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WO2002006433A1 - Composition de lessive comprenant un polymere antisalissure a base de perfluoroalkyle - Google Patents

Composition de lessive comprenant un polymere antisalissure a base de perfluoroalkyle Download PDF

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Publication number
WO2002006433A1
WO2002006433A1 PCT/EP2001/006377 EP0106377W WO0206433A1 WO 2002006433 A1 WO2002006433 A1 WO 2002006433A1 EP 0106377 W EP0106377 W EP 0106377W WO 0206433 A1 WO0206433 A1 WO 0206433A1
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Prior art keywords
fabric
ethylenically unsaturated
perfluoroalkyl
monomer
compositions
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PCT/EP2001/006377
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English (en)
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WO2002006433A8 (fr
Inventor
Yu-Tian Shi
De-Bao Su
Shang-Ren Wu
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Unilever Plc
Unilever N.V.
Hindustan Lever Limited
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Application filed by Unilever Plc, Unilever N.V., Hindustan Lever Limited filed Critical Unilever Plc
Priority to AU2001267523A priority Critical patent/AU2001267523A1/en
Publication of WO2002006433A1 publication Critical patent/WO2002006433A1/fr
Publication of WO2002006433A8 publication Critical patent/WO2002006433A8/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • 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
    • 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

Definitions

  • the present invention relates to laundry compositions, in particular fabric wash compositions and laundry rinse conditioning compositions, comprising perfluoroalkyl soil release polymers .
  • the present invention also relates to a method of treating fabric in a laundry process using perfluoroalkyl containing polymers.
  • Cellulose ether soil release polymers may be used, for example as described in GB 1534641. Polyester compositions are also well known as soil release polymers, for example as described in EP-A-0185427. The majority of soil release polymers used in practice belong to these two classes.
  • US 4043965 discloses copolymers of acrylic acid and 1,1- dihydroperfluoro-octyl methacrylate for applying a non- permanent soil release finish to fabric.
  • the composition may be used for applying a soil release finish in the rinse cycle of a home laundry process.
  • Specialised compositions for giving oil and water repellency to fabric are well known in the art of pre- treatment of fabric in the fabric manufacturing and clothes manufacturing industries .
  • Perfluoroalkyl containing polymers and their use for giving oil and water repellency to fabrics in this way are known for example from EP-A-0195323, EP-A-0351513 , EP-A-0424765 , US 4550189 and US 5753569.
  • the perfluoroalkyl containing polymers may be supplied as aqueous dispersions, dispersed using surfactants, for example as described in EP-A-0351513.
  • the compositions may be relatively concentrated, as in EP-A-0424765.
  • a resin may be used to fix the polymer onto the fabric as in EP-A-0195323.
  • Laundry compositions contain, as essential ingredients, fabric washing surfactants or fabric conditioning compounds. It is well known in the art that these compounds can interfere with the solubilisation or deposition of soil release polymers.
  • the present invention sets out to provide laundry compositions which contain high performance soil release polymers which have good deposition and provide oil and water repellency to the fabric being laundered.
  • perfluoroalkyl polymers which also contain aromatic moieties deposit well onto fabric even from laundry compositions.
  • the present invention provides a laundry composition comprising:
  • polymeric material obtained by copolymerising an ethylenically unsaturated perfluoroalkyl monomer and, optionally, other ethylenically unsaturated monomers, characterized in that polymeric material comprises aromatic moieties.
  • the present invention further provides a method of treating fabric, the treatment being carried out as part of the wash step of a laundry operation or the rinse step of a laundry operation, the method comprising treating fabric with polymeric material obtained by polymerising an ethylenically unsaturated perfluoroalkyl monomer and, optionally, other ethylenically unsaturated monomers, wherein the polymeric material comprises aromatic moieties.
  • Polymeric Material used in the present invention is obtained by polymerising the monomers defined above. Methods of polymerisation will be discussed further below.
  • Any suitable ethylenically unsaturated perfluoroalkyl monomer may be used.
  • the perfluoroalkyl moiety of the monomer is a group R f according to the general formula (I) :
  • m an integer in the range 3-12, preferably 6-12
  • X is a halogen atom, wherein at least 50% of the halogen atoms X are fluorine atoms and the remainder are chlorine or bromine atoms .
