EP1692251B1 - Procede pour eviter ou minimiser la redeposition de couleur par utilisation de polyesters - Google Patents

Procede pour eviter ou minimiser la redeposition de couleur par utilisation de polyesters Download PDF

Info

Publication number
EP1692251B1
EP1692251B1 EP04802921A EP04802921A EP1692251B1 EP 1692251 B1 EP1692251 B1 EP 1692251B1 EP 04802921 A EP04802921 A EP 04802921A EP 04802921 A EP04802921 A EP 04802921A EP 1692251 B1 EP1692251 B1 EP 1692251B1
Authority
EP
European Patent Office
Prior art keywords
proceeding
dye
acid
polyester
compounds
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.)
Active
Application number
EP04802921A
Other languages
German (de)
English (en)
Other versions
EP1692251A1 (fr
Inventor
Herbert Koch
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.)
Sasol Germany GmbH
Original Assignee
Sasol Germany GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sasol Germany GmbH filed Critical Sasol Germany GmbH
Priority to EP08016119A priority Critical patent/EP2009087A3/fr
Publication of EP1692251A1 publication Critical patent/EP1692251A1/fr
Application granted granted Critical
Publication of EP1692251B1 publication Critical patent/EP1692251B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • the present invention relates to a method for preventing or minimizing color position on fabric during a decoloring process, especially during a "stone-wash" process.
  • the fabric is preferably indigo-dyed cotton or cotton-containing fabrics.
  • the anti-color redeposition agent used is a polyester, preferably a terephthalic acid polyester-polyether polymer.
  • the pumice stone was discovered to accelerate the aging process of the indigo-dyed parts.
  • the "stone-wash look” is made possible by the fact that the dye is essentially only applied to the outer regions of the fibers. This is characteristic of an indigo dye. This is referred to as a so-called coat color, in which the color does not penetrate into the yarn, but it envelops like a coat and the core of the yarn or the fibers is not discolored.
  • the enzyme used here is usually a cellulase.
  • the cellulase is temporarily bound to the cellulose by an anchor and cleaves it to its 1,4-betaglucosidic linkage.
  • the cellulase is temporarily bound to the cellulose by an anchor and cleaves it to its 1,4-betaglucosidic linkage.
  • the cellulase is temporarily bound to the cellulose by an anchor and cleaves it to its 1,4-betaglucosidic linkage.
  • the cellulase is temporarily bound to the cellulose by an anchor and cleaves it to its 1,4-betaglucosidic linkage.
  • the surface of the cotton fiber on which the indigo dye is located partially detached.
  • underneath, not colored and thus white areas of the cotton fiber come to light.
  • the use of the cellulases achieves an optical effect, which corresponds to the use of pumice.
  • the cellulases used in the enzymatic stone-wash process can be divided into two groups: acidic and neutral cellulases.
  • the terms “acidic” and “neutral” are used to describe the pH at which the enzyme develops its optimum performance. For acid cellulases, this is the range of about 4 to 6, while neutral cellulases show their optimum performance at pH values of about 6 to 8.
  • a major difference is the higher abrasion that allows acidic cellulases compared to neutral ones.
  • acidic cellulases the same abrasion properties can be set when using 10 to 20% of the amount of neutral cellulase.
  • acid cellulases allow shorter treatment times and are also significantly cheaper, which leads to an overall economic advantage. Disadvantages, however, are the so-called "backstaining" (color printing position).
  • Under color printing position refers to a back discoloration or mulch including the cotton with peeled dye or dye on fiber remains. These deposits can be observed at various points, such as inside pockets, labels, seams, zippers, but also in particular on the inner and outer surface of the denim. Backstaining creates an undesirable low-contrast appearance of the product.
  • the color printing position is a function of the cellulase mixture used, the dye, the type of surfactant used, the surfactant concentration and the pH.
  • nonionic fatty alcohol ethoxylates with anionic alkanesulfonate to achieve an anti-redepositon effect is described.
  • anionic surfactants lead to a negative interaction with the cellulase, such that their abrasiveness is reduced.
  • the WO 01/57173 describes an enzymatic 2-component system by means of which it is possible to produce a good stone-wash effect on dyed cotton or cotton-containing fabrics with a simultaneously very low Backstaining.
  • the 2-component system contains, in addition to a cellulase component, special aqueous polymer dispersions whose solid particles are styrene / (meth) acrylic acid ester copolymers which have been grafted onto starch as the graft base.
  • the WO 95/35363 describes a method for producing a stone-wash effect by using acidic cellulases in the presence of color anti redeposition agents selected from the group of natural and synthetic, inorganic silicates, polyalkylene oxides, acrylic acid polymers and natural and synthetic or semisynthetic polysaccharides.
  • color transfer inhibitors described in the prior art such as polyvinylpyrollidones, polyvinylpyridine N-oxides, etc.
  • these compounds are not effective enough when it comes to backstaining
  • indigo which may be - without wishing to be bound by theory - may be due to the extreme hydrophobicity of this dye.
  • Polyesters are already preparable by reacting polymeric waste terephthalates, such as polyethylene terephthalate, polybutylene terephthalate or poly (cyclohexanedimethanol) terephthalate, glycols and oxyalkylated polyols having at least 3 hydroxyl groups, which are used in dyeing and Entfärbereaen to prevent the color printing position.
