EP0882117A1 - Soil-repellent agent and method for treating articles based on woven cotton - Google Patents

Soil-repellent agent and method for treating articles based on woven cotton

Info

Publication number
EP0882117A1
EP0882117A1 EP97906221A EP97906221A EP0882117A1 EP 0882117 A1 EP0882117 A1 EP 0882117A1 EP 97906221 A EP97906221 A EP 97906221A EP 97906221 A EP97906221 A EP 97906221A EP 0882117 A1 EP0882117 A1 EP 0882117A1
Authority
EP
European Patent Office
Prior art keywords
agent
cationic
cotton
function
carrying
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97906221A
Other languages
German (de)
French (fr)
Other versions
EP0882117B1 (en
Inventor
Emmanuelle Chilou
Claire David
Etienne Fleury
Jean-Pierre Marchand
Kenneth Wong
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
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Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP0882117A1 publication Critical patent/EP0882117A1/en
Application granted granted Critical
Publication of EP0882117B1 publication Critical patent/EP0882117B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/3753—Polyvinylalcohol; Ethers or esters 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/60—Sulfonium or phosphonium compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the subject of the present invention is a method of anti-soiling treatment of articles based on woven cotton, by depositing an anti-soiling agent on said article during one or more washing, rinsing and / or softening or drying and an anti-fouling agent for woven cotton articles
  • a first object of the invention consists of a process for the anti-fouling treatment of articles based on woven cotton, by deposition on said article, during one or more washing, rinsing and / or softening or drying operations. , an amphiphilic anti-fouling agent soluble or dispersible in the treatment medium, said anti-fouling agent having
  • said method makes it possible to treat articles of woven cotton fibers against soiling, the latter also suitable for the treatment of articles consisting of a mixture of cotton fibers and other fibers, natural, artificial or synthetic, such as viscose, polyesters, polyacryhchic fibers ..., fibers other than cotton can represent up to 65% of the fiber mixture.
  • said motif carrying a function Is a cationic function (MC) capable of being adsorbed on the surface of the cotton and its counterion.
  • an anti-fouling treatment process for articles based on woven cotton by deposition on said article, during one or more washing, rinsing and / or softening or drying, of an amphiphilic anti-fouling agent soluble or dispersible in the treatment medium, said anti-fouling agent having
  • MC cationic function
  • MH unit of hydrophobic character
  • hydrophobic character unit capable of configuring the anti-fouling agent at the cotton / water interface, any pattern which, in the treatment medium, promotes the sharing of the anti-fouling molecule between water and the surface of the cotton-based article woven.
  • these hydrophobic character patterns are also capable of interacting with soil components.
  • the counterions capable of forming a salt with said cationic functions can be of any nature. Mention may be made of halide ions (CI “ , Br “ , ...), acetate, sulfate, sulfonate, phosphate ... Among the counter preferential ions, there may be mentioned in particular the Br “and Cl " ions. Among the units of hydrophobic nature (MH), mention may be made of hydrocarbon groups, such as alkyls, alkenyls, linear, branched or cyclic, aryls, etc. containing at least 4 carbon atoms, preferably from 8 to 20 carbon atoms . Mention may very particularly be made of C4-C20- alkyl groups.
  • Said motif with hydrophobic character can itself be one of the substituents of the heteroatom of the motif carrying a function with cationic character (MC), or be chemically linked to said motif (MC) via a hydrophilic chain.
  • hydrophilic chains mention may be made of hydrophilic oligomer or polymer chains consisting of oligomer units or similar or different polymers such as those derived from
  • polysaccha ⁇ des guar, cellulose derivatives, alginates, starch derivatives .
  • polyoxyalkylene glycols polyoxyethylene glycols
  • copolyesters in particular terephthalic (ethylene terephthalate / poly (oxyethylene) terephthalate copolymers, etc.)
  • sulfone copolyesters terephthalic in particular (copolymers derived from terephthalic, isophthalic, sulfoisophthalic and diol acids, anhydrides or diesters ). polyvinyl alcohols and their copolymers. acrylic polymers and copolymers
  • hydrophilic functions such as sulfonate, carboxylate, phosphate, etc.
  • hydrophilic functions such as sulfonate, carboxylate, phosphate, etc.
  • MC cationic
  • Amounts in the range of 0.1 to 40 parts by weight of cationic functions per 100 parts by weight of antifouling agent are generally satisfactory.
  • these can represent on the order of 0.01 to
  • HLB hydrophilic / hydrophobic balance
  • the hydrophyll of the anti-fouling molecule is such that the latter can be removed in the next wash at the same time as the soiling
  • amphiphilic anti-fouling agents which can be used, there may be mentioned in particular cationic surfactants and oligomers or polymers formed from an oligomeric trunk or hydrophilic hydrocarbon polymer having in its chain or in branching units carrying a function cationic in nature (MC) with its counterion and hydrophobic in nature (MH).
  • MC function cationic in nature
  • MH hydrophobic in nature
  • R ⁇ R ⁇ and R ⁇ are similar or different and represent H or an alkyl radical containing less than 4 carbon atoms, preferably 1 or 2 carbon atom (s) represents an alkyl radical containing more than 4 carbon atoms, preferably of the order of 8 to 20 carbon atoms.
  • X " is a halide ion, preferably bromide, acetate, sulfate ...
  • oligomeric or polymeric antifouling agents Mention may very particularly be made of dodecylt ⁇ methylammonium bromides, tetradecylt ⁇ methylammonium bromides, cetylt ⁇ methylammonium bromides.
  • At least one motif carrying a cationic (MC) function capable of adsorbing on the surface of the cotton and its counterion
  • MH hydrophobic character
  • MC cationic function
  • the functions of cationic nature are ammonium functions of formula R 1 R 2 R 3 N + - O ⁇
  • . are similar or different and represent H or an alkyl radical containing less than 4 carbon atoms, preferably 1 or 2 carbon atom (s), optionally substituted, in particular by one or more hydroxyl function (s),. or else form together, with the nitrogen atom N + , at least one aromatic or non-aromatic ring, said functions of cationic nature (MC) being chemically linked to the oligomer, polymer or copolymer chain of polyvinyl alcohol directly by CC bond or indirectly via a bivalent or polyvalent hydrocarbon group containing at least one heteroatom.
  • cationic (MC) functions mention may in particular be made of those derived from glycidylt ⁇ methylammonium chloride or bromide, chloro-1 chloride, 2-hydroxypropyl trimethylammonium
  • bivalent or polyvalent hydrocarbon groups containing at least one heteroatom mention may be made those with a free bond ether, ester, urethane, acetal, amide ...
  • halide ions CI “ , Br “ , 7), acetate, sulfate, sulfonate, phosphate ... hydrophobic (MH)
  • linear or branched alkyl radicals preferably linear, containing from 8 to 20 carbon atoms, these being able to be chemically linked to the oligomer, polymer or copolymer chain of polyvinyl alcohol directly by CC link or indirectly by through a bivalent or polyvalent hydrocarbon group containing at least one heteroatom.
  • bivalent or polyvalent hydrocarbon groups containing at least one heteroatom mention may be made of those having a free ether, ester, urethane, acetal, amide bond, etc.
  • said agent contains of the order of 0.1 to 10, preferably from 1 to 6 units carrying a cationic function (MC) per 100 monomer units of the oligomer, of the polymer or of the polyvinyl alcohol copolymer, and from 0.01 to 10, preferably from 0.1 to 5 units of hydrophobic nature (MH) per 100 monomer units of the polymer or copolymer of polyvinyl alcohol
  • MC cationic function
  • MH hydrophobic nature
  • oligomers polymers and copolymers of vinyl alcohol constituting the hydrophilic chain
  • Said anti-fouling agent which is the subject of the invention can be obtained for example by modification of a homopolymer or of a copolymer of vinyl acetate, at least partially hydrolyzed to (co) polyvinyl alcohol (that is to say -display hydrolysis up to at least 80%) by grafting using precursor compounds of the units carrying cationic function (MC) and hydrophobic units (HD), this modification by grafting involves substitution reactions (for example ester ication, acetalisatio ⁇ , Merkeléffication ..) well known to those skilled in the art and described in particular in “Polyvinyl Alcohol Developments" - Ed.
  • CA Finch (Wiley) - pages 183 and following and 84 and following II can also be prepared by radical copolymerization of vinyl acetate and of precursor comonomers of units carrying cationic function (MC) and hydrophobic units (MH) followed by hydrolysis (deacetalization). This type of process is also well known to those skilled in the art and described in "Polyvinyl Alcohol Developments” - Ed. C. A Finch (Wiley).
  • a particular antifouling agent can be obtained by modification of a polyvinyl alcohol using (2,3-epoxypropyl) tmethylammonium chloride followed by a modification using an alkylisocyanate.
  • the amounts of soiling agent that can be used according to the treatment method of the invention depend on the nature of the molecule used. These can be of the order of 0.05 to 5 grams (s) per liter of treatment medium.
  • the anti-fouling agent can be used during a washing operation by means of a washing powder or liquid formulation (detergent composition), the treatment medium being constituted by the bath. of washing. 97/31085 PC17FR97 / 00304
  • the powder or liquid detergent compositions may contain on the order of 0.02 to 20% of their weight of said anti-fouling agent.
  • additives of the type described below may be present - SURFACTANT AGENTS, in amounts corresponding to approximately 3-40% by weight relative to the detergent composition, surfactants such as anionic surfactants
  • alkyl sulfonate esters of formula R-CH (S ⁇ 3M) -COOR ' where R represents a C-8-20 alkyl radical. preferably C10-C16 'R' an alkyl radical C6 alkyl, preferably C1 -C3, and M an alkali metal cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, t ⁇ méthyl- , tetramethylammonium, dimethylpipe ⁇ dinium) or derivative of an alkanolamine (monoethanolamine, diethanolamine, triethanolamine) Mention may very particularly be made of methyl ester sulfonates whose radicals R is C - ⁇ ⁇ -C] Q, the alkyl sulfates of formula ROSO3M, or R represents a C5-C24 alkyl or hydroxyalkyl radical, preferably Cj o-Cl ⁇ 'M representing a hydrogen
