EP0948591B1 - Waschmittelzusammensetzungen enthaltend zellulosepolymere - Google Patents

Waschmittelzusammensetzungen enthaltend zellulosepolymere Download PDF

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EP0948591B1
EP0948591B1 EP97953405A EP97953405A EP0948591B1 EP 0948591 B1 EP0948591 B1 EP 0948591B1 EP 97953405 A EP97953405 A EP 97953405A EP 97953405 A EP97953405 A EP 97953405A EP 0948591 B1 EP0948591 B1 EP 0948591B1
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weight
alkyl
sodium
compositions
modified
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French (fr)
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EP0948591A2 (de
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Jiping Wang
Nodie Monroe Washington
Kathleen Brenner Hunter
Stanton Lane Boyer
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • 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
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to heavy duty laundry detergent compositions, in either liquid or granular form, which contain certain types of modified cellulose ether materials to impart appearance and integrity benefits to fabrics and textiles laundered in washing solutions formed from such compositions.
  • Short fibers are dislodged from woven and knit fabric/textile structures by the mechanical action of laundering. These dislodged fibers may form lint, fuzz or "pills" which are visible on the surface of fabrics and diminish the appearance of newness of the fabric. Further, repeated laundering of fabrics and textiles, especially with bleach-containing laundry products, can remove dye from fabrics and textiles and impart a faded, worn out appearance as a result of diminished color intensity, and in many cases, as a result of changes in hues or shades of color.
  • WO96/17917 relates to liquid personal care compositions comprising hydrophobically modified non-ionic celluloses.
  • WO95/00614 relates to rinse added liquid fabric-softening compositions comprising cationic celluloses.
  • US4329237 relates to detergent fabric-softening compositions comprising carboxymethyl cellulose.
  • US5540850 relates to detergent fabric-softening compositions comprising cellulose polymers.
  • the laundry detergent compositions herein comprise from about 1% to 80% by weight of a detersive surfactant, from about 1% to 80% by weight of an organic or inorganic detergency builder and from about 0.1% to 8% by weight of certain types of modified cellulose ether fabric treatment agents.
  • the detersive surfactant and detergency builder materials can be any of those useful in conventional laundry detergent products.
  • the modified cellulose ether materials are those which have a molecular weight of from about 10,000 to 2,000,000 and are comprised of repeating substituted anhydroglucose units corresponding to the general Structural Formula No. I, set forth hereinafter in the "Detailed Description of the Invention" section.
  • the useful type of cellulose ethers comprises hydrophobically-modified, nonionic materials with anhydroglucose ring alkyl substitution ranging from about 0.1% to 5% by weight of the cellulose ether.
  • Ring substituents are alkoxylated in amounts ranging from about 1 to 20 moles.
  • the present invention relates to the laundering or treating of fabrics and textiles in aqueous washing or treating solutions formed from effective amounts of the detergent compositions described herein, or formed from the individual components of such compositions.
  • Laundering of fabrics and textiles in such washing solutions, followed by rinsing and drying, imparts fabric appearance benefits to the fabric and textile articles so treated.
  • Such benefits can include improved overall appearance, pill/fuzz reduction, antifading, improved abrasion resistance, and/or enhanced softness.
  • the laundry detergent compositions of the present invention essentially contain detersive surfactant, detergent builder and certain modified cellulose ether fabric treatment agents which serve to enhance fabric appearance and integrity upon use of the detergent compositions to launder fabrics and textiles.
  • detersive surfactant e.g., sodium EDTA
  • detergent builder e.g., sodium EDTA
  • modified cellulose ether fabric treatment agents e.g., sodium EDTA
  • All percentages and ratios given are by weight unless other specified.
  • the detergent compositions herein essentially comprise from about 1% to 80% by weight of a detersive surfactant. Preferably such compositions comprise from about 5% to 50% by weight of this surfactant.
  • Detersive surfactants utilized can be of the anionic, nonionic, zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types.
  • Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980. Of all the surfactants, anionics and nonionics are preferred.
  • Useful anionic surfactants can themselves be of several different types.
  • water-soluble salts of the higher fatty acids i.e., "soaps"
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to 15, preferably I to 6 ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S.
