EP0839899B1 - Compositions adoucissantes pour matières textiles - Google Patents

Compositions adoucissantes pour matières textiles Download PDF

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Publication number
EP0839899B1
EP0839899B1 EP96870134A EP96870134A EP0839899B1 EP 0839899 B1 EP0839899 B1 EP 0839899B1 EP 96870134 A EP96870134 A EP 96870134A EP 96870134 A EP96870134 A EP 96870134A EP 0839899 B1 EP0839899 B1 EP 0839899B1
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EP
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Prior art keywords
weight
composition
oxide
alkyl
moieties
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EP96870134A
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German (de)
English (en)
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EP0839899A1 (fr
Inventor
Raphael Angeline Alfons Ceulemans
Bruno Albert Jean Hubesch
Franciscus Joseph Madeleine De Block
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT96870134T priority Critical patent/ATE235544T1/de
Priority to EP96870134A priority patent/EP0839899B1/fr
Priority to DE69626985T priority patent/DE69626985T2/de
Priority to ARP970105034A priority patent/AR010731A1/es
Priority to BR9712716-7A priority patent/BR9712716A/pt
Priority to CA002270383A priority patent/CA2270383C/fr
Priority to PCT/US1997/019794 priority patent/WO1998018890A1/fr
Publication of EP0839899A1 publication Critical patent/EP0839899A1/fr
Application granted granted Critical
Publication of EP0839899B1 publication Critical patent/EP0839899B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D1/65—Mixtures of anionic with cationic 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • 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
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • the present invention relates to fabric softening compositions, and more particularly to diluted fabric softening compositions.
  • Fabric softening compositions are known in the art for imparting benefits such as softness and/or antistatic properties to the treated fabric.
  • consumer acceptance of fabric softening compositions is determined not only by the performance achieved with these products but also by the aesthetics associated therewith. Viscosity of the product is therefore an important aspect of the successful formulation of such commercial products, stable medium to medium-high viscosities being highly preferred by consumers.
  • medium-high viscosities it is meant viscosities of 50cps to 150cps when the fabric softening composition is in a diluted form, that is containing less than 10% by weight of fabric softening agents, and viscosities of 30cps to 90cps when the fabric softening composition is in a concentrated form, that is containing from 10% to 80% by weight of fabric softening agents.
  • a diluted softening composition comprising fatty acids which exhibits suitable viscosity stability under shear conditions.
  • sensitivity to shear it is meant that the viscosity of the freshly made product does not stay to its initial value after shear.
  • low sensitivity to shear it is meant that the viscosity of the sheared product is substantially the same as the viscosity of the freshly made product.
  • the present invention is a diluted fabric softening composition comprising:
  • a method for treating fabrics which comprises the step of contacting said fabrics in the rinse cycle with an aqueous medium containing said composition.
  • a cationic fabric softener is an essential ingredient of the invention.
  • Typical levels of said fabric softener components within the diluted softening compositions are from less than 10% by weight, preferably from 1% to 9% by weight, and more preferably from 2% to 7% by weight of the composition.
  • the preferred, typical cationic fabric softening components include the water-insoluble quaternary-ammonium fabric softeners, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate.
  • Preferred cationic softeners among these include the following:
  • the quaternary ammonium compounds and amine precursors herein have the formula (I) or (II), below: wherein Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR 4 -C(O)-, -C(O)-NR 4 -; R 1 is (CH 2 ) n -Q-T 2 or T 3 ; R 2 is (CH 2 ) m -Q-T 4 or T 5 or R 3 ; R 3 is C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl or H; R 4 is H or C 1 -C 4 alkyl or C 1 -C 4 hydroxyalkyl; T 1 , T 2 , T 3 , T 4 , T 5 are independently C 6 -C 22 alkyl or alkenyl; n and m are integers from 1 to 4; and X - is a softener-compatible anion.
  • Non-limiting examples of softener-compatible anions include chloride or methyl sulfate.
  • the alkyl, or alkenyl, chain T 1 , T 2 , T 3 , T 4 , T 5 must contain at least 6 carbon atoms, preferably at least 11 carbon atoms, more preferably at least 16 carbon atoms.
  • the chain may be straight or branched.
  • Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material.
  • the compounds wherein T 1 , T 2 , T 3 , T 4 , T 5 represents the mixture of long chain materials typical for tallow are particularly preferred.
  • Specific examples of quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include :
  • compounds 1-7 are examples of compounds of Formula (I); compound 8 is a compound of Formula (II). Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where the tallow chains are at least partially unsaturated.
  • the level of unsaturation of the tallow chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25.
  • the anion is merely present as a counterion of the positively charged quaternary ammonium compounds.
  • the nature of the counterion is not critical at all to the practice of the present invention.
  • the scope of this invention is not considered limited to any particular anion.
