EP2459785B1 - Procédé de fabrication de fibres de polyester colorées, fils colorés et/ou tissus colorés - Google Patents

Procédé de fabrication de fibres de polyester colorées, fils colorés et/ou tissus colorés Download PDF

Info

Publication number
EP2459785B1
EP2459785B1 EP10737320.1A EP10737320A EP2459785B1 EP 2459785 B1 EP2459785 B1 EP 2459785B1 EP 10737320 A EP10737320 A EP 10737320A EP 2459785 B1 EP2459785 B1 EP 2459785B1
Authority
EP
European Patent Office
Prior art keywords
polyester
process according
fibers
yarn
dyed
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
EP10737320.1A
Other languages
German (de)
English (en)
Other versions
EP2459785A1 (fr
Inventor
Pia Baum
Klaus Scheuermann
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to PL10737320T priority Critical patent/PL2459785T3/pl
Priority to EP10737320.1A priority patent/EP2459785B1/fr
Publication of EP2459785A1 publication Critical patent/EP2459785A1/fr
Application granted granted Critical
Publication of EP2459785B1 publication Critical patent/EP2459785B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/06—Dyes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/54—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads coloured
    • 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
    • D06P3/34—Material containing ester groups
    • D06P3/36—Material containing ester groups using dispersed dyestuffs
    • 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
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/54—Polyesters using dispersed dyestuffs
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/14—Dyeability

