WO2022005087A1 - Résine de polyester pour la production de cc-pet et résine composite de cc-pet la comprenant - Google Patents

Résine de polyester pour la production de cc-pet et résine composite de cc-pet la comprenant Download PDF

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WO2022005087A1
WO2022005087A1 PCT/KR2021/007832 KR2021007832W WO2022005087A1 WO 2022005087 A1 WO2022005087 A1 WO 2022005087A1 KR 2021007832 W KR2021007832 W KR 2021007832W WO 2022005087 A1 WO2022005087 A1 WO 2022005087A1
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pet
resin
acid
glycol
mol
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PCT/KR2021/007832
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English (en)
Korean (ko)
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손정아
구자정
김도현
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도레이첨단소재 주식회사
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Priority to CN202180051627.8A priority Critical patent/CN116234853A/zh
Publication of WO2022005087A1 publication Critical patent/WO2022005087A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention provides a CD-PET composite resin manufactured using a polyester resin and a recycled PET (polyethyleneterephthalate) resin, and a polyester resin for CD-PET manufacturing that enables cationic dyeing when manufacturing fibers and/or yarns using the same, and It relates to fibers and/or yarns dyed with cationic dyes, circular knitted fabrics, and the like.
  • a known modifier capable of ion bonding with a cationic dye is used in the production of polyester fibers with terephthalic acid (TPA) and ethylene glycol (EG). and EG to directly esterify.
  • TPA terephthalic acid
  • EG ethylene glycol
  • a modifier is added to each polymerization process for transesterification. It must be prepared by reaction.
  • ethylene glycol (EG) is added to the flake manufactured in the bottle, melted at 180 ° C. ⁇ 240 ° C., and then a glycolysis reaction is sent under nitrogen pressure to After manufacturing bishydroxyethyl terephthalate), recycled polyester is manufactured through a polycondensation reaction.
  • DMS input to enable cationic dyeing has to be added during the polyification reaction because nitrogen pressurization is performed during the ES reaction. have to do Due to such a process, since the amount of DEG (Diethylene glycol) generated is higher than that of the existing cationic dyeable polyester products, there is a problem in that spinning operability and dyeability after final dyeing are different.
  • CD-PET Cationic dyeable polyesters
  • Na-SIPA 5-sulfoisophthalic acid
  • Na-SIPA sodium 5-sulfo-isophthalic acid
  • CD-PET has acidic properties, which increases the formation of diethylene glycol (DEG) in the polyethylene terephthalate esterification step, thereby lowering the melting point and increasing the acidity. Due to the properties, it is difficult to prepare a fiber by promoting TiO 2 agglomeration.
  • DEG diethylene glycol
  • BHT is generated by glycolysis depolymerization under nitrogen pressure with flakes supplied from the bottle in the esterification polymerization step, and then in the polypolymerization step.
  • Bis (hydroxyethyl) isophthalate-5-sulfonate must be added, but as mentioned above, the amount of DEG generated increases, which leads to problems with poor spinning performance due to lowering of the melting point and formation of oligomers.
  • modified copolyester that is, flame retardant polyester, polyester containing high concentration TiO 2 , polyester with latent crimping performance, and recycled polyester
  • the amount of DEG generated increases when DMS is applied to enable cationic dye dyeing.
  • aggregation with TiO 2 occurs due to acidity, or it cannot be added during the ester reaction and must be added only in the form of bis (hydroxyethyl) isophthalate-5-sulfonate.
  • the present invention was devised in consideration of the above problems, and the optimal composition and composition ratio of the polyester resin for CD-PET production, which can ensure excellent dyeability of cationic dyes for recycled PET resins, was completed to complete the present invention.
  • the CD-PET resin prepared by using the polyester resin for producing CD-PET can minimize the moisture adsorption rate, and can provide a yarn with an improved cationic dye dyeing rate. That is, the present invention is to provide a polyester resin for producing CD-PET, a CD-PET resin including the same, and a yarn manufactured using the same.
