WO2023058632A1 - ポリエステル樹脂及びその製造方法、並びに、樹脂組成物、成形体、光学部材 - Google Patents
ポリエステル樹脂及びその製造方法、並びに、樹脂組成物、成形体、光学部材 Download PDFInfo
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- WO2023058632A1 WO2023058632A1 PCT/JP2022/037066 JP2022037066W WO2023058632A1 WO 2023058632 A1 WO2023058632 A1 WO 2023058632A1 JP 2022037066 W JP2022037066 W JP 2022037066W WO 2023058632 A1 WO2023058632 A1 WO 2023058632A1
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- WIPO (PCT)
- Prior art keywords
- polyester resin
- diol
- derived
- resin according
- general formula
- Prior art date
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- 239000007809 chemical reaction catalyst Substances 0.000 claims description 14
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- KYQRDNYMKKJUTH-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)CC1C2 KYQRDNYMKKJUTH-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GGHTWSNOKADVAG-UHFFFAOYSA-N butan-1-olate germanium(4+) Chemical compound [Ge+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] GGHTWSNOKADVAG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical compound CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 1
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- CTCOPPBXAFHGRB-UHFFFAOYSA-N ethanolate;germanium(4+) Chemical compound [Ge+4].CC[O-].CC[O-].CC[O-].CC[O-] CTCOPPBXAFHGRB-UHFFFAOYSA-N 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- IBENSVMKFVWLLF-UHFFFAOYSA-N germanium(4+) methanolate Chemical compound [Ge+4].[O-]C.[O-]C.[O-]C.[O-]C IBENSVMKFVWLLF-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- CHDRADPXNRULGA-UHFFFAOYSA-N naphthalene-1,3-dicarboxylic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC(C(O)=O)=C21 CHDRADPXNRULGA-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- LIYKJALVRPGQTR-UHFFFAOYSA-M oxostibanylium;chloride Chemical compound [Cl-].[Sb+]=O LIYKJALVRPGQTR-UHFFFAOYSA-M 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- HZJQZHXRILHFBL-UHFFFAOYSA-L sodium oxalate titanium(4+) Chemical compound C(C(=O)[O-])(=O)[O-].[Na+].[Ti+4] HZJQZHXRILHFBL-UHFFFAOYSA-L 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- 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
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/863—Germanium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Definitions
- the present invention relates to a polyester resin, a method for producing the same, a resin composition, a molded article, and an optical member.
- PET Polyethylene terephthalate
- NBDM norbornene diol derivative
- NBDM is easy to manufacture and is expected to be used as an optical resin raw material due to its structure.
- NBDM tends to have low polymerization reactivity in polyester formation reactions, and its applications are limited.
- NBDM tends to have low polymerization reactivity in polyester formation reactions, and its applications are limited.
- it is necessary to increase the amount of catalyst for the transesterification reaction and tighten the reaction conditions.
- There were problems such as deterioration of moldability (fluidity) and coloration of the resin.
- the present invention aims to provide a polyester resin capable of achieving both excellent mechanical properties and moldability, a method for producing the same, a resin composition, a molded article, and an optical member. do.
- Mw/Mn molecular weight dispersity
- R 1 represents an alkyl group having 1 to 3 carbon atoms
- R 2 represents an alkyl group having 1 to 8 carbon atoms
- m represents an integer of 0 to 8.
- Mw weight average molecular weight
- MVR melt volume flow rate
- ⁇ 5> The polyester resin according to any one of ⁇ 1> to ⁇ 4>, which has a flexural modulus of 3000 MPa or more.
- ⁇ 6> Any one of ⁇ 1> to ⁇ 5>, wherein the ring structure of the unit (B) derived from the diol having a ring structure is a polycyclic structure, and two hydroxyl groups are respectively bonded to different rings.
- the unit (B) derived from the diol having a ring structure is derived from at least one diol selected from the following general formula (A-1) and the following general formula (A-2), according to ⁇ 6>
- a method for producing a polyester resin according to any one of A method for producing a polyester resin, wherein the production method includes at least a transesterification step and a polycondensation step, and in the transesterification step, at least a manganese compound and a calcium compound are used as transesterification reaction catalysts.
- R 1 represents an alkyl group having 1 to 3 carbon atoms
- R 2 represents an alkyl group having 1 to 8 carbon atoms
- m represents an integer of 0 to 8.
- Diol having a straight-chain alkyl structure relative to the total amount of the dicarboxylic acid ester (A1) represented by the general formula (1), the diol (B1) having a ring structure, and the diol (C1) having a straight-chain alkyl structure The method for producing a polyester resin according to any one of ⁇ 10> to ⁇ 12>, wherein the content of (C1) is 1 to 20 mol%.
- a resin composition comprising the polyester resin according to any one of ⁇ 1> to ⁇ 9>.
- ⁇ 15> A molded article formed using the polyester resin according to any one of ⁇ 1> to ⁇ 9>.
- the present invention it is possible to provide a polyester resin capable of achieving both excellent mechanical properties and moldability, a method for producing the same, a resin composition, a molded article, and an optical member.