  • the alkylamide sulfates of formula RCONHROSO3M or R represents an alkyl radical in C2-C22. preferably in C5-C20.
  • R 'a C2-C3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylene derivatives (OE) and / or propoxylenes (OP), having an average of 0, 5 to 60 OE and / or OP patterns,.
  • the salts of saturated or unsaturated C8-C24 fatty acids preferably C14-C20.
  • 'C9-C20 alkylbenzenesulfonates primary or secondary C 6 -C 22 alkyl sulfonates.
  • alkylglycerol sulfonates sulfonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccmamates alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, alkyl glycoside sulfates, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, t ⁇ methyl-, tetramethylammonium, dimethylpipe ⁇ dinium) or derivative of an alkanolamine (monoethanolamine, diethanolamine, triethanolamine), nonionic surfactants polyoxyalkylene alkylphenols (polylphenols
  • polyoxyalkylenated Cg-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units oxyethylene, oxypropylene
  • ethoxylated amines amphoteric and zwitterionic surfactants alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, Islands of condensation products of fatty acids and protein hydrolysates
  • builders agents such as adjuvants (“builders”) inorganic polyphosphates (t ⁇ polyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines
  • silicates in particular those having a Si ⁇ 2 / Na2 ⁇ ratio of the order of 1.6 / 1 to
  • alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates).
  • alkali metal silicates and alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A-488 868.
  • crystalline or amorphous aminosilicates of alkali metals (sodium, potassium) or ammonium such as zeolites A, P, X, zeolite A with a particle size of the order of 0.1-10 micrometers is preferred as adjuvants ( organic "builders"
  • water-soluble polyphosphonates ethane 1-hydroxy-1, 1 -phosphonates, methylene salts diphosphonates
  • polycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic tartrate acid and its salts, distrustic tartrate acid and its salts.
  • hydroxypolycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic tartrate acid and its salts, distrustic tartrate acid and its salts.
  • citric acid and its salts citric acid and its salts, mellitic acid, succinic acid and their salts.
  • the salts of polyacetic acids ethylenediaminetetraacetates, nitnlot ⁇ acetates, N- (2 hydroxyethyD-nit ⁇ lodiacetates) C5-C20 alkyl succinic acids and their salts (2-dodecenylsucc ⁇ nates, lauryl succinates,)
  • polyacetal carboxylic esters polyaspartic acid, polyglutamic acid and their salts, polyimides derived from the polycondensation of aspartic acid and / or glutamic acid. polycarboxymethyl derivatives of I glutamic acid or other amino acids
  • BLEACHING AGENTS in amounts of about 0.1-20%, preferably about 1 -10% by weight, optionally combined with BLEACHING ACTIVATORS, in amounts of about 0.1 -60%, preferably d '' about 0.5-40% by weight, agents and activators such as bleaches
  • perborates such as sodium perborate monohydrate or tetrahydrate peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate preferably associated with a whitening activator generating in located in the washing medium, a peroxyacidic carboxylic acid, among these activators, one can mention, tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, p-acetoxybenzene sulfonate sodium, pentaacetyl glucose, octaacetyl lactose. .
  • percarboxylic acids and their salts such as magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylam ⁇ no-4-oxoperoxybutyr ⁇ que acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, nonoxamide peroxysuccinic acid, decyldiperoxysuccinic acid.
  • These agents can be combined with at least one of the anti-fouling or anti-redeposition agents mentioned below.
  • non-oxygenated bleaching agents acting by photoactivation in the presence of oxygen, agents such as sulfonated aluminum and / or zinc phthalocyanms
  • agents such as. cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose polyvinylesters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048) .
  • polyvinyl alcohols such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose
  • polyvinylesters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048) .
  • polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units with a molar ratio (number of units) ethylene terephthalate and / or propylene terephalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 at 10/1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 to 5000, preferably of the order of 600 to 5000 (US-A-3,959,230, US-A-3,893,929, US-A-4,116,896, US-A-4,702,857, US-A-4,770,666); .
  • sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethylterephthalate and 1,2 propylene diol, having from 1 to 4 sulfone groups (US Pat. No. 4,968,451)
  • polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl or methyl units (US-A-4 71 1 730) or polyester oligomers terminated with alkylpolyethoxy groups (US-A-4 702 857) or sulfopolyethoxy anionic groups (US-A-4,721,580), sulfoaroyl groups (US-A-4,877,896)
  • sulphonated polyester copolymers derived from terephthalic, isophthalic and sulphoisophthalic acid, anhydride or diester and a diol FR-A-2 720 399) - ANTI-REDEPOSITION AGENTS, in amounts of about 0.01 -10% by weight for a powder detergent composition from about 0.01 -5% by weight for a liquid detergent composition, agents such as . ethoxylated monoamines or polyamines, polymers of ethoxylated amines (US-A-4,597,898, EP-A-1 1,984).
  • polyester sulfonated oligomers obtained by condensation of isophthalic acid, dimethyl sulfosuccinate and diethylene glycol (FR-A-2 236 926).
  • polyvinylpyrollidones obtained by condensation of isophthalic acid, dimethyl sulfosuccinate and diethylene glycol (FR-A-2 236 926).
  • aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethyl ethylenediaminet ⁇ acetates, nit ⁇ lot ⁇ acetates
  • aminophosphonates such as neutrillates (methylene phosphonates)
  • polyfunctional aromatic compounds such as dihydroxydisulfobenzenes
  • agents such as. the water-soluble salts of polycarboxylic acids of molecular mass of the order of 2000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and in particular polyacrylates of molecular mass of the order of 2,000 to 10,000 (US-A-3,308,067), copolymers of arylic acid and maleic anhydride of mass molecular of the order of 5,000 to 75,000 (EP-A-66,915).
  • agents such as
  • Q "24 C-OR 'ors is's alkali, ammonium or alkanolamine, of fatty acid triglycerides
  • saturated or aliphatic, alicyclic, aromatic or heterocyclic unsaturated hydrocarbons such as paraffins, waxes, N-alkylaminot ⁇ azines
  • monostearylphosphates monostearyl alcohol phosphates oils or polyorganosiloxane resins optionally combined with silica particles - SOFTENING AGENTS, in amounts of about 0.5-10% by weight, agents such as clays
  • - ENZYMES in quantities up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent composition, enzymes such as. proteases, amylases, lipases, cellulases, peroxidases (US-A-3 553 139, US-A-4 101 457, US-A-4 507 219, US-A-4 261 868
  • alcohols methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin. buffering agents
  • the anti-fouling agent can also be used for rinsing and / or softening by means of a liquid formulation for rinsing and / or softening of articles, the treatment medium consisting of the rinsing bath and / or softening.
  • liquid rinsing and / or softening compositions may contain of the order of
  • additives of the type may be present - associations of anionic surfactants (lauryl ether sulfate, etc.), non-ionic surfactants (lauryl ether sulfate, etc.), non-ionic surfactants (lauryl ether sulfate, etc.), non-ionic surfactants (lauryl ether sulfate, etc.), non-ionic surfactants (lauryl ether sulfate, etc.), non-ionic surfactants (lauryl ether sulfate, etc.), non-ionic surfactants (lauryl ether sulfate, etc.), non-ionic surfactants (lauryl ether sulfate, etc.), non-ionic surfactants (lauryl ether sulfate, etc.), non-ionic surfactants (lauryl ether sulfate, etc.), non-ionic surfactants (lauryl ether sulfate, etc.), non-
  • the anti-fouling agent can also be introduced on drying in the damp linen to be dried, by means of a support constituted for example by a strip of nonwoven fabric impregnated with said anti-fouling agent, support which can contain approximately 20% of its weight of antifouling agent.
  • composition of detergent parts by weight Composition of detergent parts by weight
  • the rinse pretreatment is carried out at 100 cycles / minute for 20 minutes at
  • test pieces are used as a reference and pretreated with water alone (30 ° TH).
  • the washing is carried out at 40 ° C for 20 minutes, using 5g of the detergent described above for 1 liter of water of 30 ° TH, then 3 rinses of 5 minutes in cold water and 2 dryings under ice
  • test pieces The results observed on the pretreated test pieces, compared to those observed on the reference test pieces, are the following test pieces tested in% those of reference 57 those treated CTAB 68 those treated TTAB 72
  • the antifouling agent tested is a cationic alkylguar (AGC), having a viscosity at 1% in water of 1000 mPa s, containing 1.7% by weight of nitrogen derived from hydroxypropylt ⁇ methylammonium chloride and having derived alkyl groups.
  • AAC cationic alkylguar
  • PVQH polyvinyl alcohol
  • the proportion of grafted ammonium groups is then obtained by comparing the integral of the CHp protons of polyvinyl alcohol (between 1.2 and 1.5 ppm) with that of the ammonium protons l (CH3) 3N + J to 3 , 1 ppm
  • the mixture is heated to 90 ° C. to dissolve the polymer
  • reaction medium is maintained at 90 ° C for 8 hours, then the polymer is separated by precipitation with ethyl acetate
  • the proportion of grafted hydrophobic units is then obtained by comparing the integral of the CH2 protons of polyvinyl alcohol (between 1.2 and 1.5 ppm) with that of methyl at the end of the alkyl chain (at 0.8 ppm). ) or with that of the methylene group of the alkyl chain in alpha of the carbamate group (at 2.9 ppm)
  • the performances of the antifouling agent prepared in Example 4 are evaluated at 0.2 g / l of water, vis-à-vis the drain oil and a purple pigmentary stain (olive oil colored by a purple organic pigment)
  • the results observed on the pretreated test pieces, compared to those observed on the reference test pieces, are as follows