  • the polyester resin for producing CD (cation dye)-PET of the present invention is a polymer obtained by polycondensation of an ester compound obtained by esterifying an acid component and a diol component, wherein the acid component is a compound represented by the following Chemical Formula 1, a fatty acid and a carboxylic acid Including, the diol component is ethylene glycol (EG); or a glycol mixture comprising a linear glycol and a pulverized glycol represented by the following formula (2).
  • EG ethylene glycol
  • a glycol mixture comprising a linear glycol and a pulverized glycol represented by the following formula (2).
  • R 1 and R 2 are each independently a C 1 to C 5 linear alkyl group or a C 3 to C 5 pulverized alkyl group, and K is a monovalent cation.
  • each of R 1 and R 4 is independently a hydrogen atom, a C 1 to C 10 alkyl group, a C 2 to C 5 alkylene group, a C 5 to C 6 cycloalkyl group or a phenyl group
  • R 2 and Each of R 3 is independently a C 1 to C 5 alkylene group, with the proviso that R 1 and R 4 are both hydrogen atoms, except for the case.
  • the acid component may include 7 to 15 mol% of the compound represented by Formula 1, 7 to 10 mol% of the fatty acid, and the remainder of the carboxylic acid.
  • the fatty acid may include at least one selected from adipic acid, succinic acid, and glutaric acid.
  • the carboxylic acid may be at least one selected from C 6 to C 14 aromatic polyvalent carboxylic acid and C 2 to C 16 aliphatic polyvalent carboxylic acid.
  • the C 6 to C 14 aromatic polyhydric carboxylic acid may include terephthalic acid alone, or two types of terephthalic acid and isophthalic acid.
  • the glycol mixture among the diol components may include 4 to 10 mol% of the pulverized glycol and the remaining amount of the linear glycol.
  • the straight-chain glycol may include C 1 to C 5 straight-chain glycol.
  • the polyester resin for producing CD-PET of the present invention may be a polymer having a polymerization degree of 120 to 180.
  • the polyester resin for producing CD-PET of the present invention has an intrinsic viscosity of 0.40 to 0.80 dl/g, a glass transition temperature (Tg) of 58°C to 75°C, and a melting temperature (Tm) It may be 180 °C ⁇ 220 °C.
  • Another object of the present invention is to provide a masterbatch chip for producing CD-PET comprising the above-described polyester resin for producing CD-PET.
  • another object of the present invention is a CD-PET composite resin, including the aforementioned polyester resin and PET resin for producing CD-PET.
  • the CD-PET composite resin may include 10 to 35% by weight of the polyester resin and the remaining amount of the PET resin.
  • the PET resin among the CD-PET composite resin components may include recycled PET resin derived from waste products.
  • Another object of the present invention is to provide a CD-PET fiber and/or a CD-PET yarn manufactured using the CD-PET composite resin.
  • the CD-PET fiber may include a CD-PET resin, a cation dye, and an additive.
  • the CD-PET fiber is a yarn in which the PET fiber prepared from the CD-PET composite resin is dyed with a cationic dye, and the fiber dyed with the cationic dye has a surface dye concentration (K /S) 9.0 ⁇ 15.0 can be satisfied.
  • Another object of the present invention is to provide a circular knitted fabric comprising the CD-PET fiber and/or the CD-PET yarn.
  • Another object of the present invention relates to a method for manufacturing the CD-PET fiber and/or CD-PET yarn, comprising a chip containing the above-described various types of CD-PET manufacturing polyester resin and a non-ionic PET resin.
  • Step 1 of preparing each chip a second step of forming fibers by mixing the masterbatch in which the chip containing the polyester resin is melted and the resin in which the chip containing the nonionic PET resin is melted and spinning with a spinneret; And after dyeing the fiber with cationic dye, the third step of reducing washing; by performing a process comprising a CD-PET fiber and / or yarn can be prepared.
  • the cationic dye may include at least one selected from Kayacryl yellow 3RL, Kayacryl Red GRL, and Kayacryl Blue GSL.
  • the spinning may be performed under a temperature of 250 ⁇ 330 °C and a spinning speed of 1,500 ⁇ 4,500 MPM.