- this embodiment the form for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be appropriately modified and implemented within the scope of the gist thereof.
- the polyester resin of the present embodiment comprises a unit (A) derived from a dicarboxylic acid ester represented by the following general formula (1), a unit (B) derived from a diol having a cyclic structure, and a diol having a linear alkyl structure. and a unit (C) derived from and a molecular weight distribution (Mw/Mn; Mw indicates a weight average molecular weight and Mn indicates a number average molecular weight) of 2.3 to 2.5.
- Mw/Mn molecular weight distribution
- R 1 represents an alkyl group having 1 to 3 carbon atoms
- R 2 represents an alkyl group having 1 to 8 carbon atoms
- m represents an integer of 0 to 8.
- the polyester resin of the present embodiment is a norbornene diol derivative (NBDM) and a diol having a decahydro-1,4,5,8-dimethanonaphthalene ring skeleton (hereinafter sometimes referred to as "a diol having a dinorbornane ring”). ) and other units derived from a specific diol compound, and are excellent in mechanical properties such as strength relative to molecular weight. Therefore, it is possible to achieve both excellent mechanical properties such as bending strength, bending elastic modulus and Tg (heat resistance) and fluidity (moldability).
- NBDM norbornene diol derivative
- a diol having a decahydro-1,4,5,8-dimethanonaphthalene ring skeleton hereinafter sometimes referred to as "a diol having a dinorbornane ring”
- polyester resins are often industrially continuously supplied to a mold to form a molded article when producing a molded article.
- continuous molding is usually carried out by adjusting the temperature, molding speed, etc. in consideration of the physical properties of the molding resin.
- the molding resin has low strength, fluidity, etc.
- the allowable range of temperature and molding speed conditions is narrow, which is disadvantageous in terms of production.
- the polyester resin of the present embodiment has high heat resistance, high strength and excellent fluidity, and therefore has a wide allowable range of temperature and molding speed conditions during continuous molding and is excellent in continuous moldability.
- NBDM is attracting attention as an optical resin raw material because of its structure.
- the method for producing a polyester resin of the present embodiment at least a manganese compound and a calcium compound are used as transesterification reaction catalysts in the transesterification reaction step, so that the molecular weight dispersity is within the range of 2.3 to 2.5. and the total amount of catalyst used can be reduced.
- the polyester resin of the present embodiment has sufficient properties (transparency, birefringence, heat resistance) as an optical material, and can be suitably used as an optical member.
- the polyester resin of the present embodiment has a unit (A) derived from a dicarboxylic acid ester represented by the general formula (1) as a unit derived from a dicarboxylic acid.
- R 1 represents an alkyl group having 1 to 3 carbon atoms
- R 2 represents an alkyl group having 1 to 8 carbon atoms
- m represents an integer of 0 to 8.
- R 1 represents an alkyl group having 1 to 3 carbon atoms.
- the alkyl group represented by R 1 is not particularly limited, but examples thereof include a methyl group, an ethyl group, and a propyl group, with a methyl group being preferred from the viewpoint of ease of transesterification.
- R 2 represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 4 to 8 carbon atoms.
- the alkyl group represented by R 2 may be a linear, branched or cyclic alkyl group, and is not particularly limited, but preferred examples include cyclic alkyl groups such as cyclopentane, cyclohexane, and norbornane. mentioned.
- m represents an integer of 0 to 8, preferably 0 to 6 from the viewpoint of reactivity.
- dicarboxylic acid (1A) represented by the general formula (1) is not particularly limited, examples thereof include the following compounds.
- the polyester resin ester of the present embodiment may contain units derived from other dicarboxylic acids in combination with the units (A).
- Units derived from other dicarboxylic acids are not particularly limited, but terephthalic acid, isophthalic acid, phthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2 ,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, dimethyl terephthalate, 2-methylterephthalic acid, biphenyldicarboxylic acid, tetralin dicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid , sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohe
- polyester resin From the viewpoint of the mechanical strength, heat resistance, and availability of the polyester resin, structural units derived from at least one selected from terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid are preferred. From the viewpoint of economy, structural units derived from terephthalic acid and isophthalic acid are more preferred, and from the viewpoint of reactivity, dimethyl terephthalate is particularly preferred.
- the proportion of the above-mentioned units (A) in the units derived from the dicarboxylic acid is 99 mol% or less, preferably 80%. or less, more preferably 60% or less, particularly preferably 50% or less.
- the polyester resin of the present embodiment contains, as diol-derived units, a unit (B) derived from a diol having a cyclic structure and a unit (C) derived from a diol having a linear alkyl structure.
- the unit (B) derived from a diol having a ring structure is not particularly limited, and is preferably derived from a diol compound having a ring structure in its main skeleton.
- the ring structure is not particularly limited, and may be either a monocyclic structure or a polycyclic structure (including condensed rings), and may be any of an alicyclic, aromatic, and heterocyclic ring.
