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WO2018135787A1 - Polymère de polyéthylène téréphtalate copolymérisé, fil/bcf/film le contenant, et leur procédé de production - Google Patents

Polymère de polyéthylène téréphtalate copolymérisé, fil/bcf/film le contenant, et leur procédé de production Download PDF

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Publication number
WO2018135787A1
WO2018135787A1 PCT/KR2018/000322 KR2018000322W WO2018135787A1 WO 2018135787 A1 WO2018135787 A1 WO 2018135787A1 KR 2018000322 W KR2018000322 W KR 2018000322W WO 2018135787 A1 WO2018135787 A1 WO 2018135787A1
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Prior art keywords
polyethylene terephthalate
pdms
modified polydimethylsiloxane
copolymerized
weight
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PCT/KR2018/000322
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English (en)
Korean (ko)
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김천기
김무송
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(주)효성
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Priority claimed from KR1020170009575A external-priority patent/KR101888070B1/ko
Priority claimed from KR1020170009576A external-priority patent/KR101949403B1/ko
Priority claimed from KR1020170009577A external-priority patent/KR101949401B1/ko
Priority claimed from KR1020170009463A external-priority patent/KR101947491B1/ko
Application filed by (주)효성 filed Critical (주)효성
Publication of WO2018135787A1 publication Critical patent/WO2018135787A1/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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the present invention is in addition to the existing polyethylene terephthalate bond ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid) in addition to polyethylene glycol (PEG) chain number of 1 to 50 one-way end group modified PDMS
  • the present invention relates to a copolymer of polyethylene terephthalate having improved wear resistance prepared by introducing (polydimethylsiloxane) and a medical or industrial yarn, a BCF or a film for a carpet.
  • polyester resins especially polyethylene terephthalate resins, are linear polymers synthesized from dicarboxylic acids or their ester-forming derivatives and diols or their ester-forming derivatives, and are inexpensive, yet have excellent mechanical and chemical properties. In addition to excellent gas barrier properties, it is widely used in the manufacture of various containers, films, fibers and the like.
  • polyester is produced by the condensation polymerization method, the equilibrium reaction according to external conditions to obtain a commercially available viscosity through the conditions of high temperature, high vacuum, wherein a certain amount of oligomers remain in the final polymer.
  • PDMS polydimethylsiloxane
  • PEG polyethylene glycol
  • PEG polyethylene glycol
  • PDMS polydimethylsiloxane
  • the modified polydimethylsiloxane (PDMS) is added in an amount of 0.1 to 20% by weight based on the total weight of the copolymerized polyethylene terephthalate.
  • PET polyethylene terephthalate
  • polyethylene terephtalate (PET) 80 to 99.9% by weight; And 0.1 to 20% by weight of unidirectional end group-modified polydimethylsiloxane (PDMS), wherein the unidirectional end group-modified polydimethylsiloxane (PDMS) is a chain of polyethyleneglycol (PEG) of the general formula (I)
  • PEG polyethyleneglycol
  • I polyethyleneglycol
  • the present invention is prepared by the method of direct copolymerization of the copolymerized polyethylene terephthalate and a method of copolymerizing one-way end group-modified polydimethylsiloxane (PDMS) to polyethylene terephthalate at high concentration and using it as a master batch.
  • PDMS polydimethylsiloxane
  • the copolymerized polyethylene teretate is a slurry (Slurry) step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid); Esterification of the slurry; And a polycondensation reaction step, wherein the abrasion resistance is improved medical or industrial polyethylene, including copolymerized polyethylene terephthalate prepared by a method of injecting one aromatic end group-modified polydimethylsiloxane (PDMS) into the rear end of the polycondensation reaction.
  • PDMS polydimethylsiloxane
  • Polyethylene terephtalate (PET) 80 to 99.9% by weight; And 0.1 to 20% by weight of unidirectional end-modified polydimethylsiloxane (PDMS), wherein the unidirectional end-group modified polydimethylsiloxane (PDMS) has a number of chains of polyethylene glycol (PEG) of general formula (I)
  • PEG polyethylene glycol
  • a BCF for a carpet having improved abrasion resistance including copolymerized polyethylene terephthalate, having 1 to 50 and a number average molecular weight of 800 to 50,000.
