EP0458599B1 - Textilbehandlungsmittel - Google Patents

Textilbehandlungsmittel Download PDF

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Publication number
EP0458599B1
EP0458599B1 EP91304603A EP91304603A EP0458599B1 EP 0458599 B1 EP0458599 B1 EP 0458599B1 EP 91304603 A EP91304603 A EP 91304603A EP 91304603 A EP91304603 A EP 91304603A EP 0458599 B1 EP0458599 B1 EP 0458599B1
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EP
European Patent Office
Prior art keywords
fabric
treatment composition
polymer
fabric treatment
compositions
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EP91304603A
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English (en)
French (fr)
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EP0458599A2 (de
EP0458599B2 (de
EP0458599A3 (en
Inventor
Martin Alan Smith
Edwin Willis
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • the present invention relates to fabric treatment compositions in aqueous medium and containing a relatively high proportion of fabric conditioner.
  • the present invention relates to fabric treatment compositions which comprise as conditioners one or more fabric-softening materials and one or more emulsion forming components to result in a structure of a dispersion of an emulsion and a dispersion of lamellar droplets in a continuous aqueous phase.
  • Lamellar droplets are a particular class of surfactant structures which, inter alia , are already known from a variety of references, e.g. H.A.Barnes, 'Detergents', Ch.2. in K.Walters (Ed), 'Rheometry: Industrial Applications', J.Wiley & Sons, Letchworth 1980.
  • Lamellar fabric-softening compositions are for example known from EP 303 473 (Albright and Wilson). This patent application describes fabric-softening compositions comprising an aqueous base, a cationic fabric softener having two long alkyl or alkenyl groups and dissolved electrolyte to form an optically anisotropic spherulitic composition.
  • lamellar droplets in a fabric-softening product may be detected my means known to those skilled in the art, for example optical techniques, various rheometrical measurements, X-ray or neutron diffraction, and electron microscopy.
  • the droplets consist of an onion-like configuration of concentric bi-layers of molecules of fabric-softening material, between which is trapped water or electrolyte solution (aqueous phase).
  • Systems in which such droplets are nearly or fully close-packed provide a very desirable combination of physical stability and useful flow properties.
  • the viscosity and stability of the fabric softening composition There are two main factors determining the viscosity and stability of the fabric softening composition, the combined volume fraction of the dispersed lamellar phase and the emulsion and their state of aggregation. Generally speaking, the higher the volume fraction of the dispersed lamellar phase (droplets) and emulsion phase (particles), the higher the viscosity which in the limit can result in an unpourable or gelled product. When the volume fraction is around 0.6, or higher, the droplets are just touching (space-filling). This allows reasonable stability with an acceptable viscosity (say no more than 2.5 Pas, preferably no more than 1 Pas most preferably no more than 0.5Pas at a shear rate of 21s -1 ).
  • flocculation of the particles can also occur.
  • the lamellar dispersion can cause depletion flocculation of the emulsion component.
  • Flocculation of either the lamellar dispersion or the emulsion can lead to instability because reduction of the inter-particle inter-droplet spacings will make their packing more efficient. Consequently, more lamellar droplets or emulsion will be required for stabilisation which will again lead to a further increase of the viscosity.
  • the volume fraction of the droplets is increased by increasing the softener concentration, and may be reduced by increasing the electrolyte level.
  • the stability of the emulsion component is very sensitive to electrolyte levels. When electrolyte is added to an emulsion it reduces the effects of depletion but the levels required to prevent depletion are sufficient to cause flocculation of the emulsion by an electrostatic mechanism and thus the problem is not solved.
  • the present invention relates to a fabric treatment composition
  • a fabric treatment composition comprising an aqueous base, one or more fabric-softening materials, and an emulsion component, said composition having a structure of lamellar droplets of the fabric-softening material in combination with an emulsion, said composition also comprising a deflocculating polymer comprising a hydrophilic backbone and one or more hydrophobic side chains.
  • the deflocculating polymer allows, if desired, the incorporation of greater amounts of softening materials and/or emulsion components than would otherwise be compatible with the need for a stable, easily dispersable product of acceptable viscosity. It also allows (if desired) incorporation of greater amounts of certain other ingredients to which lamellar dispersions and emulsions have been highly stability-sensitive.
  • the present invention allows formulation of stable, pourable products wherein the volume fraction of the lamellar droplets and the emulsion is 0.5 or higher.
  • the volume fraction of the lamellar droplet phase and emulsion component may be determined by the following method.
  • the composition is centrifuged, say at 40,000 G for 12 hours, to separate the composition into a clear (continuous aqueous) layer, a turbid active-rich (lamellar/emulsion) layer and (if solids or liquids are suspended) a third layer.
  • the conductivity of the continuous aqueous phase, the lamellar phase and of the total composition before centrifugation are measured. From these, the volume fraction of the lamellar phase and emulsion component is calculated or estimated, using the Bruggeman equation, as disclosed in American Physics, 24 , 636 (1935).
