WO2012099261A1 - Copolymère de carbonate de polyester et procédé de production de celui-ci - Google Patents

Copolymère de carbonate de polyester et procédé de production de celui-ci Download PDF

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Publication number
WO2012099261A1
WO2012099261A1 PCT/JP2012/051280 JP2012051280W WO2012099261A1 WO 2012099261 A1 WO2012099261 A1 WO 2012099261A1 JP 2012051280 W JP2012051280 W JP 2012051280W WO 2012099261 A1 WO2012099261 A1 WO 2012099261A1
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Prior art keywords
polyester carbonate
mol
carbonate copolymer
formula
acid
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PCT/JP2012/051280
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English (en)
Japanese (ja)
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和徳 布目
学 松井
丹藤　和志
輝幸 重松
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帝人化成株式会社
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Priority to JP2012553794A priority Critical patent/JP5719854B2/ja
Priority to CN2012800056379A priority patent/CN103328536A/zh
Publication of WO2012099261A1 publication Critical patent/WO2012099261A1/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
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups

Definitions

  • the present invention relates to a polyester carbonate copolymer having good moldability and extremely small coloring during molding, and a method for producing the same.
  • Amorphous engineering plastics include aromatic polyester carbonates derived from aromatic diols, aromatic dicarboxylic acids and carbonate precursors.
  • Aromatic polyester carbonates are used in lenses, light covers and the like because they are excellent in heat resistance, transparency, impact resistance and the like.
  • an amorphous aromatic polyester carbonate composed of 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as bisphenol A) as an aromatic diol and terephthalic acid or isophthalic acid as an aromatic dicarboxylic acid Since it has a higher heat distortion temperature than polycarbonate mainly composed of bisphenol A, it has excellent transparency and a relatively balanced characteristic, it is used in various applications.
  • Various methods for producing these polyester carbonates are known.
  • the general method is a melt polycondensation method in which aromatic diols, carbonic acid diesters and aromatic dicarboxylic acid diesters are polymerized in a molten state by a transesterification method.
  • This melt polycondensation method has a feature that it does not use a solvent and basically does not use a halogen-based raw material, but has a problem that the resulting polymer is highly colored due to the reaction at a high temperature.
  • Patent Document 1 discloses a method for controlling the terminal in the produced wholly aromatic polyester carbonate. According to the publication, it is described that the obtained polyester carbonate resin is excellent in heat resistance and less colored.
  • Patent Document 2 discloses a polyester carbonate resin composed of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and an aromatic dicarboxylic acid. According to the publication, it is described that the obtained polyester carbonate resin exhibits good optical properties.
  • the polyester carbonate resin specifically shown in the examples has a high proportion of phenyl ends in the polymer molecule ends, and thus the phenyl ends may be decomposed during processing such as molding and film formation, and phenol may be generated. .
  • the objective of this invention is providing the polyester carbonate copolymer excellent in a moldability and a hue, and its manufacturing method.
  • Another object of the present invention is to provide a method for producing an optical member excellent in hue at a low molding defect rate.
  • the inventors of the present invention have achieved excellent polyester moldability and hue by controlling the polymer species and amount to be used within a specific range of the polymer molecule terminal composition. The inventors have found that a carbonate copolymer can be obtained and have reached the present invention. That is, according to the present invention, the following inventions are provided. 1.
  • Y represents a phenylene group or a naphthalenediyl group.
  • the polyester carbonate copolymer according to item 1 above wherein the proportion of phenyl ends relative to all the ends of the polymer is 0 to 30 mol%, the proportion of hydroxyl ends is 30 to 98 mol%, and the proportion of methyl ester ends is 2 to 70 mol%. 3.
  • the polyester carbonate copolymer according to item 1 which contains 75 to 95 mol% of the unit represented by the formula (I) and 25 to 5 mol% of the unit represented by the formula (II). 4).
