WO2004022680A2

WO2004022680A2 - Polymer-based textile rinsing formulation

Info

Publication number: WO2004022680A2
Application number: PCT/FR2003/002648
Authority: WO
Inventors: Cédric GEFFROY
Original assignee: Rhodia Chimie
Priority date: 2002-09-09
Filing date: 2003-09-08
Publication date: 2004-03-18
Also published as: US20050097678A1; AU2003278263A8; AU2003278263A1; WO2004022680A3

Abstract

The invention relates to a formulation which is used to rinse textile fibre items in a hydroalcoholic or aqueous medium. The inventive formulation consists of active matter comprising a solid hydrophobic organic polymer in particulate form, a surface active agent and a carrier comprising a water-soluble organic polymer, which can convey the active matter towards the surface of the textile fibre items during rinsing.

Description

POLYMER-BASED FORMULATION FOR FLUSHING

TEXTILES

The subject of the present invention is an improved formulation intended for rinsing articles of textile fibers, comprising an active material of a particulate solid organic polymer; it also relates to a process for improving the anti-creasing and / or ironing and / or anti-fouling properties of textile fiber articles, by contacting, during a rinsing operation , said articles with said improved formulation.

The use, in compositions for the treatment in an aqueous medium of articles of textile fibers, of insoluble particles of organic polymers or aqueous dispersions of insoluble particles of organic copolymers, has already been described (US Pat. No. 3,340,217). Dispersions of polymers have been claimed in washing compositions, to impart anti-felting properties (US-A-4,746,455). Dispersions of alkali-soluble polymers have been proposed to improve the removal of soiling (EP-A-279 134). The use, in compositions for the treatment of linen in an aqueous or wet medium (washing formulations, rinsing and / or softening, drying, ironing, prespotting), of nanoparticles or aqueous dispersions of nanoparticles of insoluble polymer or copolymer, such as anti-creasing and / or ironing aid agent is described in WO 02/18451. Furthermore, the use of polymer particles as a reservoir containing perfumes or an active detergency material has already been described in WO 99/38944 and WO 01/46357.

It has been found that the adsorption thus obtained, on textile surfaces, of this type of compound, may not be sufficient to bring a significant benefit to the surfaces thus treated.

The Applicant has now found that the addition, in a formulation comprising insoluble organic polymer particles, intended for rinsing articles of textile fibers, of a small amount of a suitable soluble carrier agent of said polymer, makes it possible to improve significantly the deposition of particles on the surface of said articles, and thus to bring to said articles significant benefits, in particular anti-creasing and / or ironing aid and / or anti-fouling properties. A first object of the invention consists of a formulation (F), intended to be used during a rinsing operation (R) of articles made of textile fibers (S) using an aqueous medium or hydroalcoholic (MR), said formulation (F) - comprising at least one active material (A) in at least one organic polymer, solid, in particulate form and a carrier (V) in at least one organic polymer, capable of bringing said active material (A) towards the surface of said textile fiber articles (S) during the rinsing operation (R), - having:. in the form of a stable dispersion, of pH 2 to 5, of said active material (A), in an aqueous or hydroalcoholic medium (MAV) comprising said carrier agent (V), or

. in solid form obtained by drying said dispersion, the nature of the active material (A), of the aqueous or hydroalcoholic medium (MAV) and of the vector agent (V) being such that

* the active ingredient (A)

• is insoluble in the medium (AVM)

• present in the medium (MAV) a total cationic charge or zero, • is stabilized in the medium (MAV) using a cationic surfactant (TAC), said cationic surfactant (TAC) being able to be in all or part replaced by a nonionic surfactant when the polymer constituting the active material (A) is intrinsically cationic or intrinsically potentially cationic in the medium (MAV)

• remains insoluble in the rinsing medium (MR) or is liable to swell in the rinsing medium (MR);

* the vector agent (V)

• is soluble or dispersible in the medium (AVM) and in the rinsing medium (MR)

• has a zero or cationic global ionic charge in the medium (AVM)

• is capable of developing at the pH of the rinsing operation in the rinsing medium (MR) anionic charges in sufficient number to destabilize the active material (A) in the rinsing medium (MR). The formulation according to the invention is intended to be used both for carrying out a rinsing operation in a washing machine and for a rinsing operation by hand.

This operation is usually carried out at a pH which can range from 5.5 to 8 (pH of the water in the supply circuit); it most often takes place at room temperature.

In a conventional washing operation, the rinse formulation is implemented on the last rinse.

A dispersion of particles is considered to be stable, if no sedimentation, phase separation or evolution of turbidite is observed over time. This dispersion is destabilized when the particles aggregate together.

According to the invention, the active material (A) is considered to be destabilized in the rinsing medium (MR) comprising the vector agent (V), when the turbidity of said medium is at least 5 times greater than the turbidity which the same medium in the absence of vector agent (V).

According to the invention, the active material (A) is made of an organic polymer, solid, in particulate form, insoluble in the medium (MAV), present in the medium (MAV) a global cationic charge or zero, remains insoluble in the medium rinse aid (MR) or is likely to swell in the rinse aid

(MR).

The term “polymer” is used here to denote both a homopolymer and a copolymer. The term copolymer will be used when it is a polymer derived from at least two monomers of different type.

Among the polymers which can constitute the active material (A), there may be mentioned:

. a) nonionic polymers derived from at least one nonionic hydrophobic monomer. b) copolymers derived from at least one hydrophobic nonionic monomer and from at least one cationic or potentially cationic monomer in the medium (MAV), and optionally from at least one neutral monomer in the medium (MAV) and potentially anionic in the rinsing medium (MR).

. c) copolymers derived from at least one non-ionic hydrophobic monomer and from at least one monomer which is neutral in the medium (MAV) and potentially anionic in the rinsing medium (MR).

The monomer composition from which said polymer is derived may also contain: at least one uncharged or non-ionizable hydrophilic monomer, preferably in an amount not exceeding 50% of the total mass of the monomers and / or at least one zwitterionic monomer, preferably in an amount not exceeding 30% of the total mass monomers. and / or at least one crosslinking monomer, preferably in an amount not exceeding 10% of the total mass of the monomers.

In the case of the copolymers b) above, the monomer composition from which the said copolymers are derived, may optionally also contain a small amount of anionic monomer whose first pKa is less than 3, the copolymer b) however having to be present in the medium (MAV) a global cationic charge.

In the case of ionic or ionizable copolymers, the choice and the relative amounts of monomers from which said copolymers are derived are such as the active material (A):

. is insoluble in the medium (MAV)

. presents in (MAV) a global cationic charge or zero. remains insoluble in the rinsing medium (MR) or is not likely to swell more than 8 times, preferably not more than 4 times, its volume in the rinsing medium (MR). So,

. when a monomer neutral in the medium (MAV) and potentially anionic in the rinsing medium (MR) is present in the monomer composition, the latter preferably does not represent more than 50% of the total mass of the monomers, so that the copolymer obtained does not swell more than 8 times, preferably not more than 4 times, its volume in the rinsing medium (MR);

. when an anionic monomer (whose first pKa is less than 3) is present in the monomer composition, this preferably does not represent more than 20%, more particularly not more than 10% of the total mass of the monomers, so that said copolymer has in the medium (MAV) an overall cationic charge.

. when a zwitterionic monomer is present in the monomer composition, this preferably does not represent more than 30%, preferably not more than 20% of the total mass of the monomers, so that said copolymer has in the medium (MAV) a overall cationic charge.

Said polymer constituting the active material (A) is in particulate solid form. Said particles may have an average diameter ranging from from 10nm to 10μm, preferably from 10nm to 1μm and more preferably from 10nm to δOOnm.

The diameter of said particles can be determined in a well known manner by light scattering or by transmission electron microscopy.

Preferably, the monomers from which the polymers constituting the active material (A) are derived are α-β monoethylenically unsaturated or diethylenically unsaturated in the case of crosslinking monomers. As examples of hydrophobic nonionic monomers. we can mention:

• vinylaromatic monomers such as styrene, vinyltoluene ...

• alkyl esters of α-β monoethylenically unsaturated acids such as methyl and ethyl acrylates and methacrylates ... ^" vinyl or allyl esters of saturated carboxylic acids such as acetates, propionates, vinyl versatates or d allyl

• monoethylenically unsaturated α-β nitriles such as acrylonitrile ...

• α-olefins such as ethylene ...

As examples of cationic hydrophilic monomers. we can mention:

• ammoniumacryloyl or acryloyloxy monomers such as trimethylammoniumpropylmethacrylate chloride, trimethylammoniumethylacrylamide chloride or bromide, trimethylammoniumbutylacrylamide or methacrylamide methcrylamide, (methylethylmethacrylamide) (3-acrylamidopropyl) trimethylammonium chloride (APTAC), methacryloyloxyethyl trimethylammonium chloride or methyl sulfate, acryloyloxyethyl trimethylammonium chloride; • bromide, chloride or methyl sulfate of 1-ethyl 2-vinylpyridinium, of 1-ethyl 4-vinylpyridinium;

• N, N-dialkyldiallylamine monomers such as N, N-dimethyldiallylammonium chloride (DADMAC);

• polyquaternary monomers such as dimethylaminopropylmethacrylamide chloride, N- (3-chloro-2-hydroxypropyl) trimethylammonium (DIQUAT) ... • carboxybetaine monomers

As examples of hydrophilic monomers potentially cationic in the medium (MAV), one can mention:

• N, N (dialkylaminoωalkyl) amides of monoethylenically unsaturated α-β carboxylic acids such as N, N-dimethylaminomethyl

-acrylamide or -methacrylamide, 2 (N, N-dimethylamino) ethyl-acrylamide or -methacrylamide, 3 (N, N-dimethylamino) propyl-acrylamide or -methacrylamide, 4 (N, N-dimethylamino) butyl-acrylamide or

-methacrylamide ^" the monoethylenically unsaturated α-β aminoesters such as 2 (dimethyl amino) ethylmethacrylate (DMAM), 3 (dimethyl amino) propylmethacrylate, 2 (tertiobutylamino) ethyl methacrylate, 2 (dipentylamino) ethyl methacrylate (ethyl methacrylate)

• precursor monomers of amino functions such as N-vinyl formamide, N-vinyl acetamide, etc. which generate primary amine functions by simple acid or basic hydrolysis. As examples of hydrophilic monomers neutral in the medium (MAV) and potentially anionic in the rinsing medium (MR), there may be mentioned: • monomers having at least one carboxylic function, such as α-β ethylenically unsaturated carboxylic acids or the corresponding anhydrides, such as acrylic, methacrylic, maleic acids or anhydrides, fumaric acid, itaconic acid, N-methacroyl alanine, N-acryloylglycine and their water-soluble salts • precursor monomers of carboxylate functions, such as tert-butyl acrylate, which generate, after polymerization, carboxylic functions by hydrolysis. As examples of anionic hydrophilic monomers (the first pKa of which is less than 3), there may be mentioned: • monomers having at least one sulfate or sulfonate function, such as 2-sulfooxyethyl methacrylate, vinylbenzene sulfonic acid, l allyl sulfonic acid, 2-acrylamido-2methylpropane sulfonic, sulfoethyl acrylate or methacrylate, sulfopropyl acrylate or methacrylate and their water-soluble salts • monomers having at least one phosphonate or phosphate function, such as acid vinylphosphonic, ... esters of ethylenically unsaturated phosphates such as phosphates derived from methacrylate of hydroxyethyl (Empicryl 6835 from RHODIA) and those derived from polyoxyalkylene methacrylates and their water-soluble salts. As examples of hydrophilic monomers which are uncharged or non-ionizable. we can mention: • hydroxyalkylesters of ethylenically unsaturated α-β acids such as hydroxyethyl and hydroxypropyl acrylates and methacrylates, glycerol monomethacrylate, etc.