  • amine precursors thereof is meant the secondary or tertiary amines corresponding to the above quaternary ammonium compounds, said amines being substantially protonated in the present compositions due to the pH values.
  • the pH of the liquid compositions herein is a preferred parameter of the present invention. Indeed, it influences the stability of the quaternary ammonium or amine precursors compounds, especially in prolonged storage conditions.
  • the pH as defined in the present context, is measured in the neat compositions at 20°C.
  • the neat pH measured in the above-mentioned conditions, must be in the range of from 2.0 to 4.5.
  • the pH of the neat composition is in the range of 2.0 to 3.5, while if it is in a diluted form, the pH of the neat composition is in the range of 2.0 to 3.0.
  • the pH of these compositions herein can be regulated by the addition of a Bronsted acid.
  • suitable acids include the inorganic mineral acids, carboxylic acids, in particular the low molecular weight (C 1 -C 5 ) carboxylic acids, and alkylsulfonic acids.
  • Suitable inorganic acids include HCl, H 2 SO 4 , HNO 3 and H 3 PO 4 .
  • Suitable organic acids include formic, acetic, citric, methylsulfonic and ethylsulfonic acid.
  • Preferred acids are citric, hydrochloric, phosphoric, formic, methylsulfonic acid, and benzoic acids.
  • Another essential component of the invention is a fatty acid compound.
  • Suitable fatty acids include those containing from 10 to 25, preferably from 12 to 25 total carbon atoms, with the fatty moiety containing from 10 to 22, preferably from 16 to 22, carbon atoms.
  • the shorter moiety contains from 1 to 4, preferably from 1 to 2 carbon atoms.
  • the level of unsaturation of the tallow chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100, more preferably in the range of from 0 to 25.
  • IV Iodine Value
  • fatty acid compounds suitable for use in the aqueous fabric softening compositions herein include compounds selected from lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, coconut fatty acid, tallow fatty acid, partially hydrogenated tallow fatty acid and mixtures thereof.
  • a most preferred fatty acid compound is tallow fatty acid with an Iodine Value (IV) of 18.
  • the fatty acids will preferably be present in a weight ratio of said biodegradable fabric softening agents to said fatty acid compounds of from 25:1 to 6.5:1, more preferably from 20:1 to 10:1 and most preferably from 20:1 to 15:1. Indeed, it is within these ratios ranges that the diluted fabric softening compositions of the invention exhibit best storage stability as well as viscosity.
  • Another essential ingredient for the purpose of the invention is a nonionic compound selected from the group consisting of block copolymers of terephthalate and ethylene oxide or propylene oxide; block copolymers of propylene oxide and ethylene oxide in which the central block is polypropylene oxide; and mixtures thereof.
  • Block copolymers of terephthalate and polyethylene oxide or polypropylene oxide for use herein are those conventionally known as soil release polymers and are typically present in an amount of from 0.005% to 1% by weight, preferably from 0.01% to 0.5% by weight of the composition.
  • a preferred block copolymer for use herein is a copolymer having blocks of terephthalate and polyethylene oxide. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and polyethylene oxide terephthalate at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of from 25:75 to 35:65, said polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights of from 200 to 2000. The molecular weight of this polymeric soil release agent is in the range of from 600 to 55,000.
  • Another preferred polymeric soil release agent is a crystallizable polyester with repeat units of ethylene terephthalate units containing from 10% to 15% by weight of ethylene terephthalate units together with from 10% to 50% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of from 300 to 6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1.
  • this polymer include the commercially available materials Zelcon 4780 (from Dupont) and Milease T (from ICI).
  • Highly preferred soil release agents are polymers of the generic formula: in which each T is an O, or NH linkage, preferably O linkage, each X can be a suitable capping group, with each X typically being selected from the group consisting of H, and alkyl or acyl groups containing from 1 to 4 carbon atoms.
  • p is selected for water solubility and generally is from 6 to 113, preferably from 8 to 50.
  • u is critical to formulation in a liquid composition having a relatively high ionic strength. There should be very little material in which u is greater than 10. Furthermore, there should be at least 20%, preferably at least 40%, of material in which u ranges from 1 to 6.
  • the R 14 moieties are essentially 1,4-phenylene moieties.
  • the term "the R 14 moieties are essentially 1,4-phenylene moieties” refers to compounds where the R 14 moieties consist entirely of 1,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof.
  • Arylene and alkarylene moieties which can be partially substituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene, and mixtures thereof.
  • Alkylene and alkenylene moieties which can be partially substituted include 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and mixtures thereof.
  • the degree of partial substitution with moieties other than 1,4-phenylene which can generally be tolerated will depend upon the backbone length of the compound, i.e., longer backbones can have greater partial substitution for 1,4-phenylene moieties.
  • compounds where the R 14 comprise from 50% to 100% 1,4-phenylene moieties are adequate.
