EP1419231B1 - Additive for a textile treatment composition and the use thereof as a care product - Google Patents

Abstract

Preformulated additive for a composition for treating textile fiber articles in aqueous or wet medium, comprising: a particulate solid organic polymer (P) dispersed in and/or encapsulated by a matrix (M) and a surfactant (S) at the matrix (M)/polymer (P) interface, said matrix (M) being soluble or dispersible in said medium and the polymer (P) insoluble and capable of dispersing in said medium in the form of nanoparticles. Use of the preformulated additive as care agent, in particular as crease-resistance agent, in detergent formulations, rinsing/softening formulations, tumble dryer additives and washing additives for textile fiber articles.

Description

The subject of the present invention is a preformulated additive for processing composition of textile fiber articles, the compositions comprising said additive; it also relates to the use of said additive, in compositions for the treatment of articles made of textile fibers, as an agent care of said articles, especially as an anti-crease agent; she aims also said treatment compositions.

Care of textile fiber articles means the protection of these with respect to physical or chemical degradation and / or the contribution to these benefits such as softening properties and / or anti-crease ; the contribution of an anti-crease benefit is particularly targeted.

• en ce qu'il comprend :
  • au moins un polymère organique (P) solide particulaire, dispersé dans et/ou encapsulé par une matrice (M) en au moins un composé organique ou inorganique
  • et au moins un agent tensioactif (S) à l'interface matrice (M) /polymère (P)
• en ce que ladite matrice (M) est soluble ou dispersable dans ledit milieu
• et en ce que ledit polymère (P) est insoluble et susceptible de se disperser dans ledit milieu sous forme de nanoparticules.

A first object of the invention consists of a preformulated additive for treatment composition of textile fiber articles in aqueous or wet medium, characterized:

• in that it comprises:
  • at least one particulate solid organic polymer (P) dispersed in and / or encapsulated by a matrix (M) in at least one organic or inorganic compound
  • and at least one surfactant (S) at the matrix (M) / polymer (P) interface
• in that said matrix (M) is soluble or dispersible in said medium
• and in that said polymer (P) is insoluble and capable of dispersing in said medium in the form of nanoparticles.

• de 5 à 90%, de préférence de 10 à 60% de son poids de polymère (P)
• de 3-90%, de préférence de 10 à 80%, tout particulièrement de 15 à 75% de son poids de matrice (M)
• de 0,01 à 20%, de préférence de 0,02 à 5% en poids de tensioactif (S).

For a good embodiment of the invention, said preformulated additive comprises, expressed in sec:

• from 5 to 90%, preferably from 10 to 60% of its weight of polymer (P)
• from 3 to 90%, preferably from 10 to 80%, most preferably from 15 to 75% of its matrix weight (M).
• from 0.01 to 20%, preferably from 0.02 to 5% by weight of surfactant (S).

The terms "dispersible" or "disperse" mean that it does not form of aggregates in the middle.

Preferably, said polymer (P) has a glass transition temperature Tg of the order of -40 ° C to 150 ° C, preferably of the order of -40 ° C to 100 ° C, especially of the order of -40 ° C to 40 ° C.
The term "polymer" means both a homopolymer and a copolymer derived from two or more monomers.

• des unités monomères (N) hydrophobes non chargées ou non-ionisables au pH d'usage de la composition de l'invention,
• éventuellement au moins une unité monomère (F) hydrophile choisie parmi les unités monomères
  • (F1) cationiques ou cationisables au pH d'usage de ladite composition,
  • (F2) amphotères au pH d'usage de ladite composition,
  • (F3) anioniques ou anionisables au pH d'usage de ladite composition,
  • (F4) non chargées ou non-ionisables, à caractère hydrophile, au pH d'usage de ladite composition,
  • ou leurs mélanges
• et éventuellement au moins une unité réticulante (R).

For a good embodiment of the invention, said polymer (P) comprises:

• hydrophobic monomer units (N) that are not loaded or non-ionizable at the use pH of the composition of the invention,
• optionally at least one hydrophilic monomeric unit (F) chosen from monomeric units
  • (F1) cationic or cationizable at the pH of use of said composition,
  • (F2) amphoteric at the pH of use of said composition,
  • (F3) anionic or anionizable at the use pH of said composition,
  • (F4) non-charged or nonionizable, of hydrophilic nature, at the pH of use of said composition,
  • or their mixtures
• and optionally at least one crosslinking unit (R).

Preferably, said monomer units (N) and (F) are derived from monomers α-β monoethylenically unsaturated.

Preferably, said monomeric units (R) derive from diethylenically unsaturated monomers.

The average molar mass of said polymer (measured by gel permeation chromatography (GPC) THF and expressed in equivalents polystyrene) may preferably be at least 20,000.

• les monomères vinylaromatiques tels que styrène, vinyltoluène...
• les alkylesters d'acides α-β monoéthyléniquement insaturés tels que les acrylates et méthacrylates d'alkyle en C₁-C₁₀ linéaire ou ramifié, comme ceux de méthyle, éthyle, butyle, isobutyle, heptyle, nonyle ...
• les esters de vinyle ou d'allyle d'acides carboxyliques saturés tels que les acétates, propionates, versatates de vinyle ou d'allyle
• les nitriles α-β monoéthyléniquement insaturés comme l'acrylonitrile ...
• les α-oléfines comme l'éthylène ...

As examples of monomers from which the hydrophobic units (N) are derived, mention may be made of:

• vinylaromatic monomers such as styrene, vinyltoluene ...
• the alkyl esters of α-β monoethylenically unsaturated acids such as linear or branched C ₁ -C ₁₀ alkyl acrylates and methacrylates, such as those of methyl, ethyl, butyl, isobutyl, heptyl or nonyl.
• vinyl or allyl esters of saturated carboxylic acids such as vinyl, allyl acetates, propionates, versatates
• α-β monoethylenically unsaturated nitriles such as acrylonitrile ...
• α-olefins such as ethylene ...

• les N,N(dialkylaminowalkyl)amides d'acides carboxyliques α-β monoéthyléniquement insaturés comme le N,N-diméthylaminométhyl acrylamide ou méthacrylamide, le N,N-diméthylaminoéthyl acrylamide ou méthacrylamide, le N,N-diméthylamino-3-propyl acrylamide ou méthacrylamide, le N,N-diméthylaminobutyl acrylamide ou méthacrylamide
• les aminoesters α-β monoéthyléniquement insaturés comme le diméthyl aminoéthyl méthacrylate (DMAM), diméthyl aminopropyl méthacrylate, le ditertiobutylaminoéthylméthacrylate, le dipentylaminoethylméthacrylate
• des monomères précurseurs de fonctions amines tels que le N-vinyl formamide, le N-vinyl acétamide, ... qui engendrent des fonctions amines primaires par simple hydrolyse acide ou basique.

As examples of monomers from which the cationic or cationizable hydrophilic (F1) units are derived, mention may be made of:

• the N, N (dialkylaminowalkyl) amides of α-β monoethylenically unsaturated carboxylic acids such as N, N-dimethylaminomethyl acrylamide or methacrylamide, N, N-dimethylaminoethyl acrylamide or methacrylamide, N, N-dimethylamino-3-propyl acrylamide or methacrylamide, N, N-dimethylaminobutyl acrylamide or methacrylamide
• monoethylenically unsaturated α-β aminoesters such as dimethylaminoethyl methacrylate (DMAM), dimethylaminopropyl methacrylate, ditertiobutylaminoethylmethacrylate, dipentylaminoethylmethacrylate
• monomers precursors of amine functions such as N-vinyl formamide, N-vinyl acetamide, ... which generate primary amine functions by simple acid or basic hydrolysis.

• la N,N-diméthyl-N-méthacryloyloxyéthyl-N-(3-sulfopropyl) ammonium sulfobétaïne (SPE de RASCHIG), la N,N-diméthyl-N-(2-méthacrylamidoéthyl)-N-(3-sulfopropyl) ammonium bétaïne (SPP de RASCHIG), la 1-vinyl-3-(3-sulfopropyl) imidazolidium bétaïne, la 1-(3-sulfopropyl)-2-vinylpyridinium bétaïne (SPV de RASCHIG),
• les dérivés de la réaction de quaternisation des N(dialkylaminowallcyl)amides d'acides carboxyliques α-β éthyléniquement insaturés, comme le N,N-diméthylaminométhyl acrylamide ou méthacrylamide, le N,N-diméthylamino-3-propyl acrylamide ou méthacrylamide, ou des aminoesters éthyléniquement insaturés comme le ditertiobutylaminoéthylméthacrylate, le dipentylaminoethylméthacrylate, par un chloroacétate de métal alcalin (sodium en particulier) ou de propane sultone.

By way of examples of monomers from which the hydrophilic (F 2) amphoteric units are derived, mention may be made of:

• N, N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine (RASCHIG SPE), N, N-dimethyl-N- (2-methacrylamidoethyl) -N- (3-sulfopropyl) ammonium betaine (RASCHIG SPP), 1-vinyl-3- (3-sulfopropyl) imidazolidium betaine, 1- (3-sulfopropyl) -2-vinylpyridinium betaine (RASCHIG SPV),
• derivatives of the quaternization reaction of N (dialkylaminowalkyl) amides of α-β ethylenically unsaturated carboxylic acids, such as N, N-dimethylaminomethyl acrylamide or methacrylamide, N, N-dimethylamino-3-propyl acrylamide or methacrylamide, or ethylenically unsaturated aminoesters such as ditertiobutylaminoethyl methacrylate, dipentylaminoethyl methacrylate, with an alkali metal chloroacetate (particularly sodium) or propane sultone.

• des monomères possédant au moins une fonction carboxylique, comme les acides ou anhydrides carboxyliques α-β éthyléniquement insaturés, les acides ou anhydrides acrylique, méthacrylique, maleique, fumarique, itaconique, N-méthacroyl alanine, N-acryloyl-hydroxy-glycine et leurs sels hydrosolubles
• des monomères possédant au moins une fonction sulfate ou sulfonate, comme le 2-sulfooxyéthyl méthacrylate, l'acide vinylbenzène sulfonique, l'acide allyl sulfonique, le 2-acrylamido-2méthylpropane sulfonique, l'acrylate ou le méthacrylate de sulfoéthyle, l'acrylate ou le méthacrylate de sulfopropyle et leurs sels hydrosolubles
• des monomères possédant au moins une fonction phosphonate ou phosphate, comme l'acide vinylphosphonique,... les esters de phosphates éthyléniquement insaturés tels que les phosphates dérivés du méthacrylate d'hydroxyéthyle (Empicryl 6835 de RHODIA) et ceux dérivés des méthacrylates de polyoxyalkylènes et leurs sels hydrosolubles
• des monomères α-β monoéthyléniquement insaturés précurseurs de fonction(s) anionique(s), tels que ceux dont l'hydrolyse engendre des fonctions carboxylates (acrylate de tertiobutyle, acrylate de diméthyl aminoéthyle, anhydride maléique, ...)

As examples of monomers from which the hydrophilic units (F3) anionic or anionizable are derived, mention may be made of:

• monomers having at least one carboxylic function, such as α-β ethylenically unsaturated carboxylic acids or anhydrides, acrylic, methacrylic, maleic, fumaric, itaconic, N-methacroyl alanine, N-acryloyl-hydroxy-glycine acids and anhydrides and their salts; soluble
• monomers having at least one sulphate or sulphonate function, such as 2-sulphooxyethyl methacrylate, vinylbenzene sulphonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulphonic acid, acrylate or sulphoethyl methacrylate, acrylate or sulfopropyl methacrylate and their water-soluble salts
• monomers having at least one phosphonate or phosphate function, such as vinylphosphonic acid, esters of ethylenically unsaturated phosphates such as phosphates derived from hydroxyethyl methacrylate (Empicryl 6835 from Rhodia) and those derived from polyoxyalkylene methacrylates and their water-soluble salts
• monoethylenically unsaturated α-β monomers precursors of anionic function (s), such as those whose hydrolysis gives rise to carboxylate functions (tertiary butyl acrylate, dimethylaminoethyl acrylate, maleic anhydride, etc.)

• les hydroxyalkylesters d'acides α-β éthyléniquement insaturés comme les acrylates et méthacrylates α-β d'hydroxyéthyle, d'hydroxypropyle...
• les amides d'acides α-β éthyléniquement insaturés comme l'acrylamide, le N,N-diméthyl méthacrylamide, le N-méthylolacrylamide ...
• les monomères α-β éthyléniquement insaturés portant un segment polyoxyalkyléné hydrosoluble du type polyoxyde d'éthylène, comme les polyoxyde d'éthylène α-méthacrylates (BISOMER S20W, S10W, ... de LAPORTE) ou α-ω diméthacrylates, le SIPOMER BEM de RHODIA (méthacrylate de polyoxyéthylène ω-béhényle), le SIPOMER SEM-25 de RHODIA (méthacrylate de polyoxyéthylène ω-tristyrylphényle) ...
• les monomères α-β éthyléniquement insaturés précurseurs d'unités ou de segments hydrophiles tels que l'acétate de vinyle qui, une fois polymérisé, peut être hydrolysé pour engendrer des unités alcool vinylique ou des segments alcool polyvinylique
• les monomères α-β éthyléniquement insaturés de type uréido et en particulier le méthacrylamido de 2-imidazolidinone éthyle (Sipomer WAM Il de RHODIA).