• ethylenically unsaturated α-β amides such as acrylamide, N, N-dimethyl methacrylamide, N-methylolacrylamide ... ^“ ethylenically unsaturated α-β monomers carrying a water-soluble polyoxyalkylenated segment of the polyethylene oxide type, such as polyethylene oxide α-methacrylates (BISOMER S20W, S10W, ... from LAPORTE) or α, ω-dimethacrylates, SIPOMER BEM from RHODIA (polyoxyethylene methacrylate ω-behenyl), SIPOMER SEM-25 from RHODIA (methacrylate oxy-tristyrylphenyl polyoxyethylene) ...

• ethylenically unsaturated α-β monomers precursors of hydrophilic units or segments such as vinyl acetate which, once polymerized, can be hydrolyzed to generate vinyl alcohol units or polyvinyl alcohol segments • ethylenically α-β monomers unsaturated ureido type and in particular the methacrylamido of 2-imidazolidinone ethyl (Sipomer WAM II from RHODIA). As examples of zwitterionic monomers. we can mention:

• sulfobetaine monomers such as sulfopropyl dimethylammonium ethyl methacrylate (SPE from RASCHIG), sulfopropyl dimethylammonium propyl mehacrylamide (SPP from RASCHIG), sulfopropyl 2-vinylpyridinium (SPV from RASCHIG)

• phosphobetaine monomers, such as phosphatoethyl trimethylammonium ethyl methacrylate. As examples of crosslinking monomers. we can mention: divinylbenzene ethylene glycol dimethacrylate allyl methacrylate methylene bis (acrylamide) • glyoxal bis (acrylamide) butadiene trial lyl isocyanurate. The average molar mass of said polymer (measured by gel permeation chromatography (GPC) THF and expressed in polystyrene equivalents) can be at least 20,000 g / mol, preferably from 50,000 to

1,000,000 g / mol, more preferably on the order of 100,000 to 1,000,000 g / mol.

Said polymers constituting the active material (A) can be obtained in a known manner, preferably by radical polymerization in aqueous medium of the ethylenically unsaturated monomers. Dispersions of particles of polymers or copolymers can in particular be obtained by radical polymerization in emulsion in water. The level of dry extract in polymer can be of the order of 5 to 60% by weight. Methods for obtaining nanoparticulate dispersions of small diameter 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 of preparing dispersions of particles of average size less than 100 nm, in particular of average size ranging from 1 to 60 nm, very particularly from 5 to 40 nm is described in EP-A-644205.

Preferably, the choice and the relative amounts of the monomer or monomers from which the polymer constituting the active material (A) is derived are such that said polymer has a glass transition temperature Tg of the order of - 80 ° C. + 150 ° C, especially around - 80 ° C to + 40 ° C.

A first embodiment of the invention consists in using, as active material (A), an organic polymer insoluble in the medium (MAV) and in the rinsing medium (MR).

According to the invention, said polymer constituting the active material (A) is considered to be insoluble when less than 15%, preferably less than 10% of its weight, is soluble in the medium (MAV) and the rinsing medium (MR) . The level in units derived from potentially anionic monomer which may possibly be present depends on the nature of the other monomers used to prepare the active material; this rate is generally less than 10% of the total mass of monomers.

Preferably, said polymer constituting the insoluble active material (A) is a polymer derived from at least one nonionic hydrophobic monomer, or a copolymer derived from at least one nonionic hydrophobic monomer and from 0, 1 to 20% of its weight of at least one potentially cationic monomer in the medium (MAV). A second embodiment of the invention consists in using, as active material (A), an organic copolymer insoluble in the medium (MAV) with a pH of the order of 2 to 5, capable of swelling in the medium of rinsing (MR) with a pH of around 5.5 to 8 and likely to dissolve in the washing bath during a subsequent washing operation at a pH of around 8.5 to 11.

Preferably, said copolymer capable of swelling derives from at least one non-ionic hydrophobic monomer and from 10 to 50% of its weight from at least one potentially anionic monomer in the rinsing medium (M R)

As examples of polymers constituting the active material (A), there may be mentioned:

• butyl polyacrylates having a Tg of the order of -55 ° C, and an average particle size of the order of 50 nm • tertiary butyl polyacrylates having an average particle size of the order of 45 nm

• butyl acrylate / diethylaminoethylmethacrylate copolymers, with a weight ratio of 98/2, having a Tg of the order of -50 ° C., and an average particle size of the order of 60 nm • butyl acrylate / glycerol monomethacrylate copolymers, 95/5 weight ratio, having a Tg of the order of -50 ° C, and an average particle size of the order of 50 nm

• butyl acrylate / MAPTAC copolymers, of 95/5 weight ratio, having a Tg of the order of -40 ° C., and an average particle size of the order of 50 nm

• butyl acrylate / trimethylammonium chloride methylmethacrylate copolymers, with a 95/5 weight ratio, having a Tg of the order of -40 ° C., and an average particle size of the order of 50 nm.

They can be obtained by emulsion polymerization in the presence of 10% by weight of a cationic surfactant such as Dehyquart® ACA from

Cognis.

According to the invention, the active material (A) is placed in stable dispersion in the medium (MAV) using a surfactant (TAC).

Said surfactant (TAC) present to stabilize (A) in the formulation, can be used at least in part during the synthesis of the polymer constituting the active material (A).

Said surfactant (TAC) can be a nonionic surfactant and / or a cationic surfactant when the polymer constituting the material active (A) is intrinsically cationic or intrinsically potentially cationic in the medium (AVM).

Said surfactant (TAC) is a cationic surfactant or a mixture of cationic surfactant and nonionic surfactant when said polymer constituting the active material (A) is not charged or has a zero charge; the quantity of nonionic surfactant representing less than 70% of the weight of all the surfactants

(TAC).

For a good implementation of the invention, the mass ratio of polymer constituting the active material (A) / mass of surfactant (TAC) ranges from

0.01 to 10, preferably 0.01 to 1.

The cationic charges, generated by any cationic or potentially cationic units of the copolymer constituting the active material (A) and / or by the cationic surfactant (s), on the surface of the polymer constituting the active active material (A) in dispersion in the medium (MAV), are such that the zeta potential of said polymer or copolymer in dispersion in (MAV) is from 0 to +50 mV, preferably of

+10 to +40 mV.

Among the cationic surfactants, there may be mentioned in particular the quaternary ammonium salts of formula

R ¹ R ² R ³ R ⁴ N ⁺ X ^" where

1 2 3

. R, R and R, similar or different, represent H or an alkyl group containing less than 4 carbon atoms, preferably 1 or 2 carbon atom (s), optionally substituted by one or more hydroxyl function (s), or can form together with the nitrogen atom N ⁺ at least one aromatic or heterocyclic ring

. R represents a C8-C22 alkyl or alkenyl group. preferably Ci 2-C22, an aryl or benzyl group, and

. X ^" is a solubilizing anion such as halide (for example chloride, bromide, iodide), sulfate or alkylsulfate (methylsulfate), carboxylate (acetate, propionate, benzoate), alkyl or arylsulfonate.

Mention may in particular be made of dodecyltrimethylammonium, tetradecyltrimethylammonium, cetyltrimethylammonium bromides, stearyl pyridinium chloride, RHODAQUAT® TFR and RHODAMINE ® C15 marketed by RHODIA, cetyltrimethylammonium chloride (Dehyquart ACA and / or AOR from Cognis), cocobis (2-hydroxyethyl) ethylammonium chloride (Ethoquad C12 from Akso Nobel). Mention may also be made of other cationic surfactants having softening properties, such as:

• the quaternary ammonium salts of formula

R ^{1 '} R ^2' R ³ 'R ⁴ ' N ⁺ X ^" where the 2 '. R and R, similar or different, represent H or an alkyl group containing less than 4 carbon atoms, preferably 1 or 2 atom (s) of carbon, optionally substituted by several hydroxyl function (s), or can form together with the nitrogen atom N ⁺ a heterocyclic ring

3 '4'

. R and R represent a C8-C22 alkyl or alkenyl group. preferably in C10-C22. an aryl or benzyl group, and

. X ^" is an anion such as halide (for example chloride, bromide, iodide), sulfate or alkylsulfate (methylsulfate), carboxylate (acetate, propionate, benzoate), alkyl or arylsulfonate.

Mention may in particular be made of: dialkyldimethyl ammonium chlorides such as ditallow dimethyl ammonium chloride or methylsulfate, etc., alkylbenzyldimethylammonium chlorides.

• Cιo-C25alkylimidazolium salts such as C10-C25alkylimidazolinium methylsulfates

• the salts of substituted polyamines such as N-tallow-N, N ', N', tri-ethanol-1, 3-propylenediamine dichloride or dimethylsulfate, N-tallow-N, N, N ', N', N'- pentamethyl-1, 3-propylene diamine dichloride

Among the nonionic surfactants, there may be mentioned 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 (phenyl-1 ethyl) phenols - ethoxylated or ethoxy-propoxylated tri (phenyl-ethyl) phenols

- ethoxylated or ethoxy-propoxylated alkyl phenols The dispersion medium (AVM) of the active material (A) is an aqueous or hydroalcoholic polar medium.

Among the alcohols which may be present, mention may be made of ethanol, isopropanol, propylene glycol, butoxyethanol, etc. These alcohols may represent up to 70% of the volume of medium (MAV). , the medium (MAV) is water. The medium can be brought to the desired pH from 2 to 5 by adding an acid, such as hydrochloric acid, citric acid, phosphoric acid, benzoic acid ... The rinse formulation (F) making the object of the invention comprises a carrier agent (V) capable of bringing the active material (A) to the surface of the articles of textile fibers during the rinsing operation. According to the invention, said vector agent (V),

• is made of an organic polymer soluble or dispersible in the medium (AVM) and in the rinsing medium (MR)

• has a zero or cationic global ionic charge in the medium (AVM)

• is capable of developing at the pH of the rinsing operation in the rinsing medium (MR) anionic charges in sufficient number to destabilize the active material (A) in the rinsing medium (MR).

Said organic polymer constituting the vector agent (V) can be any polymer which is soluble or dispersible in an aqueous or hydroalcoholic medium with a pH between 2 and 8, comprising at least one unit which is neutral in the medium (MAV) and potentially anionic (HA) in the rinsing medium (MR).

They can also comprise at least one cationic or potentially cationic unit (HC) in the medium (MAV) and / or at least one hydrophilic or hydrophobic nonionic unit.

The term "dispersible" means that the vector agent (V) does not form a macroscopic precipitate in an aqueous or hydroalcoholic medium.

Preferably, the polymer constituting the carrier agent (V) is a copolymer comprising:

. at least one hydrophilic unit neutral in the medium (MAV) and potentially anionic (HA) in the rinsing medium (MR) and. at least one cationic or potentially cationic hydrophilic unit

(HC) in the middle (MAV)

. and optionally at least one hydrophilic or hydrophobic nonionic unit. The polymer constituting the carrier agent (V) may optionally contain anionic units (the first pKa of which is less than 3), but this in a very small amount, for example in an amount much less than 5% by weight relative to the 'all units. The relative amounts of the different units of the polymer constituting the carrier agent (V) are such that, in the medium (MAV), the overall charge of the polymer or copolymer is zero or cationic.