  • the volume fraction of the emulsion component can be calculated if desired, provided the density is known and the volume fraction of the lamellar phase calculated.
  • the viscosity of the aqueous continuous phase is less than 25mPas, most preferably less than 15mPas, especially less than 10mPas, these viscosities being measured using a capillary viscometer, for example an Ostwald viscometer.
  • the term 'deflocculating' in respect of the polymer means that the equivalent composition, minus the polymer, has a significantly higher viscosity and/or becomes unstable. It is not intended to embrace the use of polymers which would increase the viscosity but not enhance the stability of the composition. It is also not intended to embrace polymers which would lower the viscosity simply by a dilution effect, i.e. only by adding to the volume of the continuous phase.
  • relatively high levels of the deflocculating polymers can be used in those systems where a viscosity reduction is brought about; typically levels as low as from about 0.01% by weight to about 5.0% by weight can be capable of reducing the viscosity at 21 s -1 by up to 2 orders of magnitude.
  • Especially preferred embodiments of the present invention exhibit less phase separation on storage and have a lower viscosity than an equivalent composition without any of the deflocculating polymer.
  • stability for these systems can be defined in terms of the maximum separation compatible with most manufacturing and retail requirements. That is, the 'stable' compositions will yield no more than 2% by volume phase separation as evidenced by appearance of 2 or more separate phases when stored at 25°C for 21 days from the time of preparation.
  • such systems may be stable or unstable, according to whether or not the droplets or particles are flocculated.
  • the degree of phase separation may be relatively small, e.g. as for the unstable non-flocculated systems with the lower volume fraction.
  • the phase separation will often not manifest itself by the appearance of a distinct layer of continuous phase but will appear distributed as 'cracks' throughout the product. The onset of these cracks appearing and the volume of the material they contain are almost impossible to measure to a very high degree of accuracy.
  • Especially preferred embodiments of the present invention yield less than 0.1% by volume visible phase separation after storage at 25°C for 21 days from the time of preparation.
  • compositions according to the invention may contain only one, or a mixture of deflocculating polymer types.
  • the term 'polymer types' is used because, in practice, nearly all polymer samples will have a spectrum of structures and molecular weights and often impurities.
  • any structure of deflocculation polymers described in this specification refers to polymers which are believed to be effective for deflocculation purposes as defined hereabove. In practice these effective polymers may constitute only part of the polymer sample, provided that the amount of deflocculation polymer in total is sufficient to effect the desired deflocculation effects.
  • any structure described herein for an individual polymer type refers to the structure of the predominating deflocculating polymer species and the molecular weight specified is the weight average molecular weight of the deflocculation polymers.
  • Suitable deflocculating polymer types for use in compositions of the invention are for instance described in our copending European patent application EP-A-0 346 995 and in our copending patent applications EP-A-0 498 806, EP-A-0 499 623, and GB-A-2 237 813.
  • a preferred class of polymers are biodegradeable polymers having a hydrophilic backbone and at least one hydrophobic side chain.
  • the basic structure of polymers having a hydrophilic backbone and one or more hydrophobic side chains is described in EP-A-0 346 995.
  • the hydrophilic backbone of the polymer generally is a linear, branched or cross-linked molecular composition containing one or more types of relatively hydrophilic monomer units, possibly in combination with minor amounts of relatively hydrophobic units.
  • the only limitations to the structure of the hydrophilic backbone are that the polymer must be suitable for incorporation in an active-structured aqueous liquid softener composition and the hydrophilic backbone is relatively soluble in water in that the solubility in water of 20°C at a pH of 7.0 is preferably more than 1 g/l, more preferably more than 5 g/l, most preferably more than 10 g/l.
  • the hydrophilic backbone is predominantly linear in that the main chain of the backbone constitutes at least 50% by weight, preferably more than 75%, most preferably more than 90% by weight of the backbone.
  • the hydrophilic backbone is constituted by monomer units, which can be selected from a variety of units available for the preparation of polymers.
  • the polymers can be linked by any possible chemical link, although the following types of linkages are preferred:
  • Water-soluble monomers suitably employed to form the hydrophilic backbone are for example those which are sufficiently water-soluble to form at least a one weight percent solution when dissolved in water and readily undergo polymerisation to form polymers which are water-soluble at ambient temperature and at a pH of 3.0 to 12.5, preferably more than 1 gram per litre, more preferably more than 5 grams per litre, most preferably more than 10 grams per litre.
  • Exemplary water-soluble monomers include ethylenically unsaturated amides such as acrylamide, methacrylamide and fumaramide and their N-substituted derivatives such as 2-acrylamido-2-methylpropane sulphonic acid, N-(dimethylaminomethyl) acrylamide as well as N-(trimethylammoniummethyl) acrylamide chloride and N-(trimethylammoniumpropyl) methacrylamide chloride; ethylenically unsaturated carboxylic acids or dicarboxylic acids such as acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and citroconic acid; and other ethylenically unsaturated quaternary ammonium compounds such as vinylbenzyl trimethyl ammonium chloride; sulphoalkyl esters of unsaturated carboxylic acids such as 2 sulphoethyl methacrylate; aminoalkyl est
  • the hydrophilic backbone may contain small amounts of relatively hydrophobic units, e.g. those derived from polymers having a solubility of less than 1 g/l in water, provided that the overall solubility of the hydrophilic polymer backbone still satisfies the solubility requirements as specified here above.
