EP0763090B1 - Composition de detergent hautement active renfermant des sarcosinates d'oleoyle destines a ameliorer la solubilite - Google Patents

Composition de detergent hautement active renfermant des sarcosinates d'oleoyle destines a ameliorer la solubilite Download PDF

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Publication number
EP0763090B1
EP0763090B1 EP95920683A EP95920683A EP0763090B1 EP 0763090 B1 EP0763090 B1 EP 0763090B1 EP 95920683 A EP95920683 A EP 95920683A EP 95920683 A EP95920683 A EP 95920683A EP 0763090 B1 EP0763090 B1 EP 0763090B1
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Prior art keywords
detergent composition
weight
alkyl
compositions
detergent
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EP0763090A1 (fr
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Ronald Allen Ii Swift
Theodore James Adams, Jr.
Kenneth William Willman
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Procter and Gamble Co
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Procter and Gamble 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention generally relates to a detergent composition having improved solubility in aqueous laundering solutions. More particularly, the invention is directed to a detergent composition containing at least 10% by weight of a surfactant system containing one or more surfactants selected from the group of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof and an effective amount of oleoyl sarcosinate for improved cleaning performance and solubility or agglomerate dissolution in aqueous laundering solutions.
  • a surfactant system containing one or more surfactants selected from the group of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof and an effective amount of oleoyl sarcosinate for improved cleaning performance and solubility or agglomerate dissolution in aqueous laundering solutions.
  • conventional detergent compositions contain mixtures of various surfactants in order to remove a wide variety of soils and stains from surfaces.
  • various anionic surfactants especially the alkyl benzene sulfonates, are useful for removing particulate soils
  • various nonionic surfactants such as the alkyl ethoxylates and alkylphenol ethoxylates, are useful for removing greasy soils.
  • alkyl sulfate surfactants including both primary and secondary alkyl sulfates
  • cold temperature e.g. 5°C to 30°C
  • compact detergent products For the consumer, the smaller package size attendant with compact detergent products provides for easy storage and handling. For the manufacturer, unit storage costs, shipping costs and packaging costs are lowered.
  • compact detergents have its difficulties.
  • in a typical compact detergent formulation the so-called "inert" ingredients such as sodium sulfate are substantially eliminated.
  • such ingredients do play a role in enhancing solubility of conventional detergents.
  • compact detergents often suffer from solubility problems, especially in cold temperature laundering solutions.
  • conventional compact or low density detergent granules are usually prepared by spray drying processes which result in extremely porous detergent particles that are quite amenable to being dissolved in aqueous washing solutions.
  • compact detergents are typically comprised of less porous, high density detergent particles which are less soluble.
  • the compact form of granular detergents typically comprise particles or granules which contain high levels of detersive ingredients with little or no room for solubilizing agents, and since such particles are intentionally manufactured at high bulk densities, the net result can be a substantial problem with regard to in-use solubility
  • Oleoyl sarcosinate is described in the following patents and publications: U.S. 2,542,385; U.S. 3,402,990; U.S. 3,639,568; U.S. 4,772,424; U.S. 5,186,855; European Patent Publication 505,129; British Patent Publication 1,211,545; Japanese Patent Publication 59/232194; Japanese Patent Publication 62/295997, Japanese Patent Publication 02/180811, and Chemical Abstracts Service abstracts No.s 61.3244q, 70:58865x, and 83:181020p, EP 229690-A 2 and US-4,398,045.
  • the present invention meets the needs identified above by providing a detergent composition which exhibits improved solubility or dissolution of the surfactants in aqueous washing solutions as well as under high water hardness conditions resulting in improved cleaning performance.
  • the detergent composition comprises a high level (at least 10% by weight) of a surfactant system containing one or more surfactants selected from the group of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof, in combination with an effective amount of oleoyl sarcosinate.
  • the solubility of the anionic surfactants in the surfactant system is unexpectedly improved.
  • the phase "improved solubility" means that the detergent agglomerates or granules dissolution in the laundering solution is increased by a specific amount, e.g. 5%.
  • the extent of the increased agglomerate or granular dissolution can be measured by the amount of the anionic surfactants of the detergent composition solubilized which is enhanced by at least 5% in the laundering solution when employed in the manner of this invention, as compared to the solubility of the same anionic surfactants per se, under the same test conditions (i.e. water temperature and pH, stirring speed and time, particle size and water hardness).