The relative amounts of carrier agent polymer (V), surfactant (TAC) and polymer constituting active material (A), are such that during the rinsing operation, the number of anionic charges developed in the rinsing medium (MR) with the carrier agent polymer (V) is sufficient to destabilize the active material (A) in the rinsing medium (MR), in particular by electrostatic attraction with the surface charges of the active material (A) in the middle (MR). According to the invention, the active material (A) is considered to be destabilized in the rinsing medium (MR) comprising the vector agent (V), when the turbidity of said medium reaches, in less than 5 minutes, a value at least 5 times greater than the turbidity that the same medium would have in the absence of a vector (V). The number of anionic charges developed in the rinsing medium (MR) by the carrier agent polymer (V) to destabilize the active material is preferably at least 1% relative to the number of cationic surface charges of the active material (A ) in the middle (MR). This number of anionic charges can range up to 200% relative to the number of cationic surface charges of the active material (A) in the medium (MR).

As examples of polymers which can constitute the vector agent (V), mention may in particular be made of polymers derived from ethylenically unsaturated monomers, as well as native polysaccharides and substituted or modified polysaccharides, as well as mixtures of said polymers derived from ethylenically unsaturated monomers and said polysaccharides.

A first example of a polymer which can constitute the vector agent (V), are the derived polymers:. at least one monoethylenically unsaturated α-β monomer, neutral in the medium (MAV) and potentially anionic (HA) in the rinsing medium (MR) and . optionally at least one monoethylenically unsaturated, cationic or potentially cationic (HC) α-β monomer in the medium (MAV) and

. optionally at least one monoethylenically unsaturated α-β monomer nonionic hydrophilic or hydrophobic, preferably hydrophilic Preferably, (V) is a copolymer, random, block or grafted, derivative:

. at least one hydrophilic α-β monoethylenically unsaturated monomer neutral in the medium (MAV) and potentially anionic (HA) in the rinsing medium (MR) and. at least one cationic or potentially cationic (HC) monoethylenically unsaturated α-β hydrophilic monomer in the medium (MAV)

. and optionally at least one hydrophilic or hydrophobic non-ionic monoethylenically unsaturated α-β monomer, preferably hydrophilic.

The relative amounts of monomers from which derivative (V) are such that in the medium (MAV), the overall charge of the copolymer (V) is zero or cationic.

The average molar mass of said polymer or copolymer (V) derived from one or more monoethylenically unsaturated α-β monomers (measured by aqueous gel permeation chromatography (GPC) and expressed in polyoxyethylene equivalents) is greater than 5000 g / mol, generally on the order of 20,000 to 500,000 g / mol.

As examples of monoethylenically unsaturated α-β hydrophilic neutral in the medium (MAV) and potentially anionic (HA) in the rinsing medium (MR), there may be mentioned • monomers having at least one carboxylic function, such as α carboxylic acids -β ethylenically unsaturated or the corresponding anhydrides, such as acrylic, methacrylic, maleic acids or anhydrides, fumaric acid, itaconic acid, N-methacroyl alanine, N-acryloylglycine and their water-soluble salts • the precursor monomers of carboxylate functions, such as tert-butyl acrylate, which generate, after polymerization, carboxylic functions by hydrolysis.

As examples of cationic or potentially cationic hydrophilic monoethylenically unsaturated α-β monomer (HC) in the medium (MAV), there may be mentioned

• ammoniumacryloyl or acryloyloxy monomers such as trimethylammoniumpropylmethacrylate chloride, trimethylammoniumethylacrylamide or methacrylamide chloride or bromide, methylsulfate trimethylammoniumbutylacrylamide or methacrylamide, trimethylammoniumpropylmethacrylamide methyl sulfate (MES), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), (3-acrylamidopropyl) trimethylammonium chloride (APTAC), methyl chloride or methyl methacrylate 'acryloyloxyethyl trimethylammonium;

• bromide, chloride or methyl sulfate of 1-ethyl 2-vinylpyridinium, of 1-ethyl 4-vinylpyridinium;

• polyquaternary monomers such as dimethylaminopropylmethacrylamide chloride, N- (3-chloro-2-hydroxypropyl) trimethylammonium (DIQUAT) ...

• carboxybetaine monomers • N, N (dialkylaminoωalkyl) amides of α-β monoethylenically unsaturated carboxylic acids such as N, N-dimethylaminomethyl -acrylamide or -methacrylamide, 2 (N, N-dimethylamino) ethyl-acrylamide or -methacrylamide , 3 (N, N-dimethylamino) propyl-acrylamide or -methacrylamide, 4 (N, N-dimethylamino) butyl-acrylamide or -methacrylamide

• monoethylenically unsaturated α-β aminoesters such as 2 (dimethyl amino) ethylmethacrylate (DMAM), 3 (dimethyl amino) propylmethacrylate, 2 (tertiobutylamino) ethyl methacrylate, 2 (dipentylamino) ethyl methacrylate, 2 (diethylamethyl) monomers precursors of amino functions such as N-vinyl formamide, N-vinyl acetamide, etc. which generate primary amino functions by simple acid or basic hydrolysis.

As examples of uncharged or non-ionizable hydrophilic monoethylenically unsaturated α-β monomers. mention may be made of: hydroxyalkylesters of ethylenically unsaturated α-β acids such as hydroxyethyl and hydroxypropyl acrylates and methacrylates, glycerol monomethacrylate, etc.

• ethylenically unsaturated α-β amides such as acrylamide, N, N-dimethyl methacrylamide, N-methylolacrylamide ... • ethylenically unsaturated α-β monomers carrying a water-soluble polyoxyalkylenated segment of the polyethylene oxide type, such as polyethylene oxide α-methacrylates (BISOMER S20W, S10W, ... from LAPORTE) or α, ω-dimethacrylates, SIPOMER BEM from RHODIA (polyoxyethylene methacrylate ω-behenyl), SIPOMER SEM-25 from RHODIA (methacrylate polyoxyethylene ω-tristyrylphenyl) ... • the ethylenically unsaturated α-β monomers precursors of hydrophilic units or segments such as vinyl acetate which, once polymerized, can be hydrolyzed to generate vinyl alcohol units or alcohol segments polyvinyl

• the ethylenically unsaturated α-β monomers of the ureido type and in particular the methacrylamido of 2-imidazolidinone ethyl (Sipomer WAM II of

Rhodia). As examples of hydrophobic nonionic monoethylenically unsaturated α-β monomers. we can mention:

• vinylaromatic monomers such as styrene, vinyltoluene ... ^" the alkylesters of monoethylenically unsaturated α-β acids such as methyl and ethyl acrylates and methacrylates ...

• vinyl or allyl esters of saturated carboxylic acids such as acetates, propionates, vinyl or allyl versatates

• monoethylenically unsaturated α-β nitriles such as acrylonitrile, etc. As examples of anionic hydrophilic monoethylenically unsaturated α-β monomer (the first pKa of which is less than 3), mention may be made of

• monomers having at least one sulfate or sulfonate function, such as 2-sulfooxyethyl methacrylate, vinylbenzene sulfonic acid, allyl sulfonic acid, 2-acrylamido-2methylpropane sulfonic, acrylate or sulfoethyl methacrylate, sulfopropyl acrylate or methacrylate and their water-soluble salts

• monomers having at least one phosphonate or phosphate function, such as vinylphosphonic acid, ... the esters of ethylenically unsaturated phosphates such as the phosphates derived from hydroxyethyl methacrylate (Empicryl 6835 from RHODIA) and those derived from polyoxyalkylene methacrylates and their water-soluble salts As examples of polymers derived from ethylenically unsaturated monomers constituting the carrier agent (V), there may be mentioned: • polyacrylic or polymethacrylic acids, polyacrylates or polymethacrylates of alkali metals, preferably of molar mass in weight from 100,000 to 1,000,000 g / mol • acrylic acid / DADMAC copolymers, with a molar ratio of 50/50 to 30/70, preferably with a molar mass by weight of 70,000 to 350,000 g / mol

• acrylic acid / MAPTAC copolymers, with a molar ratio of 60/40 to 30/70, preferably with a molar mass by weight of 90,000 to 300,000 g / mol

• acrylic acid / MAPTAC / alkyl methacrylate terpolymers whose alkyl radical is linear in C -Cι ₈ , terpolymers comprising from 0.005 to 10% by mass of alkyl methacrylate with an acrylic acid / MAPTAC molar ratio ranging from 60 / 40 to 30/70, and preferably having a molar mass by weight of 50,000 to 250,000 g / mol

• acrylic acid / dimethylaminoethyl methacrylate copolymers (DMAEMA), with a molar ratio of 60/40 to 30/70, preferably with a molar mass by weight of 50,000 to 300,000 g / mol A second example of a polymer which can constitute the vector agent

(V), are the potentially anionic native polysaccharides and the substituted or modified, potentially anionic or amphoteric polysaccharides.

Potentially anionic native polysaccharides are formed from similar or different non-ionic monosaccharide units and monosaccharide neutral in the medium (AVM) and potentially anionic in the rinsing medium (MR). They can be linear or branched.

More particularly, said potentially anionic native polysaccharides are branched polysaccharides formed • of a main chain comprising similar or different anhydrohexose units • and of branches comprising at least one anhydropentose and / or anhydrohexose unit neutral in the medium (AVM) and possibly potentially anionic in the rinsing medium (MR). The hexose units (similar or different) of the main chain can be D-glucose, D- or L-galactose, D-mannose, D- or L- fucose, L-rhamnose ... units.

The pentose and / or hexose units (similar or different) nonionic or neutral in the medium (MAV) and potentially anionic in the medium (MR) of the branches can be D-xylose ..., L- or D- units arabinose, D-glucose, D- or L-galactose, D-mannose, D- or L-fucose, L- rhamnose, D-glucuronic acid, D-galacturonic acid, D-mannuronic acid, D-mannose substituted by a group pyruvic, ... As examples of native polysaccharides neutral in the medium (MAV) and potentially anionic in the rinsing medium (MR), there may be mentioned xanthan gums (such as RHODOPOL® from RHODIA), succinoglycans, rhamsans, gums gellan, welan ... Their molar mass by weight can range from 2,000 to 5,000,000, preferably from 10,000 to 5,000,000, most particularly from 10,000 to 4,000,000 g / mol.

The molar mass by weight Mw of said polysaccharides can be measured by size exclusion chromatography. When they are substituted or modified polysaccharides, their native skeleton is formed of nonionic monosaccharide units and / or monosaccharide units neutral in the medium (AVM) and potentially anionic in the rinsing medium (MR) or different, said monosaccharide units being substituted or modified: ^" by one or more group (s) carrying at least one charge neutral in the medium (MAV) and potentially anionic in the medium (MR) • and optionally by one or more group (s) carrying at least one cationic or potentially cationic charge in the medium (MAV), the degree of substitution or modification of the monosaccharide units by all of the groups carrying potentially anionic charges and possible groups carrying cationic charges, being such that said substituted or modified polysaccharide is soluble or dispersible in aqueous or hydroalcoholic medium and present in the medium (MAV) a char zero or cationic global age. Said substituted or modified polysaccharides may also contain at least one nonionic substituent or modifying group.

Among the native skeletons that can be used, mention may be made of linear or branched polysaccharides.

More particularly, said polysaccharide is a substituted or modified branched polysaccharide, the native skeleton of which is formed

• a main chain comprising similar or different anhydrohexose units

• and of ramifications comprising at least one anhydropentose and / or anhydrohexose unit neutral in the medium (MAV) and possibly potentially anionic in the rinsing medium (MR), the anhydrohexose and / or anhydropentose units of said polysaccharide being substituted or modified by one or groups carrying at least one charge neutral in the medium (MAV) and potentially anionic in the medium (MR) and optionally at least one cationic or potentially cationic charge in the medium (MAV), the degree of substitution or modification DSi of the anhydrohexoses and / or anhydropentoses units by all of said groups carrying ionic or potentially ionic charges ranging from 0.01 to less than 3, preferably from 0.01 to 2.5, with a ratio of the number of potentially anionic charges in the medium (MR) to the number of cationic or potentially cationic charges in the medium (MAV) ranging from 100/0 to 30/70, preferably from 100/0 to 50/50. When it is an amphoteric polysaccharide, the ratio of the number of potentially anionic charges in the medium (MR) to the number of cationic or potentially cationic charges in the medium (AVM) ranges from 99.5 / 0.5 to 30/70, preferably from 99.5 / 0.5 to 50/50.