  • the polyester resin for cation dye-polyethyleneterephthalate (CD-PET) fiber production of the present invention can greatly increase the dyeing rate when a cation dye is added to a fiber and/or yarn manufactured using a recycled PET resin regenerated from waste PET. It is possible to increase the properties of the yarn by controlling the moisture content.
  • 1 is a schematic diagram of a process for producing fibers and/or yarns by mixing and spinning a molten polyester resin (master batch) for producing CD-PET and recycled PET resin.
  • Fibers manufactured using recycled PET resin from recycled PET had a problem with a very low dyeing rate for cationic dyes. was used, but there was a problem in that the productivity was very low or the physical properties of the fibers manufactured using the recycled PET resin were lowered.
  • PE resin When manufacturing fibers using recycled PET resin, mixing and spinning the polyester resin for CD-PET production of the present invention (hereinafter referred to as “PE resin” or “master batch”) prevents deterioration of the physical properties of the fiber while preventing degradation of cationic dyes. It relates to an invention capable of increasing the dyeing rate.
  • the PE resin of the present invention includes a polymer obtained by polycondensation of an ester compound obtained by esterifying an esterification product, and the esterification product includes an acid component and a diol component.
  • the acid component of the ester compound includes a compound represented by the following Chemical Formula 1, a fatty acid, and a carboxylic acid.
  • R 1 and R 2 are each independently a C 1 to C 5 linear alkyl group or C 3 to C 5 pulverized alkyl group, preferably a C 1 to C 5 linear alkyl group, More preferably, it is a C 1 ⁇ C 3 straight-chain alkyl group.
  • K is a monovalent cation, preferably Na + or K + .
  • the content of the compound represented by Formula 1 among the total mol% in the acid component may include 5 to 15 mol% (mol%), preferably 6 to 13 mol%, more preferably 7 to 12 mol%, , If the compound represented by Formula 1 contains less than 5 mol%, an excess of master batch (or PE resin) must be added to enable cationic dye expression when preparing CD-PET composite resin for fiber or yarn production If it is used in excess of 15 mol%, the molecular weight of the polymer (or PE resin) is too high and there may be a problem of rapid viscosity increase, so it is better to use it within the above range.
  • the fatty acid of the acid component may include at least one selected from adipic acid, succinic acid, and glutaric acid, preferably adipic acid.
  • the amount of fatty acid used in the total mol% in the acid component is 7 to 10 mol%, preferably 7.2 to 9.5 mol%. At this time, if the fatty acid content is less than 5 mol%, it is impossible to control the increase in the viscosity of the polymer, so there is a problem that the polymerization reaction is terminated without meeting the intrinsic viscosity (IV) of 0.40 ⁇ 0.80 dl/g level of the PE resin to be prepared.
  • IV intrinsic viscosity
  • the glass transition temperature (Tg) and melting temperature (Tm) of the PE resin are too low to chip the PE resin, and then, when manufacturing fibers or yarn, the chip melting and discharging process Discharge failure may occur during medium discharging, and when the PE resin is chipped, it has to be dried at a low temperature of 60° C. or less for a long time, so drying operability is poor.
  • the carboxylic acid may include at least one selected from C 6 to C 14 aromatic polyvalent carboxylic acid and C 2 to C 16 aliphatic polyvalent carboxylic acid, preferably C 6 to C 14 aromatic polyhydric carboxylic acids.
  • the aromatic polyhydric carboxylic acid is terephthalic acid; or terephthalic acid and isophthalic acid; and when using isophthalic acid mixed, terephthalic acid and isophthalic acid are used in a molar ratio of 1: 0.02 to 0.15, preferably 1: 0.04 to 0.10 to ensure low chip moisture content during chipping; It is advantageous in terms of securing a high glass transition temperature for polymerization.
  • the aliphatic polyhydric carboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, suberic acid, citric acid, pimeric acid, azelaic acid, sebacic acid, nonanoic acid, decanoic acid, dodecanoic acid and hexanodecanoic acid It may include one or more selected from among.
  • At least one selected from linear glycol and pulverized glycol may be used as a diol component for reducing crystallinity for improving dyeability in the preparation of the esterified compound, preferably ethylene glycol (EG); Or a glycol mixture comprising a linear glycol and a pulverized glycol represented by the following formula (2); may be used.