  • the present invention is prepared by the method of directly copolymerizing the copolymerized polyethylene terephthalate or a method of copolymerizing unidirectional end-group-modified polydimethylsiloxane (PDMS) to polyethylene terephthalate at high concentration and using it as a master batch.
  • PDMS polydimethylsiloxane
  • a BCF for a carpet.
  • the copolymerized polyethylene teretate is a slurry (Slurry) step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid); Esterification of the slurry; And a polycondensation reaction step; and a copolymer-containing BCF for a copolymer including a copolymerized polyethylene terephthalate prepared by a method of introducing one aromatic end group-modified polydimethylsiloxane (PDMS) into the rear end of the polycondensation reaction.
  • Slurry slurry
  • EG ethylene glycol
  • TPA Terephthalic acid
  • Esterification of the slurry And a polycondensation reaction step
  • a copolymer-containing BCF for a copolymer including a copolymerized polyethylene terephthalate prepared by a method of introducing one aromatic end group-modified polydimethylsiloxane (PD
  • a polyethylene terephthalate BCF carpet with improved wear resistance prepared using the copolymerized polyethylene terephthalate.
  • polyethylene terephtalate PET
  • PDMS unidirectional end group-modified polydimethylsiloxane
  • PEG polyethylene glycol
  • the present invention is prepared by the method of directly copolymerizing the copolymerized polyethylene terephthalate or a method of copolymerizing unidirectional end-group-modified polydimethylsiloxane (PDMS) to polyethylene terephthalate at high concentration and using it as a master batch. It provides a polyethylene terephthalate film characterized by improved wear resistance and release force.
  • PDMS polydimethylsiloxane
  • the copolymerized polyethylene teretate is a slurry (Slurry) step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid); Esterification of the slurry; And a polycondensation reaction step, wherein the polyethylene has improved abrasion resistance and releasing force, including copolymerized polyethylene terephthalate prepared by a method of injecting one aromatic end group-modified polydimethylsiloxane (PDMS) into the rear end of the polycondensation reaction.
  • PDMS polydimethylsiloxane
  • the present invention is a polyethylene glycol (PEG) chain number of 1 to 50, copolymerized polyethylene terephthalate with improved wear resistance by adding one-way terminal group-modified PDMS having a molecular weight of 800 to 50,000 and a medical or industrial yarn comprising the same , BCF or film for the mat.
  • PEG polyethylene glycol
  • Figure 1 shows a wear test specimen for the friction wear characteristics analysis.
  • Figure 2 shows the structure of the wear test apparatus for the friction wear characteristics analysis.
  • Method for producing a copolymerized polyethylene terephthalate according to the present invention is a slurry (Slurry) step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid); Esterification step; And a polycondensation reaction step, wherein one side end group-modified PDMS having 1 to 50 chains of polyethylene glycol (PEG) is introduced into the rear end of the polycondensation reaction.
  • Slurry ethylene glycol
  • TPA Terephthalic acid
  • the modified PDMS it is preferable to add the modified PDMS to the end of the polycondensation reaction in order to express the wear resistance improving effect of polyethylene terephthalate.
  • the modified PDMS is added after the polycondensation reaction, a binding degree of 99% or more is obtained.
  • Polydimethylsiloxane further added in the present invention is a compound having a structure of the following general formula (I).
  • the modified PDMS is composed of OH, -COOH, or NH2 in one aromatic terminal group, and in the present invention, the polymerizable polyethylene terephthalate is mainly used using OH, -COOH, and most preferably, existing diols (-OH).
  • the modified PDMS having OH is mainly used by utilizing the polymerization bond of the group).
  • the modified PDMS molecular weight of the present invention is preferably in the range of 800 to 50,000, more preferably 1,000 to 15,000. At this time, when the molecular weight of the modified PDMS is less than 800, the wear resistance and the release force is lowered, and when it exceeds 50,000, the polycondensation reactivity is lowered.
