US20230050671A1 - Colored synthetic fiber - Google Patents

Colored synthetic fiber Download PDF

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US20230050671A1
US20230050671A1 US17/757,049 US202017757049A US2023050671A1 US 20230050671 A1 US20230050671 A1 US 20230050671A1 US 202017757049 A US202017757049 A US 202017757049A US 2023050671 A1 US2023050671 A1 US 2023050671A1
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Prior art keywords
synthetic fiber
polyester
unit
process according
aliphatic diol
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Hélène Amedro
Nicolas Jacquel
René Saint-Loup
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Roquette Freres SA
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Roquette Freres SA
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Assigned to ROQUETTE FRERES reassignment ROQUETTE FRERES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AMEDRO, HELENE, JACQUEL, Nicolas, SAINT-LOUP, RENE
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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
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters

Definitions

  • the present invention relates to the field of polymers, in particular to the field of polyester fibers, and relates more specifically to a process for manufacturing a colored synthetic fiber, and to the uses thereof.
  • Synthetic fibers are mostly derived from petroleum and are generally favored because of their low production cost and ease of manufacture.
  • the main known synthetic fibers are for example polyester, polyamide, polyurethane, elastane or acrylic fibers.
  • document FR1657031 in the name of the applicant, discloses synthetic fibers obtained from a semicrystalline thermoplastic polyester comprising isosorbide.
  • the polyester fiber is formed from a polyester resin having a structure in which a dicarboxylic acid and a diol are polymerized.
  • the polyester resin comprises especially 1 to 20 mol % of diol units derived from isosorbide and 2 to 5 mol % of diol units derived from ethylene glycol, and also comprises 1.3% by weight of an oligomer.
  • an additive can be added during the preparation.
  • the added additive can be a compound derived from cobalt, such as cobalt acetate, or if necessary, an organic compound such as an anthraquinone, perinone, azo or methine compound.
  • an organic compound such as an anthraquinone, perinone, azo or methine compound.
  • an amount of 1 to 50 ppm must necessarily be respected in order to sufficiently mask the yellowing without altering the physical properties.
  • Patent U.S. Pat. No. 3,223,752 relates to polyolefins modified to improve dyeability and spinnability. Particularly, this document discloses improved fiber-forming polyolefin compositions, as well as polyolefin fibers and filaments with improved dye affinity, particularly for disperse dyes, without significantly altering their physical properties. The improvement is obtained by combining the polyolefins with up to 1% to 20% by weight of modified polyesters.
  • a modified polyester according to this document refers to polyesters prepared from dicarboxylic acids and glycols, the modification being carried out using a mixture of acids or glycols.
  • a first object of the present invention relates to a process for manufacturing a colored synthetic fiber comprising the following steps of: 1) providing a semicrystalline thermoplastic polyester comprising at least one 1,4:3,6-dianhydrohexitol unit (A), at least one aliphatic diol unit (B) other than the 1,4:3,6-dianhydrohexitol units (A), and at least one aromatic dicarboxylic acid unit (C), wherein the (A)/[(A)+(B)] molar ratio is at least 0.05 and at most 0.30, and the reduced viscosity in solution (35° C.; ortho-chlorophenol; 5 g/l of polyester) of which is greater than 50 ml/g.
  • Another object of the invention relates to a synthetic fiber colored by a disperse dye, said synthetic fiber consisting substantially of semicrystalline thermoplastic polyester comprising at least one 1,4:3,6-dianhydrohexitol unit (A), at least one aliphatic diol unit (B) other than the 1,4:3,6-dianhydrohexitol units (A), at least one aromatic dicarboxylic acid (C), wherein the (A)/[(A)+(B)] molar ratio is at least 0.05 and at most 0.30, the reduced viscosity in solution (35° C.; ortho-chlorophenol; 5 g/l of polyester) of which is greater than 50 ml/g.
  • Another object of the invention relates to the use of the colored synthetic fiber disclosed hereinbefore in the field of furnishings, textiles or sporting goods.
  • the present invention thus relates to a process for manufacturing a colored synthetic fiber comprising the following steps of:
  • a semicrystalline thermoplastic polyester comprising at least one 1,4:3,6-dianhydrohexitol unit (A), at least one aliphatic diol unit (B) other than the 1,4:3,6-dianhydrohexitol units (A), and at least one aromatic dicarboxylic acid (C), wherein the (A)/[(A)+(B)] molar ratio is at least 0.05 and at most 0.30, the reduced viscosity in solution (35° C.; ortho-chlorophenol; 5 g/l of polyester) of which is greater than 50 ml/g. 2) preparing the synthetic fiber from said semicrystalline thermoplastic polyester, 3) dyeing said synthetic fiber with an aqueous solution of at least one disperse dye.