  • the polyester carbonate copolymer as described in 1 above comprising 0.5 to 100 ppm of Ti atoms based on the weight of the polyester carbonate copolymer. 6). 2. The polyester carbonate copolymer as described in 1 above, comprising 1.0 to 50 ppm of Ti atoms based on the weight of the polyester carbonate copolymer. 7). 2. The polyester carbonate copolymer according to item 1 above, wherein when the molded plate having a thickness of 1 mm is molded at a cylinder temperature of 280 ° C., the YI value of the molded plate is 1.0 to 6.0. 8).
  • the amount of carbonic acid diester (c) used satisfies the following formula (1), and the titanium compound is used in a ratio of 10 ⁇ 5 to 10 ⁇ 3 mol as a titanium element with respect to a total of 1 mol of diol and dicarboxylic acid.
  • a method for producing an optical member comprising injection-molding a resin composition containing the polyester carbonate copolymer according to item 1 above. 10. 10. The production method according to item 9 above, wherein the injection molding is performed at a cylinder temperature of 260 to 300 ° C. and a mold temperature of 100 to 140 ° C. 11. 10. The method according to item 9, wherein the molding defect rate is 10% or less. 12 10. The manufacturing method according to 9 above, wherein the optical member is a lens.
  • the polyester carbonate copolymer of the present invention contains a unit represented by the following formula (I) and a unit represented by the following formula (II).
  • Y represents a phenylene group or a naphthalenediyl group.
  • Y is preferably a 1,4-phenylene group, a 1,3-phenylene group or a 2,6-naphthalenediyl group.
  • the optical properties are particularly good when the content of the unit of the formula (I) in the copolymer of the present invention is 67 to 95 mol% and the content of the unit of the formula (II) is 33 to 5 mol%. It is preferable.
  • the content of the unit of the formula (I) is preferably 75 to 95 mol%.
  • the content of the unit of the formula (II) is preferably 25 to 5 mol%.
  • the copolymer of the present invention contains at least one phenyl end, hydroxyl end, and methyl ester end in the polymer.
  • the ratio of the phenyl terminal with respect to all the terminals of the copolymer of this invention is 30 mol% or less, 20 mol% or less is more preferable, and 10 mol% or less is still more preferable.
  • the phenyl terminal, hydroxyl terminal, and methyl ester terminal ratios are as follows: the phenyl terminal ratio is 0-30 mol%, the hydroxyl terminal is 30-98 mol%, and the methyl ester terminal is 2-70 mol%. It is preferable that More preferably, the phenyl terminal ratio is 0 to 20 mol%, the hydroxyl terminal is 50 to 98 mol%, and the methyl ester terminal is 2 to 50 mol%.
  • the phenyl terminal ratio is 0 to 10 mol%
  • the hydroxyl terminal is 70 to 98 mol%
  • the methyl ester terminal is 2 to 30 mol%.
  • the specific viscosity of the copolymer of the present invention is preferably in the range of 0.12 to 0.55, more preferably in the range of 0.12 to 0.45, and in the range of 0.12 to 0.30. Is more preferable. A specific viscosity of less than 0.12 is not preferable because the molded product becomes brittle.
  • the copolymer of the present invention mainly contains 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as a diol component.
  • Other diol components may be contained to such an extent that the properties of the copolymer are not impaired.
  • Examples of other diol components used in combination with the 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene include aliphatic diols such as ethylene glycol and hexanediol, and tricyclo [5.2.1.1.02. 6] Alicyclic ring such as decanedimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiroglycol, etc.
  • the copolymer of the present invention mainly contains terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid or ester-forming derivatives thereof as a dicarboxylic acid component.
  • the dicarboxylic acid component may contain other dicarboxylic acid components to the extent that the properties of the resulting copolymer are not impaired.
  • the content of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol based on 100 mol% of the dicarboxylic acid component. % Or more.
  • dicarboxylic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, methylmalonic acid, and ethylmalonic acid.
  • monocyclic aromatic dicarboxylic acids such as phthalic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, anthracene dicarboxylic acid
  • polycyclic aromatic dicarboxylic acids such as phenanthrene dicarboxylic acid.
