EP1537271A2

EP1537271A2 - Textile rinsing formulation

Info

Publication number: EP1537271A2
Application number: EP03769587A
Authority: EP
Inventors: Cédric GEFFROY
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 2002-09-09
Filing date: 2003-09-08
Publication date: 2005-06-08
Also published as: JP2005538262A; AU2003278279A1; US20050028293A1; WO2004022839A3; WO2004022839A2; AU2003278279A8; BR0314149A

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 liquid or solid hydrophobic organosilicon or organic material 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

FORMULATION FOR RINSING TEXTILES

The subject of the present invention is an improved formulation intended for rinsing articles of textile fibers, comprising a hydrophobic active material made of a particulate, liquid or solid organic or organosilicon material.

It is known to use hydrophobic organic or organosilicon materials in rinsing compositions for textiles. US-A-4,818,242 describes an aqueous rinse aid for ironing, comprising a cationic silicone oil dispersed in water, a fatty acid and polyamine condensate, and a cationic film-forming agent.

Patent US-A-4,923,622 proposes rinsing compositions comprising an emulsifiable concentrate containing cationic surfactants and an oil capable of exhibiting librifying properties with respect to the textiles to be treated, such as mineral oils and vegetable oils containing 8 with 22 carbon atoms, fatty acid esters.

The Applicant has found that the addition, in a formulation comprising particles of insoluble organic or organosilicon hydrophobic active material, intended for rinsing articles of textile fibers, of a small amount of a suitably chosen soluble carrier agent of said active material , made it possible to significantly improve the deposition of particles on the surface of said articles, and thus to bring to said articles significant benefits, such as lubrication benefits, softness to the touch, anti-creasing properties and / or helps with ironing and / or antifouling, abrasion resistance.

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 or organosilicon material, liquid or solid, in particulate form and a vector agent (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),

- presenting themselves: . 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)

• 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 wholly or partly replaced by a nonionic surfactant when the material constituting the active ingredient (A) is inherently cationic or inherently potentially cationic in the medium (AVM)

• remains insoluble 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 turbidity 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 size of the objects of the dispersion is at least twice that of the of the same objects in the absence of a vector agent (V). According to the invention, the active material (A) is made of an organic or organosilicon material, liquid or solid, in particulate form, insoluble in the medium (MAV), present in the medium (MAV) with a total cationic charge or zero, remains insoluble in the rinsing medium (MR).

According to the invention, the material 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) .

Said material constituting the active material (A) is in liquid or particulate solid form.

Preferably it is in the form of an oil or a fusible solid (a wax for example).

Said particles can have an average diameter ranging from 10 nm to

200μm, preferably from 10nm to 5μm and more preferably from 10nm to

2000nm.

The diameter of said particles can be determined in a well known manner by light scattering, by laser diffraction or by microscopic technique.

Among the materials which can constitute the active material (A), mention may be made in particular of those having a lubricating action, capable of bringing lubrication properties to textile fiber articles, which can result in the provision of benefits such as softness, anti-crease, ironing aid, abrasion resistance, anti-fouling ...

According to a first embodiment of the invention, said material constituting active material (A), is an organosilicon material.

It is in particular an oil, a wax or a polyorganosiloxane resin which is linear, cyclic, branched or crosslinked.

Said polyorganosiloxane preferably has a dynamic viscosity measured at 25 ° C. and at a shear rate of 0.01 Hz for a stress of

1500 Pa (performed on a Carrimed ® type CSL2-500) between 10 ⁴ and 10 ⁹ cP. According to the invention, these are:

• a non-ionic polyorganosiloxane

• a polyorganosiloxane having at least one cationic or potentially cationic function in the medium (MAV) • an amphoteric polyorganosiloxane having at least one cationic or potentially cationic function in the medium (MAV) and at least one neutral function in the medium (MAV) and potentially anionic in the rinsing medium (MR) • a polyorganosiloxane having at least one neutral function in the medium (AVM) and potentially anionic in the rinsing medium (MR).

As examples of polyorganosiloxanes, there may be mentioned

> linear, cyclic or crosslinked polyorganosiloxanes formed from nonionic organosiloxane units of general formula

(R) a (X) bSi (0) [4- (a + b)] / 2 (') formula in which

the symbols R are identical or different and represent an alkyl hydrocarbon radical, linear or branched, having from 1 to 4 carbon atoms, aryl, phenyl in particular;

- the symbols X are identical or different and represent a hydroxyl group, an alkoxy radical, linear or branched, having from 1 to 12 carbon atoms, an OCOR ¹ function, where R 'represents an alkyl group containing from 1 to 12 atoms carbon, preferably 1 carbon atom;

- a is 0, 1, 2 or 3

- b is 0, 1, 2 or 3

- a + b is 0, 1, 2 or 3

Preferably, said polyorganosiloxane is at least substantially linear, and most preferably linear.