- the unit (B) is preferably a unit derived from a diol compound in which two hydroxyl groups are bonded to non-adjacent carbon atoms. Examples of the unit (B) include diols having alicyclic and aromatic rings, bisphenols and the like.
- the unit (B) derived from a diol having a ring structure includes, for example, i) a unit derived from a diol compound in which the ring structure is a polycyclic structure and two hydroxyl groups are bonded to different rings, and ii) A unit derived from a diol compound in which the ring structure is a monocyclic structure and two hydroxyl groups are respectively bonded to non-adjacent carbon atoms.
- a unit derived from a diol having a polycyclic structure and having two hydroxyl groups bonded to different rings has a polycyclic structure and two hydroxyl groups
- a diol compound in which hydroxyl groups are bonded to different rings can be used.
- polycyclic structure means having two or more ring structures in one molecule, and includes, for example, compounds having condensed rings such as fluorene rings and norbornene rings.
- two hydroxyl groups are bonded to different rings means that the two hydroxyl groups of the diol compound are bonded to different rings. It means that a hydroxyl group is bonded to a separate ring in each ring to form.
- the unit derived from a diol compound in which the ring structure is a polycyclic structure and two hydroxyl groups are bonded to different rings for example, from the viewpoint of reducing the birefringence of the polyester resin, the following general formula (A-1 ) and units derived from a diol represented by at least one selected from the following general formula (A-2).
- Y is H, CH 3 or C 2 H 5 , preferably H or CH 3 .
- the diol compound represented by the general formula (A-1) can be synthesized, for example, according to the monomer synthesis examples described in International Publication WO2016/052370A1.
- the unit derived from a diol in which the ring structure is a polycyclic structure and two hydroxyl groups are respectively bonded to different rings includes units derived from the following diols.
- a unit derived from a diol having a monocyclic structure and having two hydroxyl groups bonded to non-adjacent carbon atoms The unit (B) has a monocyclic structure and two hydroxyl groups are attached to non-adjacent carbon atoms
- Units derived from bound diol compounds can be used.
- “monocyclic structure” means having one ring structure in one molecule, and does not include condensed rings.
- two hydroxyl groups are bonded to non-adjacent carbon atoms means that two hydroxyl groups are bonded to non-adjacent carbon atoms, particularly carbon atoms separated by one or more on the ring structure It is preferable that two hydroxyl groups are bonded to the .
- Units derived from a diol having a monocyclic structure and having two hydroxyl groups bonded to non-adjacent carbon atoms include, for example, units derived from the following diols.
- the polyester resin of the present embodiment contains, as diol-derived units, a unit (B) derived from a diol having a cyclic structure and a unit (C) derived from a diol having a linear alkyl structure.
- the straight-chain alkyl structure of the unit (C) is not particularly limited, but from the viewpoint of the boiling point, it is preferably a straight-chain alkyl structure having 2 to 6 carbon atoms, and from the viewpoint of handling properties, etc., it has 2 to 4 carbon atoms. is more preferred.
- Examples of the unit (C) include ethylene glycol, propanediol, butanediol, heptanediol, and hexanediol, and from the viewpoint of the number of carbon atoms, ethylene glycol, propanediol, and butanediol are preferred.
- the polyester resin of the present embodiment may have diol structures other than the above-described units (B) and (C) as diol structural units.
- diol structural units include structural units derived from polyether compounds and the like.
- the proportion of the total amount of the units (B) and (C) in the units derived from the diol is 20 mol% or more and 100 mol% or less. is preferably 25 mol % or less and 100 mol % or less, more preferably 30 mol % or more and 100 mol % or less, and particularly preferably 35 mol % or more and 100 mol % or less.
- the molar ratio of the units (A) to the total amount of the polyester resin of the present embodiment is preferably 20 mol % or more, more preferably 25 mol % or more, and particularly preferably 30 mol % or more.
- the molar ratio of the units (B) to the total amount of the polyester resin of the present embodiment is preferably 20 mol % or more, more preferably 25 mol % or more, and particularly preferably 30 mol % or more.
- the molar ratio of the units (C) to the total amount of the polyester resin of the present embodiment is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and particularly preferably 5 to 15 mol%.
- the polyester resin of this embodiment is mainly composed of units (A), units (B), and units (C).
- “mainly” means that the total proportion of the diol structural unit and the dicarboxylic acid structural unit in all the structural units of the polyester resin is 70 mol% or more, preferably 80 mol% or more, It is more preferably 90 mol % or more, still more preferably 100 mol %.
- the polyester resin of the present embodiment may contain units other than the units (A), (B), and (C) as long as the object of the present embodiment is not impaired.
- a unit derived from a monoalcohol a unit derived from a trihydric or higher polyhydric alcohol, a unit derived from a monocarboxylic acid, a polyvalent carboxylic acid Units derived from and units derived from oxyacids can be included.
- Examples of monoalcohols include, but are not limited to, butyl alcohol, hexyl alcohol, octyl alcohol, and the like.