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Woven Fabrics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

A soil-repellent treatment method for articles based on woven cotton, wherein an amphiphilic soil-repellent agent soluble or dispersible in the treatment medium is deposited on the article during one or more washing, rinsing and/or softening or dying steps, is disclosed. Said soil-repellent agent comprises at least one unit with a function (FAd) capable of being absorbed onto the surface of the cotton by electrostatic interaction; and at least one hydrophobic unit (MH) capayble of configuring said agent at the cotton/water interface. A soil-repellent agent comprising at least one unit with a cationic function (MC) capable of being absorbed onto the surface of the cotton, and the counter-ion thereof, as well as at least one hydrophobic unit (MH) containing at least four carbon atom chemically bonded to the unit having said cationic function (MC) via an oligomeric, polymeric or copolymeric vinyl alcohol chain, is also disclosed.

Description

AGENT ANTISALISSURE ET PROCEDE DE TRAITEMENT DES ARTICLES A BASE DE COTON TISSEANTIFOULING AGENT AND PROCESS FOR TREATING WOVEN COTTON ARTICLES
La présente invention a pour objet un procédé de traitement anti-salissure des articles à base de coton tissé, par dépôt d'un agent anti-salissure sur ledit article au cours d'une ou d'opératιon(s) de lavage, rinçage et/ou adoucissage ou séchage et un agent antisalissure des articles a base de coton tisséThe subject of the present invention is a method of anti-soiling treatment of articles based on woven cotton, by depositing an anti-soiling agent on said article during one or more washing, rinsing and / or softening or drying and an anti-fouling agent for woven cotton articles
Un premier objet de l'invention consiste en un procédé de traitement antisalissure des articles à base de coton tissé, par dépôt sur ledit article, au cours d'une ou d'opératιon(s) de lavage, rinçage et/ou adoucissage ou séchage, d'un agent antisalissure amphiphile soluble ou dispersible dans le milieu de traitement, ledit agent anti-salissure présentantA first object of the invention consists of a process for the anti-fouling treatment of articles based on woven cotton, by deposition on said article, during one or more washing, rinsing and / or softening or drying operations. , an amphiphilic anti-fouling agent soluble or dispersible in the treatment medium, said anti-fouling agent having
. au moins un motif porteur d'une fonction (FAd.) susceptible de s'adsorber sur la surface du coton par interaction électrostatique . et au moins un motif a caractère hydrophobe (MH) susceptible de configurer ledit agent à l'interface coton/eau, ledit motif (MH) pouvant être lui-même un des constituants du motif porteur d'une fonction (FAd ) ou pouvant être lié chimiquement au motif porteur d'une fonction (FAd.) par l'intermédiaire d'une chaîne hydrophile, ledit agent anti-salissure étant mis en oeuvre au lavage par l'intermédiaire d'une formulation de lavage, au rinçage et/ou adoucissage par l'intermédiaire d'une formulation de rinçage et/ou d'adoucissage ou au séchage par l'intermédiaire d'un support absorbant. at least one motif carrying a function (FAd.) capable of being adsorbed on the surface of the cotton by electrostatic interaction. and at least one motif of hydrophobic nature (MH) capable of configuring said agent at the cotton / water interface, said motif (MH) being able to be itself one of the constituents of the motif carrying a function (FAd) or possibly being chemically linked to the motif carrying a function (FAd.) via a hydrophilic chain, said anti-fouling agent being used for washing by means of a washing formulation, for rinsing and / or softening by means of a rinse and / or softening formulation or by drying by means of an absorbent support
Selon l'invention, ledit procède permet de traiter contre la salissure les articles en fibres de coton tissées , celui-ci convient également pour le traitement d'articles constitués de mélange de fibres de coton et de fibres autres, naturelles, artificielles ou synthétiques, telles que viscose, polyesters, fibres polyacryhques ..., les fibres autres que le coton pouvant représenter jusqu'à 65% du mélange de fibres.According to the invention, said method makes it possible to treat articles of woven cotton fibers against soiling, the latter also suitable for the treatment of articles consisting of a mixture of cotton fibers and other fibers, natural, artificial or synthetic, such as viscose, polyesters, polyacryhchic fibers ..., fibers other than cotton can represent up to 65% of the fiber mixture.
D'une manière préférentielle, ledit motif porteur d'une fonction (FAd.) est une fonction à caractère cationique (MC) susceptible de s'adsorber sur la surface du coton et son contre-ion.Preferably, said motif carrying a function (FAd.) Is a cationic function (MC) capable of being adsorbed on the surface of the cotton and its counterion.
Il s'agit donc, d'une manière préférentielle, d'un procédé de traitement antisalissure des articles a base de coton tissé, par dépôt sur ledit article, au cours d'une ou d'opératιon(s) de lavage, rinçage et/ou adoucissage ou séchage, d'un agent antisalissure amphiphile soluble ou dispersible dans le milieu de traitement, ledit agent anti-salissure présentantIt is therefore, preferably, an anti-fouling treatment process for articles based on woven cotton, by deposition on said article, during one or more washing, rinsing and / or softening or drying, of an amphiphilic anti-fouling agent soluble or dispersible in the treatment medium, said anti-fouling agent having
. au moins un motif porteur d'une fonction a caractère cationique (MC) susceptible de s'adsorber sur la surface du coton et son contre-ion . et au moins un motif a caractère hydrophobe (MH) susceptible de configurer ledit agent à l'interface coton/eau, ledit motif (MH) pouvant être lui-même un des constituants du motif porteur d'une fonction à caractère cationique (MC) par liaison chimique à l'hétéroatome du motif (MC), ou pouvant être lié chimiquement au motif porteur d'une fonction à caractère cationique (MC) par l'intermédiaire d'une chaîne hydrophile, ledit agent anti-salissure étant mis en oeuvre au lavage par l'intermédiaire d'une formulation de lavage, au rinçage et/ou adoucissage par l'intermédiaire d'une formulation de rinçage et/ou d'adoucissage ou au séchage par l'intermédiaire d'un support absorbant On entend par fonction a caractère cationique (MC), toute fonction qui est soit cationique en tant que telle soit présentant un atome électrophile.. at least one motif carrying a cationic function (MC) capable of being adsorbed on the surface of the cotton and its counterion . and at least one unit of hydrophobic character (MH) capable of configuring said agent at the cotton / water interface, said unit (MH) being able itself to be one of the constituents of the unit carrying a function of cationic nature (MC) by chemical bond to the heteroatom of the motif (MC), or which can be chemically linked to the motif carrying a cationic function (MC) via a hydrophilic chain, said anti-fouling agent being used washing using a washing formulation, rinsing and / or softening using a rinsing and / or softening formulation or drying using an absorbent support cationic function (MC), any function which is either cationic as such or having an electrophilic atom.
Parmi les fonctions a caractère cationique, on peut citer les groupements ammonium, phosphonium, les groupements dérivés de bases de Lewis comme les aminés primaires, secondaires ou tertiaires, les bétaines, les sultaines, les glycinates ... On entend par motif a caractère hydrophobe (MH) susceptible de configurer l'agent antisalissure a l'interface coton/eau, tout motif qui, dans le milieu de traitement, favorise le partage de la molécule antisalissure entre l'eau et la surface de l'article à base de coton tissé.Among the functions of a cationic nature, mention may be made of ammonium, phosphonium groups, groups derived from Lewis bases such as primary, secondary or tertiary amines, betaines, sultaines, glycinates, etc. The term “hydrophobic character unit” is intended to mean. (MH) capable of configuring the anti-fouling agent at the cotton / water interface, any pattern which, in the treatment medium, promotes the sharing of the anti-fouling molecule between water and the surface of the cotton-based article woven.
Ces motifs à caractère hydrophobe permettent d'augmenter, au moins localement, l'épaisseur de la couche superficielle de charges électrostatiques sur le coton.These hydrophobic patterns make it possible to increase, at least locally, the thickness of the surface layer of electrostatic charges on the cotton.
D'une manière préférentielle, ces motifs à caractère hydrophobe sont également susceptibles d'interagir avec des composants des salissures.Preferably, these hydrophobic character patterns are also capable of interacting with soil components.
Les contre-ions susceptibles de former un sel avec lesdites fonctions cationiques, peuvent être de nature quelconque On peut citer les ions halogenures (CI", Br", ...), acétate, sulfate, sulfonate, phosphate ... Parmi les contre-ions préférentiels, on peut citer notamment les ions Br" et Cl". Parmi les motifs a caractère hydrophobe (MH), on peut citer les groupements hydrocarbonés, tels que alkyles, alcényles, linéaires, ramifiés ou cycliques, aryles ... contenant au moins 4 atomes de carbone, de préférence de 8 à 20 atomes de carbone. On peut citer tout particulièrement les groupements alkyles en C4-C20-The counterions capable of forming a salt with said cationic functions can be of any nature. Mention may be made of halide ions (CI " , Br " , ...), acetate, sulfate, sulfonate, phosphate ... Among the counter preferential ions, there may be mentioned in particular the Br "and Cl " ions. Among the units of hydrophobic nature (MH), mention may be made of hydrocarbon groups, such as alkyls, alkenyls, linear, branched or cyclic, aryls, etc. containing at least 4 carbon atoms, preferably from 8 to 20 carbon atoms . Mention may very particularly be made of C4-C20- alkyl groups.
Ledit motif a caractère hydrophobe (MH) peut être lui-même un des substituant de l'hétéroatome du motif porteur d'une fonction a caractère cationique (MC), ou être lié chimiquement audit motif (MC) par l'intermédiaire d'une chaîne hydrophile.Said motif with hydrophobic character (MH) can itself be one of the substituents of the heteroatom of the motif carrying a function with cationic character (MC), or be chemically linked to said motif (MC) via a hydrophilic chain.
Parmi les chaînes hydrophiles, on peut mentionner les chaînes oligomères ou polymères hydrophiles constituées de motifs oligomeres ou polymères semblables ou différents tels que ceux dérives desAmong the hydrophilic chains, mention may be made of hydrophilic oligomer or polymer chains consisting of oligomer units or similar or different polymers such as those derived from
. polysacchaπdes (guar, dérives cellulosiques, alginates, dérivés de l'amidon ...) . polyoxyalkylene glycols (polyoxyethylene glycols ) . copolyesters, téréphtaliques notamment (copolymères ethylènetéréphtalate / poly(oxyéthylène)téréphtalate .. ). polysacchaπdes (guar, cellulose derivatives, alginates, starch derivatives ...). polyoxyalkylene glycols (polyoxyethylene glycols) . copolyesters, in particular terephthalic (ethylene terephthalate / poly (oxyethylene) terephthalate copolymers, etc.)
. copolyesters sulfones, téréphtaliques notamment (copolymères dérivés des acides, anhydrides ou diesters téréphtaliques, isophtaliques, sulfoisophtaliques et d'un diol ...) . alcools polyvinyliques et leurs copolymères . polymères et copolymères acryliques. sulfone copolyesters, terephthalic in particular (copolymers derived from terephthalic, isophthalic, sulfoisophthalic and diol acids, anhydrides or diesters ...). polyvinyl alcohols and their copolymers. acrylic polymers and copolymers
portant éventuellement des fonctions hydrophiles telles que sulfonate, carboxylate, phosphate ... Les quantités de motifs porteurs de fonctions à caractère cationique (MC) sont telles qu'elles assurent lors du traitement un accrochage suffisant de la molécule d'agent antisalissure à la surface de l'article en coton.optionally carrying hydrophilic functions such as sulfonate, carboxylate, phosphate, etc. The quantities of units carrying cationic (MC) functions are such that they ensure, during treatment, sufficient adhesion of the molecule of antifouling agent to the surface cotton article.
