EP0415698B2 - Composition adoucissante pour textile - Google Patents

Composition adoucissante pour textile Download PDF

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Publication number
EP0415698B2
EP0415698B2 EP90309376A EP90309376A EP0415698B2 EP 0415698 B2 EP0415698 B2 EP 0415698B2 EP 90309376 A EP90309376 A EP 90309376A EP 90309376 A EP90309376 A EP 90309376A EP 0415698 B2 EP0415698 B2 EP 0415698B2
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Prior art keywords
fabric
polymer
weight
formula
absent
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EP0415698A2 (fr
EP0415698B1 (fr
EP0415698A3 (en
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Mansur Sultan Mohammadi
Edwin Willis
Peter Graham Montague
Johannes Cornelis Van De Pas
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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
    • 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
    • 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
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/217—Polyoxyalkyleneglycol ethers with a terminal carboxyl group; Anhydrides, halides or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/37—Polymers
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/02—Processes in which the treating agent is releasably affixed or incorporated into a dispensing means

Definitions

  • the present invention relates to fabric-softening compositions, in particular to fabric-softening compositions which comprise one or more fabric-softening materials and, optionally, sufficient dissolved electrolyte to result in a structure of lamellar droplets dispersed 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.Watter (Ed), 'Rheometry: Industrial Applications', J.Wiley & Sons, Letchworth 1980.
  • Lamellar fabric-softening compositions are for example known from EP-A-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 by means known to those skilled in the art, for example optical techiques, 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 of fully close-packed provide a very desirable combination of physical stability and useful flow properties.
  • the viscosity and stability of the product depend on the volume fraction of the liquid which is occupied by the droplets. Generally speaking, the higher the volume fraction of the dispersed lamellar phase (droplets), the better the stability. However, higher volume fractions also lead to increased viscosity which in the limit can result in an unpourable or gelled product. This results in a compromise being reached. 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 at a shear rate of 21s -1 ). Conductivity measurements are known to provide a useful way of measuring the volume fraction, when compared with the conductivity of the continuous phase.
  • flocculation occurs between the lamellar droplets at a given volume fraction, the viscosity of the corresponding product will increase due to the formation of a network throughout the liquid.
  • Flocculation may also lead to instability because deformation of the lamellar droplets, owing to flocculation, will make their packing more efficient. Consequently, more lamellar droplets will be required for stabilization by the space-filling mechanism, which will again lead to a further increase of the viscosity.
  • the volume fraction of droplets is increased by increasing the softener concentration, and may be reduced by increasing the electrolyte level, however, flocculation between the lamellar droplets may occur when a certain threshold value of the electrolyte concentration is crossed at a given level of fabric-softening material (and fixed ratio between any different softening components).
  • the effects referred to above mean that there is a limit to the amounts of fabric-softening material and electrolyte which can be incorporated whilst still having an acceptable product.
  • higher levels of fabric-softening materials are desired for convenience and for reduction of costs.
  • Increased electrolyte levels can also be used for better performance, or are sometimes sought for secondary benefits such as carry-over protection.
  • EP-A-0299 787 discloses concentrated fabric softener compositions containing viscosity modifying polymers which are copolymers of a cationic surfactant monomer and at least one other vinyl monomer.
  • the comonomer may be a hydrophobic monomer and it may also include a hydrophilic monomer as well as a second cationic monomer which is relatively water-soluble compared to the first.
  • the ratio of hydrophilic to hydrophobic comonomers in the polymers exemplified in the reference is 3.4:1 or below.
  • EP-A-0 346 995 discloses detergent, rather than fabric softener, compositions containing deflocculating polymers.
  • EP-A-0 385 749 and WO-A-90/12862 disclose the inclusion, in fabric conditioning compositions of polymers which have the effect of increasing the viscosity of the composition.
  • WO-A-90/15857 discloses heavy duty detergent compositions which contain, in addition to a bleach and a pH adjusting jump system, a stability enhancing polymer which is a copolymer of a hydrophilic and a hydrophobic monomer.
  • the present invention relates to a fabric-softening composition according to claim 1.
  • the deflocculating polymer allows, if desired, the incorporation of greater amounts of softening materials and/or electrolytes 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, hitherto, lamellar dispersions have been highly stability-sensitive.
