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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
  • C11D3/0015—Softening compositions liquid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
• • 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
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

• the present invention relates to a thickener/stabilizer, in particular used in softening compositions for laundry. It is a cationic polymer obtained by polymerization of cationic monomers and of monomers with a hydrophobic nature.
• thickeners in softening compositions makes it possible to improve their rheological profile and therefore to modify the properties of the softening formulation.
• the role of the softener is to provide a much more pleasant feel by lubrication of the animal textile fibres (wool in particular) and plant textile fibres (cotton) and of the synthetic fibres after treatment. It also provides antistatic properties by reducing the friction between fibres, it provides sensations of freshness by virtue of the fragrances incorporated, and it makes it possible to bring out the colours and to facilitate ironing.
• thickener is intended to mean, without implied distinction, thickener and/or stabilizer
• Patent application PCT/EP2009/050077 still by the Applicant, describes cationic polymers, in the form of an inverse emulsion, which are very heavily crosslinked and have a maximum insoluble material content of 15%. These polymers can be used in softening compositions.
• EP 0 172 723 and EP 0 172 724 describe polymer compositions and an inverse emulsion polymerization process for preparing anionic or cationic, linear or crosslinked polymers containing hydrophobic groups having more than 8 carbon atoms.
• the presence of the semihydrophobic vinyl surfactant monomer is essential for the stability of the emulsions comprising this copolymer.
• Document EP 1 449 862 describes the use of a cationic polymer as a thickener in a cosmetic or pharmaceutical composition, as a thickener for printing pastes for the textile industry, as a thickener for industrial or household detergents or else in the petroleum industry.
• Said polymer comprises a cationic monomer, a neutral monomer and a nonionic surfactant monomer.
• thickeners used in the fabric softener compositions described in the prior art certainly make it possible to thicken the compositions, there is, however, a need to control the rheological profile of the formulation better and to obtain an increased stability of the composition.
• these polymers are more compatible with the other ingredients contained in the softening compositions and in particular the softeners of quaternized ester type.
• the present invention relates to a thickener containing a cationic polymer obtained by polymerization:
• R1 H or CH3
• R2 alkyl chain having at least 16 carbon atoms
• An alkyl chain is a saturated linear or branched acyclic hydrocarbon-based chain of general formula C n H 2n+1 .
• the thickener according to the present invention comprises a cationic polymer, and more specifically a cationic terpolymer, obtained by polymerization:
• R1 H or CH3
• R2 alkyl chain having at least 16 carbon atoms
• the thickener according to the present invention consists of said cationic terpolymer.
• the cationic polymer may be crosslinked or non-crosslinked.
• the crosslinking is carried out optionally in the presence of a transfer agent in order to control the molecular weight.
• the cationic monomers are advantageously chosen from the group comprising diallyldialkylammonium salts, such as diallyldimethylammonium chloride (DADMAC); acidified or quaternized salts of dialkylaminoalkyl acrylates and methacrylates, in particular of dialkylaminoethyl acrylate (ADAME) and of dialkylaminoethyl methacrylate (MADAME); acidified or quaternized salts of dialkyl-aminoalkylacrylamides or methacrylamides, such as, for example, methacrylamidopropyltrimethylammonium chloride (MAPTAC), acrylamidopropyltrimethylammonium chloride (APTAC) and the Mannich products, such as quaternized dialkylaminomethylacrylamides.
• DADMAC diallyldimethylammonium chloride
• ADAME dialkylaminoethyl acrylate
• MADAME dialkylaminoe
• the acidified salts are obtained by means known to those skilled in the art, and in particular by protonation.
• the quaternized salts are also obtained by means known to those skilled in the art, in particular, by reaction with benzyl chloride, methyl chloride (MeCl), aryl chlorides, alkyl chlorides or dimethyl sulphate.
• the content of cationic monomer represents between 25% by weight and 99.9% by weight relative to the weight of the cationic polymer, preferably between 50% by weight and 99.5% by weight.