Des quantités de l'ordre de 0,1 a 40 parties en poids de fonctions cationiques pour 100 parties en poids d'agent antisalissure sont généralement satisfaisantes. Dans le cas des fonctions ammonium, celles-ci peuvent représenter de l'ordre de 0,01 àAmounts in the range of 0.1 to 40 parts by weight of cationic functions per 100 parts by weight of antifouling agent are generally satisfactory. In the case of the ammonium functions, these can represent on the order of 0.01 to
4 gramme(s) d'azote pour 100 grammes d'agent antisalissure.4 gram (s) of nitrogen per 100 grams of antifouling agent.
Les quantités de motifs a caractère hydrophobes (MH) sont telles qu'elles assurent lors du traitement, à la molécule antisalissure une balance hydrophile/hydrophobe (HLB) lui permettant de se partager entre l'eau et la surface de l'article à base de coton tissé. Une HLB supérieure a 15 est généralement satisfaisanteThe quantities of units of hydrophobic character (MH) are such that they ensure during the treatment, to the anti-fouling molecule a hydrophilic / hydrophobic balance (HLB) allowing it to be divided between water and the surface of the article based woven cotton. An HLB greater than 15 is generally satisfactory
L'hydrophihe de la molécule antisalissure est telle que cette dernière puisse s'éliminer au lavage suivant en même temps que les salissuresThe hydrophyll of the anti-fouling molecule is such that the latter can be removed in the next wash at the same time as the soiling
Parmi les agents antisalissures amphiphiles pouvant être mis en oeuvre, on peut citer notamment des agents tensio-actifs cationiques et des oligomeres ou polymères formés d'un tronc oligomere ou polymère hydrocarboné hydrophile présentant dans sa chaîne ou en ramification des motifs porteurs d'une fonction à caractère cationique (MC) avec son contre-ion et des motifs à caractère hydrophobe (MH).Among the amphiphilic anti-fouling agents which can be used, there may be mentioned in particular cationic surfactants and oligomers or polymers formed from an oligomeric trunk or hydrophilic hydrocarbon polymer having in its chain or in branching units carrying a function cationic in nature (MC) with its counterion and hydrophobic in nature (MH).
Parmi les agents antisalissures tensio-actifs cationiques, on peut citer notamment ceux de formule R 1 R2R3R4 N+ X" OÙAmong the cationic surface-active antifouling agents, mention may in particular be made of those of formula R 1 R 2 R3R4 N + X " OÙ
. R\ R^ et R^ sont semblables ou différents et représentent H ou un radical alkyle contenant moins de 4 atomes de carbone, de préférence 1 ou 2 atome(s) de carbone représente un radical alkyle contenant plus de 4 atomes de carbone, de préférence de l'ordre de 8 à 20 atomes de carbone . X" est un ion halogénure, bromure de préférence, acétate, sulfate .... R \ R ^ and R ^ are similar or different and represent H or an alkyl radical containing less than 4 carbon atoms, preferably 1 or 2 carbon atom (s) represents an alkyl radical containing more than 4 carbon atoms, preferably of the order of 8 to 20 carbon atoms. X " is a halide ion, preferably bromide, acetate, sulfate ...
On peut citer tout particulièrement les bromures de dodécyltπméthylammonium, de tétradécyltπmethylammonium, de cetyltπmethylammonium Parmi les agents antisalissures oligomères ou polymères, on peut citer notamment les guars alkyles cationiques, les hydroxypropylguars alkyles cationiques.Mention may very particularly be made of dodecyltπmethylammonium bromides, tetradecyltπmethylammonium bromides, cetyltπmethylammonium bromides Among the oligomeric or polymeric antifouling agents, mention may in particular be made of cationic alkyl guars and cationic alkyl hydroxypropylguars.
On peut également citer, à titre de produit industriel nouveau constituant un deuxième objet de l'invention, un agent antisalissure oligomère, polymère ou copolymere présentantMention may also be made, as a new industrial product constituting a second subject of the invention, of an oligomeric, polymer or copolymer antifouling agent having
. au moins un motif porteur d'une fonction à caractère cationique (MC) susceptible de s'adsorber sur la surface du coton et son contre-ion. at least one motif carrying a cationic (MC) function capable of adsorbing on the surface of the cotton and its counterion
. et au moins un motif à caractère hydrophobe (MH) contenant au moins 4 atomes de carbone, de préférence de 8 a 20 atomes de carbone, susceptible de configurer ledit agent à l'interface coton/eau, lié chimiquement au motif porteur d'une fonction à caractère cationique (MC) par l'intermédiaire d'une chaîne hydrophile constituée par un oligomère, polymère ou copolymere de l'alcool vinylique.. and at least one unit of hydrophobic character (MH) containing at least 4 carbon atoms, preferably from 8 to 20 carbon atoms, capable of configuring said agent at the cotton / water interface, chemically linked to the unit carrying a cationic function (MC) via a hydrophilic chain consisting of an oligomer, polymer or copolymer of vinyl alcohol.
D'une manière préférentielle, les fonctions à caractère cationique (MC) sont des fonctions ammonium de formule R1 R2R3 N+- OÙPreferably, the functions of cationic nature (MC) are ammonium functions of formula R 1 R 2 R 3 N + - OÙ
R1 , R2 et R3R 1 , R 2 and R3
. sont semblables ou différents et représentent H ou un radical alkyle contenant moins de 4 atomes de carbone, de préférence 1 ou 2 atome(s) de carbone, éventuellement substitué, notamment par une ou plusieurs fonctιon(s) hydroxyle(s), . ou bien forment ensemble, avec l'atome d'azote N+, au moins un cycle aromatique ou non aromatique, lesdites fonctions à caractère cationique (MC) étant liées chimiquement à la chaîne oligomère, polymère ou copolymere de l'alcool polyvinyhque directement par liaison C-C ou indirectement par l'intermédiaire d'un groupement bivalent ou polyvalent hydrocarboné contenant au moins un hétéroatome.. are similar or different and represent H or an alkyl radical containing less than 4 carbon atoms, preferably 1 or 2 carbon atom (s), optionally substituted, in particular by one or more hydroxyl function (s),. or else form together, with the nitrogen atom N + , at least one aromatic or non-aromatic ring, said functions of cationic nature (MC) being chemically linked to the oligomer, polymer or copolymer chain of polyvinyl alcohol directly by CC bond or indirectly via a bivalent or polyvalent hydrocarbon group containing at least one heteroatom.
Parmi les fonctions à caractère cationique (MC), on peut notamment mentionner celles dérivées du chlorure ou bromure de glycidyltπméthylammonium, chlorure du chloro-1 , hydroxy-2 propyl triméthylammonium Parmi les groupement bivalents ou polyvalents hydrocarbonés contenant au moins un hétéroatome, on peut citer ceux présentant une liaison libre éther, ester, urethane, acétal, amide ...Among the cationic (MC) functions, mention may in particular be made of those derived from glycidyltπmethylammonium chloride or bromide, chloro-1 chloride, 2-hydroxypropyl trimethylammonium Among the bivalent or polyvalent hydrocarbon groups containing at least one heteroatom, mention may be made those with a free bond ether, ester, urethane, acetal, amide ...
Parmi les contre-ions susceptibles de former un sel avec ces fonctions à caractère cationique, on peut citer les ions halogenures (CI", Br", ...), acétate, sulfate, sulfonate, phosphate ... Parmi les motifs a caractère hydrophobe (MH), on peut mentionner les radicaux alkyles linéaires ou ramifies, linéaires de préférence, contenant de 8 à 20 atomes de carbone, ceux-ci pouvant être lies chimiquement à la chaîne oligomere, polymère ou copolymere de l'alcool polyvinyhque directement par liaison C-C ou indirectement par l'intermédiaire d'un groupement bivalent ou polyvalent hydrocarboné contenant au moins un hétéroatome.Among the counterions capable of forming a salt with these functions of a cationic nature, mention may be made of the halide ions (CI " , Br " , ...), acetate, sulfate, sulfonate, phosphate ... hydrophobic (MH), mention may be made of linear or branched alkyl radicals, preferably linear, containing from 8 to 20 carbon atoms, these being able to be chemically linked to the oligomer, polymer or copolymer chain of polyvinyl alcohol directly by CC link or indirectly by through a bivalent or polyvalent hydrocarbon group containing at least one heteroatom.
Parmi les groupement bivalents ou polyvalents hydrocarbonés contenant au moins un hétéroatome, on peut citer ceux présentant une liaison libre éther, ester, urethane, acétal, amide ...Among the bivalent or polyvalent hydrocarbon groups containing at least one heteroatom, mention may be made of those having a free ether, ester, urethane, acetal, amide bond, etc.
D'une manière préférentielle, ledit agent contient de l'ordre de 0,1 à 10 , de préférence de 1 à 6 motifs porteurs d'une fonction a caractère cationique (MC) pour 100 unités monomères de l'oligomère, du polymère ou du copolymere d'alcool polyvinylique, et de 0,01 à 10 , de préférence de 0,1 à 5 motifs a caractère hydrophobe (MH) pour 100 unités monomères du polymère ou copolymere d'alcool polyvinyliquePreferably, said agent contains of the order of 0.1 to 10, preferably from 1 to 6 units carrying a cationic function (MC) per 100 monomer units of the oligomer, of the polymer or of the polyvinyl alcohol copolymer, and from 0.01 to 10, preferably from 0.1 to 5 units of hydrophobic nature (MH) per 100 monomer units of the polymer or copolymer of polyvinyl alcohol
Parmi les oligomeres, polymères et copolymères d'alcool vinylique constituant la chaîne hydrophile, on peut mentionner ceux de masse moléculaire de l'ordre de 500 à 500 000, de préférence de l'ordre de 1000 a 100 000 , lesdits copolymères peuvent contenir jusqu'à 5% en mole d'unités dérivées d'au moins un comonomère tel que l'acétate de vinyle, l'éthylène, l'anhydride maleique ...Among the oligomers, polymers and copolymers of vinyl alcohol constituting the hydrophilic chain, mention may be made of those of molecular mass of the order of 500 to 500,000, preferably of the order of 1000 to 100,000, said copolymers may contain up to '' at 5% by mole of units derived from at least one comonomer such as vinyl acetate, ethylene, maleic anhydride ...
Ledit agent antisalissure faisant l'objet de l'invention peut être obtenu par exemple par modification d'un homopolymere ou d'un copolymere de l'acétate de vinyle, au moins partiellement hydrolyse en alcool (co)polyvιnylιque (c'est-à-dire hydrolyse jusqu'à au moins 80%) par greffage a l'aide de composés précurseurs des motifs porteurs de fonction cationique (MC) et des motifs hydrophobes (MH) , cette modification par greffage fait intervenir des réactions de substitution (par exemple estérif ication, acétalisatioπ, éthéπfication .. ) bien connues de l'homme de l'art et décrites en particulier dans "Polyvinyl Alcohol Developments" - Ed. C. A. Finch (Wiley) - pages 183 et suivantes et 84 et suivantes II peut également être prépare par copolymérisation radicalaire de l'acétate de vinyle et de comonomères précurseurs des motifs porteurs de fonction cationique (MC) et des motifs hydrophobes (MH) suivie d'une hydrolyse (déacétalisation). Ce type de procédé est également bien connu de l'homme de l'art et décrit dans "Polyvinyl Alcohol Developments" - Ed. C. A Finch (Wiley). Ainsi un agent antisalissure particulier peut être obtenu par modification d'un alcool polyvinyhque à l'aide de (2,3-epoxypropyle) chlorure de tπméthylammonium suivie d'une modification a l'aide d'un alkylisocyanate.Said anti-fouling agent which is the subject of the invention can be obtained for example by modification of a homopolymer or of a copolymer of vinyl acetate, at least partially hydrolyzed to (co) polyvinyl alcohol (that is to say -display hydrolysis up to at least 80%) by grafting using precursor compounds of the units carrying cationic function (MC) and hydrophobic units (HD), this modification by grafting involves substitution reactions (for example ester ication, acetalisatioπ, étééffication ..) well known to those skilled in the art and described in particular in "Polyvinyl Alcohol Developments" - Ed. CA Finch (Wiley) - pages 183 and following and 84 and following II can also be prepared by radical copolymerization of vinyl acetate and of precursor comonomers of units carrying cationic function (MC) and hydrophobic units (MH) followed by hydrolysis (deacetalization). This type of process is also well known to those skilled in the art and described in "Polyvinyl Alcohol Developments" - Ed. C. A Finch (Wiley). Thus a particular antifouling agent can be obtained by modification of a polyvinyl alcohol using (2,3-epoxypropyl) tmethylammonium chloride followed by a modification using an alkylisocyanate.
