EP0746648B1 - Procede de teinture de fibres de terephtalate de polytrimethylene et utilisation des fibres teintes par ce procede - Google Patents

Procede de teinture de fibres de terephtalate de polytrimethylene et utilisation des fibres teintes par ce procede Download PDF

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EP0746648B1
EP0746648B1 EP95909689A EP95909689A EP0746648B1 EP 0746648 B1 EP0746648 B1 EP 0746648B1 EP 95909689 A EP95909689 A EP 95909689A EP 95909689 A EP95909689 A EP 95909689A EP 0746648 B1 EP0746648 B1 EP 0746648B1
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Prior art keywords
temperature
fibers
dye
liquor
ptmt
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Revoked
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EP95909689A
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German (de)
English (en)
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EP0746648A1 (fr
Inventor
Peter Hirt
Gilbert KÜHL
Hermann Piana
Hansjörg TRAUB
Heinz Herlinger
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EIDP Inc
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Degussa GmbH
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    • 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
    • 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
    • D06P1/0004—General aspects of dyeing
    • 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
    • D06P1/0032—Determining dye recipes and dyeing parameters; Colour matching or monitoring
    • 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
    • D06P1/16—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 dispersed, e.g. acetate, dyestuffs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber

Definitions

  • the invention relates to a method for staining Fibers of polytrimethylene terephthalate with Disperse dyes in an aqueous liquor at or below the cooking temperature of the fleet as well as the Use of the fibers dyed according to the invention.
  • Polytrimethylene terephthalate is a polyester that as the diol component 1,3-propanediol and terephthalic acid as Has dicarboxylic acid component.
  • Large-scale Polyester synthesis can basically be done in two ways various procedures can be carried out (H.-D. Schumann in man-made fibers / textile 40/92 (1990), p. 1058ff).
  • dimethyl terephthalate is transesterified with 1,3-propanediol with the addition of catalysts at temperatures of 160-210 ° C. and the methanol released is distilled off from the reaction mixture at normal pressure.
  • the reaction mixture which mainly consists of bis (3-hydroxypropyl) terephthalate, is further heated to 250-280 ° C. under reduced pressure and the 1,3-propanediol released is removed.
  • the formation of the polytrimethylene terephthalate from bis (3-hydroxypropyl) terephthalate can be catalyzed by the same catalyst as in the transesterification or a different polycondensation catalyst is added after the same has been deactivated.
  • a composite fiber made of polyethylene terephthalate and GB 1075689 describes polytrimethylene terephthalate the representation of the polytrimethylene terephthalate is from Dimethyl terephthalate and 1,3-propanediol and Titanium tetrabutylate as transesterification and Polycondensation catalyst used.
  • Manganese (II) acetate tetrahydrate is used as the transesterification catalyst used and as a polycondensation catalyst finds hexagonal crystalline germanium dioxide with a Particle size less than 2 ⁇ m use.
  • This Catalysts can also be used to make dipolymers from terephthalic acid, 1,2-ethanediol and 1,3-propanediol be used.
  • polyester fibers e.g. B.
  • polyethylene terephthalate fibers Series of investigations into the coloring Behavioral. So you know (Herlinger, Gutmann and Jiang in CTI, man-made fibers / textile industry 37/89, February 1987, Pp. 144 - 150) that the use of polyethylene terephthalate in textile technology with regard to dyeing was associated with certain problems.
  • polyester can only be used with carriers or under so-called HT conditions - d. H. with increased Temperature, e.g. B. 130 ° C in pressure vessels - optimal with Stain disperse dyes (Béla v. Falkai in "Synthesemaschine", Verlag Chemie, Weinheim, 1981, p. 176).
  • Carriers are special aids that the Dye liquors must be added to the To enable dye absorption practically only.
  • Examples for carriers also known as fiber swelling agents can be u. a. o-hydroxybiphenyl or Trichlorobenzene. It is believed that such auxiliaries Lower the freezing temperature, above which the larger one Molecular segments of the fibers in the non-crystalline Areas become agile, causing the staining process accelerates.
  • polyethylene terephthalate polymer PETP
  • polyether blocks consisting of Polyethylene glycol (PEG) units in the PETP chains installed, which due to their Mobility makes it easier to draw up the dye.
  • PEG Polyethylene glycol
  • Attempts have also been made to replace the PEG units Polybutylene glycol units in polyethylene terephthalate polymerize.
  • There is also one in these polyester types Decrease in glass transition temperature, and the coloring behavior is significantly improved.
