EP0799887B1 - Textilweichmacherzusammensetzungen - Google Patents

Textilweichmacherzusammensetzungen Download PDF

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Publication number
EP0799887B1
EP0799887B1 EP96870041A EP96870041A EP0799887B1 EP 0799887 B1 EP0799887 B1 EP 0799887B1 EP 96870041 A EP96870041 A EP 96870041A EP 96870041 A EP96870041 A EP 96870041A EP 0799887 B1 EP0799887 B1 EP 0799887B1
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EP
European Patent Office
Prior art keywords
acid
fabric softener
group
composition according
polycarboxylic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP96870041A
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English (en)
French (fr)
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EP0799887A1 (de
Inventor
Raphael Angeline Alfons Ceulemans
Franciscus Joseph Madeleine De Block
Bruno Albert Jean Hubesch
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Priority to EP96870041A priority Critical patent/EP0799887B1/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AU25951/97A priority patent/AU2595197A/en
Priority to CN97195086A priority patent/CN1220694A/zh
Priority to US09/155,776 priority patent/US6020304A/en
Priority to PCT/US1997/005107 priority patent/WO1997036981A1/en
Priority to BR9710451A priority patent/BR9710451A/pt
Priority to CA002250909A priority patent/CA2250909C/en
Priority to PH56016A priority patent/PH11997056016B1/en
Priority to ZA9702774A priority patent/ZA972774B/xx
Priority to ARP970101300A priority patent/AR006473A1/es
Publication of EP0799887A1 publication Critical patent/EP0799887A1/de
Priority to MX9808114A priority patent/MX204196B/es
Application granted granted Critical
Publication of EP0799887B1 publication Critical patent/EP0799887B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • 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
    • 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
    • C11D3/3726—Polyurethanes

Definitions

  • the present invention relates to fabric softening compositions showing excellent stability upon storage. More particularly, it relates to liquid fabric softening compositions.
  • Fabric softening compositions in particular fabric softening compositions to be used in the rinse cycle of laundry washing processes, are well-known to the consumer to provide fabrics with a soft and agreeable feeling.
  • Such compositions are provided in two forms: concentrated compositions comprising more than 10% by weight of fabric softening agents and diluted compositions comprising less than 10% by weight of fabric softening agents.
  • 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 consumer.
  • medium-high viscosities it is meant viscosities of 50cps to 150cps when the fabric softening composition is in a diluted form and viscosities of 30cps to 90cps when the fabric softening composition is in a concentrated form.
  • diluted compositions a problem encountered with diluted compositions is that, contrary to concentrated compositions which exhibit a "self-building viscosity" due to their high amount of active, diluted compositions show a phase instability as well as a viscosity problem. Such a problem can be encountered either with an already-made diluted product or with a concentrated product as it is diluted.
  • thickeners such as compounds of the polyacrylamide, polysacharide or polyurethanes type have been widely used in such compositions. Disclosure of such compounds may be found in EP 0,422,179 and EP 0,309,052.
  • a problem encountered with such thickeners is the necessity for them to be present at high levels to provide effective thickening effect. Whilst the use of such high levels would provide a good remedy to the problem, this would increase the formulation cost.
  • the softening composition comprises electrolytes.
  • thickener is meant a component which has thickening properties, that is a compound which, when incorporated in a fabric softening composition, produces compositions with a higher viscosity in the presence of the polymer than in the absence of the polymer.
  • components having soil release properties such as those defined in US 4,702,857.
  • the present invention relates to a liquid fabric softening composition
  • a liquid fabric softening composition comprising:
  • An essential component of the invention is a fabric softener component.
  • the fabric softening materials may be selected from the group consisting of cationic, nonionic, amphoteric or anionic fabric softening material.
  • the fabric softener components herein are present at levels of from 0.01% to 10% by weight, with a preferred level of fabric softening components from 1% to 5% by weight of the composition.
  • compositions typically contain a water-insoluble quaternary-ammonium fabric softening active, the most commonly used having been di-long alkyl chain ammonium chloride.
  • 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 11 carbon atoms, 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.
  • 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).
  • N,N-di(tallowyl-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.
  • IV Iodine Value
  • 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 claimed pH values.
  • the pH of the compositions herein is an essential 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 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 3.0.
  • 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.