As examples of monomers from which the hydrophilic units (F4) are unfilled or nonionizable, mention may be made of:

• hydroxyalkyl esters of α-β ethylenically unsaturated acids such as hydroxyethyl and hydroxypropyl α-β acrylates and methacrylates.
• amides of α-β ethylenically unsaturated acids such as acrylamide, N, N-dimethyl methacrylamide, N-methylolacrylamide, etc.
• α-β ethylenically unsaturated monomers bearing a water-soluble polyoxyalkylene segment of the polyethylene oxide type, such as ethylene polyoxide α-methacrylates (BISOMER S20W, S10W, ... from LAPORTE) or α-ω dimethacrylates, SIPOMER BEM from RHODIA (polyoxyethylene ω-behenyl methacrylate), SIPOMER SEM-25 from RHODIA (oxy-tristyrylphenyl polyoxyethylene methacrylate) ...
• α-β ethylenically unsaturated monomers precursors of hydrophilic units or segments such as vinyl acetate which, once polymerized, can be hydrolysed to generate vinyl alcohol units or polyvinyl alcohol segments
• α-β-ethylenically unsaturated monomers of the ureido type and in particular 2-imidazolidinone ethyl methacrylamido (Sipomer WAM II from RHODIA).

• le divinylbenzène
• le diméthacrylate d'éthylène glycol
• le méthacrylate d'allyle
• le méthylène bis (acrylamide)
• le glyoxal bis (acrylamide)
• le butadiène.

As examples of monomers from which the crosslinking units (R) are derived, mention may be made of:

• divinylbenzene
• ethylene glycol dimethacrylate
• allyl methacrylate
• methylene bis (acrylamide)
• glyoxal bis (acrylamide)
• butadiene.

By polymer nanoparticles is meant, according to the invention, particles with a diameter of the order of 10 to 500 nm, preferably 20 to 300 nm, more particularly 20 to 100 nm, even more particularly 20 to 50 nm. nm.
The diameter of said particles can be determined in a well known manner by light scattering or by transmission electron microscopy.

Said polymers (P) can be obtained in a known manner by radical polymerization in aqueous medium of the ethylenically unsaturated monomers, in particular by radical emulsion polymerization in water.
Methods for obtaining small particle size latices are described in Colloid Polym. Sci. 266: 462-469 (1988) and in Journal of Colloid and Interface Science. Flight. 89. No. 1, September 1982 pages 185 and following. A method for preparing latex of particles of average size less than 100 nm, in particular of average size ranging from 1 to 60 nm, more particularly from 5 to 40 nm, is described in EP-A-644 205.

The choice and the relative amounts of the monomer or monomers from which the (N), (F) and (R) units of the polymer (P) are derived are such that said polymer (P) has a glass transition temperature Tg of order of -40 ° C to 150 ° C, preferably of the order of -40 ° C to 100 ° C, more particularly of the order of -40 ° C to 40 ° C, and remains insoluble under the conditions of use of the additive of the invention.
According to the invention, said polymer (P) is considered insoluble when less than 15%, preferably less than 10% of its weight is soluble in the aqueous or wet medium of use of the additive of the invention, c that is to say in particular under the conditions of temperature and pH of said medium.

• les polypeptides (PP) d'origine naturelle ou synthétique hydrosolubles ou hydrodispersables
• les polyélectrolytes (PE) sous forme acide, appartenant à la famille des polyacides faibles, ayant une masse moléculaire inférieure à 20 000 g/mole, de préférence comprise entre 1 000 et 5 000 g/mole
• les polyéthylène glycols (PEG) ayant une masse moléculaire comprise entre 4000 et 100 000 g/mole
• les polyvinylpyrrolidones (PVP) ayant une masse moléculaire inférieure à 20 000 g/mole, de préférence comprise entre 1 000 et 10 000 g/mole
• les alcools polyvinyliques (APV) ayant une masse moléculaire inférieure à 100 000 g/mole, et présentant de préférence un taux de désacétylation de 80 à 99% molaire, de préférence de 87 à 95% molaire
• les polymères ampholytes (PA) filmogènes hydrosolubles ou hydrodispersables
• les oses, osides ou polyholosides (O) hydrosolubles ou hydrodispersables
• les acides aminés (AA) ou sels hydrosolubles ou hydrodispersables d'acides aminés
• l'urée
• les agents tensioactifs (TA) dont le diagramme de phases binaire eau-tensioactif, comporte une phase isotrope fluide à 25°C jusqu'à une concentration d'au moins 50 % en poids de tensio-actif, suivie d'une phase cristal liquide rigide de type hexagonale ou cubique à des concentrations supérieures, stable au moins jusqu'à 60°C
• les silicates (Sil) et les phosphates (Phos) de métal alcalin ou alcalino-terreux hydrosolubles ou hydrodispersables
• ou leurs mélanges.

Among the compounds capable of forming the matrix (M), mention may be made of the following water-soluble or water-dispersible organic and inorganic compounds:

• the polypeptides (PP) of natural or synthetic origin that are water-soluble or water-dispersible
• polyelectrolytes (PE) in acid form, belonging to the family of weak polyacids, having a molecular mass of less than 20 000 g / mol, preferably of between 1000 and 5000 g / mol
• polyethylene glycols (PEG) having a molecular weight between 4000 and 100,000 g / mol
• polyvinylpyrrolidones (PVP) having a molecular weight of less than 20 000 g / mol, preferably of between 1000 and 10 000 g / mol
• polyvinyl alcohols (PVA) having a molecular weight of less than 100,000 g / mol and preferably having a deacetylation level of 80 to 99 mol%, preferably 87 to 95 mol%
• water-soluble or water-dispersible film-forming ampholytic (PA) polymers
• water-soluble or water-dispersible oses, osides or polyholosides (O)
• amino acids (AA) or water-soluble or water-dispersible salts of amino acids
• urea
• the surfactants (TA) whose water-surfactant binary phase diagram comprises an isotropic fluid phase at 25 ° C. up to a concentration of at least 50% by weight of surfactant, followed by a liquid crystal phase rigid hexagonal or cubic type at higher concentrations, stable at least up to 60 ° C
• water - soluble or water-dispersible alkali or alkaline earth silicates (Sil) and phosphates (Phos)
• or their mixtures .

Among the water-soluble or water-dispersible synthetic polypeptides (PP) , there may be mentioned homopolymers or copolymers derived from the polycondensation of amino acids or precursors of amino acids, in particular aspartic acid and glutamic acid or their precursors, and hydrolysis . These polymers can be homopolymers derived from aspartic acid or glutamic acid as well as copolymers derived from aspartic acid and glutamic acid in any proportions, or copolymers derived from aspartic and / or glutamic acid and amino acids other. Among the copolymerizable amino acids, mention may be made of glycine, alanine, leucine, isoleucine, phenylalanine, methionine, histidine, proline, lysine, serine, threonine, cysteine, etc.

Among the polypeptides (PP) of vegetable origin, mention may be made of proteins vegetable origin; these are preferably hydrolysed, with a degree hydrolysis less than or equal to 40%, for example from 5 to less than 40%.

Among the proteins of vegetable origin, mention may be made proteins derived from protein seeds, in particular peas, faba bean, lupine, bean, and lentil; proteins from grains cereals including wheat, barley, rye, maize, rice, oats, and millet; proteins from oilseeds soybean, peanut, sunflower, rapeseed, coconut; proteins from leaves including alfalfa, and nettles; and proteins from buried reserve plant organs especially that of potato and beetroot.

Among the proteins of animal origin, there may be mentioned, for example, the muscle proteins including stromal proteins, and gelatin; the proteins derived from milk including casein, lactoglobulin; and the fish protein.

The protein is preferably of plant origin, and more particularly comes from soy or wheat.

• un atome d'hydrogène,
• un radical hydrocarboné contenant de 1 à 4 atomes de carbone, méthyle de préférence
• une fonction -COOH
• un radical -R-COOH, où R représente un reste hydrocarboné contenant de 1 à 4 atomes de carbone, de préférence un reste alkylène contenant 1 ou 2 atomes de carbone, méthylène tout particulièrement.

The polyelectrolyte (PE) may be chosen from those resulting from the polymerization of monomers which have the following general formula (R ¹ ) (R ² ) C = C (R ³ ) COOH wherein R ¹ , R ² , and R ³ are the same or different and represent

• a hydrogen atom,
• a hydrocarbon radical containing from 1 to 4 carbon atoms, preferably methyl
• a -COOH function
• a radical -R-COOH, where R represents a hydrocarbon residue containing from 1 to 4 carbon atoms, preferably an alkylene radical containing 1 or 2 carbon atoms, methylene in particular.

By way of nonlimiting examples, mention may be made of acrylic acids, methacrylic, maleic, fumaric, itaconic, crotonic.

Copolymers obtained from the monomers are also suitable. according to the preceding general formula and those obtained using these monomers and other monomers, particularly vinyl derivatives such as vinyl alcohols and copolymerizable amides, such as acrylamide or methacrylamide. Copolymers obtained from alkyl vinyl ether and maleic acid as well as those obtained from vinyl styrene and maleic acid which are described in particular in the encyclopedia KIRK-OTHMER entitled "ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY" - Volume 18 - 3rd edition - Wiley interscience publication - 1982.

Preferred polyelectrolytes have a degree of polymerization low. The molecular weight of polyelectrolytes is more especially less than 20000 g / mol. Preferably, it is included between 1000 and 5000 g / mole.

• les monomères aminoacryloyles ou acryloyloxy comme le chlorure de triméthylaminopropylméthacrylate, le chlorure ou le bromure de triméthylaminoéthylacrylamide ou méthacrylamide, le méthylsulfate de triméthylaminobutylacrylamide ou méthacrylamide, le méthylsulfate de triméthylaminopropylméthacrylamide (MES), le chlorure de (3-méthacrylamidopropyl)triméthylammonium (MAPTAC), le chlorure de (3-acrylamidopropyl)triméthylammonium (APTAC), le chlorure ou le méthylsulfate de méthacryloyloxyéthyl triméthylammonium, le chlorure d'acryloyloxyéthyl triméthylammonium ;
• le bromure, chlorure ou méthylsulfate de 1-éthyl 2-vinylpyridinium ;
• les monomères N,N-dialkyldiallylamines comme le chlorure de N,N-diméthyldiallylammonium (DADMAC) ;
• les monomères polyquatemaires comme le chlorure de diméthylaminopropylméthacrylamide,N-(3-chloro-2-hydroxypropyl)triméthylammonium (DIQUAT) ...

An ampholytic polymer is a polymer which comprises anionic or potentially anionic charges as a function of pH and cationic or potentially cationic charges as a function of the pH, the potentially anionic or potentially cationic charges being taken into account for the calculation of the ratio of the total number of anionic charges to the total number of cationic charges.
The ampholytic film-forming polymer (AP) generally has a molecular weight of less than 500,000 g / mol as determined by aqueous gel permeation chromatography (GPC).
The ampholytic film-forming polymer (PA) can be obtained from anionic and cationic ethylenically unsaturated monomers. It can also be obtained from a monomer mixture containing more neutral monomers.
The anionic ethylenically unsaturated monomers may be chosen from acrylic, methacrylic, fumaric, maleic, itaconic, N-methacrylalanine, N-acryloyl-hydroxy-glycine acids or anhydrides, or their water-soluble salts; water-soluble sulfonated or phosphonated ethylenically unsaturated monomers, such as sulfopropyl acrylate or its water-soluble salts, water-soluble styrene sulfonates, vinylsulfonic acid and its water-soluble salts or vinylphosphonic acid and its water-soluble salts.
The cationic ethylenically unsaturated monomers can be chosen from

• aminoacryloyl or acryloyloxy monomers such as trimethylaminopropylmethacrylate chloride, trimethylaminoethylacrylamide or methacrylamide chloride or bromide, trimethylaminobutylacrylamide or methacrylamide methylsulfate, trimethylaminopropylmethacrylamide methylsulfate (MES), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), (3-acrylamidopropyl) trimethylammonium chloride (APTAC), methacryloyloxyethyltrimethylammonium chloride or methylsulfate, acryloyloxyethyltrimethylammonium chloride;
• bromide, chloride or methylsulfate of 1-ethyl-2-vinylpyridinium;
• N, N-dialkyldiallylamine monomers such as N, N-dimethyldiallylammonium chloride (DADMAC);
• polyquatemary monomers such as dimethylaminopropylmethacrylamide chloride, N- (3-chloro-2-hydroxypropyl) trimethylammonium (DIQUAT) ...

The neutral monomers with ethylenic unsaturation can be chosen among acrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, dimethylaminoethylmethacrylate (DMAEMA), the dimethylaminopropylmethacrylamide, vinyl alcohol, acrylates or alkyl or hydroxyalkyl methacrylates, acrylates or methacrylates of polyoxyalkylene glycols ...