  • the one environmentally friendly permanent coloring of the Permits polytrimethylene terephthalate fibers and beyond leads to dyed polyester fibers that both over have excellent processing properties as well in thermal and mechanical terms Polyester fibers meet the demands made.
  • the colored fibers are said to have an increased Color fastness when using fibers and always have textile products made from them there, where there is increased abrasion on the fiber surface can come.
  • PTMT fibers polytrimethylene terephthalate fibers
  • the Temperature at or below the cooking temperature of the fleet no carrier is present, work is carried out without pressure, while staining at a liquor temperature temperature between 20 and 50 ° C is started within 20 - 90 min, preferably within 45 min, to the cooking temperature of the fleet or to a maximum 20 ° C below the cooking temperature of the fleet Dyeing temperature is brought, the dyeing at least 20 min at the dyeing or boiling temperature, preferred 30 - 90 min, is continued and then on a Temperature of 20 - 50 ° C, preferably with a cooling rate of 1 ° C per min, is cooled, so that at least 95% by weight of the dye on offer in the fleet PTMT fibers and the disperse dye at least at a relative depth of 5% based on the Diameter of the fiber to be dyed penetrates into it environmentally friendly dyeing of PTMT fibers possible and it are dyed PTMT fibers with
  • Polytrimethylene terephthalate fibers dyed out Polytrimethylene terephthalate are available, which under Use of a single catalyst are preferred Titanium compounds, for the transesterification and the subsequent Polycondensation was made.
  • the transesterification catalyst is not converted to an ineffective form before polycondensation must become.
  • the catalytically effective one Species in many cases only in the reaction mixture generated and it can at the end of the reaction in the polymer remain.
  • polyester staple fibers obtained can be optional before staining with a person known to the person skilled in the art Stretching system at temperatures of 110 ° C (heating mandrel) and 90 ° C (block heater).
  • Disperse dyes are not on certain connections are limited but include all dyes of low water solubility, which in the Are capable of hydrophobic fibers from an aqueous dispersion stain.
  • the disperse dyes in question are familiar to those skilled in the art as examples
  • Dye classes of the azo series amino or aminohydroxyanthraquinones or called nitro dyes.
  • Monoazo dyes which are several nitro or Possess cyano substituents, and heterocyclic azo and Polymethine dyes. Representatives of these dye classes can be used alone or in a mixture of several be, including representatives of different classes can be mixed together, for example to or to produce black tones.
  • dyes for dyeing processes like they're basically for dyeing cotton can be applied, whereby a diaminoazo compound after colors the dispersion process, diazotizes on the fiber and with a suitable coupling component to the black Trisazo body implements.
  • a diaminoazo compound after colors the dispersion process, diazotizes on the fiber and with a suitable coupling component to the black Trisazo body implements.
  • the disperse dyes are in the beginning of the invention an aqueous liquor. They spread out when staining between aqueous liquor and the fiber treated with it as between two immiscible or limited miscible Liquids and finally pull at suitable Reaction management and substance selection on the fiber.
  • the treatment of the fibers takes place in the invention Process essentially by contacting fibers and Liquor (in aqueous the disperse dyes and if necessary. solution containing necessary auxiliaries), for example by immersing in and staying in the fibers Fleet instead.
  • This process takes place essential to the invention without the addition of carriers and without pressure, d. H. without applying the atmospheric pressure presses at the boiling point of the fleet or at a temperature below the boiling point of the fleet in such a way that at least 95% by weight of that in the fleet offered dye on the PTMT fibers.
  • the procedure is used to stain the Polytrimethylene terephthalate fibers used a liquor between 3.0 and 7.0 g of disperse dye per kg PTMT fiber to be dyed.
  • Especially advantageous process design contains fleet used between 4.5 and 5.5 g Disperse dye per kg of PTMT fiber.
  • the above Amounts of disperse dye each relate to the im Commercial dye contained pure dye.
  • Commercial dyes are known to contain large amounts of Auxiliaries (up to 80 wt .-%) contain.
  • the fibers are particularly penetrating quickly inside the fiber. Based on the Diameters of the fiber to be dyed penetrate the Disperse dyes according to the invention in at least one relative depth of 5% in this one. Particularly advantageous the fibers are among those according to the invention Coloring conditions are completely colored, in contrast to Polyethylene terephthalate fibers, which are compared under identical staining conditions only stained in a ring will.