Definitions

  • the present invention relates to a process for producing spinnable and dyed polyester fibers from a terephthalate polyester and at least one polyester-containing additive.
  • Polyester are polymers with ester bonds - [- CO-O -] - in their backbone.
  • Polyesters today are the large family of synthetic polymers (plastics), which include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). PET is one of the most important thermoplastic polyesters. It is used, for example, in fibers (microfibers) for textiles and nonwovens.
  • PES fibers are produced by the melt spinning process. The action of heat produces a melt which is extruded through spinnerets.
  • Dyeing of PES fibers is usually carried out by the use of disperse dyes, which are contained in the form of pigments in mostly aqueous formulation in emulsion paints.
  • the dyeing process of PES fibers is generally carried out by the exhaust or the Thermosolvon at temperatures of 130 ° C or more. If the dyeing of a PES material is to be carried out at a lower temperature in order to be able to dispense, for example, with pressure vessels, then a so-called “carrier”, ie a chemical substance which allows penetration of the dye into the fiber even at lower temperatures, must also be used. be used.
  • An example of a carrier for dyeing PES materials is in EP 0 364 792 B1 described.
  • JP-A 8074124 is reported by the preparation of a good dyeable polybutylene terephthalate fiber by copolymerization with a comonomer from 0.5 to 5mol% - based on all acid contents in the fiber - of a sodium salt of sulfoisophthalic acid, 15 to 85 ppm of titanium and 0.02% to 2.0% by weight of the antioxidant phenol (hypo) phosphite is obtained. Subsequent staining is done using cationic stains that bind to the comonomer.
  • EP 1 217 024 B1 is reported by spun and dyeable polyester resins such as polybutylene terephthalate.
  • the polyester is here constructed from an alkyl diol, terephthalic acid and a complex comonomer which may contain a metal or alkyl phosphonium sulfone, trivalent aromatic rings and ester functional groups.
  • the polymerization is carried out using a titanium catalyst.
  • the incorporated comonomer is also the receptor site for a cationic stain. The coloring takes place at a temperature of 100 ° C.
  • the object is to provide a process for producing a PES material (for example, polyethylene terephthalate or polybutylene terephthalate as a base polyester), wherein the PES material produced has no complex polymerization steps in the production, has good spinning properties and the produced PES material even at temperatures below 130 ° C, preferably at and below 100 ° C, light and fast wash without using a carrier.
  • a PES material for example, polyethylene terephthalate or polybutylene terephthalate as a base polyester
  • the production according to the invention of PES fibers which takes place by fusing in particular PBT or PET and at least one polyester-containing additive (B), is distinguished by the fact that no complex polymerization processes are necessary, but only two or more components, ie. H. at least (A) and (B) are mixed and fused together and the melt is spun, with the addition of the polyester-containing additive (B) often facilitating even the melt spinning process.
  • Dyeing of polymer compositions containing, in addition to the standard polyesters such as PET or PBT, at least one of said polyester-containing additives (B) has the effect of using a disperse dye according to the exhaust process at temperatures below 130 ° C and can even run off just 100 ° C.
  • polyester fibers, yarns and textile fabrics produced by the process according to the invention are distinguished by intensive and uniform dyeability. They also have a wide range of applications in the color spectrum, good rubfastness and very good wash fastness.
  • the use of the polyester fiber (C) according to the invention for the dyeing process means a simplification in terms of machine technology.
  • the energy consumption is reduced and it saves time.
  • the inventive method has a gentle effect on the material to be dyed.
  • the polyester fibers (C) are supple and soft both before and after dyeing.
  • the polyester fibers (C) in step (III) can be further processed into yarn (E) and / or textile fabrics (F) before the polyester fibers (C) or the yarn (E) or the textile fabric produced therefrom (F) is dyed at a temperature ⁇ 130 ° C.
  • the polyester fibers (C) are spun into a yarn (E) in step (III).
  • a textile fabric (F) can be prepared before the dyeing is carried out in step (IV).
  • the fibers can be dyed first and then further processed into yarn (E) and / or textile fabrics (F) or from the undyed polyester fibers (C) first yarn (E) are made, this the first dyed and then textile fabrics getting produced.
  • undyed fibers consisting essentially of polyester are prepared by intensive mixing of the components terephthalate-polyester (A) and at least one polyester-containing additive (B) and optionally one or more components (D) in the melt and subsequent spinning.
  • the undyed polyester fibers (C) comprise after completion as far as possible a terephthalate polyester (A) as the main component and at least one polyester-containing additive (B), wherein (B) before fiber production in a further preferred embodiment, up to 7 wt.% - Based on the Sum of all components of the respective component - at least one chain extender (V), which is in particular 1,6-hexamethylene diisocyanate, may contain.
  • V chain extender
  • the terephthalate polyester (A) is selected from polyethylene terephthalate (PET) or polybutylene terephthalate (PBT).
  • the polyester fibers (C) contain preferably 80 to 99% PBT or PET, more preferably PET is used, particularly preferably a polyester of terephthalic acid and ethylene glycol is used as a textile fiber.
  • An example of a commercially available PBT is Ultradur B 4520® from the manufacturer BASF SE in Ludwigshafen.
  • the terephthalate polyester (A) is generally a polyester having a melting point of 200 to 280 ° C, another example being textile fibers such as e.g. Dralon of the company Trevira.
  • the polyester-containing additives (B) can be prepared from monomers m which have at least two different dicarboxylic acid units m2) and m3).
  • This total of monomers m - based on the total weight of the polyester-containing additive (B) - contains, for example, at least 5 to 80% phthalic acid units and 20 to 95% units of aliphatic 1- ⁇ - dicarboxylic acids having 4 to 10 carbon atoms.
  • the monomers m1): m2): m3) are present in a molar ratio of 2: 1: 1.
  • polyester-containing additives (B) used according to the invention for the preparation of the polyester fibers (C) comprise at least the carboxylic acids described and a diol unit.
  • the monomers m are subjected to a polymerization step. It happens that a certain amount of monomer is not polymerized, that is, "free” in the polyester-containing additive (B), which optionally has influence on the polyester fiber (C) prepared from (B).
  • the total amount of the carboxylic acid units m2) and m3), which are free or polymerized in the polyester-containing additive (B), is at least 50%.
  • the aromatic 1, ⁇ - dicarboxylic acid m3) is terephthalic acid.
  • the aliphatic 1- ⁇ - dicarboxylic acids m2) may, for example, be succinic acid, glutaric acid, adipic acid or sebacic acid.
  • the aliphatic 1, ⁇ - dicarboxylic M2) adipic acid.
  • the amount of terephthalic acid units and adipic acid units is 1: 1.
  • the diols m1) are selected from the group of aliphatic, cycloaliphatic and / or polyether diols, wherein a maximum of 52% aliphatic 1- ⁇ diols are present and the percentages are based on the total amount of all diols present in the polyester-containing additive free or as an ester are.
