EP2297394B1 - Composition additive pour auxiliaires textiles - Google Patents
Composition additive pour auxiliaires textiles Download PDFInfo
- Publication number
- EP2297394B1 EP2297394B1 EP09746146A EP09746146A EP2297394B1 EP 2297394 B1 EP2297394 B1 EP 2297394B1 EP 09746146 A EP09746146 A EP 09746146A EP 09746146 A EP09746146 A EP 09746146A EP 2297394 B1 EP2297394 B1 EP 2297394B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- textile
- composition according
- knits
- fabrics
- 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.)
- Not-in-force
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
- D06P1/621—Compounds without nitrogen
- D06P1/622—Sulfonic acids or their salts
- D06P1/623—Aliphatic, aralophatic or cycloaliphatic
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
- D06P1/6491—(Thio)urea or (cyclic) derivatives
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
Definitions
- the present invention relates to additive compositions for the preparation of textile auxiliaries, in particular used to increase the dye affinity of textile fibers.
- the knitted polyamide fibers are thus treated at temperatures of between 170 and 200 ° C. or even more, particularly according to the elastane content of the knits.
- An increase in the elastane content leads to increasing the processing temperature to obtain the required dimensional stability.
- this heat treatment also has the effect, especially in the case of polyamide fibers, to deteriorate the mechanical properties of the son.
- This mechanical deterioration is already penalizing in itself, but the observations made in the factory on decommissioned lots or in the laboratory systematically correlate this deterioration of the mechanical properties with a decrease in the dye affinity of the fibers, and with a problem of unison of the colour.
- Knits that are not uniformly dyed or are too pale in color must be re-used in a darker color, or re-painted a second time, and are often downgraded, resulting in significant economic loss.
- nonionic surfactants such as ethoxylated fatty alcohols, ethoxylated or non-ethoxylated fatty acids, ethoxylated fatty amines, alkyl phenols and the like.
- compositions systematically preserve good mechanical properties of the fibers and a very good dyeing affinity, higher than those obtained with textile auxiliaries of the state of the art, whatever the origin of the fibers, for example polyamides. and for high values of treatment temperatures.
- additives for textile auxiliaries according to the invention can be handled safely by the operators. It is also possible to formulate additives according to the invention comprising a minimum of toxicity, as neutral as possible for the environment, and therefore preferably easily removable and biodegradable.
- compositions according to the invention (a) represents from 1 to 15% by weight, preferably from 2 to 10% by weight, or even more preferably from 6 to 9% by weight, (b) represents from 10 to 50% by weight. by weight, preferably from 15 to 40%, or even more preferably from 25 to 35% by weight, (c) and / or (d) represent 3 to 15% by weight, and the amount of water represents less than 75% by weight of the composition, preferably from 10 to 70%, preferably 50 to 60% by weight.
- compositions according to the invention where the sequestering agents represent from 0.2 to 2% by weight in the composition.
- At least one hydroxyalkylamine (a) is such that X 1 and X 2 represent hydrogen, and n is an integer ranging from 2 to 6.
- the hydroxyalkylamine (a) is chosen from monoethanolamine, diethanolamine, or triethanolamine.
- the alkyl groups of the anionic surfactants (b) comprise from 8 to 22 carbon atoms, preferably from 10 to 18 carbon atoms.
- At least one radical R 1 , R 2 , R 3 or R 4 represents hydrogen, preferably R 1 , R 2 , R 3 and R 4 represent hydrogen.
- the alkyl sulphosuccinate dialkyl groups of the compounds (d) contain from 8 to 22, preferably 8 to 12, carbon atoms.
- the compounds (d) are chosen from alkali and alkaline earth metal salts, preferentially sodium, preferentially sodium dioctyl sulfosuccinate.
- the glycol ethers of the composition (d) have the formula: RO- (CH 2 -CH (X)) n 3 -O-R ', with X being either an atom of hydrogen is a CH 2 group, R, R 'being carbon chains comprising between 1 and 5 carbon atoms, and n 3 is an integer between 1 and 10, preferably 1 and 5, preferably 1.
- the composition according to the invention comprises the compounds (a), (b) (c) and a sequestering agent as described above or comprises the compounds (a), (b) and ( d) as described above.