  • dyed PTMT fibers can be used in a variety of ways. Basically, they can be used in all sectors that also open to previously known dyed polyester fibers stood. Those in an invention are preferred Processed colored PTMT fibers for Manufacture of woven, knitted or crocheted fabrics used. Because of the excellent mechanical Properties of the colored PTMT fibers, especially the high ones Elasticity and recoverability is also a stake in heavily used textiles or as highly elastic Fabric preferred.
  • the batch size is 45 moles based on the amount used Dimethyl terephthalate, the ratio 1,3-propanediol (Diol batch D with a 1,3-propanediol content of 99.96%, 0.011% 3-hydroxymethyltetrahydropyran content, 0.005% 2-hydroxyethyl-1,3-dioxane content, 0.02% carbonyls and 0.04% Water content) to dimethyl terephthalate becomes 1: 2.25 selected and titanium tetrabutylate comes as 10 wt .-% Catalyst solution in n-butanol in a concentration of 600 ppm with respect to dimethyl terephthalate.
  • Dimethyl terephthalate, 1,3-propanediol and the Catalyst solution are in the polycondensation filled and under a constant light Nitrogen stream heated to 140 ° C. After that Dimethyl terephthalate has melted, the stirrer switched on and the temperature increased to 220 ° C. That at the transesterification released methanol is distilled off until the calculated amount has almost been reached.
  • the pressure in the polycondensation apparatus is gradually reduced and the 1,3-propanediol used in excess and the 1,3-propanediol formed during the condensation are distilled off.
  • the temperature is slowly increased to 270 ° C and the pressure is further reduced until finally oil pump vacuum (p ⁇ 0.05 mbar) is reached.
  • the end of polycondensation is reached when the dropping rate of the 1,3-propanediol has dropped below 0.5 drops per minute.
  • This information applies to the 2 dm 3 polycondensation plant.
  • the power consumption of the agitator motor was used in the 2 dm 3 system as an indirect measure of the progressive condensation. In the 20 dm 3 system, the torque is determined as a measure of the progress of the polycondensation.
  • the vacuum in the polycondensation apparatus is released and the finished polytrimethylene terephthalate is discharged into a water bath with a gear pump under nitrogen pressure, drawn off with a take-off device and immediately
  • the reproducible temperature control during synthesis is controlled by a microprocessor-controlled temperature program guaranteed.
  • the other conditions like pressure and The stirrer speed is always manually the same Time program changed.
  • the specified final temperature the polycondensation apparatus is at 240 ° C. This Temperature is reached 75 minutes before the end of the polycondensation reached and then until the end of polycondensation kept constant.
  • the melting temperature rises to the end of the Polycondensation continues continuously up to 267 ° C.
  • the heat required for this is not from the outside through the Heating supplied, but arises from the heat of stirring in of the apparatus itself. That this effect only occurs towards the end of the Polycondensation occurs with the steadily increasing Explain the viscosity of the polycondensation melt.
  • the weight average molecular weight is determined using the static light scattering determined.
  • This Polymer solutions with concentrations of 2, 4, 6, 8 and 10 g / l made in 1,1,1,3,3,3-hexafluoroisopropanol.
  • ⁇ 633 nm
  • the refractive index increment is determined using the Wyatt Opilab 903 Interferometric Refractometer from Wyatt Technology Corporation.
  • the color of the polymers is determined using the CIELAB color values specified.
  • the polymer granules are with the Minolta CR 310, whose spectral sensitivity is close the CIE 2 ° normal observer function is adapted, measured.
  • the measuring field diameter is 5 cm and the Calibration is carried out using a white standard.
  • the polymers are dried in batches of about 25 kg each in a tumble dryer with a capacity of 100 dm 3 from Henkhaus Apparatebau.
  • the polymer batches PTMT 20/14 + PTMT 20/11 + PTMT 20/13, PTMT 20/12 + PTMT 20/18 + PTMT 20/19 and PTMT 20/15 + PTMT 20/16 + PTMT 20/17 are received of mixed batches A), B) and C) mixed (see Table 1).
  • Table 2 shows the drying conditions. 1 hour 80 ° C [130 ° C] p ⁇ 0.2 mbar 1 hour 100 ° C [130 ° C] p ⁇ 0.2 mbar 10 hours 165 ° C [180 ° C] p ⁇ 0.2 mbar
  • the tumble dryer is then left for 12 hours Cool to room temperature and aerate with nitrogen.
  • the water contents of the dried polymers are below 0.0025%, making a significant Polymer degradation in the melt spinning process must be excluded.
  • An aqueous emulsion of 10% limanol is used as the preparation PVK and 1.6% Ukanol R.