  • relatively water-insoluble polymers are polyvinyl acetate, polymethyl methacrylate, polyethyl acrylate, polyethylene, polypropylene, polystyrene, polybutylene oxide, polypropylene oxide, polyhydroxypropyl acrylate.
  • Suitable hydrophobic monomers for forming the side chains generally include those which are (1) water-insoluble, i.e. less than 0.2 weight part of the hydrophobic monomer will dissolve in 100 weight parts water and (2) ethylenically unsaturated compounds having hydrophobic moieties.
  • the hydrophobic moieties (when isolated from their polymerisable linkage) are relatively water-insoluble, preferably less than 1 g/l, more preferably less than 0.5 g/l, most preferably less than 0.1 g/l at ambient temperature and a pH of 3.0 to 12.5.
  • the hydrophobic moieties preferably have at least 3 carbon atoms and are most preferably pendant organic groups having hydrophobicities comparable to one of the following: aliphatic hydrogen groups having at least three carbons such as C 3 to C 50 alkyls and cycloalkyls; polynuclear aromatic hydrocarbon groups such as napthyls; alkylaryls wherein the alkyl groups has one or more carbons; haloalkyls of 3 or more carbons, preferably perfluoroalkyls; polyalkyleneoxy groups wherein alkylene is propylene or high alkylene and there is at least one alkyleneoxy unit per hydrophobic moiety; and siloxane moieties.
  • Exemplary hydrophobic monomers include butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and the corresponding methacrylates, the higher alkyl esters of alpha, beta-ethylenically unsaturated carboxylic acids such as dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl, methacrylate, tetradeculacrylate, octadecyl acrylate, octadecyl methacrylate, octyl half ester of maleic anhydride, doictyl diethyl maleate, and other alkyl esters and half esters derived from the reactions of alkanols having from 3 to 50 carbon atoms with ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid and aconitic
  • the hydrophobic monomer may be used singly or mixtures thereof may be employed.
  • the ratio of hydrophilic to hydrophobic monomers may vary from about 500:1 to 5:1.
  • the weight average molecular weights (Mw.) of the resultant polymers vary from 500 to 500,000 when measured by gel permeation chromatography using a polyacrylate standard, or by specific viscosity (SV) measurements using a polyacrylate standard.
  • Products of the invention preferably comprise polymers of the general formula: wherein z is 1; (x+y):z is from 4:1 to 1,000:1; preferably from 6:1 to 250:1 in which the monomer units may be in random order; y being from 0 up to a maximum equal to the value of x; and n is at least 1;
  • Each B 1 is independently selected from -CH 2 OH, -OH or -H.
  • Another class of polymers in accordance with the present invention comprises those of formula II: wherein:
  • the salts of the polymers of formulae I and II may be formed with any organic or inorganic cation defined for A 1 -A 4 and which is capable of forming a water-soluble salt with a low molecular weight carboxylic acid.
  • Preferred are the alkali metal salts, especially of sodium or potassium.
  • Another class of polymers in accordance with the present invention comprises those of formula III: wherein Q 3 is derived from a monomeric unit IIIa comprising: Q 4 is derived from the molecular entity IIIb: and Q 5 is derived from a monomeric unit IIIc:
  • the anions represented by B 1 , B 2 , B 3 , B 4 are exemplified by the halide ions, sulphate, sulphonate, phosphate, hydroxide, borate, cyanide, carbonate, bicarbonate, thiocyanate, sulphide, cyanate, acetate and the other common inorganic and organic ions.
  • Preferred anions are chloride and methosulphate.
  • Another class of polymers in accordance with the present invention comprise those of formula IV where R 1 -R 6 are defined as in formula I, z is 1 and j:z is from 5:1 to 500:1, in which the monomer units may be in random order, and n is at least 1;
  • polysaccharides are hydrophobically modified polysaccharides.
  • Possible sugar units for use in those polymers include glucosides and fructosides for example maltoses, fructoses, lactoses, glucoses and galactoses.
  • mixtures of sugar groups may be used.
  • the sugar groups may be connected to each other via any suitable linkage, although 1-4 linkages and/or 1-6 linkages are preferred.
  • the polysaccharides are preferably predominantly linear, but also branched polymers may be used.
  • An example of a preferred polysaccharide has the following formula: Wherein:
  • a weigth average molecular weight in the region of from 500 to 500,000, preferably from 1000 to 200,000 more preferably from 1500 to 50,000, even more preferably from 3,000 to 6,000 when measured by GPC using polyacrylate standards.
  • the molecular weights of the standards are measured by the absolute intrinsic viscosity method described by Noda, Tsoge and Nagasawa in Journal of Physical Chemistry, Volume 74, (1970), pages 710-719.