  • polyesters with a 40:60 mole ratio of isophthalic (1,3-phenylene) to terephthalic (1,4-phenylene) acid can be used.
  • the R 14 moieties consist entirely of (i.e., comprise 100%) 1,4-phenylene moieties, i.e., each R 14 moiety is 1,4-phenylene.
  • suitable moieties are ethylene or substituted ethylene moieties which include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene, and mixtures thereof.
  • the R 15 moieties are essentially ethylene moieties, 1,2-propylene moieties, or mixtures thereof.
  • inclusion of a greater percentage of 1,2-propylene moieties tends to improve the water solubility of compounds. Therefore, the use of 1,2-propylene moieties or a similar branched equivalent is desirable for incorporation of any substantial part of the component in the liquid fabric softener compositions.
  • the value for each p is at least 6, and preferably is at least 8.
  • the value for each n usually ranges from 6 to 113. Typically, the value for each p is in the range of from 6 to 113.
  • block copolymers of terephthalate and polyethylene oxide or polypropylene oxide suitable for use herein, are the copolymers sold under the tradename HOE S3639, HOE S3702 type 566 from Hoechst, and Zelcon 7201 from Dupont.
  • Block copolymers of propylene oxide and ethylene oxide in which the central block is poly(propylene oxide) for use herein are typically present in an amount of from 0.005% to 1% by weight, more preferably of from 0.01% to 0.5% by weight of the composition.
  • the copolymers for use herein preferably have an average molecular weight of at least 4000 and contains 5% to 30%, preferably 5% to 20%, and more preferably 10% poly(ethylene oxide) by weight of the copolymer.
  • Suitable examples of such copolymers include PLURADYNE (trademark) FL-11, BASF-Wyandotte Corporation, a product reported to have an average molecular weight of 3800, a density of 1.02 at 25°C and a Brookfield viscosity of 800 cP at 25°C; PLURONIC (trademark) PE 10100, BASF United Kingdom, Ltd., a product reported to have an average molecular weight of 3600, a density of 1.02 at 20°C and a viscosity of 300 mm 2 /sec at 40°C; and SYNPERONIC (trade mark) PE L-121, Imperial Chemical Industries, P.L.C., a product reported to have an average molecular weight of 4400, a density of 1.02 at 25°C and a viscosity of 1600 cP at 25°C. Each such copolymer was reported to contain 10% poly(ethylene oxide).
  • the resulting diluted fabric softening composition exhibits a low sensitivity to shear.
  • Determination of the shear sensitivity is made as follows: A 150ml sample of a composition, to be tested for shear sensitivity, is placed in a glass vial and sheared with a magnetic stirrer at maximum speed (approximately 1000rpm). The measurement of the viscosity is then made at 0 and after 5, 15, 30 and 60 minutes of shearing using a Brookfield viscosity meter set to a speed of 60 rpm (1 Hertz).
  • Products which have a low sensitivity to shear are those having a viscosity which is substantially the same as the viscosity measured with the unsheared product, that is at 0 minutes.
  • substantially it is meant that the viscosity of the sheared product does not vary by more than 20% after each of the above mentioned time measurements when compared to the viscosity of the unsheared product, that is at 0 minutes.
  • the diluted softening composition of the invention will also comprise a liquid carrier.
  • Suitable liquid carriers are selected from water, organic solvents and mixtures thereof.
  • the liquid carrier employed in the instant compositions is preferably at least primarily water due to its low cost relative availability, safety, and environmental compatibility.
  • the level of water in the liquid carrier is preferably at least 60%, most preferably at least 80%, by weight of the carrier.
  • Mixtures of water and low molecular weight, e.g., ⁇ 200, organic solvent, e.g., lower alcohol such as ethanol, propanol, isopropanol or butanol are useful as the carrier liquid.
  • Low molecular weight alcohols include monohydric, dihydric (glycol, etc.) trihydric (glycerol, etc.), and higher polyhydric (polyols) alcohols.
  • the composition may also contain optional components which may be suitable for further improving the aesthetic appearance of the fabrics treated therewith.
  • optional components include a polyethylene glycol, additional fabric softening components, enzymes, cyclodextrin/perfume complexes and free perfume delivery systems, and mixtures thereof.
  • a polymeric material which can optionally be included is polyethylene glycol (PEG).
  • PEG polyethylene glycol
  • PEG will provide an increase in the viscosity stability upon storage of the composition of the invention.
  • 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.
  • a most preferred molecular weight is 4000.
  • typical levels of polyethylene glycols are from 0.01 to 1% by weight, preferably from 0.05% to 0.5% by weight of the composition.
  • Additional fabric softening materials may be used in addition or alternatively to the cationic fabric softener. These may be selected from nonionic, amphoteric or anionic fabric softening material. Disclosure of such materials may be found in US 4,327,133; US 4,421,792; US 4,426,299; US 4,460,485; US 3,644,203; US 4,661,269; U.S 4,439,335; U.S 3,861,870; US 4,308,151; US 3,886,075; US 4,233,164; US 4,401,578; US 3,974,076; US 4,237,016 and EP 472,178.