  • biphenyl dicarboxylic acids such as 2,2′-biphenyl dicarboxylic acid
  • aliphatic carboxylic dicarboxylic acids such as 1,4-cyclodicarboxylic acid and 2,6-decalin dicarboxylic acid
  • acid chlorides and esters are used as these derivatives.
  • the copolymer of the present invention preferably contains 0.5 to 100 ppm of Ti atoms, more preferably 1.0 to 50 ppm relative to the polyester carbonate copolymer. It is particularly preferable that the Ti atomic weight is within the above range because both reaction control and hue can be achieved.
  • the copolymer of the present invention preferably has a YI value of 1.0 to 6.0 when a molded plate having a thickness of 1 mm is formed at a cylinder temperature of 280 ° C.
  • a transesterification reaction of diol (a), dicarboxylic acid (b) and bisaryl carbonate is preferably employed.
  • the copolymer of the present invention comprises a diol (a), a dicarboxylic acid (b) and a carbonic acid diester (c) prepared by a melt polycondensation method in the presence of a mixed catalyst comprising a basic compound catalyst or a transesterification catalyst or both.
  • the first reaction tank separates unreacted carbonic acid diester (c) and monomer and by-product monohydroxy compound, and a rectifying column for refluxing unreacted carbonic acid diester (c) and monomer in the reaction system. It is preferable to use a vertical stirring tank provided.
  • the reaction is carried out at 120 to 300 ° C., preferably 150 to 280 ° C. under a slightly reduced pressure of 20 to 90 kPa, preferably 40 to 80 kPa, to distill off the by-produced monohydroxy compound out of the system.
  • the reaction is carried out at normal pressure, the amount of residual phenol after the reaction is increased and the hue is lowered, which is not preferable.
  • the distillation rate of phenol becomes slow and the reaction time is long, it is not preferable.
  • the liquid feeding from the first reaction tank to the second reaction tank is preferably performed when the distillate amount of the by-produced monohydroxy compound has reached 50 to 90%, preferably 60 to 80% of the theoretical distillate amount. .
  • the distillate amount is less than 50%, the amount of unreacted carbonic acid diester (c) and monomer is large, and the molar balance of the raw material may be lost in the second reaction tank, which is not preferable.
  • the distillate amount is larger than 90%, the viscosity of the resin becomes high, and it takes a long time for liquid feeding, which is not preferable.
  • filtration for the purpose of removing foreign substances can also be performed between the first reaction tank and the second reaction tank.
  • a filter having an opening of 10 ⁇ m or less is often used.
  • the monohydroxy compounds are phenols by-produced by the reaction of the diol (a) and the carbonic acid diester, alkyl alcohols such as methanol by-produced by the reaction of the diol (a) and the dicarboxylic acid (b), and water. .
  • the theoretical distillation amount of the monohydroxy compound is the amount of the monohydroxy compound distilled when all of the charged diol (a), dicarboxylic acid (b) and carbonic acid diester (c) are reacted.
  • the reaction pressure is often high vacuum, and there is no unreacted carbonic acid diester that affects the molar balance of the raw material.
  • a rectifying column is not installed, and the evaporated product is taken out of the system as it is.
  • the stirring blade used in the second reaction tank is excellent in the surface renewability of the reaction mixture and the ability to crush the generated bubbles, such as a helical ribbon blade or an anchor blade that exhibits excellent performance with high viscosity, good.
  • monohydroxy by changing the degree of vacuum stepwise from 150 to 320 ° C., preferably from 180 to 300 ° C., and finally reducing the pressure to 1 to 500 Pa.
  • the condensation reaction is carried out while distilling the compound out of the system.
  • the stirring speed of the stirrer used in the first reaction tank is such that the viscosity of the reaction mixture is low and a large amount of energy is required for evaporation of the produced monohydroxy compound.
  • the stirring speed of the stirrer used in the second reaction tank is often several tens to 200 rpm, and the viscosity of the reaction mixture is high, so that the stirring speed is lower than that of the first reaction tank, for example, several to several tens rpm. It is preferable that In many cases, the polyester carbonate polymer produced in the second reaction tank is taken out as a sheet or a strand by pressurizing the inside of the second reaction tank, cooled with water or the like, and commercialized as pellets.