- the present invention also relates to textile auxiliaries incorporating the compositions according to the invention obtained by dilution in water of these compositions.
- the total amount of water is more than 75% by weight, preferably 95 to 99% by weight.
- the total amount by weight of active material represented by the compounds (a), (b), (c) and / or (d) ranges from 0.2% to 25%, preferably from 1% to 5%.
- the present invention also relates to a process for treating textile yarns, fabrics or knits, intended to undergo a heat treatment, possibly followed by dyeing, comprising, upstream of the heat treatment, a pretreatment of said yarns, fabrics or knits by immersion in a padding bath containing a textile auxiliary according to the invention.
- said fabrics or knits are expressed so that they are coated with 0.1 to 5% by weight, preferably 1 to 4%, more preferably 2 to 4% by weight of material.
- the fibers undergo a multitude of treatments and conditioning various, during spinning operations, winding, knitting, weaving, dimensional stabilization treatment, dyeing, ...
- the fibers can thus be in contact with a large quantity of additives, for example wetting agents, detergents, lubricants, antistatic agents, biocides, bactericidal agents, sequestering agents, hydrogen peroxide stabilizers, agents and the like. sizing agents, dispersants, pH stabilizers, antifoams, unison agents, dyes, dye accelerators, etc.
- additives for example wetting agents, detergents, lubricants, antistatic agents, biocides, bactericidal agents, sequestering agents, hydrogen peroxide stabilizers, agents and the like.
- compositions according to the invention can be introduced into the processing line of knits and textile fabrics prior to the thermal dimensional stabilization operation, which itself precedes the dyeing operation, without changing the process conditions.
- compositions according to the invention are in aqueous solutions or emulsions, they are directly diluted in the padding water bath present upstream of the heat treatment furnace.
- the present invention also relates to the use of these textile auxiliaries to preserve the tenacity and the elongation before breaking of textile fibers and yarns made of textile fibers intended to undergo a heat treatment.
- Another object of the present invention is the use of these textile auxiliaries to preserve the dye affinity of textile fibers, yarns, fabrics or knits of textile fibers, intended to undergo a heat treatment.
- hydroxyalkylamines of the compositions according to the invention correspond to the formula NX 1 X 2 (C n H 2n OH), where X 1 and X 2 are independently of each other either hydrogen or hydroxyalkyl radicals of formulas respectively C n1 H 2n1 OH and C n2 H 2n2 OH, and n, n 1 , n 2 are integers ranging from 2 to 6.
- These compounds provide the additive compositions according to the invention with cold stability properties. Thus, they can be stored cold (around 0 ° C), without the various compounds dissolved in aqueous solution precipitate.
- the hydroxyalkylamines also enhance the antioxidant properties of the additive and auxiliary textile compositions according to the invention, resulting in an increased capacity for preserving the dye affinity and the mechanical properties of the textile fibers.
- MEA Monoethanolamine, (MEA), diethanolamine, triethanolamine will be preferred.
- the additive compositions according to the invention preferably contain from 1 to 15% by weight of one or more hydroxyalkyl amines, or else from 2 to 15%, or from 3 to 10% by weight, preferably from 5 to 10% by weight. more preferably 6 to 9% by weight of one or more hydroxyalkylamine.
- the anionic surfactants (b) according to the invention also participate in the antioxidant properties of the additive and auxiliary textile compositions according to the invention.
- the compounds (b) according to the invention are chosen from alkyl sulphates, alkyl sulphonates, alkylaryl sulphonates, alkyl ether phosphates and alkyl carboxylates.
- the alkyl groups of these surfactants comprise from 8 to 22 carbon atoms, preferably from 8 to 18 or even from 10 to 18 carbon atoms. They are preferentially paraffinic. Paraffin sulfates, sulfonates, especially lauryl are preferred.
- alkali and alkaline earth metal salts in particular sodium, or magnesium.
- compositions according to the invention preferably contain from 10 to 50% by weight of one or more surfactants (b), or from 15 to 40% by weight, or from 20 to 40% by weight, even more preferably from 25 to 35% by weight.
- the thioureas of formula R 1 R 2 N (CS) NR 3 R 4 , where R 1 , R 2 , R 3 , R 4 are either hydrogen or hydrocarbon radicals may play a role in preventing the phenomenon of 'oxidation.