  • nonionic fabric softener materials typically have a HLB of from 2 to 9, more typically from 3 to 7.
  • Such nonionic fabric softener materials tend to be readily dispersed either by themselves, or when combined with other materials such as single-long-chain alkyl cationic surfactant described in detail hereinafter. Dispersibility can be improved by using more single-long-chain alkyl cationic surfactant, mixture with other materials as set forth hereinafter, use of hotter water, and/or more agitation.
  • the materials selected should be relatively crystalline, higher melting, (e.g. >40°C) and relatively water-insoluble.
  • Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains from 2 to 18, preferably from 2 to 8, carbon atoms, and each fatty acid moiety contains from 12 to 30, preferably from 16 to 20, carbon atoms.
  • such softeners contain from one to 3, preferably 2 fatty acid groups per molecule.
  • the polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. Sorbitan esters and polyglycerol monostearate are particularly preferred.
  • the fatty acid portion of the ester is normally derived from fatty acids having from 12 to 30, preferably from 16 to 20, carbon atoms, typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid.
  • sorbitan esters which are esterified dehydration products of sorbitol, and the glycerol esters.
  • Commercial sorbitan monostearate is a suitable material.
  • Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between 10:1 and 1:10, and 1,5-sorbitan esters are also useful.
  • Glycerol and polyglycerol esters especially glycerol, diglycerol, triglycerol, and polyglycerol mono- and/or di-esters, preferably mono-, are preferred herein (e.g.
  • polyglycerol monostearate with a trade name of Radiasurf 7248.
  • Useful glycerol and polyglycerol esters include mono-esters with stearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is understood that the typical mono-ester contains some di- and tri-ester, etc.
  • the "glycerol esters” also include the polyglycerol, e.g., diglycerol through octaglycerol esters.
  • the polyglycerol polyols are formed by condensing glycerin or epichlorohydrin together to link the glycerol moieties via ether linkages.
  • the mono- and/or diesters of the polyglycerol polyols are preferred, the fatty acyl groups typically being those described hereinbefore for the sorbitan and glycerol esters.
  • softening clays such as the low ion-exchange-capacity ones described in EP-A-0,150,531.
  • Enzymes may also optionally be included in the composition of the invention. Enzymes suitable for use herein are selected from proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof. A preferred enzyme for use herein is a cellulase.
  • Cellulases which may be usable herein include both bacterial and fungal types.
  • U.S 4,435,307 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® are especially useful. See also WO 9117243 to Novo.
  • compositions herein will typically comprise from 0.001% to 5%, preferably 0.01% to 1% by weight of a commercial enzyme preparation.
  • the products herein can also contain from 0.5% to 60%, preferably from 1 % to 50%, cyclodextrin/perfume inclusion complexes and/or free perfume, as disclosed in U.S 5,139,687; and 5,234,610.
  • Perfumes are highly desirable, can usually benefit from protection, and can be complexed with cyclodextrin.
  • Fabric softening products typically contain perfume to provide an olfactory aesthetic benefit and/or to serve as a signal that the product is effective.
  • Suitable perfume component for use in the present invention comprise compounds having an ester of a perfume alcohol.
  • the ester includes at least one free carboxylate group and has the formula wherein R is selected from the group consisting of substituted or unsubstituted C 1 -C 30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl or aryl group; R' is a perfume alcohol with a boiling point at 760 mm Hg of less than 300 °C; and n and m are individually an integer of 1 or greater.
  • the perfume component may comprise from 0.01% to 10% by weight of the composition.
  • R is selected from the group consisting of substituted or unsubstituted C 1 - C 20 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, aryl group or ring containing a heteroatom.
  • R' is preferably a perfume alcohol selected from the group consisting of geraniol, nerol, phenoxanol, floralol, ⁇ -citronellol, nonadol, cyclohexyl ethanol, phenyl ethanol, phenoxyethanol, isoborneol, fenchol, isocyclogeraniol, 2-phenyl-1-propanol, 3,7-dimethyl-1-octanol, and combinations thereof and the ester is preferably selected from maleate, succinate adipate, phthalate, citrate or pyromellitate esters of the perfume alcohol.
  • esters having at least one free carboxylate group are then selected from the group consisting of geranyl succinate, neryl succinate, (b-citronellyl) maleate, nonadol maleate, phenoxanyl maleate, (3,7-dimethyl-1-octanyl) succinate, (cyclohexylethyl) maleate, floralyl succinate, (b-citronellyl) phthalate and (phenylethyl) adipate.