  • the aliphatic diols having 4 to 10 carbon atoms may be, for example, 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol.
  • the aliphatic 1, ⁇ - diol m1) is 1,4-butanediol.
  • At least one chain extender (V) can be used to prepare the polyester-containing additive (B).
  • the at least one chain extender (V) is usually selected from compounds containing at least three ester-capable groups (V1) and selected from compounds containing at least two isocyanate groups (V2).
  • the compounds V1 are generally used in amounts of 0.01 to 15, preferably 0.05 to 10, particularly preferably 0.1 to 4 mol%, based on the components m2 and m3.
  • component V2 one or a mixture of different isocyanates are used. It is possible to use aromatic or aliphatic diisocyanates. However, it is also possible to use higher functional isocyanates.
  • an aromatic diisocyanate V2 is in particular toluylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, Naphthylene-1,5-diisocyanate or xylylene diisocyanate understood.
  • 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate as component V2 are particularly preferred.
  • the latter diisocyanates are used as a mixture.
  • Trinuclear isocyanate V2 is also tri (4-isocyanophenyl) methane.
  • the polynuclear aromatic diisocyanates are obtained, for example, in the preparation of mono- or binuclear diisocyanates.
  • component V2 may also contain urethione groups, for example, for capping the isocyanate groups.
  • an aliphatic diisocyanate V2 is in particular linear or branched alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example 1,6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane), Understood.
  • Particularly preferred aliphatic diisocyanates V2 are 1,6-hexamethylene diisocyanate and isophorone diisocyanate.
  • Preferred isocyanurates include the aliphatic isocyanurates derived from alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane).
  • the alkylene diisocyanates can be both linear and branched.
  • the component V2 is used in amounts of 0.01 to 5, preferably 0.05 to 4 mol%, particularly preferably 0.1 to 4 mol%, based on the sum of the molar amounts of m1, m2 and m3.
  • the Tg value (in degrees C) denotes the glass transition temperature at which amorphous or crystalline polymers change from the hard-elastic or glassy state into the liquid or rubber-elastic state.
  • a standard PES material has a Tg of about 80 ° C.
  • the Tg of the polyester-containing additive (B) is between -50 and 0 ° C, preferably between -45 and -10 ° C, and more preferably between -40 and -20 ° C.
  • the dyeing at ⁇ 130 ° C preferably ⁇ 120 ° C, more preferably ⁇ 110 ° C, most preferably ⁇ 100 ° C and particularly preferably ⁇ 90 ° C allows.
  • a lowered glass transition temperature entails increased mobility in the PES chains; At the same time, any added colorant preferably penetrates into these soft segments of the fiber. Overall, an intense color result is achieved.
  • the distribution of the polyester-containing additive (B) in the terephthalate polyester (A) takes place uniformly and without droplets.
  • the fibers obtained can easily be spun out very quickly.
  • different fiber thicknesses can be spun out in a textile fabric (F) to be produced from this later.
  • optional compatibilizers (R) can be used for optimal mixing of (A) and (B).
  • step (I) of the process according to the invention it is also possible to mix one or more components (G) with components (A) and (B).
  • the component (s) (G) are processing aids such as lubricants, process aids and waxes, additives such as compatibilizers, UV and light stabilizers, heat stabilizers, dyes and pigments, flame retardants, antioxidants, plasticizers, metal oxides such as titanium oxides, optical brighteners and fillers.
  • Their proportion is generally from 0 to 20% by weight, preferably from 0 to 10% by weight, based on the total weight of the mixture obtained in step (I) or undyed fibers prepared therefrom, of which at least 0.1 Wt .-% of component (G), if it is present.
  • the inventive method is characterized in that the polyester-containing additive (B) preferably has a number average molecular weight M w of 50,000 to 300,000 g / mol.
  • polyester-containing additive (B) used according to the invention typical reaction conditions and catalysts are known in principle to the person skilled in the art.
  • the dicarboxylic acids used for the preparation of (B) m2) and m3) can be used in a manner known in principle as free acids or in the form of conventional derivatives such as esters. Typical esterification catalysts can be used.
  • Chain extenders (V), such as HMDI (1,6-hexamethylene diisocyanate) may also optionally be used in the preparation of (B).
  • polyester diol units can first be presynthesized, which can then be linked together by means of a chain extender (V). By choosing the building blocks and / or the reaction conditions, the properties of the polyester can be easily adapted by a person skilled in the art to a specific requirement profile.
  • polyester-containing additives (B) can be used.
  • the undyed polyester fibers (C) comprise 1 to 20% by weight, preferably 5 to 10% by weight and for example 6% by weight of at least one such polyester-containing additive (B), based on the sum of all constituents of the undyed fiber.
  • Undyed, substantially polyester fibers are prepared by mixing at least the components terephthalate-polyester (A) and polyester-containing additive (B) by mixing, melting and spinning.
  • terephthalate polyester (A) and polyester-containing additive (B) are preferably metered into the mixing unit using appropriate metering devices, for example as granules.
  • appropriate metering devices for example as granules.
  • components (A) and (B) and optionally further polymers and / or additives and auxiliaries (component (D)) are first mixed intensively with one another by heating to the melt by means of suitable equipment.
  • suitable equipment for example, kneaders, single-screw extruders, twin-screw extruders or other mixing or dispersing apparatus can be used.
  • Single-screw extruders are preferably used, since the length and type of the screw, temperature and residence time in the extruder, even in the single screw extruder, a homogeneous mixing can be achieved.
  • the temperature for mixing is selected by the person skilled in the art and depends on the nature of the components (A) and (B).
  • the terephthalate polyester (A) and the other polyester-containing additive (B) should on the one hand sufficiently soften, so that mixing is possible. On the other hand, they should not be too thin, because otherwise sufficient shear energy input can no longer take place and, under certain circumstances, thermal degradation is also to be feared.
  • the mixing is carried out at a product temperature of 250 ° C. to 290 ° C., preferably at 280 ° C., without the invention being restricted thereto.
  • the undyed polyester fiber (C) is obtained from the melt by extrusion, which is then spun directly.
  • the molten mass is pressed in a manner known in principle by one or preferably several nozzles, such as a hole nozzle, for example a 24-hole nozzle with a normal screen, and a nozzle pressure of, for example, 28 to 32 bar, corresponding polyester fibers (C). (Filaments) are formed.
  • Proven for direct spinning of the mixtures used according to the invention has a regulator temperature of 280 ° C.
  • the fibers or filaments should as a rule have a diameter of less than 0.7 ⁇ m. Preferably, the diameter is 0.5 to 0.2 microns, without the invention being limited thereto.
  • the extruder speed is for example at 50 rpm, the godet speed at 300 rpm and the winding speed at 600 rpm.
  • the hotplate has for example 100 ° C at a draw of 1: 2 (50: 100 m / min).
  • polyester fibers (C) produced according to the invention by the process described above can also be processed into textile fabrics (F) and dyed.