  • agglomerates refers to particles formed by agglomerating particles which typically have a smaller mean particle size than the formed agglomerates. All percentages, ratios and proportions used herein are by weight, unless otherwise specified.
  • a detergent composition comprises at least 10% by weight of a detersive surfactant system containing at least one surfactant selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfate, secondary alkyl sulfates and mixtures thereof.
  • the composition also contains an effective amount of oleoyl sarcosinate to increase the overall solubility and cleaning performance of the detergent composition.
  • Another embodiment is directed to a high density detergent composition
  • a high density detergent composition comprising at least 10% by weight of a detersive surfactant system containing at least one surfactant selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfate, secondary alkyl sulfates and mixtures thereof, and at least 0.5% of oleoyl sarcosinate.
  • the composition has a density of at least 600 g/l to render it suitable for commercialization as a compact detergent.
  • the detergent composition further contains at least 1 % by weight of a detergency builder.
  • the detergency builder is selected from the group consisting of sodium carbonate, zeolites and mixtures thereof
  • the detergent composition of the invention also comprises adjunct ingredients selected from the group consisting of bleaches, bleach activators, suds suppressors, enzyme stabilizers, polymeric dispersing agents, dye transfer inhibitors and soil release agents.
  • the deteregent composition of the invention includes from 0.1% to 45% by weight of other surfactants such as alkyl benzene sulfonates, alkyl ester sulfonates; and, from 0.1% to 45% by weight of nonionic surfactants selected from the group consisting of alkyl ethoxylates, alkyl phenol alkoxylates, alkylpolyglucosides, and mixtures thereof.
  • other surfactants such as alkyl benzene sulfonates, alkyl ester sulfonates
  • nonionic surfactants selected from the group consisting of alkyl ethoxylates, alkyl phenol alkoxylates, alkylpolyglucosides, and mixtures thereof.
  • a detergent composition as described herein is in the form of a laundry bar.
  • Another aspect of the invention is directed to a method of laundering soiled fabrics comprising the step of contacting the soiled fabrics with an aqueous medium containing an effective amount of a detergent composition according to the invention.
  • the compositions also provide excellent color care for dyed fabrics and excellent skin mildness for handwash operations.
  • the invention is directed to a high active detergent composition having improved solubility and cleaning performance.
  • a multitude of consumers around the world launder soiled clothes in conventional washing machines unique to their particular geographic location.
  • these conventional washing machines launder the soiled clothes in water supplied at relatively cold temperatures, for example in range of 5°C to 30°C, and at high hardness concentrations, e.g. 1.1g mmol Ca ++ /litre (7 grains/gallon; rich with Ca and Mg ions).
  • Most of the modern day consumers also use compact or condensed laundry detergents to accomplish their laundering needs. Under the aforementioned conditions, solubility of current detergents in aqueous laundering solutions has been a problem.
  • the solubility and cleaning performance of a high-active (i.e. greater than 10% of anionic surfactants) detergent composition can be increased by incorporating an effective amount of oleoyl sarcosinate into the composition.
  • the preferred detergent composition of the invention comprises from at least 10%, preferably from 10% to 55%, and most preferably from 15% to 45% by weight of a surfactant system selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfate, secondary alkyl sulfates and mixtures thereof.
  • the composition contains an effective amount of oleoyl sarcosinate to improve the solubility and cleaning performance of the composition.
  • the detergent composition herein is formulated and processed to achieve a density of at least 600 g/l for purposes of producing a "compact" detergent product. Further, it is preferable for the detergent composition to be in the form of "agglomerates" as opposed to spray dried granules.
  • the "improved solubility" achieved by the detergent composition is concerned with enhanced solubility of the surfactants contained in the surfactant system.
  • the improvement represents at least a 5% increase in solubility of the anionic surfactants in the wash solution over the solubility of the same surfactants if they were dissolved alone or without being contained in a detergent composition as defined herein. More preferably, the solubility improvement is from 10% to 50%.
  • any comparison of anionic surfactant solubility snould be completed under the same laundering conditions, e.g. water temperature, hardness and pH. stirring speed and time, and particle size.
  • the amount of the surfactant system in the washing solution can be determined.