  • EG ethylene glycol
  • a glycol mixture comprising a linear glycol and a pulverized glycol represented by the following formula (2); may be used.
  • each of R 1 and R 4 is independently a hydrogen atom, a C 1 to C 10 alkyl group, a C 2 to C 5 alkylene group, a C 5 to C 6 cycloalkyl group or a phenyl group, preferably
  • Each of R 1 and R 4 is independently a hydrogen atom or a C 1 to C 5 alkyl group, more preferably each of R 1 and R 4 is independently a hydrogen atom or a C 1 to C 3 alkyl group, provided that R 1 and R 4 are all hydrogen atoms.
  • each of R 2 and R 3 is independently a C 1 to C 5 alkylene group, preferably R 2 and R 3 are each independently a C 1 to C 3 alkylene group, more preferably Each of R 2 and R 3 is independently a C 1 to C 2 alkylene group.
  • C 2 to C 6 straight-chain glycol preferably C 2 to C 4 straight-chain glycol, more preferably C 2 to C 3 straight-chain glycol can be used
  • the glycol has high crystallinity when blended with recycled PET or copolyester chips during the yarn manufacturing process, so that there may be a problem that the dye does not sufficiently penetrate into the fiber polymer to reduce crystallinity.
  • the mixture may include 4 to 10 mol% of the pulverized glycol and the balance of the linear glycol, preferably 4 to 8 mol% of the pulverized glycol and the balance of the straight-chain glycol.
  • the crystallinity control effect is insufficient and the dyeing increase effect may be insufficient
  • the pulverized glycol content exceeds 10 mol%, the crystallinity is Since it is very low, there may be a problem in that the discharging processability of the PE resin is deteriorated, or a bridge between chips occurs during drying for manufacturing chips of the PE resin.
  • the PE resin of the present invention includes a polymer obtained by polycondensation of an ester compound obtained by esterification of an acid component and a diol component, wherein the diol component is a carboxylic acid and a diol component 1:1. After mixing at a molar ratio of ⁇ 1.4, preferably 1:15 ⁇ 1.30 molar ratio, an esterification reaction and a polycondensation reaction are performed. At this time, if the molar ratio of the diol component is less than 1:1, there may be a problem that the ester reaction does not sufficiently occur. There may be a problem of lowering the quality of the yarn by lowering it.
  • the PE resin is prepared by performing an esterification reaction on an esterification product containing an acid component and a diol component in the first step of preparing an ester compound; and a second step of preparing a polycondensed reactant by polycondensation of the ester compound.
  • the esterification reaction may be performed at a temperature of 200 to 265°C, preferably at a temperature of 220 to 245°C. If the temperature is less than 200 °C, there may be a problem that the reaction does not proceed because the raw material does not melt well, and if it exceeds 265 °C, there may be problems such as decomposition due to deterioration or inability to obtain a desired degree of polymerization.
  • esterification reaction can be carried out under a stirring speed of 40 to 80 rpm, preferably 50 to 70 rpm, and if the speed is less than 40 rpm or exceeds 80 rpm, sufficient esterification reaction is achieved. There may be unsolved issues.
  • esterification reaction of the first step may be performed after adding and mixing an antifoaming agent and/or an esterification catalyst in addition to the acid component and the diol component.
  • the antifoaming agent may be a general one used in the art, and its amount may be used in an amount of 0.005 to 0.02% by weight, preferably 0.008 to 0.012% by weight, based on the total weight% of the ester reactant.
  • the esterification catalyst may include at least one of lithium acetate, magnesium acetate, and calcium acetate, preferably lithium acetate.
  • the amount of the esterification catalyst used is 0.01 to 0.03% by weight, preferably 0.015 to 0.025% by weight, based on the total weight% of the ester reactant.
  • the polycondensation reaction of the second step may be carried out at a temperature of 250 to 300 °C, preferably at a temperature of 260 to 290 °C.
  • the polycondensation reaction may be performed under a stirring speed of 45 to 70 rpm, preferably 50 to 65 rpm.