  • the polyester fibers (C) may also first be dyed and then further processed into yarn (E) and / or textile fabrics (F). It is also possible to first produce yarn (E) from the polyester fibers and to dye this. From the dyed yarn (E) then optionally textile fabric (F) can be produced.
  • the polyester fibers (C), the yarn (E) and / or the textile fabric (F) are treated prior to dyeing with a stabilizing emulsifier.
  • the yarn (E) can then be processed, for example, on a circular knitting machine to form a textile fabric (F) analogous to process step e).
  • Processes for producing textile fabric fabrics (F) from fibers (C) or yarns (E) are known in principle to the person skilled in the art.
  • the undyed polyester fibers (C), yarns (E) and textile fabrics (F) are pretreated by surfactants, for example consisting of an anionic and a nonionic surfactant, at a weight ratio of textile material to dye formulation (liquor ratio) of, for example 1 : 20 treated at elevated temperature.
  • surfactants for example consisting of an anionic and a nonionic surfactant
  • a weight ratio of textile material to dye formulation of, for example 1 : 20 treated at elevated temperature.
  • a stabilizing emulsifier is used for this pretreatment.
  • the undyed, pretreated polyester fibers (C), yarns (E) and textile fabrics (F) are dyed by treating them with a formulation comprising at least water and a dye.
  • a formulation comprising at least water and a dye.
  • An aqueous formulation for coloring textile materials is also referred to by the person skilled in the art as a "liquor".
  • the inking process g) or IV) takes place at a temperature below 130 ° C, preferably at ⁇ 120 ° C, more preferably ⁇ 110 ° C, most preferably ⁇ 100 ° C and particularly preferably ⁇ 90 ° C. ,
  • the emulsion paint in addition to the formulation and the disperse dye comprises only water.
  • water-miscible organic solvents include monohydric or polyhydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol or glycerin.
  • organic solvents include monohydric or polyhydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol or glycerin.
  • it may also be ether alcohols. Examples include monoalkyl ethers of (poly) ethylene or (poly) propylene glycols such as ethylene glycol monobutyl ether.
  • the amounts of such, different from water solvents should, however, usually 20 Wt .-%, preferably 10 wt .-% and particularly preferably 5 wt .-%, with respect to the sum of all solvents of the formulation or liquor does not exceed.
  • dyes in the formulation for dyeing PES fibers (polyester fibers (C)), yarns (E) and textile fabrics (F), it is possible in principle to use all known dyes which are suitable for dyeing polyester fibers.
  • the inventive method is characterized in particular by the fact that in the inking process g) or (IV) preferably a disperse dye and optionally a dispersing aid is used.
  • Disperse dye is known to the person skilled in the art.
  • Disperse dyes are dyes with a low water solubility, which are used in disperse, colloidal form for dyeing, in particular for dyeing fibers and textile materials.
  • any disperse dyes can be used to carry out the invention. These can have different chromophores or mixtures of the chromophores. In particular, they may be azo dyes or Anthrachinonfarbstoffe. Furthermore, it may be quinophthalone, naphthalimide, naphthoquinone or nitro dyes.
  • the nomenclature of dyes is known to those skilled in the art. The complete chemical formulas can be found in relevant textbooks and / or databases. Further details of disperse dyes and other examples are also given, for example, in Industrial Dyes ", editor Klaus Hummer, Wiley-VCH, Weinheim 2003, pages 134-158 shown in detail.
  • mixtures of different emulsion paints can be used. In this way, mixed colors can be obtained. Preference is given to those emulsion paints which have good fastness properties and in which trichromaticity is possible.
  • the amount of (disperse) dyes in the formulation will be determined by one skilled in the art according to the desired application.
  • the formulation may include other adjuvants beyond solvents and dyes.
  • suitable textile auxiliaries such as dispersing and leveling agents, acids, bases, buffer systems, surfactants, complexing agents, defoamers or UV-stabilizing stabilizers.
  • a UV absorber can be used as an aid.
  • a weakly acidic formulation for example having a pH of 4.5 to 6, preferably 5 to 5.5.
  • textile materials can be produced from the polyester fibers (C), yarns (E) and textile fabrics (F) produced by the process according to the invention.
  • textile materials is intended to include all materials throughout the textile manufacturing chain. It covers all types of finished textile goods such as clothing of all kinds, home textiles such as carpets, curtains, blankets or upholstery fabrics or technical textiles for industrial or commercial use or household applications such as rags or wipes for cleaning or covering umbrellas.
  • the term also includes the starting materials, that is fibers for textile use such as filaments or staple fibers and semi-finished or intermediate products, such as yarns, fabrics, knits, knitted fabrics, nonwovens or nonwovens. Also fillers and flakes for textiles such as pillows or stuffed animals, or as packaging material are included according to the invention. Methods for producing textile materials from yarns and / or fibers are known in principle to the person skilled in the art.
  • the textile materials (D) can be produced exclusively from the polyester compositions used according to the invention. Of course, they can also be used in combination with other materials, such as natural fibers. A combination can be made at different stages of production. For example, filaments of a plurality of polymers with a defined geometric arrangement can already be produced at the stage of melt spinning. In the manufacture of yarn, fibers of other polymers may be incorporated, or fiber blends may be made of staple fibers. Furthermore, various yarns may be processed together and, finally, fabrics, knits or the like comprising the polyester compositions of the present invention may be joined to chemically dissimilar fabrics. According to preferred textile materials (D) comprise in particular textile materials for sports and leisure clothing, carpets or nonwovens.
  • the treatment of the textile materials (D) with the aqueous dye formulation can be carried out by conventional dyeing methods, for example by dipping in the formulation (for example after the exhaustion process), spraying the formulation, printing dyeing or applying the formulation by means of suitable equipment. They can be continuous or discontinuous processes.
  • Dyeing apparatuses are known to the person skilled in the art. The dyeing may, for example, be carried out batchwise with chaff skids, yarn dyeing apparatuses, unit beam dyeing apparatuses or jets or continuously by padding, padding, spraying or foam application methods with suitable drying and / or fixing equipment.
  • the weight ratio of textile materials (D) to the dye formulation (also referred to as liquor ratio) and in particular the dye itself is determined by the skilled person depending on the desired application.
  • a weight ratio of textile materials (D) / dye formulation of from 1: 5 to 1:50, preferably 1:10 to 1:50, and also preferably from 1: 5 to 1:20, particularly preferably 1:10, has proven useful based on the textile material without the invention being set to this range.
  • the amount of dye in the formulation is preferably from about 0.5 to 5 wt .-%, preferably 1 to 4 wt .-%, based on the textile material.
  • the textile materials are heated during and / or after the treatment with the dye formulation to a temperature above the glass transition temperature Tg of the polyester fibers, but below their melting temperature.