  • fabric softening materials may be used in addition or alternatively to the biodegradable fabric softener. These may be selected from the group consisting of cationic fabric softening materials such as di-long alkyl chain ammonium chloride, nonionic, amphoteric or anionic fabric softening materials. Disclosure of such materials may be found in US 4,327,133; 4,421,792; 4,426,299; 4,460,485; 3,644,203 and 4,661,269.
  • nonionic fabric softener materials typically have an HLB of from about 2 to about 9, more typically from about 3 to about 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.
  • Highly preferred optional nonionic softening agents for use in the present invention are the sorbitan esters, which are esterified dehydration products of sorbitol, and the glycerol esters.
  • sorbitan monostearate is a suitable material. Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between about 10:1 and about 1:10, and 1,5-sorbitan esters are also useful.
  • Glycerol and polyglycerol esters especially glycerol, diglycerol, triglycerol, and polyglycerol mono- andlor 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- andlor diesters of the polyglycerol polyols are preferred, the fatty acyl groups typically being those described hereinbefore for the sorbitan and glycerol esters.
  • the second essential component of the invention is a thickening agent.
  • Typical levels of such a thickener is of at least 0.001%, preferably from 0.001 to 3%, more preferably from 0.01% to 1% and most preferably from 0.1% to 0.5% by weight of the composition.
  • Suitable thickening agents are selected from the group consisting of associative polymers having a hydrophilic backbone and at least two hydrophobic groups per molecule attached to the hydrophilic backbone, cross-linked cationic polymers that are derivable from a water-soluble cationic ethylenically unsaturated monomer or blend of monomers which is cross-linked by 5 to 45ppm of a cross-linking agent comprising polyethylenic functions, and mixtures thereof.
  • Associative polymers having a hydrophilic backbone and at least two hydrophobic groups per molecule attached to the hydrophilic backbone
  • the polymeric thickeners for use in fabric softener compositions according to the invention preferably have a nonionic or cationic hydrophilic backbone.
  • the polymeric thickeners are hydrophobically modified nonionic polymers.
  • Preferred hydrophobically modified nonionic polymers are based on polyoxyalkylene or polyvinylalcohol hydrophilic backbones, to which a small number of alkyl groups have been attached. Examples of these materials are:
  • Hydrophobically modified poly (ethylene oxide and/or propylene oxide/urethanes) according to formula (iii) are marketed by UNION CARBIDE under the UCAR SCT trademark for the thickening of latex systems and generally have a molecular weight in the region of 40.000.
  • the number of hydrophobic groups attached to the hydrophilic backbone is relatively small.
  • the hydrophobic groups constitute less than 5 % by weight of the polymer, more preferably between 0.5 and 2 % by weight of the polymer.
  • Preferred hydrophobic groups are linear or branched alkyl or alkenyl groups, preferably having a chain length of less than 40, more preferably between 8 and 24 carbon atoms.
  • hydrophobically modified nonionic polymers based on polyoxyalkylene hydrophilic backbones to which a small number of alkyl groups have been attached are the hydrophobically modified polyacrylic acid polymers such as the polyalkyl acrylic acid sold under the tradenames Viscalex, Rheovis CRX, Rheovis CR, Rheovis CR2 available from Allied Colloid, Acusol 810, Acusol 820, Acusol 823, Acusol 830, Acusol 842 available from Rohm & Haas.
  • Viscalex the polyalkyl acrylic acid sold under the tradenames Viscalex, Rheovis CRX, Rheovis CR, Rheovis CR2 available from Allied Colloid, Acusol 810, Acusol 820, Acusol 823, Acusol 830, Acusol 842 available from Rohm & Haas.
  • the preferred molecular weight of the above mentionned thickener materials to be used is preferably above 10 000 more preferred from 10 000 to 1 000 000 more preferred from 15 000 to 100 000, especially preferred from 20 000 to 70 000.
  • Cross-linked cationic polymers that are derivable from a water-soluble cationic ethylenically unsaturated monomer or blend of monomers which is cross-linked bv 5 to 45ppm of a cross-linking agent comprising polyethylenic functions
  • the cross-linked, cationic polymers are formed from monoethylenically unsaturated monomer that is either a water soluble cationic monomer or is a cationic blend of monomers that may consist of cationic monomers alone or may consist of a mixture of cationic and non-ionic monomers in the presence of a cross-linking agent. If a blend of monomers is being used, then part of the blend may have a low water solubility, providing the blend is water soluble.
  • the monomers can be allyl monomers but are generally vinyl, preferably acrylic.
