WO2003104374A1 - Composition pour le traitement des articles en fibres textiles comprenant un polymere dendritique - Google Patents
Composition pour le traitement des articles en fibres textiles comprenant un polymere dendritique Download PDFInfo
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- WO2003104374A1 WO2003104374A1 PCT/FR2003/001704 FR0301704W WO03104374A1 WO 2003104374 A1 WO2003104374 A1 WO 2003104374A1 FR 0301704 W FR0301704 W FR 0301704W WO 03104374 A1 WO03104374 A1 WO 03104374A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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- 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
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- 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
- C11D3/3719—Polyamides or polyimides
Definitions
- the subject of the present invention is a composition for treating textile fiber articles intended to be used for washing and / or rinsing, drying in a dryer or ironing textile fiber articles comprising a dendritic polymer (a polyamide hyper-connected in particular).
- the subject of the invention is also the use, in a composition for treating textile fiber articles intended to be used for washing and / or rinsing, drying in a dryer or ironing textile fiber articles, a dendritic polymer (in particular hyperbranched polyamide) as an anti-wrinkling agent or an ironing aid ("ease-of-ironing").
- the cleaning of the linen in a washing machine which includes a spinning operation, results in a crumpled linen; creasing is accentuated during drying, in particular by the formation of inter-fiber hydrogen bonds. An ironing operation is therefore necessary to obtain a presentable appearance of the laundry.
- Dendritic polymers are polymer structures with numerous branches.
- a first subject of the invention consists of a composition for treating textile fiber articles intended to be used for washing and / or rinsing, drying in a dryer or ironing textile fiber articles, comprising at least a water-soluble or water-dispersible dendritic or hyperbranched polymer (P) capable of being obtained by:
- . f is an integer greater than or equal to 2, preferably goes from 2 to 10, very particularly is equal to 2.
- the symbol A represents a reactive function or a group carrying a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors
- the symbol B represents a reactive function or a group carrying a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato or their precursors, antagonist of A
- R represents a polyvalent linear or branched aliphatic, cycloaliphatic or aromatic hydrocarbon residue containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, sulfur or of phosphorus, said residue optionally carrying functions or functional groups which are not capable of reacting with functions A and B.
- the symbol B represents a reactive function antagonistic to the reactive function A; this means that function B is likely to react with function A by condensation. So the antagonistic functions
- an amino function are in particular the carboxy (formation of an amide), isocyanato (formation of a urea), oxiranyl (formation of a secondary or tertiary ⁇ -hydroxylated amine) functions
- . of a carboxy function are in particular the amino functions (formation of an amide), hydroxy (formation of an ester), isocyanato (formation of an amide),. of a hydroxy function, are in particular the carboxy (formation of an ester), oxiranyl (formation of an ether), isocyanato (formation of an amide) functions. of an oxiranyl function, are in particular the hydroxy (formation of an ether), carboxy (formation of an ester), amino (formation of a secondary or tertiary ⁇ -hydroxylated amine) functions,
- . of an isocyanato function are especially the amino, hydroxy, carboxy,. of a halo function, are in particular the hydroxy functions.
- amino function precursors mention may in particular be made of amine salts, such as hydrochlorides.
- precursors of carboxy function mention may be made in particular of esters, preferably of C1-C4, very particularly of C1-C2, acid halides, anhydrides, amides.
- hydroxy function precursors mention may in particular be made of epoxies.
- said polycondensation operation is also carried out in the presence
- a ' identical to or different from A, represents a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonists of B and B'
- the symbol B ' identical to or different from B, represents a reactive function chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist of A and A'
- R ' identical to or different from R, represents a polyvalent linear or branched aliphatic hydrocarbon residue, cycloaliphatic or aromatic containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, sulfur or phosphorus, said residue possibly carrying functions or functional groups which are not capable of reacting with functions A, A ', B and B'
- N is an integer greater than or equal to 1, preferably ranges from 1 to
- B "" represents a reactive function, identical or different from B or B ', chosen from amino, carboxy, hydroxy, oxiranyl, halogen, isocyanato, or their precursors, antagonist of A and A'
- R 1 represents a polyvalent linear or branched aliphatic, cycloaliphatic or aromatic hydrocarbon residue containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, sulfur or of phosphorus, or an organosiloxane or polyorganosiloxane residue, said residue R 1 optionally carrying functions or functional groups which are not capable of reacting with the functions A, A, B, B 'and B "
- the symbol A represents a reactive function, identical to or different from A or A, chosen from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist of B, B 'and B” functions.