  • the number of chains of polyethylene glycol (PEG) of the modified PDMS of the present invention is preferably in the range of 1 to 50, more preferably 1 to 20. At this time, when the number of chains of polyethylene glycol (PEG) of the modified PDMS is less than one, the polycondensation reactivity is lowered, and when it exceeds 50, the wear resistance and the release force are lowered.
  • the present invention is characterized in that the modified PDMS is added to the rear end of the polycondensation reaction.
  • the modified PDMS is preferably added at the end of the polycondensation reaction in order to express the wear resistance improving effect of polyethylene terephthalate.
  • a binding degree of 99% or more is obtained.
  • polycondensation reaction conditions should be set unlike the existing polyester polymerization conditions.
  • 0.1-20 weight% is preferable with respect to the gross weight of copolymerized polyethylene terephthalate, and, as for the quantity of polydimethylsiloxane added, 0.5-5 weight% is more preferable. If the content of polydimethylsiloxane is less than 0.1% by weight, the amount of migration to the surface is small, and the effect of improving the wear resistance and the release force is insignificant. If the content exceeds 20% by weight, the productivity is reduced.
  • a polyethylene terephthalate (PET) / polydimethylsiloxane (PDMS) masterbatch chip may be prepared.
  • the master batch chip uses a twin screw extruder composed of 28 or more L / D in consideration of the effectiveness of the kneading.
  • the operating temperature of the axial extruder is 240 ° C to 250 ° C, and the mixing ratio of polyethylene terephthalate and polydimethylsiloxane (PDMS) on the master batch ranges from 5% to 50% by weight, preferably 10% to 20% by weight. It is preferable to set it as.
  • the melt-kneaded mixture through the twin screw extruder passes through a cooling water tank maintained at 25 ° C. to 30 ° C. and is solidified into chips using a chip cutter.
  • the final content of the PDMS contained in the fiberized polyethylene terephthalate is preferably 0.1 to 20% by weight, 0.5-5 weight% is more preferable.
  • the content of polydimethylsiloxane is less than 0.1% by weight, the amount of migration to the surface is small, so that the effect of improving wear resistance is insignificant.
  • the productivity is reduced.
  • the polyethylene terephthalate polymer or the masterbatch chip may be melt-spun according to a general process well known in the textile industry to prepare fibers of a desired shape.
  • the form and production method are not particularly limited.
  • the master batch chip is melt-mixed at a predetermined ratio such that polyethylene terephthalate having an intrinsic viscosity of 0.6 to 1.3 and PDMS is 0.1 to 20% by weight, or copolymerized polyethylene terephthalate containing PDMS in a conventional process.
  • the mixture is spun and stretched to produce polyethylene terephthalate yarns.
  • the polyethylene terephthalate chip is melt-spun through a pack and a nozzle at a temperature of 280 to 310 ° C.
  • Static mixers, etc. can be installed on the top of the pack to provide this.
  • the melt-discharge yarn produced in the spinning step is passed through the cooling zone to solidify.
  • a heating device may be installed at a distance from the nozzle directly to the start point of the cooling zone, that is, the length of the hood. .
  • This zone is called delayed cooling zone or heating zone, and may have a length of 100 to 800 mm and a temperature of 300 to 400 ° C.
  • open quenching, circular closed quenching, and radial outflow quenching may be applied depending on the method of blowing the cooling air. Does not. Subsequently, the discharged sand solidified while passing through the cooling zone may be oiled by 0.5 to 1.0% by the emulsion applying device.
  • the final stretched yarn is obtained by stretching, wherein the temperature of the second stage stretching is adjusted to 100 to 210 ° C. More specifically, first, 1 to 10% of free draw (free draw) is given, and then the first step stretching at 1.2 to 7 times at 80 to 200 °C, the second step stretching at 1.2 to 2.0 times at 130 to 200 °C
  • the steam jet method may be applied.
  • the finished yarn can be heat set to a temperature of 200 to 260 ° C (relaxing) to 1 to 6%.
  • the spinning oil used in the production of the polyethylene terephthalate multifilament yarn of the present invention it is preferable to use a spinning oil having a heating loss of 1 to 10% to 298 °C measured by TGA equipment in the state of removing solvent and water. .