  • a measure of molecular weight can be made by measuring a standard viscosity (S.V.), determined at 15.0% solids, 23°C in a 1.0 molar sodium chloride solution using a Brookfield Synchro-lectric (R) viscometer, Model LVT with an LCP adaptor, at a speed of 60 RPM. It is preferred to have a polymer with an S.V. from 1 to 100 mPas, more preferably from 2-50 mPas, most preferably 3-25 mPas.
  • Polymers according to formulas V-VII preferably have a molecular weight of 500-250,000, more preferably from 2,000 to 50,000, even more preferably from 3,000 to 6,000.
  • polymers for use in compositions of the present invention are prepared by the method as described in UK Patent application No. 8813966.2 (EP-A-0 346 834).
  • the deflocculating polymer will be used at from 0.01% to 5.0% by weight in the composition, preferably from 0.02 to 2.0%, most preferably from 0.03 to 1%.
  • Compositions of the present invention preferably comprise from 1 to 80%, by weight of fabric-softening materials, more preferably from 2 to 70% by weight, most preferably from 5 to 50% by weight of the composition.
  • the fabric softening materials may be selected from cationic, nonionic, amphoteric or anionic fabric softening material.
  • Suitable amphoteric fabric-conditioning materials for use in a composition according to the invention are fabric-substantive amphoteric materials forming a particulate dispersion at a concentration of less than 1 g/l at at least one temperature between 0 and 100°C, preferably at least one temperature between 10 and 90°C, more preferably between 20 and 80°C.
  • a fabric-substantive amphoteric material is preferably an amphoteric or zwitterionic tertiary or quaternary ammonium compound having either one single long hydrocarbyl side chain or two long hydrocarbyl chains. From these compounds the use of amphoteric or zwitterionic ammonium compounds having two long hydrocarbyl chains is particularly preferred for many reasons including costs, ease of processing and better stability and performance.
  • Suitable amphoteric materials are for example disclosed in EP 236 213.
  • hydrocarbyl chain refers to linear or branched alkyl or alkenyl chains optionally substituted or interrupted by functional groups such as -OH, -O-, -CONH-, -COO-.
  • amphoteric fabric-substantive materials are water insoluble and have a solubility in water at pH 2.5 at 20°C of less than 10 g/l.
  • the HLB of the amphoteric fabric-substantive material is preferably less than 10.0.
  • Suitable cationic fabric-softener materials for use in a composition according to the present invention are cationic materials which are water-insoluble in that the material has a solubility in water at pH 2.5 and 20°C of less than 10 g/l.
  • Highly preferred materials are cationic quaternary ammonium salts having two C 12 -C 24 hydrocarbyl chains.
  • R 1 and R 2 represent hydrocarbyl groups from about 12 to about 24 carbon atoms
  • R 3 and R 4 represent hydrocarbyl groups containing from 1 to about 4 carbon atoms
  • X is an anion, preferably selected from halide, methosulphate and ethyl sulphate radicals.
  • quaternary softeners include ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulphate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulphate; dihexadecyl diethyl ammonium chloride; di(coconut) dimethyl ammonium chloride.
  • ditallow dimethyl ammonium chloride, di(hydrogenated tallow) dimethyl ammonium chloride, di(coconut) dimethyl ammonium chloride and di(coconut) dimethyl ammonium methosulphate are preferred.
  • Suitable materials also include dialkyl ethoxyl methyl ammonium methosulphate based on soft fatty acid, dialkyl ethoxyl methyl ammonium methosulphate based on hard fatty acid, and a material in which R 3 and R 4 represent methyl, R 1 is C 13-15 , R 2 is CH 2 CH 2 OCOR, where R is stearyl, and X is methosulphate.
  • Ditallow dimethyl ammonium chloride, di(hydrogenated tallow alkyl) dimethyl ammonium chloride, di(coconut alkyl) dimethyl ammonium chloride and di(coconut alkyl) dimethyl ammonium methosulfate are preferred.
  • R 5 being tallow, which is available from Stepan under the tradename Stepantex VRH 90, and wherein R 8 , R 9 and R 10 are each alkyl or hydroxyalkyl groups containing from 1 to 4 carbon atoms, or a benzyl group.
  • R 6 and R 7 are each an alkyl or alkenyl chain containing from 11 to 23 carbon atoms, and X - is a water-soluble anion.
  • hydrocarbylimidazolinium salts believed to have the formula: wherein R 13 is a hydrocarbyl group containing from 1 to 4, preferably 1 or 2 carbon atoms, R 11 is a hydrocarbyl group containing from 8 to 25 carbon atoms, R 14 is an hydrocarbyl group containing from 8 to 25 carbon atoms and R 12 is hydrogen or an hydrocarbyl containing from 1 to 4 carbon atoms and A - is an anion, preferably a halide, methosulphate or ethosulphate.