• MAPTAC/acide acrylique ou méthacrylique ; DIQUAT/acide acrylique ou méthacrylique ; DADMAC/acide acrylique ou méthacrylique ;
• MES/acide acrylique ou méthacrylique/DMAEMA ;
• MAPTAC/acide acrylique/acrytamide ; MAPTAC/anhydride maléique/acrylamide ; MAPTAC/acide vinyl sulfonique/acrylamide ;
• DADMAC/acide acrylique/acrylamide ; DADMAC/anhydride maléique/acrylamide ; DADMAC/acide vinyl sulfonique/acrylamide ;
• DIQUAT/acide acrylique/acrylamide ; DIQUAT/anhydride maléique/acrylamide ; DIQUAT/acide vinyl suifonique/acrytamide ;

avec un rapport du nombre total de charges anioniques au nombre total de charges cationiques pouvant aller de 0,1 à 10.As the ampholytic polymer (PA), mention may especially be made of copolymers or terpolymers

• MAPTAC / acrylic or methacrylic acid; DIQUAT / acrylic or methacrylic acid; DADMAC / acrylic or methacrylic acid;
• MES / acrylic or methacrylic acid / DMAEMA;
• MAPTAC / acrylic acid / acrytamide; MAPTAC / maleic anhydride / acrylamide; MAPTAC / vinyl sulfonic acid / acrylamide;
• DADMAC / acrylic acid / acrylamide; DADMAC / maleic anhydride / acrylamide; DADMAC / vinyl sulfonic acid / acrylamide;
• DIQUAT / acrylic acid / acrylamide; DIQUAT / maleic anhydride / acrylamide; DIQUAT / vinyl sulfonic acid / acrytamide;

with a ratio of the total number of anionic charges to the total number of cationic charges ranging from 0.1 to 10.

Among the monosaccharides (O), mention may be made of aldoses such as glucose, mannose, galactose, ribose and ketoses such as fructose.

Osseids are compounds that result from condensation, with elimination of water, molecules of oses between them or molecules of oses with non-carbohydrate molecules. among the osides are preferred holosides that are formed by the union of exclusively carbohydrate motifs and more particularly oligoholosides (or oligosaccharides) which do not comprise a small number of these reasons, that is to say, a generally lower number or as 10. As examples of oligoholosides, mention may be made of sucrose, lactose, cellobiose, maltose, sucrose and trehalose.

The water-soluble polyholosides (or polysaccharides) or water-dispersible are highly depolymerized; they are described for example in P. ARNAUD's book "Cours de chimie organique", Gaultier-Villars publishers, 1987. More specifically, these polyholosides have a mass molecular weight of less than 500 000 g / mol, preferably less than 20,000 g / mole.

By way of non-limiting example of polyholosides, mention may be made of celluloses and cellulose derivatives (carboxymethyl cellulose), carrageenans ; among the highly depolymerized polyholosides, mention may be made of dextran, starch, xanthan gum and galactomannans such as guar or carob, these polysaccharides preferably having a melting point greater than 100 ° C and a solubility in water of between 5 and 500g / l.

Among the amino acids (AA) , mention may be made of monoamino monocarboxylic or dicarboxylic acids, monocarboxylic diamino acids and their water-soluble derivatives. Preferably amino acids (AA) have a side chain with acid-base properties; they are chosen in particular from arginine, lysine, histidine, aspartic acid, glutamic acid, hydroxyglutamic acid; they may also be in the form of derivatives, preferably water-soluble; it may be for example salts of sodium, potassium or ammonium, such as glutamate, aspartate or sodium hydroxyglutamate.

With regard to the surfactants (TA) likely to constitute the matrix (M), the description of the fluid isotropic phases and rigid liquid crystal of the hexagonal or cubic type is given in the book by RG LAUGHLIN entitled "The AQUEOUS PHASE BEHAVIOR OF SURFACTANTS "- ACADEMIC PRESS - 1994. Their identification by radiation scattering (X and neutrons) is described in the book by V. LUZZATI entitled" BIOLOGICAL MEMBRANES, PHYSICAL FACT AND FUNCTION "- ACADEMIC PRESS - 1968.
More particularly, the rigid liquid crystal phase is stable to a temperature at least equal to 55 ° C. The fluid isotropic phase can be cast, whereas the rigid liquid crystal phase can not.
Among the surfactants (TA), mention may be made of ionic glycolipid surfactants, in particular derivatives of uronic acids (galacturonic acid, glucuronic acid, D-mannuronic acid, L-iduronic acid, L-guluronic acid, etc.), having a substituted hydrocarbon chain or no, saturated or unsaturated having from 6 to 24 carbon atoms and preferably from 8 to 16 carbon atoms, or their salts. This type of product is described in particular in the patent application EP 532 370.
Other examples of surfactants (TA) are amphoteric surfactants such as the amphoteric derivatives of alkyl polyamines such as amphionic XL®, Mirataine H2C-HA® marketed by Rhône Poulenc and Ampholac 7T / X ® and Ampholac 7C / X® marketed by Berol Nobel.

Among the silicates of alkali metal or alkaline earth metal (Sil), there may be mentioned those having a SiO ₂ / M ₂ O molar ratio of 1.6 to 3.5 with M representing a sodium or potassium atom.

Among the alkali or alkaline earth metal phosphates (Phos), mention may in particular be made of sodium hexametaphosphate.

The preformulated additive according to the invention further comprises at the interface matrix (M) / polymer (P) at least one nonionic surfactant (S), anionic, cationic or amphoteric.

• les alcools gras éthoxylés ou éthoxy-propoxylés
• les triglycérides éthoxylés ou éthoxy-propoxylés
• les acides gras éthoxylés ou éthoxy-propoxylés
• les esters de sorbitan éthoxylés ou éthoxy-propoxylés
• les amines grasses éthoxylées ou éthoxy-propoxylées
• les di(phényl-1 éthyl) phénols éthoxylés ou éthoxy-propoxylés
• les tri(phényl-1 éthyl) phénols éthoxylés ou éthoxy-propoxylés
• les alkyls phénols éthoxylés ou éthoxy-propoxylés

Among the nonionic surfactants, mention may in particular be made of polyoxyalkylenated derivatives such as

• ethoxylated or ethoxy-propoxylated fatty alcohols
• ethoxylated or ethoxy-propoxylated triglycerides
• ethoxylated or ethoxy-propoxylated fatty acids
• ethoxylated or ethoxy-propoxylated sorbitan esters
• ethoxylated or ethoxy-propoxylated fatty amines
• ethoxylated or ethoxy-propoxylated di (1-phenylethyl) phenols
• ethoxylated or ethoxy-propoxylated tri (1-phenylethyl) phenols
• ethoxylated or ethoxy-propoxylated alkyl phenols

The number of oxyethylene (OE) and / or oxypropylene (OP) units of these Nonionic surfactants usually range from 2 to 100 depending on the HLB (balance hydrophilic / lipophilic) desired. In particular, the number of EO and / or OP is between 5 and 50.

Ethoxylated or ethoxy-propoxylated fatty alcohols include generally from 6 to 22 carbon atoms, the OE and OP units being excluded from these numbers. Preferably, these units are ethoxylated units.

Ethoxylated or ethoxy-propoxylated triglycerides may be triglycerides of vegetable or animal origin (such as lard, tallow, oil of peanut, butter oil, cottonseed oil, linseed oil, oil olive oil, fish oil, palm oil, grapeseed oil, olive oil, soy, castor oil, rapeseed oil, coconut oil, coconut oil and are preferably ethoxylated.

Ethoxylated or ethoxy-propoxylated fatty acids are acid esters fatty acids (such as, for example, oleic acid, stearic acid), and are preferably ethoxylated.

The ethoxylated or ethoxy-propoxylated sorbitan esters are esters of sorbitol cyclized fatty acid comprising from 10 to 20 carbon atoms as lauric acid, stearic acid or oleic acid, and are preferably ethoxylates.

The term ethoxylated triglyceride is intended in the present invention, as well the products obtained by ethoxylation of a triglyceride by ethylene oxide those obtained by transesterification of a triglyceride with a polyethylene glycol.

Similarly, the term ethoxylated fatty acid includes both the products obtained not ethoxylation of a fatty acid by ethylene oxide than those obtained by transesterification of a fatty acid with a polyethylene glycol.

Ethoxylated or ethoxy-propoxylated fatty amines generally have 10 to 22 carbon atoms, the OE and OP units being excluded from these numbers, and are preferably ethoxylated.

The ethoxylated or ethoxy-propoxylated alkylphenols are generally 1 or 2 alkyl groups, linear or branched, having 4 to 12 carbon atoms. As examples that may be mentioned include octyl, nonyl or dodecyl groups.

Among the anionic surfactants, mention may be made of water-soluble salts of alkyl sulphates, alkyl ether sulphates, alkyl isethionates and alkyl taurates or their salts, alkyl carboxylates, alkyl sulphosuccinates or alkyl succinamates, alkyl sarcosinates, alkyl derivatives of protein hydrolysates, acylaspartates, alkyl ester phosphates and / or alkyl ether and / or alkylaryl ether.
The cation is generally an alkali metal or alkaline earth metal, such as sodium, potassium, lithium, magnesium, or an ammonium group NR ₄ ⁺ with R, identical or different, representing an alkyl radical substituted or not by a oxygen or nitrogen atom.

Among the amphoteric surfactants, mention may be made of alkylbetaines, alkyldimethylbetaines, alkylamidopropylbetaines, alkylamido-propyldimethylbetaines, alkyltrimethylsulfobetaines, derivatives thereof, imidazoline such as alkylamphoacetates, alkylamphodiacetates, alkylamphopropionates, alkyl-amphodipropionates, alkylsultaines or alkylamidopropyl-hydroxysultaines, the condensation products of fatty acids and of protein hydrolysates, the amphoteric derivatives of alkylpolyamines as Amphionic XL® marketed by Rhône-Poulenc, Ampholac 7T / X® and Ampholac 7C / X® marketed by Berol Nobel, proteins or hydrolysates of proteins.

• R^1' et R^2', semblables ou différents, représentent un groupe alkyle en C₁-C₂₀, un groupe aryle ou benzyle
• R^3' et R^4', semblables ou différents , représentent un groupe alkyle en C₁-C₂₀, un groupe aryle ou benzyle, ou un condensat oxyde d'éthylène et/ou oxyde de propylène pouvant contenir jusqu'à 30 motifs oxyalkylène et
• X^- est un anion solubilisant tel qu'halogénure (par exemple chlorure, bromure, iodure), sulfate ou méthylsulfate.

On peut mentionner en particulier le bromure de cétyltriméthylammonium, le RHODAQUAT ® TFR commercialisé par RHODIA.
Ledit agent tensioactif (S) peut être semblable à l'agent tensioactif (TA).Among the cationic surfactants, mention may in particular be made of alkylammonium salts of formula R ^{1 '} R ^2' R ^{3 '} R ^4' N ⁺ X ^- or

• R ^{1 '} and R ^2' , which are the same or different, represent a C ₁ -C ₂₀ alkyl group, an aryl or benzyl group
• R ^{3 '} and R ^4' , which may be identical or different, represent a C ₁ -C ₂₀ alkyl group, an aryl or benzyl group, or an ethylene oxide and / or propylene oxide condensate containing up to 30 oxyalkylene units; and
• X ^- is a solubilizing anion such as halide (eg chloride, bromide, iodide), sulfate or methylsulfate.

There may be mentioned in particular cetyltrimethylammonium bromide, RHODAQUAT ® TFR marketed by RHODIA.
Said surfactant (S) may be similar to the surfactant (TA).

• par addition du ou des composés hydrosolubles ou hydrodispersables susceptibles de former la matrice (M) à un nanolatex de polymère (P) en présence d'au moins un tensioactif (S) ;
• puis élimination de l'eau/séchage de la dispersion aqueuse obtenue.

The preformulated additive according to the invention is preferably in solid form of dry appearance, for example in the form of powder or granules of dry appearance.
Said preformulated additive can be obtained

• by addition of the water-soluble or water-dispersible compound (s) capable of forming the matrix (M) to a polymer nanolatex (P) in the presence of at least one surfactant (S);
• then removing the water / drying the aqueous dispersion obtained.

By polymer nanolatex is meant a stable aqueous dispersion of solid nanoparticles of polymer having an average size of the order of 10 to 500 nm, preferably preferably 20 to 300 nm, more particularly 10 to 200 nm, even more particularly from 20 to 50 nm.
Such a dispersion generally has a solids content of the order of 10 to 50% by weight, preferably of the order of 20 to 40% by weight.
The polymer particles (P) of the nanolatex have on their surface at least one emulsifier (or surfactant (S)) whose rate is a function of the size of the nanolatex particles.
Said nanolatex may optionally be diluted before it is used.

• de 5 à 90% en poids, de préférence de 10 à 60% en poids de polymère (P)
• - de 3 à 90%, de préférence de 10 à 80%, tout particulièrement de 15 à 70% de composé(s) hydrosoluble(s) ou hydrodispersable(s) susceptible(s) de former la matrice (M)
• et de 0,01 à 20%, de préférence de 0,02 à 5% en poids de tensioactif (S).

L'extrait sec de la dispersion obtenue peut être de l'ordre de 5 à 60%, de préférence de l'ordre de 10 à 50%.The respective amounts of polymer nanolatex (P), surfactant (S) and water-soluble or water-dispersible compound (s) capable of forming the matrix (M) are such that the dispersion obtained contains, expressed in sec, of

• from 5 to 90% by weight, preferably from 10 to 60% by weight of polymer (P)
• from 3 to 90%, preferably from 10 to 80%, most preferably from 15 to 70% of water-soluble or water-dispersible compound (s) capable of forming the matrix (M);
• and from 0.01 to 20%, preferably from 0.02 to 5% by weight of surfactant (S).

The solids content of the dispersion obtained can be of the order of 5 to 60%, preferably of the order of 10 to 50%.