  • the spinning emulsion having a heating loss ratio of less than 1% up to 298 ° C. is hardly present, and when the spinning emulsion having a heating loss ratio of 10% or more is applied, the effect of improving the strong retention rate after high temperature heat treatment is not sufficient.
  • the polyethylene terephthalate multifilament yarn prepared according to the present invention may be used in fabrics, but not limited to seat belts, industrial webbing, ropes, and the like.
  • the polyethylene terephthalate polymer prepared according to the present invention is melt-spun at 245 to 335 ° C. to pass a spinneret.
  • the polyethylene terephthalate resin underlying in the present invention contains 90 mol% or more of repeating units of ethylene terephthalate.
  • the cooling temperature is adjusted to 10 ⁇ 35 °C.
  • the speed of the cooling air is less than 0.2m / sec, the cooling effect is insufficient, if it exceeds 1.0m / sec, the shaking of the yarn is excessive, which is a problem in the spinning workability.
  • the cooling temperature is less than 10 °C economically disadvantageous, if it exceeds 35 °C cooling effect is inferior.
  • the first and second stages are oiled using neat or water-soluble emulsions to improve the cohesion, lubricity and smoothness of the yarn. Increase it.
  • the feed roller is supplied to the stretching roller at a speed of 100 to 1,000 m / min, preferably 400 to 800 m / min, wherein the stretching roller is at a temperature of 100 to 230 ° C. and 2.5 to 6.0 of the feed roller speed.
  • stretching is preferably from 3.5 to 5.0 fold.
  • the filament passed through the stretching roller passes through a texturing unit with a texturing nozzle to impart bulkiness.
  • the filament is irregularly formed by spraying a heating fluid of 150 to 270 ° C at a pressure of 3 to 10 kg / cm2 inside the texturing unit. It is crimped to a dimension and the crimp rate at this time is 3 to 50%.
  • the temperature of the heating fluid is preferably 150 ⁇ 270 °C, which is less than 150 °C texturing effect and exceeds 270 °C causes damage to the filament.
  • the pressure of the heating fluid is preferably 3 to 10 kg / cm 2, which is less than the texture effect of less than 3 kg / cm 2 and causes damage to the filament exceeds 10 kg / cm 2.
  • the filament After passing through the texturing unit, the filament is cooled while passing through the cooling section.
  • a slight twist and a knot are applied at a pressure of 2.0 to 8.0 kg / m 2.
  • the range is 0 to 40 times / m, preferably 10 to 25 times.
  • the rollers are passed through at a speed of 0.65 to 0.95 times the speed of the stretching roller to give a relaxation rate of 5 to 35%, and then wound up at the final winding machine.
  • the speed of the winder is usually adjusted so that the tension of the thread is in the range of 50 to 350 g.
  • the tension in the winding machine is less than 50g, the winding is impossible, and if it exceeds 350g, the bulkiness is reduced, the yarn shrinks greatly and causes high tension, which causes trouble in the work.
  • the speed of the relaxation roller is less than 0.65 times of the stretching roller speed, it is not wound, and if it exceeds 0.95 times, the bulkiness is decreased, the yarn shrinks greatly, and high tension causes the work.
  • the method relates to a BCF made of polyethylene terephthalate resin only, the step-by-step process is the same as above when producing the primary yarn according to the carpet application.
  • the raw material supply it is also possible to prepare the yarn by adding a predetermined amount of colorant to the base chip input amount.
  • the polyethylene terephthalate multifilament prepared according to the present invention as described above is produced into a carpet through a post-process.
  • Carpets made with the BCF company of the present invention can be produced in any manner known to those skilled in the art.
  • Preferably a plurality of BCF yarns are cable twisted and heat set together and then weave to the primary back side.
  • the latex adhesive and the secondary backside are then applied. Cut pile style carpets or loop pile style carpets with pile heights of approximately 2-20 mm can be made.
  • the film produced according to the present invention contains inorganic particles comprising silica beads having a methyl group on the surface.
  • Silica beads generally have a hydroxy group (OH) having a hydrophilicity on the surface.
  • silica beads in which the hydroxy group on the surface is substituted with a methyl group (CH3) play a lubricating role in the film to effectively reduce the coefficient of friction of the film.