  • samples of the aqueous laundering solution containing the detergent composition can be taken after one minute and filtered with 0 45 um nylon filter paper, after which the filtered solution can be titrated with a cationic titrant, which can be commercially purchased, e.g. from Sigma Chemical Company under the trade name Hyamine, in the presence of anionic dyes. From the foregoing, the amount of anionic surfactant which was dissolved in the washing solution can be determined.
  • compositions comprise oleoyl sarcosinate, in its acid and/on salt form selected as desired for the compositions and uses herein, having the following formula: wherein M is hydrogen or a cationic moiety. Preferred M are hydrogen and alkali metal salts, especially sodium and potassium.
  • Oleoyl sarcosinate is commercially available, for example as Hamposyl O supplied by W. R. Grace & Co. Oleoyl sarcosinates according to the present invention are present in an effective amount, which typically comprises from 0.5%. to 80%, preferably from 1% to 40%, and most preferably from 2% to 30%, of oleoyl sarcosinate by weight of the detergent composition.
  • oleoyl sarcosinate useful herein can also preferably be prepared from the ester (preferably the methyl ester) of oleic acid and a sarcosine salt (preferably the sodium salt ) under anhydrous reaction conditions in the presence of a base catalyst with a basicity equal to or greater than alkoxide catalyst (preferably sodium methoxide).
  • a base catalyst with a basicity equal to or greater than alkoxide catalyst preferably sodium methoxide
  • the preferred method for preparing oleoyl sarcosinate is conducted at a temperature from 80°C to 200°C, especially from 120°C to 200°C. It is preferred to conduct the reaction without solvent although alcohol solvents which have a boiling point of at least 100°C and are stable to the reaction conditions (ie. glycerol is not acceptable) can be used.
  • the reaction may proceed in 85% yield with a molar ratio of methyl ester reactant to sarcosine salt reactant to basic catalyst of 1:1:0.05-0.2.
  • Methyl ester mixtures derived from high oleic content natural oils are especially preferred as starting materials. Examples include high-oleic sunflower and rapeseed/canola oil. In addition, a high-oleic methyl ester fraction derived from either palm kernel oil or tallow is acceptable. It is to be understood that such oils typically will contain some levels of impurities, including some fatty acid impurities that may be converted to sarcosinate compounds by this synthesis method.
  • commodity canola/rapeseed oil may comprise a majority of oleic acid, and a mixture of fatty acid impurities such as palmitic, stearic, linoleic, linolenic and/or eicosenoic acid, some or all of which are converted to the sarcosinate by this reaction method. If desired for formulation purposes, some or all of such impurity materials may be excluded from the starting oil before preparing the oleoyl sarcosinate to be used in the present compositions.
  • sarcosine remaining in the reaction mixture can be converted to an amide by addition of maleic or acetic anhydride to the mixture, thereby minimizing the sarcosine content and any potential for formation of undesired nitrogen-containing impurities.
  • oleoyl sarcosinate The synthesis of oleoyl sarcosinate may be carried out as follows to prepare the sodium oleoyl sarcosinate.
  • reaction mixture is heated to 170°C for 1 hr to drive off any water.
  • the reaction is initiated by the addition of sodium methoxide 25% in methanol (15.4 g, 0.0714 mol). Reaction is kept at 170°C for 2.5 hr during which methanol is collected in the Dean-Stark trap. The reaction is allowed to cool slightly and then methanol (200 g) is added. Maleic anhydride (9.43 g, 0.095 mol) is added to the methanol solution and the reaction is stirred at 60°C for 0.5 hr. Then most of the methanol is removed by rotary evaporation and acetone (2 L) is added to precipitate the product.
  • the product is collected by suction filtration and allowed to air dry to give an off-white solid. Analysis of the reaction mixture by GC indicates the majority of the product is oleoyl sarcosinate, with minor amounts of the following impurities: sarcosine, oleic acid, and the sarcosinates derived from palmitic acid, stearic acid, and linoleic acid.
  • Nonlimiting examples of the preferred surfactants useful in the surfactant system include the conventional primary, branched-chain and random C 10 -C 20 alkyl sulfates ("AS"), the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 where x and (y -1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, and the C 10 -C 18 alkyl alkoxy sulfates (“AE x S”), especially x up to 7 EO ethoxy sulfates).