  • the perfluoroalkyl group R f is preferably of general formula C q F 2q+ ⁇ or C q F 2q Cl-, wherein q is an integer in the range 3-12. It is preferred that q is in the range 6-12, most preferably 8-10.
  • the ethylenically unsaturated perfluoroalkyl monomer is suitably of general formula (II) :
  • the divalent linking group A is preferably selected from Ci-Cis (optionally substituted) alkenyl, 1,4 phenyl, substituted 1,4 phenyl, Ci-C 18 alkenyl chains interrupted by -CO-, -COO-, -OCO-, -NH-, (1,4) phenyl or any other suitable linking group or any combination of such linking groups.
  • Particularly preferred linking groups are alkenyl groups of general formula (III) :
  • Any suitable ethylenically unsaturated residue X may be used. It is suitably according to general formula IV:
  • Z is a hydrogen atom, an alkyl group, preferably having 1 to 4 carbon atoms, or a hydroxy alkyl group, preferably having 1 to 4 carbon atoms
  • the ethylenically unsaturated residue is vinyl, substituted vinyl, acrylate, methacrylate, acrylonitrile or the like. It is particularly preferred that the ethylenically unsaturated perfluoroalkyl monomer is selected from the group consisting of:
  • the aromatic moiety may be included in the polymeric material in any suitable manner.
  • the aromatic moiety is introduced by copolymerising the perfluoroalkyl monomer with an ethylenically unsaturated monomer comprising at least one aromatic group.
  • the ethylenically unsaturated monomer comprising at least one aromatic group is any suitable monomer.
  • it is selected from aromatic esters of unsaturated compounds, for example benzyl or phenyl ethyl acrylate, benzyl or phenyl ethyl methacrylate, or alkenyl substituted phenyl, for example styrene, alpha-methyl styrene, paramethyl styrene, 3,4-dimethyl styrene, m-ethyl styrene, 2,5-diethyl styrene and mixtures thereof.
  • the aromatic group is introduced as a phenylene group in the divalent linking group A, as noted above .
  • the ethylenically unsaturated monomer comprising at least one aromatic group is not necessary, but is still preferred.
  • the optional ethylenically unsaturated co-monomer is selected from the group consisting of ethylene and carboxy, chloro, fluoro, amido and cyano derivatives of ethylene such as vinyl chloride, vinylidene chloride, vinyl fluoride, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N, N-dimethyl acrylamide, tetrafluoroethylene, hexafluoropropylene, acrylic acid, methacrylic acid, acrylate, methacrylate monomers, and mixtures thereof.
  • ethylene and carboxy chloro, fluoro, amido and cyano derivatives of ethylene
  • esters of (meth) acrylic acid with alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl or substituted alkyl with 1-18 carbon atoms such as n-propylmethacrylate, 2- methylcyclohexylmethacrylate, methyl methacrylate, tertiary butyl methacrylate, n-butyl methacrylate, methylacrylate, ethylacrylate, propylacrylate, butylacrylate, 3 -methyl pentylacrylate, octylacrylate, tetra-decylacrylate, secondary butylacrylate, 2-ethylhexylacrylate, 2-methoxy ethylacrylate, phenylacrylate.
  • nitrogen containing vinyl monomers such as vinylpyridine , N-vinyl amides, N-vinyl succinimide, vinyl pyrrolidone, N-vinyl carbozol, vinyl esters of substituted acids for example vinyl methoxyacetate, vinyl trimethylacetate, vinyl isobutyrate, isopropenyl butyrate, vinyl lactate, vinyl caprylate, vinyl myristate, vinyl oleate, vinyl linoleate and vinyl benzoate, mixtures thereof.
  • nitrogen containing vinyl monomers such as vinylpyridine , N-vinyl amides, N-vinyl succinimide, vinyl pyrrolidone, N-vinyl carbozol, vinyl esters of substituted acids for example vinyl methoxyacetate, vinyl trimethylacetate, vinyl isobutyrate, isopropenyl butyrate, vinyl lactate, vinyl caprylate, vinyl myristate, vinyl oleate, vinyl linoleate and vinyl benzoate, mixtures thereof.
  • alkyl esters of (meth) acrylic acid are particularly preferred.
  • the polymers of the present invention are amphiphilic. This provides the polymers with valuable surface activity.