  • the inorganic particles contained in the base layer calcium carbonate, colloidal silica or a mixture thereof may be used in addition to silica beads having a methyl group.
  • silica beads having a methyl group those having a particle diameter of 2 m or less, preferably 1 m or less are used. The more the silica beads are used, the less the coefficient of friction of the release film, but the silica beads have a problem that the surface of the substrate layer is too rough when the particle size is large, so that the silica bead is excessively added.
  • Calcium carbonate is preferred as inorganic particles other than silica beads having a methyl group. Calcium carbonate with a particle diameter of 2 ⁇ m or less, preferably 1 ⁇ m or less and 0.4 to 0.8 ⁇ m is used, but a small particle size can be obtained and it is considered to be good for preventing blocking. However, calcium carbonate alone is not effective and uniform in process. It is also not easy to disperse.
  • the above inorganic particles are preferably contained within the range of 1,000 to 3,000 ppm in the base layer. When included in less than 1,000ppm it is difficult to implement the physical properties required by the present invention, when included in excess of 3,000ppm inorganic particles are agglomerated to cause a process difficulty.
  • the mixing ratio between the inorganic particles, calcium carbonate and silica beads are preferably mixed in a ratio of 1: 0.3 to 1: 0.6.
  • a copolymerized polyethylene terephthalate and inorganic particles are mixed to obtain a composition, and the composition is melted, coextruded, cooled in casting, stretched 3.2 times in the longitudinal direction, and stretched 3.2 times in the width direction to 188 ⁇ . It is made of a film of.
  • FIG. 1 shows a wear test specimen
  • FIG. 2 shows a wear test apparatus structure
  • the frictional wear characteristics were analyzed by evaluating how much force was applied and the amount of wear when a ring-shaped specimen was mounted on the tester, and a constant load and speed were selected and rotated.
  • Ring-shaped specimens are made of plastics and metals (S45C, copper, SUS, etc.) and other materials can be manufactured as needed.
  • the load was measured in the range of 0.1 kgf to 500 kgf, the speed of 1 mm / sec to 1000 mm / sec and the wear distance in the range of 1 to 10 km.
  • the wear resistance of the mat was measured under the following conditions, and the wear resistance of the mat was evaluated based on the number of wears at the time when the surface of the mat was exposed at the level equivalent to the grade 2.5 of external appearance. It was.
  • the samples are measured by a tensile tester using the ASTM 2256 method.
  • TYT-EW Textured Yarn Tester
  • the static and dynamic friction values were measured by the frictional force between the contact surfaces of two objects and the pressure ratio in the normal direction acting between them. The analysis was performed at 23 ° C. and 50% RH.
  • Static friction Static Coefficient of Friction that must be overcome by the threshold value at the start of the sliding motion
  • a release force evaluation sample was prepared, and Nitto31B Tape of Nitto was used as a reference adhesive tape for measurement, and the release force was measured through a Peel Tester (Chem Instruments, AR-1000). Measured by 180 degree Peel method, the peeling rate is carried out at 300mpm (meters per minute).
  • the prepared polymer was obtained by blending pellets at 260 ° C. using an extruder.
  • the pellets were sufficiently dried at 105 ° C. for at least 4 hours, and then a test piece was prepared at 250 ° C. using an injection machine.
  • a polymer was prepared in the same manner as in Example 1, except that 5 wt% of the aromatic terminal group-modified PDMS having a terminal group having a hydroxyl group and a molecular weight of 5,000 was added at the end of the polycondensation reaction.
  • a polymer was prepared in the same manner as in Example 1 except that no modified PDMS was added.
  • Example 1 Oil / 0.5 wt% 0.15 0.03 0.13 4.3
  • Example 2 5% by weight 0.08 0.01 0.08 2.8
  • Example 3 5% by weight 0.04 0.01 0.03 1.9 Comparative Example 1 radish 0.41 0.53 0.52 7.2
  • the polyethylene terephthalate polymer was spun by using a 36-hole nozzle, and 75 denier / 36 filament yarns were manufactured under spinning conditions in which strength 4.8 gf / denier was expressed through a stretching step.