  • the cationic polymers are derivable from cationic monomers comprising one or more of (a) dialkylaminoalkyl-acrylates or methacrylates, (b) dialkylaminoalkyl-acrylamides or methacrylamides and (c) the quaternary or acid salts of (a) or (b), for instance methacrylamidopropyl tremethyl ammonium chloride and Mannich products such as quaternised dialkylaminomethylacrylamides.
  • Alkyl groups are generally C 1-4 alkyl.
  • Suitable non-ionic monomers are acrylamide, methacrylamide, N-vinyl pyrrolidone, and lower alkyl water insoluble acrylic (or other ethylenically unsaturated) monomers such as methyl methacrylate, styrene or acryloniltrile which may be included in sufficiently small amounts so that the blend is soluble.
  • Blends of 5-90%, preferably 5-50%, acrylamide with dialkylaminoalkyl-acrylate or, preferably -methacrylate as acid addition or quaternary addition salts, or, cationic homopolymers (containing no acrylyamide groups) are preferred.
  • the allyl ether monomers are especially preferred.
  • the cationic polymer must be added while in the form of particles below 10 micrometers in size, and preferably below 2 micrometers in size. These can be made by comminuting a cross-linked polymer gel but preferably the particles are formed initially in the cross-linked state.
  • the particles may be added to the aqueous solution as disintegratable aggregates or pellets, but preferably are added as dispersion in a liquid, generally a non-aqueous liquid such as a hydrocarbon. This dispersion may be made by dispersing preformed particles in the liquid but is preferably made by reverse phase polymerisation of the monomer or monomer blend in the presence of the cross linker.
  • the monoethylenically unsaturated starting material may be contaminated with a small amount of crosslinking agent and the amount of additional cross-linking agent that is added will therefore be selected having regard to this.
  • the monoethylenically unsaturated material is as free of cross-linking agent as is commercially possible, for instance containing cross-linking agent in an amount that gives cross-linking or chain branching less than is given by e.g. 1 ppm of a cross-linking agent comprising polyethylenic functions used in the present invention.
  • polyethylenic functions as used herein and throughout the specification is meant cross-linking agents which have two or more ethylenically unsaturated groups per molecule of the agent.
  • an example of such an agent is methylene bisacrylamide (hereafter "MBA")
  • MBA methylene bisacrylamide
  • the amount of cross-linking agent with polyethylenic functions e.g. MBA that is added is at least 5 ppm and upto 45 ppm (based on monomer), generally from 10 to 40 ppm. The precise amount will depend upon the polymerisation and other processing conditions.
  • cross-linking may be equally achieved by using effective amounts of other diethylenically unsaturated compounds such as ethylene glycol di-acrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate or methacrylate and other means of cross linking, e.g. formaldehyde or glyoxal or metal salt addition.
  • a water-soluble cross-linking agent is used.
  • the degree of non-linearity can additionally be controlled by the inclusion of chain transfer agents in the polymerisation mixture.
  • Chain transfer agents Their use, in combination with cross-linking agent, will tend to promote chain branching rather than cross linking. Amounts may vary widely. For instance 1000 to 5000 ppm (based on monomer) of a moderate chain transfer agent such as isopropyl alcohol may be suitable whilst much lower amounts, typically 100 to 500 ppm, of more effective chain branching agents such as mercaptoethanol are useful. Often, however, adequate results are obtained by conducting polymerisation under conventional conditions without deliberate addition of chain transfer agents using commercially pure monoethylenically unsaturated monomer together with the specified amount of MBA or other cross-linking agent.
  • Preferred CP's are often formed with up to 40% w/w acrylamide and 100 to 60% w/w dialkylaminoethyl methacrylate quaternary salt (for instance 20% acrylamide 80% dimethylaminoethyl methacrylate quaternary salt) cross linked with 10 to 40 ppm, preferably 10-30 ppm of MBA or other cross linker. All parts and percentages are by weight. The precise optimum for any particular composition can be determined by observing the properties of the composition when thickened with the chosen amount of a range of CP's differing from one another solely by differing the amounts of MBA from 5 to 45 ppm.
  • the polymerisation conditions are preferably such that the polymer has, if uncross-linked, a notional high molecular weight of 5 million to 30 million and an intrinsic viscosity (hereafter IV) of above 4, preferably above 6, e.g., up to 10 or 15 dl/g.