- Examples of polyhydric alcohols having a valence of 3 or more include, but are not limited to, trimethylolpropane, glycerin, 1,3,5-pentanetriol, and pentaerythritol.
- Examples of monocarboxylic acids include, but are not limited to, benzoic acid, propionic acid, butyric acid, and the like.
- Examples of polyvalent carboxylic acids include, but are not limited to, trimellitic acid, pyromellitic acid, and the like.
- Examples of hydroxy acids include, but are not limited to, glycolic acid, lactic acid, hydroxybutyric acid, 2-hydroxyisobutyric acid, hydroxybenzoic acid, and the like.
- the polyester resin of this embodiment has a molecular weight distribution (Mw/Mn) of 2.3 to 2.5.
- Mw/Mn molecular weight distribution
- the degree of dispersion is in the range of 2.3 to 2.5, the flexural strength relative to the weight average molecular weight is high, and both excellent fluidity and flexural strength can be achieved.
- the molecular weight dispersity is not particularly limited, it is more preferably 2.30 to 2.45, particularly preferably 2.3 to 2.4.
- the glass transition temperature (Tg) of the polyester resin of the present embodiment is not particularly limited, but from the viewpoint of heat resistance compared to PET etc., it is preferably 90 ° C. or higher, and 140 ° C. or higher. is preferred, and 145°C or higher is particularly preferred.
- the upper limit of the glass transition temperature (Tg) is not particularly limited, but from the viewpoint of handleability, etc., it is preferably 180 ° C. or less, preferably 175 ° C. or less, and particularly 170 ° C. or less. preferable.
- the glass transition temperature can be appropriately measured by a known method, for example, it can be measured according to the method described in Examples below.
- the polyester resin of the present embodiment is not particularly limited, but from the viewpoint of moldability strength, it is preferable that the weight average molecular weight (Mw) is 45,000 to 80,000, and 48,000 to 80 ,000, and particularly preferably 50,000 to 80,000.
- the polyester resin of the present embodiment is not particularly limited, but from the viewpoint of achieving both fluidity and strength, the number average molecular weight (Mn) is preferably 18,000 to 32,000. 000 to 33,000, and particularly preferably 21,000 to 34,000.
- the number-average molecular weight and weight-average molecular weight can be appropriately measured by known methods, for example, according to the methods described in the examples below.
- the polyester resin of the present embodiment is not particularly limited, but from the viewpoint of moldability, the MVR is preferably 20 to 60 cm 3 /10 min, more preferably 25 to 50 cm 3 /10 min. Especially preferred is 30 to 45 cm 3 /10 min. MVR can be appropriately measured by a known method, for example, it can be measured according to the method described in Examples below.
- the polyester resin of the present embodiment is not particularly limited, but from the viewpoint of the strength of the molded product, the bending elastic modulus (MPa) of the molded product is preferably 3000 MPa or more, and 3,100 MPa or more. is more preferable, and 3,200 MPa or more is particularly preferable.
- the upper limit of the bending elastic modulus (MPa) is preferably 4,500 MPa or less, more preferably 4,200 MPa or less, from the viewpoint of formability during film formation.
- the flexural modulus (MPa) of the compact can be 3000 MPa or more and 4500 MPa or less, 3100 MPa or more and 4200 MPa or less, or 3200 MPa or more and 4200 MPa or less.
- the polyester resin of the present embodiment is not particularly limited, but from the viewpoint of the strength of the molded article, the bending strength (MPa) of the molded article is preferably 75 MPa or more, more preferably 80 MPa or more. , 82 MPa or more.
- the upper limit of the bending strength (MPa) is preferably 150 MPa or less, more preferably 120 MPa or less.
- the bending strength (MPa) of the compact can be 75 MPa or more and 150 MPa or less, 80 MPa or more and 120 MPa or less, or 82 MPa or more and 120 MPa or less.
- the flexural modulus and flexural strength can be appropriately measured by known methods, for example, according to the methods described in the examples below.
- the polyester resin of the present embodiment is not particularly limited, but from the viewpoint of an index showing fluidity per strength, it is preferable that the melt volume flow rate (MVR) / bending strength is 0.5 or more. It is preferably 0.51 or more, and particularly preferably 0.52 or more.
- the polyester resin of the present embodiment is not particularly limited, but from the viewpoint of reducing the curvature of the lens, the molded product preferably has a refractive index (nd) of 1.53 to 1.63. It is more preferably 53 to 1.61, particularly preferably 1.53 to 1.605.
- the refractive index can be appropriately measured by a known method, for example, it can be measured according to the method described in Examples below.
- the polyester resin of the present embodiment is not particularly limited, but from the viewpoint of the performance of the lens unit, the birefringence (nm) of the molded product is preferably 100 or less, more preferably 80 or less. , 60 or less. Birefringence can be appropriately measured by a known method, for example, according to the method described in Examples below.
- the polyester resin of the present embodiment preferably has a YI value of 15 or less at a thickness of 3 mm measured by a reflection method according to JIS K7103, and is 10 or less from the viewpoint of making the resin a particularly good hue. is more preferable, and 8 or less is particularly preferable.