Said substituted or modified branched polysaccharide may also contain at least one nonionic substituent or modifying group.

The molar mass by weight of said substituted or modified polysaccharides can range from 2000 to 5000,000, preferably from 10,000 to 5,000,000 g / mol. The molar mass by weight Mw of said polysaccharides can be measured by size exclusion chromatography.

When it is a polysaccharide carrying potentially anionic substituent groups in the medium (MR), the measurement is carried out in water at pH 9-10 containing 0.1 M of LiCl and 2/10000 of nitrate of sodium.

When it is an amphoteric polysaccharide, that is to say carrying potentially anionic substituent groups in the medium (MR) and cationic or potentially cationic groups in the medium (MAV), the measurement is carried out in an aqueous solution of 0.1 M in formic acid containing 0.05 M of sodium nitrate and 10 ppm of polyallyldimethylamine chloride of high molar mass (PDADMA) in the case of polysaccharides whose DSi in ionic or potentially ionic function is less than 0.5. For those whose DSi is greater than 0.5, an aqueous solution of 0.025 M in hydrochloric acid is used.

The molar mass by weight Mw is established in a known manner directly via the light scattering values. The degree of substitution or modification DSi corresponds to the average number of hydroxyl functions of the anhydrohexose and / or anhydropentose units substituted or modified by said ionic or potentially ionic group (s), per anhydrohexose and / or anhydropentose unit. Said ionic or potentially ionic groups are linked to the carbon atoms of the sugar skeleton either directly or via -O- bonds.

In the case of amphoteric polysaccharides, the potentially anionic charges can be provided by substituent or modifying groups different from those carrying cationic or potentially cationic charges; said polymer is then an ampholyte polysaccharide.

When the same substituent or modifying group carries both a potentially anionic charge and a cationic or potentially cationic charge; said polysaccharide is then of betaine type.

Said substituted or modified polysaccharide may also have at least one nonionic substituent or modifying group. Said nonionic groups are linked to the carbon atoms of the sugar skeleton either directly or via -O- bonds. The presence of such groups is expressed in number of moles of substitution MS, that is to say in average number of moles of precursor of said nonionic substituent having reacted by anhydrohexose and / or anhydropentose unit.

If said precursor is not capable of forming new reactive hydroxyl groups (alkylation precursor for example), the degree of substitution or modification by all of the ionic or ionizable and nonionic groups is less than 3 by definition .

If said precursor is capable of forming new reactive hydroxyl groups (hydroxyalkylation precursor for example), the number of moles of substitution MS is theoretically not limited; it can for example go up to 6, preferably up to 2.

Among the potentially anionic groups in the medium (MR), there may be mentioned those containing one or more carboxylate (carboxylic) functions. Mention may be made in particular of those of formula - [- CH ₂ -CH (R) -O] _x - (CH2) _y -COOH or - [- CH2-CH (R) -O] _x - (CH ₂ ) _y - COOM where

R is a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms x is an integer ranging from 0 to 5 y is an integer ranging from 0 to 5 M represents an alkali metal Mention may very particularly be made of the carboxy groups —COO ^′ Na * linked directly to a carbon atom of the sugar skeleton, methyl carboxy (sodium salt) —CH2-COO ^" Na ⁺ linked to a carbon atom of the sugar skeleton by the Intermediate of an —O— bond. Among the cationic or potentially cationic groups, mention may be made of those containing one or more amino, ammonium, phosphonium, pyridinium, etc. functions.

Mention may in particular be made of the cationic or potentially cationic groups of formula • -NH ₂

^• - [- CH2-CH (R) -O] _x - (CH ₂ ) y-COA-R'-N (R ") 2

• - [- CH ₂ -CH (R) -O] _x - (CH2) y-COA-R ^, -N + (R " ^, ) ₃ X"

^• - [- CH2-CH (R) -O] _x - (CH2) y-COA-R'-NH-R "" - N (R ") 2

^• - [- CH2-CH (R) -O] _x -R'-N (R ") 2 • - [- CH2-CH (R) -O] _x -R'-N + (R '") 3 X "

^• - [- CH ₂ -CH (R) -O] _x -R'-NH-R "" - N (R ") 2

• - [- CH ₂ -CH (R) -O] _x -YR "where

. R is a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms

. x is an integer ranging from 0 to 5

. y is an integer ranging from 0 to 5

. R 'is an alkylene radical containing from 1 to 12 carbon atoms, optionally carrying one or more OH substituents. the radicals R ", similar or different, represent a hydrogen atom, an alkyl radical containing from 1 to 18 carbon atoms

. the radicals R ′ ", which are similar or different, represent an alkyl radical containing from 1 to 18 carbon atoms

. R "" is a linear, branched or cyclic alkylene radical containing from 1 to 6 carbon atoms

. A represents O or NH

. Y is a heterocyclic aliphatic group comprising from 5 to 20 carbon atoms and a nitrogen heteroatom

. X ^" is a counterion, preferably a halide (chloride, bromide, iodide in particular), as well as the N-alkylpyridinium-yl groups in which the alkyl radical contains from 1 to

18 carbon atoms, with a counterion, preferably halide (chloride, bromide, iodide in particular). Among the cationic or potentially cationic groups, there may be mentioned very particularly:

- those of formula -NH ₂

-CH2-CONH- (CH ₂ ) 2-N (CH ₃ ) 2 -CH2-COO- (CH ₂ ) 2-NH- (CH2) 2-N (CH ₃ ) 2 -CH ₂ -CONH- (CH2) 3-NH- (CH2) 2-N (CH ₃ ) ₂ -CH2-CONH- (CH2) 2-NH- (CH ₂ ) 2-N (CH ₃ ) 2 -CH2-CONH- (CH ₂ ) 2- N ⁺ (CH ₃ ) 3 Cl "-CH2-CONH- (CH ₂ ) 3-N + (CH ₃ ) 3 Cl" - (CH ₂ ) 2-N (CH ₃ ) 2 - (CH2) 2-NH- ( CH ₂ ) 2-N (CH ₃ ) 2 - (CH ₂ ) 2-N + (CH ₃ ) 3 Cl-

2-hydroxypropyltrimethyl ammonium chloride -CH2-CH (OH) -CH2-N + (CH3) 3 CI-

- pyridinium-yl groups such as N-methyl pyridinium-yle, of formula

with a chloride counterion

- hindered amino groups such as those derived from HALS amines, of general formula:

where R represents CH3 or H.

Among the betaine groups, mention may very particularly be made of the function of formula: - (CH ₂ ) ₂ -N ⁺ (CH ₃ ) ₂ - (CH ₂ ) 2-COO ^" ethyl-dimethylammonium betaine function

Among the nonionic groups, mention may be made of those of formula: • - [- CH ₂ -CH (R) -O] _x -R ¹ where

R is a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms x is an integer ranging from 0 to 5 R ¹ represents

. a hydrogen atom

. an alkyl radical containing from 1 to 22 carbon atoms optionally interrupted by one or more oxygen and / or nitrogen heteroatom, cycloalkyl, aryl, arylalkyl, containing from 6 to 12 carbon atoms. a radical - (CH2) y-COOR2. a radical - (CH2) _y -CN. a radical - (CH2) _y -CONHR R ² representing an alkyl, aryl or arylalkyl radical containing from 1 to 22 carbon atoms, and y is an integer ranging from 0 to 5 • -CO-NH-R1

R ¹ having the definition given above, linked to a carbon atom of the sugar skeleton via an —O— bond Mention may very particularly be made of groups. methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dodecyl, octadecyl, phenyl, benzyl, linked to a carbon atom of the sugar skeleton via an ether, ester, amide or urethane bond,. cyanoethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, linked to a carbon atom of the sugar skeleton via a -O- bond.

The hexose units (similar or different) of the main chain of the native skeleton can be D-glucose, D- or L-galactose, D- mannose, D- or L-fucose, L-rhamnose ... Pentose units and / or hexoses (similar or different) nonionic or neutral in the medium (MAV) and potentially anionic in the medium (MR) branches of the native skeleton can be D- xylose ..., L- or D- units arabinose, D-glucose, D- or L-galactose, D-mannose, D- or L-fucose, L-rhamnose, D-glucuronic acid, D-galacturonic acid, D-mannuronic acid.

As examples of native skeleton, mention may be made of galactomannans, galactoglucomannans, xyloglucans, xanthan gums, scleroglucans, succinoglycans, rhamsans, welan gums ... Preferably, the native skeleton is a galactomannan.

Galactomannans are macromolecules comprising a main chain of D-mannopyranose units linked in position β (1-4) substituted by D-galactopyranose units in position α (1-6). Among these, we can mention guar, carob, tara gums. Most preferably, the native skeleton is a guar gum. Guar gums have a mannose / galactose ratio of 2. The substituted or modified polysaccharides used according to the invention can be obtained by functionalization of the native skeleton using precursors of ionic or potentially ionic and possibly nonionic groups.

These functionalization operations can be carried out in a known manner by oxidation, substitution, condensation, addition.

As examples of substituted or modified polysaccharides which can be used according to the invention, mention may be made of

- the carboxymethyl galactomannans, in particular the carboxymethyl guars, - the carboxymethyl hydroxypropyl galactomannans, in particular the carboxymethyl hydroxypropyl guars,

- carboxymethyl hydroxypropyltrimethylammonium chloride galactomannans, in particular carboxymethyl hydroxypropyltrimethylammonium guars, - carboxymethyl hydroxypropyl hydroxypropyltrimethylammonium galactomannans, in particular carboxymethyl hydroxypropyl chloride hydroxypropyltrimethylammonium guars.

When the vector agent (V) is a polysaccharide, it is preferable that the dispersion of the active material (A) in the medium (MAV) comprising the vector agent (V) has a pH ranging from 3 to 5 and in particular of 4.5 to 5 when said polysaccharide is a substituted or modified guar.

For a good implementation of the invention, the amount of carrier agent (V) present in the formulation according to the invention ranges from 0.001 to 5 parts by weight, preferably from 0.01 to 4 parts, very particularly from 0 0.05 to 2 parts by weight per 100 parts by weight of active material (A). The formulation (F) according to the invention can be presented

• in the form of a stable dispersion (liquid, cream, paste, gel ...)

• or in solid form (powder, granules, block, tablet ...) The formulation (F), in the form of a stable dispersion, can be obtained by

• 1) preparation of an aqueous dispersion of polymer constituting the active material (A) by polymerization in aqueous emulsion in the presence a surfactant (TAC) as a stabilizing agent; the dry extract of the dispersion obtained can be of the order of 5 to 60% by weight;

• 2) possible dilution with water or a water / alcohol mixture (depending on the desired level of active material A in formulation F) and adjustment of the pH to a value of 2.5-5 using an acid (hydrochloric, citric, phosphoric, benzoic acid ...);

• 3) addition of the carrier agent (V) to the dispersion obtained;

• 4) optionally adding an additional quantity of surfactant (TAC) before or after addition of said carrier agent, and • 5) if necessary readjustment of the pH to a value of 2.5-5 using an acid. For a good implementation of the invention, the aqueous or hydroalcoholic formulation (F) comprises per 100 parts of its weight:

- from 0.01 to 40, preferably from 0.05 to 30 parts by dry weight of active material (A)

- from 0.01 to 50, preferably from 0.01 to 35 parts by dry weight of surfactant (TAC)

- from 0.001 to 4, preferably from 0.01 to 1 parts by dry weight of carrier polymer (V). Said dispersion can have a dry extract of 0.021 to 90%, preferably 0.07 to 51% by weight.

