may be saturated or may include a single double bond in the ring.
  • the aliphatic hydrocarbon ring may have 5- or 6-carbon atom in the ring, i.e.
  • cyclopentyl cyclopentenyl, cyclohexyl, or cyclohexenyl, with one carboxyl group bonded directly to a carbon atom in the ring and the other carboxyl group bonded to the ring through a linear alkyl or alkenyl group.
  • the aliphatic linear dicarboxylic acids have at least about 6 carbon atoms in the aliphatic moiety and may be alkyl or alkenyl having up to about 14 carbon atoms, with a preferred range being from about 8 to 13 carbon atoms, especially preferably 9 to 12 carbon atoms.
  • One of the carboxylic acid groups (-COOH) is preferably bonded to the terminal (alpha) carbon atom of the aliphatic chain and the other carboxyl group is preferably bonded to the next adjacent (beta) carbon atom or it may be spaced two or three carbon atoms from the -position, i.e. on the ⁇ or ⁇ carbon atoms.
  • the alkyl or alkenyl group may be straight or branched.
  • the straight chain alkenyl groups are especially preferred. It is not necessary that R1 represent a single alkyl or alkenyl group and mixtures of different carbon chain lengths may be present depending on the starting materials for preparing the dicarboxylic acid.
  • the aliphatic monocyclic dicarboxylic acid may be either 5- or 6-membered carbon rings with one or two linear aliphatic groups bonded to ring carbon atoms.
  • the linear aliphatic groups should have at least about 6, preferably at least about 8, especially preferably at least about 10 carbon atoms, in total, and up to about 22, preferably up to about 18, especially preferably up to about 15 carbon atoms.
  • two aliphatic carbon atoms are present attached to the aliphatic ring they are preferably located para-to each other.
  • R2 and R3 are each preferably alkyl groups of from about 3 to about 10 carbon atoms, especially from about 4 to about 9 carbon atoms, with the total number of carbon atoms in R2 and R3 being from about 8 to about 15.
  • the alkyl or alkenyl groups may be straight of branched but are preferably straight chains.
  • the amount of the nonionic surfactant is generally within the range of from about 20 to about 70%, such as about 22 to 60% for example 25%, 30%, 35% or 40% by weight of the composition.
  • the amount of solvent or diluent when present is usually up to 20%, preferably up to 15%, for example, 0.5 to 15%, preferably 5.0 to 12%.
  • the weight ratio of nonionic surfactant to alkylene glycol ether as the viscosity control and anti-gelling agent, when the latter is present, is in the range of from about 100:1 to 1:1, preferably from about 50:1 to about 2:1, such as 10:1, 8:1, 6:1, 4:1 or 3:1. Accordingly, the continuous non-aqueous liquid phase may comprise from about 30% to about 70% by weight of the composition, preferably from about 50% to about 60%.
  • the amount of the dicarboxylic acid gel-inhibiting compound, when used, will be dependent on such factors as the nature of the liquid nonionic surfactant, e.g. its gelling temperature, the nature of the dicarboxylic acid, other ingredients in the composition which might influence gelling temperature, and the intended use (e.g. with hot or cold water, geographical climate, and so on).
  • the gelling temperature it is possible to lower the gelling temperature to no higher than about 3°C, preferably no higher than about 0 C, with amount of dicarboxylic acid anti-gelling agent in the range of about 1% to about 30%, preferably from about 1.5% to about 15%, by weight, based on the weight of the liquid nonionic surfactant, although in any particular case the optimum amount can be readily determined by routine experimentation.
  • the invention detergent compositions in the preferred embodiment also include as an essential ingredient water-soluble and/or water-dispersible detergent builder salts.
  • suitable builders include, for example, those disclosed in the aforementioned U.S. Patents 4,316,812, 4,264,466, 3,630,929, and many others.
  • Water-soluble inorganic alkaline builder salts which can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonates, borates, phosphates, polyphosphates, icarbonates, and silicates.
  • ammonium or substituted ammonium salts can also be used.
  • Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate, and potassium bicarbonate.
  • Sodium tripolyphosphate (TPP) is especially preferred where phosphate containing ingredients are not prohibited due to environmental concerns.
  • the alkali metal silicates are useful builder salts which also function to make the composition anticorrosive to washing machine parts. Sodium silicates of Na2O/SiO2 ratios of from 1.6/1 to 1/3.2, especially about 1/2 to 1/2.8 are preferred. Potassium silicates of the same ratios can also be used.
  • Another class of builders are the water-insoluble aliminosilicates, both of the crystalline and amorphous type.