  • Preferred imidazolinium salts include 1-methyl-1-(tallowylamido-) ethyl -2-tallowyl- 4,5-dihydro imidazolinium methosulphate and 1-methyl-1-(palmitoylamido) ethyl -2-octadecyl-4, 5- dihydro-imidazolinium chloride.
  • Other useful imidazolinium materials are 2-heptadecyl-1-methyl-1- (2-stearylamido)-ethyl-imidazolinium chloride and 2-lauryl-1-hydroxyethyl-1-oleyl-imidazolinium chloride.
  • Also suitable herein are the imidazolinium fabric-softening components of US patent No. 4 127 489.
  • Representative commercially available materials of the above classes are the quaternary ammonium compounds Arquad 2HT (trademark of Akzo); Noramium M2SH (trademark of CECA); Aliquat-2HT (trademark of General Mills, Inc), Stepantex Q185 (trademark of Stepan); Stepantex VP85 (trademark of Stepan); Stepantex VRH90 (trademark of Stepan); Synprolam FS (trademark of ICI) and the imadazolinium compounds Varisoft 475 (trademark of Sherex Company, Columbus Ohio) and Rewoquat W7500 (trademark of REWO).
  • compositions according to the invention may also contain, possibly in addition to the above mentioned softening agents, one or more amine softening materials.
  • R 15 is a C 6 to C 24 , hydrocarbyl group
  • R 16 is a C 1 to C 24 hydrocarbyl group
  • R 17 is a C 1 to C 10 hydrocarbyl group.
  • Suitable amines include those materials from which the quaternary ammonium compounds disclosed above are derived, in which R 15 is R 1 , R 16 is R 2 and R 17 is R 3 .
  • the amine is such that both R 15 and R 16 are C 6 -C 20 alkyl with C 16 -C 18 being most preferred and with R 17 as C 1-3 alkyl, or R 15 is an alkyl or alkenyl group with at least 22 carbon atoms and R 16 and R 17 are C 1-3 alkyl.
  • these amines are protonated with hydrochloric acid, orthophosphoric acid (OPA), C 1-5 carboxylic acids or any other similar acids, for use in the fabric-conditioning compositions of the invention.
  • R 18 is a C 6 to C 24 hydrocarbyl group
  • R 19 is an alkoxylated group of formula - (CH 2 CH 2 O) y H, where y is within the range from 0 to 6
  • R 20 is an alkoxylated group of formula -(CH 2 CH 2 O) z H where z is within the range from 0 to 6, and m is an integer within the range from 0 to 6, and is preferably 3.
  • m it is preferred that R 18 is a C 16 to C 22 alkyl and that the sum total of z and y is within the range from 1 to 6, more preferably 1 to 3.
  • m is 1, it is preferred that R 18 is a C 16 to C 22 alkyl and that the sum total of x and y and z is within the range from 3 to 10.
  • Ethomeen (trademark of Armour) and Ethoduomeen (trademark of Armour).
  • the amines of type (ii) or (iii) are also protonated for use in the fabric-conditioning compositions of the invention.
  • amine is of type (iv) given above
  • a particularly preferred material is: where R 22 and R 23 are divalent alkenyl chains having from 1 to 3 carbon atoms, and R 24 is an acyclic aliphatic hydrocarbon chain having from 15 to 21 carbon atoms.
  • a commercially available material of this class is Ceranine HC39 (trademark of Sandoz).
  • compositions also contain an emulsion component such as hydrocarbons, perfumes, natural fats and oils, fatty acids and/or esters thereof, fatty alcohols and silicones.
  • an emulsion component such as hydrocarbons, perfumes, natural fats and oils, fatty acids and/or esters thereof, fatty alcohols and silicones.
  • paraffins and olefines but alkynes and halogenated paraffins such as myristyl chloride are not excluded.
  • Materials known generally as paraffin oil, soft paraffin wax, petroleum and petroleum jelly are especially suitable. Examples of specific materials are tetradecane, hexadecane, octadecane and octodecene.
  • Preferred perfumes are Portia 40 (trademark of IFF Ltd), LFU 384 (trademark of Quest) and Coccoon SN3000 (trademark of Givaudan).
  • Examples of natural oils are coconut, corn, olive and sunflower as well as naturally occuring waxy solids such as lanolin.
  • animal fats are butter, tallow and sardine.
  • Preferred fatty acids and esters are lauric, myristic, palmitic and stearic acids, methyl laurate, ethyl myristate, ethyl stearate, methyl palmitate and ethylene glycol monostearate.
  • fatty alcohols include decanol, dodecanol, tetradecanol, pentadecanol, hexadecanol and lauryl and palmityl alcohols.
  • estols include isopropylmyristate.
  • silicones and aminosilicones suitable for use in the invention are disclosed in DE 2 631 419 (Procter and Gamble/Dumbrell) and those supplied commercially as VP 1487E (trademark of Wacker) and the Magnasoft range (trademark of Union Carbide).
  • emulsion component is improved when the particles are positively charged.