Formulation (F), in the form of a solid, can be obtained by

• 1) preparation of an aqueous dispersion of polymer constituting the active material (A) by polymerization in aqueous emulsion in the presence of a surfactant (TAC) as stabilizing agent; the dry extract of the dispersion obtained can be of the order of 5 to 60% by weight;

• 2) adjustment of the pH to a value of 2.5-5 using an acid (hydrochloric, citric, phosphoric, benzoic acid ...);

• 3) addition of the carrier agent (V) to the dispersion obtained; 4) optionally adding an additional quantity of surfactant (TAC) before or after addition of said carrier agent, and

• 5) if necessary readjustment of the pH to a value of 2.5-5 using an acid;

• evaporation / drying. The evaporation / drying step: can be carried out by any means known to those skilled in the art, in particular by lyophilization (that is to say freezing, then sublimation) or preferably by spray drying. Spray drying can be carried out in any known device, such as an atomization tower associating a spraying carried out by a nozzle or a turbine with a stream of hot air. The conditions of implementation depend on the type of atomizer used; these conditions are generally such that the temperature of the entire product during drying is at least 30 ° C and does not exceed 150 ° C.

The evaporation / drying step can be facilitated by the presence, within the dispersion subjected to said step, of a protective agent, in particular by the presence of at least one water-soluble or water-dispersible ose, oside or polyholoside, a preferably dare. The amount of protective agent can represent of the order of 10 to 50 parts by weight per 100 parts by weight of active material (A).

Among the dares, there may be mentioned aldoses such as glucose, mannose, galactose, ribose and ketoses such as fructose. The granules obtained can be ground to obtain a powder or compacted in a known manner to obtain tablets, for example.

The formulation (F) can also comprise other usual constituents of the cationic rinse formulations.

It can in particular comprise at least one cationic and / or non-ionic softening agent, such as acyclic quaternary ammonium compounds, alkoxylated polyamines, diamido quaternary ammonium salts, quaternary ammonium esters, imidazolium quaternary salts, primary, secondary amines or tertiary, alkoxylated amines, cyclic amines, nonionic sugar derivatives, ... mentioned in particular in WO 00/68352. Examples of some of these cationic softeners have already been mentioned above as a surfactant (TAC).

The softening agents may be present in an amount of 0.5 to 90%, preferably from 0.5 to 40%, depending on the concentration of said formulation.

(F). May also be present:

- optical brighteners (0.1 to 0.2%);

- anti-color transfer agents (polyvinylpyrrolidone, polyvinyloxazolidone, polymethacrylamide ... 0.03 to 25%, preferably 0.1 to 15%) - water-soluble monovalent mineral salts, such as sodium chlorides, nitrates or sulfates, potassium or ammonium (especially when the carrier (V) is a polysaccharide), for example, from 0.01 to 2 moles per liter - silicone oils,

- mineral, vegetable, animal, hydrocarbon oils or waxes,

- dyes,

- perfumes, - foam limiters

- enzymes

- bleaching agents

The formulation (F) of the invention can be used to carry out a rinsing operation following a washing operation by hand or in a washing machine of articles made of textile fibers. Said articles can be made of natural and / or artificial fibers and / or synthetic fibers.

Said formulation is particularly advantageous for rinsing cotton or cotton-based articles. It can be implemented in the rinsing bath, at a rate of 0.001 to 5 g / l, preferably from 0.005 to 2 g / l, the formulation rate being expressed as dry matter. This rinsing operation can be carried out at room temperature.

This rinsing operation makes it possible to provide said articles, in addition to the conventional benefits of softness brought by the cationic and / or non-ionic softening agent (s), with anti wrinkle properties and / or ironing aid (“Ease of ironing”), as well as anti-fouling properties (“soil release”) brought about by the deposition of the active material (A) on the surface of said articles, deposition favored by the presence of the vector agent (V ). Interesting soil release properties are brought about in particular by the use, as active material (A) in formulation (F), of a copolymer capable of swelling in the rinsing medium ( MR). Such a type of copolymer has the advantage, after deposition on the textile surface at the rinsing pH, of being removed in the following washing at basic pH, at the same time as the soiling,

According to an alternative embodiment of the first object of the invention, said solid active material (A) in particulate form of the formulation (F) contains, encapsulated in its particles, at least one liquid or solid hydrophobic organic active material (MAO) other that (A).

The hydrophobic active ingredient (MAO) is not miscible with water or is only very slightly miscible with water; this means that its solubility in water at pH 7 is less than 20% by weight, preferably less than 10% by weight. The term active ingredient (MAO) means both a pure active ingredient as such or in a solvent, as well as a mixture of active ingredients as such or in a solvent. As an example of an active ingredient (MAO), mention may be made of perfumes, biocidal agents (bactericides, fungicides, etc.), hydrophobic agents, anti-UV agents (vanillin, etc.), optical brighteners (derivatives of stilbene, etc.). ), silicone oils or amino silicones, mineral or vegetable oils, etc. Said active material (MAO) can be introduced into the particles of the active material (A), in a known manner.

It can be introduced in particular during the actual synthesis of the particles of active material (A), in particular in the solubilized state in at least one of the monomers from which the active material (A) is derived. If it is liquid and sufficiently "swelling" of the polymer or copolymer constituting the active material (A), the material (MAO) can also be introduced directly into the dispersion of active material (A) obtained by emulsion polymerization; if necessary, a swelling “transfer” solvent for the polymer or copolymer can be used. As an example of transfer solvents, mention may be made of esters, ketones, alcohols, aliphatic, cycloaliphatic, aromatic, optionally chlorinated hydrocarbons, dialkyl ethers. The transfer solvent can then be removed by evaporation. The amount of hydrophobic organic active material (MAO) present in the particles of active material (A) can range from 20 to 70 parts, preferably from 40 to 60 parts by weight per 100 parts by weight of active material (A).

The presence of the carrier agent (V) makes it possible to increase the deposition of the organic active material (MAO), encapsulated in the active material (A), on the surface of articles made of textile fibers. This results in increased retention of the organic active material (MAO) on said surface and a better contribution to this surface of the intrinsic properties of said material (MAO). This is particularly interesting when the organic active material (MAO) is a perfume.

A second object of the invention consists in a process for treating articles made of textile fibers, by bringing them into contact, during a rinsing operation in an aqueous or aqueous-alcoholic medium, with the rinsing formulation (F) such that described above, then recovery of said rinsed articles. The operating conditions for such a treatment have already been mentioned above.

A third object of the invention relates to a process for improving the properties of anti-creasing and / or of ironing aid and / or anti-soiling of articles made of textile fibers, consisting in bringing into contact, during a rinsing operation in aqueous or hydroalcoholic medium, said articles with the rinsing formulation (F) as described above, then recovering said rinsed articles.

The conditions used to carry out such a process have already been mentioned above.

A fourth object of the invention consists in the use, in a formulation (F), intended to be used during a rinsing operation (R) of articles of textile fibers (S) using '' an aqueous or hydroalcoholic medium (MR), formulation (F) comprising at least one active material (A) made of at least one organic polymer, solid, in particulate form, and which is: in the form of a stable dispersion, of pH from 2 to 5, of said active material (A), in an aqueous or hydroalcoholic medium (AVM) or - in solid form obtained by drying of said dispersion, the nature of the active material (A) and of the aqueous or hydroalcoholic medium ( MAV) being such that the active material (A)

• is insoluble in the medium (AVM)

• has a cationic or zero global charge in the medium (MAV),

• is stabilized in the medium (MAV) using a cationic surfactant (TAC), said cationic surfactant (TAC) can be replaced in whole or in part by a nonionic surfactant when the polymer constituting the active ingredient (A) is inherently cationic or inherently potentially cationic in the medium (AVM)

• remains insoluble in the rinsing medium (MR) or is capable of swelling in the rinsing medium (MR), of at least one organic polymer. Φ soluble or dispersible in the medium (AVM) and in the rinsing medium

(MR) Φ having in the medium (AVM) a global ionic charge zero or cationic Φ and capable of developing at the pH of the rinsing operation in the rinsing medium (MR) anionic charges in sufficient number to destabilize the active material (A) in the rinsing medium (MR), as a carrier agent (V) capable of bringing said active material (A) to the surface of said articles of textile fibers (S) during the rinsing operation (R). An alternative embodiment of this fourth object of the invention consists in that the active material (A) contains, encapsulated in its particles, at least one hydrophobic organic active material (MAO), and in that said carrier agent or organic polymer (V) is capable of bringing the organic active material (MAO) encapsulated in the active material (A) to the surface of articles made of textile fibers, and in addition bringing to said surface the intrinsic properties of said organic active material ( MAO).

The nature and relative quantities of the various constituents, their conditions of use, as well as the operating conditions to be implemented have already been developed above.

A fifth object of the invention consists in a method for improving the deposition of an active material (A) in at least one organic polymer, solid, in particulate form, optionally containing, encapsulated in its particles, a hydrophobic organic material (MAO ), on the surface of textile fiber articles (S), during a rinsing operation of said articles using an aqueous or hydroalcoholic medium (MR) obtained from a formulation (F) comprising said active material (A), formulation (F) presenting:

. in the form of a stable dispersion, of pH 2 to 5, of said active material (A), in an aqueous or hydroalcoholic medium

(MAV) or

. in solid form obtained by drying said dispersion, the nature of the active material (A) and of the aqueous or hydroalcoholic medium (AVM) being such that the active material (A) • is insoluble in the medium (AVM)

• has a cationic or zero global charge in the medium (MAV),

• remains insoluble in the rinsing medium (MR) or is liable to swell in the rinsing medium (MR), by adding to said formulation (F) a vector agent (V) in at least one organic polymer Φ soluble or dispersible in the medium (AVM) and in the rinsing medium

(MR) Φ having in the medium (AVM) a global ionic charge zero or cationic Φ and capable of developing at the pH of the rinsing operation in the rinsing medium (MR) anionic charges in sufficient number to destabilize the active material (A) in the rinsing medium (MR).

The following examples are given by way of illustration.

Example 1: anti-crease and ironing aid effect Formulation 11.

An aqueous dispersion (latex) of a polybutylacrylate (active material A) having a molar mass by weight of 500,000 g / mol, a particle size of 35 nm, is obtained using emulsion polymerization of butyl acrylate in the presence 10 parts by weight of cetyl trimethylammonium bromide (surfactant TAC) per 100 parts by weight of butyl acrylate. The dispersion has a dry extract of 28% by weight. The pH of this dispersion is adjusted to 4.0 with a 1N hydrochloric acid solution. The dispersion is slightly opalescent. 20 ml of the dispersion are poured under mechanical stirring into 1 ml of water, the pH of which has been adjusted to 4. A mixture is obtained at pH = 4, the appearance of which is not significantly different from that of the original dispersion. This mixture is stable for several days, it does not form any precipitate and does not evolve into turbidite over time.

Formulation 111.

An aqueous dispersion (latex) of a polybutylacrylate (active material A) having a particle size of 35 nm is used, obtained by emulsion polymerization of butyl acrylate in the presence of 10 parts by weight of cetyl trimethylammonium bromide ( surfactant TAC) per 100 parts by weight of butyl acrylate.

The dispersion contains a dry extract of 28% by weight.