By way of example, mention may in particular be made of α-ω bis (hydroxy) polydimethylsiloxane oils, α-ω bis (trimethyl) polydimethylsiloxane oils, cyclic polydimethylsiloxanes, polymethylphenylsiloxanes.

> linear, cyclic or crosslinked polyorganosiloxanes comprising, per mole, at least one ionic or nonionic organosiloxane unit of general formula

(R) _a (X) b (B) cSi (0) _[4 - (a + b + c)] / 2 (") formula in which

- the symbols R are identical or different and represent a monovalent alkyl hydrocarbon radical, linear or branched, having from 1 to 4 carbon atoms, aryl, phenyl in particular; the symbols X are identical or different and represent a hydroxyl group, an alkoxy radical, linear or branched, having from 1 to 12 carbon atoms, an OCOR 'function, where R' represents an alkyl group containing from 1 to 12 atoms carbon, preferably 1 carbon atom; the symbols B are identical or different and represent an aliphatic and / or aromatic and / or cyclic hydrocarbon radical containing up to 30 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen and / or nitrogen and / or sulfur, optionally carrying one or more ether, ester, thiol, hydroxyl, optionally quaternized amine, carboxylate functions, the symbol B being bonded to silicon preferably via an Si-C- bond;

- a is 0, 1, or 2

- b is 0, 1 or 2

- c is equal to 1 or 2 - a + b + c is equal to 1, 2 or 3

The other organosiloxane units, present alongside those of formula (II), are preferably nonionic and of formula (I) above. Organosiloxane units having one or more strong anionic functions, of the sulfonate or phosphonate type, may also be present, when the units of formula (II) are cationic or potentially cationic in the medium (MAV). They are however present in a limited number, so that said polyorganosiloxane presents in the medium (AVM) an overall cationic charge or zero. By way of example of substituents corresponding to the symbol (B) in the formula (II) above, there may be mentioned

- the polyether groups of formula

- (CH2) n- (OC2H4) m- (OC ₃ H ₆ ) p-OR ', where n is equal to 2 or 3, m and p each go from 0 to 30 and R' represents an alkyl residue containing 1 with 12 carbon atoms, preferably e 1 to 4 carbon atoms.

- primary, secondary, tertiary or quaternized amino groups. such as those of formula - R1 -N (R ² ) (R ³ ) where * the symbol R ¹ represents an alkylene group containing from 2 to 6 carbon atoms, optionally substituted or interrupted by one or more nitrogen or oxygen atoms,

2 3

* the symbols R and R, identical or different represent. H

. an alkyl or hydroxyalkyl group containing from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms,

. an amino alkyl group, preferably primary, the alkyl group of which contains from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, optionally substituted and / or interrupted by at least one nitrogen atom and / or d oxygen, said amino group being optionally quaternized, for example by a hydrohalic acid or an alkyl or aryl halide.

We can notably mention those of formulas - (CH ₂ ) 3 NH ₂ - (CH ₂ ) ₃ NH ₃ + X-

- (CH ₂ ) ₃ N (CH ₃ ) ₂ - (CH ₂ ) ₃ N + (CH ₃ ) ₂ C ₈ H ₃₇ ) X "

- (CH ₂ ) ₃ NHCH ₂ CH ₂ NH ₂ - (CH ₂ ) ₃ N (CH ₂ CH ₂ OH) ₂

- (CH ₂ ) ₃ N (CH CH ₂ NH ₂ ) ₂

Preferably, the polyorganosiloxanes carrying amino functions, present in their chain, per 100 total silicon atoms, from 0.1 to

50, preferably from 0.3 to 10, very particularly from 0.5 to 5 aminofunctionalized silicon atoms.