  • thermoplastic polyester based on isosorbide and an aqueous solution of at least one disperse dye makes it possible to obtain colored synthetic fibers that have improved dyeing quality.
  • the presence of isosorbide in the polyester according to the invention improves the dye affinity of the synthetic fiber with respect to an isosorbide-free polyester-based synthetic fiber, while also maintaining equivalent wash fastness.
  • fiber as used in the present invention is synonymous with the terms filaments and yarns, and thus includes continuous or discontinuous mono or multi-filaments, non-twisted or interwoven multi-filaments, and base yarns. This term also refers only to a fiber of synthetic origin and therefore does not include natural fibers.
  • the first step of the process according to the invention consists in providing a semicrystalline thermoplastic polyester comprising at least one 1,4:3,6-dianhydrohexitol unit (A), at least one aliphatic diol unit (B) other than the 1,4:3,6-dianhydrohexitol units (A), and at least one terephthalic acid unit (C), wherein the (A)/[(A)+(B)] molar ratio is from 0.05 to 0.30.
  • (A)/[(A)+(B)] molar ratio” is intended to mean the molar ratio of 1,4:3,6-dianhydrohexitol units (A)/sum of the 1,4:3,6-dianhydrohexitol units (A) and of the aliphatic diol units (B) other than the 1,4:3,6-dianhydrohexitol units (A).
  • the (A)/[(A)+(B)] molar ratio is from 0.10 to 0.28, and preferentially from 0.15 to 0.25.
  • the monomer or unit (A) is a 1,4:3,6-dianhydrohexitol and may be selected from isosorbide, isomannide, isoidide, or a mixture thereof.
  • Isosorbide, isomannide and isoidide can be obtained, respectively, by dehydration of sorbitol, mannitol and iditol.
  • the 1,4:3,6-dianhydrohexitol unit (A) is isosorbide. It is for example marketed by the applicant under the trade name POLYSORB®.
  • the aliphatic diol unit (B) may be a linear, branched or cyclic aliphatic diol. It may also be a saturated or unsaturated aliphatic diol.
  • the aliphatic diol is a linear diol selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and/or 1,10-decanediol.
  • the aliphatic diol unit (B) is a saturated branched non-cyclic aliphatic diol.
  • examples of this include 2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, propylene glycol and/or neopentyl glycol.
  • the semicrystalline thermoplastic polyester is free of non-cyclic aliphatic diol units or comprises a molar amount of non-cyclic aliphatic diol units, with respect to the total number of monomer units of the polyester, of less than 1%; preferably, the polyester is free of non-cyclic aliphatic diol units.
  • the aliphatic diol unit (B) is a cyclic aliphatic diol.
  • examples of this include 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, spiroglycol, tricyclo[5.2.1.0 2,6 ]decanedimethanol (TCDDM), 2,2,4,4-tetramethyl-1,3-cyclobutanediol, tetrahydrofuran-dimethanol (THFDM), furandimethanol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, dioxane glycol (DOG), norbornane diols, adamantane diols, pentacyclopentadecane dimethanols or a mixture of these diols.
  • TCDDM 1,4-cyclohexanedimethanol
  • the aliphatic diol unit (B) is 1,4-cyclohexanedimethanol.
  • the aliphatic diol unit (B) may be in the cis configuration, in the trans configuration or may be a mixture of diols in cis and trans configuration.
  • the aliphatic diol unit (B) is an unsaturated aliphatic diol such as for example cis-2-butene-1,4-diol.
  • the aromatic dicarboxylic acid unit (C) may be selected from the aromatic dicarboxylic acids known to a person skilled in the art.
  • the aromatic dicarboxylic acid may be a derivative of naphthalates, terephthalates, furanoates, thiophene dicarboxylate, pyridine dicarboxylate or even isophthalates or mixtures thereof.
  • the aromatic dicarboxylic acid is a derivative of terephthalates and preferably, the aromatic dicarboxylic acid is terephthalic acid.
  • the reduced viscosity in solution of said semicrystalline thermoplastic polyester is greater than 50 ml/g.