  • the present invention allows formulation of stable, pourable products wherein the volume fraction of the dispersed phase is 0.5, 0.6 or higher, but with combinations or concentrations of ingredients not possible hitherto.
  • the volume fraction of the lamellar droplet phase 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) 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 is calculated or estimated, using the Bruggeman equation, as disclosed in American Physics, 24 , 636 (1035).
  • the viscosity of the aqueous continuous phase is less than 25 mPas, most preferably less than 15 mPas, especially less than 10 mPas, 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. 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 but not enhance the stability of the composition.
  • 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 0.01% by weight to 2.0% 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.
  • Preferred embodiments of the invention exhibit smaller droplet size than an equivalent composition without any of the deflocculating polymer. From US-A-3 974 076 it is known that smaller droplet sizes enhance fabric softening, but in the past such small droplets were only obtainable by high energy processing.
  • the applicants have hypothesised that the polymers exert their action on the composition by the following mechanism.
  • the hydrophobic side chain(s) could be incorporated only in the outer bi-layer of the lamellar droplets, leaving the hydrophilic backbone over the outside of the droplets and additionally the polymers could also be incorporated deeper inside the droplet.
  • the composition may be stable or unstable.
  • a phase separation occurs at a slower rate than in the flocculated case and the degree of phase separation is less.
  • 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 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.
  • phase separation occurs relatively slowly and meaningful viscosity measurement can usually be determined quite readily.
  • viscosity is not greater than 2.5 Pas, most preferably no more than 1.0 Pas, and especially not greater than 750 mPas at a shear rate of 21 s -1 .
  • 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 referes to the structure of the predominating deflocculating polymer species and the molecular weight specified is the weight average molecular weight of the deflocculation polymers.
  • 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 more than 1 g/l, preferably more than 5 g/l, more 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 hydrophilic monomer units, which can be selected from a variety of units available for the preparation of polymers.
  • the hydrophilic monomers are linked by the following types of linkages -C-C-, -C-N-,
  • 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, methyacrylamide and fumaramide and their N-substituted derivatives such as 2-acrylamido-2-methylpropane sulphonic acid, N-(dimethylaminomethyl) acrylamideas 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 citraconic acid; and other ethylenically unsaturated quaternary ammonium compounds such as vinylbenzyl trimethyl ammonium chloride; hydroxyethyl(meth) acrylate; sulphoalkyl esters of unsaturated carboxylic acids such as 2-sul
  • 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 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 5 carbon atoms and are most preferably pendant organic groups having hydrophobicities comparable to one of the following: aliphatic hydrocarbon groups having at least five carbons such as C 5 to C 50 alkyls and cycloalkyls; polynuclear aromatic hydrocarbon groups such as naphthyls; alkylaryls wherein the alkyl group has one or more carbons; haloalkyls of 5 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 the higher alkyl esters of alpha, beta-ethylenically unsaturated carboxylic acids such as dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, tetradecylacrylate, tetradecylmethacrylate, octadecyl acrylate, octadecyl methacrylate, octyl half ester of maleic anhydride, dioctyl diethyl maleate, and other alkyl esters and half esters derived from the reactions of alkanols having from 5 to 50 carbon atoms with ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid and aconitic acid; alkylaryl esters of ethylenically unsaturated carboxylic acids
  • the hydrophobic monomer may be used single or mixtures thereof may be employed.
  • the ratio of hydrophilic to hydrophobic monomers varies from 500:1 to 5:1.
  • the weight average molecular weights (Mw.) of the resultant polymers vary from 500 to 500,000 or above when measured by gel permeation chromatography using polyacrylate standards, or the polymers present a standard viscosity of from 1 to 100 mPas by standard viscosity (SV) measurements using polyacrylate standards.
  • Products of the invention preferably comprise polymers of the general formula: wherein
  • 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: R 1 -R 6 are defined as in formula I; (a + b + c): d is from 5:1 to 500:1, in which the monomer units may be in random order, a, b, c, e, f, g, h may be an integer or zero, d is an integer and n is at least 1; B 1 , B 2 , B 3 , B 4 are organic or inorganic anions; w is zero to 4; R 11 and R 11* are independently selected from hydrogen or C 1 -C 4 alkyl; and R 12 is independently selected from C 5 to C 24 alkyl or alkenyl, aryl cycloalkyl, hydroxyalkyl or alkoxyalkyl.