  • the polycondensation reaction may be performed after adding and mixing one or more additives selected from an antioxidant, a heat stabilizer, and a polycondensation catalyst in addition to the ester compound, and then performing the polycondensation reaction.
  • the heat stabilizer is trimethylphosphate, triethyl phosphate, tributylphosphate, tributoxyethyl phosphate, tricresyl phosphate, triaryl phosphate isopropyl Rated (Triaryl phosphate isopropylated), hydroquinone bis- (diphenyl phosphate) (Hydroquinone bis- (diphenyl phosphate)) and ortho- may include at least one selected from phosphoric acid (Ortho-phosphoric acid).
  • the amount of the heat stabilizer may be used in an amount of 0.05 to 0.15% by weight, preferably 0.07 to 0.13% by weight, based on the total weight% of the polycondensation reactant.
  • the antioxidant may be included in the form of pentaerythritol tetrakis (Pentaerythritol tetrakis, (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)) alone or in a mixed form with other antioxidants,
  • the amount of the inhibitor used may be 0.05 to 0.15 wt%, preferably 0.07 to 0.13 wt%, based on the total weight of the polycondensation reactant.
  • Antimony trioxide is preferably used as the polycondensation catalyst, and the amount of the polycondensation catalyst used is 0.05 to 0.15 wt%, preferably 0.07 to 0.13 wt%, based on the total weight of the polycondensation reactant.
  • the PE resin of the present invention prepared by this composition, composition ratio and manufacturing method has an intrinsic viscosity (IV) of 0.40 to 0.80 dl/g, preferably 0.45 to 0.78 dl/g, more preferably 0.55 to 0.75 dl/g can be
  • the PE resin of the present invention of the present invention may have a glass transition temperature (Tg) of 58 ⁇ 75 °C, preferably 60 ⁇ 72 °C, more preferably 60 ⁇ 68 °C.
  • Tg glass transition temperature
  • the PE resin of the present invention may have a melting point (Tm) of 180 to 220 °C, preferably 185 to 220 °C, more preferably 190 to 215 °C.
  • the PE resin of the present invention may be provided in the form of chips by chipping.
  • the PE resin is dried in multiple stages from 70° C. to 130° C. for 5 to 7 hours to undergo preliminary crystallization, and then dried at 140 to 160° C. for 4 to 6 hours to reduce the moisture content of the PE resin to 100 ppm or less. manufactures chips. At this time, if the moisture content of the PE resin chip exceeds 100 ppm, it may be hydrolyzed during spinning for fiber and/or yarn production using it, and thus there may be a problem in spinning operability is poor.
  • CD-PET fibers and/or yarns can be manufactured by the following method.
  • PE resin polyethylene resin for CD-PET manufacturing
  • the PE resin and the PE resin chip in step 1 are the same as described above.
  • the nonionic resin chip of step 1 may include at least one of a polyester-based resin, a polyamide-based resin, an acrylic resin, an olefin-based resin, and a polyurethane-based resin, preferably a polyester-based resin More preferably, the chip may be made of polyethyleneterephthalate (PET) resin, and even more preferably, recycled PET resin.
  • PET polyethyleneterephthalate
  • the CD-PET composite resin may include 10 to 35% by weight of the polyester (PE) resin and the remaining amount of the PET resin, preferably 10 to 28% by weight of the PE resin and the remaining amount of the PET resin. . At this time, if the PE resin content exceeds 35% by weight, spinning may be poor, so it is recommended to use it within the above range.
  • the spinning of the second step can be performed in the same way as schematically shown in FIG. 1 , and more specifically, by blending and spinning through a circular nozzle at a spinning speed of 1,500 to 5,000 MPM, preferably 3,000 to 4,500 MPM, fibers can be produced.
  • the spinning in the second step may be performed at a temperature of 250 ⁇ 330 °C, preferably at a temperature of 270 ⁇ 320 °C, if the temperature is less than 260 °C, the melt flow is not smooth and brittle form
  • the yarn is formed and the winding process cannot be performed, and when it exceeds 330°C, there may be a problem in that the yarn is not formed due to deterioration and flows in the form of a melt.
