WO2015186653A1 - 末端変性ポリエチレンテレフタレート樹脂、その製造方法および成形品 - Google Patents
末端変性ポリエチレンテレフタレート樹脂、その製造方法および成形品 Download PDFInfo
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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
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- 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
- C08G63/78—Preparation processes
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- 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
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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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
- C08G63/91—Polymers modified by chemical after-treatment
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- 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
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- 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
- D01F6/86—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyetheresters
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- 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 a high-melting end-modified polyethylene terephthalate resin having a low melt viscosity and excellent melt retention stability, a method for producing the same, and a molded product obtained by molding the resin.
- Polyester is used for clothing, materials, medical use and the like because of its function.
- PET polyethylene terephthalate
- PET polyethylene terephthalate
- PET is excellent in terms of versatility and practicality, and PET can be melt-processed and used for films, sheets, fibers, injection molded products, and the like.
- PET is terephthalic acid or an ester-forming derivative thereof, are produced from ethylene glycol, it is known that the higher the melt viscosity the more is the high molecular weight. If the melt viscosity can be reduced, it is possible to suppress thermal decomposition due to suppression of shear heat generation during melt processing, lower the melt processing temperature, and manufacture a molded product having a complicated shape. Thereby, it is thought that it contributes to improvement of melt residence stability, reduction of environmental load, and improvement of moldability.
- Patent Document 1 an antifouling property and an improvement in washing durability are achieved by copolymerizing PET with one end-blocked polyoxyalkylene glycol.
- Patent Document 2 flexibility is imparted by reacting an epoxy compound having an ether bond with PET during melt extrusion.
- Non-Patent Document 1 discloses a PET resin to which one end methoxy group-blocked polyethylene glycol (MPEG) is added during PET polymerization. JP-A-62-90312 JP 2004-99729 A
- Patent Document 1 when the degree of polymerization of the polyoxyalkylene glycol is high, there is a problem that the molecular weight decrease during the melt residence is remarkable.
- Patent Document 2 there is a problem that when an epoxy group reacts with a carboxyl group of PET, a hydroxyl group is generated in a side chain of the PET molecule, and when this further reacts with the carboxyl group of PET, gelation occurs. .
- the obtained PET resin was a low molecular weight substance, had a low melting point, and low mechanical properties.
- the problem to be solved by the present invention is to provide a high-melting end-modified polyethylene terephthalate resin having a low melt viscosity and excellent melt retention stability.
- the terminal-modified polyethylene terephthalate resin of the present invention has the following constitution. That is, Compound having an intrinsic viscosity of 0.50 to 1.8 dl / g, a melting point of 245 to 270 ° C., a melt viscosity ⁇ (Pa ⁇ s) at 300 ° C. satisfying the following formula (A), and represented by the following formula (B) Is a terminal-modified polyethylene terephthalate resin having 25 to 80 mol / ton bonded to the terminal.
- R 1 is selected from an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
- R 2 is one selected from a hydroxyl group, a carboxyl group, an amino group, a silanol group, and a thiol group, m is an integer of 1 to 3, and n is an integer of 1 to 29.
- X is H and / or CH 3
- Y is H and / or CH 3
- the total number of carbons excluding the carbon number of R 1 and R 2 is represented by 2 to 58 (poly) oxy A compound having an alkylene structure.
- the terminal-modified polyethylene terephthalate resin of the present invention was heated from 30 ° C. to 280 ° C. at a temperature rising rate of 10 ° C./min using a differential scanning calorimeter (DSC), held at 280 ° C. for 3 minutes, and then cooled down It is preferable that the amount of heat of crystal melting observed when the temperature is decreased from 280 ° C. to 30 ° C. at 200 ° C./min and the temperature is increased from 30 ° C. to 280 ° C. at a rate of temperature increase of 10 ° C./min is 45-80 J / g. .
- the terminal-modified polyethylene terephthalate resin of the present invention was heated from 30 ° C. to 280 ° C. at a temperature rising rate of 10 ° C./min using a differential scanning calorimeter (DSC), held at 280 ° C. for 3 minutes, and then cooled down
- the peak top temperature of the exothermic peak observed when the temperature is decreased from 280 ° C. to 30 ° C. at 200 ° C./min is preferably 170 to 210 ° C.
- the terminal-modified polyethylene terephthalate resin of the present invention preferably has an acid value of 13 mol / ton or less.
- the end-modified polyethylene terephthalate resin of the present invention was melt-retained at 280 ° C. for 15 minutes under nitrogen using a rheometer, and then subjected to vibration at a frequency of 0.5 to 3.0 Hz and a swing angle of 20%.
- the weight average molecular weight change rate is preferably in the range of 80 to 120%.
- Mw / Mn dispersion degree represented by the ratio of the weight average molecular weight Mw and the number average molecular weight Mn is 2.5 or less.
- the molded product of the present invention has the following configuration. That is, A molded product obtained by molding the terminal-modified polyethylene terephthalate resin.
- the molded product of the present invention is preferably a molded product made of the above-mentioned end-modified polyethylene terephthalate resin, wherein the molded product is a fiber or a film.
- the manufacturing method of the terminal modified polyethylene terephthalate resin of this invention has the following structure. That is, A raw material containing a compound represented by the formula (B), ethylene glycol, terephthalic acid or terephthalic acid dialkyl ester, at least a first step comprising (a) an esterification reaction step or (b) a transesterification step, (C) A method for producing a terminal-modified polyethylene terephthalate resin produced by a second step comprising a polycondensation reaction step.
- a raw material containing a compound represented by the formula (B), ethylene glycol, terephthalic acid or terephthalic acid dialkyl ester at least a first step comprising (a) an esterification reaction step or (b) a transesterification step
- C A method for producing a terminal-modified polyethylene terephthalate resin produced by a second step comprising a polycondensation reaction step.
- R 1 is selected from an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
- R 2 is one selected from a hydroxyl group, a carboxyl group, an amino group, a silanol group, and a thiol group, m is an integer of 1 to 3, and n is an integer of 1 to 29.
- the compound represented by the formula (B) is selected from (a) esterification reaction step, (b) transesterification reaction step, and (c) polycondensation reaction step. It is preferable to add in any step.
- the compound represented by the formula (B) is added in (a) esterification reaction step or (b) transesterification reaction step, It is preferable to react.
- the maximum temperature of the (c) polycondensation reaction step is in the range of 280 to 300 ° C.
- the terminal-modified polyethylene terephthalate resin obtained by the (c) polycondensation reaction step is subjected to solid phase polymerization in the range of 200 to 240 ° C.
- the terminal-modified polyethylene terephthalate resin obtained is preferably the above-mentioned terminal-modified polyethylene terephthalate resin.
- a high-melting end-modified polyethylene terephthalate resin having a low melt viscosity and excellent melt residence stability can be obtained.
- the main diol component of the polyethylene terephthalate resin portion constituting the terminal-modified polyethylene terephthalate resin is at least one selected from ethylene glycol and the main dicarboxylic acid component is selected from terephthalic acid and dialkyl esters thereof.
- the main diol component is defined as 80 mol% or more of the ethylene glycol component with respect to all the diol components constituting the terminal-modified polyethylene terephthalate of the present invention.