- the symbol R 2 represents a polyvalent linear or branched aliphatic, cycloaliphatic or aromatic hydrocarbon residue containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen, nitrogen, sulfur or phosphorus, or an organosiloxane or polyorganosiloxane residue, said residue R 2 optionally carrying functions or functional groups which are not capable of reacting with the functions A, A ', A ", B, B' and B"
- the functions A, A, A "and B, B ', B" are chosen from reactive functions or a group carrying reactive functions chosen from amino, carboxy, hydroxy, oxiranyl functions or their precursors. Even more preferably, said functions are chosen from reactive functions or a group carrying reactive amino and carboxy functions, or their precursors.
- the molar ratio of the monomer of formula (I) to the monomer of formula (II) is greater than 0.05, preferably ranges from 0.125 to 2;
- the molar ratio of the monomer of formula (III) to the monomer of formula (I) is less than or equal to 1, preferably less than or equal to 1/2, and even more preferably ranges from 0 to 1/3; said ratio is very particularly from 0 to 1/5.
- the molar ratio of the monomer of formula (IV) to the monomer of formula (I) is less than or equal to 10, preferably less than or equal to 5; said ratio goes very particularly from 0 to 2, when f is equal to 2.
- the elementary entity considered to define the different molar ratios is the molecule.
- condensation reaction also includes the notion of addition reaction when one or more antagonistic functions of at least one of the monomers used is included in a cycle (lactams, lactones, epoxides for example).
- the bifunctional monomers of formula (II) are the monomers used for the manufacture of linear thermoplastic polyamides.
- ⁇ -aminoalkanoic compounds comprising a hydrocarbon chain having from 4 to 12 carbon atoms, or lactams derived from these amino acids such as ⁇ -caprolactam.
- the preferred bifunctional monomer for implementing the invention is ⁇ -caprolactam.
- at least part of the bifunctional monomers (II) are in the form of a prepolymer.
- the monomers (III) there may be mentioned:
- aromatic or aliphatic monoamines such as dodecylamine, octadecylamine, benzylamine ...
- aromatic or aliphatic monoacids containing from 1 to 32 carbon atoms such as benzoic acid, acetic acid, propionic acid, saturated or unsaturated fatty acids (dodecanoic, oleic, palmitic, stearic acid, etc.)
- - biprimary diamines preferably saturated linear or branched aliphatics having from 6 to 36 carbon atoms such as, for example, hexamethylenediamine, trimethylhexamethylenediamine, tetramethylenediamine, n-xylenediamine - saturated aliphatic dicarboxylic acids having from 6 to 36 carbon atoms such as, for example, adipic acid, azelaic acid, sebacic acid, maleic acid or anhydride - difunctional alcohols or epoxides, such as ethylene glycol, diethylene glycol, pentanediol, glycidyl ethers of monofunctional alcohols containing from 1 to 24 carbon atoms
- diisocyanates such as toluene diisocyanates, hexamethylene diisocyanate, phenyl diisocyanate, isophorone diisocyanate
- triamines triacids or aromatic or aliphatic polyacids
- triols or polyols such as N, N, N-tris (2-aminoethyl) amine, melamine ..., citric acid, acid 1, 3.5 -benzene tricarboxylic ..., 2,2,6,6-tetra- ( ⁇ - carboxyethyl) cyclohexanone, trimethylolpropane, glycerol, pentaerythritol, glycidyl ethers of di-, tri- or polyfunctional alcohols
- polymeric compounds such as polyamines polyoxyalkylenes sold under the trademark JEFFAMINE ®,
- polysiloxanes such as amino polydimethylsiloxane.
- the monomers (III), "heart” preferred are: hexamethylenediamine, adipic acid, JEFFAMINE ® T403 sold by the company Huntsman acid, 1, 3,5-benzene tricarboxylic acid, 2,2,6, 6-tetra- ( ⁇ - carboxyethyl) cyclohexanone.