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 11-13 LAS.
  • Preferred nonionic surfactants are those of the formula R 1 (OC 2 H 4 ) n OH, wherein R 1 is a C 10 -C 16 alkyl group or a C 8 -C 12 alkyl phenyl group, and n is from 3 to about 80.
  • Particularly preferred are condensation products of C 12 -C 15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C 12 -C 13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
  • Additional suitable nonionic surfactants include polyhydroxy fatty acid amides of the formula: wherein R is a C 9-17 alkyl or alkenyl, R 1 is a methyl group and Z is glycityl derived from a reduced sugar or alkoxylated derivative thereof Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798.
  • the detergent compositions herein also essentially comprise from 1% to 80% by weight of a detergent builder.
  • a detergent builder Preferably such compositions in liquid form will comprise from 1% to 10% by weight of the builder component.
  • compositions in granular form will comprise from 1% to 50% or even from 10% to 50% by weight of the builder component.
  • Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.
  • Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
  • Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S.
  • Particularly preferred polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987. .
  • nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiO 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Also preferred are aluminosilicates including zeolites. Such materials and their use as detergent builders are more fully discussed in Corkill et al, U. S. Patent No. 4,605,509 . Also, crystalline layered silicates such as those discussed in Corkill et al, U. S. Patent No. 4,605,509 , are suitable for use in the detergent compositions of this invention.
  • the third essential component of the detergent compositions herein comprises one or more modified cellulosic polymers.
  • modified cellulosic polymers have been found to impart a number of appearance benefits to fabrics and textiles laundered in aqueous washing solutions formed from detergent compositions which contain such modified cellulosic materials.
  • Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc..
  • the modified cellulosic polymers used in the compositions and methods herein can provide such fabric appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such materials are incorporated.
  • modified cellulosic polymers useful herein are of the nonionic type, the modified cellulosic polymeric component of the compositions herein may comprise combinations of these cellulosic polymers.
  • the modified cellulosic polymer component of the compositions herein will comprise from about 0.1% to 8% by the weight of the composition. More preferably, such modified cellulosic materials will comprise from about 0.5% to 4% by weight of the compositions, most preferably from about 1% to 3%.
  • modified cellulosic polymer for use herein comprises hydrophobically-modified, nonionic cellulose ethers having a molecular weight of from about 10,000 to 2,000,000, preferably from about 50,000 to 1,000,000.
  • the hydrophobically-modified nonionic materials have repeating, substituted anhydroglucose units which correspond to the general Structural Formula No. I as follows:
  • R is a combination of H and C 8 -C 24 alkyl, preferably Cg - C16 alkyl. Alkyl substitution on the anhydroglucose rings of the polymer ranges from about 0.1% to 5% by weight, more preferably from about 0.2% to 2% by weight, of the polymer material. Also, in Structural Formula No. I, R 1 is H or methyl, and x ranges from about 1 to 20, preferably from about 1 to 10.
  • the modified cellulose ether fabric treatment agent is optionally a hydrophobically-modified, nonionic material corresponding to structural formula No.
  • R is a combination of H and C 8 to C 16 alkyl; b) R substitution of the anhydroglucose rings ranges from 0.2% to 2% by weight of the cellulose ether; c) as is H; and x d) x ranger from 1 to 10.
  • the hydrophobically-modified nonionic cellulose ethers of Structural Formula No. I include those which are commercially available and also include materials which can be prepared by conventional chemical modification of commercially available materials.
  • Commercially available cellulose ethers of the Structural Formula No. I type include Polysurf 67TM, Natrosol Plus 430TM and Natrosol Plus 330TM, all marketed by Hercules, Inc.
  • the commercially available cellulose ether materials useful herein are themselves derived from suitable natural sources of cellulose. Such sources include, for example, cotton linters and other vegetable tissues.
  • the modified cellulose ethers used in this invention are generally all water-soluble materials. They can therefore be utilized for detergent composition preparation in the form of aqueous solutions of the such cellulosic polymers if desired.
  • the detergent composition of the present invention can also include any number of additional optional ingredients.