Les quantités d'agent salissure pouvant être mises en oeuvre selon le procédé de traitement de l'invention, sont fonction de la nature de la molécule mise en oeuvre. Celles-ci peuvent être de l'ordre de 0,05 a 5 gramme(s) par litre de milieu de traitement. Selon l'invention, l'agent antisalissure peut être mis en oeuvre au cours d'une opération de lavage par l'intermédiaire d'une formulation de lavage en poudre ou liquide (composition détergente), le milieu de traitement étant constitue par le bain de lavage. 97/31085 PC17FR97/00304The amounts of soiling agent that can be used according to the treatment method of the invention, depend on the nature of the molecule used. These can be of the order of 0.05 to 5 grams (s) per liter of treatment medium. According to the invention, the anti-fouling agent can be used during a washing operation by means of a washing powder or liquid formulation (detergent composition), the treatment medium being constituted by the bath. of washing. 97/31085 PC17FR97 / 00304
Les compositions détergentes en poudre ou liquides peuvent contenir de l'ordre de 0,02 à 20% de leur poids dudit agent antisalissure.The powder or liquid detergent compositions may contain on the order of 0.02 to 20% of their weight of said anti-fouling agent.
A côté dudit agent antisalissure, peuvent être présents d'autres additifs du type de ceux décrits ci-apres - AGENTS TENSIO-ACTIFS, en quantités correspondant a environ 3-40% en poids par rapport à la composition détergente, agents tensio-actifs tels que agents tensio-actifs anioniquesBesides said anti-fouling agent, other additives of the type described below may be present - SURFACTANT AGENTS, in amounts corresponding to approximately 3-40% by weight relative to the detergent composition, surfactants such as anionic surfactants
. les alkylesters sulfonates de formule R-CH(Sθ3M)-COOR', où R représente un radical alkyle en C-8-20. de préférence en C10-C16' R' un radical alkyle en C-i -Cg, de préférence en C1 -C3 et M un cation alcalin (sodium, potassium, lithium), ammonium substitué ou non substitue (méthyl-, diméthyl-, tπméthyl-, tetraméthylammonium, diméthylpipeπdinium ) ou dérive d'une alcanolamine (monoéthanolamine, diéthanolamine, triethanolamme ) On peut citer tout particulièrement les méthyl ester sulfonates dont les radical R est en C -\ ^-C ] Q , . les alkylsulfates de formule ROSO3M, ou R représente un radical alkyle ou hydroxyalkyle en C5-C24, de préférence en C-j o-Cl β' M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérivés éthoxylénés (OE) et/ou propoxylenes (OP), présentant en moyenne de 0,5 à 30 motifs, de préférence de 0,5 a 10 motifs OE et/ou OP , . les alkylamides sulfates de formule RCONHROSO3M ou R représente un radical alkyle en C2-C22. de préférence en C5-C20. R' un radical alkyle en C2-C3, M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérives ethoxylenes (OE) et/ou propoxylenes (OP), présentant en moyenne de 0,5 a 60 motifs OE et/ou OP , . les sels d'acides gras satures ou insaturés en C8-C24, de préférence en C14-C20. 'es alkylbenzenesulfonates en C9-C20. les alkylsulfonates primaires ou secondaires en Cg- C22. 'es alkylglycerol sulfonates, les acides polycarboxyhques sulfonés décrits dans GB-A-1 082 179, les sulfonates de paraffine, les N-acyl N-alkyltaurates, les alkylphosphates, les isethionates, les alkylsuccmamates les alkylsulfosuccinates, les monoesters ou diesters de sulfosuccinates, les N-acyl sarcosinates, les sulfates d'alkylglycosides, les polyethoxycarboxylates le cation étant un métal alcalin (sodium, potassium, lithium), un reste ammonium substitué ou non substitue (méthyl-, dimethyl-, tπméthyl-, tetraméthylammonium, diméthylpipeπdinium ) ou dérive d'une alcanolamine (monoéthanolamine, diéthanolamine, triethanolamme ) , agents tensio-actifs non-ioniques les alkylphenols polyoxyalkylenes (polyethoxyethylenes, polyoxypropylénes, polyoxybutylenes) dont le substituant alkyle est en Cβ-C-| 2 et contenant de 5 a 25 motifs oxyalkylènes ; à titre d'exemple, on peut citer les TRITON X-45, X-1 14, X-100 ou. alkyl sulfonate esters of formula R-CH (Sθ3M) -COOR ', where R represents a C-8-20 alkyl radical. preferably C10-C16 'R' an alkyl radical C₆ alkyl, preferably C1 -C3, and M an alkali metal cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, tπméthyl- , tetramethylammonium, dimethylpipeπdinium) or derivative of an alkanolamine (monoethanolamine, diethanolamine, triethanolamine) Mention may very particularly be made of methyl ester sulfonates whose radicals R is C - \ ^ -C] Q, the alkyl sulfates of formula ROSO3M, or R represents a C5-C24 alkyl or hydroxyalkyl radical, preferably Cj o-Cl β 'M representing a hydrogen atom or a cation of the same definition as above, as well as their derivatives ethoxylenates (OE) and / or propoxylenes (OP), having on average from 0.5 to 30 units, preferably from 0.5 to 10 OE and / or OP units,. the alkylamide sulfates of formula RCONHROSO3M or R represents an alkyl radical in C2-C22. preferably in C5-C20. R 'a C2-C3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylene derivatives (OE) and / or propoxylenes (OP), having an average of 0, 5 to 60 OE and / or OP patterns,. the salts of saturated or unsaturated C8-C24 fatty acids, preferably C14-C20. 'C9-C20 alkylbenzenesulfonates. primary or secondary C 6 -C 22 alkyl sulfonates. 'es alkylglycerol sulfonates, sulfonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccmamates alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, alkyl glycoside sulfates, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, tπmethyl-, tetramethylammonium, dimethylpipeπdinium) or derivative of an alkanolamine (monoethanolamine, diethanolamine, triethanolamine), nonionic surfactants polyoxyalkylene alkylphenols (polyethoxyethylenes, polyoxypropylenes, polyoxybutylenes) whose alkyl substituent is Cβ-C- | 2 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the TRITON X-45, X-1 14, X-100 or
X-102 commercialisés par Rohm & Haas Cy. ;X-102 marketed by Rohm & Haas Cy. ;
. les glucosamide, glucamide, glycérolamide ;. glucosamide, glucamide, glycerolamide;
. les alcools aliphatiques en Cg-C22 polyoxyalkylénés contenant de 1 à 25 motifs oxyalkylènes (oxyéthylène, oxypropylène) ; à titre d'exemple, on peut citer les. polyoxyalkylenated Cg-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units (oxyethylene, oxypropylene); by way of example, mention may be made of
TERGITOL 15-S-9, TERGITOL 24-L-6 NMW commercialisés par Union Carbide Corp.,TERGITOL 15-S-9, TERGITOL 24-L-6 NMW marketed by Union Carbide Corp.,
NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 commercialisés parNEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 marketed by
Shell Chemical Cy., KYRO EOB commercialisé par The Procter & Gamble Cy.Shell Chemical Cy., KYRO EOB marketed by The Procter & Gamble Cy.
. les produits résultant de la condensation de l'oxyde d'ethylène le composé résultant de la condensation de l'oxyde de propylène avec le propylène glycol, tels les PLURONIC commercialisés par BASF ;. the products resulting from the condensation of ethylene oxide the compound resulting from the condensation of propylene oxide with propylene glycol, such as the Pluronic sold by BASF;
. les produits résultant de la condensation de l'oxyde d'ethylène le composé résultant de la condensation de l'oxyde de propylène avec l'éthylènediamine, tels les TETRONIC commercialisés par BASF ; . les oxydes d'ammes tels que les oxydes d'alkyl C-|0"Cl 8 diméthylamines, les oxydes d'alkoxy Cg-C22 éthyl dihydroxy éthylamines ;. the products resulting from the condensation of ethylene oxide the compound resulting from the condensation of propylene oxide with ethylenediamine, such as TETRONIC sold by BASF; . amine oxides such as C- | 0 "Cl 8 dimethylamine alkyl oxides, Cg-C22 alkoxy ethyl dihydroxy ethylamine oxides;
. les alkylpolyglycosides décrits dans US-A-4 565 647 ;. the alkylpolyglycosides described in US-A-4,565,647;
. les amides d'acides gras en Cg-C20. fatty acid amides in Cg-C20
. les acides gras éthoxylés . les amides gras éthoxylés. ethoxylated fatty acids. ethoxylated fatty amides
. les aminés éthoxylées agents tensio-actifs amphotères et zwitterioniques les alkyldiméthylbétaines, les alkylamidopropyldiméthylbétaînes, les alkyltriméthylsulfobétaines, Iles produits de condensation d'acides gras et d'hydrolysats de protéines. ethoxylated amines amphoteric and zwitterionic surfactants alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, Islands of condensation products of fatty acids and protein hydrolysates
. les alkylamphoacétates ou alkylamphodiacétates dont le groupe alkyle contient de 6 à. alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to
20 atomes de carbone.20 carbon atoms.
- ADJUVANTS AMELIORANT LES PROPRIETES DES AGENTS TENSIO-ACTIFS- ADDITIVES IMPROVING THE PROPERTIES OF SURFACTANTS
(AGENTS "BUILDERS"), en quantités correspondant à environ 5-50%, de préférence à environ 5-30% en poids pour les formules détergentes liquides, ou à environ 10-80%, de préférence 15-50% en poids pour les formules détergentes en poudres, agents builders tels que adjuvants ("builders") inorganiques les polyphosphates (tπpolyphosphates, pyrophosphates, orthophosphates, hexamétaphosphates) de métaux alcalins, d'ammonium ou d'alcanolamines("BUILDERS" AGENTS), in amounts corresponding to about 5-50%, preferably about 5-30% by weight for liquid detergent formulas, or about 10-80%, preferably 15-50% by weight for detergent formulas in powders, builders agents such as adjuvants ("builders") inorganic polyphosphates (tπpolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines
. les tetraborates ou les précurseurs de borates. tetraborates or borate precursors
. les silicates, en particulier ceux présentant un rapport Siθ2/Na2θ de l'ordre de 1 ,6/1 à. silicates, in particular those having a Siθ2 / Na2θ ratio of the order of 1.6 / 1 to
3,2/1 et les silicates lamellaires décrits dans US-A-4 664 839 . les carbonates (bicarbonates, sesquicarbonates) alcalins ou alcalino-terreux . les cogranulés de silicates hydrates de métaux alcalins et de carbonates de métaux alcalins (sodium ou de potassium) riches en atomes de silicium sous forme Q2 ou Q3, décrits dans EP-A-488 868 . les aminosilicates cristallins ou amorphes de métaux alcalins (sodium, potassium) ou d'ammonium, tels que les zeolithes A, P, X , la zeolithe A de taille de particules de l'ordre de 0,1-10 micromètres est préférée adjuvants ("builders") organiques3.2 / 1 and the lamellar silicates described in US-A-4,664,839 . alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates). the cogranules of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A-488 868. crystalline or amorphous aminosilicates of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X, zeolite A with a particle size of the order of 0.1-10 micrometers is preferred as adjuvants ( organic "builders"
. les polyphosphonates hydrosolubles (ethane 1-hydroxy-1 , 1 -dιphosphonates, sels de méthylène diphosphonates ). water-soluble polyphosphonates (ethane 1-hydroxy-1, 1 -phosphonates, methylene salts diphosphonates)
. les sels hydrosolubles de polymères ou de copolymères carboxyliques ou leurs sels hydrosolubles tels que. water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as
. les éthers polycarboxylates (acide oxydisuccinique et ses sels, tartrate monosuccinic acide et ses sels, tartrate disuccmic acide et ses sels . les éthers hydroxypolycarboxylates. polycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic tartrate acid and its salts, distrustic tartrate acid and its salts. hydroxypolycarboxylate ethers
. l'acide citrique et ses sels, l'acide mellitique, l'acide succinique et leurs sels . les sels d'acides polyacetiques (ethylenediaminetetraacetates, nitnlotπacétates, N-(2 hydroxyethyD-nitπlodiacetates) les acides alkyl C5-C20 succiniques et leurs sels( 2-dodecenylsuccιnates, lauryl succinates, ). citric acid and its salts, mellitic acid, succinic acid and their salts. the salts of polyacetic acids (ethylenediaminetetraacetates, nitnlotπacetates, N- (2 hydroxyethyD-nitπlodiacetates) C5-C20 alkyl succinic acids and their salts (2-dodecenylsuccιnates, lauryl succinates,)