  • Various cystalline zeolites i.e. aluminosilicates
  • amorphous zeolites useful herein can be found in Belgium Patent 835,351 and this patent too is incorporated herein by reference.
  • the zeolites generally have the formula (M2O) x .(Al2O3) y .(SiO2) z .WH2O wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and W is from 0 to 9, preferably 2.5 to 6 and M is preferably sodium.
  • a typical zeolite is type A or similar structure, with type 4A particularly preferred.
  • the preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, e.g. 400 meq/o g.
  • a preferred group of inorganic builders consists of inorganic phosphates.
  • organic alkaline sequestrant builder salts which can be used alone with the detergent or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylene diaminetetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA) and triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates.
  • EDTA ethylene diaminetetraacetate
  • NTA sodium and potassium nitrilotriacetates
  • triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates.
  • Suitable builders of the organic type include carboxymethylsuccinates, tartronates and glycollates and the polyacetal carboxylates.
  • the polyacetal carboxylates and their use in detergent compositions are described in 4,144,226; 4,315,092 and 4,146,494.
  • Other patents on similar builders include 4,141,676; 4,169,934; 4,201,858; 4,204,852; 4,224,420; 4,225,685; 4,226,960; 4,233,422; 4,233,423; 4,302,564 and 4,303,777.
  • the organic builders are the non-nitrogeneous polycarboxylates such as citric acid, tartaric acid and the like.
  • the preferred in this group are the sodium and potassium citrates and tartrates and most preferred are the sodium citric acid salts, especially the trisodium citrate, although the monosodium and disodium are also good.
  • a preferred group of organic builders consists of organic carboxylates.
  • the porportion of the suspended detergent builder is usually in the range of from about 30 to 70 weight percent, such as about 20 to 50 weight percent , for example about 40 to 50 weight percent of the composition.
  • the physical stability of the suspension of the detergent builder salt or salts or any other finely divided suspended solid particulate additive, such as bleaching agent, pigment, etc., in the liquid vehicle is drastically improved by the presence of small amounts of the amphiphilic polymer.
  • the stabilizer In preparing the compositions of the present invention, the stabilizer, generally in a flaked or powdered form, is admixed with the other solid ingredients and the liquid components, either in a conventional mixing apparatus, such as a crutcher-type mixer, followed by transfer to a milling apparatus or directly in a milling apparatus. In this latter case, the mill rotor of an Attritor ball mill may be employed to mix the components.
  • the stabilizer is first thoroughly mixed with the other solid ingredients, and then this admixture of solid components is mixed with the liquid components.
  • compositions of this invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it is often desirable to supplement the builder with an auxiliary builder such as a polymeric carboxylic acid having high calcium binding capacity to inhibit incrustration which would otherwise be caused by formation of an insoluble calcium phosphate, (e.g. where phosphate ion is present as from builder.
  • auxiliary builders are also well know in the art. For example, mention can be made Sokolan CP5 which is a copolymer of about equal moles of methacrylic acid and maleic anhydride, completely neutralized to form the sodium salt thereof.
  • the amount of the auxiliary builder is generally up to about 6 weight percent, preferably 1/4 to 4%, such as 1%, 2% or 3%, based on the total weight of the composition.
  • various other detergent additives or adjuvants may be present in the detergent product to give it additional desired properties, either of functional or aesthetic nature.
  • soil suspending or antiredeposition agents e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose, usually in amounts of up to 10 weight percent, for example 0.1 to 10%, preferably 1 to 5%; optical brighteners, e.g.
  • cotton, polyamide and polyester brighteners for example, stilbene, triazole and benzidone sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene benzidine sulfone, et., most preferred are stilbene and triazole combinations.
  • amount of the optical brightener up to about 2 weight percent, preferably up to 1 weight percent, such as 0.1 to 0.8 weight percent, can be used.
  • Bluing agents such as utramarine blue
  • enzymes preferable prot lytic enzymes, such as subtilisin, bormelin, papain, trypain and pensin, as well as amylasetype enzymes, lipase type enzymes, and mixtures thereof
  • bactericides e.g.
  • tetrachlorosalicylanilide hexachlorophene
  • fungicides fungicides
  • dyes pigments (water dispersible); preservatives
  • ultraviolet absorbers anti-yellowing agents, such as sodium carboxymethyl cellulose, complex of C12 to C22 alkyl alcohol with C12 to C18 alkylsulfate; pH modifiers and pH buffers
  • color safe bleaches, perfume, and anti-foam agents or suds-suppressor e.g. silicon compounds can also be sued.