- preparation of the YI value of the polyester resin is not particularly limited, but it can be appropriately adjusted, for example, by adjusting the total amount of the transesterification reaction catalyst used, the amount of the phosphorus compound added, and the like.
- the YI value can be appropriately measured by a known method, for example, it can be measured according to the method described in Examples below.
- the polyester resin of the present embodiment contains units (A) to (C), and the molecular weight distribution of the polyester resin of the present embodiment (Mw/Mn; Mw represents the weight average molecular weight, and Mn represents the number average molecular weight. ) can be 2.3 to 2.5, the manufacturing method is not particularly limited, and conventionally known methods can be applied. Examples thereof include a melt polymerization method such as an ester exchange method and a direct esterification method, or a solution polymerization method. Various stabilizers such as transesterification catalysts, esterification catalysts, etherification inhibitors, heat stabilizers and light stabilizers, polymerization modifiers and the like can also be conventionally known ones.
- the method for producing the polyester resin of the present embodiment includes a dicarboxylic acid ester (A1) represented by the above general formula (1) and a ring structure and a diol (C1) having a linear alkyl structure, and including at least a transesterification step and a polycondensation step, wherein in the transesterification step, at least a manganese compound and a calcium compound is used as a transesterification catalyst.
- A1 dicarboxylic acid ester represented by the above general formula (1) and a ring structure and a diol (C1) having a linear alkyl structure
- the production method of the present embodiment includes a transesterification step.
- a dicarboxylic acid ester (A1) represented by the general formula (1), a diol (B1) having a cyclic structure, and a diol (C1) having a linear alkyl structure are reacted in the presence of a transesterification reaction catalyst.
- a step of transesterification As the reaction conditions in the transesterification step, known ones can be appropriately adopted, and for example, the temperature can be 180 to 260° C. (preferably 200 to 250° C.) under normal pressure.
- the total amount of the dicarboxylic acid ester (A1) represented by the general formula (1), the diol (B1) having a cyclic structure, and the diol (C1) having a linear alkyl structure (A1 + B1 + C1)) From the viewpoint of the reactivity of the diol (C-1), the charged amount of the diol (C1) having a chain alkyl structure is, for example, preferably 1 to 20 mol%, more preferably 3 to 15 mol%, and 5 to 10%. is particularly preferred.
- the molar ratio (A1/B1+C1) between the dicarboxylic acid ester (A1) and the diol component (diol B1+diol C1) is preferably 2.0 to 3.0, for example, from the viewpoint of reactivity. 2.0 to 2.5 are more preferred.
- the molar ratio (B1/C1) between the diol (B1) and the diol (C1) is, from the viewpoint of reactivity, preferably 10/1 to 3/1, and 10/1 to 6/1 is more preferred.
- the transesterification reaction step at least a manganese compound and a calcium compound are used as transesterification reaction catalysts.
- the obtained polyester resin has a molecular weight distribution of 2.3 to 2.5, and mechanical properties and moldability In addition, it is possible to produce polyester resins with good optical properties.
- manganese compound used as the transesterification reaction catalyst a known catalyst can be appropriately selected and used.
- Manganese oxide can be mentioned, and from the viewpoint of reactivity and availability, manganese acetate tetrahydrate is preferred.
- a known catalyst can be appropriately selected and used, and examples thereof include fatty acid calcium salts such as calcium acetate, calcium carbonate, calcium chloride, and calcium hydroxide. , reactivity and availability, calcium acetate is preferred.
- the total amount of the transesterification reaction catalyst used in the transesterification reaction step is preferably 130 ppm or less from the viewpoint of suppressing the coloring of the obtained polyester resin and enhancing the optical properties. Specifically, 60 to 130 ppm is more preferable, and 60 to 120 ppm is particularly preferable. Further, the molar ratio (m/c) of the manganese compound (m) and the calcium compound (c) in the transesterification step is, from the viewpoint of reactivity, preferably 2/1 to 4/1, and 3/1 to 4/1 is more preferred.
- the production method of this embodiment includes a polycondensation step.
- the polycondensation step is a step of polycondensing the products of dicarboxylic acid ester (A1), diol (B1) and (C1) obtained in the transesterification reaction step under reduced pressure of the polycondensation catalyst by reducing the pressure and increasing the temperature. is.
- the site derived from the diol (C1) in the product is replaced with the site derived from the diol (B1) during the polycondensation, and the polymerization reaction progresses.
- An alkyl diol derived from the diol (C1) generated by the reaction is discharged out of the system.
- reaction conditions in the polycondensation step known conditions can be appropriately adopted.
- the reaction temperature in the polycondensation step depends on the type and amount of catalyst used, but is usually selected in the range of 150°C to 300°C, preferably 180°C to 280°C in view of the reaction rate and coloration of the resin. It is preferable that the pressure in the reaction vessel is finally adjusted to 1 kPa or less from the atmosphere, and finally to 0.5 kPa or less.
- a known polycondensation catalyst used in the production of polyester can be appropriately selected and used.