  • they have to have a hydrophobic moiety and a hydrophilic moiety.
  • the hydrophobic moiety can be provided by the perfluoroalkyl moiety or by hydrophobic ethylenically unsaturated monomers such as alkyl esters of (meth) acrylic acid, particularly long chain (C 8 -C 18 ) alkyl esters of (meth) acrylic acid, for example dodecylacrylate .
  • the hydrophilic moiety is suitably provided by ethylenically unsaturated acidic monomers.
  • Suitable ethylenically unsaturated acidic monomers are selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloro- acrylic acid, crotonic acid, cinnamic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid and mixtures thereof.
  • the ethylenically unsaturated acidic monomers may be used in acidic or neutralised form. They may be neutralised with alkalimetal, for example sodium or potassium as counterion.
  • Acrylic acid is particularly preferred.
  • the acidic ethylenically unsaturated monomer may also provide water solubility to the polymeric material.
  • any suitable ratios of starting materials may be used.
  • the ratios of starting materials are balanced to achieve the physical properties of the polymeric material discussed below.
  • the quantity of the ethylenically unsaturated perfluoroalkyl containing monomer should be high enough to obtain a good soil release effect when deposited onto fabric.
  • the quantity of perfluoroalkyl ethylenically unsaturated monomer which reflects the need to ensure that the polymer can be formulated into a stable laundry composition and to ensure that the polymer can be successfully deposited onto fabric and adhered to it .
  • the aromatic moiety is required to assist deposition onto polyester fabric.
  • ethylenically unsaturated monomers can be included to provide other suitable properties, for example water solubility.
  • the content of ethylenically unsaturated perfluoroalkyl monomer is in the range 1% by weight - 20% by weight, more preferably 5-15% by weight, most preferably around 5-12% by weight. It is surprising that an acceptable soil release benefit can be obtained with such quantities of ethylenically unsaturated perfluoroalkyl monomer.
  • Prior art compositions relating to non-laundry fabric treatment compositions typically comprise greater than 15% by weight of such monomer.
  • aromatic moiety is incorporated by being part of the ethylenically unsaturated perfluoroalkyl containing monomer, preferably at least 50% by weight of such perfluoroalkyl containing monomer also contains aromatic moeities, more preferably at least 60% by weight.
  • the quantity of ethylenically unsaturated aromatic monomer need not be very high. The quantity can be in the range 3-15% by weight, preferably 5-10% by weight.
  • the polymeric composition contains a large quantity of an ethylenically unsaturated acidic monomer such as acrylic acid.
  • the quantity of ethylenically unsaturated acidic monomer is in excess of 50% by weight, more preferably greater than 60% by weight and preferably less than 95% by weight, more preferably less than 90% by weight.
  • Polymers which are particularly preferred for use in the present invention comprise copolymers comprising:
  • the polymers used in the present invention suitably have a number average molecular weight in the range 10,000 to 500,000.
  • the polymers are suitably in the form of solids or viscous liquids .
  • the polymers are suitably soluble in water.
  • solubility is in the range 0.2-0.5wt% at 25°C and pH 9.
  • the polymers used in the present invention have a combined soil release and anti-redeposition benefit.
  • the copolymers may be block, graft or random copolymers . They may be produced by solution, emulsion or other polymerisation techniques.
  • the present invention uses polymers manufactured by solution polymerisation in organic solvent.
  • a homogeneous mixture of the starting monomers is prepared in the organic solvent. Thereafter, polymerisation is carried out, in a manner known to the person. skilled in the art. Polymerisation conditions can be determined by the person skilled in the art. A suitable radical initiator can be used to induce polymerisation.
  • Any suitable organic solvent can be used, according to the knowledge of the person skilled in the art.
  • petroleum ether or dioxane can be used.
  • the present invention may comprise industrial or domestic fabric wash compositions, fabric conditioning compositions and compositions for both washing and conditioning fabrics (so-called through the wash conditioner compositions) .
  • the perfluoroalkyl containing polymer is suitably present in the laundry fabric compositions of the present invention at levels in excess of 0.5% by weight, preferably greater than 1.0% by weight. They are preferably present at levels less than 10% by weight and preferably less than 5% by weight .