• the monomers with a hydrophobic nature, or hydrophobic monomers are of formula (I). Mention will particularly be made of ethoxylated cetyl methacrylate (EO 25) and ethoxylated behenyl methacrylate (EO 25) and mixtures thereof.
• the hydrophobic monomer is ethoxylated behenyl methacrylate (EO 25).
• the content of hydrophobic monomer represents between 0.1% by weight and 20% by weight relative to the weight of the cationic polymer, preferably between 0.5% by weight and 5% by weight.
• the cationic polymer contained in the thickener according to the invention may be prepared by polymerization of at least one cationic monomer, of at least one monomer with a hydrophobic nature, and optionally of at least one nonionic monomer and/or of at least one anionic monomer.
• the nonionic monomers are advantageously chosen from the group comprising acrylamide, methacrylamide, N-vinylmethylacetamide or N-vinylformamide, vinyl acetate, vinylpyrrolidone, methyl methacrylate or other acrylic esters, or other ethylenically unsaturated esters, or else other water-insoluble vinyl monomers, such as styrene or acrylonitrile.
• the content of nonionic monomer represents between 0 and 74.9% by weight relative to the weight of the cationic polymer, more advantageously between 0 and 30% by weight.
• the anionic monomers are advantageously chosen from the group comprising the salts of monomers having a carboxylic function in addition to a carbon-carbon double bond, such as, for example, acrylic acid salts, methacrylic acid salts, and the salts of monomers having a sulphonic acid function, such as, for example, 2-acrylamido-2-methylpropanesulphonic acid (ATBS) salts.
• the salts of monomers having a carboxylic function in addition to a carbon-carbon double bond such as, for example, acrylic acid salts, methacrylic acid salts
• the salts of monomers having a sulphonic acid function such as, for example, 2-acrylamido-2-methylpropanesulphonic acid (ATBS) salts.
• ATBS 2-acrylamido-2-methylpropanesulphonic acid
• the content of anionic monomer represents between 0 and 50% by weight relative to the weight of the cationic polymer, preferably between 0 and 20% by weight.
• the cationic polymer contained in the thickener according to the invention may be obtained by polymerization:
• the cationic polymer contained in the thickener according to the invention may be obtained by polymerization:
• the cationic polymer according to the invention can be crosslinked in the presence of a crosslinking agent and optionally in the presence of a transfer agent.
• the crosslinking agent is advantageously chosen from the group comprising: methylenebisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethyl acrylate, vinyloxyethyl acrylate or methacrylate, triallylamine, formaldehyde, glyoxal, compounds of glycidyl ether type, such as ethylene glycol diglycidyl ether, epoxies, or a mixture of these compounds.
• MBA methylenebisacrylamide
• ethylene glycol diacrylate polyethylene glycol dimethacrylate
• diacrylamide diacrylamide
• cyanomethyl acrylate vinyloxyethyl acrylate or methacrylate
• triallylamine formaldehyde
• glyoxal compounds of glycidyl ether type, such as ethylene glycol diglycidyl ether, epoxies, or a mixture of these compounds.
• the content of crosslinking agent represents between 0 and 10% by weight relative to the weight of the cationic polymer, preferably between 0 and 5% by weight.
• the transfer agent when it is present, is chosen from the group comprising: isopropyl alcohol, sodium hypophosphite, mercaptoethanol or a mixture of these compounds.
• the content of transfer agent represents between 0 and 5% by weight relative to the weight of the cationic polymer, preferably between 0 and 2% by weight.
• the constituent cationic polymer of the thickener according to the present invention can be in liquid or solid form. It can be prepared by dispersion polymerization, by inverse emulsion polymerization, by microemulsion polymerization, or by gel polymerization, it being possible for the polymer obtained to be subsequently dried and isolated in order to have a powder.
• the cationic polymer is in the form of an inverse emulsion comprising an oily phase, an aqueous phase, at least one water-in-oil (W/O) emulsifier, at least one oil-in-water (O/W) emulsifier.