- the main dicarboxylic acid component is defined as 80 mol% or more of terephthalic acid and its dialkyl ester component with respect to all dicarboxylic acid components constituting the terminal-modified polyethylene terephthalate of the present invention.
- the terminal-modified polyethylene terephthalate resin in the present invention has, as a copolymerization component, isophthalic acid, isophthalic acid-5-sulfonate, phthalic acid, naphthalene-2,6-, as long as the effects of the present invention are not substantially impaired.
- Aromatic dicarboxylic acids such as dicarboxylic acids and bisphenoldicarboxylic acids and their dialkyl esters, oxalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,12-dodecane
- Diol components such as aliphatic dicarboxylic acids such as dicarboxylic acids and their dialkyl esters, propanediol, butanediol, pentanediol, hexanediol, 2-methyl-1,3-propanediol, bisphenol A-ethylene oxide adducts, etc.
- the intrinsic viscosity of the terminal-modified polyethylene terephthalate resin needs to be in the range of 0.50 to 1.8, as measured by an o-chlorophenol solvent at 25 ° C. It is preferably 0.55 or more, and more preferably 0.60 or more. Moreover, it is preferable that it is 1.5 or less, and it is more preferable that it is 1.4 or less.
- the intrinsic viscosity is less than 0.50, there is a problem of deterioration of mechanical properties.
- the intrinsic viscosity exceeds 1.8 it is necessary to add an excessive heat history when producing a terminal-modified polyethylene terephthalate resin. There is a problem of polymer degradation.
- the weight average molecular weight (Mw) of the terminal-modified polyethylene terephthalate resin is not particularly limited, but is preferably 15,000 or more from the viewpoint of mechanical properties. It is more preferably 20,000 or more, and further preferably 25,000 or more. Moreover, it is preferable that it is 200,000 or less at the point which can suppress the thermal deterioration at the time of manufacture. It is more preferably 180,000 or less, and further preferably 150,000 or less. In addition, the weight average molecular weight is gel permeation chromatography measured at 30 ° C.
- the weight average molecular weight is a relative value to the molecular weight of standard polymethyl methacrylate. In addition, the number average molecular weight described later is also measured by the same method as described above.
- the melting point of the terminal-modified polyethylene terephthalate resin needs to be in the range of 245 ° C. to 270 ° C. Further, from the viewpoint of excellent melt processability, the temperature is preferably 245 to 265 ° C, more preferably 250 to 265 ° C. If the melting point is less than 245 ° C, there is a problem of reduced heat resistance. On the other hand, if the melting point exceeds 270 ° C, the crystallinity and the crystal size become extremely large, which requires excessive heating during melt processing. There is a problem of polymer degradation.
- the melting point of the terminal-modified polyethylene terephthalate resin is a differential scanning calorimeter (DSC), heated from 30 ° C.
- the heat of crystal fusion represented by the area of the endothermic peak is preferably 45 J / g or more, and more preferably 50 J / g or more in terms of excellent heat resistance.
- 80 J / g or less is preferable at the point which is excellent in melt processability, and 70 J / g or less is more preferable.
- the terminal-modified polyethylene terephthalate resin of the present invention was heated from 30 ° C. to 280 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC), and held at 280 ° C. for 3 minutes.
- the peak top temperature of the exothermic peak observed when the temperature is lowered from 280 ° C. to 30 ° C. at a rate of temperature reduction of 200 ° C./min (temperature-lowering crystallization temperature) is preferably 170 ° C. or more from the viewpoint of excellent crystallinity. It is more preferably 175 ° C. or higher, and further preferably 180 ° C. or higher.
- the cooling crystallization temperature is preferably 210 ° C. or less. It is more preferably 205 ° C. or lower, and further preferably 200 ° C. or lower.
- the terminal-modified polyethylene terephthalate resin of the present invention needs to have a melt viscosity ⁇ (Pa ⁇ s) at 300 ° C. satisfying the following formula (A).
- melt viscosity ⁇ (Pa ⁇ s) at 300 ° C. means that a rheometer (manufactured by Anton Paar, MCR501) is melted at 300 ° C. for 5 minutes in a nitrogen atmosphere, and then vibration mode, frequency 3.0 Hz The melt viscosity ⁇ (Pa ⁇ s) when measured at a swing angle of 20%.
- melt viscosity ⁇ (Pa ⁇ s) measured under the same conditions as described above is represented by the following approximate formula (C).
- the terminal-modified polyethylene terephthalate resin of the present invention is characterized by a remarkably low melt viscosity as compared with the terminal unmodified polyethylene terephthalate resin.
- FIG. 1 schematically shows the relationship between the weight average molecular weight (Mw) and the melt viscosity in the terminal unmodified polyethylene terephthalate resin and the terminal modified polyethylene terephthalate resin of the present invention.
- melt viscosity ⁇ exceeds the right side of the formula (A), the difference from the terminal unmodified polyethylene terephthalate resin is small, and the melt viscosity reducing effect cannot be sufficiently obtained.
- the lower limit of the melt viscosity ⁇ is not particularly limited, and the melt processability is improved as the melt viscosity ⁇ is lower.
- the polyethylene terephthalate resin needs to have a compound represented by the following formula (B) bound at 25 to 80 mol / ton at the end.
- R 1 is selected from an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
- R 2 is one selected from a hydroxyl group, a carboxyl group, an amino group, a silanol group, and a thiol group, m is an integer of 1 to 3, and n is an integer of 1 to 29.
- X is H and / or CH 3
- Y is H and / or CH 3
- the total number of carbons excluding the carbon number of R 1 and R 2 is represented by 2 to 58 (poly) oxy A compound having an alkylene structure.
- the compound represented by the formula (B) bonded to the end of the polyethylene terephthalate resin is less than 25 mol / ton, there is a problem that the effect of reducing the melt viscosity is reduced.
- the formula (B ) Exceeds 80 mol / ton, there is a problem that it is difficult to increase the molecular weight.
- a compound having a (poly) oxyalkylene structure represented by the formula (B) has an ether bond with high molecular mobility, and has a solubility parameter close to that of polyethylene terephthalate resin. ing. Therefore, a compound having a (poly) oxyalkylene structure can reduce the intermolecular interaction of the polyethylene terephthalate molecular chain during melting and increase the free volume, greatly increasing the molecular mobility of the polymer chain. Let Therefore, the melt viscosity reducing effect is remarkably exhibited.
- R 1 of the compound (B) is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. It is necessary to be at least one selected. Specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.
- Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclopentyl group, a cyclooctyl group, and a cyclodecyl group.
- Examples of the aryl group having 6 to 10 carbon atoms include phenyl group, tolyl group, dimethylphenyl group, naphthyl group and the like.
- Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, phenethyl group, methylbenzyl group, 2-phenylpropan-2-yl group, diphenylmethyl group and the like.
- R 1 is preferably an alkyl group having 1 to 30 carbon atoms, and particularly preferably a methyl group.
- R 2 of the compound (B) is a functional group capable of binding to the polyethylene terephthalate resin, and needs to be one kind selected from a hydroxyl group, a carboxyl group, an amino group, a silanol group, and a thiol group. is there.