  • This reduced viscosity in solution is measured using an Ubbelohde capillary viscometer at 35° C. in ortho-dichlorophenol after dissolving the polymer at 130° C. while stirring, the concentration of polymer introduced being 5 g/I.
  • the semicrystalline thermoplastic polyester has a reduced viscosity in solution of 50 ml/g to 120 ml/g, preferably of 60 ml/g to 100 ml/g.
  • a semicrystalline thermoplastic polyester particularly suitable for the process according to the invention comprises a molar amount of 1,4:3,6-dianhydrohexitol units (A) ranging from 2.5 to 14 mol %, a molar amount of aliphatic diol units (B) other than the 1,4:3,6-dianhydrohexitol units (A) ranging from 31 to 42.5 mol %, and a molar amount of terephthalic acid units (C) ranging from 45 to 55 mol %.
  • the amounts of different units in the polyester may be determined by 1H NMR or by chromatographic analysis of the mixture of monomers resulting from complete hydrolysis or methanolysis of the polyester, preferably by 1H NMR.
  • the analysis conditions for determining the amounts of each of the units of the polyester can readily find the analysis conditions for determining the amounts of each of the units of the polyester.
  • the chemical shifts relating to the 1,4-cyclohexanedimethanol are between 0.9 and 2.4 ppm and 4.0 and 4.5 ppm
  • the chemical shifts relating to the terephthalate ring are between 7.8 and 8.4 ppm
  • the chemical shifts relating to the isosorbide are between 4.1 and 5.8 ppm.
  • the integration of each signal makes it possible to determine the amount of each unit of the polyester.
  • the semicrystalline thermoplastic polyester used according to the invention has a melting temperature ranging from 200 to 295° C., for example from 220 to 285° C.
  • the semicrystalline thermoplastic polyesters have a glass transition temperature ranging from 40 to 120° C., for example from 50 to 115° C.
  • the glass transition temperatures and melting points are measured by conventional methods, especially using differential scanning calorimetry (DSC) using a heating rate of 10° C./min.
  • DSC differential scanning calorimetry
  • the sample is first heated under a nitrogen atmosphere in an open crucible from 10 to 320° C. (10° C. ⁇ min-1), cooled to 10° C. (10° C. ⁇ min-1), then heated again to 320° C. under the same conditions as the first step.
  • the glass transition temperatures are then taken at the mid-point of the second heating. Any melting points are determined on the endothermic peak (peak onset) at the first heating.
  • the measurement of this heat of fusion consists of subjecting a sample of this polyester to a heat treatment at 170° C. for 16 hours then of evaluating the heat of fusion by DSC by heating the sample at 10° C./min.
  • the semicrystalline thermoplastic polyester provided according to the first step of the process may be provided in the form of pellets or granules.
  • the semicrystalline thermoplastic polyester is conditioned in granule form, said granules having a residual moisture content of less than 300 ppm, preferentially less than 200 ppm such as for example about 75 ppm.
  • These polyesters are particularly well suited to the manufacture of synthetic fibers and make it possible to obtain fibers that have better dye affinity with disperse dyes and have good washing stability.
  • the first step of the process according to the invention comprises providing a mixture of semicrystalline thermoplastic polyester comprising at least one 1,4:3,6-dianhydrohexitol unit (A), at least one aliphatic diol unit (B) other than the 1,4:3,6-dianhydrohexitol units (A), and at least one aromatic carboxylic acid (C), wherein the (A)/[(A)+(B)] molar ratio is at least 0.05 and at most 0.30, the reduced viscosity in solution (35° C.; ortho-chlorophenol; 5 g/l of polyester) of which is greater than 50 ml/g.
  • the step of preparing the synthetic fiber is carried out from said mixture.
  • the second step of the process according to the invention consists of preparing the synthetic fiber from the semicrystalline thermoplastic polyester provided in the previous step.
  • the synthetic fiber can be obtained according to the methods known to a skilled person.
  • the synthetic fiber can be obtained via melt spinning or by solution processes (wet or dry).
  • the synthetic fibers are manufactured by the melt spinning method.
  • the manufacture of synthetic fibers by the melt spinning method involves first melting the polyester in an extruder. The molten material is then sent under pressure through a die consisting of a multitude of holes. At the outlet of the die, the filaments are air-cooled, drawn and wound. Generally, a sizing product is applied at the lower part of the spinning path
  • the synthetic fiber obtained according to the second step of the process of the invention can be woven or knitted before the dyeing step.