  • polymeric waste terephthalates such as polyethylene terephthalate, polybutylene terephthalate or poly (cyclohexanedimethanol) terephthalate
  • glycols and oxyalkylated polyols having at least 3 hydroxyl groups which are used in dyeing and Entfetzbeskeleton.
  • the actually disclosed polyesters are further prepared using trimellitic acid and / or isophthalic acid or their derivatives.
  • the object of the present invention is to provide a means which effectively prevents inking deposition on textile fabric during a decoloring process, ie during a stone-wash process and / or biostoning process.
  • the agent should act as an anti-redeposition agent for the released dye, in particular indigo, or the dye-coated particles, such that it not only compared to the pure denim, but also with respect to typical accessories of denim or jeans such as pocket lining, stitching , Labels and zippers, which are often not made of cotton.
  • polyesters formed from terephthalic acid units and glycols and / or polyether diols are known which are used in dyeing and decolorization processes to prevent color printing.
  • polyethylene terephthalates obtained from waste polyethylene terephthalates by reaction with glycols and oxyalkylated polyols as part of an ester cleavage or transesterification reaction. In the transesterification, isophthalic acid and optionally trimellitic acid should be present.
  • the JP-A-2002- 142760 -A teaches polyester from terephthalic acid oligoalkylene glycol units with up to 4 ethylene glycol units in total.
  • the US-A-5,486,297 relates to a finishing agent which prevents the fading of the color strength of textiles
  • the object is achieved by a.
  • soil release polymers soil release polymers
  • these are preferably amphiphilic, preferably nonionic polyester-containing polyether monomer sequences.
  • Polyetherols are used to prepare the polyether monomer sequences.
  • Polyetherols in the context of the invention are compounds having one or two hydroxyl groups containing at least 6 oxygen atoms, preferably at least 10 oxygen atoms and in particular more than 16 oxygen atoms.
  • Diols in the context of the invention are compounds which have 2 hydroxyl groups and at most one, preferably no ether groups.
  • Compounds within the meaning of the main claim of the present invention are organic compounds which, in addition to carbon, hydrogen and oxygen after reaction, i. Incorporation into the polymer, i.d.R. have no further atoms.
  • the dicarboxylic acid compounds, after incorporation into the polyester may carry not only carboxyl groups, but also carbonyl or hydroxyl groups, but e.g. have no sulfonyl or halogen groups,
  • the dicarboxylic acid compound (A) are terephthalic acid and optionally aliphatic and / or aromatic dicarboxylic acids and derivatives thereof, ie, for example, their monoesters, diesters, anhydrides or mixtures.
  • the dicarboxylic acid compounds have - based on the dicarboxylic acid or dicarboxylic acid group - preferably 3 to 40 carbon atoms.
  • aromatic dicarboxylic acid compounds may be isophthalic acid, phthalic acid, their mono- and dialkyl esters with C 1 to C 5 alcohols, such as dimethyl terephthalate, mixtures of these Connections are possible.
  • aliphatic dicarboxylic acid compounds are malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid dialkyl esters.
  • Isophthalic acid and phthalic acid, and their dimethyl, diethyl, dipropyl and dibutyl esters are particularly preferably used.
  • terephthalic acid is used as the dicarboxylic acid in the process according to the invention terephthalic acid, to greater than 90 mol%, preferably greater than 95 mol%, based on the di- or tricarboxylic acid compounds used.
  • other dicarboxylic acid compounds may also be used.
  • Aromatic dicarboxylic acids in addition to terephthalic acid, in particular isophthalic acid, phthalic acid, their mono- and dialkyl esters with C1 to C5 alcohols, such as. Dimethyl terephthalate, of course, mixtures of these components are possible.
  • aliphatic dicarboxylic acid equivalents are malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid dialkyl esters.
  • terephthalic acid and phthalic acid and their dimethyl, diethyl, dipropyl and dibutyl esters.
  • tricarboxylic acid compounds in principle, it is also possible to use tricarboxylic acid compounds, as a result of which highly branched polymer structures become accessible. Suitable for this purpose are e.g. Trimellitic acid or its derivatives such as anhydrides and esters. However, their use is usually to be avoided.
  • the polyol compounds (D) preferably have 3 to 12 carbon atoms.
  • Examples of the polyol compounds having at least 3 OH groups are: pentaerythritol, trimethylolethane, trimethylolpropane, 1,2,3-hexanetriol, sorbitol, mannitol, mono-, di- and triglycerol, 1,2,3- Butanetriol, 1,2,4-butanetriol. Preference is given to the use of glycerol.
  • polyether oleczu call which represent preferably to more than 30 wt.%, A major proportion of the polymer.
  • examples of these are polypropylene glycol, polybutylene glycol and addition products of ethylene oxide, propylene oxide, butylene oxide or their mixtures of aliphatic alcohols such as methanol. Ethanol, propanol, butanol or long-chain fatty alcohols.
  • the methylene glycols can be used with weight average molecular weights of 3000 to 8000 g / mol.
  • Polyethylene glycol monomethyl ethers having molecular weights of 2,000 to 5,000 g / mol may be preferably used.
  • diol compound (B) in addition to the ethylene glycol, 1,2- or 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 3-methoxy-1,2-propylene glycol and their dimers and trimers can be used.