  • Fabric wash compositions according to the present invention may be in any suitable form, for example powdered, tableted powders, liquid or solid detergent bars.
  • Fabric wash compositions according to the present invention preferably comprise a fabric wash detergent material selected from non-soap anionic surfactant, nonionic surfactants, soap, amphoteric surfactants, zwitterionic surfactants and mixtures thereof.
  • Suitable anionic surfactants are well known to the person skilled in the art and include alkyl benzene sulphonate, primary and secondary alkyl sulphates, particularly C 8 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates, dialkyl sulphosuccinates; ether carboxylates; isethionates; sarcosinates; fatty acid ester sulphonates and mixtures thereof.
  • the sodium salts are generally preferred.
  • Nonionic surfactants are also well known to the person skilled in the art and include primary and secondary alcohol ethoxylates, especially C 8 -C 2 n aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide) . Mixtures of nonionic surfactant may be used.
  • Detergent compositions suitable for use in domestic or industrial automatic fabric washing machines generally contain anionic non-soap surfactant or nonionic surfactant, or combinations of the two in suitable ratio, as will be known to the person skilled in the art, optionally together with soap.
  • detergent-active compounds are available and fully described in the literature, for example in Surface- Active Agents and Detergents , Volumes I and II, by Schwartz, Perry & Berch.
  • Anionic surfactant is suitably present at a level of from 5 wt% to 50 wt%, preferably 10 wt%-40 wt% based on the fabric treatment composition.
  • Nonionic surfactant is suitably present at a level of 1-20 wt%, preferably 5-15 wt%.
  • the total amount of surfactant present will depend upon the intended end use and may be as high as 60 wt% for example in a composition for washing fabrics by hand. In compositions for machine washing of fabric, an amount of from 5 to 40 wt% is generally appropriate.
  • the fabric wash compositions of the invention will generally also contain one or more detergency builders.
  • the total amount of detergency builder in the compositions will suitably range from 5 to 80 wt%, preferably from 10 to 60 wt%.
  • Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever ) ; crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble) ; and layered silicates as disclosed in EP 164 514B (Hoechst) .
  • Inorganic phosphate builders for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.
  • the fabric wash detergent compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder.
  • Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.
  • the alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula:
  • the preferred sodium aluminosilicates contain 1.5- 3.5 Si0 2 units (in the formula above) . Both the amorphous and the crystalline materials can be prepared readily be reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble) .
  • the preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof .
  • the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
  • the zeolite builder incorporated in the compositions of the invention may be maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever) .
  • Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
  • zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
  • the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboyxmethyloxysuccinates , carboxymethyloxymalonates , dipicolinates, hydroyxethyliminodiacetates, alkyl- and alkenylmalonates and succinates, ; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
  • polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboyxmethyloxysuccinates , carboxymethyloxymalonates
  • Especially preferred organic builders are citrates, suitable used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
  • Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
  • Laundry compositions according to the invention may also suitably contain a peroxy bleach system for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • a peroxy bleach system for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates .
  • organic peroxides such as urea peroxide
  • inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates .
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate .
  • sodium percarbonate having a protective coating against destabilisation by moisture Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture.
  • Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao) .
  • compositions may further comprise a photobleach system as described, for example, in EP-A-0035470.
  • the fabric treatment composition of the present invention may be a fabric conditioning composition or it may comprise fabric conditioner.
  • the fabric softening compound is preferably a cationic nonionic or anionic fabric softening compound.
  • the fabric softening compound may be a quaternary ammonium material comprising a polar head group and one or two alkyl or alkenyl chains .
  • the fabric softening compound may also be a nonionic fabric softening compound such as a fabric softening oil, a fabric softening silicone composition or a fabric softening ester composition such as sugar esters.
  • the fabric softening compound has two long chain alkyl or alkenyl chains with an average chain length greater than C 1 , more preferably each chain has an average chain length greater than C 14 , more preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of C 18 .
  • the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.
  • the fabric softening compounds are substantially water-insoluble .
  • Substantially insoluble fabric softening compounds in the context of this invention are defined as fabric softening compounds having a solubility less than 1 x 10 "3 wt% in demineralised water at 20°C, preferably the fabric softening compounds have a solubility less than l l most preferably the fabric softening compounds have a solubility at 20°C in demineralised water from 1 x 10 "3 to 1 x 10 "6 .