- aromatic or aliphatic monoamines such as dodecylamine, octadecylamine, benzylamine ...
- aromatic or aliphatic monoacids containing from 1 to 32 carbon atoms such as benzoic acid, acetic acid, propionic acid, saturated or unsaturated fatty acids (dodecanoic, oleic, palmitic, stearic acid, etc.) - monofunctional alcohols or epoxides, such as ethylene oxide, epichlorohydrin ...
- - isocyanates such as phenylisocyanate ...
- JEFFAMINE M ® monoamine polyoxyalkylenes sold under the brand JEFFAMINE M ® , such as JEFFAMINE M 1000 ® and JEFFAMINE M 2070 ®
- the dendritic polymers (P) used according to the invention can be assimilated to tree structures provided with a focal point formed by the function A and a periphery furnished with terminations B. Furthermore, when they are present, the bifunctional monomers (II) are spacers in the three-dimensional structure. They allow control of the connection density.
- the monomers (III) When they are present, the monomers (III) form nuclei.
- the monofunctional monomers (IV) "chain limiter" are themselves located at the periphery of the dendrimers. The presence of monomers (III) and (IV) makes it possible to control the molecular weight.
- the dendritic polymers (P) used according to the invention are hyperbranched polyamides; they are obtained from at least one monomer of formula (I) having, as reactive polycondensation functions, amino functions, and carboxy antagonistic functions, or from a monomer composition additionally containing at least one monomer of formula (II ) and / or (III) and / or (IV) having the same type (s) of reactive polycondensation function (s), all or part of the monomer (s) of formula (II) which can be replaced by a lactam.
- the polycondensation / polymerization operation can be carried out in a known manner in the molten or solvent phase, the monomer of formula (II), when it is present, being able to play the role of solvent favorably.
- the operation can be carried out favorably in the presence of at least one polycondensation catalyst and optionally of at least one compound. antioxidant.
- catalysts and antioxidant compounds are known to those skilled in the art.
- phosphorous compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acids, such as 2- (2'-pyridyl) ethylphosphonic acid, phosphites such as tris (2,4-di-tert-butylphenyl) phosphite.
- biobuttered phenolic-based antioxidants such as N, N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 5-tert-butyl-4-hydroxy-2- methylphenyl sulfide.
- Hyperbranched polyamides having hydrophilic functionalities which are not reactive with the functions A, A, A ", B, B 'and B" can be obtained by using a monomer of formula (III) and / or (IV) having one or more polyoxyethylene groups (monomer from the family of amino polyoxyalkylenes JEFFAMINES) and / or a monomer of formula (IV) having quaternary ammonium, nitrile, sulfonate, phosphonate, phosphate functions.
- Another embodiment consists, after preparation of a hyperbranched polyamide by polycondensation of non-functionalized monomers, in modifying the terminal functions of said hyperbranched polyamide by reaction with a compound having quaternary ammonium, nitrile, sulfonate, phosphonate, phosphate or groups functions polyoxyethylenes.
- the molar mass by weight of said dendritic polymers, hyperbranched polyamides in particular can range from 1,000 to 1,000,000 g / mol, preferably from 5,000 to 500,000 g / mol.
- the molar mass by weight can be measured by size exclusion chromatography. The measurement is carried out in an eluting phase composed of 70% by volume of Millipore water 18 megaohms and 30% by volume of methanol, containing 0.1 M NaNO 3 ; it is adjusted to pH 10 (1/1000 NH 4 OH 25%).
- the molar mass by weight is established in a known manner by means of light scattering values.
- the treatment composition according to the invention may contain from 0.001 to 10%, preferably from 0.01 to 5% of its weight of the dendritic polymer (P).
- a second object of the invention consists in the use, in a composition for treating articles made of textile fibers intended to be used for washing and / or rinsing, drying in a dryer or ironing articles made of fibers textiles, of at least one dendritic polymer (P), as an agent making it possible to provide said articles with properties anti-wrinkling or ease-of-ironing.
- a third object of the invention consists in a process for improving the properties of a composition intended for washing and / or rinsing, drying in a dryer or ironing in aqueous or wet articles of textile fibers, by adding to said composition of at least one dendritic polymer (P) in an amount effective to provide said articles with anti-crease ("anti-wrinkling") or ease of ironing ("ease-of-ironing") properties.