- sterically hindered piperidinyl groups of formula III

or

* R ⁴ is a divalent hydrocarbon radical chosen from:

* linear or branched alkylene radicals having 2 to 18 carbon atoms; * alkylene-carbonyl radicals, the linear or branched alkylene part of which contains 2 to 20 carbon atoms; * alkylene-cyclohexylene radicals, the linear or branched alkylene part of which contains 2 to 12 carbon atoms and the cyclo-hexylene part comprises an OH group and optionally 1 or 2 alkyl radicals having 1 to 4 carbon atoms;

* the radicals of formula -R ⁷ - O - R ⁷ in which the identical or different radicals R ⁷ represent alkylene radicals having 1 to 12 carbon atoms;

* the radicals of formula -R ⁷ - O - R ⁷ in which the radicals R ⁷ have the meanings indicated above and one of them or both are substituted by one or two group (s) -OH;

* the radicals of formula -R ⁷ - COO - R ⁷ in which the radicals R ⁷ have the meanings indicated above; * the radicals of formula -Rδ -O -R ⁹ - O-CO-R ⁸ in which the radicals R ⁸ and R ⁹ identical or different, represent alkylene radicals having 2 to 12 carbon atoms and the radical R ⁹ is optionally substituted with a hydroxyl radical; * U represents -O- or -NR ^" O-, R ^{" 10} being a radical chosen from a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms and a divalent radical of formula:

in which R ⁴ has the meaning indicated above, R ⁵ and R ⁶ have the meanings indicated below and R ^{1 1} represents a divalent alkylene radical, linear or branched, having from 1 to 12 carbon atoms, one of the links valentials (that of R ^{1 1} ) being connected to the atom of -NR ¹⁰ -, the other (that of R ⁴ ) being connected to a atom of silicon; * the radicals R ⁵ are identical or different, chosen from linear or branched alkyl radicals having 1 to 3 carbon atoms and the phenyl radical;

* the radical R ⁶ represents a hydrogen radical or the radical R ⁵ or O.

or the sterically hindered piperidinyl groups of formula IV

or

R ' ⁴ is chosen from a trivalent radical of formula:

(CUL) CH

^\ co - _{or m} represents a number from 2 to 20, and a trivalent radical of formula:

where p represents a number from 2 to 20; * U 'represents -O- or NR ¹² -, R ¹² being a radical chosen from a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms; * R5 and R6 have the same meanings as those given above with regard to formula III. Preferably, said polyorganosiloxanes with an amino function are polyorganosiloxanes with a sterically hindered piperydinyl function, in particular those which can be prepared according to the process described in EP-A-659930. Most preferably, said polyorganosiloxane having a sterically hindered amino function is a linear, cyclic or three-dimensional polyorganosiloxane of formula (V):

in which :

(1) the symbols Z, identical or different, represent R ¹ below and / or B;

(2) the symbols R ¹ , R ² and R ³ , which are identical and / or different, represent a monovalent hydrocarbon radical chosen from linear or branched alkyl radicals having from 1 to 4 carbon atoms, linear or branched alkoxy radicals having from 1 to 4 carbon atoms, a phenyl radical and preferably a hydroxy radical, an ethoxy radical, a methoxy radical or a methyl radical;

(3) the symbols B, identical and / or different functional groups, represent a group with sterically hindered piperidinyl (s) functions chosen from those mentioned above; and

(4) - the number of TjSi units without group B ranges from 10 to 450, preferably from 50 to 250;

- The number of rjSi units with a group B ranges from 1 to 5, preferably from 1 to 3;

- 0 <w <10 and 8 <y <448. Most preferably, said polyorganosiloxane is linear.

According to a second embodiment of the invention, said material constituting active material (A), is an organic material. As an example, we can mention

- mono-, di- or triglycerides of C1-C30 carboxylic acids or their mixtures, such as vegetable oils (rapeseed, castor oil, sunflower oil, erucic rapeseed oil, linseed oil, etc.)

- sucroesters, sucroglycerides - C1-C30 alcoholesters of C1-C30 carboxylic or C ₂ -C ₃₀ dicarboxylic acids,

- ethylene or propylene glycol monoesters or diesters of C1-C30 carboxylic acids - propylene glycols of C ₄ -C ₂ alkyl ether

- di Cβ-C-30 alkyl ethers

- organic waxes comprising alkyl chains containing from 4 to 40 carbon atoms. Among the waxes, there may be mentioned in particular:

• animal waxes (beeswax, lanolin, whale oil) ^“ vegetable waxes (carnauba, candellila, sugar cane wax, jojoba)

• fossil mineral waxes (montane, ozokerite, Utah wax)

• hydrocarbon waxes comprising from 4 to 35 carbon atoms (mineral oils, paraffins, microcrystalline waxes) ^“ synthetic waxes such as polyolefins (polyethylene, polypropylene), sterone, carbowax. According to the invention, the active material (A) is placed in stable dispersion in the medium (MAV) using a surfactant (TAC).