• the inverse emulsion generally comprises from 20% to 60% by weight, and preferably from 40% to 55% by weight, of linear, branched or crosslinked cationic polymer.
• water-in-oil emulsifier is intended to mean emulsifiers which have an HLB value that is sufficiently low to provide water-in-oil emulsions, such as the surfactant polymers sold under the name Hypermer® or such as sorbitan extracts, for instance sorbitan monooleate or sorbitan isostearate.
• oil-in-water emulsifier is intended to mean emulsifiers which have an HLB value that is sufficiently high to provide oil-in-water emulsions, such as ethoxylated sorbitan esters, for instance ethoxylated sorbitan oleate with 20 equivalents of ethylene oxide (EO 20).
• the copolymerization of the precursor monomers is carried out at a pH greater than 4 and preferably between 4 and 6.
• the inverse emulsion generally contains from 1% to 10% by weight, and preferably from 2.5% to 9% by weight, of water-in-oil (W/O) emulsifiers and from 2% to 10% by weight, and preferably from 2.5% to 6% by weight, of oil-in-water (O/W) emulsifiers.
• W/O water-in-oil
• O/W oil-in-water
• the inverse emulsion contains an oily phase representing from 15% to 40%, preferably from 20% to 25% of its total weight.
• This oily phase can be either a commercial mineral oil containing saturated hydrocarbons of paraffinic, isoparaffinic or cycloparaffinic type, having at ambient temperature a density of between 0.7 and 0.9, or a vegetable oil, or a synthetic oil, or a mixture of several of these oils.
• the inverse emulsion contains between 2% and 40% of water. It can also contain various additives, such as complexing agents, transfer agents or chain-limiting agents.
• reaction medium resulting from step b) is concentrated by distillation, before step c) is carried out.
• reaction medium resulting from step b) is completely dried.
• step c) is not carried out.
• the pH of the starting aqueous solution is adjusted to a pH greater than or equal to 4 before step c) is carried out.
• polymers of the invention obtained in the form of a powder by any one of the techniques described above, have the main advantage of being proposed without solvent. They will therefore be quite particularly suitable for compositions which are highly sensitive to residual odour, regulatory and/or toxicological profile problems.
• Another subject of the present invention is therefore a softening composition
• a softening composition comprising at least one thickener as previously described and also at least one softener.
• the present invention relates to a softening composition
• a softening composition comprising at least one thickener containing a cationic polymer, and more specifically a cationic terpolymer, obtained by polymerization:
• R1 H or CH 3
• R2 alkyl chain having at least 16 carbon atoms
• the present invention relates to a softening composition
• a softening composition comprising at least one thickener consisting of a cationic terpolymer obtained by polymerization:
• R1 H or CH 3
• R2 alkyl chain having at least 16 carbon atoms
• the softening compositions, into which the polymers of the invention are introduced, are used during or after the washing of textile materials. They are applied during washing, generally at the stage of the rinse cycle, where they are added to the rinsing water, or during the drying cycle, where they are used dry, for example, as an impregnation agent on a woven or nonwoven fabric strip.
• the content of thickener in the softening composition represents 0.05% to 10% relative to the weight of the softening composition or, preferably, 0.1 to 5%.
• the textile material softening compositions are aqueous compositions containing softeners of quaternized ester type. These molecules are not soluble in water. They have a cationic nature. They have a hydrophilic part for affinity with the textile substrate, cellulose fibres, and a hydrophobic part (a long alkyl chain) which provides the softening function by lubrication.
• Any cationic substance which is substantive when rinsing with water on the textile, and which is capable of making the textile soft, can be used as softener.
• a large number of these substances are known and comprise quaternary compounds as follows:
• the cationic softeners generally preferred are those which contain long-chain fatty alkyl groups derived from tallow or from hydrogenated tallow and the class of softeners generally preferred is that of type (i), i.e. the alkyl dimethyl ammonium compounds.