  • AS conventional primary, branched-chain and random C 10 -C 20 alkyl sulfates
  • surfactants may be useful in the composition of the invention and include C 11 -C 18 alkyl benzene sulfonates ("LAS") and C 10 -C 18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C 10-18 glycerol ethers, the C 10 -C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C 12 -C 18 alpha-sulfonated fatty acid esters.
  • LAS alkyl benzene sulfonates
  • C 10 -C 18 alkyl alkoxy carboxylates especially the EO 1-5 ethoxycarboxylates
  • C 10-18 glycerol ethers the C 10 -C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides
  • C 12 -C 18 alpha-sulfonated fatty acid esters include C 11
  • the conventional nonionic and amphoteric surfactants such as the C 12 -C 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 12 -C 18 betaines and sulfobetaines ("sultaines"), C 10 -C 18 amine oxides, and the like, can also be included in the overall compositions.
  • the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl)glucamide.
  • the N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • C 10 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., colorants, dyes, perfumes).
  • other detergent adjunct materials e.g., colorants, dyes, perfumes.
  • the following are illustrative examples of such adjunct materials.
  • Detersive Builder - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1% builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having 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, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na 2 SiO 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention.
  • Aluminosilicate builders include those having the empirical formula: M z/n [(AlO 2 ) z (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are integers usually of at least 6, the molar ratio of z to v is in the range from 1.0 to 0, and x is an integer from 0 to 264, and M is a Group IA or IIA element, e.g. Na, K, Mg, Ca with valence n.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A. Zeolite P (B), Zeoiite MAP and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ xH 2 O wherein x is from 20 to 30, especially 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the imposition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al. U.S. Patent 3,635,830, issued January 18, 1972 See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, caboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C 5 C 20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred) and 2-pentadecenylsuccinate. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 0,200,263, published November 5, 1986.
  • Fatty acids e.g., C12-C18 monocarboxylic acids such as oleic acid and/or its salts, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • Enzymes - Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents and builders. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically 0.001 mg to 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-2%, by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE The preparation of this enzyme and analogous enzymes is described in British Patent Specification No 1,243,784 of Novo.
  • protealytic enzymes suitable for removing proteinbased stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE bv Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • proteases include Protease A (see European Patent Application 130,756, published January 9, 1985), Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985); and proteases made by Genencor International, Inc., according to one or more of the following patents: Caldwell et al, U.S. Patent Nos. 5,185,258, 5,204,015 and 5,244.791.
  • Protease C is a variant of an alkaline serine protease from Bacillus, particularly Bacillus lentus , in which arginine replaced lysine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274.
  • Protease C is described in EP-A-0 451 244 U.S. Patent No. 5,185,250; and U.S. Patent No. 5,204,015.
  • protease which are described in copending application U.S. Serial No. 08/136,797, entitled Protease-containing Cleaning Compositions and copending Application U.S. Serial No. 08/136,626, entitled Bleaching Compositions Comprising Protease Enzymes. Genetically modified variants, particularly of Protease C, are also included herein.
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
  • the cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM 1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
  • suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S. It may be desired to use, in combination with these peroxidases, materials viewed as being peroxidase accelerators such as phenolsulfonate and/or phenothiazine.
  • Enzyme Stabilizers The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used.) Additional stability can be provided by the presence of various other art-disclosed stabilizers, especially borate species: see Severson, U.S. 4,537,706. Typical detergents, especially liquids, will comprise from 1 to 30, preferably from 2 to 20, more preferably from about 5 to about 15, and most preferably from 8 to 12, millimoles of calcium ion per inter of finished composition.
  • the level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition.
  • Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts.
  • a small amount of calcium ion generally from 0.05 to 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor In the alternative, natural water hardness may suffice.
  • compositions herein will typically comprise from 0.05% to 2% by weight of a water-soluble source of calcium or magnesium ions, or both.
  • the amount can vary, of course, with the amount and type of enzyme employed in the composition.
  • compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers.
  • additional stabilizers especially borate-type stabilizers.
  • such stabilizers will be used at levels in the compositions from 0.25% to 10%, preferably from 0.5% to 5%, more preferably from 0.75% to 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid).
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • boric acid e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • such materials may also be used in formulations as the sole stabilizer as well as being used in combination with added calcium and/or magnesium ions.