  • the diol compound (B) preferably has 2 to 6 carbon atoms. In principle, mixtures of different diols are possible. Preference is given to the use of ethylene glycol and propylene glycol.
  • polymers anionically can e.g. by condensation of anionic monomers, e.g. Sulfophthaloyl, Sulfoisophthaloyl- and Sulfoterephthaloyl- groups which are used in the form of their salts, in particular as alkali metal or ammonium salts.
  • anionic monomers e.g. Sulfophthaloyl, Sulfoisophthaloyl- and Sulfoterephthaloyl- groups which are used in the form of their salts, in particular as alkali metal or ammonium salts.
  • aliphatic anionic monomers derived from sulfonated aliphatic diesters e.g. Derive maleic acid, adipic acid, sebacic acid, etc.
  • nonionic PET polyethylene terephthalate
  • PET polyoxyethylene terephthalate
  • polyesters polyethylene glycols having molecular weights of 2,000 to 8,000 g / mol.
  • the recovered PET-POET copolymers are solid at room temperature and have weight average molecular weights of 5,000 to 40,000 g / mol.
  • liquid polyester-polyether copolymers represented by the formula X- (OCH 2 -CH 2 ) n - [- (OOC-R 1 -COO-R 2 ) u -] - OOC-R 1 -COO- (CH 2 -CH 2 O) n -X
  • each R 1 radical is a 1,4-phenylene radical, optionally mono- or di-C 1 -C 3 -alkyl-substituted
  • the R 2 radicals are essentially ethylene radicals, 1,2-propylene radicals or mixtures thereof
  • each X is independently hydrogen, a C1 to C12 hydrocarbon radical, especially ethyl or methyl
  • each n is independently from 7 to 115 and u is from 3 to 10.
  • the synthesis of the polymers used according to the invention can be carried out in the form of a direct reaction of all monomer building blocks in one step, so that statistically distributed polymers (so-called "random" structures) are obtained.
  • Another mode of preparation is a multi-step synthesis e.g. in such a way that a precondensation of different components takes place.
  • temperatures of about 80 to 350 ° C and pressures of normal pressure to ⁇ 1 mbar are set.
  • the condensation is carried out in the temperature range of 150 to 280 ° C in the presence of the usual polycondensation and transesterification catalysts.
  • the polymers obtained can be adjusted to different molecular weights. These are preferably between 1,000 and 40,000 g / mol.
  • Suitable catalysts are known from the literature compounds. If the free dicarboxylic acids or anhydrides are used as the component, p-toluenesulfonic acid is the preferred catalyst. If dicarboxylic acid dialkyl ester is used as the component, the usual transesterification catalysts are used, such as, for example, mixtures of calcium acetate and antimony oxide, organic and inorganic tin and zinc compounds (eg stannanes, zinc acetate or the TEGO® catalysts of Degussa) or tetraalkoxytitanates, such as titanium tetraisobutanolate or tetraisopropoxide.
  • the usual transesterification catalysts are used, such as, for example, mixtures of calcium acetate and antimony oxide, organic and inorganic tin and zinc compounds (eg stannanes, zinc acetate or the TEGO® catalysts of Degussa) or tetraalkoxytitanates,
  • the condensation can be carried out in the presence of antioxidants, e.g. substituted phenols such as 2,5-di-tert-butylphenol, 2-methylcyclohexyl-4,6-dimethylphenol, phosphorous acid or other antioxidants commonly used therefor.
  • antioxidants e.g. substituted phenols such as 2,5-di-tert-butylphenol, 2-methylcyclohexyl-4,6-dimethylphenol, phosphorous acid or other antioxidants commonly used therefor.
  • a common aftertreatment is, for example, a bleaching with hydrogen peroxide, which leads to a clear color lightening.
  • the polymers used in the process according to the invention can be obtained both in solid and in pasty to liquid form.
  • the additives are also preferred in solid form. It is possible, depending on the morphology, to use the polymers both as 100% form e.g. milled form or in supported form i. by applying the polymer to a solid support by means of the granulation methods described in the prior art.
  • these compounds can also be used in the form of a matrix.
  • matrix here is the blend of amphiphilic polyester-polyether copolymers with, for example, nonionic surfactants, such as alcohol ethoxylates, alcohol propoxylates, mixed alcohol alkoxylates, alkyl polyglucosides, glucose amides, polyethylene glycols, polypropylene glycols, mixed polyalkylene glycols, solvents such as isopropanol, propylene glycol, glycol ethers, water.
  • nonionic surfactants such as alcohol ethoxylates, alcohol propoxylates, mixed alcohol alkoxylates, alkyl polyglucosides, glucose amides, polyethylene glycols, polypropylene glycols, mixed polyalkylene glycols, solvents such as isopropanol, propylene glycol, glycol ethers, water.
  • polyester-polyether copolymers may also be supported on support materials, e.g. Zeolites, phosphates, citrates, sodium sulphate, pumice or pumice equivalents such as perlites and thereby e.g. be converted into free-flowing powdery compounds.
  • support materials e.g. Zeolites, phosphates, citrates, sodium sulphate, pumice or pumice equivalents such as perlites and thereby e.g. be converted into free-flowing powdery compounds.
  • support materials e.g. Zeolites, phosphates, citrates, sodium sulphate, pumice or pumice equivalents such as perlites.
  • Such compounds can be advantageously incorporated in powdered stone wash formulations.
  • the antiredepositol agents used in the process according to the invention are preferably used in amounts of from 0.1 to 20% by weight, based on the Stone Wash formulation (excluding abrasives).
  • formulations are based on a combination of mechanical treatment and enzyme treatment (stone-washing and biostoning). Instead of pumice sintered perlites are often used, which lead due to their hardness to less abrasion during the process. In addition, they are smaller than pumice stones, have a larger surface area, which makes it possible to rinse the stones with the wash liquor.
