EP0415698B1 - Wäscheweichmacher - Google Patents

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Publication number
EP0415698B1
EP0415698B1 EP90309376A EP90309376A EP0415698B1 EP 0415698 B1 EP0415698 B1 EP 0415698B1 EP 90309376 A EP90309376 A EP 90309376A EP 90309376 A EP90309376 A EP 90309376A EP 0415698 B1 EP0415698 B1 EP 0415698B1
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Prior art keywords
fabric
polymer
weight
hydrophobic
formula
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French (fr)
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EP0415698A2 (de
EP0415698B2 (de
EP0415698A3 (en
Inventor
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.Walter (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
  • a fabric-softening composition comprising
  • 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/I, preferably more than 5 g/I, more preferably more than 10 g/I.
  • 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: -O-, -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/I 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/I, more preferably less than 0.5 g/I, most preferably less than 0.1 g/I 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 so 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 z is 1; (x + y):z is from 5:1 to 500:1; 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;
  • 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:
  • 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.
  • 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;
  • 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/I.
  • Highly preferred materials are cationic quaternary ammonium salts having two C12-24. 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 C1 3 -15 R 2 is CH 2 CH 2 0COR, 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)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 (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 0)yH, 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, antigel- ling 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.
  • R1 COO
  • R2 is absent
  • R3 is absent
  • R5 H
  • R6 CH3
  • 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.
  • 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.
  • the following formulations were made by adding the citrate to the water of ambient temperature and subsequently adding the fabric-softening material.
  • the polymer was added as the last ingredient at ambient temperature.
  • 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. 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. Wäscheweichmacher, der folgendes enthält:
(a) ein wäßriges Medium;
(b) 1 Gew.-% bis 80 Gew.-% eines oder mehrerer Wäscheweichmacher-Substanzen in einem wäßrigen Medium, wobei jede dieser Substanzen aus kationischen Wäscheweichmachern ausgewählt ist, die in Wasser bei einem pH von 2,5 und bei 20 ° C eine Löslichkeit von weniger als 10 g/I besitzen; und
(c) 0,01 Gew.-% bis 5 Gew.-% eines Entflockungs-Polymers mit einem Molekulargewicht von 500 bis 500 000 und/oder einer Standard-Viskosität von 1 bis 100 mPas, wobei das Entflockungs-Polymer eine hydrophile Hauptkette und mindestens eine hydrophobe Seitenkette aufweist, wobei die hydrophile Hauptkette hydrophile Monomere aufweist, so daß die Löslichkeit der hydrophilen Hauptkette in Wasser bei 20 °C und bei einem pH von 7,0 1 g/I übersteigt, und wobei die mindestens eine hydrophobe Seitenkette durch mindestens ein hydrophobes Monomer bereitgestellt wird, das in dem Polymer enthalten ist, wobei die hydrophilen Monomeren und das mindestens eine hydrophobe Monomer in einem Verhältnis von 5:1 bis 500:1 vorliegen, und wobei das hydrophobe Monomer aus folgendem ausgewählt ist:
(i) in Wasser unlöslichen Monomeren mit einer Löslichkeit von weniger als 0,2 Gew.-Teilen pro 100 Teile Wasser; und
(ii) ethylenisch ungesättigten Verbindungen mit hydrophoben Resten, wobei die hydrophoben Reste ausgewählt sind aus: (1) solchen mit einer Löslichkeit bei Raumtemperatur von weniger als
1 g/I bei einem pH von zwischen 3,0 und 12,5; und (2) solchen mit mindestens 5 Kohlenstoffatomen; wobei der Weichmacher in dem wäßrigen Medium die Struktur von lamellaren Tröpfchen aufweist und die Viskosität der Zusammensetzung geringer ist als die der entsprechenden Zusammensetzung ohne das Polymer; mit der Maßgabe, daß es sich bei dem Wäscheweichmacher nicht um eine strukturierte wäßrige Hochleistungs-Reinigungs-Zusammensetzung handelt, die folgendes enthält:
(1) 1 bis 40 Gew.-% einer festen, teilchenförmigen, in Wasser im wesentlichen unlöslichen organischen Peroxysäure;
(2) 10 bis 50 Gew.-% eines oberflächenaktiven Mittels;
(3) 1 bis 40 Gew.-% eines pH-Sprungsystems, das folgendes enthält:
(a) ein Borat und;
(b) ein Polyol, wobei das Polyol und das Borat in einem Gewichtsverhältnis von 1:1 bis 10:1 vorhanden sind; und
(4) 0,1 bis 5 Gew.-% eines stabilitätserhöhenden Polymers, bei dem es sich um ein Copolymer mit einer hydrophilen Hauptkette und einer hydrophoben Seitenkette handelt.