  • additional optional ingredients include conventional detergent composition components such as bleaches and bleach activators, enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and perfumes.
  • a preferred optional ingredients for incorporation into the detergent compositions herein comprises a bleaching agent, e.g., a peroxygen bleach.
  • a bleaching agent e.g., a peroxygen bleach.
  • peroxygen bleaching agents may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.
  • Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate 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; European Patent Application EP-A-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 (NAPAA) as described in U.S. Patent 4,634,551, Issued January 6, 1987 to Burns et al.
  • NAPAA 6-nonylamino-6-oxoperoxycaproic acid
  • Inorganic peroxygen bleaching agents may also be used, generally in particulate form, in the detergent compositions herein.
  • Inorganic bleaching agents are in fact preferred.
  • Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials.
  • sodium perborate e.g. mono- or tetra-hydrate
  • Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach e.g., OXONETM, manufactured commercially by DuPont
  • OXONETM manufactured commercially by DuPont
  • inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants.
  • coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
  • Inorganic peroxygen bleaching agents e.g., the perborates, the percarbonates, etc.
  • bleach activators which lead to the in situ production in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator.
  • Various non-limiting 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 Issued November 1, 1983 to Chung et al.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • 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 about 6 carbon atoms, R 5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 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 phenol 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 the hereinbefore referenced U.S. Patent 4,634,551.
  • Another class of useful bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990.
  • a highly preferred activator of the benzoxazin-type is:
  • Still another class of useful 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 about 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, nonanoyl valerolactam, decanoyl valerolactam, undecenoyl 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 caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
  • peroxygen bleaching agent will generally comprise from about 2% to 30% by weight of the detergent compositions herein. More preferably, peroxygen bleaching agent will comprise from about 2% to 20% by weight of the compositions. Most preferably, peroxygen bleaching agent will be present to the extent of from about 3% to 15% by weight of the compositions herein.
  • bleach activators can comprise from about 2% to 10% by weight of the detergent compositions herein. Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.
  • a detersive enzymes component Another highly preferred optional ingredient in the detergent compositions herein is a detersive enzymes component.
  • Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration.
  • Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Detersive enzyme means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry detergent composition.
  • Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases.
  • Enzymes are normally incorporated into detergent compositions at levels sufficient to provide a "cleaning-effective amount".
  • cleaning-effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics.
  • typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.
  • the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% 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. Higher active levels may be desirable in highly concentrated detergent formulations.
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
  • One suitable protease is obtained from a strain of Bacillus , having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo.
  • proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
  • proteases include those of WO 9510591 A to Procter & Gamble.
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 10.
  • U.S. 4,435,307, Barbesgoard et al, March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 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® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo.
  • 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 GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P.” Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum , e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the enzyme-containing compositions herein may optionally also comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes.
  • Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
  • the detergent compositions according to the present invention can be in liquid, paste or granular forms. Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means.
  • Granular compositions are generally made by combining base granule ingredients (e.g. surfactants, builders, water, etc.) as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%).
  • base granule ingredients e.g. surfactants, builders, water, etc.
  • the remaining dry ingredients can be admixed in granular powder form with the spray dried granules in a rotary mixing drum and the liquid ingredients (e.g. organic solutions of the essential cellulosic polymers, enzymes, binders and perfumes) can be sprayed onto the resulting granules to form the finished detergent composition.
  • Granular compositions according to the present invention can also be in "compact form", i.e.
  • the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.
  • Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations.
  • Liquid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • Addition of the cellulose ether component to liquid detergent compositions of this invention may be accomplished by simply mixing into the liquid dertergent aqueous solutions of the desired cellulose ethers.
  • Cellulose ethers can alter the viscosity or other rheological characteristics of liquid detergent products. It may therefore be necessary to compensate for any rheological changes in the liquid detergent product brought about by cellulose ether addition by altering the type and amount of hydrotropes and/or solvents that are used.
  • the present invention also provides a method for laundering fabrics in a manner which imparts fabric appearance benefits provided by the cellulosic polymers used herein.
  • Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described or formed from the individual components of such compositions. Contacting of fabrics with washing solution will generally occur under conditions of agitation although the compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabric cleaning and treatment.