  • the central building block of the enzymatic formulations for producing a stone-wash effect is one or more cellulases. Essentially, two groups of cellulases are used: acid and neutral.
  • these formulations contain further constituents.
  • a buffer system which has the task of keeping the pH constant within certain limits in order to ensure optimal performance of the enzyme system.
  • the buffering of the cellulase bath is very important, since alkalinity is often introduced by the tissue in particular.
  • surfactants Another essential ingredient of these formulations are surfactants. Their task is u.a. to accomplish rapid wetting of the cellulosic fiber such that the cellulase can attack the fiber as quickly as possible. Further functions of the surfactants are the removal of excess sizing agent, the suspension of the indigo dye and the emulsification of oil and fat components. In addition, they continue to serve as dispersants and Lauffaltenverhinderer within this application.
  • Nonionic surfactants such as the fatty alcohol alkoxylates described in the prior art, castor oil ethoxylates etc. are preferred.
  • the reason for the preferred use of nonionic surfactants lies in their good wetting of the fibers with at the same time little influence on the cellulase activity.
  • Anionic surfactants can sometimes have negative effects on the enzymes, such that their activity is reduced or incompatibilities occur.
  • the proportion of surfactant within the formulations is preferably in the range from 5 to 25% by weight (excluding abrasives).
  • Stone-Wash formulations may also contain other ingredients, e.g. Enzyme activators, solubilizers, solvents, antioxidants, builders or sequestering agents.
  • Enzyme activators e.g. Enzyme activators, solubilizers, solvents, antioxidants, builders or sequestering agents.
  • Examples of typical solvents are: ethylene glycol, propylene glycol and their oligomers / polymers, terpenes, hydrocarbons.
  • Examples of enzyme activators are: proteins, salts of monosaccharides, e.g. Mannose and xylose.
  • Typical solubilizers are: short-chain alcohols, benzenesulfonate salts, propylene glycol, benzoates, etc.
  • Builders or sequestrants often used are: organic phosphates, phosphonates, polyacrylic acids, polyvinyl alcohols, polyvinylpyrollidones, borates, citrates.
  • the process of producing denim or denim consists essentially of three main steps: desizing, abrasion (stoning / biostoning) and bleaching.
  • the sizing agent which is usually starch
  • this step was accomplished by alkaline scrubbing at higher temperatures.
  • amylases or combinations of amylases and lipases These break down the starch polymers into short, water-soluble fragments that can be washed out.
  • the background of this step is the creation of soft denim surfaces, prevention of banding and preparation of the fabric for the subsequent step of abrasion.
  • surfactants are also used in this step.
  • one or more rinsing steps can take place before the next treatment step.
  • the abrasion step is the described stone-washing or biostoning or combinations of stone-washing and biostoning.
  • cellulose fragments are removed from the surface, creating the classic stone-wash look.
  • the cellulases After achieving the required abrasion, the cellulases must be deactivated to stop further degradation of the tissue. This is done in a subsequent washing process, at alkaline pH values and higher temperatures at which the enzyme denatures. Finally, the tissue i.d.R. under standard conditions bleached with the bleaching agents described in the prior art, e.g. Hypochlorite.
  • the antiredeposition agents described in the method according to the invention are also distinguished, inter alia, by their affinities for hydrophobic surfaces such as, for example, polyester, polyamide or their blended fabrics with cotton. Since the accessories of jeans such as pocket lining, zippers, labels, seams, etc. are often made of these materials, it is recommended additives of the invention not only in the actual stone-wash process but before, ie in the desizing of the fiber. Here, these accessories receive an efficient surface impregnation, which essentially means that the indigo released in the stone-wash process is less attracted to these surfaces.
  • polyesters of the example 1,2,4 are not covered by the claims.
  • a total of 640 g (1.45 mol) of polyethylene glycol monomethyl ether having a weight-average molecular weight of about 440 g / mol (MARLIPAL 1) were introduced into a 2 l multi-necked flask with glass stirrer, heating bath, inert gas inlet, distillation head, packed column, distillation bridge, vacuum distributor, distillation flask, cold trap and internal thermometer / 12 from Sasol Germany GmbH), 388 g (2.0 mol) of dimethyl terephthalate, 110.5 g (1.2 mol) of glycerol, 145.8 g (1.4 mol) of neopentyl glycol, 1.0 g of 2,6- Di-tert-butyl-p-cresol (Ionol from Shell) and 1 ml of tetraisopropyl orthotitanate submitted under inert gas.
  • MARLIPAL 1 polyethylene glycol monomethyl ether having a weight-average molecular weight of about
  • reaction mixture was slowly heated to temperatures of 150 to 220 ° C and collected the methanol formed. After most of the theoretically expected amount of methanol was collected, the reaction mixture was cooled, the column removed, vacuum applied and the mixture heated again up to a maximum of 230 ° C. The unreacted in the reaction diol / polyol mixture was collected as distillate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Textile Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Detergent Compositions (AREA)
  • Coloring (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (15)