  • 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.
  • R 1 - R 6 are defined as in formula I, R 6* represents H or C 1-4 alkyl, 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; R 13 represents -CH 2 -, -C 2 H 4 -, -C 3 H 6 - or is absent. R 14 represents from 1 to 50 independently selected alkyleneoxy groups, preferably ethylene oxide groups, or is absent. R 15 represents -OH or hydrogen.
  • the polymers of formula I, II and IV and their salts have a weight average molecular weight in the region of from 500 to 500,000, preferably 1000 to 200,000, more preferably from 1500 to 50,000 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.
  • polymers for use in compositions of the present invention are prepared by the method as described in EP-A-346 834, published 20 December 1989.
  • the deflocculating polymer will be used at from 0.01% to 5.0% by weight in the composition, preferably from 0.1% to 2.0%.
  • the aqueous continuous phase may contain dissolved electrolyte.
  • electrolyte means any ionic water-soluble material.
  • the electrolyte is necessarily dissolved but may be suspended as particles of solid because the total electrolyte concentration of the liquid is higher than the solubility limit of the elctrolyte.
  • Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or ore being substantially only in the suspended solid phase. Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g. the order of addition of components.
  • Compositions of the present invention comprise from 1 to 80% by weight of fabric-softening materials, preferably from 10 to 70% by weight, more preferably from 20 to 60% by weight of the composition.
  • the fabric-softening materials are selected from cationic fabric-softener 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 12-24 hydrocarbyl chains.
  • R 1 and R 2 represent hydrocarbyl groups from 12 to 24 carbon atoms
  • R 3 and R 4 represent hydrocarbyl groups containing from 1 to 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 where 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.
  • Another class of preferred water-insoluble cationic materials are the 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- dihydroimidazolinium chloride.
  • Other useful imidazolinium materials are 2-heptadecyl-1-methyl-1 (2-stearylamido)ethylimidazolinium 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 (ex AKZO); Noramium M2SH (ex CECA)I Aliquat-2HT (Trade Mark of General Mills Inc), Stepantex Q185 (ex Stepan); Stepantex VP85 (ex Stepan); Stepantex VRH90 (ex Stepan); Synprolam FS (ex ICI) and the imidazolinium compounds Varisoft 475 (Trade Mark of Sherex Company, Columbus Ohio) and Rewoquat W7500 (Trade Mark 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 12 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 20y 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 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 1, it is preferred that R 18 is a C 16 to C 22 alkyl and that the sum total of x and y is within the range from 3 to 10.
  • Representative commercially available materials of this class include Ethomeen (ex Armour) and Ethoduomeen (ex 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 carbons 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 (ex Sandoz).
  • 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, perfumes especially body odour reducing perfumes, perfume carriers, hydrocarbons, fluorescers, colourants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, stabilisers such as guar gum and polyethylene glycol, anti-shrinking agents, anti-wrinkle agents, silicones, soil-release agents, antioxidants, anti-corrosion agents, 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
  • examples I-XII the following polymers are used. Each polymer is obtained from National Starch and Chemical Ltd, Speciality Polymers Division 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 and the electrolyte to water under stirring, followed by adding the softening material which has been preheated to 50°C.
  • the pH of the compositions was adjusted to 4.0 with orthophosphoric acid.
  • compositions A and B were stable fabric-softening compositions which did not show any visible phase separation upon storage for several weeks at ambient temperature. They had a viscosity of about 400 mPas at 21 s -1 and had a good dispersibility in water of ambient temperature. Composition C was gel-like, translucent and of unacceptable dispersibility in water.
  • Example II The following compositions were prepared as in Example I, the fabric-softener material being an ester-linked quaternary ammonium material Stepantex VRH 90 which had been preheated to remove any solvent present.