2. Wäscheweichmacher nach Anspruch 1, wobei das Entflockungs-Polymer folgende Formel aufweist:
Figure imgb0044
in der z für 1 steht; (x + y):z im Bereich von 5:1 bis 500:1 liegt; wobei die Monomer-Einheiten zufällig angeordnet sein können; y im Bereich von 0 bis maximal gleich dem Wert von x liegt; und n mindestens für 1 steht;
R1 für -CO-O, -O-, -O-CO-, -CH2, -CO-NH- steht, oder nicht vorhanden ist;
R2 für 1 bis 50 unabhängig voneinander ausgewählte Alkylenoxy-Gruppen steht, oder nicht vorhanden ist, mit der Maßgabe, daß, wenn R3 abwesend ist und R4 für Wasserstoff steht, R2 dann eine Alkylenoxy-Gruppe mit mindestens 3 Kohlenstoffatomen enthalten muß;
R3 für eine Phenylen-Bindung steht, oder abwesend ist;
R4 für Wasserstoff oder eine Cs-2a-Alkyl- oder C5-24-Alkenyl-Gruppe steht, mit der Maßgabe, daß:
a) wenn R1 für -O-CO- steht, R2 und R3 abwesend sein müssen und R4 mindestens 5 Kohlenstoffatome enthalten muß, und
b) wenn R2 abwesend ist, R4 nicht für Wasserstoff steht und R3 abwesend ist, R4 dann mindestens 5 Kohlenstoffatome enthalten muß;
R5 für Wasserstoff oder eine Gruppe mit der Formel -COOA4 steht;
R6 für Wasserstoff oder C1 -4-Alkyl steht; und
A1, A2, A3 und A4 unabhängig voneinander aus Wasserstoff, Alkalimetallen, Erdalkalimetallen, Ammonium- und Amin-Basen ausgewählt sind.
3. Wäscheweichmacher nach Anspruch 1, wobei das Entflockungs-Polymer die folgende Formel II aufweist:
Figure imgb0045
in der:
Q2 für eine molekulare Entität mit der Formel Ila steht:
Figure imgb0046
in der z und R1-6 wie in Formel (I) definiert sind;
A1-4 wie in Formel (I) definiert sind;
Q1 für ein multifunktionelles Monomer steht, das die Verzweigung des Polymers gestattet, wobei die
Monomeren des Polymers in jeder Richtung und in jeder Reihenfolge an Q1 gebunden sein können, wodurch sich möglicherweise ein verzweigtes Polymer ergibt; n und z wie oben definiert sind; v für 1 steht; und (x + y + p + q + r): z im Bereich von 5:1 bis 500:1 liegt; wobei die Monomer-Einheiten in zufälliger Reihenfolge vorliegen können;
R7 und R8 für -CH3 oder -H stehen;
R9 und R10 jeweils Substituenten-Gruppen darstellen wie Amino-, Amin-, Amid-, Sulfonat-, Sulfat-, Phosphonat-, Phosphat-, Hydroxyl-, Carboxyl- oder Oxid-Gruppen oder (C2H4O)tH, wobei t im Bereich von 1 - 50 liegt, und wobei die Monomer-Einheiten zufällig angeordnet sein können.
4. Wäscheweichmacher nach Anspruch 1, wobei das Entflockungs-Polymer die folgende Formel III aufweist:
Figure imgb0047
in der Q3 von einer monomeren Einheit Illa abstammt, die folgendes aufweist:
Figure imgb0048
wobei Q4 von der molekulaten Entität Illb abstammt:
Figure imgb0049
und Q5 von einer monomeren Einheit IIIC abstammt:
Figure imgb0050
wobei R1 - R6 wie in Formel I definiert sind;
(a + b + c): d im Bereich von 5:1 bis 500:1 liegt, wobei die Monomer-Einheiten in zufälliger Reihenfolge vorliegen können, jedes a, b, c, e, f, g, h für eine ganze Zahl oder Null steht, d für eine ganze Zahl steht, und n mindestens 1 ist;
B1, B2, B3, B4 für organische oder anorganische Anionen stehen;
w für Null bis 4 steht;
R11 und R11* unabhängig voneinander aus Wasserstoff oder C1-C4-Alkyl ausgewählt sind; und
R12 unabhängig aus Cs-C24-Alkyl oder -Alkenyl, -Aryl, -Cycloalkyl, -Hydroxyalkyl oder -Alkoxyalkyl ausgewählt ist.