- R 1 , R 2 , R 3 and R 4 are either hydrogen or hydrocarbon radicals comprising from 1 to 5 carbon atoms.
- EDTA ethylene diamine tetraacetic acid
- NTA niotrilotetraacetic acid
- DTPA diethylene triamine pentaacetic acid
- phosphonic and gluconic acids phosphonates, gluconates, polyacrylates.
- NTA, EDTA, DTPA are particularly preferred.
- the compounds (c) represent from 2 to 10%, preferably from 3 to 7%, even more preferentially from 4 to 5% by weight.
- the respective proportions of sequestering agent and thiourea may vary, in particular depending on the nature of the thioureas, in the compositions (c).
- the content of sequestering agent is of the order of 0.2 to 2% in the additive compositions according to the invention.
- these thioureas can be totally or partially substituted by compounds (d) as wetting agents and antifreezes.
- the wetting agents contained in these compositions (d) are dialkyl sulphosuccinates of formula: where R 6 and R 7 are alkyl groups containing from 6 to 22 carbon atoms, preferably from 6 to 12 carbon atoms.
- alkali metal and alkaline earth metal salts are preferably alkali metal and alkaline earth metal salts, preferentially sodium salts.
- Dihexyl, diheptyl, dioctyl and sodium dinonyl sulfosuccinate will be used, for example.
- compositions (d) are alcohols such as methanol or isopropanol, glycols, for example glycerol, or glycol ethers, denoting ethers of ethylene glycol or propylene glycol.
- Glycol ethers of composition (d) correspond to the formula: RO- (CH 2 -CH (X)) n3 -O-R ', with X being either a hydrogen atom or a group CH 2 R, R 'being carbon chains comprising between 1 and 5 carbon atoms, and n 3 is an integer between 1 and 10, preferably 1 and 5, preferably 1.
- glycol ethers mono ethylene glycol or mono propylene glycol ethers will be preferred.
- the compounds (d) represent from 1 to 15%, preferentially from 2 to 12%, even more preferably from 3 to 5% by weight.
- dialkyl sulfosuccinate and antifreeze may vary in the antioxidant compositions (d).
- mass percentages of these compounds in the additive compositions according to the invention are identical.
- Active substance and solution or aqueous emulsion Active substance and solution or aqueous emulsion:
- compositions according to the invention contain, as active ingredient, compounds (a), (b), (c) and / or (d). They may also contain as additives any compounds other than water, suitable for their use, for example anti foam.
- compositions are intended to be applied in the form of an aqueous solution or an aqueous emulsion. It will be preferred to formulate the compositions according to the invention with compounds which are soluble in water.
- compositions according to the invention are concentrates of active material slightly diluted in water. They can thus contain less than 75% by weight of water, preferably 10 to 70%, or 50 to 60% of water, or 55 to 60% by weight of water.
- the textile auxiliaries according to the invention are prepared by dilution in water of the concentrated active material compositions described above.
- the said compositions can be diluted so that the total amount of water represents more than 75% by weight of the textile auxiliary, preferably from 95 to 99% by weight.
- the textile auxiliaries according to the invention comprise a total amount by weight of active material represented by the compounds (a), (b), (c) and / or (d) which ranges from 0.2% to 25% preferably from 1% to 5%.
- the textile auxiliaries described above are used as a dye unison agent, or to preserve the mechanical properties and the dye affinity of textile fibers, yarns, fabrics or knits made of said fibers.
- Unison agents are a class of textile auxiliaries well known to those skilled in the art whose function is to ensure even distribution of the colorant within the fiber. A lack of unison is reflected for example by the presence, on the same piece of fabric or tinted knit, different coloring areas of intensity, stains, streaks, uneven coarse dye is of no commercial value and difficult to correct.
- the mechanical properties in question here are the toughness and the elongation at break, described in detail in the examples below and which has been observed that the deterioration, during heat treatments, causes dyeing defects. They are measured on wires according to the UNI EN ISO 2026 standard.
- the mechanical properties of the textile yarns previously treated with the textile auxiliaries according to the invention are not affected by the heat treatments, in particular carried out at temperatures of the order of 170 to 210 ° C., preferably of the order of 180 to 200 ° C. ° C.