  • Ingredient A B C D % by weight Stepantex VRH 90 30 30 30 30 NaCl 1.8 2.0 2.0 2.0 2.0 Dobanol 91-6 1.0 1.5 1.5 1.0 Polymer 425/183 - 0.11 0.2 0.1 CaCl 2 (1 M) - - - 0.92
  • Formulations A-D were stable fabric-softening compositions which did not show any visible phase separation upon storage for several weeks at ambient temperature.
  • Compositions B-D were of acceptable viscosity and were well dispersible in water of ambient temperature.
  • Composition A was unacceptably viscous and of poor dispersibility.
  • compositions A-D were stable fabric-softening compositions which did not show any visible phase separation upon storage at ambient temperature.
  • Compositions A-C had a viscosity of about 400 mPas at 21s -1 and were of good dispersibility.
  • Composition D was unacceptably viscous.
  • compositions A and B were more stable than composition C.
  • Compositions A and B were pourable milky liquids, while compositions C was a semi-translucent to milky gel which showed 12% by volume phase separation upon one-day storage at ambient temperature.
  • Compositions A and B were stable, pourable milky liquids.
  • Composition C was an unstable semi-translucent to milky gel.
  • Composition D was a pourable semi-translucent liquid which separated into two translucent layers with in 2 days.
  • Compositions A-C were pourable milky liquids which were of acceptable stability.
  • Composition D was a milky pourable liquid which separated into two layers in minutes.
  • Compositions A-C were of acceptable stability, pourable and did not show any discolouration upon storage.
  • Example 1 The following fabric softening compositions were prepared as in Example 1. All compositions were stable translucent product having a viscosity of about 250 mPas at 21 s -1 and were well dispersable in water of ambient temperature.
  • Example II The following fabric softening compositions were prepared as in Example I. All compositions were stable, milky to semi-translucent products having a viscosity of about 400 mPas at 21 s -1 . The dispersability of the products in water of ambient temperature was good.
  • compositions were prepared as in Example I. All products were stable and of acceptable viscosity and dispersability.
  • Fabric softening compositions were made by adding calcium chloride to water, then adding a heated premix of fabric softener and nonionic and finally adding the polymer.
  • the fabric softening material was Arquad 2HT (a dimethyl dihydrogenated tallow ammonium chloride DMDHTAC) ex Atlas.
  • the nonionic was Genopol T050 a tallow alcohol ethoxylated with 5 moles of ethylene oxide ex Hoechst.
  • the pH was adjusted to between 3.5 and 4 with orthophosphoric acid.
  • Compositions A and B were stable fabric-softening compositions which did not show any visible phase separation on storage for several weeks at ambient temperature. They had a viscosity of about 400 mPas at 21s -1 .
  • formulations were made by dispersing the polymer in an aqueous base before adding the fabric softener.
  • Ingredient A B DMDHTAC 7.76 7.76 Polymer 442/104 0.1 0.25 CaCl 2 0.005 0.06 Water balance balance These formulations were found to have droplet sizes around 1 micron when measured by phase contrast microscopy. Formulations not containing polymer generally have droplet sizes of at least 3 microns.

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Claims (12)

  1. Composition adoucissante pour textiles, qui comprend :
    (a) un milieu aqueux ;
    (b) de 1 à 80% en poids d'une (ou plusieurs) matière adoucissante pour textiles dans le milieu aqueux, chacune de ces matières étant choisie parmi les adoucissants cationiques de textiles ayant une solubilité dans l'eau à pH 2,5 et à 20°C de moins de 10 g/l ; et
    (c) de 0,01 à 5% en poids d'un polymère défloculant ayant une masse moléculaire comprise entre 500 et 500.000 et/ou une viscosité normalisée de 1 à 100 mPas, ledit polymère défloculant comprenant un édifice de base hydrophile et au moins une chaíne latérale hydrophobe, l'édifice de base hydrophile comportant des monomères hydrophiles ces monomères hydrophiles étant liés par une liaison choisie parmi :