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

Said surfactant (TAC) is a cationic surfactant or a mixture of cationic surfactant and nonionic surfactant when said material 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 the possible cationic or potentially cationic functions of the active material (A) and by the cationic surfactant (s), on the surface of the active active material (A) dispersed in the medium (AVM), are such that the zeta potential of the active ingredient in dispersion in (MAV) is from 0 to +50 mV, preferably

+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 functions, or can form together with the nitrogen atom N ⁺ at least one aromatic or heterocyclic ring

. R represents a C8-C22, preferably C12-C22, alkyl or alkenyl group. 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 be made in particular of dodecyltrimethylammonium bromides, tetradecyltrimethylammonium, cetyltrimethylammonium, stearyl pyridinium chloride, RHODAQUAT® TFR and RHODAMINE® C15 sold by RHODIA, cetyltrimethylammonium chloride (Dehyquart ACA and / or) 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 carbon atom (s), optionally substituted by one or more hydroxyl functions, or may form together with the nitrogen atom N ⁺ a heterocyclic cycle

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 - fatty ethoxylated or ethoxy-propoxylated amines

- ethoxylated or ethoxy-propoxylated di (phenyl-1 ethyl) phenols

- tri (1-phenylethyl) ethoxylated or ethoxy-propoxylated 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, pisopropanol, propylene glycol, butoxyethanol, etc. These alcohols can represent up to 70% of the volume of medium (MAV). Preferably, the medium ( MAV) is water. The medium can be brought to the desired pH from 2 to 5 by addition of an acid, such as hydrochloric acid, citric acid, phosphoric acid, benzoic acid ...

The rinse formulation (F) forming the subject of the invention comprises a carrier agent (V) capable of bringing the active material (A) to the surface of the textile fiber articles during the rinse 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), cationic surfactant (TAC) and material constituting the 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 carrier (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.

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.

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

Preferably, (V) is a random, block or graft copolymer, 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 monoethylenically unsaturated α-β hydrophilic monomer (HC) 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 monomer α-β monoethylenically unsaturated hydrophilic neutral in the medium (MAV) and potentially anionic (HA) in the rinsing medium (MR). we can cite

• 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

• the precursor monomers of carboxylate functions, such as tert-butyl acrylate, which generate, after polymerization, carboxylic functions by hydrolysis.

As examples of a hydrophilic cationic or potentially cationic (HC) monoethylenically unsaturated α-β monomer in the medium (AVM), there may be mentioned: • ammoniumacryloyl or acryloyloxy monomers such as trimethylammoniumpropylmethacrylate chloride, trimethylammoniumethylacrylamide chloride or methacrylamide, trimethylammoniumbutylacrylamide methylsulfate or methacrylamide, trimethylammoniumpropylmethacrylamide methylsulfate (MES), (3-methacrylamidopropyl) trimethylammonium chloride (MAPTAC), (3-acrylamidopropyl) trimethylammonium chloride, methyl chloride or methylethylchloride 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

• the 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

• 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 (diethylamino) 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 monoethylenically unsaturated α-β monomers hydrophilic uncharged or non-ionizable. we can cite

• hydroxyalkyl esters of α-β ethylenically unsaturated acids such as hydroxyethyl and hydroxypropyl acrylates and methacrylates, glycerol monomethacrylate ... • α-β ethylenically unsaturated amides such as acrylamide, N, N-dimethyl methacrylamide , N-methylolacrylamide ...

• the ethylenically unsaturated α-β monomers carrying a water-soluble polyoxyalkylenated segment of the polyethylene oxide type, such as the polyethylene oxide α-methacrylates (BISOMER S20W, S10W, ... from LAPORTE) or α, ω-dimethacrylates, the SIPOMER BEM de RHODIA

(polyoxyethylene ω-behenyl methacrylate), SIPOMER SEM-25 from RHODIA (polyoxyethylene ω-tristyrylphenyl methacrylate) ...

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

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

• vinylaromatic monomers such as styrene, vinyltoluene ...

• alkyl esters of monoethylenically unsaturated α-β acids such as methyl and ethyl acrylates and methacrylates, etc.

• 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 function or sulfonate, such as 2-sulfooxyethyl methacrylate, vinylbenzene sulfonic acid, allyl sulfonic acid, 2-acrylamido-2methylpropane sulfonic, acrylate or sulfoethyl methacrylate, acrylate or sulfopropyl 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 s constituents of the vector agent (V), we can mention:

• polyacrylic or polymethacrylic acids, polyacrylates or polymethacrylates of alkali metals, preferably with 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 of 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 -C ₁₈ , 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, preferably of 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

• 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).

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, gellan gums, welan ...