- a low dye affinity of textile fibers for dye results in yarns, fabrics or knits of a lighter shade than desired.
- the dye affinity of textile fibers, yarns, fabrics, knits made of textile fibers previously treated with the textile auxiliaries according to the invention is not affected by the heat treatments, in particular carried out at temperatures of the order of 170 to 210 ° C, preferably of the order of 180 to 200 ° C.
- the textile fibers can be of natural plant origin, for example linen, cotton, jute, hemp, or of animal origin, Alpaca, Angora, cashmere, wool, silk, ...
- An artificial textile fiber is obtained by chemical treatment (dissolution then precipitation) of natural materials: milk casein for lanital, cellulose of various plants (pine bark, bamboo, soybean, birch) for viscose. This category includes cellulose actate, cellulose triacetate, viscose, ...
- a synthetic textile fiber is a crystalline polymer obtained after passing through a die. It is obtained by extrusion of polymer granules obtained from hydrocarbons or starch.
- fibers can be obtained from polylactic acid polymer, acrylic polymers, polyamide fibers, aramid fibers (aromatic polyamide) chlorofibres obtained from PVC, polyurethane fibers, elastane fiber (lycra) obtained from polyurethane, polyester fiber, polyethylene, polyphenolic, ...
- textile auxiliaries relates to textile fibers and continuous yarns, more particularly synthetic textile fibers, in particular those having problems of degradation of their mechanical properties and of their dye affinity to heat.
- a particularly preferred use relates to textile fibers and continuous filaments of polyamides, or of polyamide derivatives, for example aramidic derivatives.
- the aliphatic polyamides are generally designated by numbers relating to the number of carbon atoms contained in the repeating unit of the polymer.
- PA 6, PA 11, PA 12 denote polyamides obtained by polymerization of an amino acid or a lactam with 6, 11 or 12 atoms, respectively. carbon in the pattern, or PA 6.6, PA 4.6, PA 6.10, PA 6.12, the polyamides obtained by polycondensation of a diacid and a diamine.
- the first number corresponds to the number of carbon atoms of the diamine while the second corresponds to the number of carbon atoms of the diacid.
- the aromatic polyamides do not use a precise designation rule.
- PAA polyarylamide
- PPA polyphthalamide
- polyamide textile fibers there is mainly nylon, or polyhexamethylene adipamide or PA 6/6 fiber.
- Kevlar refers to a category of synthetic fibers from aromatic polyamides. The best known is obtained from poly para phenylenediamine, which can be found for example under the trade name Kevlar and Twaron. Other aramidic textile fibers can also be found, for example poly meta phenylene diamine.
- Natural fibers which have lengths of the order of 40 to 80 mm, are transformed into yarn in spinning mills. As far as synthetic fibers are concerned, the polymers are directly extruded as yarns into the dies.
- textile auxiliaries according to the invention are particularly suitable for such textiles obtained from such elastane-containing yarns, and which require a dimensional fixing heat treatment.
- the uses according to the invention are suitable for textiles containing up to 40% by weight of elastane, preferably up to 25%.
- Textiles broadly refer to materials obtained from textile yarns: fabrics, knits, nonwovens.
- the fabric is obtained by the weaving which is the result of the intertwining, in one and the same plane, of threads arranged in the direction of the warp and of threads arranged, perpendicularly to the warp threads, in the direction of the weft.
- Knitwear Knit is an extensible fabric with interlaced loops that can also be described as mesh. It differs from other textiles usually made of a weaving of warp threads and weft threads because it consists of a single thread wrapped around itself often with a knitting needle. All textile fibers can be knitted. The production of knit is also referred to as hosiery.
- textile auxiliaries according to the invention are particularly suitable for knits which, because of their extensible nature, require heat treatments for dimensional fastening, more particularly for knits containing elastane.
- textile auxiliaries according to the invention will be preferred for knits combining polyamide and elastane, in particular those containing from 0.1 to 25% of elastane.
- An object of the present invention also relates to methods of treatment, more precisely pretreatment of yarns, fabrics or knits using the textile auxiliaries according to the invention described above.
- the methods according to the invention are intended to improve the unison of dyeing knits or fabrics consisting of textile fibers, or to preserve their mechanical property or dye affinity during heat treatments.