The water removal / drying operation of the aqueous dispersion of polymer nanoparticles (P) and of compound capable of forming the matrix (M) can be carried out according to any means known to those skilled in the art, in particular by lyophilization (ie freezing, then sublimation) or preferably by spray drying.
Spray drying may be carried out in any known apparatus, such as an atomization tower associating a spray carried out by a nozzle or a turbine with a stream of hot air. The conditions of implementation are a function of the type of compound that can form the matrix (M) and atomizer used; these conditions are generally such that the temperature of the product as a whole during drying is at least 30 ° C and does not exceed 150 ° C.

• WO 96/17891 : séchage d'une dispersion comprenant un latex de polymère non-hydrosoluble, un polysaccharide (lactose) et un composé choisi parmi les composés ioniques alkylaromatiques et les polyvinylpyrrolidones ;
• WO 97/15617 : séchage d'une dispersion comprenant un latex de polymère non-hydrosoluble, un tensioactif du type glycolipiques ioniques(uroniques), amphotères (dérivés amphotères d'alkylpolyamines), et un composé hydrosoluble minéral (silicates, phosphates) ou organique (urèe, sucres, polyelectrolytes) ;
• WO 97/15616 : séchage d'une dispersion comprenant un latex de polymère non-hydrosoluble, un tensioactif non-ionique polyoxyalkyléné et un polyelectrolyte (polyacide faible) ;
• WO 97/25371: séchage d'une dispersion comprenant un latex de polymère non-hydrosoluble et un acide aminé.

Les techniques décrites par la Demanderesse pour la préparation de granulés dispersables dans l'eau de matières actives sous forme solide ou liquide hydrophobes peuvent également être utilisées.
On peut citer notamment :

• WO 99/38611 : visant des granulés hydrodispersables comprenant une matière active hydrophobe , un polypeptide (protéine de soja) et un agent dispersant ionique ou amphotère.

Methods of preparation of powder compositions of insoluble polymers dispersible in aqueous medium have already been described by the Applicant.
We can mention in particular

• WO 96/17891: drying a dispersion comprising a non-water-soluble polymer latex, a polysaccharide (lactose) and a compound selected from alkylaromatic ionic compounds and polyvinylpyrrolidones;
• WO 97/15617: drying a dispersion comprising a non-water-soluble polymer latex, a surfactant of the ionic glycolide (uronic), amphoteric (amphoteric alkylpolyamine derivatives) type, and a water-soluble mineral compound (silicates, phosphates) or organic (urea, sugars, polyelectrolytes);
• WO 97/15616: drying a dispersion comprising a non-water soluble polymer latex, a polyoxyalkylene nonionic surfactant and a polyelectrolyte (low polyacid);
• WO 97/25371: drying a dispersion comprising a non-water soluble polymer latex and an amino acid.

The techniques described by the Applicant for the preparation of dispersible granules in water of active substances in solid or liquid hydrophobic form can also be used.
We can mention in particular:

• WO 99/38611: targeting water-dispersible granules comprising a hydrophobic active material, a polypeptide (soy protein) and an ionic or amphoteric dispersing agent.

The said preformulated additive of the invention may optionally contain in addition to other adjuvants such as anti-caking agents or fillers, such as calcium carbonate, sodium sulphate, clay like bentonite or laponite, kaolin, silica ..., which can be added totally or partially to the aqueous dispersion before elimination of water, either during the atomization step or after drying.

According to an alternative embodiment of the invention, said preformulated additive may further comprise, in the state encapsulated in the polymer nanoparticles (P), at least one hydrophobic active material (MA).
Among these hydrophobic active materials, mention may be made of those present in the compositions for the treatment of articles made of textile fibers, in particular hydrophobic detergent active substances.

All active ingredients, whether solid, liquid (as they are or in solution in a solvent) are suitable in so far as they are not miscible or are only very slightly miscible in water.

By poorly miscible is meant active ingredients whose solubility in water at pH 7 does not exceed 20% by weight, preferably not more than 10% by weight. weight.

As examples of active ingredients (MA), mention may be made of hydrophobic detergency active substances, such as perfumes, bleaching catalysts, biocidal agents, activators of bleaching, anti-UV agents, optical brighteners, antioxidants, silicones.

The amount of active ingredient (MA) that may be present may range from 20 at 70, preferably from 40 to 60 parts by weight of active ingredient (MA) per 100 parts by weight of polymer (P).

Encapsulation of the hydrophobic active ingredient (MA) by the polymer nanoparticles (P) can be made by introducing said active ingredient (MA) in said polymer nanoparticles (P) occurring in the form of a nanolatex, the introduction of the active ingredient (MA) can be carried out during the course of the synthesis of said polymer by polymerization in aqueous emulsion, ie after the synthesis of said polymer by polymerization in aqueous emulsion.

In a preferential manner, the introduction of the active ingredient (MA) into the polymer nanolatex (P) is produced after the polymerization step in aqueous emulsion of the monomer composition.

• les esters comme l'acétate d'éthyle, le propionate de méthyle, le mélange de glutarate / adipate / succinate de méthyle (solvant "RPDE") ...
• les cétones comme la méthyléthylcétone, la cyclohexanone ...
• les alcools comme le propanol, le pentanol, le cyclohexanol ...
• les hydrocarbures aliphatiques et cycliques comme l'heptane, le décane, le cyclohexane, la décaline ...
• des dérivés aliphatiques chlorés comme le dichlorométhane ...
• des dérivés aromatiques comme le toluène, l'éthylbenzène ...
• des dérivés aromatiques chlorés comme le trichlorobenzène ...
• les dialkyléthers

The active ingredient (MA) present in the liquid state can be introduced directly into the polymer nanolatex (P), if it is sufficiently "swelling" of the polymer, or aided, if necessary, with a polymer "swelling" transfer solvent. .
Among the transfer solvents, mention may be made

• esters such as ethyl acetate, methyl propionate, the glutarate / adipate / methyl succinate mixture (solvent "RPDE") ...
• ketones such as methyl ethyl ketone, cyclohexanone ...
• alcohols such as propanol, pentanol, cyclohexanol ...
• aliphatic and cyclic hydrocarbons such as heptane, decane, cyclohexane, decalin ...
• chlorinated aliphatic derivatives such as dichloromethane ...
• aromatic derivatives such as toluene, ethylbenzene ...
• chlorinated aromatic derivatives such as trichlorobenzene ...
• dialkylethers

The active ingredient (MA) introduced is brought into contact with the nanolatex, with stirring at a temperature of 20 to 50 ° C for 1 to 24 hours.

Said "transfer" solvent can optionally be removed by evaporation under vacuum if the active ingredient (MA) is a solid.

The compound (s) capable of forming the matrix (M) are then added to the polymer nanolatex encapsulating the active ingredient.
The dispersion obtained is then dried or gelled as described above.

Said preformulated additive which is the subject of the invention can be process for the preparation of a treatment composition for the care of textile fiber articles in aqueous or wet medium. Said additive can be used in said compositions as a care agent, protecting the fibers phenomena of physical or chemical degradation and / or these benefits such as softening properties and / or anti-crease; said additive is particularly effective as an agent anti-crease.

A second object of the invention is therefore the use, in a composition for the treatment of textile fiber articles in an aqueous medium or said preformulated additive, as a care agent, especially as anti-crease agent of said articles.

A third object of the invention is a care composition textile fiber articles comprising said preformulated additive.

• sous forme d'un solide (poudre, granulés, tablettes ...) ou d'une dispersion non-aqueuse concentrée, mis en contact avec les articles à traiter, après dilution dans l'eau ;
• sous forme d'un support solide (bâton ou support textile) comprenant ledit additif, mis en contact directement avec les articles à traiter à l'état sec ou humide.

The form of the composition and the conditions of use (or treatment) can be multiple.
Said composition may occur

• in the form of a solid (powder, granules, tablets ...) or a concentrated non-aqueous dispersion, brought into contact with the articles to be treated, after dilution in water;
• in the form of a solid support (stick or textile support) comprising said additive, brought into direct contact with the articles to be treated in the dry or wet state.

• une formulation détergente solide susceptible de former directement par dilution un bain lessiviel ;
• une formulation détergente liquide non-aqueuse susceptible de former directement par dilution un bain lessiviel ;
• une formulation rinçante et/ou adoucissante susceptible de former directement par dilution un bain de rinçage et/ou d'adoucissage ;
• un matériau solide, textile notamment, comprenant l'additif de l'invention, destiné à être mis en contact avec du linge humide dans un sèche-linge (ledit matériau solide est appelé ci-après "additif de séchage") ;
• un « additif de lavage » ("prespotter") destiné à être déposé sur le linge sec préalablement à une opération de lavage à l'aide d'une formulation détergente contenant ou ne contenant pas l'additif préformulé selon l'invention.

Thus the composition of the invention can be:

• a solid detergent formulation capable of forming a washing bath directly by dilution;
• a non-aqueous liquid detergent formulation capable of forming a washing bath directly by dilution;
• a rinsing and / or softening formulation capable of forming, directly by dilution, a rinsing and / or softening bath;
• a solid material, especially textile, comprising the additive of the invention, intended to be brought into contact with wet linen in a tumble dryer (said solid material is hereinafter referred to as "drying additive");
• a "prespotter" intended to be deposited on the dry laundry prior to a washing operation using a detergent formulation containing or not containing the preformulated additive according to the invention.

The composition of the invention is particularly well suited to the care textile fibers, in particular cotton-based articles, in particular containing at least 35% cotton.

• d'une formulation détergente, le pH du bain lessiviel est généralement de l'ordre 7 à 11, préférentiellement de 8 à 10,5 ;
• d'une formulation rinçante et/ou adoucissante, le pH du bain de rinçage et/ou d'adoucissage est généralement de l'ordre 2 à 8 ;
• d'un additif de séchage, le pH à considérer est celui de l'eau résiduelle, qui peut être de l'ordre 2 à 9 ;
• d'un additif de lavage ("prespotter"), le pH à considérer est celui du pH du bain lessiviel de l'opération suivante de lavage, à savoir de l'ordre 7 à 11, préférentiellement de 8 à 10,5.

The pH of use of the composition of the invention can range from about 2 to about 12, depending on the desired use.
As it's about

• a detergent formulation, the pH of the detergent bath is generally of the order of 7 to 11, preferably 8 to 10.5;
• of a rinsing and / or softening formulation, the pH of the rinsing and / or softening bath is generally of the order of 2 to 8;
• of a drying additive, the pH to be considered is that of the residual water, which may be of the order of 2 to 9;
• of a washing additive ("prespotter"), the pH to be considered is that of the pH of the detergent bath of the following washing operation, namely of the order 7 to 11, preferably 8 to 10.5.

For a good realization of the invention, at least 70% of the mass total of the polymer (P) of the preformulated additive is formed of hydrophobic unit (s) (NOT).

When hydrophilic units (F) are present, these do not preferably not more than 30% of the total weight of the polymer (P).

When cross-linking units (R) are present, these do not generally not more than 20%, preferably not more than 10%, especially not more than 5% of the total mass of the polymer (P).

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• éventuellement au moins 1% de son poids d'unités monomères hydrophiles (F4) non chargées ou non-ionisables
• éventuellement pas plus de 20% de son poids d'unités réticulantes (R) non chargées ou non-ionisables.

Préférentiellement, ledit polymère (P1) non chargé ou non-ionisable comprend :

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• de 3 à 30% de son poids d'unités monomères hydrophiles (F4) non chargées ou non-ionisables
• éventuellement pas plus de 20%, de préférence pas plus de 10% de son poids d'unités réticulantes (R) non chargées ou non-ionisables.

L'additif préformulé comprenant ledit polymère (P1) non chargé ou non-ionisable peut être mis en oeuvre dans tous les types de compositions pour le soin des articles en fibres textiles mentionnées ci-dessus dont le pH d'usage peut aller de 2 à 12, à savoir, formulations détergentes, formulations de rinçage et/ou d'adoucissage, additifs de séchage ou additifs de lavage.A first type of composition of the invention consists of a composition (C1) comprising a preformulated additive in which the polymer (P1) is a non-charged or non-ionizable polymer comprising

• at least 70% by weight of hydrophobic monomer units (N)
• optionally at least 1% of its weight of hydrophilic monomer units (F4) not loaded or nonionizable
• possibly not more than 20% of its weight of non-charged or non-ionizable crosslinking units (R).

Preferably, said uncharged or non-ionizable polymer (P1) comprises:

• at least 70% by weight of hydrophobic monomer units (N)
• from 3 to 30% of its weight of unfiltered or non-ionizable hydrophilic monomer units (F4)
• optionally not more than 20%, preferably not more than 10% of its weight of non-charged or non-ionizable crosslinking units (R).

The preformulated additive comprising said uncharged or non-ionizable polymer (P1) may be used in all types of compositions for the care of textile fiber articles mentioned above whose use pH may range from 2 to 12, namely, detergent formulations, rinsing and / or softening formulations, drying additives or wash additives.

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• au moins 1% de son poids, de préférence de 3 à 30% de son poids, tout particulièrement de 1 à 20% de son poids d'unités monomères hydrophiles (F3) anioniques ou anionisables
• éventuellement pas plus de 29% de son poids d'unités monomères hydrophiles (F4) non chargées ou non-ionisables.