  • the bleaching agents are classified broadly for convenience, as chlorine bleaches and oxygen bleaches.
  • Chlorine bleaches are typified by sodium hypochlorite (NaOCl), potassium dichloroiosocyanuate (59% available chlorine), and tricholorisocyanuric acid (95% available chlorine).
  • Oxygen bleaches are preferred and are represented by percompounds which liberate hydrogen peroxide in solution.
  • Preferred examples include sodium and potassium perborates, percarbones, and perphosphate, and potassium monopersulfate.
  • the perborates, particularly sodium perborate monohydrate, are especially preferred.
  • the peroxygen compound is preferably used in admixture with an activator therefor.
  • Suitable activators which can lower the effective operating temperature of the peroxide bleaching agent are disclosed, for example, in U.S. Patent 4,264,466 or in column 1 of U.S. Patent 4,430.244, the relevant disclosures of which are incorporated herein by reference.
  • Polyacylated compounds are preferred activators; among these, compounds such as tetraacetyl ethylene diamine (“TAED”) and pentaacetyl glucose are particularly preferred.
  • acetylsalicylic acid derivatives include, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril ("TAGU”), and the derivatives of these.
  • TAGU tetraacetylglycouril
  • Suitable sequestering agents include, for example, in addition to those mentioned above, the compounds sold under the Dequest trademark, such as, for example, diethylene triamine pentaacetic acid (DETPA); diethylene triamine pentamethylene phosphoric acid (DTPMP); and ethylene diamine tetramethylene phosphoric acid (EDITEMPA).
  • DETPA diethylene triamine pentaacetic acid
  • DTPMP diethylene triamine pentamethylene phosphoric acid
  • EDITEMPA ethylene diamine tetramethylene phosphoric acid
  • compositions may additionally include an enzyme inhibitor compound, i.e. a compound capable of inhibiting enzyme-induced decomposition of the peroxide bleaching agent.
  • an enzyme inhibitor compound i.e. a compound capable of inhibiting enzyme-induced decomposition of the peroxide bleaching agent.
  • Suitable inhibitor compounds are disclosed in U.S. Patent 3,606,990, the relevant disclosure of which is incorporated herein by reference.
  • hydroxylamine sulfate and other water-soluble hydroxylamine salts.
  • suitable amounts of the hydroxylamine salt inhibitors can be as low as about 0.01 to 0.4%.
  • suitable amounts of enzyme inhibitors are up to about 15%, for example, 0.1 to 10%, by weight of the composition.
  • an acidic organic phosphorus compound having an acidic-POH group is an acidic organic phosphorus compound having an acidic-POH group, as dislcosed in the commonly assigned copending application Serial No. 781,189, filed September 25, 1985, to Broze, et al., acidic organic phosphorus compound, may be, for instance, a partial ester of phosphoric acid and an alcohol, such as an alkanol having a lipophilic character, having, for instance, more than 5 carbon atoms, e.g. 8 to 20 carbon atoms.
  • a specific example is a partial ester of phosphoric acid and a C16 to C18 alkanol.
  • Empiphos 5632 from Marchon is made up of about 35% monoester and 65% diester. When used amounts of the phosphoric acid compound up to about 3%, preferably up to 1%, are sufficient.
  • a nonionic surfactant which has been modified to convert a free hydroxyl group to a moiety having a free carboxyl group, such as a partial ester of a nonionic surfactant and a polycarboxylic acid, can be incorporated into the composition to further improve rheological properties.
  • Suitable ranges of these optional detergent additives are: enzymes - 0 to 2%, especially 0.1 to 1.3%; corrosion inhibitors - about 0 to 40%, and preferably 5 to 30%; anti-foam agents and suds-suppressor - 0 to 15%, preferably 0 to 5%, for example 0.1 to 3%; thickening agent and dispersants - 0 to 15%, for example 0.1 to 10%, preferably 1 to 5%; soil suspending or anti-redeposition agents and anti-yellowing agents - 0 to 10%, preferably 0.5 to 5%; colorants, perfumes, brighteners and bluing agents total weight 0% to about 2% and preferably 0% to about 1%; pH modifiers and pH buffers - 0 to 5%, preferably 0 to 2%; bleaching agent - 0 to about 40% and preferably 0% to about 25%, for example 2 to 20%; bleach stabilizers and bleach activators 0 to about 15%, preferably 0 to 10%, for example, 0.1 to 8%
  • compositions according to the invention consist of compositions including an organic carboxylate selected from ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid, and tartaric acid.