- Their main characteristic is to be applied upstream of heat treatment operations (for example heat treatment of dimensional stabilization) and dyeing.
- this amount of active material is between 0.1 and 5% by weight, preferably between 1 and 4%, more preferably between 2 and 4% by weight of active ingredient (a) + (b) + (c) and / or (d) based on the weight of yarn, fabric or dry knit.
- the squeezing rate which designates the mass percentage of textile auxiliary evacuated with respect to the weight of yarn or dry fabric, or its complement, the rate of weight, which represents the weight percentage of textile aid retained in relation to the weight of yarn or dry fabric.
- the yarns, fabrics or knits typically scroll in the pad of padding at speeds of the order of 1 to 20 meters per minute, in tanks or during a residence time of the order of a few seconds a few tens of seconds, typically less than 1 minute.
- the wringing operation is carried out by squeeze rolls whose spacing is adjusted so as to deposit the desired amount of active material on the yarns, fabrics and knits.
- the fibers, fabrics or knits thus pretreated are then subjected to a heat treatment, possibly followed by dyeing.
- the pretreatment method according to the invention does not interfere with conventional treatment processes and does not require any specific modification.
- Each batch was heat-treated for dimensional stabilization at 185 ° C, and then dyed with the same metalliferous dye.
- Toughness and elongation at break are measured according to UNI EN ISO 2026, with a Hounsfield H5KS dynamometer.
- the decitex value of the yarn is obviously not affected by the heat treatment, the minimal variations correspond to the repeatability of the method and to the fluctuations of the production process.
- the tenacity of the "regular" yarns are 4%, 13%, 15%, 15.5%, 19% higher than those of the "lighter" yarns for the respective batches 1, 2, 3, 4 and 5.
- the elongations of the "regular" yarns are 11%, 10.5%, 14.5%, 26% and 33% respectively higher than those of the "lighter" yarns for the batches 1, 2, 3, 4 and 5.
- Example 2 Influence of the pretreatment according to the invention on the mechanical properties and the dye affinity.
- a batch of polyamide yarn PA6-6, 44 decitex, consisting of 48 filaments is considered. This yarn was knitted with a 3-filament elastane yarn so as to produce a knit fabric containing 20% elastane (lot 6).
- This batch was the subject of a customer feedback following dyeing defects found with an acid dye of dark purple color with which it is particularly problematic to obtain a sustained and uniform dyeing on polyamide knits subjected to heat treatment.
- the knit is passed through a padding bath containing only water and is then spun between two squeeze rolls.
- thermofixation box at 188 ° C in which the residence time is about 30 seconds.
- the knit is then dyed with the dye on a JET device.
- the spacing of the squeezing rollers at the outlet of the padding tank has been adjusted so that the load-bearing rate of the knitting material is of the order of 60%, which represents a deposition of active material (excluding water) of the 3.5 g / 100 g of dry knit.
- the sample thus treated is of industrial size. It represents approximately 500 kg of treated thread. The entire sample showed a uniform appearance and a color with the required intensity after dyeing (regular).
- UNI EN ISO 2062 measured the elongation and tenacity of the corresponding unraveled polyamide yarn. The values are summarized in Table 3 below. ⁇ b> ⁇ u> Table 3 ⁇ / u> ⁇ /b>: Lot 6, with pretreatment according to the invention. decitex Elongation% Toughness cN / tex Regular (with pretreatment) 45.4 26.8 33.5 standard deviation: 0.3 standard deviation: 2.3 standard deviation: 1.6
- compositions according to the invention makes it possible to preserve the dye affinity of the fibers and to improve the unison of dyeing.
- This last knit (lot 7) is made with a polyamide yarn from the same reel as that of lot 6, but it has, contrary to that of lot 6, previously undergone a heat treatment at the time of shaping ( texturing).
- the result after dyeing is a knit of a shade much too light, despite the treatment with the composition according to the invention, applied before the dimensional stabilization heat treatment but after heating during texturing.
- compositions according to the invention therefore do not make it possible to restore the mechanical properties and the dye affinity of polyamide fibers already heat-treated.