  • the third step of the process according to the invention consists of dyeing the synthetic fiber with an aqueous solution of at least one disperse dye.
  • the aqueous solution of disperse dye is also referred to as “dye bath”.
  • a disperse dye is a weakly polar dye with a relatively small size, of the order of ten microns. This dye, due to its lack of solubilizing groups, is practically insoluble in water which means that it must be applied as an aqueous dispersion containing mostly dye particles.
  • this type of dye Before being placed in aqueous solution, this type of dye can generally be in paste or powder form.
  • the disperse dye according to the invention is selected from azo-type disperse dyes, anthraquinone-type disperse dyes, methine-type dyes, nitro-type dyes, naphthoquinone-type dyes, aminoketone-type dyes and mixtures thereof.
  • the disperse dye is an azo-type dye.
  • the azo-type dye can especially be selected from the di-azo or mono-azo dyes derived from azobenzene such as for example references Dispersed blue 165, C.I. Disperse Orange 5, C.I. Disperse Red 19, or C.I. Disperse Blue 183.
  • the disperse dye is an anthraquinone-type dye.
  • the anthraquinone-type dye can be selected from carmine, alizarin, purpurin, indanthrene blue, anthraquinone yellow, or anthraquinone red.
  • the disperse dye is a mixture of azo-type dye as defined hereunder and anthraquinone-type dye as defined hereinbefore.
  • anthraquinone-type dyes make it possible to obtain more uniform dyeing because they have a smaller molecular size than azo-type dyes.
  • anthraquinone dyes are preferred for light shades and azo dyes are preferred for obtaining dark shades.
  • the aqueous solution may comprise an amount from 0.01% to 15% of disperse dye, preferably from 1 to 10% and particularly from 3 to 5%. The percentage being expressed by weight of dye relative to the total weight of the solution.
  • the aqueous solution of disperse dye used for the dyeing step according to the invention may comprise from 0.1 g/I to 10 g/l of dispersing agent.
  • the dispersing agent has good wettability properties thus facilitating the dispersion of the dye in water but above all makes it possible to maintain a stable dispersion during the dyeing process.
  • the dispersing agent may belong to two classes of compounds.
  • the first relates to condensation products of aromatic compounds containing sulfonated groups and the second to lignin sulfonates.
  • the dyeing step is carried out by soaking in the aqueous solution of disperse dye.
  • the aqueous solution of disperse dye used for the dyeing step has a high temperature, that is to say a temperature of 120° C. to 140° C., preferably a temperature of 130° C.
  • the aqueous solution of disperse dye used is acidic.
  • acidic is intended in the present invention to mean that said solution has a pH of 3.5 to 5.5, preferably a pH of 4 to 5.
  • the soaking can advantageously be carried out for 10 to 120 minutes, preferably for 20 to 90 minutes, more preferably for 30 to 60 minutes.
  • the step of dyeing the synthetic fiber is carried out according to the following sequence: holding at 60° C. for 10 min, increasing the temperature at a rate of 1.5° C./min up to 80° C. and then at a rate of 1° C./min up to 130° C., holding at 130° C. for 45 min, and finally, reducing the temperature at a rate of 2.5° C./min up to 60° C.
  • the selection of this time/temperature cycle enables optimal dyeing of the synthetic fiber by the disperse dye.
  • the process comprises a step of stripping the dyed synthetic fiber so as to remove the disperse dye not fixed to said fiber.
  • the stripping may be carried out by soaking the synthetic fiber for 15 to 20 minutes in a bath at a temperature ranging from 65° C. to 80° C., said bath comprising for example a mixture of sodium hydroxide and sodium hydrosulfite.
  • the stripping may optionally be followed by a hot rinse and a cold rinse.
  • the colored synthetic fiber obtained according to the process of the invention is free of any polymer other than that provided according to the first step.
  • a second object of the invention relates to a synthetic fiber colored by a disperse dye, said synthetic fiber consisting substantially of a semicrystalline thermoplastic polyester comprising at least one 1,4:3,6-dianhydrohexitol unit (A), at least one aliphatic diol unit (B) other than the 1,4:3,6-dianhydrohexitol units (A), at least one aromatic dicarboxylic acid (C), wherein the (A)/[(A)+(B)] molar ratio is at least 0.05 and at most 0.30, the reduced viscosity in solution (35° C.; ortho-chlorophenol; 5 g/l of polyester) of which is greater than 50 ml/g.
