EP1381661A1 - Composition containing cellulose sulphoacetate and surfactant - Google Patents

Composition containing cellulose sulphoacetate and surfactant

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Publication number
EP1381661A1
EP1381661A1 EP02727695A EP02727695A EP1381661A1 EP 1381661 A1 EP1381661 A1 EP 1381661A1 EP 02727695 A EP02727695 A EP 02727695A EP 02727695 A EP02727695 A EP 02727695A EP 1381661 A1 EP1381661 A1 EP 1381661A1
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EP
European Patent Office
Prior art keywords
surfactant
composition according
alkoxylated
derivatives
cellulose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02727695A
Other languages
German (de)
French (fr)
Inventor
Etienne Fleury
Ian Harrison
Gaelle Royer
Jean-Louis Doublier
Luc Saulnier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institut National de la Recherche Agronomique INRA
Rhodia Chimie SAS
Original Assignee
Institut National de la Recherche Agronomique INRA
Rhodia Chimie SAS
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Filing date
Publication date
Application filed by Institut National de la Recherche Agronomique INRA, Rhodia Chimie SAS filed Critical Institut National de la Recherche Agronomique INRA
Publication of EP1381661A1 publication Critical patent/EP1381661A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups

Definitions

  • the present invention relates to a composition which contains at least one cellulose sulfo-acetate and / or at least one of its derivatives, and at least one surfactant.
  • Surfactants are mainly used for their specific properties which make it possible to make dispersions, in particular emulsions or suspensions. Indeed, the surfactants are substances which lower the surface tension of the water or the medium in which they are dissolved. They can be fat-soluble or water-soluble. The rheology of formulations incorporating surfactants is of great interest to manufacturers. Indeed it is important to be able to incorporate surfactants as well in liquids, solids, as gels, according to the fields of applications.
  • the present invention relates in particular to gels of surfactants, which are very useful for manufacturers.
  • gel any type of system exhibiting a viscoelastic solid behavior over long periods of time (for example, beyond 100 s in a creep experiment or below 10 "2 Hz in harmonic regime). from a rheological point of view, this results in the presence of a plateau of G '(conservative module) and values of G' greater than G "(loss module), these two criteria being obtained at low frequency (in practice between 10 "3 and 10 ⁇ 2 Hz).
  • the known gelling methods for making surfactant gels notably use phase gelling.
  • the surfactants and electrolytes are mixed in previously optimized concentrations which cause a lamellar structure.
  • One of the problems which the invention proposes to solve is in particular to be able to provide gels which dissolve quickly in an aqueous medium.
  • Another problem which the invention proposes to solve is notably to be able to supply gels incorporating large quantities of surfactants, and which dissolve quickly in an aqueous medium.
  • the invention further aims to provide gels of surfactants which are more particularly thermoreversible and thixotropic gels.
  • thermotropy means the property of a gel losing its structure under the effect of a shearing force and, then, recovering all or part of its initial state after a certain period of rest.
  • Another object of the invention is to provide a simple and inexpensive process for the preparation of the compositions according to the invention.
  • the object of the present invention is mainly to meet all of these requirements in a single formulation.
  • the solution provided by the invention is to introduce the surfactants into an aqueous composition which contains at least one cellulose sulfoacetate and / or at least one of its derivatives.
  • the subject of the present invention is an aqueous composition which contains at least one cellulose sulfo-acetate and / or at least one of its derivatives, and at least one surfactant.
  • the invention also relates to the process for the preparation of said composition, in particular in the form of a gel having the desired properties.
  • Figure 1 (1/1 and 2/1) shows the change in the apparent viscosity of the sulfo-cellulose acetate (15 g / l) / surfactant / water mixtures as a function of the amount of surfactant
  • figure n ° 2 represents the mechanical spectrum of mixtures sulfo-cellulose acetate (15 g / l) / surfactant (0 and 10 times the CMC / water for SDS and C12E8
  • figure n ° 3 (1 / 3 and 2/3) represents the evolution of the module G 'at 1 rad / s of the sulfo-cellulose acetate (15 g / l) / surfactant mixtures as a function of the amount of surfactant
  • spectrum a tensio anionic active agents SDS and LABS
  • spectrum b nonionic surfact
  • This composition can be in the form of a gel.
  • the first essential constituent of the composition consists of at least one surfactant.
  • surfactants means any substance which lowers the surface tension of the water or of the medium in which it is dissolved.
  • the surfactants used according to the invention can be ionic or nonionic, and can be used alone or in mixtures.
  • alkyl esters sulfonates alkyl sulfates and their alkoxylated derivatives (in particular ethoxylated
  • alkylbenzenesulfonates in particular (OE) and / or (OP)
  • the salts of saturated or unsaturated fatty acids and / or their alkoxylated derivatives in particular (OE) and / or (OP)
  • alkylbenzenesulfonates primary or secondary alkylsulfonates, alkyl glycerol sulfonates, polycarboxylic acids sulfones, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, 'alkylglycosides, sophorolipids, such as those in particular in acid or lactone form and derivatives of 17-hydroxyoctadecenic acid.
  • ionic surfactants
  • CQ preferably in C1-C3 and M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine
  • RCONHROSO3M type where R represents a C2-C22 alkyl radical. preferably C ⁇ -C20.
  • ionic surfactants non-limiting mention may be made of cationic surfactants such as:
  • R1 and R2 are similar or different and represent an alkyl radical in CrC 20
  • R3 and R4 are similar or different and represent an alkyl radical in CC 20
  • N-methylimidazoline tallow methyl sulfate ester di-hardened tallow-diethyl ammonium chloride (Arquad 2HT ®); • dialkyldimethylammonium chloride; alkylbenzyldimethylammonium chloride;
  • ionic surfactants non-limiting mention may be made of amphoteric and zwitterionic surfactants such as:
  • alkyldimethylbetaines alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, condensation products of fatty acids and protein hydrolysates.
  • alkoxylated alkylphenols in particular (EO) and / or (OP)
  • aliphatic alcohols more particularly of C 8 -C 22
  • the products resulting from condensation ethylene oxide or propylene oxide with propylene glycol or ethylene glycol the products resulting from the condensation of ethylene oxide or propylene oxide with ethylene diamine
  • alkoxylated fatty acids especially (OE) and / or (OP)
  • alkoxylated fatty acid amides especially (OE) and / or (OP)
  • alkoxylated amines especially (OE) and / or (OP)
  • alkoxylated amidoamines in particular (OE) and / or (OP)
  • amine oxides alkoxylated terpene hydrocarbons (in particular (OE) and / or (OP)
  • alkylpolyglycosides amphiphilic polymers or oligomers .
  • nonionic surfactants non-limiting mention may be made of surfactants such as:
  • alkoxylated alkylphenols in particular (OE) and / or (OP)
  • the alkyl substituent of which is in particular C6-C-12 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made TRITON ® X-45, X-114, X-100 or X-102 sold by Rohm and Haas Cy. ;
  • aliphatic alcohols in particular C8-C22 and their alkoxylated derivatives (in particular (OE) and / or (OP)), containing from 1 to 25 units (OE) and / or (OP); by way of example, mention may be made of TERGITOL ® 15-S-9, TERGITOL ® 24-L-6 NMW sold 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. ; • 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;
  • amine oxides such as in particular alkyl oxides, more particularly C 10 ′′ C 18 dimethylamines, C8-C22 alkoxy oxides ethyl dihydroxy ethylamines; • the alkylpolyglycosides in particular described in US-A-4,565,647;
  • nonionic amphiphilic polymers or oligomers entering into the composition according to the invention are more particularly chosen, alone or in mixtures, among the polymers, oligomers or copolymers at least partially miscible in the aqueous composition.
  • amphiphilic polymers or oligomers polymers or oligomers having a surface tension in an aqueous medium.
  • amphiphilic polymers or oligomers can have a statistical distribution or a multiblock distribution.
  • amphiphilic polymers or oligomers By way of example of such amphiphilic polymers or oligomers, mention may in particular be made of polysaccharides having hydrophobic groups, in particular alkyl groups. Examples include guars.
  • amphiphilic polymers or oligomers can also be made of triblock polymers polyhydroxystearate - polyethylene glycol - polyhydroxystearate (products of Arlacel ® range of ICI are an example), the hydrophobic polyacrylamides.
  • non-ionic amphiphilic polymers more particularly alkoxylated (in particular (OE) and / or (OP)
  • OE alkoxylated
  • OP OP
  • the latter are more particularly chosen from polymers of which at least a part (at least 50% by weight) is miscible in water.
  • polymers of this type that may be mentioned, inter alia, are polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polymers.
  • the preferred surfactants according to the invention are nonionic surfactants and anionic surfactants.
  • the preferred surfactant is mono-n-dodecyl ether octaethylene glycol, alone or as a mixture.
  • preferred anionic surfactants mention may be made of alkylbenzenesulfonates, in particular C 9 -C 2 o-
  • the concentration of nonionic surfactant in the composition is less than or equal to 150 times the critical micellar concentration of the surfactant, preferably less than or equal to 100 times the critical micellar concentration of the surfactant .
  • the concentration of ionic surfactant it is less than or equal to 10 times the critical micellar concentration.
  • critical micellar concentration of a compound is understood to mean the concentration of this compound, in the medium, above which the compound micelles are formed in this medium.
  • CMC critical micellar concentration
  • the critical micellar concentration can be determined by interfacial tension.
  • the critical micelle concentration can also be determined by conductimetry.
  • the second essential constituent of the composition consists of at least one cellulose sulfo-acetate and / or at least one of its derivatives.
  • cellulose sulfo-acetate derivatives is meant cellulose sulfo-butyrate or cellulose sulfo-aceto-butyrate or cellulose sulfo-propionate or cellulose sulfo-aceto-propionate.
  • the concentration of cellulose sulfo-acetate and / or one of its derivatives can be between 0.01% and 20%, preferably between 0.1% and 5%, more particularly between 0.5% and 3% in weight of the composition.
  • the second aspect of the present invention relates to the process for preparing the composition.
  • This process consists in contacting an aqueous phase, at least one surfactant and the cellulose sulfoacetate or one of its derivatives (step (i)).
  • the preparation process is carried out by introducing, during step (i), into an aqueous phase the cellulose sulfoacetate or one of its derivatives, then at least one surfactant.
  • the preparation process can comprise a heat treatment step after step (i) where the temperature is between 30 ° C. and 140 ° C, advantageously between 60 ° C and 120 ° C.
  • the preparation process is implemented by introducing at least one surfactant into an aqueous phase containing the cellulose sulfoacetate or one of its derivatives having undergone this same heat treatment.
  • the duration of the heat treatment can vary from 1 minute to 6 hours, preferably from 15 minutes to 4 hours.
  • said solution obtained from step (i) can be cooled to a temperature between 0 ° C and room temperature (20 ° C - 25 ° C).
  • This step is to structure the gel, when it is desired to obtain a gel.
  • compositions in the fields of cosmetics, detergency, food, paper, agrochemicals, pharmaceuticals, dyes, drilling fluids.
  • compositions according to the invention can be used in formulations as a detergent agent.
  • the invention also extends to detergent formulations comprising compositions according to the invention.
  • the final filter cake is then immersed in 192 ml of acetic acid containing 1.32 ml of sulfuric acid. The whole is then stirred at room temperature for 1 minute, after which 19.1 ml of acetic anhydride are added. After stirring for 1 minute, the medium is heated at 40 ° C for 30 minutes. The reaction is stopped by adding 46 ml of a water / acetic acid mixture (15/30). Then, the medium is partially neutralized, at room temperature, by addition of sodium hydroxide. The polymer is isolated by precipitation or dialysis then lyophilization.
  • the product obtained is analyzed by gel permeation chromatography in the elution solvent Dimethyl acetate / LiCI (DMAc / UCI).
  • the molar mass by weight measured is 80,000.
  • the content of acetate function is obtained by prior saponification of the acetate functions, the degree of substitution for acetate function calculated is then equal to 2.5.
  • the content of sulfate functions is estimated by the method described by Quemener et al. (Appl. Phycology, 9, p 179-188 1997). The degree of substitution according to sulfate is equal to 0.3
  • Example 2 Preparation of a Composition of Cellulose Sulfo Acetate and Surfactant and Appearance of the Mixtures
  • SDS sodium dodecyl sulfate
  • LAS dodecylbenzene sulfonic acid
  • C12E8 mono-n-dodecyl ether octaethylene glycol
  • the measurements are carried out using a rheometer (Rheometrics Fluid Spectrometer II, Piscataway, USA) and a "flat cone" measurement system.
  • the sample undergoes a stress between the plane perpendicular to the axis of the cone, rotating at a certain speed ⁇ and the fixed cone of radius 25 mm.
  • ⁇ 3c / 3 ⁇ r 3
  • the flow curves are established over a range of shear rates from 100 to 0.025 s "1 .
  • Figure 1 (1/1 and 2/1) shows the evolution of the apparent viscosity of the sulfo-cellulose acetate (15 g / l) / surfactant / water mixtures as a function of the amount of surfactant.
  • G' is greater than G ".
  • the modules increase with frequency from 0.01 to 100 rad / s. Again, G 'is greater than G ".
  • Figure 3 (1/3 and 2/3) shows the evolution of the G 'module at 1 rad / s of the sulfo-cellulose acetate (15 g / l) / surfactant mixtures as a function of the quantity in surfactant (spectrum a: anionic surfactants SDS and LABS; spectrum b: nonionic surfactant C12E8)
  • n ° 2 Evolution of tan ⁇ at 0.01 rad / s of cellulose sulfo-acetate gels (15 g / l), surfactant (nxCMC), water at 25 ° C.

