EP1326952B1 - Anionic polysaccharide composition for textile care - Google Patents

Abstract

The invention concerns a composition for cotton textile care in particular, comprising an anionic polysaccharide (in particular anionic polygalactomannan) having a mole weight higher than 250000. The composition can be a solid or liquid detergent formulation, a liquid rinsing and/or softening formulation, a drying additive contacted with wet textile in a dry textile, an aqueous ironing formulation, a prespotting washing additive deposited on the textile before a washing operation.

Description

The subject of the present invention is a composition comprising an anionic polysaccharide for the care of articles made of textile fibers ("textile care"), especially made from cotton, colored in particular.

Care is particularly concerned with textile fiber articles, in particular textiles, the protection of the latter against physical or chemical deterioration phenomena, in particular the protection of the colors of the colored articles, and / or the contribution to those benefits such as softening and / or anti-creasing properties.

Cleaning the machine laundry leads to physical and chemical degradation of the fibers and especially cotton fibers. The alkalinity delivered by the detergents as well as certain specific compounds such as the oxidizing substances (perborate, percarbonate) or certain enzymes can be at the origin of the chemical degradation of the cotton fibers. But it is usually the conjunction of chemical and mechanical actions that leads to fiber degradation. The mechanical action is produced during washing, rinsing, spinning or drying, when this takes place in a tumble dryer. This degradation of the fibers leads to the formation of fibrils on the surface of the textile which finally gives a loss of brightness of the colored textiles. This degradation also induces a decrease in the resistance of the textile which has the extreme can lead to tearing of the tissues. This degradation of textiles can be evaluated quantitatively either by a loss of colors of colored textiles or by a decrease in the breaking energy of the textile. It is usually necessary to carry out 10 to 20 cumulative machine washes to perceive this type of degradation.
Cleaning the washing machine which systematically involves a wringing operation also leads to a crumpled cloth which is accentuated during drying, in particular by the formation of inter-fiber hydrogen bonds. An ironing operation is therefore necessary to obtain a presentable appearance of the laundry.
In order to reduce fiber degradation during washing or rinsing, suppliers of chemicals or detergents have made changes to detergent formulas or the use of certain specific additives.
In particular, detergents which do not comprise an oxidizing system, but which have diminished cleaning capacities, may be mentioned in particular.
Silicone compounds have also been used and in particular amino silicones ( US Patent 4,585,563 ; WO 92/07927 ; WO 98/39401 ).

In addition, the document US 5612475 discloses fiber treatment compositions comprising a carboxymethyl guar. The treated fibers are not textiles, they are not assembled by weaving, knitting or other form constituting linen. Such compositions are not detergent formulations, rinse and / or softening formulations for laundry, drying additives, or prespotters, and are clearly not suitable for these uses.

In addition, the document EP290740 discloses textile sizing compositions for forming a relatively thick layer on textile materials. We often talk about textile finishes. Such compositions are not detergent formulations, rinse and / or softening formulations for laundry, drying additives, or prespotters, and are clearly not suitable for these uses.

In addition, the document EP072971 discloses agglomerates of zeolites comprising a carboxymethyl guar. D3 gives little training on the use of these agglomerates, except the need for zeolites for washing machine compositions. D3 does not mention washing clothes (it could be washing dishes - builder like zeolites are used in dishwasher products). This document does not disclose compositions which are detergent formulations, rinse and / or fabric softener formulations, drying additives, or prespotters.

In addition, the document US 5405414 discloses textile dyeing compositions comprising a carboxymethyl guar. Such compositions are not detergent formulations, rinse and / or softening formulations for laundry, drying additives, or prespotters, and are clearly not suitable for these uses.

The Applicant has found that the use, in compositions for the treatment of textile articles especially cotton-based, colored in particular, certain anionic polysaccharides of high molecular mass soluble in the conditions of use ("working conditions" ) in aqueous or wet medium of said compositions, prevented the degradation of these articles, used to protect the colors and / or provided them with anti-crease and / or softening properties.
Such compositions may in particular be compositions for washing and / or rinsing and / or softening the laundry, for staining the laundry before washing ("prespotting"), for drying wet clothes in a tumble dryer or for ironing clothes.

• * d'une chaîne principale comprenant des unités anhydrohexoses semblables ou différentes
• * et de ramifications comprenant au moins une unité anhydropentose et/ou anhydrohexose neutre ou anionique

les unités anhydrohexoses et/ou anhydropentoses dudit polysaccharide anionique étant substituées ou modifiées par au moins un groupe anionique ou anionisable au pH d'utilisation de ladite composition,
le degré de substitution ou de modification DSi des unités anhydrohexoses et/ou anhydropentoses par ledit ou lesdits groupes anioniques ou anionisables allant de 0,1 à moins de 3, de préférence de 0,2 à 2,5.A first subject of the invention consists of a composition for the care of articles of textile fibers ("fabric care"), characterized in that it comprises at least one anionic polysaccharide of molar mass by weight greater than 250,000, preferably greater than 500 000, whose native skeleton is a polysaccharide formed

• * a main chain comprising similar or different anhydrohexose units
• * and branches comprising at least one anhydropentose unit and / or anhydrohexose neutral or anionic

the anhydrohexose and / or anhydropentose units of said anionic polysaccharide being substituted or modified by at least one anionic or anionizable group at the pH of use of said composition,
the degree of substitution or modification DSi of the anhydrohexose and / or anhydropentose units by said anionic or anionizable group or groups ranging from 0.1 to less than 3, preferably from 0.2 to 2.5.

The molar mass by weight of said anionic polysaccharides may be up to 2,000,000.
The molar mass by weight Mw of said anionic polysaccharides can be measured by size exclusion chromatography. The measurement is carried out in water at pH 9-10 containing 0.1 M LiCl and 2/10000 N ₃ Na.
The molar mass by weight Mw is established in 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 the said anionic or anionizable group or groups, per anhydrohexose unit and / or anhydropentose unit.