  1. Procédé pour empêcher ou pour minimiser la redéposition de couleurs sur des tissus textiles pendant un processus de "Stone Wash" (lavage à la pierre ponce) et/ou de "Biostoning" (lavage aux enzymes) appliqué sur des tissus en coton teints indigo, en mettant en contact le tissu teint comportant des fibres en coton pendant le processus de décoloration avec un produit antiredéposition de couleurs, caractérisé en ce que le produit antiredéposition de couleurs est un polyester, susceptible d'être produit par transformation d'au moins les monomères suivants dans le cadre d'une réaction d'estérification :
    (A) un ou plusieurs composés d'acide dicarbonique, plus de 90 % en moles des composés d'acide dicarbonique utilisés étant de l'acide téréphtalique,
    (B) un ou plusieurs composés diol avec de 2 à 6 atomes de carbone, plus de 90 % en moles des composés diol utilisés étant de l'éthylène glycol et
    (C) de polyétherols avec un ou 2 groupes hydroxy comportant au moins 6 atomes de carbone, plus de 90 % en poids des polyétherols utilisés étant du polyéthylène glycol d'un poids moléculaire de 2000 à 8000 g/mole et
    les monomères (A), (B) et (C) correspondant à plus de 80 % en poids des monomères incorporés.
  2. Procédé selon la revendication 1, caractérisé en ce que les monomères (A), (B) et (C) correspondent à plus de 90 % en poids, notamment à plus de 95 % en poids des monomères incorporés.
  3. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les polyesters sont susceptibles d'être produits par ailleurs en utilisant
    (D) un ou plusieurs composés polyol avec au moins 3 groupes OH, comportant de 3 à 12 atomes de carbone, notamment de la glycérine.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les composés d'acide dicarbonique (A) comprennent de l'acide téréphtalique, de l'acide isophthalique, de l'acide phtalique et leurs dérivés.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que, indépendamment les uns des autres,
    (a) on n'utilise aucun composé d'acide tricarbonique,
    (b) pas d'acide isophthalique, ni ses dérivés.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le composé diol (B) est de l'éthylène glycol et/ou du propylène glycol.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en de que le polyester subit une modification anionique et/ou est enfermé dans le groupe terminal par incorporation de monomères anioniques.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les polyéthérols (C) sont des produits d'addition d'oxyde d'alkylène (C) d'oxyde d'éthylène, d'oxyde de propylène, d'oxyde de butylène ou leurs mélanges en alcools aliphatiques en C1 à C18, de préférence en C1 à C6, et/ou de l'eau.
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que pour la décoloration, on met on contact avec le tissu des pierres abrasives et/ou des enzymes, notamment au moins des cellulases pour obtenir un effet stone-wash.
  10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on met en contact le produit antiredéposition avec le tissu, aussi bien lors de l'étape de lavage à la pierre ponce que lors d'une étape de désencollage précédente.
  11. Procédé selon l'une quelconque des revendications précédentes, caractérisée en ce que les polyéthérols (C) comportent de 16 à 180 unités d'oxyde d'alkylène en C2 à C4.
  12. Procédé selon l'une quelconque des revendications 1 et/ou 2, caractérisé en ce que le polyester n'est pas produit en utilisant des polyols avec au moins 3 groupes OH.
  13. Utilisation d'un produit antiredéposition de couleur pour empêcher ou pour minimiser la redéposition de couleurs sur des tissus textiles pendant un processus de "stone wash" (lavage à la pierre ponce) et/ou de "Biostoning" (lavage aux enzymes) appliqué sur des tissus en coton teints indigo, en mettant en contact le tissu teint comportant des fibres en coton pendant le processus de décoloration avec un produit antiredéposition de couleurs, caractérisée en ce que le produit antiredéposition de couleurs consiste dans des polyesters, constitués selon la formule