- it is selected from the group consisting of germanium, antimony, manganese and titanium.
- Germanium-containing catalysts include germanium dioxide, germanium tetroxide, germanium tetramethoxide, germanium tetraethoxide, germanium tetrapropoxide, germanium tetrabutoxide, germanium tetrapentoxide, germanium, and tetrahexoxide. is preferred.
- antimony-containing catalysts examples include antimony trioxide, antimony acetate, antimony tartrate, antimony potassium tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, and triphenylantimony, with antimony trioxide being preferred.
- Catalysts containing titanium include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, tetra-t-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate.
- titanium alkoxide such as tetrabenzyl titanate, titanium oxide obtained by hydrolysis of titanium alkoxide, titanium-silicon and/or zirconium composite obtained by hydrolysis of a mixture of titanium alkoxide and silicon alkoxide and/or zirconium alkoxide oxides, titanium acetate, titanium oxalate, potassium titanium oxalate, sodium titanium oxalate, potassium titanate, sodium titanate, titanic acid-aluminum hydroxide mixture, titanium chloride, titanium chloride-aluminum chloride mixture, titanium bromide, Examples include titanium fluoride, potassium hexafluorotitanate, cobalt hexafluorotitanate, manganese hexafluorotitanate, ammonium hexafluorotitanate, and titanium acetylacetonate. Among them, tetra-n-butyl titanate is preferred. .
- the polycondensation catalyst is preferably antimony and germanium from the viewpoint of increasing the molecular weight of the polyester resin, and germanium from the viewpoint of suppressing deterioration of the color tone of the polyester.
- the total amount of the polycondensation catalyst used in the polycondensation step is preferably 1,000 ppm or less from the viewpoint of suppressing the coloring of the obtained polyester resin and improving the optical properties, and specifically, 100 to 900 ppm. Preferably, 100 to 700 ppm is particularly preferred.
- a phosphorus compound may be added during the polymerization reaction.
- phosphorus compounds include, but are not limited to, phosphoric acid, phosphorous acid, phosphate esters, and phosphite esters.
- Phosphates include, but are not limited to, methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, diphenyl phosphate, trimethyl phosphate, Triethyl phosphate, tributyl phosphate, triphenyl phosphate and the like can be mentioned.
- Phosphites include, but are not limited to, methyl phosphite, ethyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite and the like. These can be used individually or in combination of 2 or more types.
- the concentration of phosphorus atoms in the polyester resin of the present embodiment is preferably 1 to 500 ppm, more preferably 3 to 400 ppm, even more preferably 5 to 200 ppm.
- the phosphorus atoms contained in the polyester resin of this embodiment may be contained at any timing during the production of the resin. Although not particularly limited, for example, at the time of raw material charging, at the start or during the transesterification or esterification reaction, at the start, during or at the end of the polycondensation reaction, by adding a phosphorus compound to the reaction system, the phosphorus compound is added to the polyester resin. It can contain atoms.
- various stabilizers such as etherification inhibitors, heat stabilizers, and light stabilizers, polymerization modifiers, and the like can be used during the production of the polyester resin of the present embodiment.
- the polyester resin of this embodiment can be used as a resin composition containing a polyester resin for various purposes.
- the resin composition containing the polyester resin of the present embodiment may contain only one type of the polyester resin of the present embodiment, or may contain two or more types.
- the resin composition contains an antioxidant, a light stabilizer, an ultraviolet absorber, a plasticizer, an extender, a delustering agent, a drying control agent, and an antistatic agent, as long as the effects of the polyester resin of the present embodiment are not impaired. , anti-settling agents, surfactants, flow improvers, drying oils, waxes, fillers, coloring agents, reinforcing agents, surface smoothing agents, leveling agents, curing reaction accelerators, and other additives and molding aids. be able to.
- the resin composition may contain other polyester resins, polyolefin resins, polyamide resins, polycarbonate resins, acrylonitrile resins, vinyl chloride resins, vinyl acetate resins, polyacryl resins, as long as the effects of the polyester resin of the present embodiment are not impaired.
- Acid resin, polymethacrylic acid resin, polystyrene, ABS resin (acrylonitrile, butadiene, styrene copolymer resin), polyimide resin, AS resin (copolymerization of acrylonitrile, styrene) resins) and oligomers can also be added.
- the other polyester resin include polyethylene terephthalate and polybutylene terephthalate.
- the polyester resin of the present embodiment and the composition containing the polyester resin can be used in various forms in various applications, for example, as a molded article.
- the molded body may be a part or member.
- applications of the polyester resin of the present embodiment include injection moldings, extrusion moldings, press moldings, sheets, films, extrusion moldings such as pipes, bottles, foams, adhesives, adhesives, paints, etc. can be used.
- the injection-molded article may be insert-molded or two-color molded.
- the sheet may be single-layered or multi-layered, the film may be single-layered or multi-layered, may be unstretched, stretched in one direction or two directions, and may be laminated on a steel plate or the like.
- the film may be inflation molded.