• compositions can contain other optional ingredients, for example, emulsifiers for polyorganosiloxanes, fragrances, optical brighteners and dyes.
• Particularly preferred optional ingredients of aqueous fabric softener compositions are certain nonionic emulsifiers, such as fatty acid esters of monoalcohols and polyalcohols, for example glyceryl monostearate, sorbitan monolaurate and sorbitan monooleate. These esters can be used in proportions that are conventional for softening compositions, preferably from approximately 1 to 5% of the weight of the aqueous composition.
• An aqueous phase of water-soluble monomers is prepared by mixing the following compounds:
• An organic phase is prepared by adding the following compounds:
• the two phases are mixed in a 1 L stirred reactor, with the aqueous phase being poured into the organic phase, and then they are subjected to a strong shear (of rotor stator type) for 1 minute in order to form a water-in-oil emulsion. This emulsion is then deoxygenated by bubbling nitrogen for 30 minutes.
• the polymerization is carried out by simple addition of a redox couple of the type sodium metabisulphite and tert-butyl hydroperoxide in solution in water.
• the emulsion After having reached the maximum polymerization temperature (adiabatic polymerization) the emulsion is maintained at 65° C. for 1 h.
• Vacuum distillation makes it possible to remove the water and the volatile light oil so as to obtain a final concentration of polymer of approximately 58%.
• the final step consists in adding an oil-in-water surfactant: 6.0% by weight of ethoxylated fatty alcohol (trideceth-6) is added to 100% by weight of distilled products.
• an oil-in-water surfactant 6.0% by weight of ethoxylated fatty alcohol (trideceth-6) is added to 100% by weight of distilled products.
• Example 1 The protocol of Example 1 is reproduced without ethoxylated behenyl methacrylate (EO 25).
• Example 1 is reproduced in the absence of the crosslinking agent, methylenebisacrylamide.
• Example 1 is reproduced in the absence of crosslinking agent and in the absence of ethoxylated behenyl methacrylate (EO 25).
• Example 1 is reproduced with the ethoxylated behenyl methacrylate (EO 25) being replaced with ethoxylated cetyl methacrylate (EO 25).
• Example 1 is reproduced, but with the ethoxylated behenyl methacrylate being replaced with ethoxylated dodecyl methacrylate (EO 25).
• the viscosity of the base obtained is then measured with a Brookfield RVT viscometer, 10 rpm, 25° C. The value is 160 cps.
• the viscosity of the final product obtained is then measured with a Brookfield RVT viscometer, 10 rpm, 25° C.
• the polymers of the invention P1, P2 and P3 therefore make it possible to significantly increase the viscosity of a softening composition and its stability over time.

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

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• 2010
  • 2010-05-27 FR FR1054095A patent/FR2960548B1/fr not_active Expired - Fee Related
• 2011
  • 2011-05-27 CN CN201180025698.7A patent/CN102918144B/zh active Active
  • 2011-05-27 WO PCT/FR2011/051208 patent/WO2011148110A1/fr active Application Filing
  • 2011-05-27 ES ES11727273.2T patent/ES2635101T3/es active Active
  • 2011-05-27 BR BR112012029741-4A patent/BR112012029741B1/pt active IP Right Grant
  • 2011-05-27 CN CN201510757493.8A patent/CN105331458B/zh active Active
  • 2011-05-27 PL PL11727273T patent/PL2576752T3/pl unknown
  • 2011-05-27 MX MX2012013666A patent/MX336902B/es active IP Right Grant
  • 2011-05-27 EP EP11727273.2A patent/EP2576752B1/fr active Active
• 2012
  • 2012-11-21 US US13/683,919 patent/US20130090282A1/en not_active Abandoned
• 2013
  • 2013-10-28 US US14/064,856 patent/US9018154B2/en active Active
• 2015
  • 2015-03-23 US US14/665,100 patent/US9290720B2/en active Active

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