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Abstract

The invention concerns a composition containing at least a cellulose sulphoacetate and/or at least one of its derivatives, and at least a surfactant. The invention also concerns the method for preparing said composition, in particular in gel form. The invention further concerns the use of said composition.

Description

COMPOSITION CONTENANT DU SULFO-ACETATE DE CELLULOSE ET DU TENSIO-ACTIF COMPOSITION CONTAINING CELLULOSE SULFO-ACETATE AND SURFACTANT

La présente invention est relative à une composition qui contient au moins un sulfo-acétate de cellulose et / ou au moins un de ses dérivés, et au moins un tensio- actif.The present invention relates to a composition which contains at least one cellulose sulfo-acetate and / or at least one of its derivatives, and at least one surfactant.

Elle concerne également le procédé de préparation de ladite composition. Elle a également pour objet l'utilisation de cette composition. De nombreuses industries incorporent dans leurs formulations des tensio-actifs.It also relates to the process for the preparation of said composition. It also relates to the use of this composition. Many industries incorporate surfactants into their formulations.

Les tensio-actifs sont utilisés majoritairement pour leurs propriétés spécifiques qui permettent de faire des dispersions, notamment des émulsions ou des suspensions. En effet les tensio-actifs sont des substances qui abaissent la tension superficielle de l'eau ou du milieu dans lequel ils sont dissous. Ils peuvent être liposolubles ou hydrosolubles. La rhéologie des formulations incorporant des tensio-actifs est d'un grand intérêt pour les industriels. En effet il est important de pouvoir incorporer des tensio-actifs aussi bien dans des liquides, des solides, que des gels, en fonction des domaines d'applications.Surfactants are mainly used for their specific properties which make it possible to make dispersions, in particular emulsions or suspensions. Indeed, the surfactants are substances which lower the surface tension of the water or the medium in which they are dissolved. They can be fat-soluble or water-soluble. The rheology of formulations incorporating surfactants is of great interest to manufacturers. Indeed it is important to be able to incorporate surfactants as well in liquids, solids, as gels, according to the fields of applications.

La présente invention est notamment relative aux gels de tensio-actifs, qui sont très utiles pour les industriels.The present invention relates in particular to gels of surfactants, which are very useful for manufacturers.

On entend par gel, tout type de système présentant un comportement de solide viscoélastique aux temps longs (par exemple, au-delà de 100 s dans une expérience de fluage ou en dessous de 10"2 Hz en régime harmonique). D'un point de vue rhéologique, ceci se traduit par la présence d'un plateau de G' (module conservatif) et des valeurs de G' supérieures à G" (module de perte), ces deux critères étant obtenus à basse fréquence (en pratique entre 10"3 et 10~2 Hz).By gel is meant any type of system exhibiting a viscoelastic solid behavior over long periods of time (for example, beyond 100 s in a creep experiment or below 10 "2 Hz in harmonic regime). from a rheological point of view, this results in the presence of a plateau of G '(conservative module) and values of G' greater than G "(loss module), these two criteria being obtained at low frequency (in practice between 10 "3 and 10 ~ 2 Hz).

Les méthodes de gélification connues pour faire des gels de tensio-actifs utilisent notamment la gélification par phase. Dans ces méthodes on mélange les tensio-actifs et des électrolytes dans des concentrations préalablement optimisées qui provoquent une structuration lamellaire.The known gelling methods for making surfactant gels notably use phase gelling. In these methods, the surfactants and electrolytes are mixed in previously optimized concentrations which cause a lamellar structure.