- a hydroxyl group and a carboxyl group are preferred because of excellent reactivity with the polyethylene terephthalate resin.
- m in the compound (B) needs to be an integer of 1 to 3 in terms of excellent heat resistance. Further, it is preferably an integer of 1 to 2, and more preferably 1. By setting m to 3 or less, ether bonds occupying the terminal portion increase, and the melt viscosity reduction effect can be increased.
- n in the compound (B) needs to be an integer of 1 to 29 from the viewpoint of excellent melt viscosity reduction effect and melt residence stability.
- n is preferably an integer of 3 or more, and more preferably an integer of 5 or more.
- n is preferably an integer of 27 or less, and more preferably an integer of 25 or less.
- X in the compound (B) needs to be H and / or CH 3 .
- X in the compound (B) needs to be H and / or CH 3 .
- Y in the compound (B) needs to be H and / or CH 3 .
- X the affinity with the polyethylene terephthalate portion serving as the main skeleton can be improved, and the melt viscosity reduction effect can be increased.
- the total number of carbon atoms of the oxyalkylene structure portion excluding the carbon number of R 1 and R 2 of the compound (B) needs to be 2 to 58.
- a terminal-modified polyethylene terephthalate resin excellent in melt viscosity reduction effect and melt residence stability can be obtained.
- the concentration of the compound having a (poly) oxyalkylene structure represented by the formula (B) bonded to the end of the polyethylene terephthalate resin needs to be in the range of 25 to 80 mol / ton. In order to increase the melt viscosity reduction effect, it is preferably 30 mol / ton or more, and more preferably 35 mol / ton or more. Further, in order to increase the molecular weight of the terminal-modified polyethylene terephthalate resin, it is preferably 75 mol / ton or less, and more preferably 70 mol / ton or less.
- the weight ratio of the compound having a (poly) oxyalkylene structure represented by the formula (B) bonded to the terminal of the polyethylene terephthalate resin is preferably 0.5% by weight or more.
- the content By setting the content to 0.5% by weight or more, the effect of reducing the melt viscosity can be increased. 1.5% by weight or more is more preferable, and 3.0% by weight or more is more preferable.
- it In order to increase the molecular weight of the terminal-modified polyethylene terephthalate resin, it is preferably 7.0% by weight or less. It is more preferably 5.0% by weight or less, and further preferably 4.0% by weight or less.
- the terminal-modified polyethylene terephthalate resin of the present invention requires that a specific amount of a compound having a (poly) oxyalkylene structure represented by the formula (B) is bonded to the polymer terminal.
- a compound having a (poly) oxyalkylene structure represented by the formula (B) is bonded to the polymer terminal.
- the terminal-modified polyethylene terephthalate resin of the present invention has a low melt viscosity, shear heat generation during polymerization can be suppressed, and decomposition can be suppressed, so that generation of carboxyl groups can be suppressed.
- the terminal-modified polyethylene terephthalate resin preferably has an acid value (carboxyl group concentration) of 13 mol / ton or less in view of excellent hydrolysis resistance.
- an acid value is not specifically limited, It is more preferable that it is 11 mol / ton or less, and it is further more preferable that it is 9 mol / ton or less.
- hydrolysis resistance refers to the weight average molecular weight retention ratio obtained by dividing the weight average molecular weight of the terminal-modified polyethylene terephthalate resin after being treated at 121 ° C. and 100% RH for 24 hours by the weight average molecular weight before the treatment. It can be evaluated by seeking.
- the weight average molecular weight retention is preferably 60% or more, and more preferably 70%.
- the weight average molecular weight can be measured by gel permeation chromatography as described above.
- the terminal-modified polyethylene terephthalate resin is melted and retained at 280 ° C. for 15 minutes under nitrogen using a rheometer, and then vibrates at a frequency of 0.5 to 3.0 Hz and a swing angle of 20%.
- the rate of change in weight average molecular weight after addition is preferably in the range of 80 to 120%. By setting it within this range, the viscosity change during the melt residence can be kept to a minimum, and stable melt processing can be performed. More preferably, it is 85 to 115%, and still more preferably 90 to 110%.
- the dispersity (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the terminal-modified polyethylene terephthalate resin is preferably 2.5 or less. 2.3 or less is more preferable, and 2.0 or less is more preferable. Since the terminal-modified polyethylene terephthalate resin of the present invention has a low melt viscosity, the polymerization proceeds more uniformly and the degree of dispersion tends to be small during melt polymerization.
- the lower limit of the dispersity is not particularly limited, but is theoretically 1.0 or more. When the degree of dispersion exceeds 2.5, relatively low molecular weight components increase, so mechanical properties such as toughness tend to be reduced.
- the terminal-modified polyethylene terephthalate resin since the terminal-modified polyethylene terephthalate resin has a low melt viscosity, it can be easily processed into an injection-molded product, fiber, film or the like. This effect makes it possible to process the terminal-modified polyethylene terephthalate resin at a low temperature, thereby reducing heat energy and reducing the environmental load.
- the fiber has conventionally had a problem that melt spinning becomes difficult due to an increase in melt viscosity accompanying an increase in molecular weight.
- melt spinning of the high molecular weight material is facilitated, and decomposition can be avoided along with suppression of shear heat generation at the time of melting, so that high strength fibers can be obtained.
- the film also has a problem that, as with the fiber, melt film formation becomes difficult due to an increase in melt viscosity accompanying an increase in molecular weight.
- the terminal-modified polyethylene terephthalate resin of the present invention it becomes easy to melt and form a high molecular weight body, and it is possible to avoid decomposition with suppression of shearing heat generation at the time of melting, so that a high strength film can be obtained. it can.
- the production method of the terminal-modified polyethylene terephthalate resin obtained using the dicarboxylic acid and / or dicarboxylic acid dialkyl ester, diol, and the compound represented by the formula (B) of the present invention as raw materials comprises the following two steps. That is, a first stage process comprising (a) an esterification reaction process or (b) a transesterification reaction process, followed by a second stage process comprising (c) a polycondensation reaction process.
- the esterification reaction step is an esterification reaction of dicarboxylic acid and diol at a predetermined temperature, and the reaction is carried out until a predetermined amount of water is distilled off. It is the process of obtaining.
- the step (b) transesterification reaction is a step in which a dialkyl dialkyl ester and a diol are transesterified at a predetermined temperature, and a reaction is performed until a predetermined amount of alcohol is distilled to obtain a low polycondensate. .
- dediol reaction is carried out by reducing the pressure while heating the low polycondensate obtained by (a) esterification reaction or (b) transesterification reaction. This is a step of proceeding to obtain a terminal-modified polyethylene terephthalate resin.
- the compound of the formula (B) in the method for producing a terminal-modified polyethylene terephthalate resin of the present invention, it is possible to add the compound of the formula (B) at any stage selected from the step (a) or (b) and the subsequent step (c). This is preferable because it can be quantitatively introduced into the. More preferably, it is added in the step (a) or (b). It can also be produced by melt-kneading the terminal unmodified polyethylene terephthalate resin and the compound of the formula (B) with an extruder, but the introduction rate of the compound of the formula (B) at the terminal of the polyethylene terephthalate is reduced and unreacted. The compound of formula (B) tends to bleed out during heat treatment.