  • R 1 and R 2 represent hydrocarbyl groups having from 12 to 24 carbon atoms
  • R 3 and R 4 represent hydrocarbyl groups containing 1 to 4 carbon atoms
  • X is an anion, preferably selected from halide, methyl sulphate and ethyl sulphate groups are preferred.
  • quaternary softeners include di (tallow alkyl) dimethyl ammonium methyl sulphate; dihexadecyl dimethyl ammonium chloride; di (hydrogenated tallow alkyl) dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride; di (hydrogenated tallow alkyl) dimethyl ammonium methyl sulphate; dihexadecyl diethyl ammonium chloride; di (coconut alkyl) dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium chloride and di (hydrogenated tallow alkyl) dimethyl ammonium chloride (Arquad 2HT Trade Mark) .
  • esters or amide links for example those available under the trade names Accosoft 580, Varisoft 222, and Stepantex.
  • Particularly preferred fabric softening compounds are water-insoluble quaternary ammonium materials which comprise a compound having two C 12-18 alkyl or alkenyl groups connected to the molecule via at least one ester link. It is more preferred if the quaternary ammonium material has two ester links present.
  • the preferred ester-linked quaternary ammonium material for use in the invention can be represented by the formula:
  • each R 1 group is independently selected from C 1- alkyl, hydroxyalkyl or C 2- alkenyl groups; and wherein each R 2 group is independently selected from C 8-8 alkyl or alkenyl groups;
  • T is -C-O- or -0-C-;
  • X " is any suitable anion and n is an integer from 0-5. Particularly preferred is di (ethyl ester) dimethyl ammonium chloride (DEEDMAC) .
  • a second preferred type of quaternary ammonium material can be represented by the formula:
  • Preferred materials of this class such as 1,2 bis [hardened tallowoyloxy] -3-trimethylammonium propane chloride and their methods of preparation are, for example, described in US 4 137 180 (Lever Brothers) .
  • these materials comprise small amounts of the corresponding monoester as described in US 4 137 180 for example 1-hardened tallowoyloxy-2-hydroxy trimethylammonium propane chloride.
  • the fabric softening agent may also be a polyol ester quat (PEQ) as described in EP 0 638 639 (Akzo) .
  • PEQ polyol ester quat
  • the present invention may be in the form of a dilute or concentrated aqueous solution or suspension, for example as described in WO 97/15651, WO 95/27769.
  • the fabric softening composition may be in the form of a powder for use in the rinse cycle of an automatic washing machine.
  • the fabric softening composition may be in the form of a sheet comprising fabric conditioning compositions for use in a tumble dryer, for example as disclosed in WO 95/27777.
  • Fabric wash detergent compositions according to the present invention may further include through the wash softening material, such as cationic fabric softener.
  • the laundry compositions of the invention can also contain one or more optional ingredients, selected from pH buffering agents, perfume carriers, fluorescers, colorants, hydrotropes, antifoaming agents, antiredeposition agents, enzymes, optical brightening agents, opacifiers, anti- shrinking agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids
  • a 0.2 wt% aqueous solution of polymer was prepared.
  • 3.5cm x 3.5cm test sheets of fabric were taken.
  • the fabrics were desized before use by boiling in 1 molar sodium carbonate for 30 minutes. After washing to a neutral pH, the fabric is boiled continuously for a further 30 minutes and oven dried at 50°C in an oven.
  • the desized fabrics were soaked in the aqueous solution at 25°C. After soaking for 30 minutes, the cloths were removed and rinsed with distilled water. The resulting cloths were oven dried at 50°C for 1 hour25. The increase in dry weight was measured. Polyester and cotton test sheets were tested separately.
  • Polyester fabric was treated as set out above. Soil release was tested by placing 17 x 0.1.ml drops of oil comprising 15 mg Sudan IV oil dissolved in 100 ml of sesame oil on the approximate centre of each test specimen using a laboratory pipette. Oil was allowed to wick for 24 hours. The test cloths were then washed at 25°C for 30 minutes of 375 revolutions per minute in water only. The reflectance data at 520 mm were measured for fabric after oil staining and after washing. Comparison with reflectance data after washing shows the extent of soil release of the polymer. Reflection is measured using a colour-eye spectrometer at 520 mm.