- the bottle may be a direct blow bottle, an injection blow bottle, or injection molded.
- the foam can be bead foam or extruded foam.
- the polyester resin of the present embodiment is used for optical members, products used in vehicles such as automobiles, packaging materials for export and import, food packaging materials that undergo retort processing and microwave heating, and baby bottles and tableware that undergo heat sterilization. Containers and others can be preferably used.
- the molded article using the polyester resin of the present embodiment has particularly small refractive index and birefringence, and is excellent in transparency with suppressed coloring (yellow), so that it can be suitably used as an optical member.
- the optical members include lenses, films, sheets, automobile headlamps, and the like.
- Glass transition temperature (Tg) The glass transition temperature of the polyester resin was measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation, product name: DSC/TA-60WS), about 10 mg of the polyester resin was placed in a non-sealed aluminum container, and nitrogen gas (50 ml /min) The sample was heated to 280°C at a heating rate of 20°C/min. The sample was measured under the same conditions, and the glass transition temperature was defined as the temperature at which the DSC curve changed by 1/2 of the difference between the base lines before and after the transition.
- Mw and Mn Weight average molecular weight (Mw) and number average molecular weight (Mn)
- GPC gel permeation chromatography
- Resin is press-molded into a disk with a diameter of 40 mm and a thickness of 3 mm (molding conditions: 200° C., 100 kgf/cm 2 , 2 minutes), and a test piece cut at right angles is measured with a precision refractometer ( It was measured using a product name “KPR-200” manufactured by Calnew).
- the obtained polyester resin was made into a film having a thickness of 100 ⁇ m, and was uniaxially stretched 1.5 times at the glass transition temperature (Tg) of the resin +20°C.
- Tg glass transition temperature
- the retardation at 600 nm of the stretched film was measured using an ellipsometer (manufactured by JASCO Corporation, product name "M-220").
- a test piece of 80 mm ⁇ 10 mm ⁇ 3.2 mm was prepared by injection molding, and Autograph AGS-X (manufactured by Shimadzu Corporation) was used at a temperature of 23 ° C., a relative humidity of 50%, and a test speed of 2 mm / min. The flexural modulus and flexural strength of the test piece were measured under the conditions.
- YI A plate having a thickness of 3 mm was formed by injection molding using the obtained polyester resin.
- the YI value of each sample was measured using a colorimetric color difference meter (trade name: Color Meter ZE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.).
- Continuous moldability evaluation Using an injection molding machine manufactured by FANUC, continuous molding was performed with a cylinder temperature of 280° C., a mold temperature of 130° C., and a cycle time of 30 seconds. If the mold was broken when the mold was opened or the mold was not released when the mold was ejected, it was regarded as "molding failure", and the number of times of continuous molding until failure occurred was measured. Continuous moldability was evaluated according to the following criteria. A: 100 times or more of continuous molding B: 21 to 99 times of continuous molding C: 20 times or less of continuous molding
- NBDM dicarboxylic acid ester (A1): NBDM was prepared by subjecting cyclopentadiene and dimethyl maleate to a Diels-Alder reaction at 200° C. according to a known method, and reducing the unsaturated portion using nickel as a hydrogenation catalyst to synthesize the following compound.
- D-NDM (diol (B1) having a ring structure)
- a compound represented by the following formula (1a) was synthesized according to "Monomer Synthesis Example 1" of International Publication WO2016/052370A1. The resulting compound was an isomer mixture of a 2,6-position isomer (76% by mass) and a 2,7-position isomer (24% by mass).
- NBDM 203.20 g (0.730 mol)
- D-NDM 136.33 g (0.613 mol)
- EG 61.62 g (0.993 mol)
- manganese acetate tetrahydrate 0.114 g (4 .6 ⁇ 10 ⁇ 4 mol)
- calcium acetate 0.020 g (1.1 ⁇ 10 ⁇ 4 mol) are placed in a 500 mL reactor equipped with a stirrer and distiller and stirred under atmospheric pressure (760 torr) and nitrogen atmosphere. While the temperature was raised to 250° C. over 3 hours while distilling off the methanol generated by the reaction, the temperature was maintained at 250° C. for 2 hours to carry out the transesterification reaction.
- phosphoric acid 0.081 g (8.2 ⁇ 10 -4 mol) and germanium dioxide: 0.302 g (2.9 ⁇ 10 -3 mol) were added, and after the addition, temperature elevation and pressure reduction were started. bottom. While distilling off EG, the temperature was raised to 275° C. over 1.5 hours, the pressure was reduced to 1 Torr, and the temperature was maintained for 180 minutes for polycondensation reaction to obtain a polyester resin.
- Examples 2-6, Comparative Examples 1-2 Polyester resins were obtained in the same manner as in Example 1, except that in each of the examples and comparative examples, the resin type and the amount used were changed according to Table 1 below. The same evaluation as in Example 1 was performed on the obtained polyester resin. Further, as Reference Example 1, data of polycarbonate (PC) are shown.