  • a cationic fabric softener it is convenient to make the fabric treatment composition in a one-stage process where the fabric softener acts as emulsifier. When this is not possible it may be necessary to make the emulsion separately in which case a separate emulsifier may be required.
  • Suitable emulsifiers are single or di-alkyl ammonium salts, the esters of sorbitan, glycerol or polyethylene glycol and ethoxylated alcohols.
  • the levels of emulsion component in the composition is typically from 1 to 80%, by weight preferably from 2 to 70% and most preferably from 5 to 50%.
  • the compositions according to the invention may optionally contain electrolyte.
  • the level of dissolved electrolyte is typically from 0% to 0.2%, preferably 0.05 to 0.2%.
  • compositions according to the present invention preferably have a pH of less than 6.0, more preferred less than 5.0, especially from 1.5 to 4.5, most preferred from 2.0 to 4.0.
  • compositions can also contain one or more optional ingredients selected from non-aqueous solvents such as C 1 -C 4 alkanols and polyhydric alcohols, pH-buffering agents such as weak acids, e.g. phosphoric, benzoic or citric acids, re-wetting agents, viscosity modifiers, aluminium chlorohydrate, antigelling agents, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, stabilisers such as guar gum and polyethylene glycol, anti-shrinking agents, antioxidants, anti-corrosion agnets, preservatives such as Bronopol (Trade Mark), a commercially available form of 2-bromo-2-nitropropane-1,3-diol, to preserve the fabric treatment composition, dyes, bleaches and bleach precursors, drape-imparting agents, antistatic agents and ironing aids.
  • pH-buffering agents such as weak acids
  • Example I-II the following polymers were used. Each polymer was obtained from National Starch as an aqueous solution of from 30-60% by weight solids level. All percentages for the polymer refer to 100% active polymers.
  • Fabric softening compositions were made by adding the deflocculating polymer under sturring, to a preheated (70°C) mixture of the emulsion component and fabric softening material in aqueous dispersion.
  • the fabric softening material was Arquad 2HT (a dimethyl ditallow ammonium chloride) ex Atlas.
  • the emulsion component was a combination of Sirius M85 a mineral oil ex Dalton & Co., Silkolene 910 ex Dalton & Co., a petroleum jelly and optionally lanolin.
  • compositions were obtained: Component A B C D E F % by weight Arquad 2HT 4.25 4.25 4.25 4.25 9 9 Sirius M85 10.70 10.70 10.70 10.70 24 24 Silkolene 910 5.30 5.30 5.30 12 12 Lanolin 2.0 2.0 3.0 3.0 - - Polymer 433/20 - 0.13 - 0.09 - 0.1 Water - - - - - - balance -- - - - - - - - - - - - - - - - - - - - - - - - - - - - -
  • compositions B, D and F a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer.
  • compositions E and F a reduction in viscosity from 0.7 Pas to 0.3 Pas was measured at a shear rate of 21s -1 .
  • Fabric softening compositions were made according to the method of Example I.
  • the fabric softening material was either Arquad 2HT as used in Example I or Arquad 2T ex Atlas. In Arquad 2T the tallow is not hardened.
  • Component A B C D % by weight Arquad 2HT 7 7 - - Arquad 2T - - 7 7 Sirius M85 18.7 18.7 18.7 18.7
  • Silkolene 910 9.3 9.3 9.3 9.3 Polymer 435/174 - 0.27 - 0.3 Water - - - - - balance - - - - - - - - - - - Viscosity mPas 110s -1 2952 338 729 182 21s -1 14721 709 3458 404
  • Fabric softening compositions were made according to the method of Example 1 excepting that the electrolyte (when present) was added along with the polymer.
  • Component A B C D E Arquad 2HT 7 7 7 7 7 7 Sirius M85 18.7 18.7 18.7 18.7 18.7
  • Silkolene 910 9.3 9.3 9.3 9.3 Polymer 435/173 0.3 0.3 0.3 0.3 0.3 NaCl - 0.05 0.1 0.15 0.2 Water - - - - - - balance - - - - -- - - - - - Viscosity mPas 110s -1 210 65 125 160 295 21s -1 658 473 431 616 879
  • Example IIIB From comparison with Example IIA it can be seen that a reduction in viscosity from 14.7 Pas to 0.6 Pas occurs on addition of the deflocculating polymer. The addition of electrolyte (Example IIIB) then reduces this viscosity further. Continued addition of electrolyte however leads eventually to a viscosity increase.
  • a typical formulation for use as a rinse conditioner comprises: % by weight Arquad 2HT 7 Sirius M85 18.7 Silkolene 910 9.3 Lanolin 0.5 Polymer 442/25 0.04 Water to balance
  • This composition has a viscosity at 21s -1 of 0.44 Pas.
  • Fabric softening compositions were made according to the method of Example I.
  • the fabric softening material was Rewoquat W75 (a 1-methyl-1 (tallowylamido-) ethyl-2-tallowyl-4,5-dihydroimidazolinium methosulphate).
  • compositions C, D, E and F a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer.