  • the ability of the polymers to prevent soil redeposition was assessed as follows. An untreated polyester or cotton cloth was washed in 100 ml of water comprising 0.1% by weight carbon black and 0.25 Wt% of a detergent composition containing the polymer at 25°C for 1.5 hours at 375 rs/m, rinsed and oven dried at 50°C.
  • the detergent compositions were as follows: NaCl - 33% by weight
  • Anionic surfactant (LAS) 20% by weight
  • Polymeric material - 4% by weight.
  • a homogeneous mixture of monomeric starting materials in 1,4 dioxane was prepared.
  • the monomer mixture comprised the following:
  • AIBN azobisiso-butyronitrile
  • Monomer concentration in the solvent was 10 wt% approximately.
  • the solvent comprised 1 wt% AIBN based upon the total monomer content .
  • Polymerisation was carried out at 80°C for 6 hours with continuous stirring. Before polymerisation, the components were degassed by the application of the freeze-thaw technique .
  • the polymer product was isolated by triturating in petroleum ether. The isolated product was dried under vacuum at 60°C to give a final product. Yield was approx 90wt%. The experiment was repeated with various comparative monomer mixtures. The compositions of the monomer mixtures are set out in Table 1 below.
  • the polymers were all solid precipitates.
  • the polymer products were analysed using infrared spectroscopy (using a Shimadzu IR-440 or Digilab FTS-20E Spectrometer [trade mark] ) .
  • H spectra were recorded with a Bruker (trade mark) AM-300 Spectrometer.
  • 19F NMR spectra were then recorded busing the same spectrometer.
  • C and H elements were assessed using a Carlo-Erba 1106 Elemental Alalyser.
  • the fluorine content could also be analysed using a Thorium salt titration method.
  • the analytical techniques described were used to assess the quantities of monomers in the resulting polymers. The results are shown in Table 1.
  • T-AN and AA have the meaning set out above, or their corresponding repeat units. The following species are found to be present :
  • Y is -C0 2 C 12 H 25 ,
  • P is C 6 H 5 _
  • R is -C0 2 CH 2 CH 2 C 8 F 17
  • Gerol (trade mark) , a commercially available soil release polymer. Table 2 below sets out the polymers used, pH and resulting deposition with polymers according to the present invention (polymer e) , and fluoroalkyl/acrylic acid polymer (polymer a) and Gerol as
  • polymer e according to the invention gives a much improved deposition compared to the fluoroalkyl/acrylic acid polymer and a comparable deposition to the product Gerol (trade mark) .
  • Soil release properties were assessed according to the methods set out above.
  • the soil release properties obtainable using polymer according to the present invention (polymer e) was compared with soil release obtained with an acrylic acid/perfluoroalkyl copolymer (polymer a) and
  • the effect on soil deposition was then assessed by the methods set out above.
  • the antiredeposition effect of polymers used according to the present invention was compared with that of the polymer Gerol (trade mark) and of a composition containing no anti-redeposition polymer.
  • composition comprising no anti-reposition polymer comprised 33% by weight sodium chloride instead of 29% by weight sodium chloride, to make up the weight.
  • a further comparison was conducted by washing with water only. The results are shown in Table 4.
  • the decrease in reflectivity (which is a measure of the tendency of the carbon black to deposit onto the fabric during washing) is significantly less for polymers used according to the present invention than for compositions containing no polymer.
  • the decrease in reflectance is not as good as for the commercial product Gerol, but it is still acceptable.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne une matériau polymère, obtenu par polymérisation d'un monomère éthyléniquement insaturé à base de perfluoroalkyle et éventuellement d'autres monomères éthyléniquement insaturés. Ce polymère comprenant des groupes aromatiques peut être utilisé afin de conférer à un tissu des propriétés anti re-dépôt de salissure, antisalissure et oléophobes, lorsqu'il est utilisé lors des étapes de lavage ou de rinçage d'une lessive.