- the maximum temperature in the (a) esterification reaction step or (b) transesterification reaction step is preferably set to 230 ° C. or higher.
- the maximum temperature is more preferably 235 ° C. or higher, and further preferably 240 ° C. or higher.
- the maximum temperature is preferably 260 ° C. or lower.
- the thermal decomposition and volatilization of the compound of Formula (B) can be suppressed. It is preferably 255 ° C. or lower, and more preferably 250 ° C. or lower.
- the maximum temperature of the polycondensation reaction step is preferably 280 ° C. or higher.
- the maximum temperature of a polycondensation reaction process shall be 300 degrees C or less. By setting it to 300 ° C. or lower, thermal decomposition of the terminal-modified polyethylene terephthalate resin can be suppressed. 295 ° C. or lower is more preferable.
- the terminal-modified polyethylene terephthalate resin obtained by the above-described method is further subjected to solid phase polymerization.
- the apparatus for solid-phase polymerization is not particularly limited, but is carried out by heat treatment under an inert gas atmosphere or under reduced pressure. Any inert gas may be used as long as it is inert with respect to the polyethylene terephthalate resin.
- nitrogen, helium, carbon dioxide gas and the like can be mentioned, and nitrogen is preferably used.
- a pressure reduction condition it is preferable that the pressure in an apparatus is 133 Pa or less, and it is more preferable to use a pressure reduction condition because the solid-state polymerization time can be shortened.
- the maximum temperature of solid phase polymerization is preferably 200 ° C. or higher. By setting the temperature to 200 ° C. or higher, high polymerization can be efficiently performed. 210 degreeC or more is more preferable, and 220 degreeC or more is further more preferable. Moreover, it is preferable that the maximum temperature of solid phase polymerization shall be 240 degrees C or less. By making it 240 degrees C or less, thermal decomposition can be suppressed. 235 ° C. or lower is more preferable, and 230 ° C. or lower is further preferable.
- the terminal-modified polyethylene terephthalate resin of the present invention can be produced by batch polymerization, semi-continuous polymerization, or continuous polymerization.
- compounds such as manganese, cobalt, zinc, titanium, and calcium are used as the catalyst used in the esterification reaction.
- the esterification reaction can also be carried out without a catalyst.
- compounds, such as magnesium, manganese, calcium, cobalt, zinc, lithium, titanium are used.
- compounds, such as antimony, titanium, aluminum, tin, germanium, etc. are used.
- Antimony compounds include antimony oxides, antimony carboxylic acids, antimony alkoxides, and the like.
- oxide of antimony include antimony trioxide and antimony pentoxide.
- antimony carboxylic acid include antimony acetate, antimony oxalate, and antimony potassium tartrate.
- antimony alkoxide include antimony tri-n-butoxide and antimony triethoxide.
- titanium compounds include titanium alkoxides such as titanium complexes, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, titanium oxides obtained by hydrolysis of titanium alkoxide, and titanium acetylacetonate. Etc.
- a titanium complex having a polycarboxylic acid and / or hydroxycarboxylic acid and / or a polyhydric alcohol as a chelating agent is preferable because the thermal stability and color tone deterioration of the polymer can be prevented.
- the chelating agent for the titanium compound include lactic acid, citric acid, mannitol, tripentaerythritol and the like.
- Examples of the aluminum compound include aluminum carboxylate, aluminum alkoxide, aluminum chelate compound, basic aluminum compound and the like. Specific examples include aluminum acetate, aluminum hydroxide, aluminum carbonate, aluminum ethoxide, aluminum isopropoxide, aluminum acetylacetonate, and basic aluminum acetate.
- tin compounds include monobutyltin oxide, dibutyltin oxide, methylphenyltin oxide, tetraethyltin oxide, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, monobutyltin trichloride, and dibutyltin sulfide.
- germanium compounds include germanium oxides and germanium alkoxides
- specific examples of germanium oxides include germanium dioxide, germanium tetroxide, and germanium alkoxides such as germanium tetraethoxide and germanium tetrabutoxide. It is done.
- magnesium compound examples include magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, and magnesium carbonate.
- manganese compounds include manganese chloride, manganese bromide, manganese nitrate, manganese carbonate, manganese acetylacetonate, and manganese acetate.
- the calcium compound examples include calcium oxide, calcium hydroxide, calcium alkoxide, calcium acetate, and calcium carbonate.
- cobalt compound examples include cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt acetylacetonate, cobalt naphthenate, and cobalt acetate tetrahydrate.
- the zinc compound examples include zinc oxide, zinc alkoxide, and zinc acetate.
- These metal compounds may be hydrates.
- the terminal-modified polyethylene terephthalate resin of the present invention may contain a phosphorus compound as a stabilizer.
- a phosphorus compound as a stabilizer.
- phosphoric acid trimethyl phosphate, triethyl phosphate, ethyl diethylphosphonoacetate, 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8, 10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, tetrakis (2,4-di-t-butyl-5-methylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite Etc.
- the terminal-modified polyethylene terephthalate resin of the present invention may contain an antioxidant.
- the antioxidant is not particularly limited, and specific examples include hindered phenol-based, sulfur-based, hydrazine-based, and triazole-based antioxidants. These may be used alone or in combination of two or more.
- hindered phenol antioxidants include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-t. -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6-bis (octylthiomethyl) -0-cresol, etc. It is done.
- pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (IRGANOX1010: manufactured by Ciba Japan) is preferable because it has a high effect of suppressing coloring.
- Sulfur-based antioxidants include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol-tetrakis (3-lauryl thiopropionate) And pentaerythritol-tetrakis (3-dodecylthiopropionate).
- hydrazine-based antioxidants examples include decamethylene dicarboxylic acid-bis (N'-salicyloyl hydrazide), bis (2-phenoxypropionyl hydrazide) isophthalate, N-formyl-N'-salicyloyl hydrazine, etc. Is mentioned.
- triazole antioxidant examples include benzotriazole, 3- (N-salicyloyl) amino-1,2,4-triazole, and the like.
- a dye used for a resin or the like as a color tone adjusting agent may be added.
- COLOR INDEX GENERIC NAME gives blue color tone modifiers such as SOLVENT BLUE 104 and SOLVENT BLUE 45, and purple color tone modifiers such as SOLVENT VIOLET 36, which have good heat resistance at high temperatures and color development. It is preferable because it is excellent. These may be used alone or in combination of two or more.
- additives such as fluorescent whitening agents including pigments and dyes, colorants, lubricants, and antistatic agents are used as long as the effects of the present invention are not impaired.
- additives flame retardants, ultraviolet absorbers, antibacterial agents, nucleating agents, matting agents, plasticizers, mold release agents, antifoaming agents or other additives may be added as necessary. it can.
- the terminal-modified polyethylene terephthalate resin of the present invention is excellent in melt processability due to low melt viscosity, it can be melt-processed by various known methods such as fibers, films, bottles and injection-molded products.