Their molar mass by weight can range from 2000 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 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.

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 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 neutral charge 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 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 1 00/0 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 5,000,000, 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 in particular be made of those of formula - [- CH ₂ -CH (R) -O] _x - (CH2) _y -COOH or - [- CH ₂ -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 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 through 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 cationic or potentially cationic groups of formula

^• -NH ₂

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

-CH ₂ -CONH- (CH ₂ ) 2-N (CH ₃ ) 2

-CH ₂ -COO- (CH2) 2-NH- (CH2) 2-N (CH ₃ ) 2

-CH2-CONH- (CH ₂ ) 3-NH- (CH2) 2-N (CH ₃ ) 2 -CH2-CONH- (CH ₂ ) 2-NH- (CH2) 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 - (CH ₂ ) 2-NH- (CH2) 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-yl, of formula

^0Ha 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 be made most particularly of the formula function:

- (CH) 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 ^" l 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 heteroatoms, cycloalkyl, aryl, arylalkyl, containing from 6 to 12 carbon atoms . a radical - (CH2) y-COOR ² . a radical - (CH2) _y -CN. a radical - (CH ₂ ) _y -CONHR ² 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 the 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 ...

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 ramifications of the native skeleton can be units D- xylose ..., L- or D-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 a native skeleton, we may mention gaiactomannans, galactoglucomannans, xyloglucans, xanthan gums, scleroglucans, succinoglycans, rhamsans, welan gums ...

Preferably, the native skeleton is a galactomannan. Gaiactomannans 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 gaiactomannans, in particular the carboxymethyl guars,

- carboxymethyl hydroxypropyl gaiactomannans, in particular carboxymethyl hydroxypropyl guars,

- carboxymethyl hydroxypropyltrimethylammonium chloride gaiactomannans, in particular carboxymethyl hydroxypropyltrimethylammonium guars chloride,

- the carboxymethyl hydroxypropyl hydroxypropyltrimethylammonium chloride gaiactomannanes, in particular the carboxymethyl hydroxypropyl chloride of 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 ...)

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

• 1) preparation of an aqueous dispersion (emulsion, microemulsion, suspension) of the material constituting the active material (A) using a surfactant (TAC) as stabilizing agent;

• 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 cationic 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) using a surfactant (TAC) as stabilizing agent;

• 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 ose, oside or polyholoside or water-dispersible, preferably a dare. The amount of protective agent can represent on 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, potassium or ammonium chlorides, nitrates or sulphates (especially when the vector agent (V) is a polysaccharide), for example, from 0.01 to 2 moles per liter - 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”), antiabrasion, as well as anti-fouling (“soil release”) properties brought about by the deposition of the active material (A) on the surface of said articles, deposition favored by the presence 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 silicone oil, in particular of a silicone oil with hindered piperidinyl function.

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 method for improving the properties of anti-creasing and / or of ironing aid and / or of anti-soiling and / or of resistance to abrasion of articles of textile fibers. , consisting in bringing into contact, during a rinsing operation in an aqueous or aqueous-alcoholic medium, said articles with the rinsing formulation (F) as described above, then in 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 or organosilicon material, liquid or solid, in particulate form, and 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) or in solid form obtained by drying of said dispersion, the nature of the active material ( A) and aqueous or hydroalcoholic medium

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

• is insoluble in the medium (AVM)

• has a cationic or zero overall charge in the medium (MAV), ^“ 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 material constituting the active material (A) is intrinsically cationic or intrinsically potentially cationic in the medium (MAV)

• remains insoluble in the rinsing medium (MR); at least one organic polymer,

Φ soluble or dispersible in the medium (MAV) and in the rinsing medium (MR) Φ having in the medium (MAV) a global ionic charge zero or cationic Φ and capable of developing at the pH of the rinsing operation in the medium rinsing (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).

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 of a method for improving the deposition of an active material (A) in at least one organic or organosilicon material, liquid or solid, in particulate form, on the surface of articles of textile fibers ( 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) is 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 of said dispersion, the nature of the active material ( A) and aqueous or hydroalcoholic medium

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

• is insoluble in the medium (AVM)

• remains insoluble in the rinsing medium (MR); by adding to said formulation (F) a carrier agent (V) in at least one organic polymer

Φ soluble or dispersible in the medium (MAV) and in the rinsing medium (MR)

Φ having a zero or cationic overall ionic charge in the medium (MAV) 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 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.