5. Wäscheweichmacher nach Anspruch 1, wobei das Entflockungs-Polymer die folgende Formel IV aufweist:
Figure imgb0051
in der Rl - R6 wie in Formel I definiert sind, R6* für H oder C1-4-Alkyl steht; z für 1 steht und j:z im Bereich von 5:1 bis 500:1 liegt, wobei die Monomer-Einheiten in zufälliger Reihenfolge vorliegen können, und n mindestens für 1 steht;
R13 für -CH2-, -C2H4-, -C3H6- steht, oder abwesend ist;
R14 für 1 bis 50 unabhängig ausgewählte Alkylenoxy-Gruppen steht, oder abwesend ist;
R15 für -OH oder Wasserstoff steht.
6. Wäscheweichmacher nach einem der vorhergehenden Ansprüche, der 0,1 bis 2,0 Gew.-% der Zusammensetzung an Entflockungs-Polymeren enthält.
7. Wäscheweichmacher nach einem der vorhergehenden Ansprüche, der 20 - 60 Gew.-% Wäscheweichmacher-Substanz enthält.
8. Wäscheweichmacher nach einem der vorhergehenden Ansprüche, der außerdem 0,1 bis 5,0 Gew.-% gelösten Elektrolyt enthält.
9. Wäscheweichmacher nach einem der vorhergehenden Ansprüche, der einen pH von weniger als 6,0 besitzt.
10. Verfahren zur Herstellung eines Wäscheweichmachers nach einem der vorhergehenden Ansprüche, bei dem das Entflockungs-Polymer vor der Zugabe der Wäscheweichmacher-Substanz dazu in der wäßrigen Base dispergiert wird.
11. Verfahren zur Behandlung von Wäsche, bei dem die Wäsche mit einer wäßrige Lauge in Kontakt gebracht wird, die einen Wäscheweichmacher nach einem der Ansprüche 1 bis 9 in einer Konzentration von 1 bis 1000 ppm der Wäscheweichmacher-Substanzen in der wäßrigen Lauge enthält.
12. Verwendung
(a) eines Entflockungs-Polymers mit einem Molekulargewicht von 500 bis 500 000 und/oder einer Standard-Viskosität von 1 bis 100 mPas, wobei das Polymer eine hydrophile Hauptkette und mindestens eine hydrophobe Seitenkette aufweist, wobei die hydrophile Hauptkette hydrophile Monomere aufweist, so daß die Löslichkeit der hydrophilen Hauptkette in Wasser bei 20 ° C und bei einem pH von 7,0 1 g/I übersteigt, und wobei die mindestens eine hydrophobe Seitenkette durch mindestens ein hydrophobes Monomer bereitgestellt wird, das in dem Polymer enthalten ist, wobei die hydrophilen Monomeren und das mindestens eine hydrophobe Monomer in einem Verhältnis von 5:1 bis 500:1 vorliegen, und wobei das hydrophobe Monomer aus folgendem ausgewählt ist:
(i) in Wasser unlöslichen Monomeren mit einer Löslichkeit von weniger als 0,2 Gew.-Teilen pro 100 Teile Wasser; und
(ii) ethylenisch ungesättigten Verbindungen mit hydrophoben Resten, wobei die hydrophoben Reste ausgewählt sind aus: (1) solchen mit einer Löslichkeit bei Raumtemperatur von weniger als 1 g/I bei einem pH von zwischen 3,0 und 12,5; und (2) solchen mit mindestens 5 Kohlenstoffatomen; und
(b) eines oder mehrerer kationischer Wäscheweichmacher mit einer Löslichkeit in Wasser bei pH 2,5 und 20 ° C von weniger als 10 g/I;
in einem wäßrigen Medium; zur Herstellung eines Wäscheweichmachers mit der Struktur von in dem wäßrigen Medium dispergierten lamellaren Tröpfchen und einer Viskosität unterhalb 2,5 Pas bei einer Schergeschwindigkeit von 21 S-1, wobei die Viskosität der Zusammensetzung niedriger ist als die der entsprechenden Zusammensetzung ohne das Polymer;
und mit der Maßgabe, daß es sich bei der erhaltenen Zusammensetzung nicht um eine strukturierte, wäßrige Hochleistungs-Wasch-Zusammensetzung handelt, die folgendes enthält:
(1) 1 bis 40 Gew.-% einer festen, teilchenförmigen, in Wasser im wesentlichen unlöslichen organischen Peroxysäure;
(2) 10 bis 50 Gew.-% eines oberflächenaktiven Mittels;
(3) 1 bis 40 Gew.-% eines pH-Sprungsystems, das folgendes enthält:
(a) ein Borat und;
(b) ein Polyol, wobei das Polyol und das Borat in einem Gewichtsverhältnis von 1:1 bis 10:1 vorhanden sind; und
(4) 0,1 bis 5 Gew.-% eines stabilitätserhöhenden Polymers, bei dem es sich um ein Copolymer mit einer hydrophoben Hauptkette und einer hydrophoben Seitenkette handelt.