Said ionic or ionizable groups are bonded to the carbon atoms of the sugar backbone either directly or via -O- bonds.

According to an alternative embodiment of the invention, said anionic polysaccharide may also have at least one nonionic group.

The said nonionic groups are bonded 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 reacted per anhydrohexose unit and / or anhydropentose.

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 anionic or anionizable 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.

• R est un atome d'hydrogène ou un radical alkyle contenant de 1 à 4 atomes de carbone,
• x est un nombre entier allant de 0 à 5,
• y est un nombre entier allant de 0 à 5,
• M représente un métal alcalin.

Among the anionic or anionizable groups, mention may be made of those containing one or more carboxylate, sulphonate, sulphate, phosphate or phosphonate functions.
In particular, those of formula

- [- CH ₂ -CH (R) -O] _x - (CH ₂ ) _y COOH

or

- [- CH ₂ -CH (R) -O] _x - (CH ₂ ) _y -COOM

or:

• R is a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms,
• x is an integer from 0 to 5,
• y is an integer ranging from 0 to 5,
• M represents an alkali metal.

Particularly exemplary carboxy groups --COO ^- Na ⁺ directly attached to a carbon atom of the sugar skeleton, carboxymethyl (salt of sodium) -CH ₂ -COO ^- Na ⁺ linked to a carbon atom of the sugar skeleton via an -O- bond.

• R est un atome d'hydrogène ou radical alkyle contenant de 1 à 4 atomes de carbone,
• x est un nombre entier allant de 0 à 5,
• R¹ représente :
  • un atome d'hydrogène
  • un radical alkyle contenant de 1 à 22 atomes de carbone éventuellement interrompu par un ou plusieurs hétéroatome oxygène et/ou azote, cycloalkyle, aryle, arylalkyle, contenant de 6 à 12 atomes de carbone,
  • un radical -(CH₂)_y-COOR²
  • un radical -(CH₂)_y-CN
  • un radical -(CH₂)_y-CONHR²
• R² représentant un radical alkyle, aryle ou arylalkyle contenant de 1 à 22 atomes de carbone, et
• y est un nombre entier allant de 0 à 5
• • -CO-NH-R¹
• R¹ ayant la définition donnée ci-dessus,

lié à un atome de carbone du squelette sucre par l'intermédiaire d'une liaison -O-.Among the nonionic groups, mention may be made of those of formula:

• - [- CH ₂ -CH (R) -O] _x -R ¹

or :

• R is a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms,
• x is an integer 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 heteroatom oxygen and / or nitrogen, cycloalkyl, aryl, arylalkyl, containing from 6 to 12 carbon atoms,
  • a radical - (CH ₂ ) _y -COOR ²
  • a radical - (CH ₂ ) _y -CN
  • a radical - (CH ₂ ) _y -CONHR ²
• R ² represents 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-R ¹
• R ¹ having the definition given above,

bound to a carbon atom of the sugar backbone via a -O- bond.

• . méthyle, éthyle, propyle, isopropyle, butyle, hexyle, octyle, dodécyle, octadécyle, phényle, benzyle, liés à un atome de carbone du squelette sucre par l'intermédiaire d'une liaison éther, ester, amide ou uréthane,
• . cyanoéthyle, hydroxyéthyle, hydroxypropyle, hydroxybutyle, liés à un atome de carbone du squelette sucre par l'intermédiaire d'une liaison -O-.

We can particularly mention the groups:

• . methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, dodecyl, octadecyl, phenyl, benzyl, bonded to a carbon atom of the sugar backbone via an ether, ester, amide or urethane bond,
• . cyanoethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, bonded to a carbon atom of the sugar backbone through a -O- bond.

The hexose units (similar or different) of the main backbone of the native skeleton can be D-glucose, D-or L-galactose, D-mannose, D- or L-fucose, L-rhamnose, etc.

The neutral or anionic pentose and / or hexose (similar or different) units of the native backbone branches may be D-xylose ..., L- or D-arabinose, D-glucose, D- or L-galactose, D-xylose units. -mannose, D- or L-fucose, L-rhamnose ..., D-glucuronic acid, D-galacturonic acid, D-mannuronic acid ...

As examples of the native skeleton, there may be mentioned galactomannans, galactoglucomannans, xyloglucans, xanthan gums, scleroglucannes, succinoglycans, rhamsans, welan gums, etc.

In a preferred manner, the native skeleton is a galactomannan. Galactomannans are macromolecules comprising a main chain of β (1-4) -linked D-mannopyranose units substituted with D-galactopyranose units in the α (1-6) position. Among these, there may be mentioned gums guar, carob, tara.

Most preferably, the native skeleton is a guar gum. Guar gums have a mannose / galactose ratio of 2.

The anionic polysaccharides according to the invention can be obtained in known manner.

These are mostly commercial products.

• les carboxyméthyle galactomannanes, en particulier les carboxyméthyle guars,
• les carboxyméthyle hydroxypropyle galactomannanes, en particulier les carboxyméthyle hydroxypropyle guars.

As examples of anionic polysaccharides according to the invention, mention may be made of:

• carboxymethyl galactomannans, in particular carboxymethyl guars,
• carboxymethyl hydroxypropyl galactomannans, in particular carboxymethyl hydroxypropyl guars.

A second object of the invention consists of a method for treating textile fiber articles, by treating them with a composition, in an aqueous or wet medium, comprising at least one anionic polysaccharide according to the invention.

A third object of the invention is the use, in a composition for the treatment of textile fiber articles in aqueous or wet medium of at least one anionic polysaccharide according to the invention, as a care agent for textile articles.