  • perfume ingredients and compositions of this invention are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations. Suitable perfume compounds and compositions can be found in the art including U.S 4,145,184; 4,209,417; 4,515,705; and 4,152,272. Many of the art recognized perfume compositions are relatively substantive to maximize their odor effect on substrates. However, it is a special advantage of perfume delivery via the perfume/cyclodextrin complexes that nonsubstantive perfumes are also effective. If a product contains both free and complexed perfume, the escaped perfume from the complex contributes to the overall perfume odor intensity, giving rise to a longer lasting perfume odor impression. As disclosed in U.S 5,234,610, by adjusting the levels of free perfume and perfume/CD complex it is possible to provide a wide range of unique perfume profiles in terms of timing (release) and/or perfume identity (character).
  • longer lasting perfume odor impression can also be provided by the use of nonionic or anionic esters of an allylic alcohol perfume described in WO 96/02625 and having the formula: wherein R is selected from the group consisting of nonionic or anionic substituted or unsubstituted C 1 - C 30 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, or aryl group; each of R', R", and R'" is independently selected from the group consisting of hydrogen, or a nonionic or anionic substituted or unsubstituted C 1 - C 25 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, or aryl group; and n is an integer of 1 or greater.
  • the most preferred nonionic or anionic ester of an allylic alcohol perfume are then selected from the group consisting of digeranyl succinate, dineryl succinate, geranyl neryl succinate, geranyl phenylacetate, neryl phenylacetate, geranyl laurate, neryl laurate, and mixtures thereof.
  • the perfume component may be comprised in an amount of from 0.01% to 10% by weight of the composition.
  • composition may also optionally contain additional components such as surfactant concentration aids, electrolyte concentration aids, stabilisers, such as well known antioxidants and reductive agents, emulsifiers, bacteriocides, colorants, perfumes, preservatives, optical brighteners, anti ionisation agents, and antifoam agents.
  • surfactant concentration aids such as sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfit
  • Stabilisers may also optionally be used. When used, said stabiliser will help achieving the desired finished product viscosity as well as stabilising the finished product upon storage.
  • Stabilisers are typically selected from single long chain alkyl cationic surfactants, nonionic alkoxylated surfactants, amine oxides, fatty acids, and mixtures thereof, typically used at a level of from 0 to 15% by weight of the composition.
  • Such mono-long-chain-alkyl cationic surfactants useful in the present invention are, preferably, quaternary ammonium salts of the general formula: [R 2 N + R 3 ] X - wherein the R 2 group is C 10 -C 22 hydrocarbon group, preferably C 12 -C 18 alkyl group of the corresponding ester linkage interrupted group with a short alkylene (C 1 -C 4 ) group between the ester linkage and the N, and having a similar hydrocarbon group, e.g., a fatty acid ester of choline, preferably C 12 -C 14 (coco) choline ester and/or C 16 -C 18 tallow choline ester at from 0.1% to 20% by weight of the softener active.
  • R 2 group is C 10 -C 22 hydrocarbon group, preferably C 12 -C 18 alkyl group of the corresponding ester linkage interrupted group with a short alkylene (C 1 -C 4 ) group between the ester
  • Each R is a C 1 -C 4 alkyl or substituted (e.g., hydroxy) alkyl, or hydrogen, preferably methyl, and the counterion X - is a softener compatible anion, for example, chloride, bromide, methyl sulfate, etc.
  • cationic materials with ring structures such as alkyl imidazoline, imidazolinium, pyridine, and pyridinium salts having a single C 12 -C 30 alkyl chain can also be used. Very low pH is required to stabilize, e.g., imidazoline ring structures.
  • alkyl imidazolinium salts and their imidazoline precursors useful in the present invention have the general formula: wherein Y 2 is -C(O)-O-, -O-(O)C-, -C(O)-N(R 5 )-, or -N(R 5 )-C(O)- in which R 5 is hydrogen or a C 1 -C 4 alkyl radical; R 6 is a C 1 -C 4 alkyl radical or H (for imidazoline precursors); R 7 and R 8 are each independently selected from R and R 2 as defined hereinbefore for the single-long-chain cationic surfactant with only one being R 2 .
  • Some alkyl pyridinium salts useful in the present invention have the general formula : wherein R 2 and X - are as defined above. A typical material of this type is cetyl pyridinium chloride.
  • Suitable nonionic alkoxylated surfactants for use herein include addition products of ethylene oxide and, optionally, propylene oxide, with fatty alcohols, fatty acids and fatty amines.
  • Suitable compounds are substantially water-soluble surfactants of the general formula : R 2 - Y - (C 2 H 4 O) z - C 2 H 4 OH wherein R 2 is selected from primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups; said hydrocarbyl groups having a hydrocarbyl chain length of up to 20, preferably from 10 to 18 carbon atoms.
  • Y is typically -O-, -C(O)O-, -C(O)N(R)-, or -C(O)N(R)R-, in which R 2 and R, when present, have the meanings given hereinbefore, and/or R can be hydrogen, and z is of from 5 to 50, preferably of from 1- to 30.