  • This can preferably be carried out by heating the entire formulation to the relevant temperature and immersing the textile materials in the formulation.
  • the glass transition temperature Tg of the polyester fibers depends on the type of polymer composition used and can be measured by methods known to those skilled in the art.
  • the temperature in the treatment depends naturally on the type of polyester composition used and the dye used. Temperatures of 90 to 145 ° C., preferably 95 to 130 ° C., have proven useful.
  • the duration of the dyeing process is determined by the person skilled in the art, depending on the type of polymer composition, formulation and the dyeing conditions. It is also possible to change the temperature as a function of the duration of treatment. For example, at intervals of 2 to 3 ° C / min in aqueous liquor initially heated to 100 ° C, then held for about 25 to 35 minutes, the temperature and then at a distance of 2 to 3 ° C / min to 70 ° C and then cooled to 30 ° C.
  • the dyeing may be followed by a customary aftertreatment, for example with detergents or oxidative or reductive-acting secondary cleaning agents or fastness improvers.
  • a customary aftertreatment for example with detergents or oxidative or reductive-acting secondary cleaning agents or fastness improvers.
  • Such post-treatments are known in principle to the person skilled in the art.
  • a possible after-wash can be with hydrogen sulfite and NaOH, for example at 70 ° C, followed by warm water and cold rinsing and acidification.
  • the undyed textile materials (D) can also be printed.
  • those textile materials (D) which have a sufficient surface area are suitable for printing.
  • nonwovens, nonwovens, woven fabrics, knitted fabrics, knitted fabrics or films can be printed.
  • fabrics are used for printing.
  • Dyeing and printing can be combined with each other, for example by first dyeing a textile material (D) in a specific color and then imprinting a pattern, logo or the like.
  • a further subject of the present invention is the use of the fibers (C), yarns (E) and textile fabrics (F) produced by the inventive process described in detail above for the production of textile materials (D) and textile fabrics, in particular for the production of fibers, Yarn, fillers, flakes, woven, knitted, knitted, nonwovens, nonwovens, decorative and technical textiles and carpets.
  • the polyester fibers (C) are used for the production of dyed or undyed pure or mixed fibers for clothing, home or utility textiles.
  • B a polyester-containing additive
  • the homogeneous melt was then extruded through the hole dies and the polyester fiber (C) was obtained in the form of filaments spun on.
  • the extruder speed was set to 50 rpm, the godet speed was 300 rpm, and the winding speed was 600 rpm.
  • the draw was 1: 2 (50 / 100m / min) and the temperature of the hotplate was 100 ° C.
  • the spun polyester fibers (C) were then spun into a yarn (E) in a second spinning operation.
  • Table 1 shows the ratios of polyester (PBT) (A) to polyester-containing additive (B) and the yarn yield point (E) obtained therefrom.
  • Table 1 Experiment no. A [%] B [%] Insertion titer [d / tex] Comparative experiment 1 100 - 125 2 98 2 122 3 96 4 127 4 92 8th 127
  • Ansch manend could from the yarns (E) on a circular knitting machine, a textile fabric (F) are created.
  • the dyeings were carried out by adding the knitted pieces prepared as described with the addition of commercial disperse dyes (for example DianixDeepRed SF) in an amount of 2% by weight, based on the amount of undyed textile used, and 1 g / L of Basojet XP® as CO Color additive in desalted water at pH 5 to 5.5 in a standard dyeing apparatus of initially 30 ° C within 30 to 40 minutes to 100 ° C (or 115 ° C) left.
  • commercial disperse dyes for example DianixDeepRed SF
  • Basojet XP® Basojet XP® as CO Color additive
  • the mixture was cooled to 2.5 ° C / min to 70 ° C, then to 30 ° C.
  • Table 2 gives a list of the different blended fabrics, the color temperature and the color strengths (washed and unwashed).
  • the washfastness and lightfastness of the textile materials were rated with grades of 1 to 5, the bleeding of the dyed substance and thus the dyeing of the textiles wool, polyacrylate, polyester, polyamide, cotton and viscose was tested. The higher the value, the lower the staining of the various textiles, which indicates less bleeding of the dyed polyester fiber knit.
  • Polyethylene terephthalate having an intrinsic viscosity (IV) of 0.65 dl / g was reacted with and without the addition of 5.5% by weight of a polyester-containing additive (B) from the monomers 1,4-butanediol (50 mol%), adipic acid (25 Mole%) and terephthalic acid (25 mole%) (prepared according to WO 98/12242 ) processed in analogy to Example 1 to polyester fibers (C).
  • a multifilament polyester fiber with additive (B) (according to the invention) and without additive (comparison) was prepared.
  • the polyester fibers thus obtained were now dyed with different dyes.
  • dyeing commercially available dyes from DyStar Textilmaschine GmbH & Co Germany were used, the red dye was Dianix Rubin CC, the yellow dye was Dianix Yellow CC, the blue dye was Dianix blue CC.
  • the dye was used in each case in an amount of 2 wt .-%, based on the amount of textile to be dyed, and 1 g / L Basojet XP ® as a co-color additive in deionized water.
  • the temperature was increased at a heating rate of 2.5 ° C / min to 100, 105 and 130 ° C and held at this temperature for only 40 min. It was then cooled to 70 ° C at a cooling rate of 2.5 ° C / min. It was attenuated reductive - alkaline after treatment and then neutralized. These aftertreatment methods are known to the person skilled in the art.
  • the color strength of the dyed textiles was determined visually. The results are shown in Table 5. The color depth achieved at the respective dyeing temperature is based on the dyeing result of the pure polyester fiber at 130 ° C.
  • Table 5 Fiber from example colour Color depth at dyeing temperature 100 ° C 105 ° C 130 ° C 5-1 (comparison) yellow 5-10% 10-20% 100% 5-2 (according to the invention) yellow 90% 95% 5-1 (comparison) red 5-10% 10-20% 100% 5-2 (according to the invention) red 80% 90% 5-1 (comparison) blue 5-10% 10-20% 100% 5-2 (according to the invention) blue 60% 70% 5-3 (comparison) yellow 5-10% 10-20% 100% 5-4 (according to the invention) yellow 90% 95% 5-3 (comparison) red 5-10% 10-20% 100% 5-4 (according to the invention) red 80% 90% 5-3 (comparison) blue 5-10% 10-20% 100% 5-4 (according to the invention) blue 60% 70%
  • the color fastness of the textiles from the fibers 5-1 to 5-4 was tested in various test methods.
  • a standardized test fabric which side by side strips of triacetate, cotton, polyamide fibers, polyester fibers, polyacrylic fibers and viscose fibers, each sewn onto a sample of the dyed textile and subjected to the test. Subsequently, the staining of the different types of fiber contained in the sewn standard fabric sample was visually determined. Different test methods were used.
  • the sublimation test according to ISO 105 PO1 determines the dry heat fixation fastness (except ironing) of the dyed fabric.
  • the perspiration fastness (acid) according to ISO 105 E04 and the perspiration fastness (alkaline) according to ISO 105 E04 determine the change of the dye caused by perspiration.
  • the wash fastness at 60 ° C and the abrasion according to ISO 105 X12 were tested according to ISO 105 PO1.
  • the results are summarized in Table 6. The rating follows a scale of 1 to 5, the higher the value, the lower the staining of the tissue contained in the standard fabric sample. From this it is possible to conclude on the color fastness of the tested textile.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Knitting Of Fabric (AREA)
  • Woven Fabrics (AREA)