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

• * sous forme d'un solide (poudre, granulés, tablettes ...) ou d'une dispersion

ou d'une solution aqueuse concentrée, mis en contact avec les articles à traiter, après dilution dans l'eau ;

• * sous forme d'une dispersion ou d'une solution aqueuse concentrée préalablement déposée sur les articles secs à traiter avant dilution dans l'eau ;
• * sous forme d'une dispersion ou d'une solution aqueuse à déposer directement sur les articles secs à traiter sans dilution ou d'un support solide (bâton) comprenant ledit polysaccharide anionique, à appliquer directement sur les articles secs à traiter ;
• * sous forme d'un support solide insoluble comprenant ledit polysaccharide anionique mis en contact directement avec les articles à traiter à l'état humide.

Said composition may occur

• * in the form of a solid (powder, granules, tablets ...) or a dispersion

or a concentrated aqueous solution, brought into contact with the articles to be treated, after dilution in water;

• in the form of a dispersion or a concentrated aqueous solution previously deposited on the dry articles to be treated before dilution in water;
• in the form of a dispersion or an aqueous solution to be deposited directly on the dry articles to be treated without dilution or of a solid support (stick) comprising said anionic polysaccharide, to be applied directly to the dry articles to be treated;
• in the form of an insoluble solid support comprising said anionic polysaccharide placed in direct contact with the articles to be treated in the wet state.

• une formulation détergente solide ou liquide susceptible de former directement par dilution un bain lessiviel ;
• une formulation rinçante et/ou adoucissante liquide susceptible de former directement par dilution un bain de rinçage et/ou d'adoucissage ;
• un matériau solide, textile notamment, comprenant ledit polysaccharide anionique, destiné à être mis en contact avec les articles humides dans un sèche-linge (ledit matériau solide est appelé ci-après "additif de séchage") ;
• une formulation aqueuse de repassage ;
• un additif de lavage ("prespotter") destiné à être déposé sur les articles secs préalablement à une opération de lavage à l'aide d'une formulation détergente contenant ou ne contenant pas ledit polysaccharide anionique (ledit additif est appelé ci-après "additif de lavage").

Thus the composition of the invention can be:

• a solid or liquid detergent formulation capable of forming a washing bath directly by dilution;
• a liquid rinse and / or softening formulation capable of directly forming a rinsing and / or softening bath by dilution;
• a solid material, in particular a textile, comprising said anionic polysaccharide, intended to be brought into contact with the wet articles in a tumble dryer (said solid material is hereinafter referred to as "drying additive");
• an aqueous ironing formulation;
• a washing additive ("prespotter") intended to be deposited on dry articles prior to a washing operation using a detergent formulation containing or not containing said anionic polysaccharide (said additive is hereinafter referred to as "additive washing ").

The composition of the invention is particularly well suited to the care of linen, especially cotton-based, in particular containing at least 35% cotton. It is particularly suitable for the care of colored linen.

The anionic polysaccharides according to the invention are soluble under the conditions of use ("working conditions") in an aqueous or wet medium of said composition.

Said anionic polysaccharides are considered as soluble when more than 50%, preferably more than 70% of their weight are soluble in the aqueous or wet medium of use of the composition of the invention, that is to say in particular in the temperature and pH conditions of said medium.

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

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

• a detergent formulation, the pH of the detergent bath is generally of the order of 7 to 11, preferably 8 to 10.5;
• of a rinsing and / or softening formulation, the pH of the rinsing and / or softening bath is generally of the order of 2 to 8;
• of a drying additive, the pH to be considered is that of the residual water, which may be of the order of 2 to 9;
• of an aqueous ironing formulation, the pH of said formulation is generally of the order of 5 to 9;
• of a washing additive ("prespotter"), the pH to be considered is that of the pH of the detergent bath of the following washing operation, namely of the order 7 to 11, preferably 8 to 10.5.

The amount of anionic polysaccharide present in the care composition according to the invention may range from 0.05 to 10% by dry weight of said composition in dry state, and this according to the desired application.

Thus, said anionic polysaccharide (PA) can be implemented as follows: % of (PA) (in sec) in a care composition according to the invention used as 0.05 - 5
preferably 0.1 - 3 detergent formulation 0.05-3
preferably 0.1-2 rinse and / or softening formulation 0.05 - 10 drying additive 0.05-10
preferably 0.1-5 ironing formulation 0.05-10
preferably 0.1-5 washing additive

Other constituents may be present, beside the anionic polysaccharide, in the care composition according to the invention. Said composition may contain at least one surfactant and / or a detergent and / or rinsing and / or softening additive for textile fiber articles and / or a solid support (textile in particular) of said anionic polysaccharide. The nature of these constituents is a function of the desired use of said composition.

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

Thus, when it comes to a detergent formulation, for washing laundry, it generally comprises:

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

The detergent formulation may comprise surfactants in an amount corresponding to about 3 to 40% by weight, based on the detergent formulation, surfactants such as

Anionic surfactants

• . alkyl ester sulphonates of formula R-CH (SO ₃ M) -COOR ', where R is an alkyl radical C _8-20, preferably C ₁₀ -C _16, R' an alkyl radical in C ₁ -C _6, preferably C ₁ -C ₃ and M an alkali metal cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or an alkanolamine derivative ( monoethanolamine, diethanolamine, triethanolamine ...). Mention may in particular be made of methyl ester sulphonates whose R radical is C ₁₄ -C ₁₆ ;
• . alkyl sulphates of formula ROSO ₃ M, in which R represents a C ₅ -C ₂₄ , preferably C ₁₀ -C ₁₈ , alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average from 0.5 to 30 units, preferably from 0.5 to 10 EO and / or OP units;
• . sulfated alkylamides of formula RCONHR'OSO ₃ M where R represents a C ₂ -C ₂₂ , preferably C ₆ -C ₂₀ , alkyl radical, R 'represents a C ₂ -C ₃ alkyl radical, M represents an atom of hydrogen or a cation of the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average from 0.5 to 60 EO and / or OP units;
• . saturated or unsaturated C ₈ -C ₂₄ , preferably C ₁₄ -C ₂₀ fatty acid salts, C ₉ -C ₂₀ alkylbenzenesulfonates, primary or secondary C ₈ -C ₂₂ alkylsulfonates, alkylglycerol sulphonates, the sulfonated polycarboxylic acids described in GB-A-1,082,179 paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, sulfosuccinate monoesters or diesters, N-acyl sarcosinates, alkylglycoside sulfates, polyethoxycarboxylates; the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium, etc.) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine); ...);