  • the dyed synthetic fiber according to the invention is likely to be obtained according to the previously disclosed process.
  • thermoplastic polyester and the disperse dye are as disclosed previously.
  • Consisting substantially of is intended in the present invention to mean that 98% by weight, preferably 99% by weight, and particularly 100% by weight, relative to the total weight of the synthetic fiber consists of said semicrystalline thermoplastic polyester.
  • Another object of the invention is a dyed synthetic fiber as defined previously for use in the field of textiles, furnishings or sporting goods.
  • the fibers may be used for the production of textiles and non-woven.
  • the textiles can especially be obtained by weaving or knitting.
  • a non-woven is a manufactured product consisting of a web, a cloth, a lap, or a mat of directionally or randomly distributed fibers, the internal cohesion of which is provided by mechanical, physical or chemical methods or else by a combination of these methods.
  • An example of internal cohesion may be adhesive bonding, and results in obtaining a non-woven cloth, said non-woven cloth possibly then being made into the form of a mat of fibers.
  • the fibers may be transformed into non-woven according to the techniques known to a skilled person, such as the dry route, the melt route, the wet route or flash spinning.
  • the formation of the non-woven by dry route may especially be carried out by calendering or by an air laid process.
  • melt route it can be carried out by extrusion (spinbonding technology or spunbonded fabric) or by extrusion blow-molding (melt-blown).
  • FIG. 1 Synthetic fibers colored with the light hue bath. From left to right: Synthetic fiber F (PET); Synthetic fiber D (PEI10T), Synthetic fiber A (PT15T); Synthetic fiber B (PTI10T), Synthetic fiber C (PTT).
  • Synthetic fiber F PET
  • Synthetic fiber D PEI10T
  • Synthetic fiber A PEI10T
  • Synthetic fiber A P15T
  • Synthetic fiber B PI10T
  • Synthetic fiber C PTT
  • FIG. 2 Synthetic fibers colored with the medium hue bath. From left to right: Synthetic fiber F (PET); Synthetic fiber D (PEI10T), Synthetic fiber A (PT15T); Synthetic fiber B (PTI10T), Synthetic fiber C (PTT).
  • Synthetic fiber F PET
  • Synthetic fiber D PEI10T
  • Synthetic fiber A P15T
  • Synthetic fiber B PI10T
  • Synthetic fiber C PTT
  • FIG. 3 Synthetic fibers colored with the dark hue bath. From left to right: Synthetic fiber F (PET); Synthetic fiber D (PEI10T), Synthetic fiber A (PT15T); Synthetic fiber B (PTI10T), Synthetic fiber C (PTT).
  • Synthetic fiber F PET
  • Synthetic fiber D PEI10T
  • Synthetic fiber A PEI10T
  • Synthetic fiber A P15T
  • Synthetic fiber B PI10T
  • Synthetic fiber C PTT
  • FIG. 4 Comparison of the colorings obtained with dye baths 1 to 3 on fabrics knitted with synthetic fibers E and F. From left to right: fabrics knitted with synthetic fiber F and dyed with bath 1; fabrics knitted with a synthetic fiber E and dyed with bath 1; fabrics knitted with a synthetic fiber F and dyed with bath 2; fabrics knitted with a synthetic fiber E and dyed with bath 2; fabrics knitted with a synthetic fiber F and dyed with bath 3; fabrics knitted with a synthetic fiber E and dyed with bath 3.
  • Polymer A poly(trimethylene-co-isosorbide terephthalate).
  • Polymer A is a semicrystalline thermoplastic polyester according to the invention.
  • This polymer is carried out by melt route in 2 steps, via a transesterification and a polycondensation step. This synthesis takes place in a 60-l reactor equipped with a stirrer with torque measurement, a distillation column, a vacuum line and a nitrogen inlet.
  • the reactor is preheated to 100° C. before being loaded with the previously prepared reaction mixture.
  • the reaction mixture consists of:
  • the reactor is then inerted by 4 vacuum/nitrogen cycles.
  • the reaction medium is then heated to 220° C. for 1:30 h and then to 245° C. until the end of the trans-esterification reaction.
  • This first step is carried out under 1.5 bar of nitrogen.