  • the nonionic surfactants herein are characterized by an HLB (hydrophilic-lipophilic balance) of from 7 to 20, preferably from 8 to 15. Examples of particularly suitable nonionic surfactants include
  • Suitable amine oxides include those with one alkyl or hydroxyalkyl moiety of 8 to 28 carbon atoms, preferably from 8 to 16 carbon atoms, and two alkyl moieties selected from alkyl groups and hydroxyalkyl groups with 1 to 3 carbon atoms.
  • Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecyl-amine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide, and coconut fatty alkyl dimethylamine oxide.
  • a preferred stabiliser for use herein is a nonionic alkoxylated surfactant.
  • nonionic alkoxylated surfactant When used, such nonionic alkoxylated surfactant will be present in an amount of 0.01% to 10% by weight, preferably from 0.05% to 2% by weight of the composition.
  • Inorganic viscosity control agents which can also act like or augment the effect of the stabilisers, include water-soluble, ionizable salts which can also optionally be incorporated into the compositions of the present invention. Incorporation of these components to the composition must be processed at a very slow rate.
  • ionizable salts can be used. Examples of suitable salts are the halides of the Group IA and IIA metals of the Periodic Table of the Elements, e.g., calcium chloride, magnesium chloride, sodium chloride, potassium bromide, and lithium chloride.
  • the ionizable salts are particularly useful during the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity.
  • the amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desires of the formulator. Typical levels of salts used to control the composition viscosity are from 20 to 2000 parts per million (ppm), preferably from 20 to 1100 ppm, by weight of the composition.
  • Alkylene polyammonium salts can be incorporated into the composition to give viscosity control in addition to or in place of the water-soluble, ionizable salts above.
  • these agents can act as scavengers, forming ion pairs with anionic detergent carried over from the main wash, in the rinse, and on the fabrics, and may improve softness performance. These agents may stabilise the viscosity over a broader range of temperature, especially at low temperatures, compared to the inorganic electrolytes.
  • Specific examples of alkylene polyammonium salts include I-lysine monohydrochloride and 1,5-diammonium 2-methyl pentane dihydrochloride.
  • the present invention also encompasses a method for treating fabrics which comprises the step of contacting said fabrics in the rinse cycle with an aqueous medium containing a composition as defined hereinbefore.
  • the aqueous medium is at a temperature between 2 to 40°C, preferably between 5 to 25°C.
  • compositions are in accordance with the present invention: Component A B C D E F G DEQA 5.0 5.0 5.0 4.0 4.0 4.0 5.0 Fatty acid 0.5 0.5 0.5 0.4 0.4 0.4 0.5 Nonionic 1 0.1 - - 0.05 - - 0.05 Nonionic 2 - 0.2 - - 0.1 - 0.10 Nonionic 3 - - 0.2 - - 0.1 - PEG 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

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Claims (11)

  1. Composition diluée assouplissante des tissus comprenant :
    a) un agent cationique assouplissant des tissus, en une quantité inférieure à 10 % en poids ;
    b) un acide gras, et
    c) un composé non ionique choisi dans le groupe constitué par :
    i) des copolymères séquencés de téréphtalate et d'oxyde d'éthylène ou d'oxyde de propylène ;
    ii) des copolymères séquencés d'oxyde de propylène et d'oxyde d'éthylène dans lesquels la séquence centrale est l'oxyde de polypropylène ; et
    iii) leurs mélanges.
  2. Composition suivant la revendication 1, dans laquelle l'assouplissant des tissus cationique et l'acide gras sont présents en un rapport pondéral dudit assouplissant des tissus audit acide gras de 25:1 à 6,5:1, de préférence de 20:1 à 10:1.
  3. Composition suivant l'une des revendications 1 ou 2, dans laquelle ledit assouplissant des tissus cationique est un assouplissant des tissus biodégradable choisi entre :
    Figure 00270001
    où Q est choisi entre -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR4-C(O)-, -C(O)-NR4-;
    R1 est (CH2)n-Q-T2 ou T3 ;
    R2 est (CH2)m-Q-T4 ou T5 ou R3 ;
    R3 est un groupe alkyle en C1 à C4 ou hydroxyalkyle en C1 à C4, ou H ;
    R4 est H ou un groupe allyle en C1 à C4 ou hydroxyalkyle en C1 à C4 ;
    T1, T2, T3, T4, T5 représentent indépendamment un groupe alkyle ou alcényle en C11 à C22;
    n et m sont des nombres entiers de 1 à 4 ; et
    X- est un anion compatible avec un assouplissant.
  4. Composition suivant l'une quelconque des revendications 1-3,
    dans laquelle ledit assouplissant des tissus est présent en une quantité inférieure à 10 % en poids, de préférence de 1 % à 9 % en poids, et en particulier de 2 % à 7 % en poids de la composition.