            X- (OCH2-CH2) n- [- (OOC-R1-COO-R2) u-] -OOC-R1-COO-(CH2-CH2O) n-X

    dans laquelle chaque radical R1 est un radical 1,4-phényle, le cas échéant, mono ou di-alkylsubstitué en C1 à C3; les radicaux R2 sont principalement des radicaux d'éthylène, des radicaux de 1,2-propylène ou des mélanges de ces derniers ; chaque X signifie indépendamment l'un de l'autre un radical d'hydrocarbure, notamment de l'éthyl ou du méthyl ; chaque n s'élève à de 7 à 115 et u s'élève à de 3 à 10.
  14. Utilisation selon la revendication 13, caractérisée en ce que le polyester ou le mélange de polyesters est liquide à température ambiante.
  15. Utilisation selon la revendication 13, caractérisée en ce que les polyesters présentent des poids moléculaires inférieurs à 5000 g/mole.
EP04802921A 2003-12-10 2004-12-10 Procede pour eviter ou minimiser la redeposition de couleur par utilisation de polyesters Active EP1692251B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08016119A EP2009087A3 (fr) 2003-12-10 2004-12-10 Procédé pour eviter ou minimiser la redeposition de couleur par utilisation de polyester

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10358097A DE10358097A1 (de) 2003-12-10 2003-12-10 Verfahren zum Verhindern bzw. Minimieren der Farbredeposition unter Verwendung von Polyestern
PCT/DE2004/002716 WO2005056742A1 (fr) 2003-12-10 2004-12-10 Procede pour eviter ou minimiser la redeposition de couleur par utilisation de polyesters

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP08016119A Division EP2009087A3 (fr) 2003-12-10 2004-12-10 Procédé pour eviter ou minimiser la redeposition de couleur par utilisation de polyester

Publications (2)

Publication Number Publication Date
EP1692251A1 EP1692251A1 (fr) 2006-08-23
EP1692251B1 true EP1692251B1 (fr) 2008-11-19

Family

ID=34672624

Family Applications (2)

Application Number Title Priority Date Filing Date
EP08016119A Withdrawn EP2009087A3 (fr) 2003-12-10 2004-12-10 Procédé pour eviter ou minimiser la redeposition de couleur par utilisation de polyester
EP04802921A Active EP1692251B1 (fr) 2003-12-10 2004-12-10 Procede pour eviter ou minimiser la redeposition de couleur par utilisation de polyesters

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP08016119A Withdrawn EP2009087A3 (fr) 2003-12-10 2004-12-10 Procédé pour eviter ou minimiser la redeposition de couleur par utilisation de polyester

Country Status (13)