- a usual melt spinning-drawing process can be applied to a method of processing a terminal-modified polyethylene terephthalate resin into a fiber. Specifically, after the terminal-modified polyethylene terephthalate resin is heated to the melting point of the terminal-modified polyethylene terephthalate resin to be melted, it is discharged from the pores, cooled and solidified with cooling air, and then an oil agent is applied thereto.
- the undrawn yarn can be collected by taking up and taking up with a take-up device arranged after the take-up roller.
- the undrawn yarn wound in this way becomes a fiber to which physical properties such as mechanical properties according to the application are given by drawing with a pair of heated rollers or more and finally applying tension or relaxation heat treatment.
- stretching process after taking up in the above-mentioned melt spinning process, it can carry out continuously, without winding once, and it can be set as continuous extending
- the draw ratio, the stretching temperature, and the heat treatment conditions can be appropriately selected depending on the fineness, strength, elongation, shrinkage, etc. of the target fiber.
- terminal-modified polyethylene terephthalate resin After terminal-modified polyethylene terephthalate resin is vacuum-heated and dried at 180 ° C for 3 hours or longer, it is supplied to a single-screw or twin-screw extruder heated to 270-320 ° C under a nitrogen stream or under vacuum so that the intrinsic viscosity does not decrease. Then, the polymer is plasticized, melt-extruded from a slit-shaped die, and cooled and solidified on a casting roll to obtain an unstretched film. At this time, it is preferable to use various types of filters, for example, filters made of materials such as sintered metal, porous ceramic, sand and wire mesh, in order to remove foreign substances and denatured polymers.
- the sheet-like material molded as described above is biaxially stretched.
- the film is stretched biaxially in the longitudinal direction and the width direction and heat-treated.
- a sequential biaxial stretching method such as stretching in the width direction after stretching in the longitudinal direction, a simultaneous biaxial stretching method in which the longitudinal direction and the width direction are simultaneously stretched using a simultaneous biaxial tenter, etc. Examples include a method in which the sequential biaxial stretching method and the simultaneous biaxial stretching method are combined.
- it is desirable that the heat treatment after the stretching process is effectively performed without causing relaxation of molecular chain orientation due to excessive heat treatment.
- the terminal-modified polyethylene terephthalate resin of the present invention takes advantage of its excellent melt processability due to the effect of reducing melt viscosity, making it a part having a thin part of 0.01 to 1.0 mm, a part having a complicated shape, fluidity and appearance. Can be easily processed into a large-sized molded product that requires the above.
- Intrinsic viscosity A sample was dissolved in an o-chlorophenol solvent to prepare solutions having concentrations of 0.5 g / dL, 0.2 g / dL, and 0.1 g / dL. Thereafter, the relative viscosity ( ⁇ r) at 25 ° C. of the obtained solution having the concentration C was measured with an Ubero-de viscometer, and ( ⁇ r ⁇ 1) / C was plotted against C. And the intrinsic viscosity was calculated
- a WATERS differential refractometer WATERS410 was used as a detector, a MODEL510 high-performance liquid chromatography was used as a pump, and Shodex GPC HFIP-806M (two) and Shodex GPC HFIP-LG were used as columns. Hexafluoroisopropanol (with 0.005N-sodium trifluoroacetate added) was used as a solvent, and a solution in which the sample concentration was 1 mg / mL was prepared. The flow rate was 1.0 mL / min, and 0.1 mL of the solution was injected for analysis.
- a solution having a sample concentration of 50 mg / mL was used using deuterated HFIP as a measurement solvent.
- the integrated intensity of the peak derived from the R 1 and R 2 portion of the compound represented by the formula (B) and the peak derived from the polyethylene terephthalate component which is the main skeleton of the terminal-modified polyethylene terephthalate resin is calculated,
- the composition ratio was determined by dividing by the number of hydrogen atoms, and the amount (mol / ton) of compound (B) introduced into the terminal-modified polyethylene terephthalate resin was calculated.
- (5) Thermal characteristics were measured using a differential scanning calorimeter (DSC Q20) manufactured by TA Instruments. Heat generated when 5 mg of sample was heated from 30 ° C.
- the peak top temperature of the peak was defined as the temperature-falling crystallization temperature Tc, the area of the exothermic peak as the temperature-falling crystallization heat amount, ⁇ Hc. Subsequently, the peak top temperature of the endothermic peak when the temperature was increased from 30 ° C. to 280 ° C. at a rate of 10 ° C./min was defined as the melting point Tm, and the peak area of the endothermic peak as the crystal melting heat amount ⁇ Hm.
- Example 1 After maintaining the esterification reaction vessel charged with 110 g of bis (hydroxyethyl) terephthalate obtained in Production Example 1 at a temperature of 250 ° C., 143 g of terephthalic acid, 61.5 g of ethylene glycol, (poly) oxyalkylene described in Table 1 12.7 g of the compound represented by the formula (B) having a structure (the compound represented by the formula (B) is 4 with respect to 100 parts by weight of the total amount of bis (hydroxyethyl) terephthalate, terephthalic acid, and ethylene glycol). (Corresponding to 0.0 parts by weight) of the slurry was sequentially supplied over 4 hours, and after the completion of the supply, the esterification reaction was further performed over 1 hour to obtain an esterification reaction product.
- the obtained esterification reaction product was put into a test tube and kept in a molten state at 250 ° C., and then the resulting polymer was antimony trioxide equivalent to 250 ppm in terms of antimony atoms and phosphorus equivalent to 50 ppm in terms of phosphorus atoms.
- Acid, cobalt acetate equivalent to 6 ppm in terms of cobalt atom was added as an ethylene glycol solution. Thereafter, the reaction system was decompressed while stirring at 90 rpm to start the reaction. The reactor was gradually heated from 250 ° C. to 290 ° C., and the pressure was reduced to 110 Pa. The time to reach the maximum temperature and final pressure was both 60 minutes.
- the mixture was supplied to a twin screw extruder (PCM-30 type, manufactured by Ikekai Steel) set at a cylinder temperature of 280 ° C. and a screw rotation speed of 200 rpm, and melt kneaded.
- Polymer pellets were obtained by pelletizing the extruded gut. After the obtained terminal-modified polyethylene terephthalate resin pellets are dissolved in hexafluoroisopropanol, a solution containing the terminal-modified polyethylene terephthalate resin is gradually added to 10 times the amount of methanol stirred. Re-precipitated. The precipitate was recovered and dried in a vacuum dryer at room temperature for 3 hours or more.
- Example 1 The compound (B) introduced into the polymer terminal, which was obtained from the NMR spectrum of the polymer after the final precipitation purification, was 53% of Example 1.
- Example 1 Example 1 was repeated except that 1 part by weight of trimethyl 1,3,5-benzenetricarboxylate was added to 100 parts by weight of the total amount of bis (hydroxyethyl) terephthalate, terephthalic acid, and ethylene glycol. .
- Comparative Example 12 The reaction was performed in the same manner as in Example 1 except that R 2 which is a reactive functional group of the compound represented by the formula (B) was changed from a hydroxyl group to an epoxy group.