Mais ces méthodes sont limitées aux structurations lamellaires et sont insatisfaisantes. En effet de nombreux problèmes surviennent au cours de l'élaboration de ces gels notamment des problèmes de compatibilité des milieux et des problèmes de perte de viscosité des gels obtenus. De plus lorsque l'on recherche une formulation sous forme de gel, incorporant des tensio-actifs, les méthodes connues ne permettent pas d'obtenir des formulations qui se solubilisent vite en milieu aqueux. Un autre inconvénient est la limite dans le choix des tensio-actifs entrant dans la composition de ces gels. En effet tous les tensio-actifs ne permettent pas d'obtenir des phases structurées.However, these methods are limited to lamellar structures and are unsatisfactory. Indeed, many problems arise during the preparation of these gels, in particular problems of compatibility of the media and problems of loss of viscosity of the gels obtained. In addition, when a formulation is sought in the form of a gel, incorporating surfactants, the known methods do not make it possible to obtain formulations which dissolve quickly in an aqueous medium. Another drawback is the limit in the choice of surfactants used in the composition of these gels. In fact, not all surfactants make it possible to obtain structured phases.

Un des problèmes que se propose de résoudre l'invention est notamment de pouvoir fournir des gels qui se solubilisent vite en milieu aqueux.One of the problems which the invention proposes to solve is in particular to be able to provide gels which dissolve quickly in an aqueous medium.

De plus un autre problème que se propose de résoudre l'invention est notamment de pouvoir fournir des gels incorporant de grandes quantités de tensio-actifs, et qui se solubilisent vite en milieu aqueux.In addition, another problem which the invention proposes to solve is notably to be able to supply gels incorporating large quantities of surfactants, and which dissolve quickly in an aqueous medium.

L'invention a en outre pour but de proposer des gels de tensio-actifs qui soient plus particulièrement des gels thermoréversibles et thixotropes.The invention further aims to provide gels of surfactants which are more particularly thermoreversible and thixotropic gels.

On entend par thermoréversible un gel qui se forme après refroidissement et après avoir subi un traitement thermique au-delà de sa température de fusion, et qui possède une température de fusion. Cette température de fusion est la température au- delà de laquelle le gel fond. Par thixotropie, on entend la propriété d'un gel de perdre sa structure sous l'effet d'une force de cisaillement et, ensuite, de retrouver tout ou partie de son état initial après un certain délai au repos.The term “thermoreversible” means a gel which forms after cooling and after having undergone a heat treatment beyond its melting point, and which has a melting point. This melting temperature is the temperature above which the gel melts. The term “thixotropy” is understood to mean the property of a gel losing its structure under the effect of a shearing force and, then, recovering all or part of its initial state after a certain period of rest.

Un autre but de l'invention est de fournir un procédé simple et peu coûteux pour la préparation des compositions selon l'invention. Le but de la présente invention est principalement de répondre à l'ensemble de ces exigences en une seule formulation.Another object of the invention is to provide a simple and inexpensive process for the preparation of the compositions according to the invention. The object of the present invention is mainly to meet all of these requirements in a single formulation.

D'autres avantages et caractéristiques de la présente invention apparaîtront clairement à la lecture de la description et des exemples qui vont suivre.Other advantages and characteristics of the present invention will become apparent on reading the description and examples which follow.

La solution apportée par l'invention est d'introduire les tensio-actifs dans une composition aqueuse qui contient au moins un sulfo-acétate de cellulose et / ou au moins un de ses dérivés.The solution provided by the invention is to introduce the surfactants into an aqueous composition which contains at least one cellulose sulfoacetate and / or at least one of its derivatives.

Ainsi la présente invention a pour objet une composition aqueuse qui contient au moins un sulfo-acétate de cellulose et / ou au moins un de ses dérivés, et au moins un tensio-actif. L'invention a également pour objet le procédé de préparation de ladite composition, notamment sous la forme d'un gel ayant les propriétés désirées.Thus the subject of the present invention is an aqueous composition which contains at least one cellulose sulfo-acetate and / or at least one of its derivatives, and at least one surfactant. The invention also relates to the process for the preparation of said composition, in particular in the form of a gel having the desired properties.

Elle a également pour objet l'utilisation de cette composition dans différents domaines industriels.It also relates to the use of this composition in various industrial fields.

La présente invention va maintenant être décrite de manière détaillée dans ces objets et autres caractéristiques et à l'aide d'exemples donnés à titre purement illustratif et non limitatif en référence aux figures annexées dans lesquelles : la figure n°1 (1/1 et 2/1) représente l'évolution de la viscosité apparente des mélanges sulfo-acétate de cellulose (15 g/l)/tensio-actif/eau en fonction de la quantité de tensio-actif, la figure n°2 représente le spectre mécanique des mélanges sulfo-acétate de cellulose (15 g/l)/tensio-actif (0 et 10 fois la CMC/eau pour le SDS et le C12E8, la figure n° 3 (1/3 et 2/3) représente l'évolution du module G' à 1 rad/s des mélanges sulfo-acétate de cellulose (15 g/l)/tensio-actif en fonction de la quantité en tensio actif (spectre a : tensio-actifs anioniques SDS et LABS ; spectre b : tensio-actif non ionique C12E8). L'invention concerne tout d'abord une composition qui contient au moins un sulfo- acétate de cellulose et / ou au moins un de ses dérivés, et au moins un tensio-actif.The present invention will now be described in detail in these objects and other characteristics and with the aid of examples given purely by way of non-limiting illustration with reference to the appended figures in which: Figure 1 (1/1 and 2/1) shows the change in the apparent viscosity of the sulfo-cellulose acetate (15 g / l) / surfactant / water mixtures as a function of the amount of surfactant , figure n ° 2 represents the mechanical spectrum of mixtures sulfo-cellulose acetate (15 g / l) / surfactant (0 and 10 times the CMC / water for SDS and C12E8, figure n ° 3 (1 / 3 and 2/3) represents the evolution of the module G 'at 1 rad / s of the sulfo-cellulose acetate (15 g / l) / surfactant mixtures as a function of the amount of surfactant (spectrum a: tensio anionic active agents SDS and LABS; spectrum b: nonionic surfactant C12E8) The invention relates first of all to a composition which contains at least one cellulose sulfoacetate and / or at least one of its derivatives, and to the minus a surfactant.

Cette composition peut se présenter sous forme d'un gel.This composition can be in the form of a gel.

Le premier constituant essentiel de la composition est constitué par au moins un tensio-actif. Par tensio-actifs, on entend toutes substances qui abaissent la tension superficielle de l'eau ou du milieu dans lequel elles sont dissoutes.The first essential constituent of the composition consists of at least one surfactant. The term "surfactants" means any substance which lowers the surface tension of the water or of the medium in which it is dissolved.

Les tensio-actifs utilisés selon l'invention peuvent être ioniques ou non ioniques, et peuvent être utilisés seuls ou en mélanges.The surfactants used according to the invention can be ionic or nonionic, and can be used alone or in mixtures.

A titre de tensio-actifs ioniques, on peut citer de façon non limitative les alkylesters sulfonates, les alkylsulfates ainsi que leurs dérivés alcoxylés (notamment ethoxylésAs ionic surfactants, non-limiting mention may be made of alkyl esters sulfonates, alkyl sulfates and their alkoxylated derivatives (in particular ethoxylated

(OE) et/ou propoxylés (OP)), les alkylamides sulfates ainsi que leurs dérivés alcoxylés(OE) and / or propoxylated (OP)), alkylamide sulfates and their alkoxylated derivatives

(notamment (OE) et/ou (OP)), les sels d'acides gras saturés ou insaturés et/ou leurs dérivés alcoxylés (notamment (OE) et/ou (OP)), les alkylbenzènesulfonates, les alkylsulfonates primaires ou secondaires, les alkylglycérol sulfonates, les acides polycarboxyliques sulfones, les sulfonates de paraffine, les N-acyl N-alkyltaurates, les alkylphosphates, les iséthionates, les alkylsuccinamates, les alkylsulfosuccinates, les monoesters ou diesters de sulfosuccinates, les N-acyl sarcosinates, les sulfates d'alkylglycosides, les sophorolipides, tels que ceux notamment sous forme acide ou lactone et dérivés de l'acide 17-hydroxyoctadécénique. A titre d'exemples de tensio-actifs ioniques, on peut citer de façon non limitative des tensio-actifs anioniques comme :(in particular (OE) and / or (OP)), the salts of saturated or unsaturated fatty acids and / or their alkoxylated derivatives (in particular (OE) and / or (OP)), alkylbenzenesulfonates, primary or secondary alkylsulfonates, alkyl glycerol sulfonates, polycarboxylic acids sulfones, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, 'alkylglycosides, sophorolipids, such as those in particular in acid or lactone form and derivatives of 17-hydroxyoctadecenic acid. As examples of ionic surfactants, non-limiting mention may be made of anionic surfactants such as:

• les alkylesters sulfonates de formule du type R-CH(Sθ3M)-COOR', où R représente un radical alkyle en Cβ-20. de préférence en C-|o-Cl6' R' un radical alkyle en C- -• the alkyl esters sulfonates of formula of the R-CH (Sθ3M) -COOR 'type, where R represents a Cβ-20 alkyl radical. preferably at C- | o-Cl6 'R' a C- - alkyl radical

CQ, de préférence en C1-C3 et M un cation alcalin (sodium, potassium, lithium), ammonium substitué ou non substitué (méthyl-, diméthyl-, triméthyl-, tetraméthylammonium, diméthylpiperidinium...) ou dérivé d'une alcanolamineCQ, preferably in C1-C3 and M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine

(monoéthanolamine, diéthanolamine, triéthanolamine...). On peut citer tout particulièrement les méthyl ester sulfonates dont le radical R est en C14-C-16 ; • les alkylsulfates de formule du type ROSOβM, où R représente un radical alkyle ou hydroxyalkyle en C5-C24, de préférence en C-|0"c18' M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérivés alcoxylés (notamment (OE) et/ou (OP)), présentant en moyenne de 0,5 à 30 motifs, de préférence de 0,5 à 10 motifs OE et/ou OP ;(monoethanolamine, diethanolamine, triethanolamine ...). Mention may very particularly be made of methyl ester sulfonates whose radical R is C14-C-16; • alkylsulphates of formula ROSOβM type wherein R represents an alkyl or hydroxyalkyl radical, C5-C24, preferably C- | 0 "c 18 'M representing a hydrogen atom or a cation with the same definition as above , as well as their alkoxylated derivatives (in particular (OE) and / or (OP)), having on average from 0.5 to 30 units, preferably from 0.5 to 10 OE and / or OP units;

• les alkylamides sulfatés notamment de formule du type RCONHROSO3M où R représente un radical alkyle en C2-C22. de préférence en Cβ-C20. R' un radical alkyle en C2-C3, M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérivés alcoxylés (notamment (OE) et/ou (OP)), présentant en moyenne de 0,5 à 60 motifs OE et/ou OP ;• sulfated alkylamides in particular of formula of the RCONHROSO3M type where R represents a C2-C22 alkyl radical. preferably Cβ-C20. R 'a C2-C3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their alkoxylated derivatives (in particular (OE) and / or (OP)), having on average of 0.5 to 60 OE and / or OP motifs;

• les sels d'acides gras saturés ou insaturés notamment et/ou leur dérivés alcoxylés (notamment (OE) et/ou (OP)), en C8-C24, de préférence en C14-C20, les alkylbenzènesulfonates en Cg-C20> 'es alkylsulfonates primaires ou secondaires en C8-C22. les alkylglycérol sulfonates, les sulfonates de paraffine, les N-acyl N- alkyltaurates, les alkylphosphates, les iséthionates, les alkylsuccinamates les alkylsulfosuccinates, les monoesters ou diesters de sulfosuccinates, les N-acyl sarcosinates, les sulfates d'alkylglycosides; le cation étant un métal alcalin (sodium, potassium, lithium), un reste ammonium substitué ou non substitué (méthyl-, diméthyl-, triméthyl-, tetraméthylammonium, diméthylpiperidinium...) ou dérivé d'une alcanolamine (monoéthanolamine, diéthanolamine, triéthanolamine...) ;• the salts of saturated or unsaturated fatty acids in particular and / or their alkoxylated derivatives (in particular (EO) and / or (OP)), in C8-C24, preferably in C14-C20, Cb-C20 alkylbenzenesulfonates > ' es primary or secondary C8-C22 alkylsulfonates. alkyl glycerol sulfonates, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, alkylglycoside sulfates; the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...);

A titre d'exemples de tensio-actifs ioniques, on peut citer de façon non limitative des tensio-actifs cationiques comme :By way of examples of ionic surfactants, non-limiting mention may be made of cationic surfactants such as:

• des sels d'alkylammonium de formule du type R1 R2R3R4N+X" où X" est un ion halogène, methylsulfate (CH3SO4 ~) ou éthylsulfate (C2H5SO4 ), R1 et R2 sont semblables ou différents et représentent un radical alkyl en CrC20, un radical benzyl ou alkylbenzyl en C1-C4, R3 et R4 sont semblables ou différents et représentent un radical alkyl en C C20, un radical benzyl ou alkylbenzyl en Cι-C ou un condensât oxyde d'éthylène et/ou de propylène (CH2CH2O)x-(CH2CHCH3O)y-H, où x et y vont de 0 à 30 et ne sont jamais nuls ensemble, comme le bromure de céthylméthylammonium, les halogénures d'alkylammonium, les halogénures d'alkylpyrtdinium ; diester de triéthanolamine quaternisé ;• alkylammonium salts of formula of the type R1 R2R3R4N + X " where X " is a halogen ion, methylsulfate (CH 3 SO 4 ~ ) or ethylsulfate (C 2 H 5 SO 4 ), R1 and R2 are similar or different and represent an alkyl radical in CrC 20 , a benzyl or alkylbenzyl radical in C 1 -C 4 , R3 and R4 are similar or different and represent an alkyl radical in CC 20 , a benzyl or alkylbenzyl radical in Cι-C or an oxide condensate d ethylene and / or propylene (CH 2 CH 2 O) x - (CH 2 CHCH 3 O) y -H, where x and y range from 0 to 30 and are never zero together, such as methyl methyl bromide, alkylammonium halides, alkylpyrtdinium halides; quaternized triethanolamine diester;

N-méthylimidazoline tallow ester méthyl sulfate; di-hardened tallow-diethyl ammonium chloride (Arquad 2HT ®) ; • chlorure de dialkyldiméthylammonium ; chlorure d'alkylbenzyldiméthylammonium ; A titre d'exemples de tensio-actifs ioniques, on peut citer de façon non limitative des tensio-actifs amphotères et zwitterioniques comme :N-methylimidazoline tallow methyl sulfate ester; di-hardened tallow-diethyl ammonium chloride (Arquad 2HT ®); • dialkyldimethylammonium chloride; alkylbenzyldimethylammonium chloride; By way of examples of ionic surfactants, non-limiting mention may be made of amphoteric and zwitterionic surfactants such as:

• les alkyldiméthylbétaïnes, les alkylamidopropyldiméthylbétaïnes, les alkyltriméthylsulfobétaïnes, les produits de condensation d'acides gras et d'hydrolysats de protéines.• alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, condensation products of fatty acids and protein hydrolysates.

A titre de tensio-actifs non ioniques, on peut citer de façon non limitative les alkylphénols alcoxylés (notamment (OE) et/ou (OP)), les alcools aliphatiques plus particulièrement en C8-C22, les produits résultant de la condensation de l'oxyde d'éthylène ou de l'oxyde de propylène avec le propylène glycol ou l'éthylène glycol, les produits résultant de la condensation de l'oxyde d'éthylène ou de l'oxyde de propylène avec l'éthylène diamine, les acides gras alcoxylés (notamment (OE) et/ou (OP)), les amides d'acides gras alcoxylés (notamment (OE) et/ou (OP)), les aminés alcoxylés (notamment (OE) et/ou (OP)), les amidoamines alcoxylés (notamment (OE) et/ou (OP)), les oxydes d'aminés, les hydrocarbures terpéniques alcoxylés (notamment (OE) et/ou (OP)), les alkylpolyglycosides, les polymères ou oligomères amphiphiles.As nonionic surfactants, non-limiting mention may be made of alkoxylated alkylphenols (in particular (EO) and / or (OP)), aliphatic alcohols more particularly of C 8 -C 22 , the products resulting from condensation ethylene oxide or propylene oxide with propylene glycol or ethylene glycol, the products resulting from the condensation of ethylene oxide or propylene oxide with ethylene diamine, alkoxylated fatty acids (especially (OE) and / or (OP)), alkoxylated fatty acid amides (especially (OE) and / or (OP)), alkoxylated amines (especially (OE) and / or (OP) )), alkoxylated amidoamines (in particular (OE) and / or (OP)), amine oxides, alkoxylated terpene hydrocarbons (in particular (OE) and / or (OP)), alkylpolyglycosides, amphiphilic polymers or oligomers .