The pH of this dispersion is adjusted to 4.0 with a 1N hydrochloric acid solution. The dispersion is slightly opalescent. 32

An aqueous solution containing 2.2% by weight of a 1: 1 molar copolymer (vector agent) of acrylic acid and of DADMAC (with a molar mass of 100,000 g / mol) is prepared, solution of which adjusted the pH to 4.0 with a 10% by weight hydrochloric acid solution. 20 ml of the dispersion of active material (A) are poured into 1 ml of the vector agent copolymer solution (V) with mechanical stirring. A mixture is obtained at pH = 4, the appearance of which is not significantly different from that of the original dispersion. This mixture is stable for several days, it does not form any precipitate and does not evolve into turbidite over time.

Diluted formulations h (a) and 111 (a) obtained by diluting formulations M and 111 in water at pH = 4

Two beakers are prepared, each containing 200 ml of water, the pH of which has been adjusted to 4 with hydrochloric acid.

0.1 ml of formulation 11 is added with mechanical stirring in one beaker and 0.1 ml of formulation 111 in the other, and the turbidity of the mixture is monitored over time. The evolution of turbidite remains weak and we do not see any particle formation over time. The results are given in Table 1.

The turbidite measurements were carried out using a turbidimetry cell

Metrohm coupled to a Metrohm photometer; the turbidity value is obtained by comparing the light intensity transmitted in the cell in the air, then in the medium studied.

Table 1:

Diluted formulations I1 (b) and 111 (b) obtained by diluting formulations 11 and 111 in water at pH = 7.2

Two beakers are prepared, each containing 200 ml of water at its natural pH of 7.2. 0.1 ml of formulation 11 is added with mechanical stirring to a beaker and

0.1 ml of formulation 111 in the other, and the turbidity of the mixture is monitored over time. The results are given in Table 2.

It is found that the turbidity of the solution containing the copolymer of acrylic acid and DADMAC increases sharply over time.

Table 2:

Influence of the weight ratio (V) / (A): amount of carrier agent (V) / amount of active material (A) An aqueous dispersion (latex) of a polybutylacrylate (active material A) having a size is used 35nm particles, obtained by emulsion polymerization of butyl acrylate in the presence of 10 parts by weight of cetyl trimethylammonium bromide (surfactant TAC) per 100 parts by weight of butyl acrylate. The dispersion contains a dry extract of 28% by weight.

The pH of this dispersion is adjusted to 4.0 with a 1N hydrochloric acid solution. The dispersion is slightly opalescent. In addition, a 22% by weight aqueous solution of a 1: 1 molar copolymer (vector agent V) of acrylic acid and DADMAC (of molar mass of 100,000 g / mol) is prepared, the solution of which has been adjusted. pH 4.0 with 10% hydrochloric acid solution by weight.

20ml of the dispersion of active material (A) are poured into 4ml (formulation 1), 0.1ml (formulation 2), 0.05ml (formulation 3) and 0.025ml (formulation 4) of the carrier agent copolymer solution ( V) with mechanical stirring.

Formulations 2, 3 and 4 are completed with 3.9 ml, 3.95 ml and 3.975 ml of water respectively, in order to maintain the concentration of active material (A) constant. Four formulations of pH = 4 are obtained, the appearance of which is not significantly different from that of the original dispersion, the weight ratios (V) / (A) of which are 14.8 / 100, 0.37 / 100 respectively. , 0.18 / 100 and 0.09 / 100

Four beakers are prepared, each containing 200 ml of water at its natural pH of 7.2.

0.1 ml of formulation is added with mechanical stirring to each beaker, and the turbidity of the mixture is monitored over time.

Turbidity measurements were carried out using a Metrohm turbidimetry cell coupled to a Metrohm photometer; the turbidity value is obtained by comparing the light intensity transmitted in the cell in the air, then in the medium studied.

The turbidity measurement results are given in Table 3 following Table 3

These results show that the ratio (V) / (A) has an influence on the capacity of the vector agent (V) to cause the active material (V) to flocculate.

Asset deposit on cotton

The turbidity of formulations 11 (a), 111 (a), 11 (b) and 111 (b) above is measured, 30 minutes after their preparation (this turbidity is called “initial turbidity” in Table 4 below. ).

Soaking 3 squares of woven cotton of 6x6 cm each, in each of said formulations 11 (a), 111 (a), 11 (b) and 111 (b) maintained under mechanical stirring.

The cotton squares are removed from the beakers after 30 minutes of soaking.

The turbidity of the remaining diluted formulations is then measured. The results are given in Table 4. Table 4

For the same formulation, the variation in turbidity (between the “initial turbidity” and the turbidity after 30 minutes of soaking and removing the cotton squares) is directly linked to the variation in the concentration of active materials in said formulation after 30 minutes of soaking and removing the cotton squares. The variation in turbidity observed therefore makes it possible to evaluate the deposition efficiency, that is to say the% of active materials which have deposited on the cotton squares. It is noted that the presence of the copolymer of acrylic acid and of DADMAC in formulation 111b (formulation 111 diluted to reach a final pH of 7.2) makes it possible to considerably increase (more than 200%) the efficiency of the deposition on the cotton particles present in the dispersion.

Washing machine test

The following three rinsing formulations are prepared or used: * 50ml a commercial FR softening formulation containing only cationic surfactants (15% dry matter).

* a softening formulation FRI1 (a) consisting of 10 ml of the diluted formulation FM (a) of pH 4 above, which corresponds to 186 mg of active material (A) per liter of formulation FRI1 (a) * a softening formulation FRIH (a) consisting of 10 ml of the diluted formulation FI 11 (a) of pH 4 above, which corresponds to 186 mg of active material (A) per liter of formulation FRII1 (a)

1.5 kg of 50cmx50cm flat cotton fabric samples (previously stripped by three successive washes with demineralized water at 90 ° C) are washed at 30 ° C using a commercial powder detergent formulation, in a Miele® type washing machine (from Miele).

At the end of the washing cycle, one of the samples is put in reserve and rinsed with

15 liters of city water at 23 ° C, then wrung out; the rinsing cycle lasts 5 minutes.

The other samples are divided into three lots. The first batch is rinsed for 5 minutes with 15 liters of city water at 23 ° C added with 50ml of FR formulation, then wrung under the same conditions as the sample placed in reserve.

The second batch is rinsed for 5 minutes with 15 liters of tap water at

23 ° C plus 10ml of FRI1 formulation (a), then wrung under the same conditions as the sample placed in reserve.

The third batch is rinsed for 5 minutes with 15 liters of city water to

23 ° C plus 10ml of FRIH formulation (a), then wrung under the same conditions as the sample placed in reserve.

During the rinsing cycle, the pH of the medium reaches 7.

After wringing, the articles are put to dry on a shelf.

After drying, a digital color photograph is taken of an area of the dry samples, which is then transformed into 256 gray levels (gray scale from 0 to 255).

We count the number of pixels corresponding to each gray level. For each histogram obtained, the standard deviation σ of the gray level distribution is measured.

If the crumpling is important, the distribution of the gray level is wide, σl corresponds to the standard deviation corresponding to the sample placed in reserve (rinsing without rinsing formulation). σ2 corresponds to the standard deviation obtained with the rinse formulation considered. σ3 corresponds to the standard deviation obtained on flat starting samples which have not undergone a washing, rinsing or spinning operation.

The performance value WR ("Wrinkle Recovery") is given by the following equation

WR (%) = [(σl-σ2) / σl] f x 100 celebrating a normalization factor, equal to 1 / [(σl-σ3) / σl] A value of:

- 0% corresponds to zero benefit - 100% corresponds to a flat surface The results of the crease test are as follows

Ironing ease test

The ease of ironing is evaluated by comparison with the ironing of the sample placed in reserve (rinsed without formulation, wrung and dried) The values given have the following meaning:

. 0 means no difference is noticeable . 1 means that ironing is a little easier. 2 means that ironing is much easier. 3 means that ironing is very easy even more important The results obtained are as follows:

The feel of the treated samples was also evaluated by a group of testers. The results are shown in the table above.

The above results show that the addition of the vector agent (V) improves the deposition of the active material (A) on the tissue, which results in an improvement in the anti-creasing effect of the active material (A ).

Example 2: anti-fouling effect (“soil release”)

Formulation 12

A cationic aqueous dispersion (latex) of a poly (tert-butyl polyacrylate) is used, having a particle size of 45 nm, obtained by emulsion polymerization in the presence of 10% by weight of surfactant.

Dehyquart ACA.

The dispersion has a dry extract of 30% by weight.

The units derived from tert-butyl acrylate are capable of hydrolyzing at basic pH, generating sufficient acrylic functions to make the polymer swell at the pH of the rinsing medium, and soluble at the pH of the following washing medium.

20 ml of the dispersion are poured under mechanical stirring into 1 ml of water, the pH of which has been adjusted to 4.5.

2g of sodium chloride are added (for a better comparison with formula II2 which follows).

Formulation II2.

Dehyquart® ACA.

The dispersion has a dry extract of 30% by weight.

A 1% by weight solution of carboxymethyl guar having a degree of substitution of 0.04 and a molar mass by weight of 100,000 g / mol is also prepared in water of pH 4.5. 20 ml of the dispersion are poured under mechanical stirring into 1 ml of the carboxymethyl guar solution.

2 g of sodium chloride are added to stabilize the dispersion over time.

Test

The test is carried out in a Tergotometer laboratory apparatus, well known to formulators of detergent compositions. The device simulates the mechanical and thermal effects of washing machines of the American type with pulsator; thanks to the presence of 6 washing pots, it makes it possible to carry out series of simultaneous tests with appreciable time savings. The composition of the detergent used is as follows:

The following three rinse formulations are tested:

* 8ml of a commercial FR softening formulation containing only cationic surfactants (15% dry matter).

* a softening formulation FRI2 consisting of 1 ml of formulation FI2 above, * a softening formulation FRII2 consisting of 1 ml of formulation FII2 above.

(a) Pre-washing / rinsing / drying: 3 test pieces of size 10 x10 cm, in flat woven cotton and 3 polyester test pieces of size 15 x15 cm, are prewashed in a TERGOTOMETER for 20 minutes at 23 ° C, with the above washing formula; the water used has a hardness of 30 ° HT (diluted Contrexéville® mineral water); the amount of detergent used is 5g per 1 liter of water; the number of test tubes per jar is 6. The tissue squares are then rinsed 3 times for 5 minutes (each time), including twice with cold water and the third time with cold water with additives

8ml of commercial FR rinse formula or 1 ml of rinse formulas

FRI2 or FRII2.

The fabric squares are then wrung out, then dried on clotheslines. (b) Staining:

4 drops of dirty motor oil (DMO) are deposited on the test tubes thus prewashed.

To ensure good stain fixation, soiled fabrics are placed in an oven at 60 ° C for 1 hour. To allow good reproducibility of the results, the fabrics are washed within 24 hours.

(c) Washing / rinsing / drying:

The soiled test pieces are washed, rinsed, wrung and dried under the same conditions as described in (a). Evaluation

The reflectance of the fabrics before and after washing is measured using the DR colorimeter. LANGE / LUC1 100.

The effectiveness of the polymer tested as an anti-fouling agent is assessed by the

% of stain removal calculated by formula E in% = 100 x (R3-R2) / (R1 -R2)

R1 representing the reflectance before washing the soiled fabric (step (a))

R2 representing the reflectance, before washing, of the soiled fabric (steps (a) and (b)

R3 representing the reflectance, after washing, of the soiled fabric (steps (a), (b) and (c)

For each product tested, the average of the% stain removal is calculated. The results obtained are as follows:

Example 3: retention of perfume

FI3 formulation

To 21 ml of an aqueous solution containing 3% of its weight of Dehyquart® ACA, 1.5% of perfume is added; the mixture is homogenized with ultraturrax.