  • composition A compared to composition D or composition B compared to compositions C, E or F.
  • Fabric softening compositions were made according to the method of Example I.
  • Component Compositions A B C D Rewoquat W75 16 16 16 Sirius M85 3 3 3 3 CaCl 2 0.01 0.01 0.01 0.01 0.01 Polymer 442/44 - 0.36 - - Polymer 442/60 - - 0.47 - Polymer 448/20 - - - 0.40 Water -------balance------- Viscosity mPas 21s -1 907 160 80 289 110s -1 282 60 37 125
  • compositions B, C and D a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer (A).
  • Fabric softening compositions were made according to the method of Example I.
  • compositions B and C a significant reduction in viscosity was observed when compared to that of the corresponding compositions without polymer (A).
  • Fabric softening compositions were made according to the method of Example I.
  • Component Composition A B C D Rewoquat W75 15 15 15 15 Octadecane 12 12 12 12 Polymer 442/44 - 0.89 - - Polymer 442/60 - - 0.36 - Polymer 448/20 - - - 0.40 Water ------balance------- Viscosity mPas 21s -1 5853 1760 1614 1891 110s -1 1016 453 482 496
  • compositions B, C and D a significant reduction in viscosity was observed when compared to that of the corresponding composition without polymer (A).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Textile Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (13)

  1. Ein Textilbehandlungsmittel, enthaltend eine wässerige Base, ein oder mehrere gewebeweichmachende Materialien und eine Emulsionskomponente, wobei das Mittel eine Struktur von lamellaren Tröpfchen des gewebeweichmachenden Materials in Kombination mit einer Emulsion aufweist, wobei das Mittel auch ein entflokkendes Polymeres umfaßt, enthaltend eine hydrophile Hauptkette und eine oder mehrere hydrophobe Seitenketten und welches ein durchschnittliches Molekulargewicht von 500 bis 500 000 aufweist, wenn unter Verwendung eines Polyacrylat-Standards durch Gel-Permeations-Chromatographie gemessen, oder durch spezifische Viskositäts-(SV)-Messungen unter Verwendung eines Polyacrylat-Standards.
  2. Ein Textilbehandlungsmittel nach Anspruch 1, worin das entflockende Polymere ein solches der allgemeinen Formel I, wie hierin definiert, ist.
  3. Ein Textilbehandlungsmittel nach Anspruch 1, worin das entflockende Polymere ein solches der allgemeinen Formel II, wie hierin definiert, ist.
  4. Ein Textilbehandlungsmittel nach Anspruch 1, worin das entflockende Polymere ein solches der allgemeinen Formel III, wie hierin definiert, ist.
  5. Ein Textilbehandlungsmittel nach Anspruch 1, worin das entflockende Polymere ein solches der allgemeinen Formel IV, wie hierin definiert, ist.
  6. Ein Textilbehandlungsmittel nach Anspruch 1, worin das entflockende Polymere ein solches der allgemeinen Formel V, wie hierin definiert, ist.
  7. Ein Textilbehandlungsmittel nach Anspruch 1, worin das entflockende Polymere ein solches der allgemeinen Formel VI, wie hierin definiert, ist.
  8. Ein Textilbehandlungsmittel nach Anspruch 1, worin das entflockende Polymere ein solches der allgemeinen Formel VII, wie hierin definiert, ist.
  9. Ein Textilbehandlungsmittel nach einem der vorstehenden Ansprüche, worin das Mittel von 0,01 bis 5 Gewichtsprozent an entflockendem Polymeren enthält.
  10. Ein Textilbehandlungsmittel nach einem der vorstehenden Ansprüche, worin das Weichmachermaterial ein kationisches gewebeweichmachendes Material enthält.
  11. Ein Textilbehandlungsmittel nach einem der vorstehenden Ansprüche, worin die Emulsionskomponente Kohlenwasserstoffe enthält.
  12. Ein Textilbehandlungsmittel nach einem der vorstehenden Ansprüche, worin die Emulsionskomponente ein Parfum enthält.
  13. Ein Textilbehandlungsmittel nach einem der vorstehenden Ansprüche, das einen pH-Wert von niedriger als 6,0 aufweist.
EP91304603A 1990-05-25 1991-05-21 Textilbehandlungsmittel Expired - Lifetime EP0458599B2 (de)

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GB9011785 1990-05-25
GB909011785A GB9011785D0 (en) 1990-05-25 1990-05-25 Fabric treatment compositions

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EP0458599A3 EP0458599A3 (en) 1992-07-08
EP0458599B1 true EP0458599B1 (de) 1997-01-29
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JP (1) JP2818632B2 (de)
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008040785A1 (en) 2006-10-06 2008-04-10 Dow Corning Corporation Process for preparing fabric softener compositions
EP2080711A1 (de) 2008-01-17 2009-07-22 Unilever PLC Verbesserungen im Zusammenhang mit Weichspülmitteln
EP2319910A2 (de) 2005-12-02 2011-05-11 Unilever PLC Verbesserungen im Zusammenhang mit Textilbehandlungszusammensetzungen
WO2011147752A2 (en) 2010-05-25 2011-12-01 Unilever Plc Improvements relating to fabric conditioning compositions
WO2018060056A1 (en) 2016-09-29 2018-04-05 Unilever Plc Laundry composition
WO2018059892A1 (en) 2016-09-29 2018-04-05 Unilever Plc Laundry composition

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SK53294A3 (en) 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
ES2140667T5 (es) † 1994-03-31 2004-07-16 Unilever N.V. Composiciones detergentes.