Country Link
US (1) US20080028539A1 (fr)
EP (2) EP2009087A3 (fr)
JP (1) JP2007514064A (fr)
CN (1) CN1890361A (fr)
AT (1) ATE414758T1 (fr)
BR (1) BRPI0417424A (fr)
CA (1) CA2549108A1 (fr)
DE (2) DE10358097A1 (fr)
DK (1) DK1692251T3 (fr)
ES (1) ES2318356T3 (fr)
PT (1) PT1692251E (fr)
TN (1) TNSN06177A1 (fr)
WO (1) WO2005056742A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080221973A1 (en) * 2005-10-24 2008-09-11 Megdal Myles G Using commercial share of wallet to rate investments
GB0625046D0 (en) 2006-12-15 2007-01-24 Dow Corning Granular materials for textile treatment
DE102007051279A1 (de) 2007-10-26 2009-04-30 Clariant International Ltd. Abwaschbare Farbmittelzubereitung
DE102008023803A1 (de) * 2008-05-15 2009-11-26 Clariant International Ltd. Additive für Wasch- und Reinigungsmittel
JP5537826B2 (ja) * 2009-03-30 2014-07-02 三洋化成工業株式会社 衣料洗浄剤用再汚染防止剤及び衣料洗浄剤
US8425727B2 (en) * 2010-01-22 2013-04-23 Clariant Finance (Bvi) Limited Method for increasing glueability of paper or paperboard
CN102493234B (zh) * 2011-12-22 2013-09-18 东莞市广利行洗涤原料有限公司 一种牛仔服装水洗的防染剂及其制备方法
CN103276615B (zh) * 2011-12-22 2014-12-03 东莞市广利行洗涤原料有限公司 一种牛仔服装水洗的防染剂及其制备方法
US10435647B2 (en) * 2017-08-08 2019-10-08 The Seydel Companies, Inc. Polyesters made from bio-renewable raw materials for preventing dye redeposition on fabrics and garments in textile finishing and garment washing processes
CN107604414B (zh) * 2017-08-22 2020-03-24 珠海市奥美伦精细化工有限公司 一种铝及铝合金阳极氧化高温无镍封闭剂
CN108049224A (zh) * 2017-12-07 2018-05-18 珠海宏河纺织材料有限公司 一种靛蓝染料的高浓聚酯改性表面活性剂的制备方法
CN108396560A (zh) * 2018-03-07 2018-08-14 广州市德鹏新材料科技有限公司 一种防染剂的制备方法
EP3680317B1 (fr) * 2019-01-11 2022-08-24 Henkel AG & Co. KGaA Détergents de protection des couleurs
TWI750456B (zh) * 2019-02-22 2021-12-21 南亞塑膠工業股份有限公司 一種經染色的聚酯纖維脫色方法
US20210095229A1 (en) * 2019-09-30 2021-04-01 The Procter & Gamble Company Fabric care compositions that include a copolymer and related methods
CN111118936A (zh) * 2020-01-03 2020-05-08 湖南金全立生物科技股份有限公司 一种多功能绿色环保防染剂及其制备方法
CN114016293A (zh) * 2021-12-15 2022-02-08 张家港市德宝化工有限公司 一种用于牛仔服装防反沾色剂及其制备方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4832864A (en) * 1987-09-15 1989-05-23 Ecolab Inc. Compositions and methods that introduce variations in color density into cellulosic fabrics, particularly indigo dyed denim
CA2164849C (fr) 1993-06-11 2006-01-03 Kathleen A. Clarkson Compositions enzymatiques et methodes pour donner un aspect delave a du tissu denim colore a l'indigo
JP3324860B2 (ja) * 1994-02-01 2002-09-17 明治製菓株式会社 染料付着防止剤及びそれを用いたあらかじめ染色された繊維又は繊維製品の処理方法
US5486297A (en) * 1994-06-14 1996-01-23 The Procter & Gamble Company Dye fading protection from soil release agents
IL113714A0 (en) 1994-06-22 1995-08-31 Ivax Ind Inc Method of treating dyed cellulosic fabric
US5486207A (en) * 1994-09-20 1996-01-23 Mahawili; Imad Thermal pad for portable body heating/cooling system and method of use
DE19606619A1 (de) 1996-02-22 1997-08-28 Henkel Kgaa Feste, praktisch wasserfreie Zubereitungen
DE19735715A1 (de) * 1997-08-18 1999-02-25 Huels Chemische Werke Ag Amphiphile Polymere auf Basis von Polyestern mit einkondensierten acetalischen Gruppen, die bei Raumtemperatur flüssig sind, sowie ihr Einsatz in Wasch- und Reinigungsmitteln
US6008182A (en) * 1998-06-22 1999-12-28 Seydel Research, Inc. Prevention of dye redeposition in fabric washing processes
DE10004893A1 (de) 2000-02-04 2001-08-16 Bayer Ag 2-Komponentensystem zur Herstellung eines Stone-wash-Effektes auf gefärbtem Baumwoll- oder baumwollhaltigen Geweben
AU2001263777A1 (en) 2000-06-02 2001-12-11 Novozymes A/S Redeposition or backstain inhibition during stonewashing process
DE10043604A1 (de) 2000-09-02 2002-03-28 Rwe Dea Ag Fließfähige, amphiphile und nichtionische Oligoester
JP4648536B2 (ja) * 2000-11-10 2011-03-09 明治製菓株式会社 ポリマーを含有するセルラーゼ調製物及び繊維処理方法
JP4393004B2 (ja) * 2001-02-06 2010-01-06 三菱化学株式会社 ポリエステル樹脂