  • the temperature of the high roller 4 was produced at 220 ° C.
  • Example 4 Same as Example 4 except that 1.0% by weight of one-way terminal group-modified PDMS (JNC, FMDA-21) having a terminal group of hydroxyl group, one polyethylene glycol (PEG) and a molecular weight of 5,000 was added.
  • the polymer was prepared by the method.
  • Example 4 Same as Example 4, except that 1.0% by weight of one-way terminal group-modified PDMS (JNC, FMDA-26) having a molecular weight of 15,000 and one chain having a hydroxyl group and one polyethylene glycol (PEG).
  • JNC one-way terminal group-modified PDMS
  • FMDA-26 one-way terminal group-modified PDMS having a molecular weight of 15,000 and one chain having a hydroxyl group and one polyethylene glycol (PEG).
  • PEG polyethylene glycol
  • Polymerization was prepared in the same manner as in Example 4 except that no modified PDMS was added.
  • Example 4 Example 5
  • Example 6 MV 162 263 208 193 IV (dl / g) 0.68 0.80 0.80 0.77 Strength (g / d) / Elongation (%) 4.8 / 38 4.9 / 36 4.7 / 37 4.6 / 37 Wear resistance (300 times / 400 times) X / X O / O O / O O / O Static friction coefficient 0.466 0.364 0.302 0.299
  • the polyethylene terephthalate polymer produced through spinneret having 128 holes and having a Y-shaped cross section is melt-spun at 290 ° C.
  • the polymer exiting the spinneret is cooled by 0.5 m / s at 20 ° C. cooling air at the bottom of the nozzle and then passed through the emulsion feeder.
  • the emulsified yarn is subjected to a feed roller maintained at 90 ° C. at a speed of 598 m / min, and then drawn at a speed of 190 ° C. and 2,840 m / min in a drawing roller.
  • the yarn passed through the stretching roller passes through the texturing nozzle and is crimped.
  • the hot air temperature is 200 °C
  • the pressure is 7kg / cm2
  • the back pressure is 5kg / cm2.
  • 20 times / m of entanglement is applied at a pressure of 4.0 kg / m2 in the post-concentrator cooled by cooling water. It passes through the relaxation roller at 2250m / min and is relaxed by 21% and then wound up on a winding machine.
  • the strength, elongation, wear resistance, and coefficient of static friction of the polyethylene terephthalate BCF yarn prepared by this process were measured and shown in Table 3 below.
  • a polymer was prepared in the same manner as in Example 7, except that 1.0 wt% of the aromatic terminal group-modified PDMS having a terminal group of hydroxyl group and molecular weight of 5,000 was added to the rear stage of the polycondensation reaction.
  • One-way terminal group-modified PDMS having a terminal group having a hydroxyl group and a molecular weight of 15,000 was added to the rear end of the polycondensation reaction to carry out a polycondensation reaction, to prepare a polymer in the same manner as in Example 7.
  • FMNC-26 product of JNC was applied.
  • a polymer was prepared in the same manner as in Example 7, except that no modified PDMS was added.
  • Example 7 Example 8 Example 9 Strength (g / d) 4.9 4.9 4.7 4.5 Elongation (%) 37.7 35.6 36.9 36.6 Carpet fracture wear water (water supply) 300 (Level 2) 600 (Level 4) 650 (Level 4) 550 (Level 3)
  • a polymer was prepared by carrying out a polycondensation reaction by adding 5.0% by weight of one-way terminal group-modified PDMS having a hydroxyl group, a chain number of polyethylene glycol (PEG) and a molecular weight of 5,000.
  • FMNC-21 product from JNC was prepared.
  • the bidirectional end group-modified PDMS copolymerized polyethylene terephthalate polymer and 1.0 ⁇ m of silica particles were added to the extruder in the content of Table 4 and melt-extruded.
  • the melt was coextruded and then cooled in a 40 ° C. casting roll to prepare an unstretched film.
  • the unstretched film was stretched 3.2 times in the machine direction (MD) and then stretched 3.2 times in the longitudinal direction (TD) to prepare a multilayer film having a total thickness of 25 ⁇ m.