  • Basic compounds used as catalysts include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate Sodium stearate, potassium stearate, lithium stearate, sodium salt, potassium salt, lithium salt of bisphenol A, sodium benzoate, potassium benzoate, lithium benzoate and the like.
  • Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate , Calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.
  • Nitrogen-containing basic compounds used as promoters include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine Etc.
  • These catalysts may be used alone or in combination of two or more.
  • the amount of these polymerization catalysts used is 10 with respect to a total of 1 mol of the diol (a) and the dicarboxylic acid (b). -9 ⁇ 10 -3 Used in molar ratios.
  • it is particularly preferable to use a titanium compound and the amount used is 10 with respect to 1 mol in total of the diol (a) and the dicarboxylic acid (b).
  • the catalyst may be removed or deactivated after the completion of the polymerization reaction in order to maintain thermal stability and hydrolysis stability.
  • a method of deactivating a catalyst by adding a known acidic substance is preferably carried out.
  • deactivation examples include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, butyl p-toluenesulfonate, hexyl p-toluenesulfonate, and the like.
  • Sulfonic acid esters such as phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, Phosphorous esters such as di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, phosphoric acid Phosphate esters such as dibutyl, dioctyl phosphate, monooctyl phosphate, diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, etc.
  • Phosphorous esters such as di-n-butyl pho
  • Phosphonic acid esters such as phonic acids, diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane, boric acids such as boric acid and phenylboric acid, and tetrabutylphosphonium dodecylbenzenesulfonate
  • Aromatic sulfonates, stearic acid chloride, benzoyl chloride, organic halides such as p-toluenesulfonic acid chloride, alkylsulfuric acid such as dimethylsulfuric acid, and organic halides such as benzyl chloride are preferably used.
  • deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst.
  • the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient, which is not preferable.
  • it is more than 50 times mole with respect to the amount of catalyst since heat resistance falls and it becomes easy to color a molded object, it is unpreferable.
  • a step of devolatilizing and removing low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 320 ° C. may be provided.
  • the amount of phenol remaining in the copolymer of the present invention is desirably 1 to 100 ppm, more preferably 1 to 50 ppm, more preferably 1 to 10 ppm based on the weight of the polymer. If it is more than this, coloring and molecular weight reduction will occur at high temperature, and excellent moldings cannot be obtained due to coloring, silver streak, foaming, mold contamination, etc. even during molding. Usually, it is difficult to reduce the amount of phenol remaining in the resin, but the production method of the present invention, that is, phenol generated in the late stage of polymerization by advancing the reaction while reducing the pressure from the initial stage of polymerization and distilling off the phenol. Can be greatly reduced.
  • a process for producing a polyester carbonate copolymer by reacting a diol represented by the following formula (a), a dicarboxylic acid represented by the following formula (b) and a carbonic acid diester (c).
  • Y represents a phenylene group or a naphthalenediyl group.
  • the amount of carbonic acid diester (c) used satisfies the following formula (1), and the titanium compound is 10 elements as titanium element with respect to a total of 1 mol of diol and dicarboxylic acid. -5 ⁇ 10 -3
  • a method for producing a polyester carbonate copolymer is provided, which is used in a molar ratio.
  • the present invention includes a resin composition containing the copolymer of the present invention and various additives. It does not specifically limit as a method of adding various additives to the copolymer of this invention. For example, these may be added while the thermoplastic resin as a reaction product is in a molten state, or may be added after being re-melted after pelletizing the thermoplastic resin.
  • the resin composition can be molded and processed by an arbitrary method such as an injection molding method, a compression molding method, an injection compression molding method, a melt film forming method, or a casting method.
  • various additives include mold release agents, heat stabilizers, ultraviolet absorbers, and bluing agents.
  • a mold release agent that whose 90 weight% or more consists of ester of alcohol and a fatty acid is preferable.
  • Specific examples of the ester of alcohol and fatty acid include monohydric alcohol and fatty acid ester, partial ester or total ester of polyhydric alcohol and fatty acid.