- P dendritic polymer
- the form of the composition and the conditions of use (or treatment) can be multiple. Said composition can be presented
- composition according to the invention can be:
- liquid rinsing formulation capable of directly forming by dilution a rinsing bath
- a solid material, textile in particular, comprising said dendritic polymer, intended to be brought into contact with wet articles in a dryer (said solid material is hereinafter called "drying additive");
- composition according to the invention is particularly well suited to the treatment of linen, in particular cotton-based, in particular containing at least 35% cotton.
- the pH of use of the composition according to the invention can range from approximately 2 to approximately 12, depending on the desired use. As it's about
- the pH of the detergent bath is generally of the order of 7 to 11, preferably of 8 to 10.5;
- - of a rinsing formulation, the pH of the rinsing bath is generally of the order of 2 to 8;
- the pH to be considered is that of residual water, which can be of the order of 2 to 9;
- an aqueous ironing formulation the pH of said formulation is generally of the order of 5 to 9.
- the amount of dendritic polymer (P) present in the composition to provide anti-wrinkling or ease-of-ironing properties according to the invention can range from 0.001 to 10 % by dry weight of said composition, depending on the desired application.
- said dendritic polymer (P) can be used as follows:
- Said composition may contain at least one surfactant and / or a detergency and / or rinsing additive for articles made of textile fibers and / or a solid support (especially textile) of said dendritic polymer (P).
- the detergent formulation may include surfactants in an amount corresponding to about 3 to 40% by weight based on the detergent formulation, surfactants such as anionic surfactants.
- surfactants such as anionic surfactants.
- R 1 an alkyl radical in C-
- alkyl sulphates of formula ROSO3M where R represents a C5-C24, preferably C-
- R 'a C2-C3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenes (OP) derivatives, having an average of 0, 5 to 60 OE and / or OP patterns; .
- alkyl glycerol sulfonates polycarboxylic acid sulfones described in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates 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-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...); Nonionic surfactants.
- alkali metal sodium, potassium, lithium
- polyoxyalkylene polyoxyethylenated, polyoxypropylenated, polyoxybutylenated alkylphenols in which the alkyl substituent is C6-C12 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the Triton X-45, X-114, X-100 or X-102 sold by Rohm & Haas Cy. ; . glucosamide, glucamide, glycerolamide; .
- polyoxyalkylene C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units oxyethylene, oxypropylene
- amine oxides such as alkyl oxides C10-C18 dimethylamines, alkoxy oxides C8-C22 ethyl dihydroxy ethylamines; . the alkylpolyglycosides described in US-A-4565647;
- alkyldimethylbetaines alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, condensation products of fatty acids and protein hydrolysates; alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms.
- Detergency builders that improve the properties of surfactants can be used 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, detergency adjuvants such as:
- polyphosphates tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates of alkali metals, ammonium or alkanolamines
- silicates in particular those having a Si ⁇ 2 / Na 2 O ratio of the order of 1.6 / 1 to 3.2 / 1 and the lamellar silicates described in US-A-4664839;
- 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-488868;
- crystalline or amorphous aluminosilicates 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 microns is preferred.
- Organic detergency builders water-soluble polyphosphonates (1-hydroxy-1 ethane, 1-diphosphonates, methylene salts diphosphonates ...); water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as: polycarboxylate ethers (oxidisuccinic acid and its salts, acid monosuccinic tartrate and its salts, disuccinic acid tartrate and its salts); hydroxypolycarboxylate ethers; - citric acid and its salts, mellitic acid, succinic acid and their salts; the salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, N- (2 hydroxyethyl) -nitrilodiacetates); C5-C20 succinic alkyl acids and their salts (2-dodecenylsuccinates, lauryl succinates); polyacetal carboxylic esters; polyaspartic acid, poly
- the detergent formulation may further comprise at least one oxygen-releasing bleaching agent comprising a per-compound, preferably a persalt.
- Said bleaching agent can be present in an amount corresponding to approximately 1 to 30%, preferably from 4 to 20% by weight relative to the detergent formulation.