  • Salting of the cationic dye in three steps can be performed by a general method used in the art, and a general cationic dye used in the art can be used, and preferably, the cationic dye is Kayacryl yellow 3RL, Kayacryl Red One or a mixture of two or more selected from GRL and Kayacryl Blue GSL may be used.
  • Cationic dyeable PET (CD-PET) fiber of the present invention prepared by this composition and method has a fineness of 50 to 600 De, preferably a fineness of 50 to 300 De, more preferably a fineness of 50 to 260 De. can have
  • the prepared CD-PET fiber of the present invention may have a strength of 2.50 to 4.50 g/de, preferably a strength of 3.00 to 4.30 g/de, and more preferably a strength of 3.60 to 4.25 g/de.
  • the prepared CD-PET fiber of the present invention may have an elongation of 30 to 45%, preferably 30 to 42%, more preferably 32.0 to 40.0%.
  • the CD-PET fiber of the present invention dyed with a cationic dye may have a surface dye concentration (K/S) of 9.0 to 15.0, preferably 10.0 to 14.5, more preferably 10.0 to 13.5.
  • An acid component, a diol component, an antifoaming agent (silicone-based TSF-433) and lithium acetate (esterification catalyst) are added as an esterification reactant, and the temperature is raised from 200°C to 250°C and mixing and esterification reaction at a speed of 60 rpm to prepare an ester compound (reaction product).
  • ethylene glycol was used alone as the diol component, and the diol component was used in a molar ratio of 1:1.2 based on the carboxylic acid of the acid component.
  • the antifoaming agent was used in an amount of 0.01% by weight based on the total weight% of the prepared ester reactant, and the esterification catalyst was used in an amount of 0.2% by weight based on the total weight% of the prepared ester reactant.
  • the prepared polyester (PE) resin was dried in multiple stages at a temperature of 70 to 130° C. for 6 hours, and then dried at 150° C. for 5 hours to prepare a masterbatch chip for CD-PET production with a moisture content of 100 ppm or less.
  • Example 2 In the same manner as in Example 1, a polyester resin for producing CD-PET and a masterbatch chip obtained by chipping the same were prepared, but as shown in Tables 1 to 2, by changing the acid component and/or the diol component, respectively, Examples 2 to 6 and Comparative Examples 1 to 4 were performed, respectively.
  • glycols represented by the following Chemical Formula 2-1 or 2-2 were used as the pulverized glycol among the diol components.
  • R 1 is a methyl group
  • R 4 is a hydrogen atom
  • R 2 and R 3 are a methylene group.
  • R 1 and R 4 are a methyl group
  • R 2 and R 3 are a methylene group.
  • Ortho-chlorophenol (Ortho-Chloro Phenol) as a solvent was melted at 110°C, 2.0 g/25m concentration for 30 minutes, then at 25°C for 30 minutes, and analyzed from an automatic viscometer connected to a CANON viscometer. did
  • the glass transition temperature was measured using a differential calorimeter, and the analysis condition was a temperature increase rate of 20 °C/min.
  • the cutting operation is carried out while passing it through cold water at a level of 10 to 15 ° C. At this time, whether elution occurs in cold water and whether or not the sticking phenomenon between chips (Bridge) occurs was confirmed.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 6 Mountain Castle minute adipic acid 8 mol% 8 mol% 8 mol% 8 mol% 8 mol% 9.5 mol% Formula 1-1 7.5 mol% 7.5 mol% 7.5 mol% 7.5 mol% 7.5 mol% 7.5 mol% isophthalic acid 5 mol% - - 5 mol% 5 mol% 5 mol% terephthalic acid Remaining remaining amount mole % diol ingredient ethylene glycol 100 mol% 95 mol% 95 mol% 90 mol% 90 mol% 95 mol% Formula 2-1 - 5 mol% - 9 mol% - 5 mol% Formula 2-2 - - 5 mol% - 9 mol% - Diol usage (based on 1 molar ratio of carboxylic acid) 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio 1.2
  • Comparative Examples 2 and 3 prepared in excess of 10 mol% of the diol represented by Formula 2-1 or Formula 2-2 among the diol components, compared with Examples 4 to 5, relatively too low It has a glass transition temperature, and there is a problem in that the moisture content of the chip greatly increases during chipping.