The following examples are given by way of illustration. Example 1: anti-crease and ironing aid effect

30% of a sunflower oil of the Lubrirob® type TOD18.80 (from Rhodia / Novance) is emulsified in water with a microfluidizer (4 bars, 3 cycles) when hot (50 ° C) in the presence of 3% by weight cationic surfactants (cetyltrimethylammonium bromide type).

An emulsion (E) having a dry extract of 30% by weight of active material is obtained, an emulsion the size of which, measured by laser diffraction (Horiba granulometer) is 250 nm. This size is a mass average size of the size distribution of the emulsion. This emulsion (E) is used to make different formulations.

Formulation H.

The pH of the emulsion (E) is adjusted to 4.0 with a 1N hydrochloric acid solution. The dispersion obtained is milky. 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 develop in turbidity over time.

Formulation 111.

The pH of the emulsion (E) is adjusted to 4.0 with a 1N hydrochloric acid solution. The dispersion obtained is milky.

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 develop in turbidity over time.

Diluted formulations H (a) and 111 (a) obtained by diluting formulations 11 and 111 in water at PH = 4 In a Horiba granulometer tank, water is introduced whose pH has been adjusted to 4 ( about 100ml).

0.1 ml of formulation 11 is added thereto with mechanical stirring and the evolution of the size of the emulsion is monitored over time. The same operation is repeated with 0.1 ml of the formulation 111. The results are given in Table 1.

Table 1:

This size does not change over time.

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

In the granulometer tank, water is introduced at its natural pH of 7.2 (approximately 100 ml). 0.1 ml of formulation 11 is added thereto with mechanical stirring and the evolution of the size of the emulsion is monitored over time. The same operation is repeated with 0.1 ml of formulation 111. The results are given in Table 2.

Table 2:

Influence of the weight ratio (V) / (A): amount of carrier (V) / amount of active material (A)

The pH of the emulsion (E) at 30% by weight of active material is adjusted to 4.0 with a 1N hydrochloric acid solution. The dispersion obtained is milky.

An 11% by weight aqueous solution of a 1: 1 molar copolymer (carrier agent V) of acrylic acid and DADMAC (of molar mass of 100,000 g / mol) is also prepared, the solution of which has been adjusted. pH 4.0 with 10% hydrochloric acid solution by weight. 20ml of the active ingredient dispersion (A) are poured into 4ml respectively

(formulation 1), 0.1 ml (formulation 2) and 0.05 ml (formulation 3) of the vector agent copolymer solution (V) with mechanical stirring.

Formulations 2 and 3 are completed with 3.9 ml and 3.95 ml of water respectively, in order to maintain the concentration of active material (A) constant.

Three 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 7.2 / 100, 0.18 / 100 respectively. and 0.09 / 100

Three 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 development of the appearance of the dispersions is monitored.

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

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 obtained by adding 50 ml of the formulation FR to 10 ml of the formulation 11 of pH 4 above, which corresponds to 196 mg of active material (A) per liter of water in the machine

* a softening formulation FRII1 obtained by adding 50 ml of the formulation FR to 10 ml of the formulation 111 of pH 4 above, which corresponds to 190 mg of active material (A) per liter of water in the machine.

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; 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 city water at 23 ° C. added with the 60 ml of FRI1 formulation, 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 at 23 ° C. added with the 60 ml of FRII1 formulation, 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 creasing 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 being a normalization factor, equal to 1 / [(σl-σ3) / σl]

A value of:

- 0% corresponds to zero profit - 100% corresponds to a flat surface

The results of the crease test are as follows

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

An emulsion is used comprising 30% by weight of silicone with hindered piperidinyl functions (Rhodorsil® 21645 from Rhodia) and 3% of nonionic surfactant of ethoxylated fatty alcohol type (Symperonic A7). 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.

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

Formulation II2.

An emulsion is used comprising 30% by weight of silicone with hindered piperidinyl functions (Rhodorsil® 21645 from Rhodia) and 3% of nonionic surfactant of ethoxylated fatty alcohol type (Symperonic A7).

A 1% by weight solution of xanthan gum (Rhodopol® T from Rhodia) with a molar mass by weight of 4,000,000 g / mol is prepared in water of pH 4.5.

20 ml of the dispersion are poured under mechanical stirring into 1 ml of the xanthan gum solution. The final dispersion has a pH of 4.5.

0.1 g of sodium chloride is 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 3 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:

* 7ml of a commercial FR softening formulation containing only cationic surfactants (15% dry matter).

* a FRI2 softening formulation obtained by adding 0.3 ml of formulation 12 above to 7 ml of the FR formulation,

* a FRII2 softening formulation obtained by adding 0.3ml of formulation II2 above to 7ml of the FR formulation.