Claims (16)

  1. Procédé de fabrication de fibres de polyester colorées (C), d'un fil coloré (E) et/ou d'un tissu textile coloré (F) à partir des composants suivants :
    a) 80 à 99 % en poids, par rapport à la somme de tous les constituants des fibres, d'au moins un polyester téréphtalate (A),
    b) 1 à 20 % en poids, par rapport à la somme de tous les constituants des fibres, d'au moins un additif contenant un polyester (B), pouvant être obtenu à partir des monomères m
    m1) 1, ω-diol aliphatique,
    m2) acide 1, ω-dicarboxylique aliphatique,
    m3) acide 1,ω-dicarboxylique aromatique et
    éventuellement au moins un allongeur de chaînes (V), et
    c) éventuellement au moins un composant (G),
    comprenant les étapes suivantes :
    I) le mélange des composants (A), (B) et éventuellement d'un ou de plusieurs composants (G),
    II) la fabrication de fibres de polyester (C) à partir du mélange obtenu à l'étape I),
    III) éventuellement la transformation des fibres de polyester (C) en un fil (E) et/ou en un tissu textile (F), et
    IV) la coloration des fibres de polyester (C), du fil (E) et/ou du tissu textile (F) à une température < 130 °C.
  2. Procédé selon la revendication 1, caractérisé en ce qu'à l'étape II), le mélange obtenu à l'étape I) est fondu dans une extrudeuse et extrudé et filé par des buses de filage.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'à l'étape III), les fibres de polyester (C) sont filées en un fil (E).
  4. Procédé selon la revendication 3, caractérisé en ce qu'à l'étape III), les fibres de polyester (C) et/ou le fil (E) sont transformés en un tissu textile.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les fibres de polyester (C), le fil (E) et/ou le tissu textile (F) sont traités avec un émulsifiant à effet stabilisant avant la coloration.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le polyester téréphtalate (A) est choisi parmi le polytéréphtalate d'éthylène et/ou le polytéréphtalate de butylène.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les monomères m1):m2):m3) sont présents en un rapport molaire de 2:1:1.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que jusqu'à 7 % en poids du ou des allongeurs de chaînes (V) sont utilisés.
  9. Procédé selon la revendication 8, caractérisé en ce que l'allongeur de chaînes (V) est le diisocyanate de 1,6-hexaméthylène.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le 1,ω-diol aliphatique m1) est le 1,4-butanediol.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que l'acide 1, ω-dicarboxylique aliphatique m2) est l'acide adipique.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que l'acide 1, ω-dicarboxylique aromatique m3) est l'acide téréphtalique.
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que l'additif contenant un polyester (B) présente un poids moléculaire moyen en nombre Mn de 50 000 à 180 000 g/mol.
  14. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que la température de transition vitreuse de l'additif contenant un polyester (B) est comprise entre -50 °C et 0 °C, de préférence entre -45 °C et -10 °C et de manière particulièrement préférée entre -40 °C et -20 °C.
  15. Procédé selon l'une quelconque des revendications 1 à 14, caractérisé en ce qu'un colorant dispersé et éventuellement un adjuvant de dispersion sont utilisés lors de l'étape de coloration (IV).
  16. Utilisation des fibres de polyester colorées (C), du fil coloré (E) et/ou du tissu textile coloré (F) fabriqués par le procédé selon l'une quelconque des revendications 1 à 15 pour la fabrication de matériaux textiles (D).
EP10737320.1A 2009-07-31 2010-07-27 Procédé de fabrication de fibres de polyester colorées, fils colorés et/ou tissus colorés Active EP2459785B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL10737320T PL2459785T3 (pl) 2009-07-31 2010-07-27 Sposób wytwarzania barwionych włókien poliestrowych, przędzy i/lub płaskich tkanin tekstylnych
EP10737320.1A EP2459785B1 (fr) 2009-07-31 2010-07-27 Procédé de fabrication de fibres de polyester colorées, fils colorés et/ou tissus colorés