  • chlorine scavengers especially to protease-containing compositions, to protect the enzymes from chlorine typically present in municipal water supplies.
  • Such materials are described, for example, in U.S. Patent 4,810,413 to Pancheri et al.
  • bleaching agents may be at levels of from 1% to 30%, more typically from 5% to 20%, of the detergent composition, especially for fabric laundeering. If present, the amount of bleach activators will typically be from 0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthlate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446. Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al. published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 micrometers to 1.000 micrometers, not more than 10% by weight of said particles being smaller than 200 micrometers and not more than 10% by weight of said particles being larger than 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • Mixtures of bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbonates, etc, are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
  • the nonanoyloxybenzene, sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
  • amido-derived bleach activators are those of the formulae R 1 N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R 2 C(O)L wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to 6 carbon atoms, R 5 is H or alkyl, aryl, or alkaryl containing from about 1 to 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl )oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4.634.551.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae : wherein R 6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms.
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which discloses acyl caprolactam, including benzoyl caprolactam, adsorbed into sodium perborate.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0,025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594, U.S. Pat. 5,194,416, U.S. Pat. 5,114,606, and European Pat. App. Pub. Nos 549,271A1, 549,272A1, 544,440A2, and 544,490A1.
  • 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 IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (ClO 4 ) 4 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2 -(1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH 3 ) 3 (PF 6 ), and mixtures thereof.
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161, and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the laundry liquor.
  • Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least 25% oxyethylene units and more preferably, especially for such components having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 200, although higher levels can be used, preferably from 3 to 150, more preferably from 6 to 100.
  • Suitable oxy C 4 -C 6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH 2 ) n OCH 2 CH 2 O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1 -C 4 alkyl and C 4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester) e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C 1 -C 6 vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e. g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from 25.000 to 55.000 See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an ologomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U. S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711 730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • soil release agents will generally comprise from 0.01% to 10.0%, by weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably from 0.2% to 3.0%.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the ivention when at lease low levels of total phosphorus are permutted in detergent compositions, and include ethylenediaminetetrakis(methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • these chelating agents will generally comprise from 0.1% to 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1% to 3.0% by weight of such compositions.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylates amines.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • CMC carboxy methyl cellulose
  • Polymeric Dispersing Agents can advantageously be utilized at levels from 0.1% to 7%, by weight, in the compositions herein.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene and ethylene is suitable provided that such segments do not constitute more than 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from 2,000 to 100,000.
  • a preferred copolymer has an average molecular weight of 2.000 to 15.000, more preferably 6,000 to 13,000, and most preferably 7,000 to 12,000.
  • Other preferred copolymers have an average molecular weight from 5,000 to 75,000, most preferably from 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1:2, more preferably from 10:1 to 1:1, and most preferably 2,5:1 to 1:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • Particutarly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers.
  • Such copolymers contain as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salt and have the general formula :-[(C(R 2 )C(R 1 )(C(O)OR 3 )]- wherein the incomplete valencies inside the square braces are hydrogen and at least one of the substituents R 1 , R 2 or R 3 , preferably R 1 or R 2 , is a 1 to 4 carbon alkyl or hydroxyalkyl group, R 1 or R 2 can be a hydrogen and R 3 can be a hydrogen or alkali metal salt.
  • R 1 is methyl
  • R 2 is hydrogen and R 3 is sodium.
  • the low molecular weight polyacrylate dispersant polymer preferably has a molecular weight of less than 15,000, preferably from 500 to 10,000, most preferably from 1,000 to 5,000.
  • the most preferred polyacrylate copolymer for use herein has a molecular weight of 3500 and is the fully neutralized form of the polymer comprising 70% by weight acrylic acid and 30% by weight methacrylic acid.
  • Suitable modified polyacrylate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents 4,530,766, and 5,084,535.
  • Agglomerated forms of the present invention may employ aqueous solutions of polymer dispersants as liquid binders for making the agglomerate (particularly when the composition consists of a mixture of sodium citrate and sodium carbonate).
  • aqueous solutions of polymer dispersants as liquid binders for making the agglomerate (particularly when the composition consists of a mixture of sodium citrate and sodium carbonate).
  • polyacrylates with an average molecular weight of from about 1,000 to 10,000
  • acrylate/maleate or acrylate/ fumarate copolymers with an average molecular weight of from 2,000 to 80,000 and a ratio of acrylate to maleate or fumarate segments of from 30:1 to 1:2.
  • Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are disclosed in European Patent Application No. 66,915, published December 15, 1982.
  • dispersant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from 950 to 30,000 which can be obtained from tne Dow Chemical Company of Midland, Michigan. Such compounds for example, having a melting point within the range of from about 30° to 100°C can be obtained at molecular weights of 1450, 3400, 4500, 6000, 7400, 9500, and 20,000. Such compounds are formed by the polymerization of ethylene glycol or propylene glycol with the requisite number of moies of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol.
  • the polyethylene, polypropylene and mixed glycols are referred to using the formula HO(CH 2 CH 2 O) m (CH 2 CH(CH 3 )O) n (CH(CH 3 )CH 2 O) O H wherein m, n, and o are integers satisfying the molecular weight and temperature requirements given above.
  • dispersant polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • Sodium cellulose sulfate is the most preferred polymer of this group.
  • Suitable dispersant polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates, described in U.S. Pat. No. 3,723.322, Diehl, issued Mar. 27, 1973; the dextrin esters of polycarboxylic acids disclosed in U.S. Pat. No. 3,929,107, Thompson, issued Nov. 11, 1975; the hydroxyalkyl starch ethers, starch esters, oxidized starches, dextrins and starch hydrolysates described in U.S. Pat. No 3,803,285, Jensen, issued Apr. 9, 1974, the carboxylated starches described in U.S. Pat. No 3,629,121, Eldib, issued Dec. 21, 1971; and the dextrin starches described in U.S. Pat. No 4,141,841, McDanald, issued Feb. 27, 1979.
  • Preferred cellulose-derived dispersant polymers are the carboxymethyl celluloses.
  • organic dispersant polymers such as polyaspartate.
  • PEG polyethylene glycol
  • PEG polyethylene glycol
  • Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • compositions containing detergent builders it is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, especially zeolite and/or silicate builders, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.
  • Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.05% to 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arfic White CC and Artic White CWD, available from Hilton-Davis, located in Italy, the 2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles, 4,4'-bis-(1,2,3-triazol-2-yl)-stil- benes, 4,4'-bis(stryl)bisphenyls, and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin, 1,2-bis(-venzimidazol-2-yl)ethylene, 1,3-diphenyl-phrazolines, 2,5-bis(benzoxazol-2-yl)thiophene, 2-stryl-napth-[1,2-d]oxazole, and 2-(stilbene-4-yl)-2H-naphtho-[1.2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489.455 and 4,489.574 and in front-loading European-style washing machines.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor 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.
  • the detergent compositions herein may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols and aliphatic C 18 -C 40 ketones (e.g., stearone).
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-akyldiamine 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, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl dialkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40°C and 50°C, and a minimum boiling point not less than 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,214,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • typical laundry detergent compositions with controlled suds will optionally comprise from 0,001 to 1, preferably from 0,01 to 0,7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which compnses (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b)
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than 2 weight %, preferably more than about 5 weight %.
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
  • Preferred is a weight ratio of between 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the C 6 -C 16 alkyl alcohols having a C 1 -C 16 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem
  • Mixed suds suppressors typically comprise mixtures of alcohol - silicone at a weight ratio of 1:5 to 5:1.
  • suds should not form to the extent that they overflow the washing machine.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • compositions herein will generally comprise from 0% to 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to 5%, by weight, of the detergent composition.
  • from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from 0 01% to 1% of silicone suds suppressor is used, more preferably from 0.25% to 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1% to 2%, by weight, of the composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01% to 5.0%, although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al. March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01% to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures: wherein R 1 , R 2 , R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or blocks copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000, more preferred 1,000 to 500,000, most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • polyamine N-oxide useful in the detergent compositions herein is poly-(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine x-oxide ratio of 1:4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinylpyrrolidone (“PVP”) having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example EP-A-262,897 and EP-A-256,696.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
  • the detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dve transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01% to 1% by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are 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.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solid fillers for bar compositions, etc.
  • suds boosters such as the C 10 -C 16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
  • the C 10 -C 14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl 2 and MgSO 4 can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C 13-15 ethoxylated alcohol (EO 7) nonionic surfactant.
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, and are well known to those skilled in the art.