  • the polymer of said compositions contains maleic acid or anhydride moieties, such a particular polymer being an ⁇ , ⁇ -monoethylenically unsaturated monomer-maleic anhydride interpolymer.
  • such a composition will comprise from about 20% to about 70% by weight of the non-ionic surfactant, from about 20% to about 70% by weight of the organic builder, the polymer being a vinyl C1 to C4 alkyl ether-maleic anhydride interpolymer and the weight percentages being based on the total weight of the composition, said composition further including a diol cross-linking agent in a weight ratio of polymer to cross-linking agent of from about 10:1 to 1:5, where the cross-linking agent is a polyethylene glycol, the ratio of polymer to the glycol will range from about 3:1 to 1:1.
  • An even more preferred polymer will be a partial C1 to C16 aliphalic ester such as a monobutyl ester.
  • Said composition may preferrably further comprise a bleaching compound and especially a peroxygen compound such as a perborate monohydrate salt.
  • the preferred amount of interpolymer added to the composition varies from 0.5 to 1.5 weight percent. More preferrably, the composition will further include up to 10% enzymes such as enzymes comprising a mixed enzyme system.
  • the non-ionic surfactant of the composition may be an ethylene-propylene oxide condensate with a reactive-hydrogen-containing hydrophobic chain of at least 8 carbon atoms, which may have preferrably the molecular configuration of a condensate of a C9 or greater alcohol with first 7 moles of ethylene oxide and then 4 moles of propylene oxide.
  • the mixture of liquid nonionic surfactant and solid ingredients is subjected to grinding, for example, by a san mill or ball mill.
  • a san mill or ball mill Especially useful are the attrition types of mill, such as those sold by Wiener-Amsterdam or Netzsch-Germany, for example, in which the particle sizes of the solid ingredients are reduced to about 1-10 »m , e.g. to an average particle size of 4 to 5 »m or even lower (e.g. 1 »m ).
  • Preferably less than about 10%, especially less than about 5 of all the suspended particles have particle sizes greater than 15 »m , preferably 10 »m.
  • the average particle size be at least 3 »m , especially about 4 microns.
  • Other types of grinding mills such as toothmill, peg mill and the like, may also be used.
  • the proportion of solid ingredients be high enough (e.g. at least about 40%, such as about 50% that the solid particles are in contact with each other and are not substantially shielded from one another by the nonionic surfactant liquid.
  • Mills which employ grinding balls. (ball mills) or similar mobile grinding elements have given very good results.
  • For larger scale work a continuously operating mill in which there are 1 mm of 1.5 mm diameter grinding balls working in a very small gap between a stator and a rotor operating at a relatively high speed (e.g.
  • a CoBall mill may be employed; when using such a mill, it is desirable to pass the blend of nonionic surfactant and solids first through a mill which does not effect such fine grinding (e.g. a colloid mill) to reduce the particle size to less than 100 »m (e.g. to about 40 »m) prior to the step of grinding to an average particles diameter below about 18 or 15 »m in the continuous ball mill.
  • a mill which does not effect such fine grinding (e.g. a colloid mill) to reduce the particle size to less than 100 »m (e.g. to about 40 »m) prior to the step of grinding to an average particles diameter below about 18 or 15 »m in the continuous ball mill.
  • the powdery solid particles may be finely ground to the desired size before blending with the liquid matrix, for instance, in a jet-mill.
  • non-aqueous means absence of water, however, small amounts of water, for example up to about 5%, preferably up to about 2%, may be tolerated in the compositions and, therefore, “non-aqueous" compositions can include such small amounts of water, whether added directly or as a carrier or solvent for one of the other ingredients in the composition.
  • liquid fabric treating compositions of this invention may be packaged in conventional glass or plastic vessels and also in single use packages, such as the doserrettes and disposable sachet dispensers disclosed in commonly assigned copending application Serial No. 063,199, filed June 12, 1987 (Attorney's Docket IR-347LG), the disclosure of which is incorporated herein by reference thereto.
  • Another object of the invention concerns a method for laundering clothes, which comprises washing the clothes in an aqueous bath containing the composition of the invention.
  • the product is exceptionally stable with no separation or settling of solids after more than 2 months.