  • the preparation pad is about 0.5%.
  • Polytrimethylene terephthalate is also commercially available Spun polyethylene terephthalate.
  • the Spinning speeds are at a spin titer of 16 tex with 32 single filaments in the range from 2000 to 5000 m / min varies.
  • the spin titer is at one constant spinning speed of 3500 m / min in the area from 9.6 to 22.4 tex with 32 individual filaments each varies. This corresponds to a fineness of 0.3 to 0.7 tex per single filament.
  • the Spinning temperature in the range between 240 and 270 ° C varies with the best results at 250 ° C will.
  • the staple fibers obtained are drawn on a drawing system
  • the stretch factors are chosen so that the drawn fiber is about 25% Has stretch.
  • Polyethylene terephthalate staple fiber Polyethylene terephthalate staple fiber
  • the glass transition temperature of the polymers in aqueous medium is of greater importance for the dyeing behavior of the synthetic fibers.
  • DR Buchanan and JP Walters, text. Res. J., 47 (1977), 398 define a color transition temperature.
  • the dye absorption of the synthetic fibers is determined as a function of the temperature.
  • the temperature at which the dye absorption reaches 50% of the equilibrium value is defined as the color transition temperature.
  • the color transition temperature depends on the dyeing time and the structure of the dye.
  • Knitted fabrics made from the following fibers are used for the dyeing tests: polymer Spinning speed [m / min] Spinning titer [tex] Stretch factor Stretch titer [tex] PTMT 3500 16.1 1.44 12.1 PET 3500 19.0 1.55 126
  • the fibers are knitted on a Circular knitting machine washed around when spinning remove the applied preparation.
  • the knitted fabric is washed as follows: Washing conditions: apparatus Mathis LAB Jumbo Jet with washing drum temperature 30 ° C Duration 120 min Wash liquor 1 g / l Kieralon® EDB from Bayer AG Fleet ratio 1:50
  • thermofixed knitted fabrics show a greater surface shrinkage in the case of polytrimethylene terephthalate than in the case of polyethylene terephthalate.
  • Fixing conditions apparatus Mathis dryer temperature 180 ° C Duration 1 min
  • dye Diffusion coefficient [10 10th cm -2 ⁇ S]
  • CI Disperse Blue 139 0.8 Mono-azo dye resolin navy blue GLS from Bayer AG
  • CI Disperse Red 60 3.4 Antrachinone dye Resolin Red FB from Bayer AG
  • the dyeing temperatures are in the range between 60 ° C and 140 ° C varies.
  • the coloring is always started at 40 ° C and the Heating rate selected so that after 45 minutes Dyeing temperature is reached.
  • the cooling rate is always 1 K / min until the bath temperature reaches 40 ° C.
  • the dyeings reductively treated.
  • the heating rate of the Reduction liquor is 2 K / min, the cooling rate is 1 K / min.
  • the fibers dyed at different temperatures are extracted exhaustively with chlorobenzene.
  • the extracts are diluted to a defined volume and the extinctions of the solution are determined using a Lambda 7 UV / VIS spectrophotometer from Perkin Elmer in Bodensee. From the extinction of the extraction solution at the characteristic wavelength CI Disperse Blue 139 604 nm and CI Disperse Red 60 516 nm the dye content can be determined using the corresponding calibration line.
  • Figures 2 and 3 show the dye uptake of Polytrimethylene terephthalate fibers depending on the Dyeing temperature compared to Polyethylene terephthalate fibers.
  • the maximum determinable dye absorption is around 95% of the maximum possible dye absorption because the Reductive treatment of fiber samples before extraction will. In doing so, the one adhering to the fiber surface Dye reductively destroyed and the maximum determinable This lowers the dye content.
  • Fig. 2 also shows that at a dyeing temperature of 100 ° C the entire dye from the dye liquor on the Polytrimethylene terephthalate fiber absorbs. Against pulls at 100 ° C dyeing temperature only about 15% of the offered Dye on the polyethylene terephthalate fiber.
  • the C.I. Disperse Red 60 a disperse dye with higher diffusion coefficient, is almost identical Course of the dye uptake with the dyeing temperature as observed at C.I. Disperse Blue 139.
  • the color transition temperature of polytrimethylene and polyethylene terephthalate are thus: PTMT PET CI Disperse Blue 139 91 ° C 107 ° C CI Disperse Red 60 84 ° C 100 ° C
  • the dyeing transition temperature is in both dyeings Polymers with C.I. Disperse Red 60, due to its higher Diffusion coefficient, about 7 K lower than at Staining with C. I. Disperse Blue 139.