. les esters polyacetals carboxyliques . l'acide polyaspartique, l'acide polyglutamique et leurs sels les polyimides dérives de la polycondensation de l'acide aspartique et/ou de l'acide glutamique . les dérives polycarboxymethyles de I acide glutamique ou d'autres acides aminés. polyacetal carboxylic esters. polyaspartic acid, polyglutamic acid and their salts, polyimides derived from the polycondensation of aspartic acid and / or glutamic acid. polycarboxymethyl derivatives of I glutamic acid or other amino acids
- AGENTS DE BLANCHIMENT, en quantités d'environ 0,1-20%, de préférence environ 1 -10% en poids, éventuellement associes a des ACTIVATEURS DE BLANCHIMENT, en quantités d'environ 0,1 -60%, de préférence d'environ 0,5-40% en poids, agents et activateurs tels que agents de blanchiment- BLEACHING AGENTS, in amounts of about 0.1-20%, preferably about 1 -10% by weight, optionally combined with BLEACHING ACTIVATORS, in amounts of about 0.1 -60%, preferably d '' about 0.5-40% by weight, agents and activators such as bleaches
. les perborates tels que le perborate de sodium monohydrate ou tetrahydraté les composes peroxygenes tels que le carbonate de sodium peroxyhydraté, le pyrophosphate peroxyhydraté, l uree peroxyhydratee, le peroxyde de sodium, le persulfate de de sodium de préférence associes a un activateur de blanchiment générant in situ dans le milieu lessiviel, un peroxyacide carboxylique , parmi ces activateurs, on peut mentionner, la tetraacetylethylene diamine, la tetraacétyl méthylène diamine, le tetraacétyl glycoluryl, le p-acetoxybenzene sulfonate de sodium, le pentaacetyl glucose, l'octaacetyl lactose . . les acides percarboxyliques et leurs sels (appelés "percarbonates") tels que le monoperoxyphtalate de magnésium hexahydraté, le métachloroperbenzoate de magnésium, l'acide 4-nonylamιno-4-oxoperoxybutyrιque, l'acide 6-nonylamino-6- oxoperoxycaproique, l'acide diperoxydodécanedioique, le nonylamide de l'acide peroxysuccinique, I' acide decyldiperoxysuccinique.. perborates such as sodium perborate monohydrate or tetrahydrate peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate preferably associated with a whitening activator generating in located in the washing medium, a peroxyacidic carboxylic acid, among these activators, one can mention, tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, p-acetoxybenzene sulfonate sodium, pentaacetyl glucose, octaacetyl lactose. . percarboxylic acids and their salts (called "percarbonates") such as magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamιno-4-oxoperoxybutyrιque acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, nonoxamide peroxysuccinic acid, decyldiperoxysuccinic acid.
Ces agents peuvent être associes a au moins un des agents anti-salissures ou anti- redéposition mentionnes ci-apresThese agents can be combined with at least one of the anti-fouling or anti-redeposition agents mentioned below.
Peuvent également être mentionnés des agents de blanchiment non oxygénés, agissant par photoactivation en présence d'oxygène, agents tels que les phtalocyanmes d'aluminium et/ou de zinc sulfonéesMention may also be made of non-oxygenated bleaching agents, acting by photoactivation in the presence of oxygen, agents such as sulfonated aluminum and / or zinc phthalocyanms
- AGENTS ANTI-SALISSURES autres, en quantités d'environ 0,01 -10%, de préférence environ 0,1 -5%, et tout particulièrement de l'ordre de 0,2-3% en poids, agents tels que . les dérivés cellulosiques tels que les hydroxyéthers de cellulose, la méthylcellulose, l'éthylcellulose, l'hydroxypropyl méthylcellulose, l'hydroxybutyl méthylcellulose les polyvinylesters greffés sur des troncs polyalkylenes tels que les polyvinylacétates greffés sur des troncs polyoxyethylenes (EP-A-219 048) . les alcools polyvinyliques- ANTI-FOULING AGENTS other, in amounts of approximately 0.01 -10%, preferably approximately 0.1 -5%, and very particularly of the order of 0.2-3% by weight, agents such as. cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose polyvinylesters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048) . polyvinyl alcohols
. les copolymères polyesters a base de motifs ethylène téréphtalate et/ou propylène téréphtalate et polyoxyéthylène téréphtalate, avec un rapport molaire (nombre de motifs) ethylène téréphtalate et/ou propylène terephalate / (nombre de motifs) polyoxyéthylène téréphtalate de l'ordre de 1/10 a 10/1 , de préférence de l'ordre de 1 /1 à 9/1 , les polyoxyéthylène térephtalates présentant des unîtes polyoxyéthylène ayant un poids moléculaire de l'ordre de 300 a 5000, de préférence de l'ordre de 600 à 5000 (US-A-3 959 230, US-A-3 893 929, US-A-4 1 16 896, US-A-4 702 857, US-A-4 770 666) ; . les oligomeres polyesters sulfones obtenus par sulfonation d'un oligomere dérivé de de l'alcool allylique éthoxyle, du dimethyltérephtaiate et du 1 ,2 propylène diol, présentant de 1 à 4 groupes sulfones (US-A-4 968 451 ). polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, with a molar ratio (number of units) ethylene terephthalate and / or propylene terephalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 at 10/1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 to 5000, preferably of the order of 600 to 5000 (US-A-3,959,230, US-A-3,893,929, US-A-4,116,896, US-A-4,702,857, US-A-4,770,666); . sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethylterephthalate and 1,2 propylene diol, having from 1 to 4 sulfone groups (US Pat. No. 4,968,451)
. les copolymères polyesters a base de motifs propylène téréphtalate et polyoxyéthylène téréphtalate et termines par des motifs ethyles, méthyles (US-A-4 71 1 730) ou des oligomeres polyesters termines par des groupes alkylpolyéthoxy (US-A-4 702 857) ou des groupes anioniques sulfopolyethoxy (US-A-4 721 580), sulfoaroyles (US-A-4 877 896). polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl or methyl units (US-A-4 71 1 730) or polyester oligomers terminated with alkylpolyethoxy groups (US-A-4 702 857) or sulfopolyethoxy anionic groups (US-A-4,721,580), sulfoaroyl groups (US-A-4,877,896)
. les copolymères polyesters sulfones dérives d'acide, anhydride ou diester téréphtalique, isophtahque et sulfoisophtalique et d'un diol (FR-A-2 720 399) - AGENTS ANTI-REDEPOSITION, en quantités d'environ 0,01 -10% en poids pour une composition détergente en poudre d'environ 0,01 -5%en poids pour une composition détergente liquide, agents tels que . les monoamines ou polyamines ethoxylees, les polymères d'aminés éthoxylées (US-A-4 597 898, EP-A-1 1 984) . la carboxyméthylcellulose. sulphonated polyester copolymers derived from terephthalic, isophthalic and sulphoisophthalic acid, anhydride or diester and a diol (FR-A-2 720 399) - ANTI-REDEPOSITION AGENTS, in amounts of about 0.01 -10% by weight for a powder detergent composition from about 0.01 -5% by weight for a liquid detergent composition, agents such as . ethoxylated monoamines or polyamines, polymers of ethoxylated amines (US-A-4,597,898, EP-A-1 1,984). carboxymethylcellulose
. les oligomeres polyesters sulfones obtenus par condensation de l'acide isophtalique, du sulfosuccinate de diméthyle et de diethylene glycol (FR-A-2 236 926) . les polyvinylpyrollidones. polyester sulfonated oligomers obtained by condensation of isophthalic acid, dimethyl sulfosuccinate and diethylene glycol (FR-A-2 236 926). polyvinylpyrollidones
- AGENTS CHELATANTS du fer et du magnésium, en quantités de l'ordre de 0,1 -10%, de préférence de l'ordre de 0,1-3% en poids, agents tels que- CHELATING AGENTS of iron and magnesium, in quantities of the order of 0.1 -10%, preferably of the order of 0.1-3% by weight, agents such as
. les aminocarboxylates tels que les éthylenediaminetétraacétates, hydroxyéthyl éthylenediaminetπacetates, nitπlotπacetates. aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethyl ethylenediaminetπacetates, nitπlotπacetates
. les aminophosphonates tels que les nιtrιlotrιs(méthylene phosphonates). aminophosphonates such as neutrillates (methylene phosphonates)
. les composes aromatiques polyfonctionnels tels que les dihydroxydisulfobenzenes. polyfunctional aromatic compounds such as dihydroxydisulfobenzenes
- AGENTS DISPERSANTS POLYMERIQUES, en quantité de l'ordre de 0,1 -7% en poids, pour contrôler la dureté en calcium et magnésium, agents tels que . les sels hydrosolubles d'acides polycarboxyliques de masse moléculaire de l'ordre de 2000 à 100 000, obtenus par polymérisation ou copolymérisation d'acides carboxyliques ethyleniquement insatures tels que acide acryliqiue, acide ou anhydride maleique, acide fumaπque, acide itaconique, acide aconitique, acide mesaconique, acide citraconique, acide méthylenemalonique , et tout particulièrement les polyacrylates de masse moléculaire de l'ordre de 2 000 a 10 000 (US-A-3 308 067), les copolymères d'acide arylique et d'anhydride maleique de masse moléculaire de l'ordre de 5 000 a 75 000 (EP-A-66 915) . les polyéthyleneglycols de masse moléculaire de l'ordre de 1000 a 50 000- POLYMERIC DISPERSING AGENTS, in an amount of the order of 0.1 -7% by weight, to control the hardness of calcium and magnesium, agents such as. the water-soluble salts of polycarboxylic acids of molecular mass of the order of 2000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaic acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and in particular polyacrylates of molecular mass of the order of 2,000 to 10,000 (US-A-3,308,067), copolymers of arylic acid and maleic anhydride of mass molecular of the order of 5,000 to 75,000 (EP-A-66,915). polyethylene glycols of molecular mass of the order of 1000 to 50,000
- AGENTS DE FLUORESCENCE (BRIGHTENERS), en quantité d'environ 0,05-1 ,2% en poids, agents tels que les dérives de stilbene, pyrazoline, coumaπne, acide fumaπque, acide cinnamique, , azoles, methinecyanines, thiophenes ("The production and application of fluorescent bπghtemng agents" - M Zahradnik, publie par John Wiley & Sons, New York-1982-)- FLUORESCENCE AGENTS (BRIGHTENERS), in an amount of about 0.05-1.2% by weight, agents such as stilbene, pyrazoline, coumaπne derivatives, fumaπque acid, cinnamic acid,, azoles, methinecyanines, thiophenes (" The production and application of fluorescent bπghtemng agents "- M Zahradnik, published by John Wiley & Sons, New York-1982-)
- AGENTS SUPPRESSEURS DE MOUSSES, en quantités pouvant aller jusqu'à 5% en poids, agents tels que- FOAM SUPPRESSANTS, in amounts up to 5% by weight, agents such as
. les acides gras monocarboxyliques en C-| Q"C-24 OU 'eurs se's alcalins, d'ammonium ou alcanolamines, les triglycérides d acides gras. C- monocarboxylic fatty acids | Q "24 C-OR 'ors is's alkali, ammonium or alkanolamine, of fatty acid triglycerides
. les hydrocarbures satures ou insatures aliphatiques, alicycliques, aromatiques ou héterocycliques, tels que les paraffines, les cires les N-alkylaminotπazines. saturated or aliphatic, alicyclic, aromatic or heterocyclic unsaturated hydrocarbons, such as paraffins, waxes, N-alkylaminotπazines
. les monostearylphosphates, les monostearyl alcool phosphates les huiles ou résines polyorganosiloxanes éventuellement combinées avec des particules de silice - AGENTS ADOUCISSANTS, en quantités d'environ 0,5-10% en poids, agents tels que les argiles. monostearylphosphates, monostearyl alcohol phosphates oils or polyorganosiloxane resins optionally combined with silica particles - SOFTENING AGENTS, in amounts of about 0.5-10% by weight, agents such as clays
- ENZYMES en quantité pouvant aller jusqu'à 5mg en poids, de préférence de l'ordre de 0,05-3mg d'enzyme active /g de composition détergente, enzymes telles que . les protéases, amylases, lipases, cellulases, peroxydases (US-A-3 553 139, US-A-4 101 457, US-A-4 507 219, US-A-4 261 868- ENZYMES in quantities up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent composition, enzymes such as. proteases, amylases, lipases, cellulases, peroxidases (US-A-3 553 139, US-A-4 101 457, US-A-4 507 219, US-A-4 261 868
- AUTRES ADDITIFS tels que- OTHER ADDITIVES such as
. des alcools (méthanol, ethanol, propanol, isopropanol, propanediol, ethylène glycol, glycérine) . des agents tampons. alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin). buffering agents
. des parfums. perfumes
. des pigments. pigments
L'agent antisalissure peut également être mis en oeuvre au rinçage et/ou adoucissage par l'intermédiaire d'une formulation liquide de rinçage et/ou d'adoucissage d'articles, le milieu de traitement étant constitué par le bain de rinçage et/ou d'adoucissage.The anti-fouling agent can also be used for rinsing and / or softening by means of a liquid formulation for rinsing and / or softening of articles, the treatment medium consisting of the rinsing bath and / or softening.