A titre d'exemples de tensio-actifs non ioniques, on peut citer de façon non limitative des tensio-actifs comme :By way of examples of nonionic surfactants, non-limiting mention may be made of surfactants such as:

• les alkylphénols alcoxylés (notamment (OE) et/ou (OP)), dont le substituant alkyle est notamment en C6-C-12 et contenant de 5 à 25 motifs oxyalkylènes; à titre d'exemple, on peut citer les TRITON® X-45, X-114, X-100 ou X-102 commercialisés par Rohm & Haas Cy. ;• alkoxylated alkylphenols (in particular (OE) and / or (OP)), the alkyl substituent of which is in particular C6-C-12 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made TRITON ® X-45, X-114, X-100 or X-102 sold by Rohm and Haas Cy. ;

• les glucosamide, glucamide, glycérolamide ;• glucosamide, glucamide, glycerolamide;

• les alcools aliphatiques notamment en C8-C22 et leurs dérivés alcoxylés (notamment (OE) et/ou (OP)), contenant de 1 à 25 motifs (OE) et/ou (OP); à titre d'exemple, on peut citer les TERGITOL® 15-S-9, TERGITOL® 24-L-6 NMW commercialisés par Union Carbide Corp., NEODOL® 45-9, NEODOL® 23-65, NEODOL® 45-7, NEODOL® 45-4 commercialisés par Shell Chemical Cy., KYRO EOB® commercialisé par The Procter & Gamble Cy. ; • les produits résultant de la condensation de l'oxyde d'éthylène, le composé résultant de la condensation de l'oxyde de propylène avec le propylène glycol, tels les PLURONIC® commercialisés par BASF ;• aliphatic alcohols, in particular C8-C22 and their alkoxylated derivatives (in particular (OE) and / or (OP)), containing from 1 to 25 units (OE) and / or (OP); by way of example, mention may be made of TERGITOL ® 15-S-9, TERGITOL ® 24-L-6 NMW sold 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. ; • 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;

• les produits résultant de la condensation de l'oxyde d'éthylène, le composé résultant de la condensation de l'oxyde de propylène avec l'éthylènediamine, tels les TETRONIC® commercialisés par BASF ;• 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;

• les oxydes d'aminés tels que notamment les oxydes d'alkyl plus particulièrement en c10"c18 diméthylamines, les oxydes d'alkoxy C8-C22 éthyl dihydroxy éthylamines ; • les alkylpolyglycosides notamment décrits dans US-A-4 565 647 ;• amine oxides such as in particular alkyl oxides, more particularly C 10 ″ C 18 dimethylamines, C8-C22 alkoxy oxides ethyl dihydroxy ethylamines; • the alkylpolyglycosides in particular described in US-A-4,565,647;

• les amides d'acides gras plus particulièrement en C8-C20• fatty acid amides, more particularly C8-C20

Quant aux polymères ou oligomères amphiphiles non ioniques entrant dans la composition selon l'invention, ils sont plus particulièrement choisis, seuls ou en mélanges, parmi les polymères, oligomères ou copolymeres au moins miscibles en partie dans la composition aqueuse.As for the nonionic amphiphilic polymers or oligomers entering into the composition according to the invention, they are more particularly chosen, alone or in mixtures, among the polymers, oligomers or copolymers at least partially miscible in the aqueous composition.

Par polymères ou oligomères amphiphiles, on entend des polymères ou oligomères ayant une tension de surface en milieu aqueux.By amphiphilic polymers or oligomers is meant polymers or oligomers having a surface tension in an aqueous medium.

Les polymères ou oligomères amphiphiles peuvent avoir une répartition statistique ou une répartition multibloc.The amphiphilic polymers or oligomers can have a statistical distribution or a multiblock distribution.

A titre d'exemple de tels polymères ou oligomères amphiphiles, on peut citer notamment les polysaccharides ayant des groupements hydrophobes, notamment des groupements alkyle. A titre d'exemples on peut citer les guars.By way of example of such amphiphilic polymers or oligomers, mention may in particular be made of polysaccharides having hydrophobic groups, in particular alkyl groups. Examples include guars.

A titre d'exemple de polymères ou oligomères amphiphiles on peut également citer les polymères triblocs polyhydroxystéarate - polyéthylène glycol - polyhydroxystéarate (les produits de la gamme Arlacel® de ICI en sont un exemple), les polyacrylamides hydrophobes.Examples of amphiphilic polymers or oligomers can also be made of triblock polymers polyhydroxystearate - polyethylene glycol - polyhydroxystearate (products of Arlacel ® range of ICI are an example), the hydrophobic polyacrylamides.

Pour ce qui a trait aux polymères amphiphiles non ioniques plus particulièrement alcoxylés (notamment (OE) et/ou (OP)), ces derniers sont plus particulièrement choisis parmi les polymères dont au moins une partie (au moins 50 % en poids) est miscible dans l'eau.As regards non-ionic amphiphilic polymers more particularly alkoxylated (in particular (OE) and / or (OP)), the latter are more particularly chosen from polymers of which at least a part (at least 50% by weight) is miscible in water.

A titre d'exemples de polymères de ce type, on peut citer entre autres les polymères triblocs polyéthylène glycol / polypropylène glycol / polyéthylène glycol.Examples of polymers of this type that may be mentioned, inter alia, are polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polymers.

Les tensio-actifs préférés selon l'invention sont les tensio-actifs non-ioniques et les tensio-actifs anioniques.The preferred surfactants according to the invention are nonionic surfactants and anionic surfactants.

A titre de tensio-actifs non ioniques préférés on peut citer les alcools gras alcoxylés (OE et/ou OP).Mention may be made, as preferred nonionic surfactants, of alkoxylated fatty alcohols (EO and / or OP).

Selon un mode préféré de l'invention, le tensio-actif préféré est le mono-n-dodécyl éther octaéthylène glycol, seul ou en mélange. A titre de tensio-actifs anioniques préférés on peut citer les alkylbenzènesulfonates notamment en C9-C2o-According to a preferred embodiment of the invention, the preferred surfactant is mono-n-dodecyl ether octaethylene glycol, alone or as a mixture. As preferred anionic surfactants, mention may be made of alkylbenzenesulfonates, in particular C 9 -C 2 o-

On peut également citer, à titre de tensio-actifs anioniques préférés, le sodium dodécyl sulfate ou le sel de sodium de l'acide dodécylbenzène sulfonique.Mention may also be made, as preferred anionic surfactants, of sodium dodecyl sulfate or the sodium salt of dodecylbenzene sulfonic acid.

Dans le cadre de la présente invention la concentration en tensio-actif non ionique dans la composition est inférieure ou égale à 150 fois la concentration micellaire critique du tensio-actif, de préférence inférieure ou égale à 100 fois la concentration micellaire critique du tensio-actif. En ce qui concerne la concentration en tensio-actif ionique, elle est inférieure ou égale à 10 fois la concentration micellaire critique.In the context of the present invention the concentration of nonionic surfactant in the composition is less than or equal to 150 times the critical micellar concentration of the surfactant, preferably less than or equal to 100 times the critical micellar concentration of the surfactant . As for the concentration of ionic surfactant, it is less than or equal to 10 times the critical micellar concentration.

On entend par concentration micellaire critique (CMC) d'un composé, la concentration de ce composé, dans le milieu, au-delà de laquelle on a formation de micelles du composé dans ce milieu. Pour des concentrations inférieures à la CMC, les molécules de tensio-actifs sont libres et pour des concentrations supérieures à la CMC, une agrégation de ces molécules de tensio-actifs apparaît pour former des micelles.The term “critical micellar concentration” (CMC) of a compound is understood to mean the concentration of this compound, in the medium, above which the compound micelles are formed in this medium. For concentrations lower than CMC, the surfactant molecules are free and for concentrations higher than CMC, an aggregation of these surfactant molecules appears to form micelles.

Il est à noter que la concentration micellaire critique peut-être déterminée par tension interfaciale. Dans le cas des tensio-actifs ioniques, la concentration micellaire critique peut- être déterminée également par conductimétrie.It should be noted that the critical micellar concentration can be determined by interfacial tension. In the case of ionic surfactants, the critical micelle concentration can also be determined by conductimetry.