Also Published As

Publication number Publication date
JP2007514064A (ja) 2007-05-31
ATE414758T1 (de) 2008-12-15
ES2318356T3 (es) 2009-05-01
WO2005056742A1 (fr) 2005-06-23
EP1692251A1 (fr) 2006-08-23
DE10358097A1 (de) 2005-07-14
DE502004008502D1 (de) 2009-01-02
EP2009087A2 (fr) 2008-12-31
DK1692251T3 (da) 2009-03-23
EP2009087A3 (fr) 2009-01-07
CA2549108A1 (fr) 2005-06-23
BRPI0417424A (pt) 2007-03-06
PT1692251E (pt) 2009-02-18
US20080028539A1 (en) 2008-02-07
CN1890361A (zh) 2007-01-03
TNSN06177A1 (en) 2007-11-15

Similar Documents

Publication Publication Date Title
EP1692251B1 (fr) Procede pour eviter ou minimiser la redeposition de couleur par utilisation de polyesters
EP2084321B1 (fr) Procédé de traitement de substrats
DE69926385T2 (de) Behandlung von geweben
EP2504379B1 (fr) Utilisation de concentrés de polyester ayant une grande stabilité de solution et un effet antiredéposition dans des compositions detergentes
KR100501765B1 (ko) 폴리에틸렌 테레프탈레이트 또는 테레프탈레이트들로부터의 설포아릴 개질된 수용성 또는 수분산성 수지
EP2504380B1 (fr) Polymères facilitant le lavage ayant un effet antiredéposition et une grande stabilité en solution
EP3222647A1 (fr) Polyester, son procédé de fabrication et d'utilisation
EP1313787A1 (fr) Oligoesters non ioniques, amphiphiles et a ecoulement libre
EP2552994B1 (fr) Polyesters colorés
EP2159233A1 (fr) Procédé pour la coloration des compositions polymériques comprenant les polyoléfines.
US20080210395A1 (en) Light-Colored Engineered Wood Boards
DE102008028409A1 (de) Verfahren zur Herstellung von Polyester-Granulaten
DE102004056785A1 (de) Fließfähige, amphiphile und nichtionische Oligoester
EP2313550B1 (fr) Procédé de post-traitement ménagé de textiles teints
WO1999067350B1 (fr) Procede empechant la teinture de se redeposer pendant le lavage d'un textile
DE102004058271A1 (de) Verwendung von wässrigen Dispersionen von wasserlöslichen (Co)polymerisaten von mindestens einem ethylenisch ungesättigten Monomer MON zur Herstellung von Textilhilfsmitteln
DE2343145A1 (de) Klarspuelmittel fuer das maschinelle spuelen von geschirr
EP2162582A2 (fr) Formulations aqueuses et leur utilisation pour colorer ou enduire des substrats
EP0801165B1 (fr) Prétraitement de textiles
MXPA06006589A (en) Method for preventing or minimizing color deposits using polyesters
EP1348800B1 (fr) Utilisation d'alkyl-benzoates comme agents égalisants pour la teinture de matériaux fibreux en polyester
EP1659153B1 (fr) Utilisation de dispersions aqueuses à base des copolymères hydrosolubles d'au moins un monomère "MON" pour la préparation d'adjuvants textiles
EP3409753B1 (fr) Renforcement de l'effet de blanchiment lors du lavage et du nettoyage
AT371854B (de) Verwendung von neuen hydrophilen polyacetalen als anti-absetzmittel und schmutzabweisende mittel fuer textilfasern
EP1347091A1 (fr) Adjuvant de teinture

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060607

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20061208

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502004008502

Country of ref document: DE

Date of ref document: 20090102

Kind code of ref document: P

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20081229

Year of fee payment: 5

Ref country code: NL

Payment date: 20081219

Year of fee payment: 5

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20090211

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20081219

Year of fee payment: 5

REG Reference to a national code

Ref country code: GR

Ref legal event code: EP

Ref document number: 20090400304

Country of ref document: GR

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20081119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081119

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2318356

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081119

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090319

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081119

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081119

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BG

Payment date: 20081220

Year of fee payment: 5

Ref country code: DE

Payment date: 20090225

Year of fee payment: 5

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E004961

Country of ref document: HU

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20081219

Year of fee payment: 5

Ref country code: GR

Payment date: 20090204

Year of fee payment: 5

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081119

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081119

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081231

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081119

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20090107

Year of fee payment: 5

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081119

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090219

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20081223

Year of fee payment: 5

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081119

26N No opposition filed

Effective date: 20090820

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: HU

Payment date: 20091204

Year of fee payment: 6

Ref country code: TR

Payment date: 20091202

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20091207

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090119

BERE Be: lapsed

Owner name: SASOL GERMANY G.M.B.H.

Effective date: 20091231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081210

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20100701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081210

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081119

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20091210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100701

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100701

Ref country code: BG

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091210

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100104

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110302

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091210

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20110614

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110614

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091211

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101211

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20111209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101210