  • Step A Preparation of Surfactant Paste -
  • the objective is to combine the surfactants and liquid in the compositions into a common mix in order to aid in surfactant solubilization and agglomeration.
  • the surfactants and other liquid components in the composition are mixed together in a Sigma Mixer at 140°F (60°C) at 40 rpm to 75 rpm for a period of from 15 minutes to about 30 minutes to provide a paste having the general consistency of 20 to 40 Pascal seconds (20,000-40,000 centipoise).
  • the paste is stored at 140°F (60°C) until agglomeration Step (B) is ready to be conducted.
  • Step B Agglomeration of Powders with Surfactant Paste -
  • the purpose of this Step is to transform the base formula ingredients into flowable detergent agglomerates having a mean particle size range of from 800 microns to 1600 microns.
  • the powders including materials such as zeolite, citrate, citric acid builder, layered silicate builder (as SKS-6), sodium carbonate, ethylenediaminedisuccinate, magnesium sulfate and optical brightener
  • the Eirich Mixer R-Series
  • mixed briefly ca. 5 seconds - 10 seconds
  • the surfactant paste from Step A is then charged into the mixer and the mixing is continued at 1500 rpm to 3000 rpm for a period from about 1 minute to about 10 minutes, preferably 1-3 minutes, at ambient temperature.
  • the mixing is stopped when course agglomerates (average particle size 200-1600 microns) are formed.
  • mixing apparatus commercially available from Lödige (CB and/or KM) can be used to transform the surfactant paste and powders into free-flowing detergent agglomerates.
  • Step C The purpose of this Step is to reduce the agglomerates, stickiness by removing/drying moisture and to aid in particle size reduction to the target particle size (in the mean particle size range from 200 to 1600 microns, as measured by sieve analysis).
  • the wet agglomerates are charged into a fluidized bed at an air stream temperature of from about 41°C to about 60°C and dned to a final moisture content of the particles from 4% to 10%.
  • Step D Coat Agglomerates and Add Free-Flow Aids -
  • the objective in this Step is to achieve the final target agglomerate size range of from 200 microns to 1600 microns, and to admix materials which coat the agglomerates, reduce the caking/lumping tendency of the particles and help maintain acceptable flowability.
  • the dried agglomerates from Step C are charged into the Eirich Mixer (R-Series) and mixed at a rate of 1500 rpm to 3000 rpm while adding 2-6% Zeolite A (median particle size 2-5 ⁇ m) during the mixing. The mixing is continued until the desired median particle size is achieved (typically from 5 seconds to 45 seconds). At this point, from 0.1% to 1.5% by weight of precipitated silica (average article size 1-3 microns) is added as a flow aid and the mixing is stopped.
  • This example illustrates a detergent composition made in accordance with the invention.
  • a base formula of the starting liquids and powdered materials are combined via a variety of known processes including conventional spray drying techniques or agglomeration in apparatus such as powder mixers and fluid beds commercially available from Lödige and Aeromatic, respectively.
  • Agglomeration is especially suitable for preparing modern compact granular detergents and entails initially forming a surfactant paste using standard mixers, after which the paste is agglomerated into agglomerates and dried.
  • Such processing techniques are well known in the art.
  • the enzymes such as cellulases are dry mixed into the base formula and the perfumes used herein are subsequently sprayed onto the base formula so as to form the final granular detergent compositions exemplified herein.
  • compositions B, C and D are made in accordance with the agglomeration process described above.
  • Compositions B and C are within the scope of the invention and composition D is outside of the invention and is presented for purposes of comparison as described in Example III hereinafter.
  • the relative proportions of compositions B, C and D in agglomerate form are listed in Table II below.
  • (% weight) Component B C D C 12-18 alkyl ethoxy (0.6) sulfate 24.0 20.0 30.0 Oleoyl sarcosinate 6.0 10.0 - Aluminosilicate 42.5 42.5 42.5 Sodium carbonate 22.0 22.0 22.0 Minors (water, perfume, etc.) 5.5 5.5 5.5 100.0 100.0 100.0 100.0
  • This Example illustrates the surprisingly improved solubility achieved by the detergent composition of the invention.
  • standard dosages of compositions B, C and D (1170 ppm) are dissolved in an aqueous laundering solution having a water temperature of 10°C and a water hardness of 1.1g mmol Ca ++ /litre (7 grains/gallon)(Ca:Mg ratio of 3:1).