- per-compounds capable of being used as bleaching agents mention should be made in particular of perborates such as sodium perborate monohydrate or tetrahydrate; peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate.
- perborates such as sodium perborate monohydrate or tetrahydrate
- peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate.
- the preferred bleaches are sodium perborate, mono- or tetrahydrate and / or sodium carbonate peroxyhydrate.
- Said agents are generally combined with a bleach activator generating in situ in the washing medium, a peroxycarboxylic acid, in an amount corresponding to approximately 0.1 to 12%, preferably from 0.5 to 8% by weight relative to the detergent formulation.
- a bleach activator generating in situ in the washing medium, a peroxycarboxylic acid, in an amount corresponding to approximately 0.1 to 12%, preferably from 0.5 to 8% by weight relative to the detergent formulation.
- these activators mention may be made of tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetylglucose, octaacetyllactose. Mention 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 phthalocyan
- the detergent formulation may further comprise other soil release agents, anti-redeposition, chelating agents, dispersants, fluorescence agents, foam suppressants, softeners, enzymes and other various additives.
- Anti-fouling agents include sodium EDTA, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite, sodium metabisulfite
- They can be used in amounts of approximately 0.01-10%, preferably approximately 0.1-5%, and more preferably of the order of 0.2-3% by weight.
- agents such as:. cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose; . polyvinyl esters grafted on polyalkylene trunks such as polyvinyl acetates grafted on polyoxyethylene trunks (EP-A-219048); . polyvinyl alcohols;
- 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 terephthalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 to 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 5,000, 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);
- polyester sulfone 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-A-4,968,451); .
- polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated by ethyl or methyl units (US-A-4,711,730) or polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) or anionic sulfopolyethoxy groups (US-A-4,721,580), sulfoaroyl (US-A-4,877,896);
- polyester sulfone copolymers derived from terephthalic, isophthalic and sulfoisophthalic acid, anhydride or diester and a diol FR-A-2720399.
- Anti-redeposition agents FR-A-2720399.
- agents such as:. ethoxylated monoamines or polyamines, polymers of ethoxylated amines (US-A-4,597,898; EP-A-11,984); . carboxymethylcellulose;
- polyester sulfone oligomers obtained by condensation of isophthalic acid, dimethyl sulfosuccinate and diethylene glycol (FR-A-2 236926); . polyvinylpyrollidones. Chelating agents
- the iron and magnesium chelating agents can be present in amounts of the order of 0.1-10%, preferably of the order of 0.1-3% by weight.
- aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethylethylenediaminetriacetates, nitrilotriacetates;
- aminophosphonates such as nitrilotris- (methylenephosphonates);
- polyfunctional aromatic compounds such as dihydroxy-disulfobenzenes.
- Polymeric dispersing agents can be present 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 with a molecular mass of the order of 2,000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and in particular polyacrylates of molecular mass of the order of 2000 to 10,000 (US-A-3,308,067), copolymers of arylic acid and maleic anhydride of molecular mass of the order of
- polyethylene glycols of molecular mass of the order of 1,000 to 50,000.
- Fluorescent agents can be present in an amount of about 0.05-1.2% by weight, agents such as: stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanins, thiophesses ... ("The production and application of fluorescent brightening agents" - M. Zahradnik, published by John
- agents such as:
- polyorganosiloxane oils or resins optionally combined with silica particles.
- agents such as clays.
- Enzymes They can be present in an amount of up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent formulation, enzymes such as:
- proteases amylases, lipases, cellulases, peroxidases (US-A-3,553,139;
- the detergent formulation can be used, in particular in a washing machine, at a rate of 0.5 g / l to 20g / l, preferably from 2g / l to 10g / l to carry out washing operations at a temperature of l '' from 25 to 90 ° C.
- a second embodiment of the invention consists of an aqueous formulation for rinsing the laundry, used in particular in a washing machine. This can be carried out at a rate of 0.2 to 10 g / l, preferably from 2 to 10 g / l.