Nonionic surfactants

• . polyoxyalkylenated alkylphenols (polyoxyethylenated, polyoxypropylenated, polyoxybutylenated) whose alkyl substituent is C ₆ -C ₁₂ and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the TRITON X-45, X-114, X-100 or X-102 sold by Rohm & Haas Cy. ;
• . glucosamide, glucamide, glycerolamide;
• . polyoxyalkylenated C ₈ -C ₂₂ aliphatic alcohols containing from 1 to 25 oxyalkylene units (oxyethylene, oxypropylene); by way of example, mention may be made of TERGITOL 15-S-9, TERGITOL 24-L-6 NMW marketed by Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 marketed by Shell Chemical Cy., KYRO EOB marketed by The Procter & Gamble Cy. ;
• . the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with propylene glycol, such as PLURONIC marketed by BASF;
• . the products resulting from the condensation of ethylene oxide, the compound resulting from the condensation of propylene oxide with ethylenediamine, such as TETRONIC marketed by BASF;
• . amine oxides such as C ₁₀ -C ₁₈ alkyl dimethylamine oxides, C ₈ -C ₂₂ alkoxy ethyl dihydroxy ethylamine oxides;
• . the alkylpolyglycosides described in US-A-4,565,647 ;
• . C ₈ -C ₂₀ fatty acid amides;
• . ethoxylated fatty acids;
• . ethoxylated fatty amides;
• . ethoxylated amines.

Amphoteric and zwitterionic surfactants

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

Builder builders improving the properties of surfactants can be used in amounts of about 5-50%, preferably about 5-30% by weight for liquid detergent formulations or about 10% by weight. -80%, preferably 15-50% by weight for powder detergent formulations, detergency builders such as:

Inorganic detergency builders

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

Organic detergency additives

• . water-soluble polyphosphonates (ethane 1-hydroxy-1,1-diphosphonates, methylene diphosphonate salts ...);
• . water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as:
  • polycarboxylate ethers (oxydisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts);
  • hydroxypolycarboxylate ethers;
  • citric acid and its salts, mellitic acid, succinic acid and their salts;
  • polyacetic acid salts (ethylenediaminetetraacetates, nitrilotriacetates, N- (2-hydroxyethyl) -nitrilodiacetates);
  • C ₅ -C ₂₀ alkyl succinic acids and their salts (2-dodecenylsuccinates, lauryl succinates);
  • polyacetal carboxylic esters;
  • polyaspartic acid, polyglutamic acid and their salts;
  • polyimides derived from the polycondensation of aspartic acid and / or glutamic acid;
  • polycarboxymethyl derivatives of glutamic acid or other amino acids.

The detergent formulation may further comprise at least one oxygen-releasing bleaching agent comprising a percompound, preferably a persalt.

Said bleaching agent may be present in an amount corresponding to about 1 to 30%, preferably 4 to 20% by weight, based on the detergent formulation.

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

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

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

Mention may also be made of non-oxygenated bleaches acting by photoactivation in the presence of oxygen, agents such as aluminum phthalocyanines and / or sulphonated zinc.

The detergent formulation may further comprise soil release, anti-redeposition, chelant, dispersant, fluorescence, suds suppressor, softener, enzyme and other miscellaneous additives.

Anti-fouling agents

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

• les dérivés cellulosiques tels que les hydroxyéthers de cellulose, la méthylcellulose, l'éthylcellulose, l'hydroxypropyl méthylcellulose, l'hydroxybutyl méthylcellulose ;
• les polyvinylesters greffés sur des troncs polyalkylènes tels que les polyvinylacétates greffés sur des troncs polyoxyéthylènes ( EP-A-219 048 ) ;
• les alcools polyvinyliques ;
• les copolymères polyesters à base de motifs éthylène téréphtalate et/ou propylène téréphtalate et polyoxyéthylène téréphtalate, avec un rapport molaire (nombre de motifs) éthylène téréphtalate et/ou propylène téréphtalate/(nombre de motifs) polyoxyéthylène téréphtalate de l'ordre de 1/10 à 10/1, de préférence de l'ordre de 1/1 à 9/1, les polyoxyéthylène téréphtalates présentant des unités polyoxyéthylène ayant un poids moléculaire de l'ordre de 300 à 5 000, de préférence de l'ordre de 600 à 5 000 ( US-A-3 959 230 , US-A-3 893 929 , US-A-4 116 896 , US-A-4 702 857 , US-A-4 770 666 ) ;
• les oligomères polyesters sulfonés obtenus par sulfonation d'un oligomère dérivé de l'alcool allylique éthoxylé, du diméthyltéréphtalate et du 1,2-propylènediol, présentant de 1 à 4 groupes sulfonés ( US-A-4 968 451 ) ;
• les copolymères polyesters à base de motifs propylène téréphtalate et polyoxyéthylène téréphtalate et terminés par des motifs éthyles, méthyles ( US-A-4 711 730 ) ou des oligomères polyesters terminés par des groupes alkylpolyéthoxy ( US-A-4 702 857 ) ou des groupes anioniques sulfopolyéthoxy ( US-A-4 721 580 ), sulfoaroyles ( US-A-4 877 896 ) ;
• les copolymères polyesters sulfonés dérivés d'acide, anhydride ou diester téréphtalique, isophtalique et sulfoisophtalique et d'un diol ( FR-A-2 720 399 ).