2g of sodium chloride are added (for a better comparison with the formula FIII3 which follows).

FII3 formulation

An aqueous dispersion (latex) of a polybutylacrylate (active material A) having a particle size of 55 nm containing 5% by weight of perfume (organic active material MAO), obtained by emulsion polymerization of butyl acrylate, is used. in which the perfume has previously been dissolved (3 parts by weight of perfume per 100 parts by weight of butyl acrylate), in the presence of 10 parts by weight of Dehyquart® ACA (surfactant TAC) per 100 parts by weight of acrylate butyl.

The dispersion contains a dry extract of 30% by weight; the Tg of the polymer is -50 ° C. 20 ml of the dispersion of active material (A) are poured into 1 ml of water of pH 3.

Formulation FIII3 An aqueous dispersion (latex) of a polybutylacrylate (active material A) having a particle size of 55 nm containing 5% by weight of perfume (organic active material MAO), obtained by acrylate emulsion polymerization, is used. of butyl in which the perfume has been previously dissolved (3 parts by weight of perfume per 100 parts by weight of butyl acrylate), in the presence of 10 parts by weight of Dehyquart® ACA (surfactant TAC) per 100 parts by weight of butyl acrylate.

The dispersion contains a dry extract of 30% by weight; the Tg of the polymer is -50 ° C. An aqueous solution at 1% by weight of xanthan gum (RHODOPOL® T from Rhodia) is also prepared in water of pH 3.

20 ml of the dispersion of active material (A) are poured into 1 ml of the xanthan gum solution, vector agent (V), with mechanical stirring. 2 g of sodium chloride are added to improve the stability of the dispersion.

These three formulations include 1.5% by weight of perfume; they are fragrant.

Test

Pre-washing / rinsing / drying: 3 test tubes of dimension 6x6cm, in cotton, 3 test tubes of dimension 6x6cm in cotton / polyester blend and 3 test tubes of dimension 6x6cm in polyester blend, are introduced into each jar of a TERGOTOMETER, and prewashed for 20 minutes at 40 ° C, with a commercial washing formula; the water used has a hardness of 30 ° HT (diluted Contrexéville® mineral water); the amount of detergent used is 5g per 1 liter of water. The tissue squares are then rinsed 3 times for 5 minutes (each time), including twice with cold water; on the third rinse with tap water, 1 ml of the formulations FI3, FII3 and FIII3 above are added to each of the pots. The fabric squares are then wrung out, then dried on a rack in the open air. Testers note from 0 to 10, the intensity of the perfume on the fabrics, after 1, 3, 7 and 10 days of storage of the fabrics in the open air. The values given have the following meaning:. 0 means that no odor is perceptible. 10 means that the odor is persistent. The results obtained are as follows:

On the one hand, these results show that:

• when the perfume is not in “encapsulated” form in the active material (A), its odor on the tissues is not maintained (formulation FI3) • when the perfume is not in “encapsulated” form in the active material (A), its odor on the tissues is maintained (formulations FI 13 and FI 113).

On the other hand, and this is the object of the invention, a comparison of the results obtained with the formulations FI 13 [active material (A) "encapsulating" the perfume in the absence of carrier agent (V)] and FI 113 [active ingredient (A) "encapsulating" the fragrance in the presence of carrier agent (V)] shows that the improvement observed with the formulation FI 113 is due to the fact that the amount of active ingredient (A) "encapsulating" the perfume deposited on the fabric is more important than with the FII3 formulation containing no vector agent.

Claims

1) Formulation (F), intended to be implemented during a rinsing operation (R) of articles made of textile fibers (S) using an aqueous or hydroalcoholic medium (MR), said formulation ( F)

comprising at least one active material (A) made of at least one solid organic polymer in particulate form and a carrier agent (V) made of at least one organic polymer capable of bringing said active material (A) to the surface of said articles made of textile fibers (S) during the rinsing operation (R), - presenting:

. in the form of a stable dispersion, of pH 2 to 5, of said active material (A), in an aqueous or hydroalcoholic medium (MAV) comprising said carrier agent (V), or

* the active ingredient (A)

• is insoluble in the medium (AVM)

• has a cationic or zero global charge in the medium (MAV),

• remains insoluble in the rinsing medium (MR) or is likely to swell in the rinsing medium (MR)

* the carrier agent (V) * is soluble or dispersible in the medium (MAV) and in the rinsing medium (MR)

• has a zero or cationic global ionic charge in the medium (AVM)

• is capable of developing at the pH of the rinsing operation in the rinsing medium (MR) anionic charges in sufficient number to destabilize the active material (A) in the rinsing medium (MR). 2) Formulation according to claim 1), characterized in that the rinsing medium (MR) has a pH of 5.5 to 8.

3) Formulation according to claim 1) or 2), characterized in that the polymer constituting the active material (A) is chosen from:

. a) nonionic polymers derived from at least one hydrophobic nonionic monomer

. b) copolymers derived from at least one hydrophobic nonionic monomer and from at least one cationic or potentially cationic monomer in the medium (MAV), and optionally from at least one neutral monomer in the medium (MAV) and potentially anionic in the rinsing medium (MR).

4) Formulation according to claim 3), characterized in that the monomer composition from which said polymer is derived further contains: at least one uncharged or non-ionizable hydrophilic monomer, preferably in an amount not exceeding 50% of the total mass monomers and / or at least one zwitterionic monomer, preferably in an amount not exceeding 30% of the total mass of the monomers, and / or at least one crosslinking monomer, preferably in an amount not exceeding 10% of the total mass of monomers

5) Formulation according to claim 3) or 4), characterized in that the copolymer b) additionally contains an anionic monomer whose first pKa is less than 3, and in an amount sufficiently small so that said copolymer b) present in the medium (MAV) a global cationic charge.

6) Formulation according to any one of claims 3) to 5), characterized in that, when said polymer constituting the active material

(A) is an ionic or ionizable copolymer, the choice and the relative amounts of monomers from which said copolymers are derived such that the active material (A):

. is insoluble in the medium (MAV)

. present in (MAV) a total cationic charge or zero

. remains insoluble in the rinsing medium (MR) or is not likely to swell more than 8 times, preferably not more than 4 times, its volume in the rinsing medium (MR)

7) Formulation according to any one of claims 1) to 6), characterized in that the polymer particles constituting the active material (A) have an average diameter ranging from 10 nm to 10 μm, preferably from 10 nm to 1 μm and more preferably from 10nm to 500nm.

8) Formulation according to any one of claims 1) to 7), characterized in that the monomers from which the polymers constituting the active material are derived (A) are α-β monoethylenically unsaturated or diethylenically unsaturated in the case of crosslinking monomers.

9) Formulation according to any one of claims 1) to 8), characterized in that the choice and the relative amounts of the monomer (s) from which the polymer constituting the active material (A) is derived are such that said polymer has a temperature glass transition Tg from - 80 ° C to + 150 ° C, especially from - 80 ° C to + 40 ° C.

10) Formulation according to any one of claims 1) to 9), characterized in that the polymer constituting the active material (A) is insoluble in the medium (MAV) and in the rinsing medium (MR), and in what it is chosen from polymers derived from at least one non-ionic hydrophobic monomer, and copolymers derived from at least one non-ionic hydrophobic monomer and from 0.1 to 20% by weight of at least a potentially cationic monomer in the medium (MAV).

11) Formulation according to any one of claims 1) to 9), characterized in that the polymer constituting the active material (A) is an organic copolymer insoluble in the medium (MAV) with a pH of 2 to 5, capable of swell in the rinsing medium (MR) of pH 5.5 to 8 and likely to dissolve in the washing bath during a subsequent washing operation at a pH of 8.5 to 11.

12) Formulation according to claim 11), characterized in that said polymer constituting the active material (A) capable of swelling is a copolymer derived from at least one nonionic hydrophobic monomer and from 10 to 50% by weight of at least one potentially anionic monomer in the rinsing medium (MR)

13) Formulation according to any one of claims 1) to 12), characterized in that the quantity of nonionic surfactant represents less than 70% of the weight of all the surfactants (TAC).

14) Formulation according to any one of claims 1) to 13), characterized in that the mass ratio of polymer constituting the active material (A) / mass of surfactant (TAC) ranges from 0.01 to 10, preferably from 0.01 to 1.

15) Formulation according to any one of claims 1) to 14), characterized in that the cationic charges generated by the possible cationic or potentially cationic units of the copolymer constituting the active material (A) and by the surfactant (s) cationic, on the surface of the polymer constituting the active active ingredient (A) dispersed in the medium (MAV), are such that the zeta potential of said polymer or copolymer dispersed in (MAV) is from 0 to +50 mV, from preferably from +10 to +40 mV.

16) Formulation according to any one of claims 1) to 15), characterized in that the dispersion medium (MAV) of the active material (A) is water or a hydroalcoholic polar medium.

17) Formulation according to claim 16), characterized in that the alcohol (s) present in the hydroalcoholic polar medium represent up to 70% of the volume of the medium (MAV).

18) Formulation according to any one of claims 1) to 17), characterized in that the polymer constituting the vector agent (V) is any polymer which is soluble or dispersible in an aqueous or hydroalcoholic medium with a pH between 2 and 8, comprising at least one unit neutral in the medium (MAV) and potentially anionic (HA) in the rinsing medium (MR).

19) Formulation according to claim 18), characterized in that the carrier polymer (V) further comprises at least one cationic unit or potentially cationic (HC) in the medium (MAV) and / or at least one hydrophilic or hydrophobic nonionic unit

20) Formulation according to any one of claims 1) to 19), characterized in that the relative amounts of the different units of the polymer constituting the vector agent (V) are such that, in the medium (MAV), the charge overall of the polymer or copolymer either zero or cationic.

21) Formulation according to any one of claims 1) to 20), characterized in that the relative amounts of carrier agent polymer (V), surfactant (TAC) and of polymer constituting the active material (A), are such that during the rinsing operation, the number of anionic charges developed in the rinsing medium (MR) by the carrier agent polymer (V) is sufficient to destabilize the active material (A) in the rinsing medium (MR), in particular by electrostatic attraction with the surface charges of the active material (A) in the medium (MR).

22) Formulation according to claim 21), characterized in that the number of anionic charges developed in the rinsing medium (MR) by the carrier agent polymer (V) to destabilize the active material is at least 1% relative to the number of cationic surface charges of the active material (A) in the medium (MR), and at most 200% relative to the number of cationic surface charges of the active material (A) in the medium (MR).

23) Formulation according to any one of claims 1) to 22), characterized in that the polymer constituting the vector agent (V) is a polymer chosen from polymers derived from ethylenically unsaturated monomers, potentially anionic native polysaccharides, substituted or modified potentially anionic or amphoteric polysaccharides, or mixtures thereof.

24) Formulation according to any one of claims 1) to 23), characterized in that the polymer constituting the vector agent (V) is a derivative polymer:

. at least one monoethylenically unsaturated α-β monomer, neutral in the medium (MAV) and potentially anionic (HA) in the rinsing medium (MR) and

. optionally at least one monoethylenically unsaturated, cationic or potentially cationic (HC) α-β monomer in the medium (MAV) and

. optionally at least one hydrophilic or hydrophobic, preferably hydrophilic, monoethylenically unsaturated α-β monomer

25) Formulation according to any one of claims 1) to 24), characterized in that the polymer constituting the vector agent (V) is a copolymer, random, block or grafted, derived:

. at least one hydrophilic α-β monoethylenically unsaturated monomer neutral in the medium (MAV) and potentially anionic (HA) in the rinsing medium (MR) and

. at least one cationic or potentially cationic (HC) monoethylenically unsaturated α-β hydrophilic monomer in the medium (MAV). and optionally at least one hydrophilic or hydrophobic non-ionic monoethylenically unsaturated α-β monomer, preferably hydrophilic.