PCT/EP2001/006377 2000-07-17 2001-06-05 Composition de lessive comprenant un polymere antisalissure a base de perfluoroalkyle WO2002006433A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001267523A AU2001267523A1 (en) 2000-07-17 2001-06-05 Laundry composition comprising perfluoroalkyl soil release polymer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0017521.6 2000-07-17
GB0017521A GB0017521D0 (en) 2000-07-17 2000-07-17 Laundry composition comprising perfluoroalkyl soil release polymer and method of treating fabric in a laundry process

Publications (2)

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WO2002006433A1 true WO2002006433A1 (fr) 2002-01-24
WO2002006433A8 WO2002006433A8 (fr) 2003-02-20

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AU (1) AU2001267523A1 (fr)
GB (1) GB0017521D0 (fr)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007070380A3 (fr) * 2005-12-12 2008-03-13 Milliken & Co Adoucissant textile anti-tache et detachant
US7893014B2 (en) 2006-12-21 2011-02-22 Gregory Van Buskirk Fabric treatment for stain release
US10822577B2 (en) 2002-04-09 2020-11-03 Gregory van Buskirk Fabric treatment method for stain release
US10900168B2 (en) 2002-04-09 2021-01-26 Gregory van Buskirk Fabric treatment for stain repellency
US11421186B2 (en) 2019-02-28 2022-08-23 Ecolab Usa Inc. Hardness additives and block detergents containing hardness additives to improve edge hardening

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4550189A (en) * 1982-08-23 1985-10-29 American Hoechst Corporation Soil repellents derived from fluorinated acrylates and aromatic amines
US4695488A (en) * 1985-03-12 1987-09-22 Daikin Industries, Ltd. Soil release composition and use thereof
US4954545A (en) * 1987-07-27 1990-09-04 Phillips Petroleum Company Process for cleaning polymer processing equipment
US5753569A (en) * 1994-11-25 1998-05-19 Bayer Aktiengesellschaft Substrates which have been provided with an oil-, water- and soil-repellant treatment and fluorine-containing compositions for this purpose
EP0909802A1 (fr) * 1996-06-21 1999-04-21 Daikin Industries, Limited Hydrofuge oleofuge fluore en dispersion aqueuse
US6075003A (en) * 1997-03-14 2000-06-13 Lever Brothers Company, Division Of Conopco, Inc. Fabric laundry treatment composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4550189A (en) * 1982-08-23 1985-10-29 American Hoechst Corporation Soil repellents derived from fluorinated acrylates and aromatic amines
US4695488A (en) * 1985-03-12 1987-09-22 Daikin Industries, Ltd. Soil release composition and use thereof
US4954545A (en) * 1987-07-27 1990-09-04 Phillips Petroleum Company Process for cleaning polymer processing equipment
US5753569A (en) * 1994-11-25 1998-05-19 Bayer Aktiengesellschaft Substrates which have been provided with an oil-, water- and soil-repellant treatment and fluorine-containing compositions for this purpose
EP0909802A1 (fr) * 1996-06-21 1999-04-21 Daikin Industries, Limited Hydrofuge oleofuge fluore en dispersion aqueuse
US6075003A (en) * 1997-03-14 2000-06-13 Lever Brothers Company, Division Of Conopco, Inc. Fabric laundry treatment composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10822577B2 (en) 2002-04-09 2020-11-03 Gregory van Buskirk Fabric treatment method for stain release
US10900168B2 (en) 2002-04-09 2021-01-26 Gregory van Buskirk Fabric treatment for stain repellency
WO2007070380A3 (fr) * 2005-12-12 2008-03-13 Milliken & Co Adoucissant textile anti-tache et detachant
US7893014B2 (en) 2006-12-21 2011-02-22 Gregory Van Buskirk Fabric treatment for stain release
US11421186B2 (en) 2019-02-28 2022-08-23 Ecolab Usa Inc. Hardness additives and block detergents containing hardness additives to improve edge hardening
US11788032B2 (en) 2019-02-28 2023-10-17 Ecolab Usa Inc. Hardness additives comprising an aminocarboxylate chelant mixture and block detergents containing this mixture to improve edge hardening
US12065629B2 (en) 2019-02-28 2024-08-20 Ecolab Usa Inc. Hardness additives comprising an acrylate/aminocarboxylate mixture and block detergents containing said mixture to improve edge hardening

Also Published As

Publication number Publication date
AU2001267523A1 (en) 2002-01-30
GB0017521D0 (en) 2000-08-30
WO2002006433A8 (fr) 2003-02-20

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