Mention may be made more particularly of agents such as:

• cellulosic derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose;
• polyvinyl esters grafted on polyalkylene trunks such as polyvinyl acetates grafted onto polyoxyethylene trunks ( EP-A-219 048 );
• polyvinyl alcohols;
• polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, with a molar ratio (number of units) of ethylene terephthalate and / or propylene terephthalate (number of units) polyoxyethylene terephthalate of the order of 1/10 at 10/1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 to 5000, preferably of the order of 600 to 5,000 ( US-A-3,959,230 , US-A-3 893 929 , US-A-4,116,896 , US-A-4,702,857 , US-A-4,770,666 );
• the sulphonated polyester oligomers obtained by sulphonation of an oligomer derived from ethoxylated allyl alcohol, dimethylterephthalate and 1,2-propylene diol, having from 1 to 4 sulphonated groups ( US-A-4,968,451 );
• polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl, methyl units ( US-A-4,711,730 ) or polyester oligomers terminated by alkylpolyethoxy groups ( US-A-4,702,857 ) or sulfopolyethoxy anionic groups ( US-A-4,721,580 ), sulfoaroyles ( US-A-4,877,896 );
• sulfonated polyester copolymers derived from terephthalic, isophthalic and sulfoisophthalic acid, anhydride or diester and a diol ( FR-A-2,720,399 ).

Anti-redeposition agents,

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

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

Mention may be made in particular of agents such as:

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

Chelating agents

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

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

We can mention among others:

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

Polymeric dispersing agents

• . les sels hydrosolubles d'acides polycarboxyliques de masse moléculaire de l'ordre de 2 000 à 100 000, obtenus par polymérisation ou copolymérisation d'acides carboxyliques éthyléniquement insaturés tels que acide acrylique, acide ou anhydride maléique, acide fumarique, acide itaconique, acide aconitique, acide mésaconique, acide citraconique, acide méthylènemalonique, et tout particulièrement les polyacrylates de masse moléculaire de l'ordre de 2 000 à 10 000 ( US-A-3 308 067 ), les copolymères d'acide arylique et d'anhydride maléique de masse moléculaire de l'ordre de 5 000 à 75 000 ( EP-A-66 915 ),
• . les polyéthylèneglycols de masse moléculaire de l'ordre de 1 000 à 50 000.

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

• . water-soluble salts of polycarboxylic acids with a molecular mass of the order of 2,000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid; , mesaconic acid, citraconic acid, methylenemalonic acid, and most particularly the polyacrylates of molecular weight of the order of 2,000 to 10,000 ( US-A-3,308,067 ), copolymers aryl and maleic anhydride with a molecular mass in the range of 5,000 to 75,000 ( EP-A-66 915 )
• . polyethylene glycols with a molecular weight of the order of 1,000 to 50,000.

Fluorescence agents (brighteners),

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

Suds suppressing agents,

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

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

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

Softening agents

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

enzymes

• les protéases, amylases, lipases, cellulases, peroxydases ( US-A-3 553 139 , US-A-4 101 457 , US-A-4 507 219 , US-A-4 261 868 ).

They may be present in an amount of up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent formulation, enzymes such as:

• proteases, amylases, lipases, cellulases, peroxidases ( US-A-3,553,139 , US-A-4,101,457 , US-A-4,507,219 , US-A-4,261,868 ).

Other additives

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

We can mention among others:

• buffering agents,
• perfumes,
• pigments.

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

A second embodiment of the care composition of the invention consists of an aqueous liquid formulation for rinsing and / or softening the laundry.

This can be carried out in a proportion of from 0.2 to 10 g / l, preferably from 2 to 10 g / l.

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

In addition to the anionic polysaccharide, other components of the type may be present

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

A third embodiment of the care composition of the invention consists of a laundry drying additive in a suitable drying machine.

Said additive comprises a flexible solid support constituted for example by a woven or non-woven textile strip, a cellulose sheet, impregnated with said anionic polysaccharide; said additive is introduced on drying in the wet laundry to be dried at a temperature of the order of 50 to 80 ° C for 10 to 60 minutes.

Said additive may further comprise cationic softening agents (up to 99%) and anti-color transfer agents (up to 80%) such as those mentioned above.

A fourth embodiment of the care composition of the invention consists of an ironing formulation which can be sprayed directly onto the dry cloth before the ironing operation. Said formulation may further contain silicone-based polymers (from 0.2 to 5%), nonionic surfactants (from 0.5 to 5%) or anionic surfactants (from 0.5 to 5%), perfumes (0.1 to 3%), cellulose derivatives (0.1 to 3%) such as starch; spraying said formulation on the laundry makes it easier to iron and to limit the creasing of the laundry when worn.

A fifth embodiment of the care composition of the invention consists of a washing additive ("prespotter") in the form of an aqueous solution or dispersion or of a solid (stick). .

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

In addition to the anionic polysaccharide, other components of the type may be present.

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

The following examples are given for illustrative purposes.

The anionic polysaccharide used in the following examples is a carboxymethyl guar having a degree of substitution of 1.6 and a molar mass by weight of 1 400 000 determined as follows by size exclusion chromatography.

• Colonnes chromatographiques : 3 colonnes Shodex SB806HQ 30cm, 5 µm
• Injecteur-pompe : pompe JASCO
• Détecteur : Réfractomètre RI Waters 410 Sensibilité 8, diffusion de lumières MALLS Wyatt, Laser He 633nm
• Débit : 0.8 ml/mn.

The measurement is carried out in water at pH 9-10 containing 0.1 M LiCl and 2/10000 N ₃ Na. The features of the device are as follows:

• Chromatographic columns: 3 columns Shodex SB806HQ 30cm, 5μm
• Injector-pump: JASCO pump
• Detector: RI Waters refractometer 410 Sensitivity 8, Wyatt MALLS light scattering, Laser He 633nm
• Flow rate: 0.8 ml / min.

• C correspond à la concentration en polysaccharide
• M correspond à la masse moléculaire en poids
• n correspond à l'indice optique de la solution
• c correspond à la concentration en polysaccharide
• le rapport dn/dc est ici égal à 0,140

The injected solution (200 μl) contains about 0.5% by weight of anionic polysaccharide. The weight-average molecular weight is established directly without calibration using the extrapolated light scattering values at zero angle; these values are proportional to CxMx (dn / dc) ² .