26) Formulation according to any one of claims 1) to 25), characterized in that the polymer constituting the vector agent (V) derives from one or more monoethylenically unsaturated α-β monomers and has a higher average molar mass at 5000 g / mol, preferably from 20,000 to 500,000 g / mol.

27) Formulation according to any one of claims 1) to 26), characterized in that the polymer constituting the vector agent (V) is chosen from

• polyacrylic or polymethacrylic acids, polyacrylates or polymethacrylates of alkali metals, preferably having a molar mass by weight of 100,000 to 1,000,000 g / mol

• acrylic acid / DADMAC copolymers, with a molar ratio of 50/50 to 30/70, preferably having a molar mass by weight of 70,000 to

350,000 g / mol

• acrylic acid / MAPTAC copolymers, with a molar ratio of 60/40 to 30/70, preferably having a molar mass by weight of 90,000 to 300,000 g / mol • acrylic acid / MAPTAC / alkyl methacrylate terpolymers, the alkyl radical is linear in C -Cι ₈ , terpolymers comprising from 0.005 to 10% by mass of alkyl methacrylate with an acid molar ratio acrylic / MAPTAC ranging from 60/40 to 30/70, and preferably having a molar mass by weight of 50,000 to 250,000 g / mol • acrylic acid / dimethylaminoethylmethacrylate (DMAEMA) copolymers, with molar ratio of 60/40 to 30 / 70, and preferably having a molar mass by weight of 50,000 to 300,000 g / mol

28) Formulation according to any one of claims 1) to 23), characterized in that the polymer constituting the vector agent (V) is a native potentially anionic polysaccharide formed from nonionic monosaccharide units and monosaccharide units neutral in the medium (MAV) and potentially anionic in the rinsing medium (MR) similar or different.

29) Formulation according to claim 28), characterized in that said potentially anionic native polysaccharide is a branched polysaccharide formed

• a main chain comprising similar or different anhydrohexose units

• and of ramifications comprising at least one anhydropentose and / or anhydrohexose unit neutral in the medium (AVM) and possibly potentially anionic in the rinsing medium (MR).

30) Formulation according to claim 28 or 29), characterized in that said potentially anionic native polysaccharide is a xanthan gum, a succinoglycan, a rhamsan, a gellan gum, welan.

31) Formulation according to any one of claims 28) to 30), characterized in that said potentially anionic native polysaccharide has a molar mass by weight of 2,000 to 5,000,000, preferably 10,000 to 5,000,000, very particularly 10 000 to 4000 000 g / mol.

32) Formulation according to any one of claims 1) to 23), characterized in that the polymer constituting the vector agent (V) is a substituted or modified polysaccharide, the native skeleton of which is formed of non-monosaccharide units ionic and / or monosaccharide units neutral in the medium (MAV) and potentially anionic in the rinsing medium (MR) similar or different, said monosaccharide units being substituted or modified: • by one or more group (s) carrying at least one neutral charge in the medium (MAV) and potentially anionic in the medium (MR)

• and optionally by one or more group (s) carrying at least one cationic or potentially cationic charge in the medium (MAV), the degree of substitution or modification of the monosaccharide units by all of the groups carrying potentially anionic charges and possible groups carrying cationic charges, being such that said substituted or modified polysaccharide is soluble or dispersible in aqueous or hydroalcoholic medium and present in the medium (AVM) an overall charge zero or cationic.

33) Formulation according to claim 32), characterized in that said substituted or modified polysaccharide additionally contains at least one nonionic substituent or modifying group.

34) Formulation according to claim 32) or 33), characterized in that said substituted or modified polysaccharide is a substituted or modified branched polysaccharide, the native skeleton of which is formed

• a main chain comprising similar or different anhydrohexose units

• and of branches comprising at least one anhydropentose and / or anhydrohexose unit neutral in the medium (MAV) and possibly potentially anionic in the rinsing medium (MR), the anhydrohexoses and / or anhydropentoses units of said polysaccharide being substituted or modified by one or groups carrying at least one charge neutral in the medium (MAV) and potentially anionic in the medium

(MR) and optionally at least one cationic or potentially cationic charge in the medium (MAV), the degree of substitution or modification DSi of the anhydrohexoses and / or anhydropentoses units by all of said groups carrying ionic or potentially ionic charges ranging from 0.01 to less than 3, preferably from 0.01 to

2.5, with a ratio of the number of potentially anionic charges in the medium

(MR) the number of cationic or potentially cationic charges in the medium (MAV) ranging from 100/0 to 30/70, preferably from 100/0 to 50/50.

35) Formulation according to any one of claims 31 to 34), characterized in that said substituted or modified polysaccharide has a molar mass by weight from 2000 to 5,000,000, preferably from 10,000 to 5,000,000 g / mol.

36) Formulation according to any one of claims 31 to 35), characterized in that the native skeleton of said substituted or modified polysaccharide is a galactomannan.

37) Formulation according to any one of claims 31 to 36), characterized in that the native skeleton of said substituted or modified polysaccharide is chosen from

- carboxymethyl galactomannans, in particular carboxymethyl guars,

- carboxymethyl hydroxypropyl galactomannans, in particular carboxymethyl hydroxypropyl guars, - carboxymethyl hydroxypropyltrimethylammonium chloride galactomannans, in particular carboxymethyl hydroxypropyltrimethylammonium guars chloride,

- the carboxymethyl hydroxypropyl hydroxypropyltrimethylammonium chloride galactomannans, in particular the carboxymethyl hydroxypropyl chloride of hydroxypropyltrimethylammonium guars.

38) Formulation according to any one of claims 1 to 37), characterized in that the amount of carrier agent (V) present in said formulation ranges from 0.001 to 5 parts by weight, preferably from 0.01 to 4 parts by weight, very particularly from 0.05 to 2 parts by weight per 100 parts by weight of active material (A).

39) Formulation according to any one of claims 1 to 38), characterized in that it is in the form of an aqueous or hydroalcoholic dispersion comprising per 100 parts of its weight:

- from 0.001 to 4, preferably from 0.01 to 1 parts by dry weight of carrier polymer (V). 40) Formulation according to any one of claims 1 to 39), characterized in that it further comprises one or more usual constituents of cationic rinse formulations chosen from cationic softening agents, optical brighteners, anti-transfer agents color, water-soluble monovalent mineral salts, silicone oils, mineral, vegetable, animal or hydrocarbon oils or waxes, dyes, perfumes, foam limiters, enzymes, bleaching agents.

41) Formulation according to any one of claims 1 to 40), characterized in that the active material (A) solid in particulate form, contains, encapsulated in its particles, at least one hydrophobic organic active material (MAO) liquid or other solid that (A).

42) Formulation according to claim 41), characterized in that said liquid or solid hydrophobic organic active material (MAO) is a perfume, a biocide, an anti-UV agent, an optical brightener, an optionally amino silicone oil, a mineral oil or vegetable.

43) Process for treating articles of textile fibers, by bringing them into contact, during a rinsing operation in an aqueous or hydroalcoholic medium, with the rinsing formulation ^" (F) forming the subject of any one of claims 1) to 42), and recovery of said rinsed articles.

44) Method intended to improve the anti-creasing and / or ironing and / or anti-soiling properties of textile fiber articles. consisting in bringing into contact, during a rinsing operation in an aqueous or hydroalcoholic medium, said articles with the rinsing formulation (F) forming the subject of any one of claims 1) to 41), and in recovering said items flushed.

45) Method according to claim 44), characterized in that the active material (A) solid in particulate form of the formulation (F), contains, encapsulated in its particles, at least one hydrophobic active material (MAO) liquid or other solid that (A), and in that said process is further intended to bring to said articles of textile fibers, benefits intrinsic complements of said hydrophobic organic active material (MAO).

46) A method according to claim 45), characterized in that said hydrophobic organic active material (MAO) is a liquid or solid perfume, and in that said method is intended to additionally provide said articles of textile fibers with perfuming properties.

47) Use, in a formulation (F), intended to be used during a rinsing operation (R) of articles made of textile fibers (S) using an aqueous or hydroalcoholic (MR) medium , formulation (F) comprising at least one active material (A) made of at least one organic polymer, solid, in particulate form, and which is: in the form of a stable dispersion, of pH 2 to 5, of said active material (A), in an aqueous or hydroalcoholic medium

(MAV) or in solid form obtained by drying said dispersion, the nature of the active material (A) and of the aqueous or hydroalcoholic medium (MAV) being such that the active material (A) • is insoluble in the medium (MAV)

• has a cationic or zero global charge in the medium (MAV),

• remains insoluble in the rinsing medium (MR) or is capable of swelling in the rinsing medium (MR), of at least one organic polymer.

Φ soluble or dispersible in the medium (AVM) and in the rinsing medium

(MR) Φ having in the medium (AVM) a global ionic charge zero or cationic

Φ and capable of developing, at the pH of the rinsing operation in the rinsing medium (MR), anionic charges in sufficient number to destabilize the active material (A) in the rinsing medium (MR), as a carrier agent (V) capable of bringing said active material (A) to the surface of said articles of textile fibers (S) during the rinsing operation (R).

48) Use according to claim 47), characterized in that the active material (A) solid in particulate form contains, encapsulated in its particles, at least one hydrophobic organic active material (MAO) liquid or solid other than (A), and in that said organic carrier polymer (V) is further capable of improving the retention of said organic active material (MAO) on the surface of textile fiber articles.

49) Use according to claim 48), characterized in that the hydrophobic organic active material (MAO) is a liquid or solid perfume, and in that said organic vector polymer (V) is also capable of improving the retention of said perfume on the surface of textile fiber articles.

50) Process for improving the deposition of an active material (A) in at least one organic, solid polymer, in particulate form, optionally containing, encapsulated in its particles, at least one liquid or solid hydrophobic organic active material (MAO) other that (A), on the surface of textile fiber articles (S), during a rinsing operation of said articles using an aqueous or hydroalcoholic medium (MR) obtained from a formulation ( F) comprising said active material (A), formulation (F) having:

. in the form of a stable dispersion, of pH 2 to 5, of said active material (A), in an aqueous or hydroalcoholic medium (AVM) or

. in solid form obtained by drying said dispersion, the nature of the active material (A) and of the aqueous or hydroalcoholic medium

(MAV) being such that the active material (A)

• is insoluble in the medium (AVM)

• present in the medium (MAV) a total cationic charge or zero, • is stabilized in the medium (MAV) using a cationic surfactant (TAC), said cationic surfactant (TAC) being able to be in all or part replaced by a nonionic surfactant when the polymer constituting the active material (A) is intrinsically cationic or intrinsically potentially cationic in the medium (MAV) • remains insoluble in the rinsing medium (MR) or is capable of swelling in the rinsing medium (MR), by addition to said formulation (F) d '' a vector (V) in at least one organic polymer Φ soluble or dispersible in the medium (MAV) and in the rinsing medium

(MR) Φ having in the medium (AVM) a global ionic charge zero or cationic

Φ and capable of developing at the pH of the rinsing operation in the rinsing medium (MR) anionic charges in sufficient number to destabilize the active material (A) in the rinsing medium (MR).

51) Method according to claim 58), characterized in that the hydrophobic organic active material (MAO) is a liquid or solid perfume.

52) Methods according to any one of claims 43) to 46), 50) or

51), or use according to any one of claims 47) to 49), characterized in that the amount of formulation used, expressed as dry matter, is from 0.001 to 5 g / l, preferably 0.05 to 2g / l in the rinsing bath.