L'additif préformulé comprenant le polymère (P2) peut être mis en oeuvre dans les compositions pour le soin des articles en fibres textiles, à caractère non cationique, à savoir, formulations détergentes, additifs de séchage ou additifs de lavage.A second type of composition of the invention consists of a composition (C2) comprising a preformulated additive in which the polymer (P2) is a polymer having anionic or anionizable units and free of cationic or cationizable units, comprising

• at least 70% by weight of hydrophobic monomer units (N)
• at least 1% of its weight, preferably 3 to 30% of its weight, especially 1 to 20% of its weight of hydrophilic monomer units (F3) anionic or anionizable
• optionally not more than 29% of its weight of unfiltered or non-ionizable hydrophilic monomer units (F4).

The preformulated additive comprising the polymer (P2) can be used in compositions for the care of non-cationic textile fiber articles, namely, detergent formulations, drying additives or washing additives.

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• au moins 0,1% de son poids, de préférence pas plus de 20% de son poids, tout particulièrement pas plus de 10 % de son poids d'unités monomères hydrophiles (F2) amphotères
• éventuellement des unités monomères hydrophiles (F4) non chargées ou non-ionisables
• éventuellement des unités monomères hydrophiles (F1) cationiques ou cationisables,

l'ensemble des unités monomères hydrophiles (F) représentant de préférence au moins 1% du poids du polymère (P3), et le rapport molaire des charges cationiques au charges anioniques pouvant aller de 1/99 à 80/20 selon l'utilisation recherchée de ladite composition (C3).
L'additif préformulé comprenant le polymère (P3) présentant un rapport molaire des charges cationiques aux charges anioniques allant de 1/99 à 80/20 peut être mis en oeuvre dans les additifs de séchage.
L'additif préformulé comprenant le polymère (P3) présentant un rapport molaire des charges cationiques aux charges anioniques allant de 1/99 à 60/40, de préférence de 5/95 à 50/50, peut en outre être mis en oeuvre dans les formulations détergentes et les additifs de lavage.A third type of composition of the invention consists of a composition (C3) comprising a preformulated additive in which the polymer (P3) having amphoteric units, comprising

• at least 70% by weight of hydrophobic monomer units (N)
• at least 0.1% of its weight, preferably not more than 20% of its weight, especially not more than 10% of its weight of amphoteric hydrophilic (F2) monomeric units
• optionally hydrophilic monomer units (F4) that are not charged or non-ionizable
• optionally cationic or cationizable hydrophilic (F1) monomer units,

the set of hydrophilic monomer units (F) preferably representing at least 1% of the weight of the polymer (P3), and the molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 depending on the desired use of said composition (C3).
The preformulated additive comprising the polymer (P3) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 can be used in the drying additives.
The preformulated additive comprising the polymer (P3) having a molar ratio of cationic charges to anionic fillers ranging from 1/99 to 60/40, preferably from 5/95 to 50/50, may furthermore be used in the detergent formulations and wash additives.

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• des unités monomères hydrophiles (F1) cationiques ou cationisables
• des unités monomères hydrophiles (F3) anioniques ou anionisables
• éventuellement des unités monomères hydrophiles (F2) amphotères
• éventuellement des unités monomères hydrophiles (F4) non chargées ou non-ionisables,

l'ensemble des unités monomères hydrophiles (F) représentant de préférence au moins 1% du poids du polymère (P4), et le rapport molaire des charges cationiques aux charges anioniques pouvant aller de 1/99 à 80/20 selon l'utilisation recherchée de ladite composition (C4).
L'additif comprenant le polymère (P4) présentant un rapport molaire des charges cationiques aux charges anioniques allant de 1/99 à 80/20 peut être mis en oeuvre dans les additifs de séchage.
L'additif comprenant le polymère (P4) présentant un rapport molaire des charges cationiques aux charges anioniques allant de 1/99 à 60/40, de préférence de 5/95 à 50/50, peut en outre être mis en oeuvre dans les formulations détergentes et les additifs de lavage.A fourth type of composition of the invention consists of a composition (C4) comprising a preformulated additive in which the polymer (P4) is a polymer having both cationic or cationizable units and anionic or anionizable units, comprising

• at least 70% by weight of hydrophobic monomer units (N)
• cationic or cationizable hydrophilic (F1) monomer units
• hydrophilic monomer units (F3) anionic or anionizable
• optionally hydrophilic (F 2) amphoteric monomer units
• optionally hydrophilic monomer units (F4) which are not charged or nonionizable,

all of the hydrophilic monomer units (F) preferably representing at least 1% of the weight of the polymer (P4), and the molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 depending on the desired use of said composition (C4).
The additive comprising the polymer (P4) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 can be used in the drying additives.
The additive comprising the polymer (P4) having a molar ratio of cationic charges to anionic fillers ranging from 1/99 to 60/40, preferably from 5/95 to 50/50, can also be used in the formulations detergents and washing additives.

• au moins 70 % de son poids d'unités monomères (N) hydrophobes
• au moins 1% de son poids, de préférence de 3 à 30% de son poids, tout particulièrement de 1 à 10% de son poids d'unités monomères hydrophiles (F1) cationiques ou cationisables
• éventuellement pas plus de 20% de son poids d'unités monomères hydrophiles (F4) non chargées ou non-ionisables.

L'additif préformulé comprenant le polymère (P5) peut être mis en oeuvre dans tous les types de compositions pour le soin des articles en fibres textiles mentionnées ci-dessus dont le pH d'usage peut aller de 2 à 12, à savoir, formulations détergentes, formulations de rinçage et/ou d'adoucissage, additifs de séchage ou additifs de lavage.
D'une manière toute préférentielle, lorsque la composition (C5) est une composition détergente, lesdites unités monomères (F1) sont des unités cationisables dérivées d'au moins un monomère cationisable présentant un pKa inférieur à 11, de préférence inférieur à 10,5.A fifth type of composition of the invention consists of a composition (C5) comprising a preformulated additive in which the polymer (P5) is a polymer having cationic or cationizable units and free of anionic or anionizable units, comprising

• at least 70% by weight of hydrophobic monomer units (N)
• at least 1% of its weight, preferably 3 to 30% of its weight, more particularly 1 to 10% of its weight of cationic or cationizable hydrophilic (F1) monomer units
• optionally not more than 20% of its weight of unfiltered or non-ionizable hydrophilic monomer units (F4).

The preformulated additive comprising the polymer (P5) may be used in all types of compositions for the care of textile fiber articles mentioned above whose use pH may range from 2 to 12, namely, formulations detergents, rinsing and / or softening formulations, drying additives or washing additives.
Most preferably, when the composition (C5) is a detergent composition, said monomer units (F1) are cationizable units derived from at least one cationizable monomer having a pKa of less than 11, preferably less than 10.5 .

• méthacrylate de méthyle / acrylate de butyle / hydroxyéthylméthacrylate / acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère
• méthacrylate de méthyle / éthylène glycol diméthacrylate / acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère
• styrène / divinylbenzène / acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 100 à 140°C, selon la composition dudit polymère
• styrène / acrylate de butyle / hydroxyéthylméthacrylate / acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère
• Veova 10 (versatate en C₁₀ de vinyle) / méthacrylate de méthyle / acrylate de butyle/ acide méthacrylique, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère
• méthacrylate de méthyle / acrylate de butyle / hydroxyéthylméthacrylate / acide méthacrylique / N,N-diméthyl-N-méthacryloyloxyéthyl-N-(3-sulfopropyl) ammonium sulfobétaïne (SPE de RASCHIG), dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère
• méthacrylate de méthyle / acrylate de butyle / hydroxyéthylméthacrylate / acide méthacrylique / acide vinyl phosphonique, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère méthacrylate de méthyle / acrylate de butyle / hydroxyéthylméthacrylate / acide méthacrylique / Empicryl 6835 de RHODIA, dont la température de transition vitreuse Tg peut aller de 10°C à 80°C, selon la composition dudit polymère
• styrène / butadiène / acide acrylique dont la température de transition vitreuse Tg peut aller de -40°C à 10°C
• acrylate de butyle / acide méthacrylique dont la température de transition vitreuse Tg peut aller de -40°C à 10°C.

By way of examples of polymer (P), there may be mentioned in particular copolymers having units derived from

• methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid, whose glass transition temperature Tg can range from 10 ° C. to 80 ° C., depending on the composition of said polymer
• methyl methacrylate / ethylene glycol dimethacrylate / methacrylic acid, whose glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer
• styrene / divinylbenzene / methacrylic acid, whose glass transition temperature Tg can range from 100 to 140 ° C., depending on the composition of said polymer
• styrene / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid, whose glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer
• Veova 10 (C ₁₀ versatate vinyl) / methyl methacrylate / butyl acrylate / methacrylic acid, the temperature of vitreous transition Tg may range from 10 ° C to 80 ° C, depending on the composition of said polymer
• methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid / N, N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine (RASCHIG SPE), whose glass transition temperature T g can range from 10 ° At 80 ° C., according to the composition of said polymer
• methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid / vinyl phosphonic acid, whose glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate / methacrylic acid / Empicryl 6835 from RHODIA, whose glass transition temperature Tg can range from 10 ° C. to 80 ° C., depending on the composition of said polymer
• styrene / butadiene / acrylic acid whose glass transition temperature Tg can range from -40 ° C to 10 ° C
• butyl acrylate / methacrylic acid whose glass transition temperature Tg can range from -40 ° C to 10 ° C.

The amount of preformulated additive, expressed as dry polymer (P), present in the care composition according to the invention can range from 0.05 to 10% by weight of the dry composition, and application sought. Thus, the preformulated additive can be implemented as follows: % of polymer (P) (in dry) in a care composition used as 0.05 - 5 preferably 0.1 - 3 detergent formulation 0.05 - 3 preferably 0.1 - 2 Rinse and / or softening formulation 0.05 - preferably 0.1 - 5 drying additive 0.05 - preferably 0.1 - 5 washing additive

Other constituents may be present, next to the additive preformulated in the care composition according to the invention. The nature of these constituents is a function of the intended use of said composition.

• au moins un agent tensioactif naturel et/ou synthétique,
• au moins un adjuvant de détergence ("builder")
• éventuellement un agent ou un système oxydant,
• et une série d'additifs spécifiques.

Thus, when it comes to a detergent formulation, for washing articles of textile fibers, in particular laundry, this generally comprises:

• at least one natural and / or synthetic surfactant,
• at least one builder
• optionally an oxidizing agent or system,
• and a series of specific additives.

The detergent formulation may include surfactants in an amount corresponding to about 3 to 40% by weight with respect to detergent formulation, surfactants such as

Anionic surfactants

• alkyl ester sulfonates of formula R-CH (SO ₃ M) -COOR ', in which R represents a C ₈ -C ₂₀ , preferably C ₁₀ -C ₁₆ , alkyl radical, R' a C ₁ -C ₆ alkyl radical, preferably C ₁ -C ₃ and M an alkali metal cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanolamine derivative ( monoethanolamine, diethanolamine, triethanolamine ...). Mention may in particular be made of methyl ester sulphonates whose R radical is C ₁₄ -C ₁₆ ;
• alkyl sulphates of formula ROSO ₃ M, in which R represents a C ₅ -C ₂₄ , preferably C ₁₀ -C ₁₈ , alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average from 0.5 to 30 units, preferably from 0.5 to 10 EO and / or OP units;
• sulfated alkylamides of formula RCONHR'OSO ₃ M where R represents a C ₂ -C ₂₂ , preferably C ₆ -C ₂₀ , alkyl radical, R 'represents a C ₂ -C ₃ alkyl radical, M represents an atom of hydrogen or a cation of the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average from 0.5 to 60 EO and / or OP units;
• saturated or unsaturated C ₈ -C ₂₄ , preferably C ₁₄ -C ₂₀ fatty acid salts, C ₉ -C ₂₀ alkylbenzenesulfonates, primary or secondary C ₈ -C ₂₂ alkylsulfonates, alkylglycerol sulphonates, the sulfonated polycarboxylic acids 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 alkylglycoside sulfates, polyethoxycarboxylates; the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine); ...);

Nonionic surfactants

• polyoxyalkylenated alkylphenols (polyoxyethylenated, polyoxypropylenated, polyoxybutylenated) whose alkyl substituent is C ₆ -C ₁₂ 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;
• polyoxyalkylenated C ₈ -C ₂₂ 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 marketed by Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 marketed by Shell Chemical Cy., KYRO EOB marketed by The Procter & Gamble Cy. ;
• the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with propylene glycol, such as PLURONIC marketed by BASF;
• the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with ethylenediamine, such TETRONIC marketed by BASF;
• amine oxides such as C ₁₀ -C ₁₈ alkyl dimethylamine oxides, C ₈ -C ₂₂ alkoxy ethyl dihydroxy ethylamine oxides;
• the alkylpolyglycosides described in US-A-4,565,647;
• C ₈ -C ₂₀ fatty acid amides;
• ethoxylated fatty acids;
• ethoxylated fatty amides;
• ethoxylated amines.

Amphoteric and zwitterionic surfactants

• alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, the condensation products of fatty acids and protein hydrolysates;
• alkylamphoacetates or alkylamphodiacetates whose alkyl group contains from 6 to 20 carbon atoms.