• C is the polysaccharide concentration
• M is the molecular weight
• n corresponds to the optical index of the solution
• c is the polysaccharide concentration
• the ratio dn / dc is here equal to 0.140

Example 1 Detergent formulation

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

A washing operation is carried out in a laboratory apparatus Tergotometer well known in the art of detergent composition formulators. The device simulates the mechanical and thermal effects of American pulsator-type washing machines, but thanks to the presence of 6 washing pots, it allows for simultaneous series of tests with appreciable time saving.

Unwrapped cotton test pieces measuring 25 x 25 cm are cut.

The cotton test pieces are first ironed in order to have all the same level of creasing before washing.

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

Les éprouvettes sont ensuite froissées sous une presse de 3kg pendant 20 secondes, puis mises à sécher verticalement pendant une nuit.They are then washed with the aid of the above detergent formulation containing the anionic polysaccharide and rinsed once, under the following conditions:

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

The test specimens are then crumpled under a 3kg press for 20 seconds and then allowed to dry vertically overnight.

The same operation is carried out using the same detergent formulation but free of anionic polysaccharide.

A color digital photograph is then taken of the dry specimens, which is then transformed into 256 gray levels (gray scale from 0 to 255).

We count the number of pixels corresponding to each level of gray.

For each histogram obtained, the standard deviation σ of the distribution of the gray level is measured.
σ1 corresponds to the standard deviation obtained with the detergent formulation containing no anionic polysaccharide.
σ2 corresponds to the standard deviation obtained with the detergent formulation containing the anionic polysaccharide.
The performance value is given by the equation -Δσ = σ2-σ1
The performance values obtained are as follows: Formulation (AT) (B) (VS) -Δσ 3.5 4 4.5 These positive values of -Δσ are representative of an anti-crease property provided by the detergent formulation comprising the anionic polysaccharide according to the invention.

Example 2 Rinse / softening formulation

constituents % in weight Cationic surfactant: ditallowdimethylammonium chloride 5% Perfume 1% HCl to obtain a pH_ = 3 0.2% anionic polysaccharide (% dry) 2%

Example 3 MEASUREMENT OF COLOR PROTECTION PRINCIPLE

It consists in carrying out, under defined conditions, 10 washes of a sampling of several colored cotton fabrics. The color protection efficiency is tested in automated washing machine. The actual evaluation is done by a reflectance measurement. The tissues are examined before and after 10 washes. The color variation thus recorded (ΔE *) constitutes the loss of color on each type of tissue.

APPARATUS - REAGENTS

• * Automated washing machine AEG Lavamat 2050 Turbo:
  • Commercial washing machine with front window - washing cycles at 40 ° C - washing water volume: 13 liters
  • Saved program: 10 wash cycles
• * LUCI100 Reflectometer - Dr Lange:
  • This is a reflectance device used to measure tissue colors before and after washing.
• * 6 Dishcloths: ecru cotton referenced 402MBLI (provenance D. PORTHAULT SA)
• * 4 Towels (as ballast): Terry towel in white cotton curettes 500 g / m ² (provenance D. PORTHAULT SA)
• * Sampling of 5 different colored commercial fabrics
  • . pink woven cotton
  • . purple woven cotton
  • . blue woven cotton
  • . green woven cotton
  • . orange woven cotton

OPERATIVE MODE Washing conditions:

Washing temperature: 40 ° C Duration: about 67 minutes Number of wash: 10 Laundry load: 3 kg dry (4 towels + 6 tea towels + colored fabrics) Volume of the bath: 13 liters ± 1 liter Water hardness : about 23 ° TH french Concentration detergent formula: 5 ± 0.1g / l

Operating method : 5 steps

• . Mesure de couleur des éprouvettes de tissus neufs
• . Couture des éprouvettes de tissus colorés sur les torchons afin d'éviter l'effilochage au cours des lavages successifs
• . réalisation des 10 lavages sans séchage entre les cycles
• . séchage à l'air libre
• . mesure de couleurs sur les tissus lavés

Les couleurs sont mesurées sur réflectomètre LUCI100 :
Le système de mesure utilisé est le CIE-L* a* b* (DIN6174, CIE-LAB 1976).
Il se décompose comme suit :

• L* correspond au degré de blanc sur une échelle blanc - noir.
  L*=100 pour une éprouvette blanche
  L*=0_ pour une éprouvette noire
• a* situe la couleur dans une gamme allant du vert au rouge.
  a* ≥0 la couleur tire sur le rouge.
  a* ≤0 la couleur tire sur le vert
• b* situe la couleur dans lune gamme allant du jaune au bleu.
  b* ≥0 la couleur tire sur le jaune.
  b* ≤0 la couleur tire sur le bleu.

Chaque éprouvette de tissu est mesurée en 5 points différents (un au centre et un à chaque coin) et la moyenne des composantes L*, a* et b* est calculée.

• . Color measurement of new tissue specimens
• . Stitching test pieces of colored fabrics on the cloths to avoid fraying during successive washings
• . 10 washes without drying between cycles
• . Drying in the open air
• . color measurement on washed fabrics

The colors are measured on LUCI100 reflectometer:
The measuring system used is CIE- L * a * b * (DIN6174, CIE-LAB 1976).
It breaks down as follows:

• L * corresponds to the degree of white on a white-black scale.
  L * = 100 for a white test tube
  L * = 0_ for a black test tube
• a * places the color in a range from green to red.
  a * ≥0 the color is red.
  a * ≤0 the color draws on the green
• b * places the color in a range from yellow to blue.
  b * ≥0 the color draws yellow.
  b * ≤0 the color is blue.

Each tissue specimen is measured at 5 different points (one at the center and one at each corner) and the average of the L *, a * and b * components is calculated.