  • Example 10 except that the polymer was prepared by a polycondensation reaction by adding 10.0% by weight of one-way terminal group-modified PDMS having a hydroxyl group, a polyethylene glycol (PEG) chain, and a molecular weight of 5,000.
  • a polymer was prepared in the same manner as in the following.
  • a polymer was prepared in the same manner as in Example 10 except that no modified PDMS was added.
  • Example 11 Coefficient of friction 0.8 0.8 0.2 0. Release force (gf / inch) 97.3 28.9 17.8 20.8

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un polyéthylène téréphtalate copolymérisé comprenant un polyéthylène téréphtalate (PET) et un polydiméthylsiloxane modifié par un groupe terminal unidirectionnel (PDMS) et ayant une résistance à l'usure améliorée, qui est produit par un procédé de filetage direct du polyéthylène téréphtalate copolymérisé, ou par un procédé de copolymérisation d'une concentration élevée de polydiméthylsiloxane modifié par un groupe terminal unidirectionnel et de polyéthylène téréphtalate et son utilisation pour la préparation d'un mélange maître. Le polymère de polyéthylène téréphtalate ainsi produit peut être utilisé pour fabriquer un fil, un BCF pour tapis de voiture ou un film ayant une résistance à l'usure ou une force anti-adhésive améliorées.
PCT/KR2018/000322 2017-01-20 2018-01-08 Polymère de polyéthylène téréphtalate copolymérisé, fil/bcf/film le contenant, et leur procédé de production WO2018135787A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
KR1020170009575A KR101888070B1 (ko) 2017-01-20 2017-01-20 공중합 폴리에틸렌테레프탈레이트 중합물을 포함하는 의료용 또는 산업용 원사
KR1020170009576A KR101949403B1 (ko) 2017-01-20 2017-01-20 공중합 폴리에틸렌테레프탈레이트 중합물을 포함하는 bcf
KR10-2017-0009577 2017-01-20
KR1020170009577A KR101949401B1 (ko) 2017-01-20 2017-01-20 공중합 폴리에틸렌테레프탈레이트 중합물을 포함하는 필름
KR1020170009463A KR101947491B1 (ko) 2017-01-20 2017-01-20 공중합 폴리에틸렌테레프탈레이트 중합물 제조방법
KR10-2017-0009463 2017-01-20
KR10-2017-0009576 2017-01-20
KR10-2017-0009575 2017-01-20

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR950010745B1 (ko) * 1993-07-21 1995-09-22 주식회사코오롱 개질폴리에스테르섬유의 제조방법
JPH08501355A (ja) * 1993-07-02 1996-02-13 ローヌ−プーラン ヴィスコスイス ソシエテ アノニム 防汚性で耐摩耗性のモノフィラメントの製造方法およびその用途
JP2008274182A (ja) * 2007-05-07 2008-11-13 Teijin Fibers Ltd ポリエチレンナフタレート樹脂の製造方法
KR20090024780A (ko) * 2006-07-04 2009-03-09 비와이케이-케미 게엠베하 폴리하이드록시 작용성 폴리실록산을 제조하는 방법 및 그의 용도
KR20120027199A (ko) * 2009-04-01 2012-03-21 이스트만 케미칼 컴파니 폴리에스터의 개선된 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08501355A (ja) * 1993-07-02 1996-02-13 ローヌ−プーラン ヴィスコスイス ソシエテ アノニム 防汚性で耐摩耗性のモノフィラメントの製造方法およびその用途
KR950010745B1 (ko) * 1993-07-21 1995-09-22 주식회사코오롱 개질폴리에스테르섬유의 제조방법
KR20090024780A (ko) * 2006-07-04 2009-03-09 비와이케이-케미 게엠베하 폴리하이드록시 작용성 폴리실록산을 제조하는 방법 및 그의 용도
JP2008274182A (ja) * 2007-05-07 2008-11-13 Teijin Fibers Ltd ポリエチレンナフタレート樹脂の製造方法
KR20120027199A (ko) * 2009-04-01 2012-03-21 이스트만 케미칼 컴파니 폴리에스터의 개선된 제조 방법

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