Builder additives ("builders") improving the properties of surfactants, may be used in amounts corresponding to about 5-50%, preferably about 5-30% by weight for the formulas liquid detergents or at about 10-80%, preferably 15-50% by weight for detergent formulas in powders, detergency additives such as:

Inorganic detergency builders

• polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines
• tetraborates or borate precursors;
• silicates, in particular those having a SiO ₂ / Na ₂ O ratio of the order of 1.6 / 1 to 3.2 / 1 and the layered silicates described in US-A-4,664,839;
• alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates);
• the cogranulates of hydrated silicates of alkali metals and carbonates of alkali metals (sodium or potassium) rich in silicon atoms under form Q2 or Q3, described in EP-A-488,868;
• crystalline or amorphous aluminosilicates of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X ...; zeolite A from Particle size on the order of 0.1-10 microns is preferred.

Organic detergency additives

• water-soluble polyphosphonates (ethane 1-hydroxy-1, 1-diphosphonates, methylene diphosphonate salts ...);
• water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as:
  • polycarboxylate ethers (oxydisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts);
  • hydroxypolycarboxylate ethers;
  • citric acid and its salts, mellitic acid, succinic acid and their salts;
  • salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, N- (2-hydroxyethyl) -nitrilodiacetates);
  • C5-C20 alkyl succinic acids and their salts (2-dodecenylsuccinates, 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 glutamic acid or other amino acids.

The detergent formulation may further comprise at least one oxygen-releasing bleaching agent comprising a percompound, preferably a persalt.
Said bleaching agent may be present in an amount corresponding to about 1 to 30%, preferably 4 to 20% by weight, based on the detergent formulation.

As examples of percomposables likely to be used as bleaching agents, particular mention should be made of perborates such as sodium perborate monohydrate or tetrahydrate; peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, persulfate sodium.

The preferred bleaching agents are sodium perborate, mono- or tetrahydrate and / or sodium carbonate peroxyhydrate.

Said agents are generally associated with an activator of bleaching generating in situ in the washing medium, a peroxyacid carboxylic acid, in an amount corresponding to about 0.1 to 12%, preferably from 0.5 to 8% by weight relative to the detergent formulation. Among these activators, mention may be made of tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluryl, p-acetoxybenzenesulfonate sodium, pentaacetylglucose, octaacetyllactose.

Non-whiteners can also be mentioned oxygenated, acting by photoactivation in the presence of oxygen, agents such as aluminum phthalocyanines and / or sulphonated zinc.

The detergent formulation may further include antifouling agents ("soil release"), anti-redeposition, chelants, dispersants, fluorescence, suds suppressors, softeners, enzymes and others various additives.

Anti-fouling agents

They can be used in amounts of about 0.01-10%, preferably about 0.1-5%, and more preferably about 0.2-3% by weight. weight.

• 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 polyalkylènes tels que les polyvinylacétates greffés sur des troncs polyoxyéthylènes (EP-A-219 048) ;
• les alcools polyvinyliques ;
• les copolymères polyesters à base de motifs éthylène téréphtalate et/ou propylène téréphtalate et polyoxyéthylène téréphtalate, avec un rapport molaire (nombre de motifs) éthylène téréphtalate et/ou propylène téréphtalate / (nombre de motifs) polyoxyéthylène téréphtalate de l'ordre de 1/10 à 10/1, de préférence de l'ordre de 1/1 à 9/1, les polyoxyéthylène téréphtalates présentant des unités polyoxyéthylène ayant un poids moléculaire de l'ordre de 300 à 5000, de préférence de l'ordre de 600 à 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) ;
• les oligomères polyesters sulfonés obtenus par sulfonation d'un oligomère dérivé de l'alcool allylique éthoxylé, du diméthyltéréphtalate et du 1,2-propylènediol, présentant de 1 à 4 groupes sulfonés (US-A-4 968 451) ;
• les copolymères polyesters à base de motifs propylène téréphtalate et polyoxyéthylène téréphtalate et terminés par des motifs éthyles, méthyles (US-A-4 711 730) ou des oligomères polyesters terminés par des groupes alkylpolyéthoxy (US-A-4 702 857) ou des groupes anioniques sulfopolyéthoxy (US-A-4 721 580), suifoaroyles (US-A-4 877 896) ;
• les copolymères polyesters sulfonés dérivés d'acide, anhydride ou diester téréphtalique, isophtalique et sulfoisophtalique et d'un diol (FR-A-2 720 399).

Mention may be made more particularly of agents such as:

• cellulosic derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose;
• polyvinyl esters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048);
• polyvinyl alcohols;
• polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, with a molar ratio (number of units) of ethylene terephthalate and / or propylene terephthalate / (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, dimethyl terephthalate and 1,2-propylene diol, having from 1 to 4 sulfonated groups (US-A-4,968,451);
• polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl, methyl units (US-A-4,711,730) or polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) or groups sulfopolyethoxy anionics (US-A-4,721,580), sulfoyloyles (US-A-4,877,896);
• sulfonated polyester copolymers derived from terephthalic acid, anhydride or diester, isophthalic and sulfoisophthalic acid and a diol (FR-A-2,720,399).

Anti-redeposition agents ,

They can be used in amounts generally of approximately 0.01-10% by weight for a powdered detergent formulation of about 0.01-5% by weight weight for a liquid detergent formulation.

• les monoamines ou polyamines éthoxylées, les polymères d'amines éthoxylées (US-A-4 597 898, EP-A-11 984) ;
• la carboxyméthylcellulose ;
• les oligomères polyesters sulfonés obtenus par condensation de l'acide isophtalique, du sulfosuccinate de diméthyle et de diéthylène glycol (FR-A-2 236 926) ;
• les polyvinylpyrollidones.

Mention may be made in particular of agents such as:

• ethoxylated monoamines or polyamines, ethoxylated amine polymers (US-A-4,597,898, EP-A-11 984);
• carboxymethylcellulose;
• sulphonated polyester oligomers obtained by condensation of isophthalic acid, dimethyl sulphosuccinate and diethylene glycol (FR-A-2,236,926);
• polyvinylpyrollidones.

Chelating agents

The chelating agents of iron and magnesium may be present in amounts of the order of 0.1-10%, preferably of the order of 0.1-3% by weight.

• les aminocarboxylates tels que les éthylènediaminetétraacétates, hydroxyéthyléthylènediaminetriacétates, nitrilotriacétates ;
• les aminophosphonates tels que les nitrilotris-(méthylènephosphonates) ;
• les composés aromatiques polyfonctionnels tels que les dihydroxydisulfobenzènes.

We can mention among others:

• aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethylethylenediaminetriacetates, nitrilotriacetates;
• aminophosphonates such as nitrilotris- (methylenephosphonates);
• polyfunctional aromatic compounds such as dihydroxydisulfobenzenes.

Polymeric dispersing agents,

• 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 éthyléniquement insaturés tels que acide acrylique, acide ou anhydride maléique, acide fumarique, acide itaconique, acide aconitique, acide mésaconique, acide citraconique, acide méthylènemalonique, et tout particulièrement les polyacrylates de masse moléculaire de l'ordre de 2 000 à 10 000 (US-A-3 308 067), les copolymères d'acide arylique et d'anhydride maléique de masse moléculaire de l'ordre de 5 000 à 75 000 (EP-A-66 915)
• les polyéthylèneglycols de masse moléculaire de l'ordre de 1000 à 50 000.

They may be present in an amount of about 0.1-7% by weight, to control the hardness of calcium and magnesium, agents such as

• 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 most particularly polyacrylates with a molecular mass of about 2,000 to 10,000 (US-A-3,308,067), copolymers of aryl and maleic anhydride mass molecular weight of the order of 5,000 to 75,000 (EP-A-66 915)
• polyethylene glycols of molecular weight of the order of 1000 to 50 000.

Fluorescence agents (brighteners) ,

They may be present in an amount of about 0.05-1.2% by weight, agents such as: stilbene derivatives, pyrazoline, coumarin, fumaric acid, acid cinnamic, azoles, methinecyanines, thiophenes ... ("The production and application of fluorescent brightening agents "- Mr. Zahradnik, published by John Wiley & Sons, New York-1982).

Suds suppressing agents,

• les acides gras monocarboxyliques en C₁₀-C₂₄ ou leurs sels alcalins, d'ammonium ou alcanolamines, les triglycérides d'acides gras ;
• les hydrocarbures saturés ou insaturés aliphatiques, alicycliques, aromatiques ou hétérocycliques, tels que les paraffines, les cires ;
• les N-alkylaminotriazines ;
• les monostéarylphosphates, les monostéarylalcoolphosphates ;
• les huiles ou résines polyorganosiloxanes éventuellement combinées avec des particules de silice.

They can be present in amounts of up to 5% by weight, agents such as:

• C ₁₀ -C ₂₄ monocarboxylic fatty acids or their alkali metal, ammonium or alkanolamine salts, triglycerides of fatty acids;
• saturated or unsaturated aliphatic, alicyclic, aromatic or heterocyclic hydrocarbons, such as paraffins, waxes;
• N-alkylaminotriazines;
• monostearyl phosphates, monostearyl alcohol phosphates;
• polyorganosiloxane oils or resins optionally combined with silica particles.

Softening agents

They may be present in amounts of about 0.5-10% by weight, agents such as clays.

enzymes

• les protéases, amylases, lipases, cellulases, peroxydases (US-A-3 553 139, US-A-4101 457, US-A-4 507 219, US-A-4 261 868).

They may 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, US-A-4101,457, US-A-4,507,219, US-A-4,261,868).

Other additives

• des agents tampons,
• des parfums,
• des pigments.

La formulation détergente peut être mise en oeuvre, notamment en lave-linge, à raison de 0,5g/l à 20g/l, de préférence de 2g/l à 10g/l pour réaliser des opérations de lavage à une température de l'ordre de 25 à 90 °C.We can mention among others:

• buffering agents,
• perfumes,
• pigments.

The detergent formulation can be used, especially in a washing machine, at a rate of 0.5 g / l to 20 g / l, preferably from 2 g / l to 10 g / l for carrying out washing operations at a temperature of 25 to 90 ° C.

• associations d'agents tensioactifs cationiques (diester de triéthanolamine quaternisé par du diméthylsulfate, N-méthylimidazoline tallow ester méthyl sulfate, chlorure de dialkyldiméthylammonium, chlorure d'alkylbenzyldiméthylammonium, sulfate de méthyle et d'alkylimidazolinium, sulfate de méthyle et de méthyl-bis(alkylamidoéthyl)-2 - hydroxyéthylammonium...) en quantité pouvant aller de 3 à 50%, de préférence de 4 à 30% de ladite formulation éventuellement associés à des tensioactifs non ioniques (alcools gras éthoxylés, alkylphénols éthoxylés ...) en quantité pouvant aller jusqu'à 3% ;
• azurants optiques (0,1 à 0,2%);
• éventuellement agents anti-transfert de couleur (polyvinylpyrrolidone, polyvinyloxazolidone, polyméthacrylamide... 0,03 à 25%, de préférence 0,1 à 15%)
• colorants,
• parfums,
• solvants, notamment des alcools (méthanol, éthanol, propanol, isopropanol, éthylèneglycol, glycérine)
• limiteurs de mousse.

The preformulated additive according to the invention may be present in a rinse and / or softening formulation of textile fiber articles, in particular laundry.
In addition to the preformulated additive comprising the polymer (P), there may be other constituents of the type

• combinations of cationic surfactants (quaternized triethanolamine diester with dimethylsulfate, N-methylimidazoline tallow ester methyl sulfate, dialkyldimethylammonium chloride, alkylbenzyldimethylammonium chloride, methylimidazolinium methyl sulfate, methyl-bis (alkylamidoethyl) sulfate) ) -2-hydroxyethylammonium ...) in an amount ranging from 3 to 50%, preferably from 4 to 30% of said formulation optionally combined with nonionic surfactants (ethoxylated fatty alcohols, ethoxylated alkylphenols, etc.) in an amount that may be go up to 3%;
• optical brighteners (0.1 to 0.2%);
• optionally anti-color transfer agents (polyvinylpyrrolidone, polyvinyloxazolidone, polymethacrylamide ... 0.03 to 25%, preferably 0.1 to 15%)
• colorants,
• perfumes,
• solvents, in particular alcohols (methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerin)
• foam limiters.

When it is a laundry drying additive in a suitable drying machine, it comprises a flexible solid support constituted for example by a woven or non-woven textile strip, a cellulose sheet, comprising said additive preformulated composition comprising the polymer (P); said drying additive is introduced on drying in the wet laundry to be dried at a temperature of the order of 50 to 80 ° C for 10 to 60 minutes.
Said drying additive may further comprise cationic softening agents (up to 99%) and anti-color transfer agents (up to 80%) such as those mentioned above.

• tensioactifs anioniques tels que ceux déjà mentionnés ci-dessus, en quantité d'au moins 5% du poids de la composition
• tensioactifs non-ioniques tels que ceux déjà mentionnés ci-dessus, en quantité pouvant aller de 15% à 40% du poids de la composition
• des hydrocarbures aliphatiques, en quantité pouvant aller de 5% à 20% du poids de la composition.

In the case of a washing additive or "prespotter", it may be in the form of a solid (stick).
In addition to the preformulated additive comprising the polymer (P), there may be other constituents of the type

• anionic surfactants such as those already mentioned above, in an amount of at least 5% of the weight of the composition
• nonionic surfactants such as those already mentioned above, in an amount ranging from 15% to 40% by weight of the composition
• aliphatic hydrocarbons, in an amount ranging from 5% to 20% of the weight of the composition.

A final object of the invention is a method for treating textile fiber articles by treating said articles with a composition in an aqueous or wet medium comprising said preformulated additive.
The type of composition, as well as the amounts of preformulated additive, expressed as polymer (P), and other additives that can be used, have already been mentioned above.