Le second constituant essentiel de la composition est constitué par au moins un sulfo-acétate de cellulose et /ou au moins un de ses dérivés.The second essential constituent of the composition consists of at least one cellulose sulfo-acetate and / or at least one of its derivatives.

Par dérivés de sulfo-acétate de cellulose, on entend des sulfo-butyrate de cellulose ou des sulfo-acéto-butyrate de cellulose ou des sulfo-propionate de cellulose ou des sulfo-acéto-propionate de cellulose.By cellulose sulfo-acetate derivatives is meant cellulose sulfo-butyrate or cellulose sulfo-aceto-butyrate or cellulose sulfo-propionate or cellulose sulfo-aceto-propionate.

Ces produits, qui sont de manière avantageuse hydrosolubles, sont biens connus de l'homme du métier et sont préparés par estérification d'un composé cellulosique.These products, which are advantageously water-soluble, are well known to those skilled in the art and are prepared by esterification of a cellulosic compound.

La concentration en sulfo-acétate de cellulose et/ou un de ses dérivés peut être comprise entre 0,01 % et 20 %, de préférence entre 0,1 % et 5 %, plus particulièrement comprise entre 0,5 % et 3% en poids de la composition.The concentration of cellulose sulfo-acetate and / or one of its derivatives can be between 0.01% and 20%, preferably between 0.1% and 5%, more particularly between 0.5% and 3% in weight of the composition.

Le deuxième aspect de la présente invention concerne le procédé de préparation de la composition.The second aspect of the present invention relates to the process for preparing the composition.

Ce procédé consiste à mettre en contact une phase aqueuse, au moins un tensio- actif et le sulfo-acétate de cellulose ou un de ses dérivés (étape (i)).This process consists in contacting an aqueous phase, at least one surfactant and the cellulose sulfoacetate or one of its derivatives (step (i)).

De préférence le procédé de préparation est mis en œuvre en introduisant, pendant l'étape (i), dans une phase aqueuse le sulfo-acétate de cellulose ou un de ses dérivés puis au moins un tensio-actif.Preferably, the preparation process is carried out by introducing, during step (i), into an aqueous phase the cellulose sulfoacetate or one of its derivatives, then at least one surfactant.

Selon une variante de l'invention notamment pour préparer la composition selon l'invention sous forme d'un gel, le procédé de préparation peut comprendre une étape de traitement thermique après l'étape (i) où la température est comprise entre 30°C et 140°C, avantageusement entre 60°C et 120°C.According to a variant of the invention in particular for preparing the composition according to the invention in the form of a gel, the preparation process can comprise a heat treatment step after step (i) where the temperature is between 30 ° C. and 140 ° C, advantageously between 60 ° C and 120 ° C.

Selon une autre variante du procédé selon l'invention, le procédé de préparation est mis en œuvre en introduisant au moins un tensio-actif dans une phase aqueuse contenant le sulfo-acétate de cellulose ou un de ses dérivés ayant subi ce même traitement thermique.According to another variant of the process according to the invention, the preparation process is implemented by introducing at least one surfactant into an aqueous phase containing the cellulose sulfoacetate or one of its derivatives having undergone this same heat treatment.

La durée du traitement thermique peut varier de 1 minute à 6 heures, de préférence de 15 minutes à 4 heures. A l'issu du traitement thermique on peut refroidir ladite solution issue de l'étape (i), jusqu'à une température comprise entre 0°C et la température ambiante (20°C - 25°C).The duration of the heat treatment can vary from 1 minute to 6 hours, preferably from 15 minutes to 4 hours. At the end of the heat treatment, said solution obtained from step (i) can be cooled to a temperature between 0 ° C and room temperature (20 ° C - 25 ° C).

Cette étape a pour objet de structurer le gel, lorsque l'on veut obtenir un gel.The purpose of this step is to structure the gel, when it is desired to obtain a gel.

Un autre aspect de la présente invention concerne l'utilisation des compositions dans les domaines de la cosmétique, de la détergence, de l'alimentaire, du papier, de l'agrochimie, pharmaceutiques, tinctoriales, des fluides de forage.Another aspect of the present invention relates to the use of the compositions in the fields of cosmetics, detergency, food, paper, agrochemicals, pharmaceuticals, dyes, drilling fluids.

Dans ces domaines les compositions selon l'invention, quelles que soient leurs variantes, peuvent être utilisées dans des formulations en tant qu'agent détergent.In these fields, the compositions according to the invention, whatever their variants, can be used in formulations as a detergent agent.

L'invention s'étend aussi aux formulations détergentes comprenant des compositions selon l'invention.The invention also extends to detergent formulations comprising compositions according to the invention.

Les exemples suivants illustrent l'invention sans toutefois en limiter la portée.The following examples illustrate the invention without, however, limiting its scope.

EXEMPLESEXAMPLES

Exemple 1 : Préparation du sulfo-acétate de cellulose ou d'un de ses dérivésEXAMPLE 1 Preparation of Cellulose Sulfo Acetate or One of Its Derivatives

10 grammes de cellulose Avicel sont mis en suspension dans 200 ml d'acide acétique et laissés sous agitation magnétique pendant 30 minutes à température ambiante. Après filtration ou centrifugation, on élimine l'excès de liquide puis la même opération est répétée deux fois.10 grams of Avicel cellulose are suspended in 200 ml of acetic acid and left under magnetic stirring for 30 minutes at room temperature. After filtration or centrifugation, the excess liquid is removed and the same operation is repeated twice.

Le gâteau de filtration final est alors immergé dans 192 ml d'acide acétique contenant 1 ,32 ml d'acide sulfurique. On agite ensuite le tout à température ambiante pendant 1 minute à la suite de quoi on ajoute 19,1 ml d'anhydride acétique. Après agitation pendant 1 minute, le milieu est chauffé à 40°C pendant 30 minutes. La réaction est arrêtée par addition de 46 ml d'un mélange eau/acide acétique (15/30). Puis, le milieu est partiellement neutralisé, à température ambiante, par addition de soude. Le polymère est isolé par précipitation ou dialyse puis lyophilisation.The final filter cake is then immersed in 192 ml of acetic acid containing 1.32 ml of sulfuric acid. The whole is then stirred at room temperature for 1 minute, after which 19.1 ml of acetic anhydride are added. After stirring for 1 minute, the medium is heated at 40 ° C for 30 minutes. The reaction is stopped by adding 46 ml of a water / acetic acid mixture (15/30). Then, the medium is partially neutralized, at room temperature, by addition of sodium hydroxide. The polymer is isolated by precipitation or dialysis then lyophilization.

Le produit obtenu est analysé par chromatographie par perméation de gel dans le solvant d'élution Dimethyl acétate / LiCI (DMAc/UCI). La masse molaire en poids mesurée est de 80 000. La teneur en fonction acétate est obtenue par saponification préalable des fonctions acétates, le degré de substitution en fonction acétate calculé est alors égal à 2.5. La teneur en fonctions sulfate est estimée par la méthode décrite par Quemener et coll. (Appl. Phycology, 9, p 179-188 1997). Le degré de substitution en fonction sulfate est égal à 0,3 Exemple 2 : Préparation d'une composition de sulfo-acétate de cellulose et de tensio-actif et aspect des mélangesThe product obtained is analyzed by gel permeation chromatography in the elution solvent Dimethyl acetate / LiCI (DMAc / UCI). The molar mass by weight measured is 80,000. The content of acetate function is obtained by prior saponification of the acetate functions, the degree of substitution for acetate function calculated is then equal to 2.5. The content of sulfate functions is estimated by the method described by Quemener et al. (Appl. Phycology, 9, p 179-188 1997). The degree of substitution according to sulfate is equal to 0.3 Example 2 Preparation of a Composition of Cellulose Sulfo Acetate and Surfactant and Appearance of the Mixtures

15 grammes de sulfo-acétate de cellulose sont introduits dans 1 litre d'eau distillée. Le mélange est dispersé sous agitation pendant 1 heure à 80°C puis laissé 1 heure à température ambiante. Puis, la quantité de tensio-actifs est introduite et le mélange est à nouveau agité pendant 30 minutes puis laissé au repos pendant 24 heures avant la mesure.15 grams of cellulose sulfo-acetate are introduced into 1 liter of distilled water. The mixture is dispersed with stirring for 1 hour at 80 ° C and then left for 1 hour at room temperature. Then, the quantity of surfactants is introduced and the mixture is again stirred for 30 minutes then left to stand for 24 hours before the measurement.