  • the monohydric alcohol and fatty acid ester is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.
  • the partial ester or total ester of a polyhydric alcohol and a fatty acid is preferably a partial ester or total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.
  • Specific examples of the monohydric alcohol, saturated fatty acid and ester include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like. Stearyl stearate is preferred.
  • stearic acid monoglyceride As partial ester or total ester of polyhydric alcohol and saturated fatty acid, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, All or partial esters of dipentaerythritol, such as pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, etc.
  • esters can be mentioned.
  • stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.
  • the amount of the ester in the release agent is preferably 90% by weight or more, and more preferably 95% by weight or more when the release agent is 100% by weight.
  • the content of the release agent is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, with respect to 100 parts by weight of the copolymer, and 0.02 to The range of 0.5 part by weight is more preferable.
  • heat stabilizer examples include a phosphorus heat stabilizer, a sulfur heat stabilizer, and a hindered phenol heat stabilizer.
  • phosphorus heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.
  • triphenyl phosphite tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, Tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite Phyto, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol dip
  • the content of the phosphorus heat stabilizer is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the copolymer.
  • pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate)
  • Examples include dilauryl-3, 3′-thiodipropionate, dimyristyl-3, 3′-thiodipropionate, distearyl-3, 3′-thiodipropionate.
  • pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), dilauryl-3, 3′-thiodipropionate, dimyristyl-3, 3′-thio Dipropionate is preferred.
  • pentaerythritol-tetrakis (3-laurylthiopropionate).
  • the thioether compounds are commercially available from Sumitomo Chemical Co., Ltd. as Sumilizer TP-D (trade name), Sumilizer TPM (trade name), and the like, and can be easily used.
  • the content of the sulfur-based heat stabilizer is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the copolymer.
  • the hindered phenol heat stabilizer include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene bis (3,5-di-tert-butyl
  • Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is particularly preferably used.
  • the content of the hindered phenol heat stabilizer is preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the copolymer.
  • the ultraviolet absorber include at least one ultraviolet absorber selected from the group consisting of benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic imino ester ultraviolet absorbers, and cyanoacrylates. preferable.
  • benzotriazole ultraviolet absorber examples include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy- 3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1 , 3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy- 3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphen
  • 2- (2-hydroxy-5-methylphenyl) benzotriazole 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dicumyl) Phenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetra Methylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole
  • 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole 2,2′- A Chirenbisu [4- (1,1,3,3-tetramethylbutyl)
  • benzophenone-based ultraviolet absorbers examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4- Methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2- Methoxyphenyl) methane, 2-hy Examples include droxy-4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.
  • Examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- (4,6-bis ( And 2.4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-[(octyl) oxy] -phenol.
  • Examples of cyclic imino ester UV absorbers include 2,2′-bis (3,1-benzoxazin-4-one) and 2,2′-p-phenylenebis (3,1-benzoxazin-4-one).
  • 2,2′-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,5-naphthalene) bis (3,1-benzoxazin-4-one) ), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2-nitro-p-phenylene) bis (3,1- Benzoxazin-4-one) and 2,2 ′-(2-chloro-p-phenylene) bis (3,1-benzoxazin-4-one) and the like are exemplified.
  • 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) And 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) are preferred.
  • 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) is preferable.
  • Such a compound is commercially available from Takemoto Yushi Co., Ltd. as CEi-P (trade name) and can be easily used.
  • cyanoacrylate ultraviolet absorber 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenyl) Examples include acryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.
  • the content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, even more preferably 100 parts by weight of the copolymer. 0.05 to 0.8 part by weight.
  • the bluing agent examples include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer and polysynthremble-RLS manufactured by Clariant.
  • the bluing agent is effective for eliminating the yellow color of the copolymer.
  • a copolymer imparted with weather resistance since a certain amount of UV absorber is blended, there is a reality that the molded body tends to be yellowish depending on the action and color of the UV absorber, especially in sheets and lenses. In order to give a natural transparency, blending of a bluing agent is very effective.
  • the blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm based on the copolymer.