- the terminal-modified polyethylene terephthalate resins of Examples 1 to 15 have a lower melt viscosity and excellent melt residence stability than the terminal unmodified polyethylene terephthalate resins of Comparative Examples 1 to 3. It had a high melting point.
- R 2 of the compound used is the non-reactive functional group of the present invention and cannot be bonded to the polymer terminal, so the effect of reducing the melt viscosity is small and the bleed-out resistance is poor.
- R 2 of the compound used was a hydroxyl group of a reactive functional group, which was mainly taken into the polymer main chain and the end of the polyoxyalkylene structure was restrained, so the melt viscosity reducing effect was small. . Further, the melting point was lowered by copolymerization.
- Example 17 Comparative Example 13
- the polyethylene terephthalate resin obtained in Example 1 or Comparative Example 1 was crystallized with a hot air dryer at 170 ° C. for 30 minutes, and then pre-dried with a vacuum dryer at 180 ° C. for 2 hours. Then, it put in the rotary vacuum apparatus (rotary vacuum dryer) of the temperature of 220 degreeC, and the vacuum degree of 0.5 mmHg, and it heated, stirring for a predetermined time, and obtained the highly polymerized polyethylene terephthalate resin.
- Table 5 shows the characteristics of the obtained polyethylene terephthalate resin.
- the terminal-modified polyethylene terephthalate resin subjected to solid phase polymerization in Example 17 has a low melt viscosity and excellent melt residence stability and hydrolysis resistance as compared with the terminal unmodified polyethylene terephthalate resin in Comparative Example 13.
- Example 18 Comparative Examples 14 and 15
- the terminal-modified polyethylene terephthalate resin of Example 1 and the terminal unmodified polyethylene terephthalate resin obtained in Comparative Example 1 were stretched at a predetermined temperature to evaluate stretchability.
- the film that was stretchable was subjected to viscoelasticity measurement after heat treatment.
- the obtained characteristics are shown in Table 6.
- Comparison between Example 18 and Comparative Examples 14 and 15 showed that the terminal-modified polyethylene terephthalate resin can be stretched at a lower temperature and has a high storage elastic modulus as compared with the terminal unmodified polyethylene terephthalate resin.
- the terminal-modified polyethylene terephthalate resin of the present invention is excellent in melt processability due to low melt viscosity, it can be melt-processed by various known methods such as fibers, films, bottles and injection-molded products. These products are useful for agricultural materials, horticultural materials, fishery materials, civil engineering / architectural materials, stationery, medical supplies, automotive parts, electrical / electronic components or other uses.
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Abstract
Description
固有粘度が0.50~1.8dl/g、融点が245~270℃、300℃における溶融粘度μ(Pa・s)が下記式(A)を満たし、下記式(B)で表される化合物を末端に25~80mol/ton結合させた末端変性ポリエチレンテレフタレート樹脂、である。
(ただし、ここで用いた重量平均分子量Mwは、ヘキサフルオロイソプロパノール(0.005N トリフルオロ酢酸ナトリウム添加)を移動相とするゲルパーミエーションクロマトグラフィー法で求めた、標準ポリメタクリル酸メチルの分子量に対する相対的な重量平均分子量を示す。)
本発明の末端変性ポリエチレンテレフタレート樹脂は、示差走査型熱量計(DSC)を用い、昇温速度10℃/分で30℃から280℃まで昇温し、280℃で3分保持した後、降温速度200℃/分で280℃から30℃まで降温し、昇温速度10℃/分で30℃から280℃まで昇温したときに観察される結晶融解熱量が45~80J/gであることが好ましい。
上記末端変性ポリエチレンテレフタレート樹脂を成形してなる成形品、である。
式(B)で表される化合物、エチレングリコール、テレフタル酸またはテレフタル酸ジアルキルエステルを含む原料を、少なくとも(a)エステル化反応工程または(b)エステル交換反応工程からなる1段目の工程、続いて(c)重縮合反応工程からなる2段目の工程により製造する末端変性ポリエチレンテレフタレート樹脂の製造方法、である。
本発明の末端変性ポリエチレンテレフタレート樹脂の製造方法は、前記式(B)で表される化合物を(a)エステル化反応工程、(b)エステル交換反応工程、(c)重縮合反応工程から選ばれるいずれかの工程において添加することが好ましい。