Différentes expériences ont été menées avec le sodium dodécyl sulfate (SDS), le sel de sodium de l'acide dodécylbenzène sulfonique (LABS) et le mono-n-dodécyl éther octaéthylène glycol (C12E8).Different experiments have been carried out with sodium dodecyl sulfate (SDS), the sodium salt of dodecylbenzene sulfonic acid (LABS) and mono-n-dodecyl ether octaethylene glycol (C12E8).

Avec le SDS et le LABS, on obtient à 25°C un gel à une concentration de 10 x la concentration micellaire critique du tensioactif. Pour le C12E8, on obtient à 25°C un gel à une concentration de 100 x la concentration micellaire critique du tensioactifWith SDS and LABS, a gel is obtained at 25 ° C. at a concentration of 10 × the critical micellar concentration of the surfactant. For C12E8, a gel is obtained at 25 ° C at a concentration of 100 x the critical micellar concentration of the surfactant

Exemple 3 : Propriétés rhéologiques des gelsEXAMPLE 3 Rheological Properties of the Gels

Les mesures sont effectuées à l'aide d'un rhéomètre (Rheometrics Fluid Spectrometer II, Piscataway, USA) et d'un système de mesure "cône plan". L'échantillon subit une contrainte entre le plan perpendiculaire à l'axe du cône, tournant à une certaine vitesse Ω et le cône fixe de rayon 25 mm. Lors de la déformation imposée, la contrainte de cisaillement en tout point de l'entrefer est donnée par σ = 3c/3πr3 et la vitesse de cisaillement par γ = Ω / α (avec α = 0,0397 rad).The measurements are carried out using a rheometer (Rheometrics Fluid Spectrometer II, Piscataway, USA) and a "flat cone" measurement system. The sample undergoes a stress between the plane perpendicular to the axis of the cone, rotating at a certain speed Ω and the fixed cone of radius 25 mm. During the imposed deformation, the shear stress at any point of the air gap is given by σ = 3c / 3πr 3 and the shear speed by γ = Ω / α (with α = 0.0397 rad).

Les courbes d'écoulement sont établies sur une gamme de vitesse de cisaillement allant de 100 à 0,025 s"1.The flow curves are established over a range of shear rates from 100 to 0.025 s "1 .

La figure n°1 (1/1 et 2/1) représente l'évolution de la viscosité apparente des mélanges sulfo-acétate de cellulose (15 g/l)/tensio-actif/eau en fonction de la quantité de tensioactif.Figure 1 (1/1 and 2/1) shows the evolution of the apparent viscosity of the sulfo-cellulose acetate (15 g / l) / surfactant / water mixtures as a function of the amount of surfactant.

Les courbes d'écoulement présentent toutes un comportement rhéofluidifiant marqué et un plateau newtonien aux faibles vitesses de cisaillement. La viscosité apparente augmente dans un premier temps avec la concentration en tensio-actifs jusqu'à une concentration optimale qui dépend de la nature du tensio-actif. La viscosité diminue ensuite mais reste toujours supérieure ou égale à la viscosité apparente du gel témoin ne contenant pas de tensio-actif. Le comportement viscoélastique des mélanges a été étudié. La figure n°2 représente le spectre mécanique des mélanges sulfo-acétate de cellulose (15 g/l)/tensio-actif (0 et 10 fois la CMC/eau pour le SDS et le C12E8.The flow curves all exhibit marked shear thinning behavior and a Newtonian plateau at low shear rates. The apparent viscosity increases first with the concentration of surfactants up to an optimal concentration which depends on the nature of the surfactant. The viscosity then decreases but always remains greater than or equal to the apparent viscosity of the control gel containing no surfactant. The viscoelastic behavior of the mixtures has been studied. Figure 2 represents the mechanical spectrum of the sulfo-cellulose acetate (15 g / l) / surfactant (0 and 10 times the CMC / water for SDS and C12E8) mixtures.

Ainsi, en l'absence de tensio-actif, les modules G' et G" augmentent avec la fréquence et G' est supérieur à G" ce qui indique que le système est structuré (gel). En présence du tensio-actif SDS, G' et G" sont indépendants de la fréquence jusqu'à une fréquence de 0,1 rad/s puis les modules augmentent avec la fréquence. Pour les deux types de tensio-actifs, G' est supérieur à G". Avec le C12E8, les modules augmentent avec la fréquence de 0,01 à 100 rad/s. Là encore, G' est supérieur à G".Thus, in the absence of surfactant, the modules G 'and G "increase with frequency and G' is greater than G" which indicates that the system is structured (gel). In the presence of the surfactant SDS, G 'and G "are independent of the frequency up to a frequency of 0.1 rad / s then the modules increase with the frequency. For the two types of surfactants, G' is greater than G ". With the C12E8, the modules increase with frequency from 0.01 to 100 rad / s. Again, G 'is greater than G ".

Ces résultats indiquent que la structure gel est conservée en présence de tensio-actif quelle que soit leur nature.These results indicate that the gel structure is preserved in the presence of surfactant whatever their nature.

L'évolution du module G' à 1 rad/s pour les tensio-actifs SDS, LABS et C12E8 est donnée à la figure n° 3 (1/3 et 2/3). De plus, le tan δ à 0,01 rad/s est rapporté tableau n° 2.The evolution of the module G 'at 1 rad / s for the SDS, LABS and C12E8 surfactants is given in FIG. 3 (1/3 and 2/3). In addition, the tan δ at 0.01 rad / s is reported in table 2.

Ces données indiquent le caractère élastique plus ou moins prononcé de ces gels et confirment que les propriétés mécaniques de ces gels sont conservées, voire améliorées, par rapport aux gels sans tensio-actif.These data indicate the more or less pronounced elastic nature of these gels and confirm that the mechanical properties of these gels are preserved, or even improved, compared to gels without surfactant.

La figure n° 3 (1/3 et 2/3) représente l'évolution du module G' à 1 rad/s des mélanges sulfo-acétate de cellulose (15 g/l)/tensio-actif en fonction de la quantité en tensio actif (spectre a : tensio-actifs anioniques SDS et LABS ; spectre b : tensio-actif non ionique C12E8)Figure 3 (1/3 and 2/3) shows the evolution of the G 'module at 1 rad / s of the sulfo-cellulose acetate (15 g / l) / surfactant mixtures as a function of the quantity in surfactant (spectrum a: anionic surfactants SDS and LABS; spectrum b: nonionic surfactant C12E8)

Tableau n° 2 : Evolution de tan δ à 0,01 rad/s des gels de sulfo-acétate de cellulose (15 g/l), tensio-actif (nxCMC), eau à 25°C. Table n ° 2: Evolution of tan δ at 0.01 rad / s of cellulose sulfo-acetate gels (15 g / l), surfactant (nxCMC), water at 25 ° C.