- P dendritic polymer
- other constituents of the type may be present
- cationic surfactants triethanolamine diester quaternized by dimethylsulfate, N-methylimidazoline tallow methyl sulfate ester, dialkyldimethylammonium chloride, alkylbenzyl-dimethylammonium chloride, methyl and alkylimidazolinium sulfate, methyl and methyl sulfate bis (alkylamidoethyl) -2-hydroxyethylammonium ”) in an amount which can range from 3 to 50%, preferably from 4 to 30% of the said formulation optionally combined with nonionic surfactants (ethoxylated fatty alcohols, ethoxylated alkylphenols ...) in quantities up to 3%;
- alcohols methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerin
- foam limiters in particular alcohols (methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerin), - foam limiters.
- a third embodiment of the invention consists of a laundry drying additive in an appropriate drying machine.
- Said additive comprises a flexible solid support constituted for example by a strip of woven or nonwoven fabric, a cellulose sheet, impregnated with said dendritic polymer (P), said additive is introduced on drying in the damp linen to be dried at a temperature of around 50 to 80 ° C for 10 to
- Said additive may further comprise cationic softening agents
- anti-color transfer agents up to 80%
- a fourth embodiment of the invention consists of an ironing formulation, which can be sprayed directly onto the dry linen before the ironing operation.
- Said formulation can also contain non-ionic (0.5 to 5%) or anionic (0.5 to 5%) surfactants, perfumes (0.1 to 3%), cellulose derivatives (0, 1 to 3%) like starch.
- the molar mass by weight is determined as follows by size exclusion chromatography.
- the measurement is carried out in an eluting phase composed of 70% by volume of Millipore 18 megaohms water and 30% by volume of methanol, containing 0.1 M NaNO 3 ; it is adjusted to pH 10 (1/1000 NH 4 OH 25%).
- the device features are as follows:
- - Chromatographic columns 1 Shodex SB806HQ column (30 cm, 5 ⁇ m) and an ASAHI GFA30 column (60cm, 5 ⁇ m).
- - Injector-pump Waters515 for pumping the eluent and Wisp717 from Waters for injection.
- the chromatographic chain is equipped with the following detectors:
- UV2000 TSP bi wavelength 320 nm (1 DO) * Light scattering detector: MALLS Wyatt (Laser He 633 nm)
- the solution injected (200 ⁇ l) contains approximately 0.2% by weight of hyperbranched polyamide.
- the molecular weight by weight is established directly without calibration using the light scattering values extrapolated at zero angle; these values are proportional to CxMx (dn / dc) 2 .
- the dn / dc ratio is established by the refractometric detector.
- the monomers are fully loaded at the start of the test into the reactor preheated to 120 ° C. 50.72 g of 5-aminoisophthalic acid (0.28 mol), 31.6 g of ⁇ -caprolactam (0.28 mol) and 30 ⁇ l of a 50% aqueous solution (p / p) hypophosphorous acid.
- the reactor is purged by a succession of evacuation and restoration of atmospheric pressure using dry nitrogen.
- the agitation is started at 40 rpm.
- the reaction mass is gradually heated from 120 ° C to 260 ° C in 70 min.
- the temperature is then maintained at 260 ° C. in a tray.
- the reactor is placed under vacuum until the distillation stops. 73.44 g of polymer and 6.69 g of distillate are collected.
- the hyperbranched polyamide with carboxylic acid endings obtained is glassy and translucent.
- the Mn and Mw obtained by size exclusion chromatography equipped with light scattering detection are 140,000 and 150,000 g / mol, respectively.
- Example 2 Synthesis of a hyperbranched copolyamide with ammonium carboxylate endings by neutralization with ammonia of the hyperbranched copolyamide with carboxylic acid endings obtained in Example 1.
- Example 2 In a 500 ml Erlenmeyer flask, 67 g of the hyperbranched polyamide obtained in Example 1 (242 mmol COOH) are dispersed in 200 ml of water. 20.6 g of 20% by mass aqueous ammonia solution (242 mmol) are then added dropwise. The mixture is put under mechanical stirring and maintained under these conditions until complete dissolution. The unreacted ammonia is then evaporated on a rotary evaporator. The hyperbranched polyamide with ammonium carboxylate endings is then isolated by lyophilization.
- the monomers are completely loaded at the start of the test into the reactor at room temperature.
- the reactor is purged by a succession of 4 sequences of evacuation and restoration of atmospheric pressure using dry nitrogen.
- the agitation is then set at 50 rpm.