The following examples are given for illustrative purposes:

The polymer nanolatex (P) used in the examples for the preparation of a preformulated additive in powder form is a dispersion aqueous solution of methyl methacrylate / butyl acrylate / hydroxyethyl methacrylate copolymer / methacrylic acid, according to a mass ratio between the different monomers of 37/55/5/3, whose transition temperature glassy Tg is of the order of 17 ° C, having an average particle size 35 nm (determination by light scattering using a Zetasizer from Malvern Instrument) and having a dry extract of the order of 30%. Said nanolatex has been stabilized at its synthesis by 5% by weight relative to to the dry copolymer of sodium dodecyl sulphate.

Example 1

• d'une solution aqueuse de tensioactif non-ionique SYNPERONIC A7 (alcool gras éthoxylé) de ICI
• d'une solution aqueuse d'acide polyacrylique non neutralisé de masse molaire en poids de 2000 g/mole, à 67% de matière active (BEVALOID 6778 de Bevaloid).

A preformulated powder additive is prepared as follows from said polymer nanolatex (P) above, using

• of an aqueous solution of nonionic surfactant SYNPERONIC A7 (ethoxylated fatty alcohol) of ICI
• an aqueous solution of non-neutralized polyacrylic acid with a molar mass by weight of 2000 g / mol, with 67% of active matter (BEVALOID 6778 from Bevaloid).

Operating mode:

• A 1% aqueous solution of SYNPERONIC A7 (1) is prepared by mixture of 0.5 g of SYNPERONIC A7 and 12 g of water;
• a dispersion 2) is prepared at 14.5% of active ingredient, by dilution of 23g of said polymer nanolatex (P) in 24.5g of water under agitation;
• solution 1) is then added little by little to the dispersion 2) under agitation; the agitation is still maintained for 5 minutes after stopping the addition;
• the aqueous solution of polyacrylic acid is then added small to small to the above mixture with stirring; the agitation is still maintained for 5 minutes after stopping the addition.

• 0,5% de SYNPERONIC A7
• 6,9% de polymère (P) sec
• 26,8% d'acide polyacrylique sec
• 65,8% d'eau permutée.

La dispersion est ensuite séchée à l'aide d'un atomiseur Niro Majeur (température de l'air d'entrée = 140°C) ; on obtient une poudre contenant 26% de son poids de polymère (P).100 g of an aqueous dispersion are obtained having:

• 0.5% of SYNPERONIC A7
• 6.9% dry polymer (P)
• 26.8% dry polyacrylic acid
• 65.8% of permutated water.

The dispersion is then dried using a Niro Major atomizer (inlet air temperature = 140 ° C); a powder containing 26% of its weight of polymer (P) is obtained.

Example 2

A preformulated powder additive is prepared as follows from said polymer nanolatex (P) above, by use of sucrose as a matrix; the amount of sodium dodecyl sulphate from the synthesis of said polymer nanolatex (P) is sufficient to stabilize the dispersion.

Operating mode:

• 50 g of commercial sacchrose are added to 50 g of said nanolatex of polymer (P) at 30% solids stabilized with 5% dodecylsulphate sodium.
• the dispersion obtained is dried in an oven at 50 ° C .; the residue obtained is then finely ground.

Example 3 Detergent formulation

Formulation (A) with P (B) color without P (C) without P constituents % in weight % in weight % in weight NaTPP 40 Zeolite 4A 0 25 25 Silicate 2 SiO ₂ , Na ₂ O 5 5 5 Sodium carbonate 5 15 15 Sokalan CP5 Acrylate / Maleate Copolymer (BASF) 0 5 5 Sodium sulphate 8 21 8 CMC blanose 7MXF (HERCULES) 1 1 1 Perborate monohydrate 15 0 15 Pelletized TAED 5 0 5 Anionic surfactant Laurylbenzene sulfate (Nansa) 6 8 6 Symperonic A3 nonionic surfactant (ethoxylated alcohol 3 EO - ICI) 3 5 3 Symperonic A9 nonionic surfactant (Ethoxylated alcohol 9 EO ICI) 9 11 9 Enzymes (Esterases, Amylases, Cellulase, Protease) 0.5 0.5 0.5 Perfume 1 1 1 Preformulated additive of Example 1 or 2 (% expressed as polymer P dry) 1.0 1.0 1.0 polyvinylpyrrolidone 0 1 0 Dupont O TEX PF 594 antifouled sulfonated copolyester from Rhodia 0.5 0.5 0.5

• nombre d'éprouvettes par pot du Tergotomètre : 2
• volume d'eau : 1 litre
• eau de dureté française 30°TH obtenue par dilution appropriée d'eau minérale de marque Contrexéville®
• concentration en lessive : 5 g/l
• température de lavage : 40°C
• durée du lavage : 20 min
• vitesse d'agitation du Tergotomètre : 100 RPM
• rinçage à l'eau froide (environ 30°TH)
• durée de rinçage : 5 minutes

Les éprouvettes sont ensuites froissées sous une presse de 3kg pendant 20 secondes, puis mises à sécher verticalement pendant une nuit.
La même opération est réalisée à l'aide de la même formulation détergente mais exempte d'additif préformulé.
On réalise ensuite une photographie numérique en couleur des éprouvettes sèches, qui est ensuite transformée en 256 niveaux de gris (échelle de gris de 0 à 255).
On compte le nombre de pixels correspondant à chaque niveau de gris.
Pour chaque histogramme obtenu, on mesure l'écart type σ de la distribution du niveau de gris.

• σ1 correspond à l'écart type obtenu avec la formulation détergente ne renfermant pas d'additif préformulé.
• σ2 correspond à l'écart type obtenu avec la formulation détergente renfermant l'additif préformulé.

La valeur de performance est donnée par l'équation -Δσ = σ2 - σ1
Les valeurs de performance obtenues sont les suivantes : Formulation (A) (B) (C) -Δσ 3,5 4 4,5 A washing operation is carried out in a laboratory apparatus Tergotometer well known in the art of detergent composition formulators. The device simulates the mechanical and thermal effects of American pulsator-type washing machines, but thanks to the presence of 6 washing pots, it allows simultaneous series of tests with a considerable saving of time.
Cut pieces of unpainted cotton of dimensions 25x25 cm are cut.
The cotton test pieces are first ironed in order to have all the same level of creasing before washing.
They are then washed with the aid of the above detergent formulation containing the preformulated additive prepared in example 1 or 2, then rinsed once, under the following conditions:

• number of test pieces per pot of the Tergotometer: 2
• volume of water: 1 liter
• French hardness water 30 ° TH obtained by appropriate dilution of Contrexéville® brand mineral water
• concentration in laundry: 5 g / l
• washing temperature: 40 ° C
• washing time: 20 min
• Tergotometer agitation rate: 100 RPM
• rinsing with cold water (about 30 ° TH)
• flushing time: 5 minutes

The test pieces are then crumpled under a 3kg press for 20 seconds and then dried vertically overnight.
The same operation is carried out using the same detergent formulation but free of preformulated additive.
A color digital photograph of the dry specimens is then made, which is then transformed into 256 gray levels (gray scale from 0 to 255).
We count the number of pixels corresponding to each level of gray.
For each histogram obtained, the standard deviation σ of the distribution of the gray level is measured.

• σ1 corresponds to the standard deviation obtained with the detergent formulation containing no preformulated additive.
• σ2 corresponds to the standard deviation obtained with the detergent formulation containing the preformulated additive.

The performance value is given by the equation -Δσ = σ2 - σ1
The performance values obtained are as follows: Formulation (AT) (B) (VS) -Δσ 3.5 4 4.5

These positive values of -Δσ are representative of an anti-crease property provided by the detergent formulation comprising the preformulated additive according to the invention.
The matrix (M) has no impact on the anti-wrinkle properties of the preformulated additive.

Claims (47)

1. Preformulated additive for a composition for treating textile fibre articles in aqueous or wet medium, comprising:

   at least one particulate solid organic polymer (P) dispersed in and/or encapsulated by a matrix (M) made of at least one organic or inorganic compound

   and at least one surfactant (S) at the matrix (M)/polymer (P) interface

   said matrix (M) being soluble or dispersible in said medium

   and said polymer (P) being insoluble and capable of dispersing in said medium in the form of nanoparticles.
2. Preformulated additive according to Claim 1, characterized in that it comprises, expressed on a dry basis:

   from 5 to 90%, preferably from 10 to 60%, of its weight of polymer (P)

   from 3-90%, preferably from 10 to 80%, most particularly from 15 to 75%, of its weight of matrix (M)

   from 0.01 to 20%, preferably from 0.02 to 5%, by weight of surfactant (S).
3. Preformulated additive according to Claim 1 or 2, characterized in that said polymer (P) has a glass transition temperature Tg of from -40°C to 150°C, preferably of from -40°C to 100°C, most particularly of from -40°C to 40°C.
4. Preformulated additive according to any one of Claims 1 to 3, characterized in that the nanoparticles of polymer (P) have a diameter of from 10 to 500 nm, preferably from 20 to 300 nm, most particularly from 20 to 100 nm, still more particularly from 20 to 50 nm.
5. Preformulated additive according to any one of Claims 1 to 4, characterized in that the compounds capable of forming the matrix (M) are chosen from the following water-soluble or water-dispersible organic and inorganic compounds:

   water-soluble or water-dispersible polypeptides (PP) of natural or synthetic origin

   polyelectrolytes (PE) in acid form, belonging to the family of weak polyacids, having a molecular mass of less than 20 000 g/mol, preferably between 1 000 and 5 000 g/mol

   polyethylene glycols (PEG) having a molecular mass of between 4 000 and 100 000 g/mol

   polyvinylpyrrolidones (PVP) having a molecular mass of less than 20 000 g/mol, preferably between 1 000 and 10 000 g/mol

   polyvinyl alcohols (PVA) having a molecular mass of less than 100 000 g/mol, and preferably having a deacetylation value of from 80 to 99 mol%, preferably from 87 to 95 mol%

   water-soluble or water-dispersible film-forming ampholytic polymers (AP)

   water-soluble or water-dispersible monosaccharides, saccharides or polysaccharides (O)

   amino acids (AA) or water-soluble or water-dispersible salts of amino acids

   urea

   surfactants (TA) whose water-surfactant binary phase diagram comprises an isotropic phase which is fluid at 25°C up to a concentration of at least 50% by weight of surfactant, followed by a rigid liquid crystal phase of the hexagonal or cubic type at higher concentrations, which is stable at least up to 60°C

   water-soluble or water-dispersible alkali metal or alkaline-earth metal silicates (Sil) and phosphates (Phos)

   or mixtures thereof.
6. Preformulated additive according to any one of Claims 1 to 5, characterized in that the surfactant at the matrix (M)/polymer (P) interface is nonionic, anionic, cationic or amphoteric.
7. Preformulated additive according to any one of Claims 1 to 6, characterized in that said additive is provided in solid form with a dry appearance.
8. Preformulated additive according to Claims 7, characterized in that said additive is in the form of a powder or of granules.
9. Preformulated additive according to any one of Claims 1 to 8, characterized in that it can be obtained

   by adding the water-soluble or water-dispersible compound(s) capable of forming the matrix (M) to a nanolatex of polymer (P) in the presence of at least one surfactant (S);

   and then removing the water/drying the aqueous dispersion obtained.
10. Preformulated additive according to Claims 9, characterized in that said nanolatex has a mean particle size of from 10 to 500 nm, preferably 20 to 300 nm, most particularly 10 to 200 nm, still more particularly 20 to 50 nm.
11. Preformulated additive according to Claims 9 or 10, characterized in that the respective quantities of nanolatex of polymer (P), of surfactant (S) and of water-soluble or water-dispersible compound(s) capable of forming the matrix (M) are such that the dispersion obtained contains, expressed on a dry basis,

    from 5 to 90% by weight, preferably from 10 to 60% by weight of polymer (P)

    from 3 to 90%, preferably from 10 to 80%, most particularly from 15 to 70% of water-soluble or water-dispersible compound(s) capable of forming the matrix (M)

    and from 0.01 to 20%, preferably from 0.02 to 5% by weight of surfactant (S),

    the dry extract of said dispersion being from 5 to 60%, preferably from 10 to 50%.
12. Preformulated additive according to any one of Claims 9 to 11, characterized in that the operation of removing water/drying the aqueous dispersion of nanoparticles of polymer (P) and of a compound capable of forming the matrix (M) is carried out by spray-drying.
13. Preformulated additive according to any one of Claims 1 to 12, characterized in that said polymer (P) comprises:

    hydrophobic monomer units (N) that are uncharged or non-ionizable at the working pH of the treatment composition,

    optionally at least one hydrophilic monomer unit (F) chosen from monomer units

    (F1) that are cationic or cationizable at the working pH of said composition,

    (F2) that are amphoteric at the working pH of said composition,

    (F3) that are anionic or anionizable at the working pH of said composition,

    (F4) that are uncharged or non-ionizable, of hydrophilic nature, at the working pH of said composition,