  • An optical member can be produced by injection molding a resin composition containing the copolymer of the present invention. A lens is mentioned as an optical member.
  • the injection molding is preferably performed at a cylinder temperature of 260 to 300 ° C. and a mold temperature of 100 to 140 ° C. According to the present invention, the molding defect rate of injection molding is 10% or less.
  • the following examples further illustrate the present invention.
  • the evaluation was based on the following method.
  • Terminal ratio Measured using proton NMR of JNM-AL400 manufactured by JEOL Ltd. The calculation method of each terminal was calculated
  • Phenyl terminal ratio ⁇ (a) / ((a) + (b) + (c)) ⁇ ⁇ 100 Hydroxyl end ratio: ⁇ (b) / ((a) + (b) + (c)) ⁇ ⁇ 100 Methyl end ratio: ⁇ (c) / ((a) + (b) + (c)) ⁇ ⁇ 100 (A): Integrated value of 4.570 to 4.520 ppm ⁇ 4 (B): integrated value of 3.925 to 3.840 ppm ⁇ 4 (C): integral value of 3.960 to 3.925 ppm ⁇ 6 (3) Ti atomic weight: A mixture of a predetermined amount of titanium oxide and terephthalic acid was cold-pressed to prepare a molded plate having a thickness of 3 mm, and a calibration curve for the Ti atomic weight contained by fluorescent X-ray measurement was prepared.
  • polymerization is hot-pressed, a 3mm-thick molded board is created, and when the amount of Ti atoms in resin is based on the weight of polyester by fluorescent X ray measurement, the weight Obtained as a fraction.
  • ppm means 10-4 weight%.
  • Moldability A molding plate having a thickness of 1 mm was molded at an cylinder temperature of 280 ° C. using an injection molding machine [J75EIII manufactured by JSW Co., Ltd.], and the surface appearance was measured visually. The presence or absence of defects (silver, dirt, etc.) of the molded plate was determined.
  • Example 1 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter abbreviated as “BPEF”) 143.83 parts by weight, dimethyl terephthalate (hereinafter abbreviated as “DMT”) 13.98 parts by weight, diphenyl carbonate (hereinafter may be abbreviated as “DPC”) 59.98 parts by weight, titanium tetrabutoxide 20.42 ⁇ 10 ⁇ 3 parts by weight with a rectifying tower (first reaction tank) ). Then, after performing nitrogen substitution 3 times, the jacket was heated to 180 ° C. to melt the raw material.
  • DMT dimethyl terephthalate
  • DPC diphenyl carbonate
  • the pressure was reduced to 40 kPa over 20 minutes, and at the same time, the jacket was heated to 250 ° C. at a rate of 60 ° C./hr to conduct a transesterification reaction.
  • the prepolymer is transferred from the first reaction tank to the stirring tank (second reaction tank) without a rectification tower by nitrogen pressurization. Liquid was sent.
  • the pressure was reduced to 40 kPa over 20 minutes and further to 0.13 kPa over 100 minutes, and the polymerization reaction was carried out for 30 minutes under the conditions of 260 ° C. and 0.13 kPa or less. It was. After completion of the reaction, the produced polyester carbonate copolymer (A) was extracted while pelletizing, and the specific viscosity, Ti atomic weight, and terminal ratio were evaluated. The obtained polymer was vacuum-dried at 120 ° C.
  • Example 2 Polyester carbonate copolymer (B) in the same manner as in Example 1 except that the amount of DPC used in Example 1 is 64.27 parts by weight and the amount of titanium tetrabutoxide used is 34.03 ⁇ 10 ⁇ 3 parts by weight. Pellets and molded plates were obtained. The evaluation results are shown in Table 1.
  • Example 3 BPEF 157.86 parts by weight, dimethyl 2,6-naphthalenedicarboxylate (hereinafter sometimes abbreviated as “NDCM”) 9.77 parts by weight, DPC 71.98 parts by weight, titanium tetrabutoxide 13.61 ⁇ 10 ⁇ 3 parts by weight was put into a stirring tank with a rectification tower (first reaction tank).