Les compositions liquides de rinçage et/ou adoucissage peuvent contenir de l'ordre deThe liquid rinsing and / or softening compositions may contain of the order of
0,02 à 20% de leur poids dudit agent antisalissure.0.02 to 20% of their weight of said anti-fouling agent.
A côté dudit agent antisalissure, peuvent être présents d'autres additifs du type - associations d'agents tensio-actifs anioniques (lauryléther sulfate ...), non-ioniquesBesides said anti-fouling agent, other additives of the type may be present - associations of anionic surfactants (lauryl ether sulfate, etc.), non-ionic
(alcools gras éthoxylés ...) et cationiques (diester de triethanolamme quaternise par du diméthylsulfate, N-méthylimidazoline tallow ester méthyl sulfate ...)(ethoxylated fatty alcohols ...) and cationic (triethanolamine diester quaternized with dimethylsulfate, N-methylimidazoline tallow methyl sulfate ester ...)
- azurants optiques- optical brighteners
- enzymes Selon l'invention, l'agent antisalissure peut aussi être introduit au séchage dans le linge humide à sécher, par l'intermédiaire d'un support constitué par exemple par une bande de textile non-tissé imprégnée dudit agent antisalissure, support pouvant contenir environ 20% de son poids d'agent antisalissure.- enzymes According to the invention, the anti-fouling agent can also be introduced on drying in the damp linen to be dried, by means of a support constituted for example by a strip of nonwoven fabric impregnated with said anti-fouling agent, support which can contain approximately 20% of its weight of antifouling agent.
Les exemples suivants sont donnes à titre illustratif. Formulation d'une composition détergente lave-lingeThe following examples are given by way of illustration. Formulation of a washing machine detergent composition
Composition de la lessive parties en poidsComposition of detergent parts by weight
- zéolithe 4A 25- zeolite 4A 25
- carbonate léger 15 - disilicate R2A 5- light carbonate 15 - disilicate R2A 5
- copolymere acrylique/maleique SOKALAN CP5 (BASF) 5- acrylic / maleic copolymer SOKALAN CP5 (BASF) 5
- sulfate de Na 10,7- Na sulfate 10.7
- carboxyméthylcellulose 1- carboxymethylcellulose 1
- perborate monohydrate 15 - tetraacétyléthylenediamine 5- perborate monohydrate 15 - tetraacetylethylenediamine 5
- dodécylbenzenesulfonate linéaire 6- linear dodecylbenzenesulfonate 6
- SYNPERONIC A3 (alcool gras en C12-C15 éthoxylé à 3 OE 3- SYNPERONIC A3 (C12-C15 fatty alcohol ethoxylated with 3 EO 3
- SYNPERONIC A9 (alcool gras en C12-C15 éthoxylé à 9 OE 9- SYNPERONIC A9 (C12-C15 fatty alcohol ethoxylated to 9 EO 9
- enzyme Esperase 4,0 T 0,3- Esperase enzyme 4.0 T 0.3
PROPRIETES ANTISALISSURESANTI-FOULING PROPERTIES
IssiIssi
Prétraitement du coton au rinçage .Cotton pretreatment on rinsing.
Quatre éprouvettes en coton CN1 de dimension 10x12 cm, sont utilisées. Deux éprouvettes déjà lavées sont introduites dans un TERGOTOMETRE , l'agent antisalissure en poudre est ajoute, puis 1 litre d'eau (30°TH).Four cotton CN1 test tubes, size 10x12 cm, are used. Two already washed test tubes are introduced into a TERGOTOMETER, the powdered anti-fouling agent is added, then 1 liter of water (30 ° TH).
Le prétraitement au rinçage est effectue a 100 cycles/minute pendant 20 minutes àThe rinse pretreatment is carried out at 100 cycles / minute for 20 minutes at
40°C.40 ° C.
Les deux autres éprouvettes sont utilisées comme référence et prétraitées à l'eau seule (30°TH).The two other test pieces are used as a reference and pretreated with water alone (30 ° TH).
TachageStain
On dépose 4 gouttes d'huile moteur de vidange sur les éprouvettes prélavées, et, afin d'assurer une bonne fixation de la tache, on place les tissus dans une étuve à 60°C pendant 1 heure Lavage4 drops of draining motor oil are placed on the prewashed test pieces, and, in order to ensure good fixation of the stain, the fabrics are placed in an oven at 60 ° C. for 1 hour Washing
On effectue le lavage a 40°C pendant 20 minutes, à l'aide de 5g de la lessive décrite ci- dessus pour 1 litre d'eau de 30°TH, puis 3 rinçages de 5 minutes à l'eau froide et 2 séchages sous glaceuseThe washing is carried out at 40 ° C for 20 minutes, using 5g of the detergent described above for 1 liter of water of 30 ° TH, then 3 rinses of 5 minutes in cold water and 2 dryings under ice
Evaluation La réflectance des tissus avant et après lavage est mesurée à l'aide du colorimètreEvaluation The reflectance of the fabrics before and after washing is measured using the colorimeter
DR. LANGE/LUCI 100DR. LANGE / LUCI 100
L'efficacité de l'agent antisalissure teste, est appréciée par le % d'élimination des taches calculées par la formule E en % = 100 x (R3-R2)/(R1 -R2) R1 représentant la réflectance avant lavage du tissu non sali R2 représentant la réflectance, avant lavage, du tissu sali R3 représentant la réflectance, après lavage, du tissu sali Pour chaque produit teste, on calcule la moyenne du % d'élimination des taches.The effectiveness of the anti-fouling agent tested is assessed by the% of stain removal calculated by the formula E in% = 100 x (R3-R2) / (R1 -R2) R1 representing the reflectance before washing of the soiled fabric R2 representing the reflectance, before washing, of the soiled fabric R3 representing the reflectance, after washing, of the soiled fabric For each product tested, the average of the% stain removal is calculated.
Exemples 1 et 2Examples 1 and 2
Les agents antisalissure testes sont . le bromure de cetyltπmethylammonium (CTAB) de HLB = 24, a raison de 0,1 g/l d'eau . le bromure de tetradecyltπmethylammonium (TTAB) de HLB = 14, a raison de 1 g/l d'eauThe anti-fouling agents tested are. cetyltπmethylammonium bromide (CTAB) of HLB = 24, at a rate of 0.1 g / l of water. tetradecyltπmethylammonium bromide (TTAB) of HLB = 14, at a rate of 1 g / l of water
Les résultats observes sur les éprouvettes prétraitées, compares a ceux observes sur les éprouvettes de référence sont les suivants éprouvettes testées E en % celles de référence 57 celles traitées CTAB 68 celles traitées TTAB 72The results observed on the pretreated test pieces, compared to those observed on the reference test pieces, are the following test pieces tested in% those of reference 57 those treated CTAB 68 those treated TTAB 72
Exemple 3Example 3
L'agent antisalissure teste est un alkylguar cationique (AGC), présentant une viscosité à 1 % dans l'eau de 1000 mPa s , contenant 1 ,7% en poids d'azote dérivé du chlorure d'hydroxypropyltπmethylammonium et présentant des groupes alkyles dérives de l'époxyde de formuleThe antifouling agent tested is a cationic alkylguar (AGC), having a viscosity at 1% in water of 1000 mPa s, containing 1.7% by weight of nitrogen derived from hydroxypropyltπmethylammonium chloride and having derived alkyl groups. epoxy of formula
II est mis en oeuvre a raison de 2 g/l d eauIt is used at a rate of 2 g / l of water
Les résultats observes sur les éprouvettes prétraitées, comparés a ceux observes sur les éprouvettes de référence sont les suivants éprouvettes testées E en % celles de référence 57 celles traitées AGC 65 Exemple 4The results observed on the pretreated test pieces, compared to those observed on the reference test pieces, are the following test pieces tested in% those of reference 57 those treated AGC 65 Example 4
Synthèse d'un alcool polvvinylique (PVQH) modifié par des motifs porteurs de fonction cationique et de motifs à caractère hydrophobeSynthesis of a polyvinyl alcohol (PVQH) modified with units carrying cationic function and units of hydrophobic nature
- Modification par des motifs porteurs de fonction cationique - Dans un ballon tricol, on introduit 40g d'alcool polyvinyhque de masse molaire 15 000 et présentant un taux d'hydrolyse de 88%. Le polymère est ensuite dissous sous atmosphère inerte, a 40°C dans 200g d'eau- Modification with patterns carrying a cationic function - 40 g of polyvinyl alcohol with a molar mass of 15,000 and having a hydrolysis rate of 88% are introduced into a three-necked flask. The polymer is then dissolved under an inert atmosphere, at 40 ° C in 200g of water
On introduit ensuite 5,2g de soude en pastille, puis 97,6g d'une solution aqueuse de5.2 g of sodium hydroxide tablet are then introduced, followed by 97.6 g of an aqueous solution of
(2,3-époxypropyle) chlorure de tπmethylammonium a 70% (0,45 moles) sont injectés lentement dans le milieu réactionnel. Le milieu est maintenu pendant 8h à 40°C, puis refroidi et neutralise avec de l'acide acétique. Le polymère est alors séparé du milieu réactionnel par précipitation dans l'ethanol puis filtration.(2,3-epoxypropyl) tπmethylammonium chloride 70% (0.45 moles) are slowly injected into the reaction medium. The medium is maintained for 8 h at 40 ° C., then cooled and neutralized with acetic acid. The polymer is then separated from the reaction medium by precipitation in ethanol then filtration.
Après séchage pendant une nuit a 45°C, le produit est analysé par RMN 1 H dans D2O.After drying overnight at 45 ° C., the product is analyzed by 1 H NMR in D2O.
La proportion de groupements ammonium greffés est alors obtenue en comparant l'intégrale des protons CHp de l'alcool polyvinylique (entre 1 ,2 et 1 ,5 ppm) avec celle des protons de l'ammonium l(CH3)3N+J a 3,1 ppmThe proportion of grafted ammonium groups is then obtained by comparing the integral of the CHp protons of polyvinyl alcohol (between 1.2 and 1.5 ppm) with that of the ammonium protons l (CH3) 3N + J to 3 , 1 ppm
Le rapport (CH3)3N+ / PVOH est de 1/26The ratio (CH 3 ) 3 N + / PVOH is 1/26
- Modification par des motifs hydrophobes -- Modification by hydrophobic patterns -
10g du PVOH ainsi modifié par des motifs porteurs de fonction cationique sont introduits dans un ballon tricol purgé a l'argon , on introduit ensuite 50ml de diméthylsulfoxyde contenant 200ppm d'eau10 g of PVOH thus modified with units carrying a cationic function are introduced into a three-necked flask purged with argon, then 50 ml of dimethyl sulfoxide containing 200 ppm of water are introduced
Le mélange est chauffé a 90°c pour dissoudre le polymèreThe mixture is heated to 90 ° C. to dissolve the polymer
On charge ensuite 0,585g (2,77 10"3 mole) de dodécyl isocyanate.0.585 g (2.77 10 −3 mol) of dodecyl isocyanate are then loaded.
Le milieu réactionnel est maintenu a 90°C pendant 8 heures, puis le polymère est séparé par précipitation avec l'acétate d'éthyleThe reaction medium is maintained at 90 ° C for 8 hours, then the polymer is separated by precipitation with ethyl acetate
Après séchage sous vide pendant une nuit a 45°C, le produit est analysé par RMN ^ H dans D2O.After drying under vacuum overnight at 45 ° C., the product is analyzed by 1 H NMR in D2O.
La proportion de motifs hydrophobes greffés est alors obtenue en comparant l'intégrale des protons CH2 de l'alcool polyvinyhque (entre 1 ,2 et 1 ,5 ppm) avec celle du méthyl en bout de chaîne de l'alkyle (a 0,8ppm) ou encore avec celle du groupement méthylène de la chaîne alkyle en alpha du groupement carbamate (à 2,9ppm)The proportion of grafted hydrophobic units is then obtained by comparing the integral of the CH2 protons of polyvinyl alcohol (between 1.2 and 1.5 ppm) with that of methyl at the end of the alkyl chain (at 0.8 ppm). ) or with that of the methylene group of the alkyl chain in alpha of the carbamate group (at 2.9 ppm)
La teneur en motifs alkyl par rapport a 100 motifs vinyhques (unités monomères) es. "> The content of alkyl units relative to 100 vinyhques units (monomer units) is. ">
1 %. Exemple 51%. Example 5
Les performances de l'agent antisalissure préparé à l'exemple 4 sont évaluées à 0,2g/l d'eau, vis-à-vis de l'huile de vidange et d'une salissure pigmentaire violette (huile d'olive colorée par un pigment organique violet) Les résultats observes sur les éprouvettes prétraitées, comparés a ceux observés sur les éprouvettes d référence sont les suivantsThe performances of the antifouling agent prepared in Example 4 are evaluated at 0.2 g / l of water, vis-à-vis the drain oil and a purple pigmentary stain (olive oil colored by a purple organic pigment) The results observed on the pretreated test pieces, compared to those observed on the reference test pieces, are as follows
E en % E en % éprouvettes testées huile de vidange pigment violetE in% E in% test pieces tested purple pigment drain oil
celles de référence 44 79 celles traitées 58 88 those of reference 44 79 those treated 58 88