  • a CD-PET composite by using an O-shaped 2-hole spinneret and mixing the masterbatch in which the masterbatch chip (PE resin chip) of Example 1 prepared above is melted with the resin in which the recycled PET chip is melted using a side feeder After preparing the resin, spinning was performed at a spinning temperature of 285° C. and a spinning speed of 4,000 MPM to prepare a CD-PET fiber having a fineness of 150 De.
  • the mixing ratio of the master batch (PE resin) chip and the recycled PET chip during spinning was 20 wt% of polyester resin and 80 wt% of recycled PET resin.
  • the prepared fiber was dyed with a cationic dye, Kayacryl Blke GSL, at a concentration of 2% owf at 110° C. for 45 minutes, and then reduced and washed at 80° C. to complete the dyeing.
  • a cationic dye Kayacryl Blke GSL
  • the steel and elongation of the manufactured fiber were measured by applying a speed of 50 cm/m and a gripping distance of 50 cm using an automatic tensile tester (Textechno).
  • Strength and elongation are the value (g/de) obtained by dividing the applied load by the denier when the composite fiber is stretched until it is cut with a constant force. defined.
  • Example 1 Preparation 2 Preparation 3
  • Preparation 4 Preparation 5
  • Preparation 6 Masterbatch (polyester resin)
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 20% by weight 10% by weight 20% by weight 20% by weight 20% by weight 20% by weight Recycled PET resin 80% by weight 90% by weight 80% by weight 80% by weight 80% by weight 80% by weight CD-PET fiber speedy 4,000 MPM fineness 150
  • De Intensity (g/de) 4.0 3.4 4.3 4.2 3.7 3.8 Elongation (%)
  • 35 43 32 34 41 39
  • Uniformity (%) 1.00 0.8 0.9 0.9 1.0
  • dyeability Surface dye concentration (K/S) 10.5 9.6 12.5 11.8 13.5 13.2 spinning operability Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great Great
  • Comparative Preparation Example 1 prepared with a CD-PET composite resin containing 40% by weight of polyester (PE) resin in an amount exceeding 35% by weight, there was a problem in that the spinnability was very poor.
  • Comparative Preparation Example 2 prepared with a CD-PET composite resin containing less than 10% by weight of polyester (PE) resin in an amount of 6.5% by weight, less than 10% by weight, strength and elongation were not good, and dyeability was also poor. .
  • PE polyester
  • the polyester resin for producing CD-PET of the present invention not only has an appropriate intrinsic viscosity, glass transition temperature and melting point, but also has a low chip moisture content and a high bridge temperature when it is chipped. there was.
  • the CD-PET fibers prepared using the CD-PET polyester resin and waste PET resin could secure excellent cationic dyeing properties while having excellent overall mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne une résine de polyester et une résine composite de CC (colorant cationique)-PET l'utilisant. La présente invention concerne : une résine de polyester pour la production d'un CC-PET, une excellente aptitude à la coloration d'un colorant cationique par rapport à une résine de PET non ionique pouvant être obtenue ; une résine composite de CC-PET produite à l'aide de celle-ci ; et une fibre, un fil ou un article tricoté circulaire et similaire en CC-PET produit à l'aide de celui-ci et présentant un excellent taux de coloration par un colorant cationique.
PCT/KR2021/007832 2020-07-03 2021-06-22 Résine de polyester pour la production de cc-pet et résine composite de cc-pet la comprenant WO2022005087A1 (fr)

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CN202180051627.8A CN116234853A (zh) 2020-07-03 2021-06-22 用于制备cd-pet的聚酯树脂及包含其的cd-pet复合树脂

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KR10-2020-0082107 2020-07-03
KR1020200082107A KR102396242B1 (ko) 2020-07-03 2020-07-03 Cd-pet 제조용 폴리에스테르 수지 및 이를 포함하는 cd-pet 복합수지

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CN116234853A (zh) 2023-06-06

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