  • IV intrinsic viscosity
  • the polymer is cross linked (CP) it is preferably polymerised such that it would have such molecular weight if it had been made in the absence of cross linking agent. However, cross linking will reduce the IV but the shearing may then cause the IV to increase, as explained below.
  • the particle size in the emulsion of reverse phase polymerisation mixture may be controlled by the degree of shear applied to the monomers and by the possible presence of emulsifying agent.
  • Emulsion polymerisation may be utilised when polymerising, for instance, water insoluble monomers such as acrylic esters or water insoluble but acid soluble monomers such as amines (the resultant CP being distributed into acidic aqueous composition) but generally reverse phase emulsion or suspension polymerisation is utilised when the monomer or monomer blend is soluble in water.
  • the aqueous monomer is emulsified into a suitable non-aqueous liquid, generally in the presence of a water in oil emulsifier, generally in an amount below the critical micelle concentration.
  • Emulsifiers, stabilisers, non-aqueous liquids and other reverse phase polymerisation materials and process details are described in, for instance, EP-A-0,126,528.
  • the CP particles may be dehydrated, for instance by subjecting the dispersion to azeotropic distillation.
  • the liquid product from the reverse phase polymerisation or emulsion polymerisation is generally used as such, without separation of the polymer particles from it, but if desired dried polymer particles may be separated from the dispersion in known manner. Because these dry particles will be very dusty they should preferably be formed into pellets that will disintegrate upon addition to water.
  • the polymer-in-oil emulsion that results from reverse phase polymerisation may be added to the composition to be thickened in the presence of oil-in-water emulsifier in conventional manner.
  • the polymeric material is cross linked and cationic, and in particular when it is a copolymer of acrylamide with at least 5%, and preferably at least 10%, by weight dialkylamino alkyl acrylate (generally as acid addition or quaternary ammonium salt)
  • dialkylamino alkyl acrylate generally as acid addition or quaternary ammonium salt
  • the degree of non-linearity is preferably such that the CP has an ionic regain (IR) of at least 15%.
  • IR is calculated as (x-y/x)100 where x is the ionicity measured after applying standard shear and y is the ionicity of the polymer before applying standard shear.
  • the ionicity after shear, x is determined by measuring by the same technique the ionicity of this solution after subjecting it to standard shear.
  • the shear is best applied to 200ml of the solution in a substantially cylindrical pot having a diameter of about 8cm and provided in its base with a rotatable blade about 6cm in diameter, one arm of the blade pointing upwards by about 45 degrees and the other downwards by about 45 degrees.
  • the blade is about 1mm thick and is rotated at 16,500 rpm in the base of the pot for 10 minutes.
  • IR is not greatly affected by quite large changes in the amount, for instance the duration of shear, whereas at lower amounts of shear (for instance 1 minute at 16,500 rpm) IR is greatly affected by small changes in shear.
  • the value of x is determined at the time when, with a high speed blade, further shear provides little or no further change in ionicity. This generally requires shearing for 10 minutes, but sometimes longer periods, e.g., up to 30 minutes with cooling, may be desired.
  • the CP's used in the invention preferably have IR above 30%, often in the range 35 to 45%.
  • IR may increase from zero at zero cross linker up to peak or plateau at a level around, for instance 10 to 25 ppm, cross linker and preferably IR is at or near this peak or plateau, generally at as low a level of cross linking as is consistent with the high IR value.
  • a preferred example of a cross-linked polymer is as follows: A reversed phase dispersion was formed by dispersing into a conventional reverse phase non-aqueous liquid containing emulsifying agent and amphiphatic stabiliser an aqueous monomer blend consisting of 80% by weight dimethylaminoethyl methacrylate methyl chloride quaternary salt and 20% acrylamide and 15ppm methylene bis acrylamide. The mixture was degassed and initiated in the conventional manner and polymerisation was allowed to go to completion. The mixture was then subjected to azeotropic distillation to provide a substantially anhydrous dispersion of polymer particles less than 2 micrometers in size dispersed in mineral oil (50%w/w) which was Shell oil 60 Solvent Pale.
  • a preferred commercially representative of a cross-linked cationic polymer is BP 7050TM ex BP Chemicals.
  • a third essential component of the invention is a component capable of sequestering properties, that is a component which acts to sequester (chelate) metal ions.
  • a component capable of sequestering properties that is a component which acts to sequester (chelate) metal ions.
  • Such compound may be selected from the group consisting of a chelating component, a polycarboxylic building component and mixtures thereof.