- the reaction mass is gradually heated from ambient (20 ° C) to 240 ° C in 160 min.
- the temperature is then maintained at 240 ° C. in a tray for approximately 15 to 30 additional minutes.
- the stirring is stopped and the reactor is placed under nitrogen overpressure.
- the bottom valve is gradually opened and the polymer is poured at 240 ° C into a stainless steel bucket.
- the Mn and Mw obtained by steric exclusion chromatography equipped with light scattering detection are 5900 and 12200 g / mol, respectively.
- the reaction mixture is then heated to 70 ° C in 40 minutes, then kept at this temperature for 27 h.
- the solution is then transferred to a separatory funnel by rinsing the flask with 4 times 35 ml of water.
- the unreacted QUAB 151® is extracted with 2 times 150 ml of ethyl ether.
- the aqueous phase is then evaporated in a rotary evaporator and the hyperbranched copolyamide with mixed ends sodium carboxylate and quaternary ammonium is thus recovered.
- the washing formulation used to carry out the anti-crease evaluation test is as follows:
- Tissue treatment in a Tergotometer by washing using the washing formulation (L) containing the polymer to be tested, followed by rinsing with water
- a washing operation is carried out in a laboratory apparatus Tergotometer well known in the profession of formulators of detergent compositions.
- the device simulates the mechanical and thermal effects of washing machines of the American type with pulsator.
- Test pieces washed using the above washing formulations and rinsed 3 times with water, under the following conditions:
- the wet test pieces are then crumpled using a cylindrical press (5.5 cm in diameter x 7 cm in length); the pressure exerted is of 20 gx cm "2 for 90 seconds.
- This crumpling method allows reproducible crumpling on all tests.
- the standard deviation ⁇ of the distribution of the gray level is measured.
- ⁇ l corresponds to the standard deviation obtained with a washing formulation (L ') similar to (L) but free of the polymer to be tested.
- ⁇ 2 corresponds to the standard deviation obtained with the washing formulation (L) containing the polymer to be tested.
- ⁇ 3 corresponds to the standard deviation obtained on ironed starting test pieces
- stage 1 of tissue preparation not having undergone stages 2 and 3 of treatment and creasing of the tissues.
- WR (%) [( ⁇ l- ⁇ 2) / ⁇ l] f x 100 f being a normalization factor, equal to 1 / [( ⁇ l- ⁇ 3) / ⁇ l]
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03757120A EP1511831A1 (fr) | 2002-06-11 | 2003-06-06 | Composition pour le traitement des articles en fibres textiles comprenant un polymere dendritique |
US10/517,270 US20060107466A1 (en) | 2002-06-11 | 2003-06-06 | Composition for treating textile fiber articles comprising a dendritic polymer |
JP2004511435A JP2005529214A (ja) | 2002-06-11 | 2003-06-06 | 樹枝状ポリマーを含む、織物繊維製物品処理用組成物 |
AU2003251113A AU2003251113A1 (en) | 2002-06-11 | 2003-06-06 | Composition for treating textile fiber articles comprising a dendritic polymer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR02/07139 | 2002-06-11 | ||
FR0207139A FR2840622B1 (fr) | 2002-06-11 | 2002-06-11 | Composition pour le traitement des articles en fibres textiles comprenant un polymere dendritique |
Publications (1)
Publication Number | Publication Date |
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WO2003104374A1 true WO2003104374A1 (fr) | 2003-12-18 |
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ID=29559115
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2003/001704 WO2003104374A1 (fr) | 2002-06-11 | 2003-06-06 | Composition pour le traitement des articles en fibres textiles comprenant un polymere dendritique |
Country Status (6)
Country | Link |
---|---|
US (1) | US20060107466A1 (fr) |