  • Example I is repeated varying the nonionic (and citrate content) as follows
  • Example I is repeated except that the nonionic is replaced by the following in separate formulations in the percent indicated in the final formulation % (A) C13 - C15 fatty alcohol condensed with 7 moles of ethylene oxide and then 4 moles of propylene oxide 46.95 (B) C13 - C15 fatty alcohol condensed with 4 moles of propylene oxide and then 7 moles of ethylene oxide 46.95 (C) A & B in 1:1 ratio 46.95
  • Examples I to III are each repeated in all parts using, first, 0.05% of the polymer ester, then 0.08%, then 1.2%, then 1.5%.
  • Examples I, II, III, IV are each repeated using in place of the mono (i.e. 1/2)-butyl ester polymer the following (at equal weight amounts) A) mono butyl ester of ethylene maleic anhydride polymer (1:1) MW 200,000 B) mono butyl ester of styrene maleic anhydride polymer (1:1) MW 350,000 C) mono butyl ester of vinyl acetate maleic anhydride polymer (1:1) MW 305,000 D) mono ethyl ester of butyl acrylate maleic anhydride polymer (1:1) MW 450,000
  • composition is prepared % Weight C9 - C11 fatty alcohol condensed with 5 moles ethylene oxide 38.0 Sodium citrate dehydrate 27.8 Sodium perborate monohydrate 14.5 TAED activator 3.7 CMC 1.0 Titanium dioxide 0.4 Optical brightener 0.3 EDTA 0.5 Trienzymes A 0.55 Perfume 0.5 Pluronic L42 Diol 0.05 Vinyl methyl ether-maleic anhydride Polymer (Gantrez AN 119) 0.0 Propylene carbonate 12.6

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EP90400897A 1989-08-18 1990-04-02 Non-aqueous, nonionic heavy duty laundry detergent Revoked EP0413616B1 (en)

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US6699831B2 (en) 2000-06-07 2004-03-02 Kao Corporation Liquid detergent composition comprising aluminosilicate or crystalline silicate

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GB9108660D0 (en) * 1991-04-23 1991-06-12 Unilever Plc Polymers & their preparation
GB9108665D0 (en) * 1991-04-23 1991-06-12 Unilever Plc Liquid cleaning products
CZ2895A3 (en) * 1992-07-08 1995-08-16 Unilever Nv Substantially non-aqueous liquid cleansing agent
GB9216454D0 (en) * 1992-08-03 1992-09-16 Ici Plc Detergent compositions
EP0797656B2 (en) * 1994-12-13 2004-03-17 Unilever N.V. Detergent composition
ES2163091T3 (es) * 1996-01-25 2002-01-16 Unilever Nv Composicion detergente.
EP1256621B1 (en) 2001-05-08 2011-07-13 Kao Corporation Liquid detergent composition
US20030162679A1 (en) * 2002-01-15 2003-08-28 Rodrigues Klein A. Hydrophobically modified polymer formulations
US7179781B2 (en) 2003-05-02 2007-02-20 Ecolab Inc. Heterogeneous cleaning composition
US7169192B2 (en) 2003-05-02 2007-01-30 Ecolab Inc. Methods of using heterogeneous cleaning compositions
EP2083067A1 (de) 2008-01-25 2009-07-29 Basf Aktiengesellschaft Verwendung von organischen Komplexbildnern und/oder polymeren carbonsäuregruppenhaltigen Verbindungen in einer flüssigen Wasch- oder Reinigungsmittelzusammensetzung
WO2016196020A1 (en) * 2015-05-29 2016-12-08 3M Innovative Properties Company Enzyme cleaner for textiles with styrene maleic anhydride copolymers
WO2019027633A1 (en) * 2017-07-31 2019-02-07 Dow Global Technologies Llc DETERGENT ADDITIVE

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EP0028849B1 (en) * 1979-11-09 1983-09-28 Unilever N.V. Non-aqueous, built liquid detergent composition and method for preparing same
NZ211550A (en) * 1984-04-06 1987-06-30 Colgate Palmolive Co Liquid detergent composition containing acidic phosphorus compound and polyphosphate
ZA852200B (en) * 1984-04-09 1986-11-26 Colgate Palmolive Co Liquid laundry detergent composition
ZA852201B (en) * 1984-04-09 1986-11-26 Colgate Palmolive Co Liquid bleaching laundry detergent composition
US4661280A (en) * 1985-03-01 1987-04-28 Colgate Built liquid laundry detergent composition containing salt of higher fatty acid stabilizer and method of use
NZ216987A (en) * 1985-08-20 1988-09-29 Colgate Palmolive Co Nonaqueous liquid low phosphate laundry detergent

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US6699831B2 (en) 2000-06-07 2004-03-02 Kao Corporation Liquid detergent composition comprising aluminosilicate or crystalline silicate

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