    Figure 00440001
    de telle sorte que la solubilité dudit édifice de base hydrophile dépasse 1 g/l dans l'eau à 20°C et à pH 7,0, et au moins une chaíne latérale hydrophobe étant constituée par au moins un monomère hydrophobe incorporé dans ledit polymère, lesdits monomères hydrophiles et ledit monomère hydrophobe étant dans un rapport compris entre 5:1 et 500:1, et le monomère hydrophobe étant choisi parmi :
    (i) des monomères insolubles dans l'eau ayant une solubilité inférieure à 0,2 partie en poids par 100 parties d'eau ; et
    (ii) des composés à insaturation éthylénique comportant des fragments hydrophobes, lesdits fragments hydrophobes étant choisis parmi (i) ceux dont la solubilité à la température ambiante est inférieure à 1 g/l à un pH entre 3,0 et 12,5 et (2) ceux contenant au moins 5 atomes de carbone,
    ladite composition adoucissante pour textiles ayant une structure de gouttelettes lamellaires dans le milieu aqueux et la viscosité de ladite composition étant inférieure à celle d'une composition équivalente sans un tel polymère ;
    à la condition que ladite composition adoucissante pour textiles ne soit pas une composition nettoyante aqueuse structurée pour gros lavages comprenant :
    (1) de 1 à 40% en poids d'un acide peroxydé organique particulaire, solide, sensiblement insoluble dans l'eau ;
    (2) de 10 à 50% en poids d'un tensioactif ;
    (3) de 1 à 40% en poids d'un système de débattement du pH comprenant :
    (a) un borate, et
    (b) le rapport pondéral du polyol au borate étant de 1:1 à 10:1 ; et
    (4) de 0,1 à 5% en poids d'un polymère de rehaussement de stabilité qui est un copolymère ayant un édifice de base hydrophile et une chaíne latérale hydrophobe.
  2. Composition adoucissante pour textiles selon la revendication 1, dans laquelle le polymère défloculant répond à la formule :
    Figure 00460001
    dans laquelle z est 1 ; le rapport (x+y):z est compris entre 5:1 et 500:1 ; les motifs monomères peuvent être en un ordre fortuit quelconque ; y est compris entre 0 et un maximum égal à la valeur de x ; et n est au moins 1 ;
    R1 représente -CO-O, -O-, -O-CO-, -CH2, -CO-NH- ou est absent ;
    R2 représente de 1 à 50 groupes alkylèneoxy indépendamment choisis ou est absent, à la condition que lorsque R3 est absent et R4 représente l'hydrogène, alors R2 doit contenir un groupe alkylèneoxy d'au moins trois atomes de carbone ;
    R3 est une liaison phénylène ou est absent ;
    R4 représente un atome d'hydrogène ou un radical alkyle ou alcényle en C5-24, aux conditions que :
    a) quand R1 représente -O-CO-, R2 et R3 doivent être absents et R4 doit contenir au moins 5 atomes de carbone et
    b) quand R2 est absent, R4 n'est pas l'hydrogène et R3 est absent, alors R4 doit contenir au moins 5 atomes de carbone ;
    R5 est un atome d'hydrogène ou un groupe de formule -COOA4;
    R6 est un atome d'hydrogène ou un radical alkyle en C1-4 ; et
    A1, A2, A3 et A4 représentent indépendamment l'hydrogène, les métaux alcalins, alcalino-terreux ou des bases ammonium et amine.
  3. Composition adoucissante pour textiles selon la revendication 1, dans laquelle le polymère défloculant répond à la formule II :
    Figure 00470001
    dans laquelle Q2 est un ensemble moléculaire de formule IIa :
    Figure 00480001
    dans laquelle z et R1-6 sont tels que définis dans la formule (I) ;
    A1-4 sont tels que dans la formule (I) ;
    Q1 est un monomère multifonctionnel permettant la ramification du polymère, dans lequel les monomères du polymère peuvent être reliés à Q1 dans une direction quelconque, dans un ordre quelconque, en permettant éventuellement l'obtention d'un polymère ramifié, n et z sont tels que définis plus haut ; v = 1 ; et le quotient (x+y+p+q+r):z est compris entre 5:1 et 500:1 ; les motifs monomères pouvant être dans un ordre fortuit quelconque ;
    R7 et R8 représentent -CH3 ou -H ;
    R9 et R10 représentent des groupes substituants tels qu' amino, amine, amide, sulfonate, sulfate, phosphonate, phosphate, hydroxyle, carboxyle et oxyde, ou bien (C2H4O)tH dans lequel t est compris entre 1 et 50, les motifs monomères pouvant être dans un ordre fortuit.