EP (1) | EP1511831A1 (fr) |
JP (1) | JP2005529214A (fr) |
AU (1) | AU2003251113A1 (fr) |
FR (1) | FR2840622B1 (fr) |
WO (1) | WO2003104374A1 (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005032497A2 (fr) * | 2003-09-29 | 2005-04-14 | Rhodia Chimie | Emulsions comprenant un polymere dendritique et utilisation d'un polymere dendritique comme agent d'emulsification |
WO2005032498A2 (fr) * | 2003-09-29 | 2005-04-14 | Rhodia Chimie | Composition aqueuse comprenant un polymere dentrique polyonique et un agent tensioactif ionique |
WO2007134614A1 (fr) * | 2006-05-18 | 2007-11-29 | Henkel Ag & Co. Kgaa | Lessive protégeant les couleurs |
WO2011144726A1 (fr) | 2010-05-21 | 2011-11-24 | Basf Se | Ignifuge polymère |
US11377517B2 (en) | 2013-04-16 | 2022-07-05 | Basf Se | Phosphorous containing flame retardants |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006040122B3 (de) * | 2006-08-26 | 2007-10-31 | Degussa Gmbh | Enteisungsmittel und/oder Vereisungsschutzmittel |
FR2958296B1 (fr) * | 2010-04-06 | 2013-08-16 | Rhodia Operations | Composition polyamide de haute viscosite |
JP5670815B2 (ja) * | 2011-04-21 | 2015-02-18 | 花王株式会社 | 衣料用処理剤組成物 |
US9758927B2 (en) | 2011-09-01 | 2017-09-12 | Colgate-Palmolive Company | Method for ease of ironing |
US20130111675A1 (en) * | 2011-11-03 | 2013-05-09 | Ecolab Usa Inc. | Sustainable laundry sour compositions with iron control |
RU2014137016A (ru) * | 2012-02-13 | 2016-04-10 | Басф Се | Цветозащитное моющее или чистящее средство |
US10435831B1 (en) * | 2014-07-15 | 2019-10-08 | Rita Harry-Ogiste | Fabric treating accessories and associated use thereof |
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WO1995002008A1 (fr) * | 1993-07-08 | 1995-01-19 | Dsm N.V. | Procede de preparation d'une macromolecule dendritique |
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- 2002-06-11 FR FR0207139A patent/FR2840622B1/fr not_active Expired - Fee Related
-
2003
- 2003-06-06 EP EP03757120A patent/EP1511831A1/fr not_active Withdrawn
- 2003-06-06 WO PCT/FR2003/001704 patent/WO2003104374A1/fr not_active Application Discontinuation
- 2003-06-06 AU AU2003251113A patent/AU2003251113A1/en not_active Abandoned
- 2003-06-06 US US10/517,270 patent/US20060107466A1/en not_active Abandoned
- 2003-06-06 JP JP2004511435A patent/JP2005529214A/ja not_active Abandoned
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005032497A2 (fr) * | 2003-09-29 | 2005-04-14 | Rhodia Chimie | Emulsions comprenant un polymere dendritique et utilisation d'un polymere dendritique comme agent d'emulsification |
WO2005032498A2 (fr) * | 2003-09-29 | 2005-04-14 | Rhodia Chimie | Composition aqueuse comprenant un polymere dentrique polyonique et un agent tensioactif ionique |
WO2005032497A3 (fr) * | 2003-09-29 | 2005-07-21 | Rhodia Chimie Sa | Emulsions comprenant un polymere dendritique et utilisation d'un polymere dendritique comme agent d'emulsification |
WO2005032498A3 (fr) * | 2003-09-29 | 2005-07-21 | Rhodia Chimie Sa | Composition aqueuse comprenant un polymere dentrique polyonique et un agent tensioactif ionique |
WO2007134614A1 (fr) * | 2006-05-18 | 2007-11-29 | Henkel Ag & Co. Kgaa | Lessive protégeant les couleurs |
WO2011144726A1 (fr) | 2010-05-21 | 2011-11-24 | Basf Se | Ignifuge polymère |
EP2395039A1 (fr) | 2010-05-21 | 2011-12-14 | Basf Se | Moyen polymère de protection contre les flammes |
US11377517B2 (en) | 2013-04-16 | 2022-07-05 | Basf Se | Phosphorous containing flame retardants |
Also Published As
Publication number | Publication date |
---|---|
JP2005529214A (ja) | 2005-09-29 |
EP1511831A1 (fr) | 2005-03-09 |
FR2840622A1 (fr) | 2003-12-12 |
FR2840622B1 (fr) | 2004-07-23 |
AU2003251113A1 (en) | 2003-12-22 |
US20060107466A1 (en) | 2006-05-25 |
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