  • Agitation is preferably provided in a washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer.
  • An effective amount of the liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.
  • liquid detergent compositions are prepared containing various modified cellulosic polymers.
  • Such liquid detergent compositions all have the following basic formula: Component Wt. C 12-15 alkyl ether (2.5) sulfate 38 C 12 glucose amide 6.86 Citric Acid 4.75 C 12-14 Fatty Acid 2.00 Enzymes 1.02 MEA 1.0 Propanediol 0.36 Borax 6.58 Dispersant 1.48 Na Toluene Sulfonate 6.25 Modified Cellulosic Polymer (if present) 2.0 Dye, Perfume, Brighteners, Preservatives, Suds Suppressor, Balance Other Minors, Water 100%
  • Test compositions prepared as described in Examples I and II are evaluated for the effects that the various cellulosic polymers of Example III provide when samples of fabrics or garments are washed using the test compositions as described, all under identical conditions.
  • a control sample with no polymer is usually compared to one composition with a test polymer to be evaluated.
  • Testing conditions are also carefully monitored. Examples of controlled conditions include: wash time, wash water temperature and hardness; washer agitation; rinse time, rinse water temperature and hardness; dryer time and temperature; wash load fiber content and weight.
  • fabrics are washed using various test compositions containing either no cellulosic polymers or one of the Example III cellulosic polymers.
  • the fabrics so washed after ten cycles are then comparatively graded by three judges who evaluate the overall appearance of the washed fabrics. It is the decision of the judge as to what is to be evaluated unless specific direction is given to evaluate one attribute such as color, pilling, fuzz, etc.
  • laundering conditions are as follows:
  • Pill Reduction Test Results Liquids Liquid Test Composition ID Polymer Tested Pill/Fuzz Reduction (%) Control None 0 A Polysurf 67 21.5 B LK-400 42.4 C CMC(D72) 26.8 D Modified LK-400 25.9 Pill Reduction Test Results - Granular Granular Test Composition ID Polymer Tested Pill/Fuzz Reduction (%) Control None A Polysurf 67 33.3 B LK-400 51.6 C CMC(D72) 7.6 D Modified LK-400 16.6
  • % Color Protection ⁇ [dE*(control) - dE*(polymers)] / dE*(control) ⁇ x 100%
  • Color Protection Test Results Liquids Liquid Test Composition ID Polymer Tested Color Protection (%) Control None 0 A Polysurf 67 24.2 B LK-400 36.5 C CMC (D72) 26.6 D Modified LK-400 27.2 Color Protection Test Results - Granular Granular Test Composition ID Polymer Tested Color Protection (%) Control None 0 A Polysurf 67 33.9 B LK-400 39.2 C CMC (D72) 15.5 D Modified LK-400 24.7

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Claims (5)

  1. Konfektionierte Universal-Wäschewaschmittelzusammensetzung in flüssiger oder granulärer Form, welche Geweben und Textilien, welche in daraus gebildeten wässrigen Waschlösungen gewaschen werden. Textilaussehensvorteile verleiht, gewählt aus Pill-/Fusselverringerung, Antifarbverblassung, verbesserter Abriebbeständigkeit und/oder verstärkter Weichheit, wobei die Zusammensetzung gekennzeichnet ist durch:
    A) 1 bis 80 Gew.-% eines Waschtensids;
    B) 1 bis 80 Gew.-% eines organischen oder anorganischen Waschmittelbuilders;
    C) 0,1 bis 8 Gew.-% eines modifizierten Celluloseether-Textilbehandlungsmittels, gewählt aus der Gruppe, bestehend aus:
    hydrophob modifizierten, nichtionischen Celluloseethern mit einem Molekulargewicht von 10.000 bis 2.000.000, und welche wiederkehrende, substituierte Anhydroglucoseeinheiten entsprechend der allgemeinen Formel besitzen:
    Figure 00270001
       worin bedeuten:
    R eine Kombination von H und C8-C24, wobei die Alkylsubstitution der
    Anhydroglucoseringe im Bereich einer Menge von 0.1 bis 5 Gew.-% des
    Celluloseethermaterials liegt;
    R1 H oder Methyl; und
    x im Bereich von 1 bis 20.