  4. Composition adoucissante pour textiles selon la revendication 1, dans laquelle le polymère défloculant répond à la formule III :
    Figure 00490001
    dans laquelle Q3 est dérivé d'un motif monomère IIIa comprenant :
    Figure 00500001
    Q4 est dérivé de l'ensemble moléculaire IIIb :
    Figure 00510001
    et Q5 est dérivé d'un motif monomère IIIc :
    Figure 00520001
    R1-R6 sont tels que définis dans la formule I ;
    le rapport (a + b + c):d est compris entre 5:1 et 500:1, dans lequel les motifs monomères peuvent être dans un ordre fortuit ; a, b, c, e, f, g et h peuvent être des nombres entiers ou 0, d est un nombre entier et n est au moins 1 ;
    B1, B2, B3 et B4 sont des anions organiques ou minéraux ; w est un nombre de 0 à 4 ;
    R11 et R11* représentent indépendamment chacun un atome d'hydrogène ou un radical alkyle en C1-4 ; et
    R12 est choisi parmi un radical alkyle ou alcényle en C5-24, aryle, cycloalkyle, hydroxyalkyle ou alcoxyalkyle.
  5. Composition adoucissante pour textiles selon la revendication 1, dans laquelle le polymère défloculant répond à la formule IV :
    Figure 00530001
    dans laquelle R1-R6 sont tels que défini dans la formule I, R6* représente H ou un radical alkyle en C1-4, z = 1 et j:z est compris entre 5:1 et 500:1, les motifs monomères pouvant être dans un ordre fortuit et n est d'au moins 1 ;
    R13 représente -CH2-, -C2H4-, -C3H6- ou est absent.
    R14 représente 1 à 50 groupes alkylèneoxy indépendamment choisis ou est absent, et
    R15 représente -OH ou l'hydrogène.
  6. Composition adoucissante pour textiles selon l'une quelconque des revendications précédentes, comprenant de 0,1 à 2,0% en poids de la composition de polymère défloculant.
  7. Composition adoucissante pour textiles selon l'une quelconque des revendications précédentes, comprenant 20 à 60% en poids d'une matière d'adoucissement de textiles.
  8. Composition adoucissante pour textiles selon l'une quelconque des revendications précédentes, qui comprend également de 0,1 à 5,0% en poids d'un électrolyte dissous.
  9. Composition adoucissante pour textiles selon l'une quelconque des revendications précédentes, ayant un pH inférieur à 6,0.
  10. Procédé de préparation d'une composition adoucissante pour textiles selon l'une quelconque des revendications précédentes, dans lequel le polymère défloculant est dispersé dans la base aqueuse avant addition de la matière d'adoucissement de textiles.
  11. Procédé de traitement de textiles qui consiste à mettre en contact les textiles avec une liqueur aqueuse comprenant une composition adoucissante pour textiles selon l'une quelconque des revendications 1 à 9 en une concentration de 1 à 1000 ppm des matières adoucissantes dans la liqueur aqueuse.
  12. Utilisation de
    ( a ) un polymère défloculant comme spécifié dans la revendication 1 ; et
    (b) un ou plusieurs adoucissant(s) cationique(s) de textiles ayant une solubilité dans l'eau à pH 2,5 et à 20°C de moins de 10 g/l ;
    dans un milieu aqueux ;
    pour obtenir une composition adoucissante pour textiles ayant une structure de gouttelettes lamellaires dispersées dans le milieu aqueux, et une viscosité inférieure à 2,5 Pas à un taux de cisaillement de 21 s-1, la viscosité de ladite composition étant plus basse que celle d'une composition équivalente sans ledit polymère ;
    et à la condition que la composition obtenue ne soit pas une composition nettoyante aqueuse structurée pour gros lavage, comprenant :
    (1) 1 à 40% en poids d'un acide peroxydé organique solide, particulaire, sensiblement non hydrosoluble ;
    (2) 10 à 50% en poids d'un tensioactif ;
    (3) 1 à 40% en poids d'un système de débattement du pH comprenant :
    (a) un borate ; et
    (b) un polyol,
    le rapport pondéral du polyol au borate étant de 1:1 à 10:1 ;
    et
    (4) 0,1 à 5% en poids d'un polymère qui rehausse la stabilité et qui est un copolymère comportant un édifice de base hydrophile et une chaíne latérale hydrophobe.