(ただし、ここで用いた重量平均分子量Mwは、ヘキサフルオロイソプロパノール(0.005N トリフルオロ酢酸ナトリウム添加)を移動相とするゲルパーミエーションクロマトグラフィー法で求めた、標準ポリメタクリル酸メチルの分子量に対する相対的な重量平均分子量を示す。)
本発明において、300℃における溶融粘度μ(Pa・s)とは、レオメータ(AntonPaar社製、MCR501)を用いて、窒素雰囲気下、300℃で5分溶融した後、振動モード、周波数3.0Hz、振り角20%にて測定したときの溶融粘度μ(Pa・s)をいう。
本発明の末端変性ポリエチレンテレフタレート樹脂は、末端未変性ポリエチレンテレフタレート樹脂と比較して、溶融粘度が著しく低いことが特徴である。図1には、末端未変性ポリエチレンテレフタレート樹脂と本発明の末端変性ポリエチレンテレフタレート樹脂における重量平均分子量(Mw)と溶融粘度の関係を模式的に示した。
μ≦2×e(0.000085×Mw) 式(E)
溶融粘度μが式(A)の右辺を超える場合、末端未変性ポリエチレンテレフタレート樹脂との差が小さく、溶融粘度低減効果が十分に得られない。なお、溶融粘度μの下限は特に限定されず、溶融粘度μが低いほど溶融加工性は向上する。
ポリエチレンテレフタレート樹脂末端に結合させた、式(B)で表される化合物が25mol/ton未満の場合溶融粘度低減効果が小さくなる問題があり、一方、ポリエチレンテレフタレート樹脂末端に結合させた、式(B)で表される化合物が80mol/tonを超えると高分子量化が困難となる問題がある。
(1)固有粘度
試料を、o-クロロフェノール溶媒に溶解し、0.5g/dL、0.2g/dL、0.1g/dLの濃度の溶液を調整した。その後、得られた濃度Cの溶液の25℃における相対粘度(ηr)を、ウベロ-デ粘度計により測定し、(ηr-1)/CをCに対してプロットした。そして、得られた結果を濃度0に外挿することにより、固有粘度を求めた。
(2)重量平均分子量、数平均分子量、分散度
ゲルパーミエーションクロマトグラフィー(GPC)により、末端未変性ポリエチレンテレフタレート樹脂および末端変性ポリエチレンテレフタレート樹脂の重量平均分子量(Mw)および数平均分子量(Mn)の値を求めた。これらの平均分子量は、標準ポリメチルメタクリレート換算の値である。分散度は、数平均分子量(Mn)に対する重量平均分子量(Mw)の比で表される値(Mw/Mn)である。検出器にWATERS社示差屈折計WATERS410、ポンプにMODEL510高速液体クロマトグラフィー、カラムにShodex GPC HFIP-806M(2本)とShodex GPC HFIP-LGを用いた。溶媒としてヘキサフルオロイソプロパノール(0.005N-トリフルオロ酢酸ナトリウム添加)を用い、試料濃度が1mg/mLになるように溶解した溶液を調製した。流速を1.0mL/minとし、前記溶液を0.1mL注入して分析した。
(3)溶融粘度μ
レオメータ(AntonPaar社製、MCR501)を用い、130℃真空乾燥器中で12時間以上乾燥した試料0.5gを、窒素雰囲気下、300℃で5分溶融した後、振動モード、周波数3.0Hz、振り角20%にて、溶融粘度μ(Pa・s)を測定した。
(4)1H-NMR測定(ポリマー末端への化合物(B)の導入量の定量)
日本電子社製FT-NMR JNM-AL400を用いて、積算回数256回にて、1H-NMR測定した。測定溶媒として重水素化HFIPを用いて、試料濃度50mg/mLの溶液を使用した。式(B)で表される化合物のR1およびR2部分由来のピークと、末端変性ポリエチレンテレフタレート樹脂の主骨格であるポリエチレンテレフタレート成分由来のピークの積分強度を算出し、それぞれの構造単位中の水素原子数で除することで組成比を決定し、末端変性ポリエチレンテレフタレート樹脂への化合物(B)の導入量(mol/ton)を算出した。
(5)熱特性
TAインスツルメント社製示差走査熱量計(DSC Q20)を用いて、熱特性を測定した。試料5mgを窒素雰囲気下中、30℃から速度10℃/minで280℃まで昇温した後、280℃で3分間保持し、280℃から速度200℃/minで30℃まで降温したときの発熱ピークのピークトップ温度を降温結晶化温度Tc、発熱ピークの面積を降温結晶化熱量をΔHcとした。引き続き、30℃から速度10℃/minで280℃まで昇温したときの吸熱ピークのピークトップ温度を融点Tm、吸熱ピークのピーク面積を結晶融解熱量ΔHmとした。
(6)酸価
試料を、オルトクレゾールに溶解し、自動滴定装置(平沼産業社製、COM-550)を用いて、0.02規定のNaOH水溶液で滴定した。
(7)ポリマー末端への化合物(B)の導入率
前記(2)により求めた数平均分子量の逆数を2000000倍して算出した全末端基量をX(mol/ton)、前記(4)により求めたポリマー末端への化合物(B)の導入量をY(mol/ton)とし、Y×100/X(%)を算出した。
(8)耐加水分解性
130℃真空乾燥器中で12時間以上乾燥した試料を、280℃でプレスし、厚さ1mmのシートとした。エスペック社製高度加速寿命試験装置により、シート50mgを、121℃、100%RH、24時間の高湿度条件下で処理し、処理前後の重量平均分子量を前記(2)の方法で測定した。処理前の重量平均分子量に対する、処理後の重量平均分子量保持率が、70%以上である場合をA、70%未満~60%以上である場合をB、60%未満である場合をCと判定した。
(9)溶融滞留安定性
レオメータ(AntonPaar社製、MCR501)を用いて、130℃真空乾燥器中で12時間以上乾燥した試料0.5gを、窒素雰囲気下、280℃で、15分間溶融滞留させた後、周波数0.5~3.0Hzの範囲で、振り角20%にて、振動を加えた。処理前後の重量平均分子量を前記(2)の方法で測定し、処理前の重量平均分子量に対する、処理後の重量平均分子量変化率を算出した。
(10)耐ブリードアウト性
熱プレスにより作成したフィルムを、100℃のギヤオーブン中に30分投入し、目視、および手触りにて、フィルム表面の状態を、下記基準にて判定した。表面の状態に変化はない場合をA、表面の状態にはほとんど変化がない場合をB、わずかに表面に液状物または粉状物が見られる、またはわずかにべとつきまたは粉っぽさを感じる場合をC、明らかに表面に液状物または粉状物が見られる、または手で触ると明らかにべとつき、または、粉っぽさを感じる場合をDとした。
(11)延伸性
130℃真空乾燥器中で12時間以上乾燥した試料を、280℃でプレスし、厚さ0.1mmのプレスフィルムとした。自動2軸延伸装置(井元製作所社製)を用いて、表1,2に記載の延伸温度、延伸速度60%/minにて同時2軸延伸(延伸倍率3倍×3倍)を行った。破れなく延伸できたものをA、破れがあるものをBと判定した。
(12)粘弾性測定
前記(11)で得られた延伸フィルムを、熱収縮しないよう固定した状態で210℃のギアオーブンで1分間熱処理した。熱処理したフィルムから、長さ40mm、幅8mの試験片を切り出した。セイコーインスツル社製DMS6100を用い、引張モードにて、周波数1Hz、チャック間距離20mm、昇温速度2℃/分、10℃~150℃で動的粘弾性を測定し、25℃における貯蔵弾性率を求めた。
(製造例1)
得られるポリマーに対してマグネシウム原子換算で60ppm相当の酢酸マグネシウムとテレフタル酸ジメチル100gとエチレングリコール59.2gを、150℃、窒素雰囲気下で溶融後、攪拌しながら240℃まで4時間かけて昇温し、メタノールを留出させ、エステル交換反応をおこない、ビス(ヒドロキシエチル)テレフタレートを得た。
(実施例1)
製造例1で得られたビス(ヒドロキシエチル)テレフタレート110gが仕込まれたエステル化反応槽を温度250℃に保持した後、テレフタル酸143g、エチレングリコール61.5g、表1記載の(ポリ)オキシアルキレン構造を有する前記式(B)で表される化合物12.7g(ビス(ヒドロキシエチル)テレフタレート、テレフタル酸、およびエチレングリコールの合計量100重量部に対し、式(B)で表される化合物は4.0重量部に相当する)のスラリーを4時間かけて順次供給し、供給終了後もさらに1時間かけてエステル化反応を行い、エステル化反応生成物を得た。
(実施例2~15および比較例1~10)
用いる化合物の種類、製造条件を表1~表4に示すように変更した以外は、実施例1と同様に行った。
(実施例16)