(a) Prewash / rinse / dry:

6 test tubes measuring 10 x 10 cm, in flat woven cotton, are prewashed in a TERGOTOMETER for 20 minutes at 23 ° C, using the above washing formula; the water used has a hardness of 30 ° HT (diluted Contrexeville® 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 additive either 7ml of commercial FR rinse formula or 7.3ml of rinse formulas FRI2 or FRII2. The fabric squares are then wrung out, then dried on clothes lines.

(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 / LUCI 100.

The effectiveness of the polymer tested as an anti-fouling agent is assessed by the% of stain removal calculated by the formula

E in% = 100 x (R3-R2) / (R1-R2) R1 representing the reflectance before washing of the soiled fabric (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:

A significant improvement in the removal of “drain oil” type stains is observed, when xanthan gum is used as a 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)

- presenting themselves:

. 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 (MAV), • presents 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) can be wholly or partly replaced by a nonionic surfactant when the material constituting the active ingredient

(A) is inherently cationic or inherently potentially cationic in the medium (MAV)

• remains insoluble 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 material constituting the active material (A) is an oil or a fusible solid.

4) Formulation according to any one of Claims 1) to 3), characterized in that the particles of active material (A) have an average diameter ranging from 10 nm to 200 μm, preferably from 10 nm to 5 μm and more preferably from 10 nm to 2000nm.

5) Formulation according to any one of claims 1) to 4), characterized in that the active material (A) is made of a material having lubricating properties vis-à-vis articles of textile fibers.

6) Formulation according to any one of claims 1) to 5), characterized in that, the material constituting the active material (A) is a polyorganosiloxane chosen from

• nonionic polyorganosiloxanes • polyorganosiloxanes having at least one cationic or potentially cationic function in the medium (MAV)

• amphoteric polyorganosiloxanes having at least one cationic or potentially cationic function in the medium (MAV) and at least one neutral function in the medium (MAV) and potentially anionic in the rinsing medium (MR)

• polyorganosiloxanes having at least one neutral function in the medium (AVM) and potentially anionic in the rinsing medium (MR).

7) Formulation according to any one of claims 1) to 6), characterized in that the material constituting the active material (A) is an α-ω bis (hydroxy) polydimethylsiloxane, an α-ω bis (trimethyl) polydimethylsiloxane , a polymethylphenylsiloxane, a cyclic polydimethylsiloxane, preferably in the form of an oil.

8) Formulation according to any one of claims 1) to 6), characterized in that the material constituting the active material (A) is an amino polyorganosiloxane. 9) Formulation according to claim 8), characterized in that the amino polyorganosiloxane is a polyorganosiloxane having hindered piperidinyl groups.

10) Formulation according to any one of claims 6) to 9), characterized in that said polyorganosiloxane is linear.

11) Formulation according to any one of claims 1) to 5), characterized in that the active material (A) is made of a material chosen from - mono-, di- or triglycerides of Cι-C carboxylic acid ₃₀ or mixtures thereof, such as vegetable oils

- sucroesters, sucroglycerides

- the alcoolesters in Cι-C ₃₀ carboxylic acids Cι-C ₃₀ dicarboxylic or Ca-C ₃ o, - ethylene or propylene glycol monoesters or diesters of carboxylic acids, C1-C30

- C ₄ -C ₂ alkyl ether propylene glycols

- di C ₈ -C ₃ o alkyl ethers

- organic waxes comprising alkyl chains containing from 4 to 40 carbon atoms.

12) Formulation according to any one of claims 1) to 11), 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.

13) Formulation according to any one of claims 1) to 12), characterized in that the cationic charges, generated by the possible cationic or potentially cationic units of the material constituting the active material (A) and by the surfactant (s) cationic, on the surface of the material constituting the active active ingredient (A) dispersed in the medium (AVM), are such that the zeta potential of said polymer or copolymer dispersed in (AVM) is from 0 to +50 mV, from preferably from +10 to +40 mV.

14) Formulation according to any one of claims 1) to 13), characterized in that the dispersion medium (MAV) of the active material (A) is water or a hydroalcoholic polar medium. 15) Formulation according to claim 14), characterized in that the alcohol or alcohols present in the hydroalcoholic polar medium represent up to 70% of the volume of the medium (MAV).

16) Formulation according to any one of claims 1) to 15), characterized in that the polymer constituting the vector agent (V) is any polymer which is soluble or dispersible in 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).