  • a decompression ramp is applied in order to obtain the maximum vacuum in 1:40 h and the temperature is increased to 255° C. after 80 minutes of vacuum ramp.
  • the polymer When the target torque is reached, the polymer is poured into a water bath and then granulated.
  • the polymer thus obtained has a reduced viscosity in solution (IV) of 73.7 ml/g.
  • the polymer pellets then undergo a post-condensation treatment in solid state in a 50-l glass flask heated by an oil bath, stirred and under nitrogen flow.
  • the oil bath is heated to 150° C.
  • pellets are then cooled under nitrogen to 40° C. to detach if necessary any pellets attached to the walls of the flask. Then, the oil bath is reheated to 210° C. while stirring and under nitrogen flow (10 l/min) for the post-condensation step. These conditions are maintained for 15 h.
  • the final polymer denoted polymer A, has a final reduced viscosity in final solution IV of 102 ml/g, a molar ratio of isosorbide to diols of 5.2 mol %, a glass transition temperature Tg of 58° C., and a melting temperature Tm of 222° C.
  • Polymer B is a semicrystalline thermoplastic polyester according to the invention while polymer C serves as comparison and does not contain isosorbide. These two polymers are obtained according to a process similar to that of polymer A and have the final properties mentioned in Table 1 hereunder.
  • PEIT polyethylene-co-isosorbide terephthalate
  • the synthesis of polymer D is carried out by melt route in 2 steps, via an esterification and a polycondensation step. This synthesis takes place in a 100-l reactor equipped with a stirrer with torque measurement, a distillation column, a vacuum line and a nitrogen inlet.
  • the reactor is first preheated to 100° C. before being loaded with the following reagents:
  • the reactor is then inerted by 4 vacuum/nitrogen cycles.
  • the reaction medium is heated to 250° C. under 2.5 bar.
  • the esterification is continued until a transformation rate of about 80% is obtained.
  • the pressure is then reduced in 15 minutes to atmospheric pressure (1024 hPa) in order to add phosphoric acid via an addition jar (3.53 g of phosphoric acid dissolved in 50 g of ethylene glycol).
  • a vacuum ramp is then applied to reach 3 mbar in 25 minutes.
  • the temperature of the reactor is increased to 265° C.
  • the polycondensation is monitored by a torque measurement.
  • the polymer When the target torque is reached the polymer is poured into a water tray and then granulated.
  • the polymer obtained has a reduced viscosity in solution (IV) of 54 ml/g.
  • the polymer pellets then undergo a post-condensation treatment in solid state in a 50-l glass flask heated by an oil bath, stirred and under nitrogen flow.
  • the oil bath is heated to 150° C.
  • the pellets are then cooled under nitrogen to 40° C. to remove any pellets attached to the walls of the flask.
  • the oil bath is reheated to 220° C. while stirring and under nitrogen flow (10 l/min) for the post-condensation step. These conditions are maintained for 90 h.
  • the final polymer denoted polymer D has a final reduced viscosity in solution (IV) of 106 ml/g, a ratio of isosorbide to diols of 11.9 mol %, a Tg of 91° C. and a Tm of 225° C.
  • Polymer E (cyclohexanedimethylene-co-isosorbide terephthalate) (PITg)
  • polymer E The synthesis of polymer E was carried out according to example 3a of application WO2016/189239 A1.
  • the polymer has the following properties: a molar ratio of isosorbide to diols of 15.2 mol %, a reduced viscosity in solution (IV) of 85 ml/g, a Tg of 109° C. and a Tm of 263° C.
  • Polymer F serves as a comparison and does not contain isosorbide. It is a commercial poly(ethylene terephthalate) from Invista.
  • Synthetic fibers A, B, D and E according to the invention were prepared by melt spinning on a pilot line from polymers A (PTIT), B (PTIT), D (PEIT), and E (PITg), respectively.
  • Comparative synthetic fibers C and F were also prepared from the isosorbide-free polymers C (PTT) and F (PET), respectively.
  • the extrusion temperature is 260° C. for polymers A (PTIT), B (PTIT) and C (PTT), and 300° C. for polymers D (PEIT), E (PITg) and F (PET).
  • the die used comprises a head with 48 holes having a diameter of 25 ⁇ m each, the material flow rate is of 2 kg/h, the drawing speed is 1200 m/min.
  • cooling is done by air jet at room temperature (about 23° C.) then a sizing is applied to the surface of the fibers.