  • the difference of 16 K of the color transition temperatures of both polymers remains constant, however.
  • the dye distribution in the fiber can be determined using Fiber cross sections are assessed. You can do it Differentiate between color and ring color. Fiber cross sections are obtained by using the fibers in Acrylic acid esters are embedded and using a Minot microtome from Jung to a thickness of 10 ⁇ m get cut. The cross-sectional images are with taken with a Zeiss Axioplan microscope. The reality a staining, when the stained Fabric, is higher than in the case of color change in the case of a ring coloration in which the dye is only in the outer layer of the fiber is embedded.
  • the cross sections of the fibers show that the dye faster inside the polytrimethylene terephthalate fiber can penetrate like this at the Polyethylene terephthalate fiber is the case.
  • Fig. 8 shows that related to the fiber diameter Depth of penetration of the dye depending on the Dyeing temperature.
  • the polytrimethylene terephthalate fiber can be Excellent cooking temperature with C. I. Disperse Blue 139 to dye.
  • the fiber takes the whole in the Dyeing liquor offered dye.
  • the Dye concentration is at the edges highest. In the case of HT staining, the dye diffusion accelerated so that a uniform color through the entire fiber cross section can be observed.
  • the dye absorption is the Polyethylene terephthalate fiber clearly at cooking temperature less.
  • the dye absorption of the fiber is only 10% of the dye offered in the dyeing liquor. Under HT conditions can also the polyethylene terephthalate fiber stain well. The entire dye offered penetrates the fiber is on, but the fiber is colored C. I. Disperse Blue 139 not observed.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Coloring (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (6)

  1. Procédé pour teindre des fibres du polyméthylènetéréphtalate (fibres PTMT), dans lequel on traite les fibres PTMT dans un bain aqueux présentant au moins un colorant de dispersion, à la température d'ébullition du bain ou à une température inférieure à cette dernière,
    caractérisé en ce qu'on teint les fibres PTMT sans pression et en l'absence d'agent véhiculaire, dans lequel on commence la teinture à une température du bain entre 20 et 50°C, on amène la température, dans un laps de temps de 20 à 90 minutes, de préférence dans un laps de temps de 45 minutes, à la température d'ébullition du bain ou à une température de teinture qui se situe au maximum à 20°C en dessous de la température d'ébullition du bain, on poursuit la teinture pendant au moins 20 minutes à la température de teinture ou d'ébullition, de préférence pendant un laps de temps de 30 à 90 minutes, et on refroidit ensuite à une température de 20 à 50°C, de préférence avec un débit de refroidissement de 1°C par minute,
    de telle sorte qu'au moins 95% en poids du colorant disponible dans le bain monte sur les fibres PTMT et de telle sorte que le colorant de dispersion pénètre dans les fibres au moins jusqu'à une profondeur relative de 5% rapportés au diamètre des fibres à teindre.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un bain qui présente entre 3,0 et 7,0 g d'un colorant de dispersion pur par kg de fibres PTMT à teindre.
  3. Procédé selon la revendication 2, caractérisé en ce qu'on utilise un bain possédant une teneur en colorant de dispersion de 4,5 à 5,5 g de colorant pur/kg de fibres PTMT.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on effectue le traitement à une température de teinture entre 80 et 110°C, de préférence entre 90 et 100°C.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on teint complètement les fibres.
  6. Utilisation de fibres PTMT teintes que l'on obtient dans un procédé selon l'une quelconque des revendications précédentes, pour la fabrication de tissus, de tissus à mailles ou de tricotages.