17) Formulation according to claim 16), characterized in that the carrier polymer (V) further comprises at least one cationic or potentially cationic unit (HC) in the medium (MAV) and / or at least one non-ionic hydrophilic unit or hydrophobic

18) Formulation according to any one of claims 1) to 17), 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.

19) Formulation according to any one of claims 1) to 18), characterized in that the relative amounts of carrier agent polymer (V), surfactant (TAC) and of material 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).

20) Formulation according to claim 19), characterized in that the number of anionic charges developed in the rinsing medium (MR) by the carrier vector 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). 21) Formulation according to any one of claims 1) to 20), 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.

22) Formulation according to any one of claims 1) to 21), 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

23) Formulation according to any one of claims 1) to 22), characterized in that the polymer constituting the vector agent (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 monoethylenically unsaturated α-β hydrophilic monomer (HC) in the medium (MAV)

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

24) Formulation according to any one of claims 1) to 23), 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.

25) Formulation according to any one of claims 1) to 24), 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 ₄ -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 (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

26) Formulation according to any one of claims 1) to 21), 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.

27) Formulation according to claim 26), characterized in that said potentially anionic native polysaccharide is a branched polysaccharide formed

• a main chain comprising similar or different anhydrohexose units

28) Formulation according to claim 26 or 27), characterized in that said potentially anionic native polysaccharide is a xanthan gum, a succinoglycan, a rhamsan, a gellan gum, welan. 29) Formulation according to any one of claims 26) to 28), characterized in that said potentially anionic native polysaccharide has a molar mass by weight of 2000 to 5,000,000, preferably from 10,000 to 5,000,000, very particularly of 10,000 to 4,000,000 g / mol.

30) Formulation according to any one of claims 1) to 21), 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 possibly by one or more group (s) carrying (s) 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 zero or cationic overall charge.

31) Formulation according to claim 30), characterized in that said substituted or modified polysaccharide additionally contains at least one nonionic substituent or modifying group.

32) Formulation according to claim 30) or 31), 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 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, 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.

33) Formulation according to any one of claims 29 to 32), characterized in that said substituted or modified polysaccharide has a molar mass by weight of 2000 to 5,000,000, preferably from 10,000 to 5,000,000 g / mol.

34) Formulation according to any one of claims 29 to 33), characterized in that the native skeleton of said substituted or modified polysaccharide is a galactomannan.

35) Formulation according to any one of claims 29 to 34), characterized in that the native skeleton of said substituted or modified polysaccharide is chosen from

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

- the carboxymethyl hydroxypropyltrimethylammonium chloride gaiactomannans, in particular the carboxymethyl hydroxypropyltrimethylammonium guars, - the carboxymethyl hydroxypropyl hydroxypropyltrimethylammonium chloride gaiactomannanes, in particular the carboxymethyl hydroxypropyl hydroxypropyltrimethylammonium guars.

36) Formulation according to any one of claims 1 to 35), 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).

37) Formulation according to any one of claims 1 to 36), characterized in that it is in the form of an aqueous or hydroalcoholic dispersion comprising per 100 parts of its weight:

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

38) Formulation according to any one of claims 1 to 37), 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, dyes, perfumes, foam limiters, enzymes, bleaching agents.

39) Process for treating articles made of textile fibers, by bringing them into contact, during a rinsing operation in an aqueous or hydroalcoholic medium, with said rinsing formulation (F) forming the subject of any of the claims 1) to 38), and recovery of said rinsed articles.

40) Method for improving the properties of anti-creasing and / or of ironing aid and / or of anti-soiling and / or of abrasion resistance of articles made of textile fibers, 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 38), and in recovering said rinsed articles.

41) 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 medium (MR) , formulation (F) comprising at least one active material (A) in at least one organic or organosilicon material, liquid or solid, in particulate form, and 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) or in solid form obtained by drying of said dispersion, the nature of the active material ( A) and aqueous or hydroalcoholic medium

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

• is insoluble in the medium (AVM)

• has 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 material constituting the active material (A) is intrinsically cationic or intrinsically potentially cationic in the medium (MAV)

• remains insoluble in the rinsing medium (MR); at least one organic polymer,

42) Method for improving the deposition of an active material (A) in at least one organic or organosilicon material, liquid or solid, in particulate form, on the surface of articles of textile fibers (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

(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); by adding to said formulation (F) a carrier agent (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 (MAV) a global ionic charge zero or cation 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).

43) Processes according to any one of Claims 40), 41) or 43), or use according to Claim 42), characterized in that the quantity of formulation used, expressed as dry matter, is 0.001 to 5g / l, preferably 0.05 to 2g / l in the rinsing bath.