  • NDCM dimethyl 2,6-naphthalenedicarboxylate
  • the jacket was heated to 180 ° C. to melt the raw material. After complete dissolution, the pressure was reduced to 40 kPa over 20 minutes, and at the same time, the jacket was heated to 250 ° C. at a rate of 60 ° C./hr to conduct a transesterification reaction.
  • the prepolymer is transferred from the first reaction tank to the stirring tank (second reaction tank) without a rectification tower by nitrogen pressurization. Liquid was sent.
  • the pressure was reduced to 40 kPa over 20 minutes and further to 0.13 kPa over 100 minutes, and the polymerization reaction was carried out for 30 minutes under the conditions of 260 ° C. and 0.13 kPa or less. It was. After completion of the reaction, the produced polyester carbonate copolymer (C) was extracted while pelletizing, and the specific viscosity, Ti atomic weight, and terminal ratio were evaluated. The obtained polymer was vacuum-dried at 120 ° C.
  • Comparative Example 2 Polyester carbonate copolymer (E) in the same manner as in Example 1 except that the amount of DPC used in Example 1 is 65.98 parts by weight and the amount of titanium tetrabutoxide used is 136.13 ⁇ 10 ⁇ 3 parts by weight. Pellets and molded plates were obtained. The evaluation results are shown in Table 1. Comparative Example 3 A polyester carbonate copolymer (F) pellet and moldability were obtained in the same manner as in Example 1 except that the amount of DPC used in Example 1 was 83.12 parts by weight. The evaluation results are shown in Table 1.
  • the DPC charge ratio in Table 1 is DPC use amount (mol) / ⁇ diol (a) use amount (mol) -dicarboxylic acid (b) use amount (mol) ⁇ , Ti charge amount is Ti ( ⁇ mol) / A total of 1 mol of diol (a) and dicarboxylic acid (b) is shown.
  • the polyether carbonate copolymers of Examples 1 to 3 are excellent in moldability and hue because they have very few phenyl ends and a very small amount of phenol generated by thermal decomposition.
  • Comparative Example 1 (copolymer (D)) has many phenyl ends and a large amount of phenol is generated by thermal decomposition, it is inferior in moldability and hue.
  • Comparative Example 2 (copolymer (E)) has a large amount of Ti compound remaining in the resin, it is inferior in hue. Since Comparative Example 3 (copolymer (F)) has many phenyl ends and a large amount of phenol generated by thermal decomposition, moldability and hue are inferior.
  • the obtained copolymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite was added based on the weight of the obtained resin composition. 0.10% by weight and 0.10% by weight of glycerol monostearate were added, and pelletized using a ⁇ 30 mm single screw extruder with a vent.
  • a lens having a thickness of 0.3 mm, a convex curvature radius of 5 mm, and a concave curvature radius of 4 mm is molded under the molding conditions shown in Table 2, and 20 sheets are continuously molded to improve molding stability. evaluated.
  • the copolymer (D) has poor fluidity, and it becomes easier to obtain lens dimensions when the molding temperature and mold temperature are raised, but molding defects occur due to thermal decomposition when the molding temperature is raised.
  • the copolymer (F) has a fluidity equivalent to that of the copolymer (A), but has many Ph ends, so that the hue of the molded product is deteriorated and the molding is poor.
  • the polyester carbonate copolymer of the present invention has few phenyl ends and is excellent in moldability and hue. According to the production method of the present invention, a polyester carbonate copolymer having few phenyl ends and excellent moldability and hue can be obtained. According to the method for producing an optical member of the present invention, an optical member excellent in hue can be produced with a small molding defect rate.
  • polyester carbonate copolymer of the present invention is excellent in moldability and hue, it is various optical lenses such as camera lenses, protractor lenses, and pickup lenses, optical disks, optical films, plastic cells, optical cards, liquid crystal panels, and headlamp lenses. It is extremely useful as an optical member such as an OPC binder.