- a treatment with these compositions should be applied in the form of pretreatment upstream of the heat treatment.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL09746146T PL2297394T3 (pl) | 2008-05-13 | 2009-05-12 | Kompozycja z dodatkami do środków pomocniczych dla tekstyliów |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0802572A FR2931172B1 (fr) | 2008-05-13 | 2008-05-13 | Composition additive pour auxiliaires textiles |
| PCT/IB2009/005570 WO2009138851A1 (fr) | 2008-05-13 | 2009-05-12 | Composition additive pour auxiliaires textiles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2297394A1 EP2297394A1 (fr) | 2011-03-23 |
| EP2297394B1 true EP2297394B1 (fr) | 2012-09-26 |
Family
ID=40193776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP09746146A Not-in-force EP2297394B1 (fr) | 2008-05-13 | 2009-05-12 | Composition additive pour auxiliaires textiles |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US8475539B2 (https=) |
| EP (1) | EP2297394B1 (https=) |
| JP (1) | JP2011521115A (https=) |
| KR (1) | KR20110016437A (https=) |
| CN (1) | CN102089471B (https=) |
| BR (1) | BRPI0913273A2 (https=) |
| ES (1) | ES2393690T3 (https=) |
| FR (1) | FR2931172B1 (https=) |
| HR (1) | HRP20120853T1 (https=) |
| MA (1) | MA32293B1 (https=) |
| PL (1) | PL2297394T3 (https=) |
| WO (1) | WO2009138851A1 (https=) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102383319B (zh) * | 2011-06-16 | 2013-04-17 | 北京泛博化学股份有限公司 | 一种增深剂及其制备方法 |
| FR3054458B1 (fr) * | 2016-08-01 | 2021-12-03 | Altimat | Utilisation d’une eau faiblement mineralisee comme nettoyant |
| CN106351010A (zh) * | 2016-08-31 | 2017-01-25 | 常熟市新宇服饰制品有限公司 | 亚麻织物纱线的浆纱工艺 |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3794605A (en) * | 1971-07-19 | 1974-02-26 | Procter & Gamble | Built detergent composition containing whiteness maintenance additive |
| US3907746A (en) * | 1972-02-23 | 1975-09-23 | Ici Inc | Stabilized polyamides |
| US3841831A (en) * | 1972-11-29 | 1974-10-15 | Cpc International Inc | Process for dyeing polyester fiber |
| US4174305A (en) * | 1975-04-02 | 1979-11-13 | The Procter & Gamble Company | Alkyl benzene sulfonate detergent compositions containing cellulose ether soil release agents |
| US5480632A (en) * | 1987-09-16 | 1996-01-02 | Maybelline, Inc. | Non-aqueous cosmetic compositions with high solids content |
| BR9106920A (pt) * | 1990-09-28 | 1993-08-17 | Procter & Gamble | Composicoes detergentes contendo tensoativos de amida de acido poliidroxi graxo e alquil ester sulfonato |
| US5460632A (en) * | 1994-12-29 | 1995-10-24 | Olin Corporation | Low-foaming, enhanced wetting dye-leveling agent |
| HUP0104608A3 (en) * | 1998-10-20 | 2002-11-28 | Procter & Gamble | Tenzide mixture comprising modified alkylbenzene sulfonates and laundry detergents containing thereof, and process for preparation of the mixture and for use of the detergents |
| US6258928B1 (en) * | 2000-04-06 | 2001-07-10 | E. I. Du Pont De Nemours And Company | Process for improving characteristics of a polyamide |
| JP2003293272A (ja) * | 2002-04-01 | 2003-10-15 | Canon Inc | インクジェット捺染方法 |
| JP3976132B2 (ja) * | 2002-06-21 | 2007-09-12 | 富士フイルム株式会社 | インクジェット記録方法 |
| JP4639041B2 (ja) * | 2002-09-17 | 2011-02-23 | セーレン株式会社 | ポリアミド系繊維構造物の染色加工方法 |
| CN1751116A (zh) * | 2003-02-18 | 2006-03-22 | 诺和酶股份有限公司 | 洗涤剂组合物 |
| US7141104B2 (en) * | 2003-06-05 | 2006-11-28 | Agfa-Gevaert | UV-absorbing ink composition for ink-jet printing |
| US20050197419A1 (en) * | 2004-03-03 | 2005-09-08 | Graziano Louis C. | Radiation curable aqueous binders for ink jet inks |
| DE102004042738A1 (de) * | 2004-09-03 | 2006-03-23 | Cht R. Beitlich Gmbh | Schaum- und geruchsarme Textilhilfsmittel |
| ATE519836T1 (de) * | 2006-02-24 | 2011-08-15 | Unilever Nv | Flüssige weissgraderhaltungszusammensetzung |
-
2008
- 2008-05-13 FR FR0802572A patent/FR2931172B1/fr not_active Expired - Fee Related
-
2009
- 2009-05-12 JP JP2011509029A patent/JP2011521115A/ja not_active Ceased
- 2009-05-12 PL PL09746146T patent/PL2297394T3/pl unknown
- 2009-05-12 KR KR1020107025528A patent/KR20110016437A/ko not_active Ceased
- 2009-05-12 BR BRPI0913273A patent/BRPI0913273A2/pt not_active IP Right Cessation
- 2009-05-12 WO PCT/IB2009/005570 patent/WO2009138851A1/fr not_active Ceased
- 2009-05-12 ES ES09746146T patent/ES2393690T3/es active Active