IV=0.65、Mw=33000の末端未変性ポリエチレンテレフタレート樹脂100重量部、式(B)で表される化合物4.0重量部を、プリブレンドした。シリンダー温度:280℃、スクリュー回転数:200rpmに設定した二軸押出機(池貝鉄鋼製PCM-30型)へ供給し溶融混練した。押出されたガットをペレタイズすることによりポリマーペレットを得た。得られた末端変性ポリエチレンテレフタレート樹脂のペレットをヘキサフルオロイソプロパノールに溶解させた後、その溶液の10倍量のメタノールを撹拌しているところに、末端変性ポリエチレンテレフタレート樹脂を含む溶液を徐々に添加し、再沈殿させた。沈殿物を回収し、真空乾燥器で室温、3時間以上乾燥させた。最沈殿精製後のポリマーのNMRのスペクトルから求めた、ポリマー末端に導入された(B)化合物は、実施例1の53%であった。
(比較例11)
ビス(ヒドロキシエチル)テレフタレート、テレフタル酸、およびエチレングリコールの合計量100重量部に対し、トリメチル1,3,5-ベンゼントリカルボキシレートを1重量部添加した以外は、実施例1と同様に行った。
(比較例12)
式(B)で表される化合物の反応性官能基であるR2をヒドロキシル基からエポキシ基に変更した以外は、実施例1と同様に行った。
実施例1または比較例1で得られたポリエチレンテレフタレート樹脂を、170℃、熱風乾燥機で結晶化を30分行った後、180℃、真空乾燥機で予備乾燥を2時間行った。その後、温度220℃、真空度0.5mmHgの条件の回転式の真空装置(ロータリーバキュームドライヤー)に入れ、所定の時間攪拌しながら加熱し、高重合化したポリエチレンテレフタレート樹脂を得た。得られたポリエチレンテレフタレート樹脂の特性を表5に示す。実施例17の固相重合した末端変性ポリエチレンテレフタレート樹脂は、比較例13の末端未変性ポリエチレンテレフタレート樹脂と比較して、溶融粘度が低く、溶融滞留安定性、耐加水分解性に優れる。
実施例1の末端変性ポリエチレンテレフタレート樹脂、および比較例1で得られた末端未変性ポリエチレンテレフタレート樹脂を、所定の温度で延伸し、延伸性を評価した。延伸可能であったフィルムについて、熱処理後、粘弾性測定を行った。得られた特性を表6に示す。実施例18と比較例14、15の比較により、末端変性ポリエチレンテレフタレート樹脂は、末端未変性ポリエチレンテレフタレート樹脂と比べて、より低い温度で延伸することができるとともに、高い貯蔵弾性率を示した。
Claims (14)
- 固有粘度が0.50~1.8dl/g、融点が245~270℃であって、300℃における溶融粘度μ(Pa・s)が下記式(A)を満たす末端変性ポリエチレンテレフタレート樹脂であって、下記式(B)で表される化合物を末端に25~80mol/ton結合させた末端変性ポリエチレンテレフタレート樹脂。
μ≦4×e(0.000085×Mw) 式(A)
(ただし、ここで用いた重量平均分子量Mwは、ヘキサフルオロイソプロパノール(0.005N トリフルオロ酢酸ナトリウム添加)を移動相とするゲルパーミエーションクロマトグラフィー法で求めた、標準ポリメタクリル酸メチルの分子量に対する相対的な重量平均分子量を示す。)
- 示差走査型熱量計(DSC)を用い、昇温速度10℃/分で30℃から280℃まで昇温し、280℃で3分保持した後、降温速度200℃/分で280℃から30℃まで降温し、昇温速度10℃/分で30℃から280℃まで昇温したときに観察される結晶融解熱量が45~80J/gである請求項1に記載の末端変性ポリエチレンテレフタレート樹脂。
- 示差走査型熱量計(DSC)を用い、昇温速度10℃/分で30℃から280℃まで昇温し、280℃で3分保持した後、降温速度200℃/分で280℃から30℃まで降温したときに観察される降温結晶化温度が170~210℃である請求項1または2に記載の末端変性ポリエチレンテレフタレート樹脂。
- 酸価が13mol/ton以下である請求項1~3のいずれかに記載の末端変性ポリエチレンテレフタレート樹脂。
- レオメータを用いて、窒素下、280℃で15分間溶融滞留させた後、周波数0.5~3.0Hz、振り角20%にて振動を加えた後の重量平均分子量変化率が80~120%の範囲である請求項1~4のいずれかに記載の末端変性ポリエチレンテレフタレート樹脂。
- 重量平均分子量Mwと数平均分子量Mnの比で表されるMw/Mn(分散度)が2.5以下である請求項1~5のいずれかに記載の末端変性ポリエチレンテレフタレート樹脂。
- 請求項1~6のいずれかに記載の末端変性ポリエチレンテレフタレート樹脂を成形してなる成形品。
- 成形品が繊維またはフィルムである請求項7に記載の成形品。
- 式(B)で表される化合物、エチレングリコール、テレフタル酸またはテレフタル酸ジアルキルエステルを含む原料を、少なくとも(a)エステル化反応工程または(b)エステル交換反応工程からなる1段目の工程、続いて(c)重縮合反応工程からなる2段目の工程により製造する末端変性ポリエチレンテレフタレート樹脂の製造方法。
- 前記式(B)で表される化合物を(a)エステル化反応工程、(b)エステル交換反応工程、(c)重縮合反応工程から選ばれるいずれかの工程において添加する請求項9記載の末端変性ポリエチレンテレフタレート樹脂の製造方法。
- (a)エステル化反応工程または(b)エステル交換反応工程にて、前記式(B)で表される化合物を添加し、230~260℃で反応させる請求項10に記載の末端変性ポリエチレンテレフタレート樹脂の製造方法。
- (c)重縮合反応工程の最高温度が280~300℃の範囲である請求項9~11のいずれかに記載の末端変性ポリエチレンテレフタレート樹脂の製造方法。
- (c)重縮合反応工程により得られた末端変性ポリエチレンテレフタレート樹脂を、200~240℃の範囲で固相重合する請求項9~12のいずれかに記載の末端変性ポリエチレンテレフタレート樹脂の製造方法。
- 得られる末端変性ポリエチレンテレフタレート樹脂が請求項1~6のいずれか記載の末端変性ポリエチレンテレフタレート樹脂である請求項9~13のいずれかに記載の末端変性ポリエチレンテレフタレート樹脂の製造方法。
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JPS6290312A (ja) * | 1985-10-14 | 1987-04-24 | Teijin Ltd | 改質ポリエステル繊維 |
JPS6335824A (ja) * | 1986-07-29 | 1988-02-16 | Teijin Ltd | 防汚性ポリエステル繊維 |
JPH0699511A (ja) * | 1992-09-21 | 1994-04-12 | Kuraray Co Ltd | ポリエステル繊維または成形品の製造方法 |
JPH0841300A (ja) * | 1994-08-02 | 1996-02-13 | Teijin Ltd | 改善された洗濯耐久性を有するソイルリリース性ポリエステル組成物およびその繊維 |
JPH10306154A (ja) * | 1997-03-05 | 1998-11-17 | Teijin Ltd | 防汚性共重合ポリエステルおよびそれからなるポリエステル繊維 |
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JP2004099729A (ja) | 2002-09-09 | 2004-04-02 | Toray Ind Inc | 延伸ポリエステルフィルム |
JP2015065741A (ja) * | 2013-09-24 | 2015-04-09 | トヨタ自動車株式会社 | ステータコア |
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JPS6290312A (ja) * | 1985-10-14 | 1987-04-24 | Teijin Ltd | 改質ポリエステル繊維 |
JPS6335824A (ja) * | 1986-07-29 | 1988-02-16 | Teijin Ltd | 防汚性ポリエステル繊維 |
JPH0699511A (ja) * | 1992-09-21 | 1994-04-12 | Kuraray Co Ltd | ポリエステル繊維または成形品の製造方法 |
JPH0841300A (ja) * | 1994-08-02 | 1996-02-13 | Teijin Ltd | 改善された洗濯耐久性を有するソイルリリース性ポリエステル組成物およびその繊維 |
JPH10306154A (ja) * | 1997-03-05 | 1998-11-17 | Teijin Ltd | 防汚性共重合ポリエステルおよびそれからなるポリエステル繊維 |
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