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09166985 2009-07-31
PCT/EP2010/060843 WO2011012598A1 (fr) 2009-07-31 2010-07-27 Procédé de production de fibres de polyester aptes au filage et à la teinture
EP10737320.1A EP2459785B1 (fr) 2009-07-31 2010-07-27 Procédé de fabrication de fibres de polyester colorées, fils colorés et/ou tissus colorés

Publications (2)

Publication Number Publication Date
EP2459785A1 EP2459785A1 (fr) 2012-06-06
EP2459785B1 true EP2459785B1 (fr) 2015-01-28

Family

ID=41449941

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10737320.1A Active EP2459785B1 (fr) 2009-07-31 2010-07-27 Procédé de fabrication de fibres de polyester colorées, fils colorés et/ou tissus colorés

Country Status (14)

Country Link
US (1) US10202712B2 (fr)
EP (1) EP2459785B1 (fr)
JP (1) JP5575240B2 (fr)
KR (1) KR101718565B1 (fr)
CN (1) CN102471942B (fr)
AU (1) AU2010277618C1 (fr)
BR (1) BR112012001832A2 (fr)
CA (1) CA2767371A1 (fr)
ES (1) ES2535331T3 (fr)
MX (1) MX2012000799A (fr)
MY (1) MY160755A (fr)
PL (1) PL2459785T3 (fr)
WO (1) WO2011012598A1 (fr)
ZA (1) ZA201201420B (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080292831A1 (en) * 2007-03-06 2008-11-27 Futuris Automotive Interiors (Us), Inc. Tufted pet fiber for automotive carpet applications
KR20100015397A (ko) * 2007-03-06 2010-02-12 퓨튜리스 오토모티브 인테리어스 (유에스), 인코포레이티드 자동차 카펫 용도를 위한 터프티드 페트 섬유
US20110177283A1 (en) * 2010-01-18 2011-07-21 Futuris Automotive Interiors (Us), Inc. PET Carpet With Additive
TWI623659B (zh) * 2014-03-05 2018-05-11 Shinkong Synthetic Fibers Corp Polyester fiber manufacturing method, polyester fiber, yarn, and fabric
WO2018219714A1 (fr) 2017-05-31 2018-12-06 Basf Se Procédé de fabrication de fibres polyester
WO2018219708A1 (fr) 2017-05-31 2018-12-06 Basf Se Polyester aliphatique-aromatique à indice de degré de blanc élevé
ES2937083T3 (es) 2019-02-14 2023-03-23 Basf Se Composición hilable (sc) y fibras de poliéster (pf) fabricadas a partir de las mismas
EP3935211A1 (fr) 2019-03-07 2022-01-12 Basf Se Non-tissé
MX2022003366A (es) * 2019-09-20 2022-04-11 Basf Se Proceso para producir fibras mixtas te?idas, hilos de fibras mixtas te?idas y/o telas de fibras mixtas te?idas.
CN110565386A (zh) * 2019-10-09 2019-12-13 福建七匹狼实业股份有限公司 一种抗紫外线面料的制备方法和抗紫外线面料
CN111155221A (zh) * 2019-11-28 2020-05-15 江苏悦达家纺有限公司 一种变化纬密大提花家纺面料及其生产方法
EP3835360A1 (fr) * 2019-12-10 2021-06-16 Aladdin Manufacturing Corporation Filaments de polyester ayant une meilleure aptitude à la coloration
EP3835480A1 (fr) * 2019-12-10 2021-06-16 Aladdin Manufacturing Corporation Fil combiné
CN112323253B (zh) * 2020-10-26 2021-11-23 浙江王金非织造布有限公司 一种双重加固非织造擦拭材料及其制备方法
CN116121930B (zh) * 2023-02-27 2023-11-03 亿吉万(深圳)新材料科技有限公司 一种吸湿抗菌纺织物

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB769405A (en) * 1946-03-28 1957-03-06 Ici Ltd Improving the dye affinity of polyglycol terephthalates
US3652714A (en) 1970-02-20 1972-03-28 Phillips Petroleum Co Dyeable blends of poly(ethylene terephthalate) and polyesterether polymers
US4167541A (en) * 1977-05-12 1979-09-11 Fiber Industries, Inc. Continuous carrierless dyeable polyesters
DE3834737A1 (de) 1988-10-12 1990-04-19 Bayer Ag Carrier fuer das faerben von polyestermaterialien
US6495656B1 (en) * 1990-11-30 2002-12-17 Eastman Chemical Company Copolyesters and fibrous materials formed therefrom
EP0631639A4 (fr) * 1992-02-26 1998-04-29 Arrow Eng Inc Procede et compositions pour la coloration de produits polymeres hydrophobes.
KR0132155B1 (ko) 1994-01-25 1998-04-13 천성순 생분해성 폴리에스터의 제조방법
JPH0874124A (ja) 1994-08-30 1996-03-19 Kuraray Co Ltd 発色性および光沢に優れた繊維
JPH09111667A (ja) * 1995-10-16 1997-04-28 Teijin Ltd ポリエステル繊維布帛の深色性向上方法
DE19638488A1 (de) 1996-09-20 1998-03-26 Basf Ag Biologisch abbaubare Polyester
JP3753844B2 (ja) * 1997-09-17 2006-03-08 旭化成せんい株式会社 ポリトリメチレンテレフタレート鞘芯型複合繊維及びそれを用いた布帛
EP1200505B1 (fr) * 1999-08-06 2004-07-07 Eastman Chemical Company Polyesters a point de fusion controle, et fibres formees a partir desdits polyesters
IT1320126B1 (it) 2000-12-21 2003-11-18 Montefibre Spa Procedimento per la preparazione di resine poliestere filabili etingibili.
JP4527908B2 (ja) * 2001-07-04 2010-08-18 株式会社クレハ 生分解性水切りネット
CN1175023C (zh) * 2002-03-29 2004-11-10 东华大学 分散性染料易染聚酯纤维及生产方法
DE10309564A1 (de) * 2003-03-04 2004-09-16 Basf Ag Polyestermischungen mit verbesserter Biegesteifigkeit
JP2005068840A (ja) * 2003-08-26 2005-03-17 Hagihara Industries Inc 生分解性を有する畳縁
DE602004029094D1 (de) * 2004-03-04 2010-10-21 Unitika Ltd Herstellungsverfahren dafür und schaumstoff und formkörper daraus
ITMI20050452A1 (it) * 2005-03-18 2006-09-19 Novamont Spa Poliestere biodegradabile alifatico-aromatico
TW200801113A (en) 2006-06-27 2008-01-01 Far Eastern Textile Ltd The polylactic acid composition and the deep dyeing fiber manufactured from the same
DE102006057221A1 (de) * 2006-12-01 2008-06-05 Basf Se Verfahren zur Herstellung von gefärbten textilen Materialien umfassend Polypropylenfasern
DE502008002825D1 (de) * 2007-08-15 2011-04-21 Basf Se POLYESTERMISCHUNG MIT VERBESSERTER FLIEßFÄHIGKEIT UND GUTEN MECHANISCHEN EIGENSCHAFTEN
ES2397071T3 (es) 2008-08-11 2013-03-04 Basf Se Método para postratamiento suave de textiles coloreados
WO2010079030A2 (fr) 2008-12-19 2010-07-15 Basf Se Utilisation de copolymères à blocs amphiphiles comme plastifiants pour matières textiles composées de fibres de polypropylène