Claims

REVENDICATIONS 1. Composition aqueuse caractérisée en ce qu'elle contient au moins un sulfo- acétate de cellulose et /ou au moins un de ses dérivés, et au moins un tensio-actif.1. An aqueous composition characterized in that it contains at least one cellulose sulfoacetate and / or at least one of its derivatives, and at least one surfactant. 2. Composition selon la revendication 1 caractérisée en ce qu'elle est sous forme de gel.2. Composition according to claim 1 characterized in that it is in the form of a gel. 3. Composition selon l'une quelconque des revendications 1 ou 2 caractérisée en ce que le tensio-actif est choisi parmi les tensio-actifs ioniques, non ioniques, seul ou en mélange.3. Composition according to any one of claims 1 or 2 characterized in that the surfactant is chosen from ionic, nonionic surfactants, alone or as a mixture. 4. Composition selon la revendication 3 caractérisée en ce que le tensio-actif est ionique.4. Composition according to claim 3 characterized in that the surfactant is ionic. 5. Composition selon l'une quelconque des revendications 3 ou 4 caractérisée en ce que le tensio-actif ionique est choisi parmi les alkylesters sulfonates, les alkylsulfates ainsi que leurs dérivés alcoxylés (notamment ethoxylés (OE) et/ou propoxylés (OP)), les alkylamides sulfates ainsi que leurs dérivés alcoxylés5. Composition according to any one of claims 3 or 4 characterized in that the ionic surfactant is chosen from alkyl esters sulfonates, alkyl sulfates as well as their alkoxylated derivatives (in particular ethoxylated (OE) and / or propoxylated (OP)) , alkylamide sulfates and their alkoxylated derivatives (notamment (OE) et/ou (OP)), les sels d'acides gras saturés ou insaturés et/ou leurs dérivés alcoxylés (notamment (OE) et/ou (OP)), les alkylbenzènesulfonates, les alkylsulfonates primaires ou secondaires, les alkylglycérol sulfonates, les acides polycarboxyliques sulfones, les sulfonates de paraffine, les N-acyl N- alkyltaurates, les alkylphosphates, les iséthionates, les alkylsuccinamates, les alkylsulfosuccinates, les monoesters ou diesters de sulfosuccinates, les N-acyl sarcosinates, les sulfates d'alkylglycosides, les sophorolipides.(in particular (OE) and / or (OP)), the salts of saturated or unsaturated fatty acids and / or their alkoxylated derivatives (in particular (OE) and / or (OP)), alkylbenzenesulfonates, primary or secondary alkylsulfonates, alkyl glycerol sulfonates, polycarboxylic acids sulfones, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, 'alkylglycosides, sophorolipids. 6. Composition selon la revendication 3 caractérisée en ce que le tensio-actif est non-ionique.6. Composition according to claim 3 characterized in that the surfactant is non-ionic. 7. Composition selon l'une quelconque des revendications 3 ou 6 caractérisée en ce que le tensio-actif non ionique est choisi parmi les alkylphénols alcoxylés (notamment (OE) et/ou (OP)), les alcools aliphatiques plus particulièrement en C8- C22, les produits résultant de la condensation de l'oxyde d'éthylène ou de l'oxyde de propylène avec le propylène glycol ou l'éthylène glycol, les produits résultant de la condensation de l'oxyde d'éthylène ou de l'oxyde de propylène avec l'éthylène diamine, les acides gras alcoxylés (notamment (OE) et/ou (OP)), les amides d'acides gras alcoxylés (notamment (OE) et/ou (OP)), les aminés alcoxylés (notamment (OE) et/ou (OP)), les amidoamines alcoxylés (notamment (OE) et/ou (OP)), les oxydes d'aminés, les hydrocarbures terpéniques alcoxylés (notamment (OE) et/ou (OP)), les alkylpolyglycosides, les polymères ou oligomères amphiphile.7. Composition according to any one of claims 3 or 6 characterized in that the nonionic surfactant is chosen from alkoxylated alkylphenols (in particular (OE) and / or (OP)), aliphatic alcohols more particularly of C 8 - C 22 , the products resulting from the condensation of ethylene oxide or propylene oxide with propylene glycol or ethylene glycol, the products resulting from the condensation of ethylene oxide or l propylene oxide with ethylene diamine, alkoxylated fatty acids (in particular (OE) and / or (OP)), alkoxylated fatty acid amides (especially (OE) and / or (OP)), alkoxylated amines (especially (OE) and / or (OP)), alkoxylated amidoamines (especially (OE) and / or (OP)) , amine oxides, alkoxylated terpene hydrocarbons (in particular (OE) and / or (OP)), alkylpolyglycosides, amphiphilic polymers or oligomers. 8. Composition selon l'une quelconque des revendications 3 ou 6 ou 7 caractérisée en ce que le tensio-actif est le mono-n-dodécyl éther octaéthylène glycol .8. Composition according to any one of claims 3 or 6 or 7 characterized in that the surfactant is mono-n-dodecyl ether octaethylene glycol. 9. Composition selon l'une quelconque des revendications 1 à 3 et 6 à 8 caractérisée en ce la concentration en tensio-actif non ionique est inférieure ou égale à 150 fois la concentration micellaire critique du tensio-actif, de préférence inférieure ou égale à 100 fois la concentration micellaire critique du tensio-actif.9. Composition according to any one of claims 1 to 3 and 6 to 8 characterized in that the concentration of nonionic surfactant is less than or equal to 150 times the critical micellar concentration of the surfactant, preferably less than or equal to 100 times the critical micellar concentration of the surfactant. 10. Composition selon l'une quelconque des revendications 1 à 5 caractérisée en ce la concentration en tensio-actif ionique est inférieure ou égale à 10 fois la concentration micellaire critique du tensio-actif.10. Composition according to any one of claims 1 to 5 characterized in that the concentration of ionic surfactant is less than or equal to 10 times the critical micellar concentration of the surfactant. 11. Composition selon l'une quelconque des revendications 1 à 10 caractérisée en ce la concentration en sulfo-acétate de cellulose ou un de ses dérivés est comprise entre 0,01 % et 20 %, de préférence entre 0,1 % et 5 %, plus particulièrement comprise entre 0,5 % et 3% en poids de la composition.11. Composition according to any one of claims 1 to 10 characterized in that the concentration of cellulose sulfo-acetate or one of its derivatives is between 0.01% and 20%, preferably between 0.1% and 5% , more particularly between 0.5% and 3% by weight of the composition. 12. Procédé de préparation de la composition selon l'une quelconque des revendications 1 à 11, caractérisé en ce que ce procédé consiste à mettre en contact une phase aqueuse, au moins un tensio-actif et le sulfo-acétate de cellulose ou un de ses dérivés (étape (i)).12. Process for preparing the composition according to any one of claims 1 to 11, characterized in that this process consists in bringing an aqueous phase into contact, at least one surfactant and the cellulose sulfoacetate or one of its derivatives (step (i)). 13. Procédé de préparation selon la revendication 12 caractérisé en ce que l'on introduit, pendant l'étape (i), dans une phase aqueuse au moins un tensio-actif puis le sulfo-acétate de cellulose ou un de ses dérivés.13. Preparation process according to claim 12 characterized in that one introduces, during step (i), into an aqueous phase at least one surfactant and then the cellulose sulfoacetate or one of its derivatives. 14. Procédé selon l'une des revendications 12 ou 13 caractérisé en ce que l'on effectue un traitement thermique à une température comprise entre 30°C et 140°C, avantageusement entre 60°C et 120°C, après l'étape (i). 14. Method according to one of claims 12 or 13 characterized in that a heat treatment is carried out at a temperature between 30 ° C and 140 ° C, advantageously between 60 ° C and 120 ° C, after step (i). 15. Procédé selon la revendication 14 caractérisée en ce que l'on effectue le traitement thermique pendant une durée de 1 minute à 6 heures, de préférence de 15 minutes à 4 heures.15. The method of claim 14 characterized in that the heat treatment is carried out for a period of 1 minute to 6 hours, preferably from 15 minutes to 4 hours. 16. Procédé selon l'une quelconque des revendications 12 à 15 caractérisée en ce que l'on refroidit ladite solution issue de l'étape (i), jusqu'à une température comprise entre 0°C et la température ambiante.16. Method according to any one of claims 12 to 15 characterized in that said solution from step (i) is cooled to a temperature between 0 ° C and room temperature. 17. Utilisation de la composition selon l'une quelconque des revendications 1 à 11 dans des formulations destinées aux domaines de la cosmétique, de la détergence, de l'alimentaire, du papier, de l'agrochimie, pharmaceutiques, tinctoriales, des fluides de forage.17. Use of the composition according to any one of claims 1 to 11 in formulations intended for the fields of cosmetics, detergency, food, paper, agrochemistry, pharmaceuticals, dyes, drilling. 18. Formulation détergente comprenant la composition selon l'une des revendications 1 à 11. 18. Detergent formulation comprising the composition according to one of claims 1 to 11.
EP02727695A 2001-04-26 2002-04-25 Composition containing cellulose sulphoacetate and surfactant Withdrawn EP1381661A1 (en)

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FR0105618A FR2824069B1 (en) 2001-04-26 2001-04-26 COMPOSITION CONTAINING AT LEAST ONE CELLULOSE SULFOACETATE AND AT LEAST ONE SURFACTANT, PROCESS FOR PREPARING THE SAME AND USES THEREOF
PCT/FR2002/001429 WO2002088288A1 (en) 2001-04-26 2002-04-25 Composition containing cellulose sulphoacetate and surfactant

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US9167830B2 (en) * 2012-01-27 2015-10-27 Celanese Acetate Llc Substituted cellulose acetates and uses thereof
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US9212290B2 (en) 2012-01-27 2015-12-15 Celanese Acetate Llc Substituted cellulose acetates and uses thereof
US9138967B2 (en) 2012-09-24 2015-09-22 Celanese Acetate Llc Wood laminate articles comprising substituted cellulose ester adhesives and methods relating thereto
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US3184421A (en) * 1961-05-24 1965-05-18 Eastman Kodak Co Polymeric composition prepared from cellulose sulfate and alkyl acrylate and textilematerial coated therewith
US3794605A (en) * 1971-07-19 1974-02-26 Procter & Gamble Built detergent composition containing whiteness maintenance additive
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