    or mixtures thereof

    and optionally at least one crosslinking unit (R).
14. Preformulated additive according to Claims 13, characterized in that said monomer units (N) and (F) are derived from α-β monoethylenically unsaturated monomers, and the optional monomer units (R) are derived from diethylenically unsaturated monomers.
15. Preformulated additive according to Claims 13 or 14, characterized in that the hydrophobic units (N) are derived from vinylaromatic monomers, from alkyl esters of α-β monoethylenically unsaturated acids, from vinyl or allyl esters of saturated carboxylic acids, from α-β monoethylenically unsaturated nitriles or from α-olefins.
16. Preformulated additive according to any one of Claims 13 to 15, characterized in that the cationic or cationizable hydrophilic units (F1) are derived from N,N-(dialkylamino-ω-alkyl)amides of α-β monoethylenically unsaturated carboxylic acids, from α-β monoethylenically unsaturated amino esters or from monomers that are precursors of primary amine functions by hydrolysis.
17. Preformulated additive according to any one of Claims 13 to 16, characterized in that the amphoteric hydrophilic units (F2) are derived from N,N-dimethyl-N-methacryloyloxyethyl-N-(3-sulphopropyl)-ammonium sulphobetaine, N,N-dimethyl-N-(2-methacrylamidoethyl)-N-(3-sulphopropyl)ammonium betaine, 1-vinyl-3-(3-sulphopropyl)imidazolidium betaine, 1-(3-sulphopropyl)-2-vinylpyridinium betaine, derivatives of the quaternization reaction of N-(dialkylamino-ω-alkyl)amides of α-β ethylenically unsaturated carboxylic acids, or ethylenically unsaturated amino esters, with a chloroacetate of alkali metal or of propane sultone.
18. Preformulated additive according to any one of Claims 13 to 17, characterized in that the anionic or anionizable hydrophilic units (F3) are derived from α-β monoethylenically unsaturated monomers containing at least one carboxylic function, α-β monoethylenically unsaturated monomers containing at least one sulphate or sulphonate function, α-β monoethylenically unsaturated monomers containing at least one phosphonate or phosphate function, and water-soluble salts thereof, or α-β monoethylenically unsaturated monomers that are precursors of carboxylate function(s) by hydrolysis.
19. Preformulated additive according to any one of Claims 13 to 18, characterized in that the uncharged or non-ionizable hydrophilic units (F4) are derived from hydroxyalkyl esters of α-β ethylenically unsaturated acids, α-β ethylenically unsaturated acid amides, α-β ethylenically unsaturated monomers bearing a water-soluble polyoxyalkylenated segment, α-β ethylenically unsaturated monomers that are precursors of vinyl alcohol units or of polyvinyl alcohol segments by polymerization and then hydrolysis, or methacrylamidoethyl-2-imidazolidinone.
20. Preformulated additive according to any one of Claims 13 to 19, characterized in that the crosslinking units (R) are derived from divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylate, methylene bis(acrylamide), glyoxal bis(acrylamide) or butadiene.
21. Preformulated additive according to any one of Claims 13 to 20, characterized in that at least 70% of the total mass of the polymer (P) is formed from hydrophobic units (N) and in that, when they are present, the hydrophilic units (F) represent not more than 30% of the total mass of the polymer (P) and the crosslinking units (R) represent not more than 20%, preferably not more than 10% and most particularly not more than 5% of the total mass of the polymer (P).
22. Preformulated additive according to Claims 21, characterized in that the polymer (P) is an uncharged or non-ionizable polymer (P1) comprising

    at least 70% of its weight of hydrophobic monomer units (N)

    optionally at least 1% and preferably from 3 to 30% of its weight of uncharged or non-ionizable hydrophilic monomer units (F4)

    optionally not more than 20% and preferably not more than 10% of its weight of uncharged or non-ionizable crosslinking units (R).
23. Preformulated additive according to Claims 21, characterized in that the polymer (P) is a polymer (P2) containing anionic or anionizable units and being free of cationic or cationizable units, comprising

    at least 70% of its weight of hydrophobic monomer units (N)

    at least 1% of its weight, preferably from 3 to 30% of its weight and most particularly from 1 to 20% of its weight, of anionic or anionizable hydrophilic monomer units (F3)

    optionally not more than 29% of its weight of uncharged or non-ionizable hydrophilic monomer units (F4).
24. Preformulated additive according to Claims 21, characterized in that the polymer (P) is a polymer (P3) containing amphoteric units, comprising

    at least 70% of its weight of hydrophobic monomer units (N)

    at least 0.1% of its weight, preferably not more than 20% of its weight and most particularly not more than 10% of its weight, of amphoteric hydrophilic monomer units (F2)

    optionally uncharged or non-ionizable hydrophilic monomer units (F4)

    optionally cationic or cationizable hydrophilic monomer units (F1),

    the combination of hydrophilic monomer units (F) preferably representing at least 1% of the weight of the polymer (P3), and the molar ratio of the cationic charges to the anionic charges possibly ranging from 1/99 to 80/20 depending on the desired use of said treatment composition.
25. Preformulated additive according to Claims 21, characterized in that the polymer (P) is a polymer (P4) containing both cationic or cationizable units and anionic or anionizable units, comprising

    at least 70% of its weight of hydrophobic monomer units (N)

    cationic or cationizable hydrophilic monomer units (F1)

    anionic or anionizable hydrophilic monomer units (F3)

    optionally amphoteric hydrophilic monomer units (F2)

    optionally uncharged or non-ionizable hydrophilic monomer units (F4),

    the combination of hydrophilic monomer units (F) preferably representing at least 1% of the weight of the polymer (P4), and the molar ratio of the cationic charges to the anionic charges possibly ranging from 1/99 to 80/20 depending on the desired use of said treatment composition.
26. Preformulated additive according to Claims 21, characterized in that the polymer (P) is a polymer (P5) containing cationic or cationizable units and being free of anionic or anionizable units, comprising

    at least 70% of its weight of hydrophobic monomer units (N)

    at least 1% of its weight, preferably from 3 to 30% of its weight and most particularly from 1 to 10% of its weight, of cationic or cationizable hydrophilic monomer units (F1)

    optionally not more than 20% of its weight of uncharged or non-ionizable hydrophilic monomer units (F4).
27. Preformulated additive according to any one of Claims 1 to 26, characterized in that it comprises, in addition, in the encapsulated state in the particles of polymer (P), at least one hydrophobic active material (AM) chosen from the hydrophobic active materials usually present in the compositions for the treatment of textile fibre articles, preferably from the hydrophobic detergent active materials.
28. Preformulated additive according to Claims 27, characterized in that the quantity of active material (AM) ranges from 20 to 70, preferably from 40 to 60 parts by weight per 100 parts by weight of polymer (P).
29. Preformulated additive according to Claim 27 or 28, characterized in that the encapsulation of the hydrophobic active material (AM) by the nanoparticles of polymer (P) is carried out by introducing said active material (AM) into said particles of polymer (P) existing in the form of a nanolatex, the introduction of the active material (AM) being carried out either during the actual synthesis of said polymer by polymerization in aqueous emulsion, or after synthesis of said polymer by polymerization in aqueous emulsion.
30. Use, in a composition for treating textile fibre articles in aqueous or wet medium, of the preformulated additive which is the subject of any one of Claims 1 to 29, as care agent for said articles.
31. Use according to Claim 30, as crease-resistance agent for said articles.
32. Use according to Claim 30 or 31, characterized in that said composition comprises from 0.05 to 10% of said preformulated additive expressed as a polymer (P).
33. Use according to any one of Claims 30 to 32, characterized in that said composition is provided

    in the form of a solid or of a concentrated nonaqueous dispersion, placed in contact with the articles to be treated, after dilution in water;

    in the form of a solid support comprising said preformulated additive, placed in contact directly with the articles to be treated in the dry or wet state.
34. Use according to any one of Claims 30 to 33, characterized in that said composition is

    a solid detergent formulation comprising from 0.05 to 5%, preferably from 0.1 to 3%, of said preformulated additive expressed as polymer (P), capable of directly forming, upon dilution, a washing bath;

    a nonaqueous liquid detergent formulation comprising from 0.05 to 5%, preferably from 0.1 to 3%, of said preformulated additive expressed as polymer (P), capable of directly forming, upon dilution, a washing bath;

    a rinsing and/or softening formulation comprising from 0.05 to 3%, preferably from 0.1 to 2%, of said preformulated additive expressed as polymer (P), capable of directly forming, upon dilution, a rinsing and/or softening bath;

    a tumble dryer additive in a solid, in particular textile, material comprising from 0.05 to 10%, preferably from 0.1 to 5%, of said preformulated additive expressed as polymer (P), which is intended to be placed in contact with wet fabrics in a tumble dryer;

    a washing additive comprising from 0.05 to 10%, preferably from 0.1 to 5%, of said preformulated additive expressed as polymer (P), intended to be deposited on dry fabrics prior to a washing operation using a detergent formulation containing or not containing said preformulated additive.
35. Use of the preformulated additive, comprising the polymer (P1), which is the subject of Claims 22, optionally in combination with any one of Claims 27 to 29, in a detergent formulation, in a rinsing and/or softening formulation, in a tumble dryer additive or in a washing additive.
36. Use of the preformulated additive, comprising the polymer (P2), which is the subject of Claim 23, optionally in combination with any one of Claims 27 to 29, in a detergent formulation, in a tumble dryer additive or in a washing additive.
37. Use of the preformulated additive, comprising the polymer (P3), which is the subject of Claim 24, optionally in combination with any one of Claims 27 to 29, in a tumble dryer additive when the ratio of the cationic charges to the anionic charges of the polymer (P) is 1/99 to 80/20, in a detergent formulation or in a washing additive when the ratio of the cationic charges to the anionic charges of the polymer (P3) is 1/99 to 60/40, preferably 5/95 to 50/50.
38. Use of the preformulated additive, comprising the polymer (P4), which is the subject of Claim 25, optionally in combination with any one of Claims 27 to 29, in a tumble dryer additive when the ratio of the cationic charges to the anionic charges of the polymer (P4) is 1/99 to 80/20, in a washing additive when the ratio of the cationic charges to the anionic charges of the polymer (P) is 1/99 to 60/40, preferably 5/95 to 50/50.
39. Use of the preformulated additive, comprising the polymer (P5), which is the subject of Claim 26, optionally in combination with any one of Claims 27 to 29, in a detergent formulation, in a rinsing and/or softening formulation, in a tumble dryer additive or in a washing additive.
40. Method of giving crease-resistance properties to textile fibre articles, by treating said articles in an aqueous or wet medium, using a treatment composition comprising at least one preformulated additive which is the subject of any one of Claims 1 to 29.
41. Composition for textile fibre article care comprising from 0.05 to 10% by weight, expressed as polymer (P), of at least one preformulated additive which is the subject of any one of Claims 1 to 29.
42. Composition according to Claim 41, characterized in that it is provided

    in the form of a solid or of a concentrated nonaqueous dispersion, placed in contact with the articles to be treated, after dilution in water;

    in the form of a solid support comprising said preformulated additive, placed in contact directly with the articles to be treated in the dry or wet state.
43. Composition according to Claim 41 or 42, characterized in that it is

    a solid detergent formulation comprising from 0.05 to 5%, preferably from 0.1 to 3%, of said preformulated additive expressed as polymer (P), capable of directly forming, upon dilution, a washing bath;

    a nonaqueous liquid detergent formulation comprising from 0.05 to 5%, preferably from 0.1 to 3%, of said preformulated additive expressed as polymer (P), capable of directly forming, upon dilution, a washing bath;

    a rinsing and/or softening formulation comprising from 0.05 to 3%, preferably from 0.1 to 2%, of said preformulated additive expressed as polymer (P), capable of directly forming, upon dilution, a rinsing and/or softening bath;

    a tumble dryer additive in a solid, in particular textile, material comprising from 0.05 to 10% or preferably from 0.1 to 5%, of said preformulated additive expressed as polymer (P), which is intended to be placed in contact with wet fabrics in a tumble dryer;

    a washing additive comprising from 0.05 to 10%, preferably from 0.1 to 5%, of said preformulated additive expressed as polymer (P), intended to be deposited on dry fabrics prior to a washing operation using a detergent formulation containing or not containing said preformulated additive.
44. Composition according to Claim 43, characterized in that it is a detergent formulation and in that said preformulated additive is chosen from those which are the subject of any one of Claims 22, 23, 24, 26 and comprising respectively a polymer (P1), (P2), (P3) for which the ratio of the cationic charges to the anionic charges is 1/99 to 60/40, preferably 5/95 to 50/50, (P5), optionally in combination with any one of Claims 27 to 29.
45. Composition according to Claim 43, characterized in that it is a rinsing and/or softening formulation and in that said preformulated additive is chosen from those which are the subject of Claim 22 or 26 and comprising a polymer (P1) or (P5), optionally in combination with any one of Claims 27 to 29.
46. Composition according to Claim 43, characterized in that it is a tumble dryer additive and in that said preformulated additive is chosen from those which are the subject of any one of Claims 22, 23, 24, 25, 26 and comprising respectively a polymer (P1), (P2), (P3), (P4), (P5), optionally in combination with any one of Claims 27 to 29.
47. Composition according to Claim 43, characterized in that it is a washing additive and in that said preformulated additive is chosen from those which are the subject of any one of Claims 22, 23, 24, 25, 26, and comprising respectively a polymer (P1), (P2), (P3) for which the ratio of the cationic charges to the anionic charges is 1/99 to 60/40, preferably 5/95 to 50/50, (P4) for which the ratio of the cationic charges to the anionic charges is 1/99 to 60/40, preferably 5/95 to 50/50, (P5), optionally in combination with any one of Claims 27 to 29.