EP90309376A 1989-08-31 1990-08-28 Wäscheweichmacher Expired - Lifetime EP0415698B2 (de)

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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
DE69314038T2 (de) * 1992-07-29 1998-01-22 Unilever Nv Waschmittelzusammensetzung
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 (de) * 1996-04-01 2003-06-11 The Procter & Gamble Company Textilweichmacherzusammensetzungen
DE10104470A1 (de) * 2001-02-01 2002-08-08 Basf Ag Reinigerformulierungen zur Verhinderung der Verfärbung von Kunststoffgegenständen
GB0121806D0 (en) 2001-09-10 2001-10-31 Unilever Plc A method of reducing the viscosity of fabric conditioning compositions
GB0121802D0 (en) 2001-09-10 2001-10-31 Unilever Plc Fabric conditioning compositions
EP1678239A1 (de) * 2003-10-07 2006-07-12 Clariant International Ltd. Aminofunktionelle silikonwachse
GB0524659D0 (en) 2005-12-02 2006-01-11 Unilever Plc Improvements relating to fabric treatment compositions
US8242071B2 (en) 2006-10-06 2012-08-14 Dow Corning Corporation Process for preparing fabric softener compositions
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
WO2018060056A1 (en) 2016-09-29 2018-04-05 Unilever Plc Laundry composition
CN109790493B (zh) 2016-09-29 2021-03-02 荷兰联合利华有限公司 洗衣组合物
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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GB1604030A (en) * 1977-11-21 1981-12-02 Procter & Gamble Ltd Textile conditioning compositions
EP0043622B1 (de) * 1980-01-07 1984-11-21 THE PROCTER & GAMBLE COMPANY Textilweichmacherzusammensetzung
US4497716A (en) * 1982-12-23 1985-02-05 Lever Brothers Company Fabric softening composition
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties
DE3380307D1 (en) * 1982-12-23 1989-09-07 Procter & Gamble Ethoxylated amine polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4885102A (en) * 1987-07-17 1989-12-05 Kao Corporation Cloth-softening liquid composition containing quaternary ammonium compound and a polyether derivative or cationic surfactant polymer
JPS6461571A (en) * 1987-08-26 1989-03-08 Kao Corp Concentration type softening finish agent for clothing
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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ES2071030T5 (es) 2004-07-16
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JPH03119187A (ja) 1991-05-21
AU625206B2 (en) 1992-07-02
DE69017316T3 (de) 2004-07-01
MY106842A (en) 1995-08-30
CA2023950A1 (en) 1991-03-01
GB8919669D0 (en) 1989-10-11
ES2071030T3 (es) 1995-06-16
DE69017316D1 (de) 1995-04-06
JP2635205B2 (ja) 1997-07-30
CA2023950C (en) 2001-04-17
KR930007737B1 (ko) 1993-08-18
KR910004888A (ko) 1991-03-29
AU6196490A (en) 1991-03-07
ZA906971B (en) 1992-05-27
EP0415698A3 (en) 1991-04-10
BR9004321A (pt) 1991-09-03
DE69017316T2 (de) 1995-07-20

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