  • the laundering solution is continuously agitated at a rate of 75 rpm and samples of the wash solution were taken at various time intervals as shown in Table III below.
  • the amount of anionic (sulfated or sulfonated) surfactant in the laundering solution is determined by conducting the well known "catSO 3 " titration technique on the samples taken from individual wash solutions containing one of the tested compositions.
  • the amount of anionic surfactant in the laundering solution is determined by filtering the samples through 0.45 nylon filter paper to remove the insolubles and thereafter, titrating the filtered solution to which anionic dyes (dimidium bromide) have been added with a cationic titrant such as Hyamine TM commercially available from Sigma Chemical Company. Accordingly, the relative amount of anionic surfactant dissolved in the wash solution can be determined.

Claims (9)

  1. Composition détergente, caractérisée en ce qu'elle comprend des agglomérats ou granules et :
    (a) au moins 10 % en poids d'un système tensioactif détergent contenant au moins un tensioactif choisi dans l'ensemble constitué par les alkylsulfates, les alkylsulfates éthoxylés, les alkylsulfates secondaires et leurs mélanges ; et
    (b) de 0,5 à 80 % d'oléoylsarcosinate.
  2. Composition détergente selon la revendication 1, caractérisée en outre par au moins 1 % en poids d'un adjuvant de détergence.
  3. Composition détergente selon les revendications 1 et 2, caractérisée en outre par des ingrédients additifs choisis dans l'ensemble constitué par les agents de blanchiment, les activateurs de blanchiment, les anti-moussants, les stabilisants d'enzymes, les agents dispersants polymères, les inhibiteurs du transfert des colorants et les agents d'enlèvement des salissures.
  4. Composition détergente selon les revendications 1 à 3, dans laquelle ladite composition est sous la forme d'agglomérats.
  5. Composition détergente selon les revendications 1 à 4, dans laquelle ledit oléoylsarcosinate est présent en une quantité de 1 à 40 % en poids.
  6. Composition détergente selon les revendications 1 à 5, caractérisée en outre par 0,1 à 45 % d'un ou plusieurs tensioactifs non-ioniques choisis dans l'ensemble constitué par les éthoxylates d'alkyle, les alkylphénols alcoxylés, les alkylpolyglucosides, et leurs mélanges.
  7. Composition détergente selon les revendications 1 à 6, dans laquelle ladite composition est sous la forme d'un pain pour le lavage du linge.
  8. Composition détergente haute densité, caractérisée en ce qu'elle comprend des agglomérats ou granules et
    (a) au moins 10 % en poids d'un système tensioactif détergent contenant au moins un tensioactif choisi dans l'ensemble constitué par les alkylsulfates, les alkylsulfates éthoxylés, les alkylsulfates secondaires et leurs mélanges ; et
    (b) au moins 0,5 % d'oléoylsarcosinate,
    dans laquelle ladite composition a une masse volumique d'au moins 600 g/l.
  9. Procédé pour laver des tissus salis, caractérisé par l'étape de mise desdits tissus en contact avec un milieu aqueux contenant une quantité efficace d'une composition détergente selon les revendications 1 à 8.
EP95920683A 1994-06-01 1995-05-30 Composition de detergent hautement active renfermant des sarcosinates d'oleoyle destines a ameliorer la solubilite Expired - Lifetime EP0763090B1 (fr)

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US25229494A 1994-06-01 1994-06-01
PCT/US1995/006820 WO1995033032A1 (fr) 1994-06-01 1995-05-30 Composition de detergent hautement active renfermant des sarcosinates d'oleoyle destines a ameliorer la solubilite
US252294 2000-11-21

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CA611972A (en) * 1958-04-17 1961-01-03 Bissell Inc. Cleaning composition
US4772424A (en) * 1986-01-08 1988-09-20 The Proctor & Gamble Company Shampoo containing mixtures of sulfate and/or sulfonate, sarcosinate and betaine surfactants
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CA2191565A1 (fr) 1995-12-07
ZA954396B (en) 1996-01-24
MA23566A1 (fr) 1995-12-31
JPH10501284A (ja) 1998-02-03
WO1995033032A1 (fr) 1995-12-07
AU2606195A (en) 1995-12-21
TW314551B (fr) 1997-09-01

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