WO2002088288A1 - Composition containing cellulose sulphoacetate and surfactant - Google Patents
Composition containing cellulose sulphoacetate and surfactant Download PDFInfo
- Publication number
- WO2002088288A1 WO2002088288A1 PCT/FR2002/001429 FR0201429W WO02088288A1 WO 2002088288 A1 WO2002088288 A1 WO 2002088288A1 FR 0201429 W FR0201429 W FR 0201429W WO 02088288 A1 WO02088288 A1 WO 02088288A1
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- WO
- WIPO (PCT)
- Prior art keywords
- surfactant
- composition according
- alkoxylated
- derivatives
- cellulose
- Prior art date
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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.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02727695A EP1381661A1 (en) | 2001-04-26 | 2002-04-25 | Composition containing cellulose sulphoacetate and surfactant |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR01/05618 | 2001-04-26 | ||
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 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002088288A1 true WO2002088288A1 (en) | 2002-11-07 |
Family
ID=8862718
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2002/001429 WO2002088288A1 (en) | 2001-04-26 | 2002-04-25 | Composition containing cellulose sulphoacetate and surfactant |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1381661A1 (en) |
FR (1) | FR2824069B1 (en) |
WO (1) | WO2002088288A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015511253A (en) * | 2012-01-27 | 2015-04-16 | セラニーズ アセテート,エルエルシー | Substituted cellulose acetate and method of use |
US9023757B2 (en) | 2012-01-27 | 2015-05-05 | Celanese Acetate Llc | Substituted cellulose acetates and uses thereof |
US9090045B2 (en) | 2012-09-24 | 2015-07-28 | Celanese Acetate Llc | Engineered wood produced with substituted cellulose ester adhesives and methods relating thereto |
US9138967B2 (en) | 2012-09-24 | 2015-09-22 | Celanese Acetate Llc | Wood laminate articles comprising substituted cellulose ester adhesives and methods relating thereto |
US9212290B2 (en) | 2012-01-27 | 2015-12-15 | Celanese Acetate Llc | Substituted cellulose acetates and uses thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3184421A (en) * | 1961-05-24 | 1965-05-18 | Eastman Kodak Co | Polymeric composition prepared from cellulose sulfate and alkyl acrylate and textilematerial coated therewith |
US3236779A (en) * | 1960-03-01 | 1966-02-22 | Eastman Kodak Co | Detergent compositions |
US3794605A (en) * | 1971-07-19 | 1974-02-26 | Procter & Gamble | Built detergent composition containing whiteness maintenance additive |
US3994827A (en) * | 1973-12-18 | 1976-11-30 | Jujo Paper Co., Ltd. | Micro-encapsulating method |
US4321261A (en) * | 1978-01-05 | 1982-03-23 | Polymer Technology Corporation | Ionic ophthalmic solutions |
WO1999042548A1 (en) * | 1998-02-23 | 1999-08-26 | Unilever Plc | Detergent compositions |
FR2789080A1 (en) * | 1999-01-29 | 2000-08-04 | Agronomique Inst Nat Rech | PROCESS FOR THE PREPARATION OF CELLULOSE SULFOACETATE DERIVATIVES AND CORRESPONDING PRODUCTS AND MIXTURES |
-
2001
- 2001-04-26 FR FR0105618A patent/FR2824069B1/en not_active Expired - Fee Related
-
2002
- 2002-04-25 EP EP02727695A patent/EP1381661A1/en not_active Withdrawn
- 2002-04-25 WO PCT/FR2002/001429 patent/WO2002088288A1/en not_active Application Discontinuation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3236779A (en) * | 1960-03-01 | 1966-02-22 | Eastman Kodak Co | Detergent compositions |
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 |
US3994827A (en) * | 1973-12-18 | 1976-11-30 | Jujo Paper Co., Ltd. | Micro-encapsulating method |
US4321261A (en) * | 1978-01-05 | 1982-03-23 | Polymer Technology Corporation | Ionic ophthalmic solutions |
WO1999042548A1 (en) * | 1998-02-23 | 1999-08-26 | Unilever Plc | Detergent compositions |
FR2789080A1 (en) * | 1999-01-29 | 2000-08-04 | Agronomique Inst Nat Rech | PROCESS FOR THE PREPARATION OF CELLULOSE SULFOACETATE DERIVATIVES AND CORRESPONDING PRODUCTS AND MIXTURES |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015511253A (en) * | 2012-01-27 | 2015-04-16 | セラニーズ アセテート,エルエルシー | Substituted cellulose acetate and method of use |
US9023757B2 (en) | 2012-01-27 | 2015-05-05 | Celanese Acetate Llc | Substituted cellulose acetates and uses thereof |
US9167830B2 (en) | 2012-01-27 | 2015-10-27 | Celanese Acetate Llc | Substituted cellulose acetates and uses thereof |
US9212290B2 (en) | 2012-01-27 | 2015-12-15 | Celanese Acetate Llc | Substituted cellulose acetates and uses thereof |
US9090045B2 (en) | 2012-09-24 | 2015-07-28 | Celanese Acetate Llc | Engineered wood produced with substituted cellulose ester adhesives and methods relating thereto |
US9138967B2 (en) | 2012-09-24 | 2015-09-22 | Celanese Acetate Llc | Wood laminate articles comprising substituted cellulose ester adhesives and methods relating thereto |
Also Published As
Publication number | Publication date |
---|---|
FR2824069B1 (en) | 2007-03-16 |
EP1381661A1 (en) | 2004-01-21 |
FR2824069A1 (en) | 2002-10-31 |
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