  2. Zusammensetzung nach Anspruch 1, wobei
    A) das Waschtensid 5 bis 50 Gew.-% umfasst und aus anionischen und nichtionischen Tensidmaterialien gewählt ist;
    B) der Waschmittelbuilder gekennzeichnet ist durch 10 bis 50 Gew.-% und gewählt ist aus Carboxylaten, Silicaten, Aluminosilicaten, Carbonaten, Boraten und Kombinationen hiervon; und
    C) die modifizierten Celluloseether-Textilbehandlungsmittel 0,5 bis 4 Gew.-% umfassen und Molekulargewichte im Bereich von 10.000 bis 1.000.000 besitzen.
  3. Zusammensetzung nach Anspruch 2, wobei das modifizierte Celluloseether-Textilbehandlungsmittel ein hydrophob modifiziertes, nichtionisches Material ist entsprechend der Strukturformel Nr. 1, worin
    a) R eine Kombination von H und C8-C16-Alkyl ist;
    b) R-Substitution der Anhydroglucoseringe im Bereich von 0,2 bis 2 Gew.-% des Celluloseethers liegt;
    c) R1 H ist; und
    d) x im Bereich von 1 bis 10 liegt.
  4. Zusammensetzung nach Anspruch 2 in flüssiger Form, welche gekennzeichnet ist durch:
    a) 5 bis 50 Gew.-% eines Waschtensids, gewählt aus
    i) Natrium-, Kalium- und Ammoniumalkylsulfaten, worin die Alkylgruppe 8 bis 18 Kohlenstoffatom enthält;
    ii) Natrium-, Kalium- und Ammoniumalkylpolyethoxylatsulfaten, worin die Alkylgruppe 10 bis 22 Kohlenstoffatome enthält und die Polyethoxylatkette 1 bis 15 Ethylenoxideinheiten enthält;
    iii) Polyhydroxyfettsäureamiden der Formel
    Figure 00280001
       worin R ein C9-17-Alkyl oder -Alkenyl ist und Z Glycityl ist, abgeleitet aus einem reduzierten Zucker oder alkoxylierten Derivaten hiervon;
    iv) Alkoholethoxylaten der Formel R1(OC2H4)nOH, worin R1 eine C10-C16-Alkylgruppe oder eine C8-C12-Alkylphenylgruppe ist, und n 3 bis 80 ist; und
    v) Kombinationen dieser Tenside; und
    b) 1 bis 10 Gew.-% einer Waschmittelbuilderkomponente, gewählt aus Carboxylat- und Polycarboxylatbuildern.
  5. Zusammensetzung nach Anspruch 2 in granulärer Form, welche gekennzeichnet ist durch:
    a) 5 bis 50 Gew.-% eines Waschtensids, gewählt aus
    i) Natrium- und Kaliumalkylpolyethoxylatsulfaten, worin die Alkylgruppe 10 bis 22 Kohlenstoffatome enthält und die Polyethoxylatkette 1 bis 15 Ethylenoxideinheiten enthält;
    ii) Natrium- und Kalium-C9-C15-alkylbenzolsulfonaten;
    iii) Natrium- und Kalium-C8-C18-alkylsulfaten;
    iv) Polyhydroxyfettsäureamiden der Formel
    Figure 00290001
       worin R ein C9-17-Alkyl oder -Alkenyl ist, und Z Glycityl ist, abgeleitet aus einem reduzierten Zucker oder alkoxylierten Derivaten hiervon; und
    v) Kombination dieser Tenside; und
    b) 1 bis 50 Gew.-% eines Waschmittelbuilders, gewählt aus Natriumcarbonat, Silicaten, kristallinen Schichtsilicaten, Aluminosilicaten. Oxydisuccinaten und Citraten.
EP97953405A 1996-12-26 1997-12-23 Waschmittelzusammensetzungen enthaltend zellulosepolymere Expired - Lifetime EP0948591B1 (de)

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US8034123B2 (en) 2005-06-08 2011-10-11 Henkel Ag & Co., Kgaa Boosting cleaning power of detergents by means of a polymer
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