EP90309376A 1989-08-31 1990-08-28 Composition adoucissante pour textile Expired - Lifetime EP0415698B2 (fr)

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GB898919669A GB8919669D0 (en) 1989-08-31 1989-08-31 Fabric-softening compositions
GB8919669 1989-08-31

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GB8924478D0 (en) * 1989-10-31 1989-12-20 Unilever Plc Detergent compositions
GB8927361D0 (en) * 1989-12-04 1990-01-31 Unilever Plc Liquid detergents
GB9011785D0 (en) * 1990-05-25 1990-07-18 Unilever Plc Fabric treatment compositions
ES2107047T3 (es) * 1992-07-29 1997-11-16 Unilever Nv Composicion detergente.
SK53294A3 (en) 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
US6090762A (en) * 1993-05-07 2000-07-18 Albright & Wilson Uk Limited Aqueous based surfactant compositions
EP0799887B1 (fr) * 1996-04-01 2003-06-11 The Procter & Gamble Company Compositions assouplissantes pour tissus
ES2242612T3 (es) * 1999-03-25 2005-11-16 THE PROCTER & GAMBLE COMPANY Composiciones de mantenimiento de tejidos que comprenden ciertos polimeros de mantenimiento de tejidos cargados cationicamente.
DE10104470A1 (de) * 2001-02-01 2002-08-08 Basf Ag Reinigerformulierungen zur Verhinderung der Verfärbung von Kunststoffgegenständen
GB0121802D0 (en) 2001-09-10 2001-10-31 Unilever Plc Fabric conditioning compositions
GB0121806D0 (en) 2001-09-10 2001-10-31 Unilever Plc A method of reducing the viscosity of fabric conditioning compositions
EP1678239A1 (fr) * 2003-10-07 2006-07-12 Clariant International Ltd. Cires de silicone aminofonctionnels
GB0524659D0 (en) 2005-12-02 2006-01-11 Unilever Plc Improvements relating to fabric treatment compositions
CN101522877A (zh) 2006-10-06 2009-09-02 陶氏康宁公司 用于制备织物柔软剂组合物的方法
GB0800756D0 (en) 2008-01-17 2008-02-27 Unilever Plc Improvements relating tofabric conditioning compositions
US20130133140A1 (en) 2010-05-25 2013-05-30 Tamara Marie Ross Fabric conditioning compositions
WO2018059892A1 (fr) 2016-09-29 2018-04-05 Unilever Plc Composition de blanchisserie
WO2018060056A1 (fr) 2016-09-29 2018-04-05 Unilever Plc Composition de blanchisserie
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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DE3167297D1 (en) * 1980-01-07 1985-01-03 Procter & Gamble Fabric softening composition
US4497716A (en) * 1982-12-23 1985-02-05 Lever Brothers Company Fabric softening composition
EP0111984B1 (fr) * 1982-12-23 1989-08-02 THE PROCTER & GAMBLE COMPANY Polymères d'amines éthoxylées ayant des propriétés pour enlever des taches et la contre-redéposition utilisables dans des compositions détergentes
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GB8719083D0 (en) * 1987-08-12 1987-09-16 Albright & Wilson Fabric conditioners
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents

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DE69017316T2 (de) 1995-07-20
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EP0415698A2 (fr) 1991-03-06
EP0415698B1 (fr) 1995-03-01
AU6196490A (en) 1991-03-07
ES2071030T5 (es) 2004-07-16
MY106842A (en) 1995-08-30
ZA906971B (en) 1992-05-27
CA2023950C (fr) 2001-04-17
KR930007737B1 (ko) 1993-08-18
DE69017316D1 (de) 1995-04-06
ES2071030T3 (es) 1995-06-16
JP2635205B2 (ja) 1997-07-30
KR910004888A (ko) 1991-03-29
GB8919669D0 (en) 1989-10-11
BR9004321A (pt) 1991-09-03
EP0415698A3 (en) 1991-04-10
DE69017316T3 (de) 2004-07-01

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