  5. Composition suivant l'une quelconque des revendications 1-4,
    dans laquelle ledit copolymère séquencé de téréphtalate et d'oxyde d'éthylène ou d'oxyde de propylène répond à la formule :
    Figure 00280001
    dans laquelle chaque radical T représente une liaison O ou NH, de préférence une liaison O;
    dans laquelle chaque radical X est choisi dans le groupe constitué par H et des groupes alkyle ou acyle contenant 1 à 4 atomes de carbone ;
    dans laquelle p vaut au moins 6, et de préférence au moins 8, n se situe dans l'intervalle de 6 à 113, u est inférieur à 10 ;
    dans laquelle les groupements R14 sont essentiellement des groupements 1,4-phénylène ; et
    dans laquelle les groupements R15 sont des groupements éthylène ou éthylène substitués.
  6. Composition suivant l'une quelconque des revendications 1-5,
    dans laquelle ledit copolymère séquencé de téréphtalate et d'oxyde d'éthylène ou d'oxyde de propylène est présent en une quantité de 0,005 % à 1 % en poids, de préférence de 0,01 % à 0,5 %, en poids de la composition.
  7. Composition suivant l'une quelconque des revendications 1-6,
    dans laquelle ledit copolymère séquencé d'oxyde de propylène et d'oxyde d'éthylène, dans lequel la séquence centrale est constituée d'oxyde de polypropylène, possède un poids moléculaire d'au moins 4000, et dans laquelle le copolymère contient 5 à 30 % en poids de poly(oxyde d'éthylène).
  8. Composition suivant l'une quelconque des revendications 1-7,
    dans laquelle ledit copolymère séquencé d'oxyde de propylène et d'oxyde d'éthylène, dans lequel la séquence centrale est constituée d'oxyde de polypropylène, est présent en une quantité de 0,005 % à 1 % en poids, plus préférablement de 0,01 % à 0,5 %, en poids de la composition.
  9. Composition suivant l'une quelconque des revendications 1-8,
    dans laquelle ladite composition comprend en outre un polyéthylèneglycol.
  10. Procédé de traitement de tissus qui comprend l'étape consistant à mettre en contact lesdits tissus au cours du cycle de rinçage avec un milieu aqueux contenant une composition telle que définie dans l'une quelconque des revendications 1-9.
  11. Procédé suivant la revendication 10, dans lequel ledit milieu aqueux est à une température comprise entre 2 et 40 °C, de préférence entre 5 et 25 °C.
EP96870134A 1996-10-30 1996-10-30 Compositions adoucissantes pour matières textiles Expired - Lifetime EP0839899B1 (fr)

Priority Applications (7)

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AT96870134T ATE235544T1 (de) 1996-10-30 1996-10-30 Gewebeweichmacherzusammensetzungen
EP96870134A EP0839899B1 (fr) 1996-10-30 1996-10-30 Compositions adoucissantes pour matières textiles
DE69626985T DE69626985T2 (de) 1996-10-30 1996-10-30 Gewebeweichmacherzusammensetzungen
ARP970105034A AR010731A1 (es) 1996-10-30 1997-10-29 Composicion suavizante de telas diluida y un metodo para tratar telas con dicha composicion
BR9712716-7A BR9712716A (pt) 1996-10-30 1997-10-30 Composições amaciantes de tecido
CA002270383A CA2270383C (fr) 1996-10-30 1997-10-30 Compositions adoucissantes pour tissus
PCT/US1997/019794 WO1998018890A1 (fr) 1996-10-30 1997-10-30 Compositions adoucissantes pour tissus

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Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
EP1127940A1 (fr) * 2000-02-26 2001-08-29 Ciba Spezialitätenchemie Pfersee GmbH Adoucissant pour textiles à base de cyclodextrine
WO2016209617A1 (fr) * 2015-06-23 2016-12-29 Rohm And Haas Company Compositions de produit assouplissant textile et procédés d'utilisation
WO2017102307A1 (fr) * 2015-12-15 2017-06-22 Unilever Plc Composition de conditionnement de tissu
US10808206B2 (en) 2017-11-14 2020-10-20 Henkel IP & Holding GmbH Detergent boosters, detergent systems that include a detergent booster, and methods of laundering fabric

Family Cites Families (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH1824769D (fr) 1968-12-09
JPS5028515B2 (fr) 1971-09-30 1975-09-16
US3954632A (en) 1973-02-16 1976-05-04 The Procter & Gamble Company Softening additive and detergent composition
US3861870A (en) 1973-05-04 1975-01-21 Procter & Gamble Fabric softening compositions containing water-insoluble particulate material and method
US3974076A (en) 1974-01-11 1976-08-10 The Procter & Gamble Company Fabric softener