ATE229064T1 (de) * 1994-09-30 2002-12-15 Procter & Gamble Blockkopolymere für verbesserte viskositätsstabilität in konzentrierten weichspülmitteln
US6008184A (en) * 1994-09-30 1999-12-28 The Procter & Gamble Company Block copolymers for improved viscosity stability in concentrated fabric softeners
IL116638A0 (en) * 1995-01-12 1996-05-14 Procter & Gamble Method and compositions for laundering fabrics
EP0802967B2 (de) * 1995-01-12 2003-05-21 The Procter & Gamble Company Stabilisierte flüssige wäscheweichspüler
FR2732031B1 (fr) * 1995-03-23 1997-04-30 Coatex Sa Utilisation d'agents amphoteres comme modificateurs de phases lamellaires de compositions detergentes ou cosmetiques liquides ou pateuses
GB9515805D0 (en) * 1995-08-02 1995-10-04 Jeyes Group Plc Compositions
FR2752584A1 (fr) * 1996-08-26 1998-02-27 Coatex Sa Agent compatible avec les tensioactifs utilises en detergence ou cosmetique
GB9711849D0 (en) * 1997-06-06 1997-08-06 Unilever Plc Polymeric materials
US6503977B1 (en) * 1999-03-25 2003-01-07 Kimberly-Clark Worldwide, Inc. Substrate coatings, methods for treating substrates for ink jet printing, and articles produced therefrom
US6838498B1 (en) 1999-11-04 2005-01-04 Kimberly-Clark Worldwide, Inc. Coating for treating substrates for ink jet printing including imbibing solution for enhanced image visualization and retention
CA2390040C (en) 2000-01-19 2010-12-21 Kimberly-Clark Worldwide, Inc. Waterfast ink receptive coatings for ink jet printing materials and coating methods therewith
US6936648B2 (en) 2000-10-30 2005-08-30 Kimberly-Clark Worldwide, Inc Coating for treating substrates for ink jet printing including imbibing solution for enhanced image visualization and retention, method for treating said substrates, and articles produced therefrom
EP1468068B1 (de) * 2002-01-25 2007-05-16 Henkel Kommanditgesellschaft auf Aktien Konditioniermittel zur textilschonung
JP4813200B2 (ja) * 2005-02-24 2011-11-09 花王株式会社 繊維処理剤組成物
GB0623005D0 (en) * 2006-11-17 2006-12-27 Unilever Plc Fabric treatment method and composition
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FR3091878B1 (fr) 2019-01-22 2023-06-16 Calyxia Compositions de produits d’entretien avec des propriétés olfactives améliorées
FR3091877B1 (fr) 2019-01-22 2023-06-16 Calyxia Compositions de detergence avec des propriétés olfactives améliorées

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
EP2319910A2 (de) 2005-12-02 2011-05-11 Unilever PLC Verbesserungen im Zusammenhang mit Textilbehandlungszusammensetzungen
WO2008040785A1 (en) 2006-10-06 2008-04-10 Dow Corning Corporation Process for preparing fabric softener compositions
EP2080711A1 (de) 2008-01-17 2009-07-22 Unilever PLC Verbesserungen im Zusammenhang mit Weichspülmitteln
WO2011147752A2 (en) 2010-05-25 2011-12-01 Unilever Plc Improvements relating to fabric conditioning compositions
WO2018060056A1 (en) 2016-09-29 2018-04-05 Unilever Plc Laundry composition
WO2018059892A1 (en) 2016-09-29 2018-04-05 Unilever Plc Laundry composition

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EP0458599A2 (de) 1991-11-27
MY107162A (en) 1995-09-30
CA2042979C (en) 2000-10-31
KR910020262A (ko) 1991-12-19
KR940010047B1 (ko) 1994-10-21
ES2097793T3 (es) 1997-04-16
JP2818632B2 (ja) 1998-10-30
JPH04228680A (ja) 1992-08-18
ZA913958B (en) 1993-01-27
DE69124420D1 (de) 1997-03-13
EP0458599B2 (de) 2000-11-29
DE69124420T3 (de) 2001-02-22
AU7725891A (en) 1991-11-28
ES2097793T5 (es) 2001-02-16
GB9011785D0 (en) 1990-07-18
EP0458599A3 (en) 1992-07-08
BR9102126A (pt) 1991-12-24
DE69124420T2 (de) 1997-05-15
CA2042979A1 (en) 1991-11-26
AU636753B2 (en) 1993-05-06

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