Also Published As

Publication number Publication date
JP5575240B2 (ja) 2014-08-20
US20120180232A1 (en) 2012-07-19
CN102471942A (zh) 2012-05-23
CN102471942B (zh) 2014-03-12
MY160755A (en) 2017-03-15
JP2013501152A (ja) 2013-01-10
MX2012000799A (es) 2012-02-28
ES2535331T3 (es) 2015-05-08
WO2011012598A1 (fr) 2011-02-03
ZA201201420B (en) 2013-05-29
CA2767371A1 (fr) 2011-02-03
AU2010277618C1 (en) 2016-09-08
EP2459785A1 (fr) 2012-06-06
BR112012001832A2 (pt) 2016-03-15
US10202712B2 (en) 2019-02-12
PL2459785T3 (pl) 2015-06-30
AU2010277618A1 (en) 2012-01-19
KR101718565B1 (ko) 2017-03-21
KR20120040234A (ko) 2012-04-26
AU2010277618B2 (en) 2016-03-10

Similar Documents

Publication Publication Date Title
EP2459785B1 (fr) Procédé de fabrication de fibres de polyester colorées, fils colorés et/ou tissus colorés
EP0746648B1 (fr) Procede de teinture de fibres de terephtalate de polytrimethylene et utilisation des fibres teintes par ce procede
WO2008065185A2 (fr) Procédé de production de textiles colorés comprenant des fibres de polypropylène
CN109537088B (zh) 一种异收缩涤纶低弹丝的制造方法
DE112017008368B4 (de) Verfahren zum Herstellen von elastischer Polyurethanfaser
EP1891154A2 (fr) Compositions polymeres contenant des polyolefines et des copolymeres sequences amphiphiles ainsi qu&#39;eventuellement d&#39;autres polymeres et/ou des charges
EP1703003A1 (fr) Fibres de polyuréthane-urée teintées dans la masse, leur procédé de production et leur utilisation dans la production de tissus
DE2545167A1 (de) Verfahren zur herstellung von gefaerbtem wildleder
DE69726849T2 (de) Verbesserungen im -oder in bezug auf organische polyamidzusammensetzungen
DE69837169T2 (de) Polyesterfaser und daraus hergestellte Flächengebilde
DE10045624A1 (de) Einfach einzufärbende Polyester-Faser
DE19944029C2 (de) Garne aus Polymermischungsfasern oder -filamenten auf der Basis von Polyethylen-, Polybutylen- und Polytrimethylenterephthalat sowie deren Verwendung
EP2157214A1 (fr) Fils colorés et leur utilisation
DE1225857B (de) Verfahren zur Verbesserung der Anfaerbbarkeit von Formkoerpern aus Polyolefinen
DE2411257A1 (de) Polyesterfasern mit ausgezeichneter faerbbarkeit und verfahren zu ihrer herstellung
KR101003033B1 (ko) 심색성이 우수한 추출형 복합섬유
DE2449099A1 (de) Polyesteramine mit guter affinitaet zu anionischen farbstoffen und verfahren zu deren herstellung
DE2011050A1 (de) Copolyester
DD156432A1 (de) Verfahren zum faerben von acrylfaserstoffen waehrend ihrer herstellung

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: 20120229

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL 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 SM TR

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

Effective date: 20131104

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140916

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): AL 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 SM 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

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 708288

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150315

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502010008836

Country of ref document: DE

Effective date: 20150319

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2535331

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20150508

REG Reference to a national code

Ref country code: SK

Ref legal event code: T3

Ref document number: E 18268

Country of ref document: SK

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

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: 20150128

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: 20150428

Ref country code: HR

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: 20150128

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: 20150128

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: 20150428

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: 20150528

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: 20150128

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: 20150429

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502010008836

Country of ref document: DE

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

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: 20150128

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: 20150128

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: 20150128

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E024296

Country of ref document: HU

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: 20151029

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: 20150128

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: 20150128

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150727

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

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: 20150727

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

Ref country code: NL

Payment date: 20160725

Year of fee payment: 7

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

Ref country code: HU

Payment date: 20160725

Year of fee payment: 7

Ref country code: SE

Payment date: 20160726

Year of fee payment: 7

Ref country code: SK

Payment date: 20160726

Year of fee payment: 7

Ref country code: AT

Payment date: 20160727

Year of fee payment: 7

Ref country code: CZ

Payment date: 20160726

Year of fee payment: 7

Ref country code: PL

Payment date: 20160707

Year of fee payment: 7

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: 20150128

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

Ref country code: SM

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: 20150128

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: 20150128

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20170801

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 708288

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170727

REG Reference to a national code

Ref country code: SK

Ref legal event code: MM4A

Ref document number: E 18268

Country of ref document: SK

Effective date: 20170727

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

Ref country code: SE

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

Effective date: 20170728

Ref country code: NL

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

Effective date: 20170801

Ref country code: CZ

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

Effective date: 20170727

Ref country code: HU

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

Effective date: 20170728

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: 20170727

Ref country code: SK

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

Effective date: 20170727

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

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: 20150128

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: 20150128

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

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

Ref country code: AL

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: 20150128

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: 20170727

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

Ref country code: TR

Payment date: 20230707

Year of fee payment: 14

Ref country code: IT

Payment date: 20230721

Year of fee payment: 14

Ref country code: GB

Payment date: 20230725

Year of fee payment: 14

Ref country code: ES

Payment date: 20230816

Year of fee payment: 14

Ref country code: CH

Payment date: 20230801

Year of fee payment: 14

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

Ref country code: FR

Payment date: 20230725

Year of fee payment: 14

Ref country code: DE

Payment date: 20230726

Year of fee payment: 14

Ref country code: BE

Payment date: 20230726

Year of fee payment: 14