US4145184A (en) 1975-11-28 1979-03-20 The Procter & Gamble Company Detergent composition containing encapsulated perfume
US4209417A (en) 1976-08-13 1980-06-24 The Procter & Gamble Company Perfumed particles and detergent composition containing same
GB1587122A (en) 1976-10-29 1981-04-01 Procter & Gamble Ltd Fabric conditioning compositions
US4327133A (en) 1977-11-21 1982-04-27 Lever Brothers Company Additives for clothes dryers
US4237016A (en) 1977-11-21 1980-12-02 The Procter & Gamble Company Textile conditioning compositions with low content of cationic materials
EP0013780B2 (fr) 1979-01-11 1988-08-31 THE PROCTER & GAMBLE COMPANY Composition concentrée d'adoucissement pour tissus
US4233164A (en) 1979-06-05 1980-11-11 The Proctor & Gamble Company Liquid fabric softener
DK187280A (da) 1980-04-30 1981-10-31 Novo Industri As Ruhedsreducerende middel til et fuldvaskemiddel fuldvaskemiddel og fuldvaskemetode
US4308151A (en) 1980-05-12 1981-12-29 The Procter & Gamble Company Detergent-compatible fabric softening and antistatic compositions
FR2482636A1 (fr) 1980-05-14 1981-11-20 Lesieur Cotelle Et Associes Sa Composition adoucissante concentree pour fibres textiles
US4421792A (en) 1980-06-20 1983-12-20 Lever Brothers Company Additives for clothes dryers
GB2095275B (en) 1981-03-05 1985-08-07 Kao Corp Enzyme detergent composition
US4439335A (en) 1981-11-17 1984-03-27 The Procter & Gamble Company Concentrated fabric softening compositions
US4460485A (en) 1983-07-15 1984-07-17 Lever Brothers Company Polyester fabric conditioning and whitening composition
US4515705A (en) 1983-11-14 1985-05-07 The Procter & Gamble Company Compositions containing odor purified proteolytic enzymes and perfumes
GB8333816D0 (en) 1983-12-20 1984-02-01 Procter & Gamble Fabric softening compositions
US4661269A (en) 1985-03-28 1987-04-28 The Procter & Gamble Company Liquid fabric softener
US4749596A (en) 1985-08-22 1988-06-07 The Procter & Gamble Company Articles and methods for treating fabrics
US4661267A (en) 1985-10-18 1987-04-28 The Procter & Gamble Company Fabric softener composition
GB2188653A (en) 1986-04-02 1987-10-07 Procter & Gamble Biodegradable fabric softeners
US4711730A (en) 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
US4818569A (en) 1987-10-05 1989-04-04 The Procter & Gamble Company Articles and methods for treating fabrics in clothes dryer
US4877896A (en) 1987-10-05 1989-10-31 The Procter & Gamble Company Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
US4976879A (en) 1987-10-05 1990-12-11 The Procter & Gamble Company Sulfoaroyl end-capped ester oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
US5102564A (en) 1989-04-12 1992-04-07 The Procter & Gamble Company Treatment of fabric with perfume/cyclodextrin complexes
GB8905552D0 (en) * 1989-03-10 1989-04-19 Unilever Plc Fabric conditioning
US5094761A (en) * 1989-04-12 1992-03-10 The Procter & Gamble Company Treatment of fabric with perfume/cyclodextrin complexes
US4956447A (en) 1989-05-19 1990-09-11 The Procter & Gamble Company Rinse-added fabric conditioning compositions containing fabric sofening agents and cationic polyester soil release polymers and preferred cationic soil release polymers therefor
EP0531372B2 (fr) 1990-05-09 2004-04-14 Novozymes A/S Preparation de cellulase comprenant un enzyme d'endoglucanase
US5139687A (en) 1990-05-09 1992-08-18 The Proctor & Gamble Company Non-destructive carriers for cyclodextrin complexes
JPH0759792B2 (ja) 1990-08-22 1995-06-28 花王株式会社 柔軟仕上剤
EP0523956B2 (fr) * 1991-07-17 1999-02-03 Unilever Plc Composition pour le traitement du linge contenant un copolymère soluble dans l'eau ou dispersé dans l'eau avec un monomère absorbant les rayons ultraviolets
WO1994020597A1 (fr) * 1993-03-01 1994-09-15 The Procter & Gamble Company Compositions adoucissantes pour tissus concentrees et biodegradables a base d'ammonium quaternaire et composes contenant des chaines d'acide gras insature a indice d'iode intermediaire
JP3357453B2 (ja) * 1993-09-10 2002-12-16 花王株式会社 液体柔軟仕上剤組成物並びに新規第４級アンモニウム塩並びに該塩の製造法

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BR9712716A (pt) 1999-10-26
AR010731A1 (es) 2000-07-12
ATE235544T1 (de) 2003-04-15
EP0839899A1 (fr) 1998-05-06
DE69626985T2 (de) 2004-03-04

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