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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)
  • Polyesters Or Polycarbonates (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

La présente invention concerne un copolymère de carbonate de polyester ayant des propriétés optiques favorables et d'excellentes teintes et aptitude au moulage. L'invention concerne un copolymère de carbonate de polyester contenant des groupes représentés par la formule (I) et des groupes représentés par la formule (II) et la proportion de terminaisons phényle par rapport à l'ensemble des terminaisons dans le polymère est de 30 % en moles ou moins. (Dans la formule (II), Y est un groupe phénylène ou un groupe naphtalènediyle.)
PCT/JP2012/051280 2011-01-19 2012-01-16 Copolymère de carbonate de polyester et procédé de production de celui-ci WO2012099261A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016176984A (ja) * 2015-03-18 2016-10-06 帝人株式会社 熱可塑性樹脂フィルム
KR20190062046A (ko) * 2017-11-28 2019-06-05 롯데케미칼 주식회사 폴리에스테르 카보네이트 공중합체 및 제조방법과 이를 이용한 성형품
US10689486B2 (en) 2014-05-07 2020-06-23 Mitsubishi Gas Chemical Company, Inc. Resin produced by polycondensation, and resin composition
CN111527125A (zh) * 2017-12-28 2020-08-11 帝人株式会社 聚(酯)碳酸酯和聚(酯)碳酸酯的制造方法
WO2023074471A1 (fr) * 2021-10-26 2023-05-04 帝人株式会社 Résine thermoplastique et élément optique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1087800A (ja) * 1996-09-10 1998-04-07 Teijin Chem Ltd ポリエステルカーボネート樹脂
JP2002309015A (ja) * 2001-04-18 2002-10-23 Teijin Chem Ltd 光学フィルム
WO2006006731A1 (fr) * 2004-07-15 2006-01-19 Teijin Chemicals Ltd. Composition résineuse et objet moulé dans cette même composition
WO2011010741A1 (fr) * 2009-07-24 2011-01-27 帝人化成株式会社 Lentille ophtalmique et copolymère de polyester-carbonate utilisé dans des lentilles optiques

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1291374A4 (fr) * 2000-06-01 2004-04-07 Teijin Ltd Carbonate de polyester totalement aromatique et son procede de preparation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1087800A (ja) * 1996-09-10 1998-04-07 Teijin Chem Ltd ポリエステルカーボネート樹脂
JP2002309015A (ja) * 2001-04-18 2002-10-23 Teijin Chem Ltd 光学フィルム
WO2006006731A1 (fr) * 2004-07-15 2006-01-19 Teijin Chemicals Ltd. Composition résineuse et objet moulé dans cette même composition
WO2011010741A1 (fr) * 2009-07-24 2011-01-27 帝人化成株式会社 Lentille ophtalmique et copolymère de polyester-carbonate utilisé dans des lentilles optiques

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10689486B2 (en) 2014-05-07 2020-06-23 Mitsubishi Gas Chemical Company, Inc. Resin produced by polycondensation, and resin composition
US11370882B2 (en) 2014-05-07 2022-06-28 Mitsubishi Gas Chemical Company, Inc. Resin produced by polycondensation, and resin composition
JP2016176984A (ja) * 2015-03-18 2016-10-06 帝人株式会社 熱可塑性樹脂フィルム
KR20190062046A (ko) * 2017-11-28 2019-06-05 롯데케미칼 주식회사 폴리에스테르 카보네이트 공중합체 및 제조방법과 이를 이용한 성형품
KR102200878B1 (ko) 2017-11-28 2021-01-11 롯데케미칼 주식회사 폴리에스테르 카보네이트 공중합체 및 제조방법과 이를 이용한 성형품
CN111527125A (zh) * 2017-12-28 2020-08-11 帝人株式会社 聚(酯)碳酸酯和聚(酯)碳酸酯的制造方法
CN111527125B (zh) * 2017-12-28 2022-07-22 帝人株式会社 聚(酯)碳酸酯和聚(酯)碳酸酯的制造方法
US11505698B2 (en) 2017-12-28 2022-11-22 Teijin Limited Polyester carbonate and method for producing polyester carbonate
WO2023074471A1 (fr) * 2021-10-26 2023-05-04 帝人株式会社 Résine thermoplastique et élément optique

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