- 2009-05-12 US US12/992,214 patent/US8475539B2/en not_active Expired - Fee Related
- 2009-05-12 CN CN200980127262.1A patent/CN102089471B/zh not_active Expired - Fee Related
- 2009-05-12 HR HRP20120853AT patent/HRP20120853T1/hr unknown
- 2009-05-12 EP EP09746146A patent/EP2297394B1/fr not_active Not-in-force
-
2010
- 2010-11-11 MA MA33332A patent/MA32293B1/fr unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110016437A (ko) | 2011-02-17 |
| BRPI0913273A2 (pt) | 2016-07-26 |
| PL2297394T3 (pl) | 2013-01-31 |
| US20110061181A1 (en) | 2011-03-17 |
| HRP20120853T1 (hr) | 2012-11-30 |
| JP2011521115A (ja) | 2011-07-21 |
| MA32293B1 (fr) | 2011-05-02 |
| CN102089471A (zh) | 2011-06-08 |
| US8475539B2 (en) | 2013-07-02 |
| WO2009138851A1 (fr) | 2009-11-19 |
| FR2931172B1 (fr) | 2010-07-30 |
| EP2297394A1 (fr) | 2011-03-23 |
| CN102089471B (zh) | 2014-07-30 |
| ES2393690T3 (es) | 2012-12-27 |
| FR2931172A1 (fr) | 2009-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2297394B1 (fr) | Composition additive pour auxiliaires textiles | |
| US10655273B2 (en) | Dyed fibers and methods of dyeing using N,N′-diacetyl indigo | |
| EP2160489B1 (de) | Verfahren zur vergilbungsinhibierung | |
| JPH0583671B2 (https=) | ||
| DE60201572T2 (de) | Entfettungsmittel für textilfaser, verfahren zu deren herstellung sowie deren verwendung | |
| WO2018086124A1 (en) | Apparel fabric manufacturing process, system and product thereof | |
| EP4377501A1 (en) | Improvements relating to the cold-alkali process for the production of regenerated cellulosic fibers | |
| EP1021608B1 (de) | Ausrüstung von jeansmaterial | |
| BE1004655A3 (fr) | Procede de teinture des matieres textiles contenant de la cellulose. | |
| US2102789A (en) | Manufacture of textile yarns and fabrics | |
| CN118234905A (zh) | 聚酯纤维/天然纤维混纺织物的一步染色方法 | |
| BE635408A (https=) | ||
| CN121127644A (zh) | 聚电解质在纺织品处理和丝光处理和/或染色操作阶段中的用途 | |
| KR20110126211A (ko) | 폴리아미드 섬유와 폴리우레탄 섬유의 혼용직물의 정련방법 | |
| FR2497245A1 (fr) | Procede de teinture sur fibres cellulosiques et/ou synthetiques | |
| KR20020059671A (ko) | 폴리아미드 섬유와 폴리우레탄 섬유의 혼용직물의정련방법 및 혼용염색직물의 제조방법, 그리고 혼용염색직물 | |
| JP2009030214A (ja) | 繊維製品の耐光堅牢度向上剤及び耐光堅牢度向上方法 | |
| JPH01292115A (ja) | ポリエーテルエーテルケトン繊維とその染色方法 | |
| JPH04174757A (ja) | 繊維製品の精練方法 | |
| JPH04241177A (ja) | ポリアミド繊維製品の均一染色方法 | |
| DE9421551U1 (de) | Naßgleitmittel für die Erhöhung der Naßgleitfähigkeit von Textilmaterial | |
| JPS5824557B2 (ja) | 捲縮加工用未延伸糸の処理方法 | |
| DE4329959A1 (de) | Alkalisches Chloritbleichmittel | |
| CH511321A (fr) | Procédé continu de traitement antifeutrant et antirétrécissant des fibres textiles kératiniques | |
| JP2005042236A (ja) | 染色異常防止剤及び繊維材料の処理方法 |
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: 20101213 |
|
| 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 HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL BA RS |
|
| DAX | Request for extension of the european patent (deleted) | ||
| 17Q | First examination report despatched |
Effective date: 20120117 |
|
| 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 HR HU IE IS IT LI LT LU LV MC MK MT NL NO 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: AT Ref legal event code: REF Ref document number: 577134 Country of ref document: AT Kind code of ref document: T Effective date: 20121015 |
|
| REG | Reference to a national code |
Ref country code: HR Ref legal event code: TUEP Ref document number: P20120853 Country of ref document: HR |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: FRENCH |
|
| REG | Reference to a national code |
Ref country code: RO Ref legal event code: EPE |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602009010038 Country of ref document: DE Effective date: 20121122 |
|
| REG | Reference to a national code |
Ref country code: HR Ref legal event code: T1PR Ref document number: P20120853 Country of ref document: HR |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2393690 Country of ref document: ES Kind code of ref document: T3 Effective date: 20121227 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NO 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: 20121226 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: 20120926 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: 20120926 |
|
| REG | Reference to a national code |