EP95909689A 1994-02-21 1995-02-09 Procede de teinture de fibres de terephtalate de polytrimethylene et utilisation des fibres teintes par ce procede Revoked EP0746648B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4405407 1994-02-21
DE4405407 1994-02-21
PCT/EP1995/000455 WO1995022650A1 (fr) 1994-02-21 1995-02-09 Procede de teinture de fibres de terephtalate de polytrimethylene et utilisation des fibres teintes par ce procede

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Publication Number Publication Date
EP0746648A1 EP0746648A1 (fr) 1996-12-11
EP0746648B1 true EP0746648B1 (fr) 1998-01-14

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US (1) US5782935A (fr)
EP (1) EP0746648B1 (fr)
JP (1) JP4213202B2 (fr)
KR (1) KR100355721B1 (fr)
CN (1) CN1080349C (fr)
AT (1) ATE162242T1 (fr)
CA (1) CA2183736C (fr)
DE (2) DE59501289D1 (fr)
DK (1) DK0746648T3 (fr)
ES (1) ES2112046T3 (fr)
GR (1) GR3026379T3 (fr)
MX (1) MX9603276A (fr)
MY (1) MY130115A (fr)
TW (1) TW318192B (fr)
WO (1) WO1995022650A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19944029C2 (de) * 1998-09-14 2002-06-27 Inst Textil & Faserforschung Garne aus Polymermischungsfasern oder -filamenten auf der Basis von Polyethylen-, Polybutylen- und Polytrimethylenterephthalat sowie deren Verwendung
DE102005035767A1 (de) * 2005-07-29 2007-02-01 Deutsche Institute für Textil- und Faserforschung Stuttgart Polyester von Terephthalsäure, ein Verfahren zu deren Herstellung und deren Verwendung

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6652964B1 (en) 1997-08-18 2003-11-25 Asahi Kasei Kabushiki Kaisha Polyester fiber and fabric prepared therefrom
US6110405A (en) * 1997-09-15 2000-08-29 Wellman, Inc. Melt spinning colored polycondensation polymers
EP1043428B1 (fr) * 1997-12-22 2006-06-07 Asahi Kasei Kabushiki Kaisha Fibres pour flocage electrique et article floque par voie electrique
US7501373B1 (en) 1998-10-23 2009-03-10 Toyo Boseki Kabushiki Kaisha Polymerization catalyst for polyester production, polyester, and process for producing polyester
EP1295975B1 (fr) * 1999-03-30 2007-06-06 Asahi Kasei Kabushiki Kaisha Ensouple de tissage et procede d'encollage
US6297315B1 (en) * 1999-05-11 2001-10-02 Shell Oil Company Process for preparing polytrimethylene terephthalate
DE19934551A1 (de) * 1999-07-22 2001-01-25 Lurgi Zimmer Ag PTT-Stapelfasern und Verfahren zu ihrer Herstellung
DE60016447T2 (de) 1999-08-24 2005-12-08 Toyo Boseki K.K. Polymerisationskatalysatoren für Polyester, damit hergestellte Polyester und Verfahren zur Herstellung von Polyester
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AU2402401A (en) 2000-01-05 2001-07-16 Toyo Boseki Kabushiki Kaisha Polymerization catalyst for polyesters, polyesters produced with the same and process for producing polyesters
US6312805B1 (en) 2000-02-11 2001-11-06 E.I. Du Pont De Nemours And Company Cationic dyeability modifier for use with polyester and polyamide
US6685859B2 (en) 2000-03-03 2004-02-03 E. I. Du Pont De Nemours And Company Processes for making poly(trimethylene terephthalate) yarn
US6383632B2 (en) 2000-03-03 2002-05-07 E. I. Du Pont De Nemours And Company Fine denier yarn from poly (trimethylene terephthalate)
US6287688B1 (en) 2000-03-03 2001-09-11 E. I. Du Pont De Nemours And Company Partially oriented poly(trimethylene terephthalate) yarn
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CN1205381C (zh) * 2001-06-27 2005-06-08 株式会社晓星 聚对苯二甲酸丙二酯地毯的连续染色方法
KR100431784B1 (ko) * 2001-11-01 2004-05-17 주식회사 효성 폴리트리메틸렌 테레프탈레이트 카페트의 연속 염색법
US6923925B2 (en) 2002-06-27 2005-08-02 E. I. Du Pont De Nemours And Company Process of making poly (trimethylene dicarboxylate) fibers
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MX9603276A (es) 1997-03-29
DE59501289D1 (de) 1998-02-19
DE19505576A1 (de) 1995-08-24
ES2112046T3 (es) 1998-03-16
CA2183736A1 (fr) 1995-08-24
MY130115A (en) 2007-06-29
CN1154728A (zh) 1997-07-16
GR3026379T3 (en) 1998-06-30
KR100355721B1 (ko) 2003-01-06
EP0746648A1 (fr) 1996-12-11
KR970701285A (ko) 1997-03-17
JP4213202B2 (ja) 2009-01-21
JPH09509225A (ja) 1997-09-16
WO1995022650A1 (fr) 1995-08-24
CN1080349C (zh) 2002-03-06
DK0746648T3 (da) 1998-09-14
CA2183736C (fr) 2001-07-31
TW318192B (fr) 1997-10-21
ATE162242T1 (de) 1998-01-15
US5782935A (en) 1998-07-21

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