  • Chelating components are present at a level of at least 0.001% (10ppm), preferably in amount from 0.001% (10ppm) to 0.5%, more preferably from 0.005% to 0.25%, most preferably from 0.01% to 0.1% by weight of the composition.
  • Suitable chelating components for use in the present invention are selected from the group consisting of amino carboxylic acid, organo aminophosphonic acid compounds, and mixture thereof.
  • Chelating components which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • any salts/complexes are water soluble.
  • the molar ratio of said counter cation to the chelating component is preferably at least 1:1.
  • Suitable chelating components for use herein include the amino carboxylic acids such as ethylenediamine-N,N'-disuccinic acid (EDDS), ethylenediamine tetraacetic acid (EDTA), N-hydroxyethylenediamine triacetic acid, nitrilotriacetic acid (NTA), ethylene diamine tetrapropionic acid, ethylenediamine-N,N'-diglutamic acid, 2-hydroxypropylenediamine-N,N'-disuccinic acid, triethylenetetraamine hexacetic acid, diethylenetriamine pentaacetic acid (DETPA), trans 1,2 diaminocyclohexane-N,N,N',N'-tetraacetic acid or ethanoldiglycine.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • EDTA ethylenediamine tetraacetic acid
  • NTA nitrilotriacetic acid
  • Suitable chelating components for use herein include ethylenediamine tetrakis (methylenephosphonic acid), diethylene triamine-N,N,N',N",N"-pentakis (methylene phosphonic acid) (DETMP), 1-hydroxyethane 1,1-diphosphonic acid (HEDP) or hydroxyethane dimethylenephosphonic acid.
  • methylenephosphonic acid diethylene triamine-N,N,N',N",N"-pentakis
  • HEDP 1-hydroxyethane 1,1-diphosphonic acid
  • dimethylenephosphonic acid hydroxyethane dimethylenephosphonic acid
  • ethylenediamine-N,N'-disuccinic add most preferably present in the form of its S,S isomer, which is preferred for its biodegradability profile.
  • Polycarboxylic building components are present at a level of at least 0.01% (10ppm), typically at a level of at least 0.045% (450ppm), preferably at a level of from 0.045% to 0.5%, more preferably from 0.09% to 0.25%, most preferably from 0.1% to 0.2% by weight of the composition.
  • Suitable polycarboxylic building components for use herein can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Polycarboxylic acids containing two carboxy groups include succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylic acid and the sulfinyl carboxylic acids.
  • Polycarboxylic acids containing three carboxy groups include, in particular, citric acid, aconitric and citraconic as well as succinic derivatives such as the carboxymethyloxysuccinic described in British Patent No. 1,379,24I, lactoxysuccinic described in British Patent No.
  • Polycarboxylic containing four carboxy groups include oxydisuccinic disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylic, 1,1,3,3-propane tetracarboxylic and 1,1,2,3-propane tetracarboxylic.
  • Polycarboxylic containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citric described in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylic include cyclopentane-cis,cis,cis-tetracarboxylic, cyclopentadienide pentacarboxylic, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylic, 2,5-tetrahydrofuran - cis - dicarboxylic, 2,2,5,5-tetrahydrofuran - tetracarboxylic, 1,2,3,4,5,6-hexane - hexacarboxylic and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylic include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343. Although suitable for use, citric acid is less preferred for the purpose of the invention.
  • the preferred polycarboxylic are carboxylic containing up to three carboxy groups per molecule, more particularly maleic acid.
  • Suitable liquid carriers for the present invention are selected from the group consisting of 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 50%, most preferably at least 60%, 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.
  • Surfactant concentration aids may also optionally be used.
  • Surfactant concentration aids are typically selected from the group consisting of single long chain alkyl cationic surfactants, nonionic surfactants, amine oxides, fatty acids, and mixtures thereof, typically used at a level of from 0 to 15% 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 este
  • 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 the group consisting of R and R 2 as defined hereinbefore for the single-long-chain cationic surfactant with only one being R 2 .
  • 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.
  • Nonionic Surfactant Alkoxylated Materials
  • Suitable nonionic surfactants for use herein include addition products of ethylene oxide and, optionally, propylene oxide, with fatty alcohols, fatty acids, fatty amines, etc.
  • 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 the group consisting of 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 from 8 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 at least 8, preferably at least 10-11.
  • nonionic surfactants herein are characterized by an HLB (hydrophiliclipophilic balance) of from 7 to 20, preferably from 8 to 15.