Ref country code: PL Ref legal event code: T3 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D Effective date: 20120926 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20120926 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV 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: 20120926 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: 20120926 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: 20120926 Ref country code: GR 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: 20121227 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20130126 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: 20120926 Ref country code: NL 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: 20120926 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: 20120926 |
|
| 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: 20120926 Ref country code: PT 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: 20130128 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG 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: 20121226 Ref country code: DK 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: 20120926 |
|
| 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 |
|
| 26N | No opposition filed |
Effective date: 20130627 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602009010038 Country of ref document: DE Effective date: 20130627 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20120926 |
|
| BERE | Be: lapsed |
Owner name: TOTAL RAFFINAGE MARKETING Effective date: 20130531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC 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: 20120926 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20130512 |
|
| 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: 20130531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130531 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130512 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130512 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT 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: 20120926 |
|
| 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: 20130512 Ref country code: MK 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: 20120926 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20090512 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20160421 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: RO Payment date: 20160511 Year of fee payment: 8 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602009010038 Country of ref document: DE |
|
| 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 NON-PAYMENT OF DUE FEES Effective date: 20170512 |
|
| REG | Reference to a national code |
Ref country code: HR Ref legal event code: ODRP Ref document number: P20120853 Country of ref document: HR Payment date: 20180419 Year of fee payment: 10 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 10 |
|
| 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: 20171201 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: HR Payment date: 20180419 Year of fee payment: 10 Ref country code: ES Payment date: 20180601 Year of fee payment: 10 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20180502 Year of fee payment: 10 Ref country code: AT Payment date: 20180424 Year of fee payment: 10 Ref country code: IT Payment date: 20180420 Year of fee payment: 10 Ref country code: FR Payment date: 20180423 Year of fee payment: 10 Ref country code: PL Payment date: 20180423 Year of fee payment: 10 |
|
| REG | Reference to a national code |
Ref country code: HR Ref legal event code: PBON Ref document number: P20120853 Country of ref document: HR Effective date: 20190512 |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 577134 Country of ref document: AT Kind code of ref document: T Effective date: 20190512 |
|
| 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: 20190512 Ref country code: HR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190512 |
|
| 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: 20190512 |
|
| 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: 20190531 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20200930 |
|
| 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: 20190513 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190512 |
|
| 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: 20190512 |