Claims

97/31085 PCÏYFR97/0030497/31085 PCÏYFR97 / 00304
1616
REVENDICATIONS
1 ) Procédé de traitement antisalissure des articles à base de coton tissé, par dépôt sur ledit article, au cours d'une ou d'operatιon(s) de lavage, rinçage et/ou adoucissage ou séchage, d'un agent antisalissure amphiphile soluble ou dispersible dans le milieu de traitement, ledit agent anti-salissure présentant1) Method for antifouling treatment of articles based on woven cotton, by deposition on said article, during one or more washing, rinsing and / or softening or drying operations, of a soluble amphiphilic antifouling agent or dispersible in the treatment medium, said anti-fouling agent having
. au moins un motif porteur d'une fonction (FAd ) susceptible de s'adsorber sur la surface du coton par interaction électrostatique. at least one motif carrying a function (FAd) capable of being adsorbed on the surface of the cotton by electrostatic interaction
. et au moins un motif a caractère hydrophobe (MH) susceptible de configurer ledit agent à l'interface coton/eau, ledit motif (MH) pouvant être lui-même un des constituants du motif porteur d'une fonction (FAd ) ou pouvant être lie chimiquement au motif porteur d'une fonction (FAd ) par l'intermédiaire d'une chaîne hydrophile, ledit agent anti-salissure étant mis en oeuvre au lavage par l'intermédiaire d'une formulation de lavage, au rinçage et/ou adoucissage par l'intermédiaire d'une formulation de rinçage et/ou d adoucissage ou au séchage par l'intermédiaire d'un support absorbant. and at least one motif of hydrophobic nature (MH) capable of configuring said agent at the cotton / water interface, said motif (MH) being able to be itself one of the constituents of the motif carrying a function (FAd) or possibly being chemically binds to the motif carrying a function (FAd) via a hydrophilic chain, said anti-fouling agent being used for washing by means of a washing formulation, for rinsing and / or softening via a rinse and / or softening formulation or during drying via an absorbent support
2) Procède selon la revendication 1 ), caractérise en ce que ledit motif porteur d'une fonction (FAd ) susceptible de s'adsorber sur la surface du coton par interaction électrostatique est un motif porteur d'une fonction a caractère cationique (MC) et son contre-ion2) Method according to claim 1), characterized in that said unit carrying a function (FAd) capable of being adsorbed on the surface of the cotton by electrostatic interaction is a unit carrying a function of cationic nature (MC) and its counterion
3) Procède selon la revendication 1 ) ou 2), caractérise en ce que les articles à traiter renferment au moins 35% en poids de coton3) Process according to claim 1) or 2), characterized in that the articles to be treated contain at least 35% by weight of cotton
4) Procède selon la revendication 2) ou 3), caractérisé en ce que les fonctions à caractère cationique sont des groupements ammonium, phosphonium ou des groupements dérives de bases de Lewis4) Process according to claim 2) or 3), characterized in that the functions of a cationic nature are ammonium, phosphonium groups or groups derived from Lewis bases
5) Procède selon l une quelconque des revendications 2) à 4), caractérise en ce que le contre-ion du motif porteur d une fonction a caractère cationique (MC) est un ion halogénure, acétate, sulfate sulfonate, phosphate5) Method according to any one of claims 2) to 4), characterized in that the counter-ion of the unit carrying a function of cationic nature (MC) is a halide, acetate, sulphate sulfonate, phosphate ion
6) Procède selon l'une quelconque des revendications 1 ) a 5), caractérisé en ce que le motif a caractère hydrophobe (MH) est un groupement alkyle, alcényle, linéaire, ramifié ou cyclique, ou aryle, contenant au moins 4 atomes de carbone, de préférence de 8 a 20 atomes ce carbone 7) Procédé selon l'une quelconque des revendications 1 ) à 6), caractérisé en ce que la chaîne hydrophile liant le ou les motιf(s) porteur(s) d'une fonction susceptible de s'adsorber sur la surface du coton par interaction électrostatique au(x) motif(s) à caractère hydrophobe (MH) est constituée de motifs oligomeres ou polymères hydrocarbones hydrophiles semblables ou différents6) Method according to any one of claims 1) to 5), characterized in that the unit of hydrophobic character (MH) is an alkyl, alkenyl, linear, branched or cyclic, or aryl group, containing at least 4 atoms of carbon, preferably from 8 to 20 atoms this carbon 7) Method according to any one of claims 1) to 6), characterized in that the hydrophilic chain binding the motιf (s) carrying (s) a function capable of being adsorbed on the surface of the cotton by electrostatic interaction with the hydrophobic (MH) motif (s) consists of similar or different oligomeric or hydrophilic hydrocarbon polymers
8) Procède selon la revendication 7), caractérisé en ce que lesdits motifs oligomères ou polymères hydrocarbones hydrophiles semblables ou différents dérivent de polysacchaπdes, polyoxyalkyleneglycols, copolyesters, copolyesters sulfones, alcools polyvinyliques et leurs copolymères, polymères et copolymères acryliques, portant éventuellement des fonctions sulfonates, carboxylates, phosphates8) A method according to claim 7), characterized in that said oligomeric units or hydrophilic hydrocarbon polymers similar or different derive from polysacchaπdes, polyoxyalkyleneglycols, copolyesters, copolyesters sulfones, polyvinyl alcohols and their copolymers, polymers and acrylic copolymers, optionally carrying sulfonate functions , carboxylates, phosphates
9) Procède selon l'une quelconque des revendications 2) a 8), caractérisé en ce que ledit agent anti-sahssure renferme de l'ordre de 0,1 a 40 % de son poids de fonctions cationiques9) Method according to any one of claims 2) to 8), characterized in that said anti-sahssure agent contains about 0.1 to 40% of its weight of cationic functions
10) Procède selon l'une quelconque des revendications 2) à 9), caractérisé en ce que les fonctions cationiques de l'agent antisalissure sont des fonctions ammonium et représentent de l'ordre de 0,01 a 4 gramme(s) d'azote pour 100 grammes d'agent antisalissure10) Method according to any one of claims 2) to 9), characterized in that the cationic functions of the anti-fouling agent are ammonium functions and represent of the order of 0.01 to 4 gram (s) of nitrogen per 100 grams of antifouling agent
1 1) Procède selon l'une quelconque des revendications 1 ) à 10), caractérisé en ce que les quantités de motifs a caractère hydrophobe (MH) sont telles que ledit agent antisalissure présente une balance hydrophile/hydrophobe supérieure à 151 1) Method according to any one of claims 1) to 10), characterized in that the quantities of units of hydrophobic character (MH) are such that said anti-fouling agent has a hydrophilic / hydrophobic balance greater than 15
12) Procède selon l'une quelconque des revendications 1 ) à 6) ou 9) à 1 1 ), caractérisé en ce que l'agent antisalissure amphiphile mis en oeuvre est un agent tensio-actif cationique12) Method according to any one of claims 1) to 6) or 9) to 1 1), characterized in that the amphiphilic antifouling agent used is a cationic surfactant
13) Procède selon la revendication 12), caractérise en ce que l'agent antisalissure amphiphile tensio-actif cationique a pour formule13) Method according to claim 12), characterized in that the cationic surfactant amphiphilic antifouling agent has the formula
R 1 R2R3R4 N+ X- OU R 1 R 2 R3R4 N + X - OR
. Ri , R2 et R3 sont semblables ou différents et représentent H ou un radical alkyle contenant moins de 4 atomes de carbone, de préférence 1 ou 2 atome(s) de carbone . R4 représente un radical alkyle contenant plus de 4 atomes de carbone, de préférence de l'ordre de 8 à 20 atomes de carbone . X" est un ion halogénure, bromure de préférence, acétate, sulfate 14) Procédé selon la revendication 13), caractérisé en ce que l'agent antisalissure tensio-actif cationique est le bromure de dodécyltriméthylammonium, de tétradécyltriméthylammonium ou de cetyltπméthylammonium.. Ri, R 2 and R 3 are similar or different and represent H or an alkyl radical containing less than 4 carbon atoms, preferably 1 or 2 carbon atom (s). R 4 represents an alkyl radical containing more than 4 carbon atoms, preferably of the order of 8 to 20 carbon atoms. X " is a halide ion, preferably bromide, acetate, sulfate 14) Process according to claim 13), characterized in that the cationic surfactant antifouling agent is dodecyltrimethylammonium bromide, tetradecyltrimethylammonium or cetyltπmethylammonium bromide.
15) Procédé selon l'une quelconque des revendications 1 ) à 1 1 ), caractérisé en ce que l'agent antisalissure est un oligomère ou un polymère formé d'un tronc oligomère ou polymère hydrocarboné hydrophile présentant dans sa chaîne ou en ramification des motifs porteurs d'une fonction à caractère cationique (MC) avec son contre-ion et des motifs à caractère hydrophobe (MH).15) Method according to any one of claims 1) to 1 1), characterized in that the anti-fouling agent is an oligomer or a polymer formed from an oligomeric trunk or hydrophilic hydrocarbon polymer having in its chain or in branching units carrying a cationic (MC) function with its counterion and hydrophobic (MH) units.
16) Procédé selon la revendication 15), caractérisé en ce que l'agent antisalissure oligomère ou polymère est un guar alkyl cationique, un hydroxypropylguar alkyl cationique.16) Process according to claim 15), characterized in that the oligomeric or polymeric anti-fouling agent is a cationic alkyl guar, a cationic hydroxypropylguar.
17) Agent antisalissure des articles à base de coton tissé, susceptible d'être mis en oeuvre pour réaliser le procédé faisant l'objet de la revendication 15), caractérisé en ce qu'il est constitué d'un oligomere, polymère ou copolymere présentant . au moins un motif porteur d'une fonction à caractère cationique (MC) susceptible de s'adsorber sur la surface du coton et son contre-ion . et au moins un motif à caractère hydrophobe (MH) contenant au moins 4 atomes de carbone, de préférence de 8 à 20 atomes de carbone, susceptible de configurer ledit agent à l'interface coton/eau, hé chimiquement au motif porteur d'une fonction à caractère cationique (MC) par l'intermédiaire d'une chaîne hydrophile constituée par un oligomère, polymère ou copolymere de l'alcool vinyhque.17) Anti-fouling agent for articles based on woven cotton, capable of being used to carry out the process which is the subject of claim 15), characterized in that it consists of an oligomer, polymer or copolymer having . at least one motif carrying a cationic function (MC) capable of adsorbing on the surface of the cotton and its counterion. and at least one unit of hydrophobic character (MH) containing at least 4 carbon atoms, preferably from 8 to 20 carbon atoms, capable of configuring said agent at the cotton / water interface, hey chemically to the unit carrying a cationic function (MC) via a hydrophilic chain consisting of an oligomer, polymer or copolymer of vinyhque alcohol.
18) Agent salissure selon la revendication 17), caractérisé en ce que les fonctions à caractère cationique (MC) sont des fonctions ammonium de formule18) Soiling agent according to claim 17), characterized in that the functions of cationic nature (MC) are ammonium functions of formula
R1 R2R3 N+_ ou R 1 R 2 R 3 N + _ or
R1 , R2 et R3 . sont semblables ou différents et représentent H ou un radical alkyle contenant moins de 4 atomes de carbone, de préférence 1 ou 2 atome(s) de carbone, éventuellement substitué, notamment par une ou plusieurs fonctιon(s) hydroxyle(s), . ou bien forment ensemble, avec l'atome d'azote N+, au moins un cycle aromatique ou non aromatique, lesdites fonctions à caractère cationique (MC) étant liées chimiquement à la chaîne oligomère, polymère ou copolymere de l'alcool polyvinylique directement par liaison C-C ou indirectement par l'intermédiaire d'un groupement bivalent ou polyvalent hydrocarboné contenant au moins un hétéroatome 19) Agent antisalissure selon la revendication 18), caractérisé en ce que les fonctions ammonium dérivent du chlorure ou bromure de glycidyltπméthylammonium, chlorure du chloro-1 , hydroxy-2 propyl tπméthylammoniumR 1 , R 2 and R 3 . are similar or different and represent H or an alkyl radical containing less than 4 carbon atoms, preferably 1 or 2 carbon atom (s), optionally substituted, in particular by one or more hydroxyl function (s),. or else form together, with the nitrogen atom N + , at least one aromatic or non-aromatic ring, said functions of cationic nature (MC) being chemically linked to the oligomer, polymer or copolymer chain of polyvinyl alcohol directly by CC bond or indirectly via a bivalent or polyvalent hydrocarbon group containing at least one heteroatom 19) Antifouling agent according to claim 18), characterized in that the ammonium functions are derived from glycidyltπmethylammonium chloride or bromide, chloro-1 chloride, 2-hydroxypropyl tπmethylammonium
20) Agent antisalissure selon l'une quelconque des revendications 17) à 19), caractérisé en ce que les motifs a caractère hydrophobe (MH) sont des radicaux alkyles linéaires ou ramifies, linéaires de préférence, lies chimiquement à la chaîne oligomere, polymère ou copolymere de l'alcool polyvinylique directement par liaison C-C ou indirectement par l'intermédiaire d'un groupement bivalent ou polyvalent hydrocarboné contenant au moins un hétéroatome20) Antifouling agent according to any one of claims 17) to 19), characterized in that the units of hydrophobic nature (MH) are linear or branched alkyl radicals, preferably linear, chemically linked to the oligomer, polymer or polyvinyl alcohol copolymer directly by CC bond or indirectly via a bivalent or polyvalent hydrocarbon group containing at least one heteroatom
21 ) Agent antisalissure selon l une quelconque des revendications 17) à 20), caractérise en ce qu'il contient de I ordre de 0,1 a 10 , de préférence de 1 a 6 motifs porteurs d'une fonction a caractère cationique (MC) pour 100 unités monomères de l'oligomère, du polymère ou du copolymere d'alcool polyvinyhque, et de 0,01 à 10 , de préférence de 0,1 a 5 motifs a caractère hydrophobe (MH) pour 100 unités monomères du polymère ou copolymere d'alcool polyvinylique21) antifouling agent according to any one of claims 17) to 20), characterized in that it contains I of the order of 0.1 to 10, preferably from 1 to 6 units carrying a function of cationic nature (MC ) per 100 monomer units of the oligomer, of the polymer or of polyvinyl alcohol copolymer, and from 0.01 to 10, preferably from 0.1 to 5 units of hydrophobic character (MH) per 100 monomer units of the polymer or polyvinyl alcohol copolymer
22) Procède de traitement antisalissure des articles a base de coton tissé, par dépôt sur ledit article, au cours d une ou d'operatιon(s) de lavage, rinçage et/ou adoucissage ou séchage, de l'agent antisalissure faisant l'objet de l'une quelconque des revendications 17) a 21)22) Antifouling treatment for woven cotton articles, by deposition on said article, during one or more washing, rinsing and / or softening or drying operations, of the antifouling agent making the The subject of any of claims 17) to 21)
23) Procède selon l'une quelconque des revendications 1 ) a 16) ou 22), caractérisé en ce que ledit agent antisalissure est mis en oeuvre a raison d'environ 0,05 à 5 gramme(s) par litre de milieu de traitement23) Method according to any one of claims 1) to 16) or 22), characterized in that said anti-fouling agent is used at a rate of approximately 0.05 to 5 gram (s) per liter of treatment medium
24) Procède selon l une quelconque des revendications 1 ) a 17) ou 22), caractérisé en ce que ledit agent antisalissure est mis en oeuvre au cours d'une opération de lavage par l'intermédiaire d'une formulation de lavage en poudre ou liquide contenant de t ordre de 0,02 a 20% de son poids dudit agent antisalissure.24) Method according to any one of claims 1) to 17) or 22), characterized in that said anti-fouling agent is used during a washing operation by means of a washing powder formulation or liquid containing t of the order of 0.02 to 20% of its weight of said antifouling agent.
25) Procède selon l une quelconque des revendications 1 ) a 17) ou 22), caractérisé en ce que ledit agent antisalissure est mis en oeuvre au cours d'une opération de rinçage et/ou adoucissage par I intermédiaire d'une formulation de rinçage et/ou adoucissage contenant de I ordre de 0,02 a 20% de son poids dudit agent antisalissure 26) Procédé selon l'une quelconque des revendications 1) à 17) ou 22), caractérisé en ce que ledit agent antisalissure est mis en oeuvre au cours d'une opération de séchage par l'intermédiaire d'un support constitué par une bande de textile non-tissé imprégnée dudit agent antisalissure, support contenant de l'ordre de 20% de son poids dudit agent antisalissure. 25) Method according to any one of claims 1) to 17) or 22), characterized in that said anti-fouling agent is used during a rinsing and / or softening operation by means of a rinsing formulation and / or softening containing in the order of 0.02 to 20% of its weight of said anti-fouling agent 26) Method according to any one of claims 1) to 17) or 22), characterized in that said anti-fouling agent is used during a drying operation by means of a support constituted by a strip nonwoven fabric impregnated with said anti-fouling agent, support containing about 20% of its weight of said anti-fouling agent.
EP97906221A 1996-02-20 1997-02-19 Soil-repellent agent and method for treating articles based on woven cotton Expired - Lifetime EP0882117B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9602181A FR2745014B1 (en) 1996-02-20 1996-02-20 ANTI-FOULING TREATMENT PROCESS FOR ARTICLES BASED ON WOVEN COTTON
FR9602181 1996-02-20
PCT/FR1997/000304 WO1997031085A1 (en) 1996-02-20 1997-02-19 Soil-repellent agent and method for treating articles based on woven cotton

Publications (2)

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EP0882117A1 true EP0882117A1 (en) 1998-12-09
EP0882117B1 EP0882117B1 (en) 2002-11-13

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EP97906221A Expired - Lifetime EP0882117B1 (en) 1996-02-20 1997-02-19 Soil-repellent agent and method for treating articles based on woven cotton

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EP (1) EP0882117B1 (en)
JP (1) JP3253972B2 (en)
AT (1) ATE227765T1 (en)
AU (1) AU2098397A (en)
BR (1) BR9707650A (en)
CA (1) CA2246381A1 (en)
DE (1) DE69717079T2 (en)
ES (1) ES2187757T3 (en)
FR (1) FR2745014B1 (en)
WO (1) WO1997031085A1 (en)

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DE69717079T2 (en) 2003-07-24
CA2246381A1 (en) 1997-08-28
EP0882117B1 (en) 2002-11-13
ES2187757T3 (en) 2003-06-16
US6379394B1 (en) 2002-04-30
BR9707650A (en) 1999-07-27
FR2745014B1 (en) 1998-04-03
FR2745014A1 (en) 1997-08-22
DE69717079D1 (en) 2002-12-19
WO1997031085A1 (en) 1997-08-28
JP3253972B2 (en) 2002-02-04
ATE227765T1 (en) 2002-11-15
AU2098397A (en) 1997-09-10
JPH11505568A (en) 1999-05-21

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