  • nonionic surfactants examples include buthionic surfactants
  • 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 the group consisting of 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.
  • Suitable fatty acids include those containing from 12 to 25, preferably from 16 to 20 total carbon atoms, with the fatty moiety containing from 10 to 22, preferably from 15 to 17 (mid cut), carbon atoms.
  • composition of the invention may also optionally comprise one or more electrolytes. It has been found that where electrolytes concentration aids were added to diluted softening compositions comprising thickeners but no sequestering component, the problem of phase and viscosity instability upon storage was increased. Surprisingly, compositions according to the invention allow the use of electrolytes concentration aids and still exhibit excellent phase and viscosity stability upon storage.
  • Electrolyte concentration aids e.g. inorganic viscosity control agents, which can also act like or augment the effect of the surfactant concentration aids, include water-soluble, ionizable salts. These inorganic viscosity control agents 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., potassium chloride, 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 20,000 parts per million (ppm), preferably from 20 to 11,000 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.
  • alkylene polyammonium salts include I-lysine monohydrochloride and 1,5-diammonium 2-methyl pentane dihydrochloride.
  • stabilisers such as well-known antioxidants and reductive agents, Soil Release Polymers, emulsifiers, bacteriocides, colorants, perfumes, preservatives, optical brighteners, anti ionisation agents, antifoam agents and enzymes.
  • sensitive ingredients such as perfumes or enzymes can be isolated from their hostile environment by reversibly absorbing said compounds into a porous hydrophobic material.
  • the porous hydrophobic material serves as a "cage" wherein the sensitive ingredient is enclosed.
  • the pores of the filled hydrophobic porous material are sealed by dispersing said porous material into a hydrophobic liquid.
  • the hydrophobic liquid acts as a "shell", thereby protecting the sensitive ingredient from its environment, reducing the loss of activity which could be encountered in hostile environment and without reducing the ability of the sensitive ingredient to perform its normal function.
  • Exemplary disclosure of this "shell and cage” system can be found in EP-A-0,583,512.
  • composition 1 Composition 2 DEQA 20 18 Hydrochloric acid 0.02 0.02 Fatty acid - 1.0 Perfume 1.0 - Electrolyte 0.20 0.06 Silicon antifoam 0.01 0.01 Dye 0.005 - Polyethylene Glycol 4000 1.0 0.60 Water and minors to balance to 100
  • compositions were made according to a known process for preparing fabric softener compositions, e.g by injection into the hot water seat (60°-70°) containing minors the molten DEQA, followed by slowly adding the electrolyte to the desired viscosity and thereafter the perfume before leaving the product to cool.
  • composition 1 was thereafter diluted 4 times and a thickener as defined below under (5) was added while the product of composition 2 was diluted 2 times and the thickener BP7050TM ex BP Chemicals was added.
  • the resulting diluted fabric softener composition exhibited excellent viscosity and phase stability on a freshly made product as well as upon storage.
  • composition 3 Composition 4
  • Composition 1 25 50 Hydrochloric acid - - maleic acid 1200ppm - DETMP - 750ppm thickener 0.25 - BP7050TM - 0.3 Dye - 7.5ppm perfume - 2.0 Water up to 100 up to 100

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Claims (14)

  1. Flüssige Textilweichmacherzusammensetzung, umfassend:
    a) 0,01 bis 10 Gew.-% einer Textilweichmacherkomponente,
    b) mindestens 0,001% eines Verdickungsmittels, ausgewählt aus der Gruppe, bestehend aus:
    i) assoziativen Polymeren mit einem hydrophilen Grundgerüst und mindestens zwei hydrophoben Gruppen pro Molekül, angebracht an das hydrophile Grundgerüst,
    ii) vernetzten kationischen Polymeren, welche ableitbar sind aus einem wasserlöslichen, kationischen, ethylenisch ungesättigten Monomer oder einer Mischung aus Monomeren, welche vernetzt sind durch 5 bis 45 ppm eines Vernetzungsmittels, umfassend polyethylenische Funktionen, und
    iii) Mischungen davon,
    c) eine Komponente, fähig zur Maskierung von Metallionen und ausgewählt aus der Gruppe, bestehend aus:
    i) Komplexbildnern, ausgewählt aus der Gruppe, bestehend aus Aminocarbonsäuren, Organoaminophosphonsäurekomponenten, und Mischungen davon,
    ii) Polycarbonsäure-Builderkomponenten, andere als die unter i) als Komplexbildner definierten, umfassend mindestens zwei Carbonsäurereste, getrennt voneinander durch nicht mehr als zwei Kohlenstoffatome, und,
    iii) Mischungen davon.