EXPLOITATION OF RESULTS :

$$\mathrm{\Delta a}*=\mathrm{a}{*}_{\mathrm{après\; lavage}}-\mathrm{a}{*}_{\mathrm{avant\; lavage}}$$

$$\mathrm{\Delta b}*=\mathrm{b}{*}_{\mathrm{après\; lavage}}-\mathrm{b}{*}_{\mathrm{avant\; lavage}}$$

La perte de couleur pour chaque tissu est alors donnée par l'expression suivante : $$\mathrm{\Delta }{E}^{*}=\sqrt{{\left(\mathrm{\Delta }{L}^{*}\right)}^2+{\left(\mathrm{\Delta }{a}^{*}\right)}^2+{\left(\mathrm{\Delta }{b}^{*}\right)}^2}$$

La performance du polysaccharide par rapport à la référence est mesurée comme la différence de ΔE* entre les formules sans et avec polysaccharide.
La perte de couleur cumulée est calculée comme la somme des pertes de couleurs des tissus colorés.
On prépare une formulation détergente (F) par addition de 1 partie de polysaccharide anionique à 100 parties de la composition (C) ci-dessous (exprimée en parties en poids) : lauryl alkyl benzène sulfonate de sodium 19.2 Nabion 15 de Rhodia (cogranulés de silicate de sodium et de carbonate de calcium) 48,6 carbonate de sodium 10,3 sulfate de sodium 13,5 Sokalan CP5 6,4 Phosphonate Dequest 2016 2 Cette formulation (F) et la composition sans polysaccharide anionique (C) sont testées comme ci-dessus décrit.The reflectometer is equipped with software that indirectly calculates the ΔE * from previously recorded data. This value corresponds to the color variation recorded on the fabric after washing and is expressed as follows: $$\mathrm{.DELTA.L}*=\mathrm{The}{*}_{\mathrm{after\; washing}}-\mathrm{The}{*}_{\mathrm{before\; washing}}$$

$$\mathrm{.delta.a}*=\mathrm{at}{*}_{\mathrm{after\; washing}}-\mathrm{at}{*}_{\mathrm{before\; washing}}$$

$$\mathrm{.DELTA.b}*=\mathrm{b}{*}_{\mathrm{after\; washing}}-\mathrm{b}{*}_{\mathrm{before\; washing}}$$

The loss of color for each tissue is then given by the following expression: $$\mathrm{\Delta }{E}^{*}=\sqrt{{\left(\mathrm{\Delta }{\mathrm{The}}^{*}\right)}^2+{\left(\mathrm{\Delta }{\mathrm{at}}^{*}\right)}^2+{\left(\mathrm{\Delta }{b}^{*}\right)}^2}$$

The performance of the polysaccharide relative to the reference is measured as the difference of ΔE * between the formulas without and with polysaccharide.
The cumulative loss of color is calculated as the sum of the color losses of the colored tissues.
A detergent formulation (F) is prepared by adding 1 part of anionic polysaccharide to 100 parts of the composition (C) below (expressed in parts by weight): sodium lauryl alkyl benzene sulfonate 19.2 Rhodia Nabion 15 (cogranules of sodium silicate and calcium carbonate) 48.6 sodium carbonate 10.3 sodium sulphate 13.5 Sokalan CP5 6.4 Phosphonate Dequest 2016 2 This formulation (F) and the composition without anionic polysaccharide (C) are tested as described above.

The results obtained are as follows: tissue (VS) (F) Performance pink 20.20 12.21 7.99 purple 21.84 15.79 6.05 blue 2.56 1.56 1.00 green 10.99 9.04 1.95 Orange 3.60 2.59 1.01 cumulative loss of color ΔE 59.19 41.19 18 These results show that the presence of anionic polysaccharide in the formulation (F) considerably improves the color protection.

Claims (23)

1. Process for caring for articles made of textile fibres, by treating said articles, in an aqueous or wet medium, with a composition, characterized in that said composition comprises at least one anionic polysaccharide with a weight-average molar mass of greater than 250 000 and preferably greater than 500 000, the native skeleton of which is a polysaccharide formed from

   * a main chain comprising identical or different anhydrohexose units, and

   * branches comprising at least one neutral or anionic anhydropentose and/or anhydrohexose unit
   the anhydrohexose and/or anhydropentose units of said anionic polysaccharide being substituted or modified with at least one anionic group or one group that may be anionized at the working pH of said composition,
   the degree of substitution or of modification DSi of the anhydrohexose and/or anhydropentose units with said anionic or anionizable group(s) ranging from 0.1 to less than 3 and preferably from 0.2 to 2.5,

   the articles made of textile fibres being fabric,
   the composition being:

   - a solid or liquid detergent formulation capable of directly forming a washing bath by dilution;

   - a liquid rinsing and/or softening formulation capable of directly forming a rinsing and/or softening bath by dilution; .

   - a solid material, especially a textile material, comprising said anionic polysaccharide, intended to be placed in contact with the wet articles in a tumble dryer;

   - an aqueous ironing formulation; or

   - a washing additive intended to be placed on the dry articles prior to a washing operation using a detergent formulation optionally containing said anionic polysaccharide.
2. Process according to Claim 1, characterized in that the ionic or ionizable groups are linked to the carbon atoms of the sugar skeleton either directly or via -O- bonds.
3. Process according to Claim 1 or 2, characterized in that the ionic or ionizable groups contain one or more carboxylate, sulfonate, sulfate, phosphate or phosphonate functions.
4. Process according to any one of Claims 1 to 3, characterized in that the ionic or ionizable groups have the formula
   
           - [-CH₂-CH(R)-O]_x-(CH₂)_y-COOH
   
   or
   
           - [-CH₂-CH(R)-O]_x-(CH₂)_y-COOM
   
   in which:

   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.
5. Process according to any one of Claims 1 to 4, characterized in that the ionic or ionizable groups are carboxyl groups -COO^-Na⁺ linked directly to a carbon atom of the sugar skeleton, carboxymethyl (sodium salt) -CH₂-COO^-Na⁺ linked to a carbon atom of the sugar skeleton via an -O-bond.
6. Process according to any one of Claims 1 to 5, characterized in that said anionic polysaccharide also contains at least one nonionic group.
7. Process according to Claim 6, characterized in that the nonionic groups are linked to the carbon atoms of the sugar skeleton either directly or via -O- bonds.
8. Process according to Claim 6 or 7, characterized in that the nonionic groups have the formula:
   
           • -[-CH₂-CH(R)-O]_x-R¹
   
   in which:

   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,

   R¹ represents:

   . a hydrogen atom

   an alkyl radical containing from 1 to 22 carbon atoms, optionally interrupted with one or more oxygen and/or nitrogen heteroatoms, cycloalkyl, aryl or arylalkyl, containing from 6 to 12 carbon atoms,

   . a radical - (CH₂)_y-COOR²

   - a radical -(CH₂)_y-CN

   - a radical -(CH₂)_y-CONHR₂

   R² 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
   
   

   R¹ having the definition given above,

   linked to a carbon atom of the sugar skeleton via an -O- bond.
9. Process according to any one of Claims 6 to 8, characterized in that said nonionic groups are the following 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 an -O- bond.
10. Process according to any one of Claims 1 to 9, characterized in that the hexose units (identical or different) of the main chain of the native skeleton are D-glucose, D- or L-galactose, D-mannose, D- or L-fucose or L-rhamnose units.
11. Process according to any one of Claims 1 to 10, characterized in that the neutral or anionic pentose and/or hexose units (identical or different) of the branches of the native skeleton are 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 or D-mannuronic acid units.
12. Process according to any one of Claims 1 to 11, characterized in that said native skeleton is a galactomannan, galactoglucomannan or xyloglucan, a xanthan gum, a scleroglucan, succinoglycans, a rhamsan or a welan gum.
13. Process according to Claim 12, characterized in that said native skeleton is a galactomannan.
14. Process according to Claim 13, characterized in that said anionic polysaccharide is a carboxymethyl galactomannan or a carboxymethyl hydroxypropyl galactomannan.
15. Process according to Claim 14, characterized in that said anionic polysaccharide is a carboxymethyl guar or a carboxymethyl hydroxypropyl guar.
16. Process according to any one of Claims 1 to 15, characterized in that said composition is in the form of

    * a solid, a dispersion or a concentrated aqueous solution, placed in contact with the fabric to be treated, after dilution in water;

    * a dispersion or a concentrated aqueous solution prespotted onto the dry fabric to be treated before dilution in water;

    * a dispersion or an aqueous solution to be placed directly onto the dry fabric to be treated without dilution or a solid support comprising said anionic polysaccharide, to be applied directly to the dry fabric to be treated;

    * or an insoluble solid support comprising said anionic polysaccharide placed directly in contact with the fabric to be treated, while wet.
17. Process according to any one of Claims 1 to 16, characterized in that said composition comprises from 0.05% to 10% of said anionic polysaccharide, expressed as dry matter.
18. Process according to any one of Claims 1 to 17, characterized in that said composition is

    - a solid or liquid detergent formulation comprising from 0.05% to 5% and preferably from 0.1% to 3% of said anionic polysaccharide, expressed as dry matter, capable of directly forming a washing bath by dilution;

    - a liquid rinsing and/or softening formulation comprising from 0.05% to 3% and preferably from 0.1% to 2% of said anionic polysaccharide, expressed as dry matter, capable of directly forming a rinsing and/or softening bath by dilution;

    - a solid material, especially a textile material, comprising from 0.05% to 10% and preferably from 0.1% to 5% of said anionic polysaccharide, expressed as dry matter, intended to be placed in contact with wet fabric in a tumble dryer;

    - an aqueous ironing formulation comprising from 0.05% to 10% and preferably from 0.1% to 5% of said anionic polysaccharide, expressed as dry matter;

    - a washing additive comprising from 0.05% to 10% and preferably from 0.1% to 5% of said anionic polysaccharide, expressed as dry matter, intended to be placed on the dry fabric prior to a washing operation using a detergent formulation optionally containing said anionic polysaccharide.
19. Process according to any one of Claims 1 to 18, characterized in that said composition contains at least one surfactant and/or one detergent additive and/or rinsing additive and/or softening additive for articles made of textile fibres and/or one solid support for said anionic polysaccharide.
20. Process according to one of Claims 1 to 19, characterized in that said articles contain at least 35% by weight of cotton, which is preferably coloured.
21. Use, in a composition for caring for articles made of textile fibres, of at least one anionic polysaccharide as defined in any one of Claims 1 to 15.
22. Use according to Claim 21, characterized in that said composition is

    - a solid or liquid detergent formulation comprising from 0.05% to 5% and preferably from 0.1% to 3% of said anionic polysaccharide, expressed as dry matter, capable of directly forming a washing bath by dilution;

    - a liquid rinsing and/or softening formulation comprising from 0.05% to 3% and preferably from 0.1% to 2% of said anionic polysaccharide, expressed as dry matter, capable of directly forming a rinsing and/or softening bath by dilution;

    - a solid material, especially a textile material, comprising from 0.05% to 10% and preferably from 0.1% to 5% of said anionic polysaccharide, expressed as dry matter, intended to be placed in contact with wet fabric in a tumble dryer;

    - an aqueous ironing formulation comprising from 0.05% to 10% and preferably from 0.1% to 5% of said anionic polysaccharide, expressed as dry matter;

    - a washing additive comprising from 0.05% to 10% and preferably from 0.1% to 5% of said anionic polysaccharide, expressed as dry matter, intended to be placed on the dry fabric prior to a washing operation using a detergent formulation optionally containing said anionic polysaccharide.
23. Use according to Claim 21 or 22, characterized in that said articles contain at least 35% by weight of cotton, which is preferably coloured.