  • the fiber bundle is then passed over four pairs of buckets heated to different temperatures (between 30° C. and 115° C.) in order to adjust the mechanical properties, and the assembly is then wound.
  • the synthetic fibers obtained with each of the polyesters A to F are then soaked in dye baths.
  • the disperse dyes used are marketed by Huntsman and listed hereunder:
  • the mixture has a pH of 5 controlled by adding acetic acid in order to obtain the dye bath for each disperse dye.
  • Three dye baths are thus prepared by varying the amount of dye in order to obtain light, medium and dark colors.
  • the amounts of each dye used are set out in Table 2 hereunder.
  • the polyester synthetic fibers were colored with the light, medium and dark hues. For each of the dye baths, all the different fibers were put in the same bottle for dyeing.
  • the bottles are placed on an Ahiba Nuance top speed bottle-turner marketed by Datacolor.
  • the dyeing is carried out according to the time/temperature cycle having the following successive steps:
  • the stripping is carried out at 70° C. for 20 min in a bath comprising:
  • the synthetic fibers are hot and cold rinsed.
  • the wash fastness is evaluated by means of a color fastness test carried out in accordance with standard ISO 105-006:2010.
  • the test comprises a step of washing the textiles at 40° C. for 30 min in 150 ml of detergent followed by a step of rinsing in two baths of water at 40° C.
  • Each textile is washed with a white strip of fabric made of 6 different materials, namely wool, acrylic, polyester, polyamide, cotton and acetate.
  • This white strip of fabric serves as a control and thus makes it possible to check, where appropriate, whether the dye has bled out of the textile and to know onto what type(s) of material it has bled.
  • the colored synthetic fibers obtained with the different baths are presented in FIGS. 1 to 3 .
  • the synthetic fibers A, B, D, E obtained with the semicrystalline thermoplastic polyesters according to the invention absorb very rapidly a very large part of the dye.
  • the coloring obtained is perfectly uniform and has a high-quality visual appearance.
  • the dyeing kinetics are much faster with the synthetic fibers according to the invention than for comparative isosorbide-free synthetic fibers C and F in PTT and PET, respectively.
  • the delta L corresponds to the difference in lightness (light or dark).
  • the delta a corresponds to the difference in greenness-redness and finally, the delta b corresponds to the difference in blueness-yellowness.
  • the knitted fabrics obtained with synthetic fibers E have a better dye affinity than those obtained with isosorbide-free synthetic fibers F.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Coloring (AREA)
US17/757,049 2019-12-10 2020-12-10 Colored synthetic fiber Pending US20230050671A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1914005A FR3104179B1 (fr) 2019-12-10 2019-12-10 Fibre synthétique colorée
FR1914005 2019-12-10
PCT/FR2020/052381 WO2021116614A1 (fr) 2019-12-10 2020-12-10 Fibre synthétique colorée

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US20230050671A1 true US20230050671A1 (en) 2023-02-16

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US (1) US20230050671A1 (ja)
EP (1) EP4073300A1 (ja)
JP (1) JP2023505424A (ja)
KR (1) KR20220107244A (ja)
FR (1) FR3104179B1 (ja)
WO (1) WO2021116614A1 (ja)

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Publication number Priority date Publication date Assignee Title
NL128493C (ja) 1961-05-31
US6063495A (en) 1998-04-23 2000-05-16 Hna Holdings, Inc. Polyester fiber and methods for making same
CN101215728A (zh) * 2008-01-15 2008-07-09 东华大学 一种异山梨醇改性聚酯纤维及制备方法
FR3036400B1 (fr) 2015-05-22 2019-04-26 Roquette Freres Polyester de haute viscosite aux proprietes choc ameliorees
FR3054244B1 (fr) * 2016-07-22 2019-09-06 Roquette Freres Polyester thermoplastique semi-cristallin pour la fabrication de fibres
FR3070677B1 (fr) * 2016-08-03 2021-11-12 Roquette Freres Procede d'emballage a partir de polyester thermoplastique semi-cristallin
KR102568693B1 (ko) * 2017-06-02 2023-08-21 에스케이케미칼 주식회사 폴리에스테르 섬유, 이의 제조 방법 및 이로부터 형성된 성형체

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EP4073300A1 (fr) 2022-10-19
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FR3104179A1 (fr) 2021-06-11
JP2023505424A (ja) 2023-02-09

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