  2. Textilweichmacherzusammensetzung nach Anspruch 1, wobei genannte Komponente, welche fähig ist Metallionen zu maskieren, eine Komplexbildnerkomponente ist, ausgewählt aus der Gruppe, bestehend aus Aminocarbonsäure, Organoaminophosphonsäureverbindungen, und Mischungen davon.
  3. Textilweichmacherzusammensetzung nach Anspruch 2, wobei genannte Komplexbildnerkomponente eine Aminocarbonsäure ist, ausgewählt aus der Gruppe, bestehend Ethylendiamin-N,N'-dibernsteinsäure, Ethylendlamintetraessigsäure, N-Hydroxyethylendiamintriessigsäure, Nitrilotriessigsäure. Ethylendiamintetrapropansäure, Ethylendiamin-N,N'-diglutaminsäure, 2-Hydroxypropylendiamin-N,N'-dibernsteinsäure, Triethylentetraaminhexaessigsäure, Diethylentriaminpentaessigsäure, trans-1,2-Diamincyclohexan-N,N,N',N"-tetraessigsäure, Ethanoldiglycin und Mischungen davon, vorzugsweise Ethylendiamin-N,N'-dibernsteinsäure.
  4. Textilweichmacherzusammensetzung nach Anspruch 2, wobei genannte Komplexbildnerkomponente ausgewählt ist aus der Gruppe, bestehend aus Ethylendiamintetrakis (methylenphosphonsäure), Diethylentriamin-N,N,N',N",N"-pentakis (methylenphosphonsäure), 1-Hydroxyethan-1,1-diphosphonsäure, Hydroxyethandimethylenphosphonsäure und Mischungen davon, vorzugsweise 1-Hydroxyethan-1,1-diphosphonsäure.
  5. Textilweichmacherzusammensetzung nach irgendeinem der Ansprüche 1-4, wobei genannte Komplexbildnerkomponente mindestens in einer Menge von 10 ppm vorliegt.
  6. Textilweichmacherzusammensetzung nach Anspruch 1, wobei genannte Komponente, welche fähig ist Metallionen zu maskieren, eine Polycarbonsäure-Bullderkomponente ist, ausgewählt aus der Gruppe, bestehend aus Polycarbonsäuren, enthaltend zwei Carboxylgruppen, Polycarbonsäuren, enthaltend drei Carboxylgruppen, Polycarbonsäuren, enthaltend vier Carboxylgruppen, allcyclische und heterocyclische Polycarbonsäuren, aromatische Polycarbonsäuren und Mischungen davon.
  7. Textilweichmacherzusammensetzung nach Anspruch 6, wobei genannte Polycarbonsäure-Builderkomponente ausgewählt ist aus der Gruppe, bestehend aus Bernsteinsäure, Malonsäure, (Ethylendloxy)diesslgsäure, Maleinsäure. Diglykolsäure, Weinsäure, Tartronsäure, Fumarsäure, Ethercarbonsäuren, Sulfinylcarbonsäuren, Citronensäure, Aconitsäure. Citraconsäure, Bernsteinsäurederivaten. Oxypolycarbonsäurematerialien, Oxydibernsteinsäure, 1,1,2,2-Ethantetracarbonsäure, 1,1,3,3-Propantetracarbonsäure, 1,1,2,3-Propantetracarbonsäuren, Sulfosuccinatderivaten, Cyclopentan-cis,cis,cis-tetracarbonsäure, Cyclopentadienpentacarbonsäuren, 2,3,4,5-Tetrahydrofuran-cis,cis,cis-tetracarbonsäure, 2,5-Tetrahydrofuran-cis-dicarbonsäure, 2,2,5,5-Tetrahydrofuran-tetracarbonsäure, 1,2,3,4,5,6-Hexanhexacarbonsäure und Carboxymethylderivaten mehrwertiger Alkohole, Mellitsäure, Pyromellitsäure und Phthalsäurederivaten und Mischungen davon, vorzugsweise Maleinsäure.
  8. Textilweichmacherzusammensetzung nach den Ansprüchen 6 oder 7, wobei genannte Polycarbonsäure-Builderkomponente mindestens in einer Menge von 100 ppm vorliegt.
  9. Textilweichmacherzusammensetzung nach Anspruch 8, wobei genannte Polycarbonsäure-Builderkomponente mindestens in einer Menge von 450 ppm vorliegt.
  10. Textilweichmacherzusammensetzung nach irgendeinem der Ansprüche 1-9, wobei genanntes assoziatives Verdickungsmittel ausgewählt ist aus der Gruppe, bestehend aus Copolymeren von Ethylenoxid und/oder Propylenoxid mit geringen Mengen von C8-C24-Seitenketten, hydrophobisch modifizierten Poly(ethylenoxid und/oder Propylenoxid/Urethanen), Alkyl-substituierte Poly(vinyl)alkoholen, hydrophobisch modifizierten Polyacrylsäurepolymeren und Mischungen davon.
  11. Textilweichmacherzusammensetzung nach irgendeinem der Ansprüche 1-9, wobei genanntes vernetztes Verdickungsmittel ableitbar ist aus Monomeren, umfassend Acrylsäuremonomere.
  12. Textilweichmacherzusammensetzung nach irgendeinem der Ansprüche 1-11, wobei genannter Textilweichmacher ausgewählt ist aus der Gruppe, bestehend aus kationischen, nichtionischen, amphoteren oder anionschen Textilweichmachermaterialien.
  13. Textilweichmacherzusammensetzung nach Anspruch 12, wobei genannter Textilweichmacher ein kationisches, bioabbaubares Textilweichmachermaterial ist.
  14. Textilweichmacherzusammensetzung nach irgendeinem der Ansprüche 1-13, wobei genannte Zusammensetzung weiterhin eine oder mehrere Elektrolytkomponenten umfasst.
EP96870041A 1996-04-01 1996-04-01 Textilweichmacherzusammensetzungen Expired - Lifetime EP0799887B1 (de)

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Application Number Priority Date Filing Date Title
EP96870041A EP0799887B1 (de) 1996-04-01 1996-04-01 Textilweichmacherzusammensetzungen
CN97195086A CN1220694A (zh) 1996-04-01 1997-03-27 织物柔软剂组合物
US09/155,776 US6020304A (en) 1996-04-01 1997-03-27 Fabric softener compositions
PCT/US1997/005107 WO1997036981A1 (en) 1996-04-01 1997-03-27 Fabric softener compositions
BR9710451A BR9710451A (pt) 1996-04-01 1997-03-27 Composi-Æo amaciante de pano
CA002250909A CA2250909C (en) 1996-04-01 1997-03-27 Fabric softener compositions
AU25951/97A AU2595197A (en) 1996-04-01 1997-03-27 Fabric softener compositions
PH56016A PH11997056016B1 (en) 1996-04-01 1997-03-31 Fabric softener compositions
ZA9702774A ZA972774B (en) 1996-04-01 1997-04-01 Fabric softener compositions.
ARP970101300A AR006473A1 (es) 1996-04-01 1997-04-01 Composiciones liquidas suavizantes de tela
MX9808114A MX204196B (en) 1996-04-01 1998-10-01 Fabric softener compositions

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US6939844B2 (en) 1996-09-19 2005-09-06 The Procter & Gamble Company Concentrated, preferably biodegradable, quaternary ammonium fabric softener compositions containing cationic polymers and process for preparation
US7135451B2 (en) 2003-03-25 2006-11-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
US7973004B2 (en) 2009-02-12 2011-07-05 Hercules Incorporated Rheology modifier for aqueous surfactant-based formulations
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JP5385602B2 (ja) * 2007-12-14 2014-01-08 アイシン・エィ・ダブリュ株式会社 洗浄組成物
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US6939844B2 (en) 1996-09-19 2005-09-06 The Procter & Gamble Company Concentrated, preferably biodegradable, quaternary ammonium fabric softener compositions containing cationic polymers and process for preparation
US7135451B2 (en) 2003-03-25 2006-11-14 The Procter & Gamble Company Fabric care compositions comprising cationic starch
US7973004B2 (en) 2009-02-12 2011-07-05 Hercules Incorporated Rheology modifier for aqueous surfactant-based formulations
WO2023170124A1 (en) * 2022-03-10 2023-09-14 Unilever Ip Holdings B.V. Concentrated fabric conditioner

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MX9808114A (en) 1999-02-28
CA2250909C (en) 2002-10-01
CA2250909A1 (en) 1997-10-09
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