- PC polycarbonate
- NBDM 241.81 g (0.869 mol)
- CHDM (1,4-cyclohexanedimethanol) 105.23 g (0.730 mol)
- EG 73.33 g (1.182 mol)
- manganese acetate tetrahydrate 0.114 g (4.6 ⁇ 10 ⁇ 4 mol) of substance and 0.040 g (2.3 ⁇ 10 ⁇ 4 mol) of calcium acetate are placed in a 500 mL reactor equipped with a stirrer and a distiller, and nitrogen is added at atmospheric pressure. The temperature was raised to 250° C. over 3 hours while stirring under an atmosphere, and transesterification was performed while distilling methanol generated by the reaction.
- 0.085 g (8.2 ⁇ 10 ⁇ 4 mol) of phosphoric acid and 0.302 g (2.9 ⁇ 10 ⁇ 3 mol) of germanium dioxide were added.
- the temperature was raised and the pressure was reduced, and the pressure was reduced to 275°C and 1 Torr over 1.5 hours, and then the pressure was maintained for 180 minutes to obtain a polyester resin.
- YI was 13 at a thickness of 3 mm.
- NBDM 214.62 g (0.771 mol)
- TCDDM tricyclodecanedimethanol
- EG 65.09 g (1.049 mol)
- manganese acetate tetrahydrate 0.100 g (4.1 ⁇ 10 ⁇ 4 mol) and calcium acetate: 0.020 g (1.1 ⁇ 10 ⁇ 4 mol)
- the temperature was raised to 250° C. over 3 hours while stirring at , and transesterification was carried out while distilling methanol generated by the reaction.
- YI was 12 at a thickness of 3 mm.
- NBDM 174.01 g (0.625 mol)
- SPG spiroglycol: (2,2′-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl) bis( 2,2-dimethylethanol)
- EG 52.77 g (0.850 mol)
- manganese acetate tetrahydrate 0.107 g (4.4 ⁇ 10 ⁇ 4 mol )
- calcium acetate 0.026 g (1.5 ⁇ 10 -4 mol) was placed in a 500 mL reactor equipped with a stirrer and distiller and heated to 250°C over 3 hours with stirring under nitrogen atmosphere at atmospheric pressure.
- the mixture was warmed and transesterification was carried out while distilling methanol generated by the reaction.After transesterification, phosphoric acid: 0.076 g (7.8 ⁇ 10 ⁇ 4 mol), germanium dioxide: 0.302 g (2.9 ⁇ 10 ⁇ 3 mol) was added in. After the addition, the temperature was raised and the pressure was reduced, and the pressure was reduced to 275° C. and 1 Torr over 1.5 hours, and the pressure was maintained for 180 minutes to obtain a polyester resin.
- YI was 9 at a thickness of 3 mm.
- NBDM 202.09 g (0.726 mol)
- D-NDM 135.59 g (0.610 mol)
- PG propylene glycol
- manganese acetate tetrahydrate 0 .100 g (4.1 ⁇ 10 ⁇ 4 mol)
- calcium acetate 0.020 g (1.1 ⁇ 10 ⁇ 4 mol) are placed in a 500 mL reactor equipped with a stirrer and distiller and placed under nitrogen atmosphere at atmospheric pressure. While stirring, the temperature was raised to 250° C. over 3 hours, and transesterification was carried out while distilling methanol generated by the reaction.
- the polyester resin of each example had both excellent mechanical properties (Tg, flexural modulus, flexural strength) and moldability (MVR). Moreover, the polyester resin of each example was excellent in optical properties (refractive index, birefringence, YI).
- Comparative Example 1 in which only Mn was used as the transesterification catalyst and the molecular weight dispersity was 2.64, had excellent fluidity (NVR), but had a low flexural modulus and flexural strength relative to the molecular weight. I understand. In Comparative Example 2, in which no diol having a ring structure was used, no polymer could be synthesized. Comparative Example 1, which was inferior in flexural modulus and flexural strength to molecular weight, was inferior in continuous productivity and had a high YI value.
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Abstract
Description
下記一般式(1)で示されるジカルボン酸エステルに由来する単位(A)と、
環構造を有するジオールに由来する単位(B)と、
直鎖アルキル構造を有するジオールに由来する単位(C)と、
を含み、分子量分散度(Mw/Mn;Mwは重量平均分子量を示し、Mnは数平均分子量を示す)が2.3~2.5である、ポリエステル樹脂。
(一般式(1)において、R1は、炭素数1~3のアルキル基を示す。R2は、炭素数1~8のアルキル基を示す。mは、0~8の整数を示す。)
<2>
重量平均分子量(Mw)が、45,000~80,000である、前記<1>に記載のポリエステル樹脂。
<3>
メルトボリュームフローレイト(MVR)が20~60cm3/10minである、前記<1>又は前記<2>に記載のポリエステル樹脂。
<4>
曲げ強度が75MPa以上である、前記<1>~前記<3>のいずれかに記載のポリエステル樹脂。
<5>
曲げ弾性率が3000MPa以上である、前記<1>~前記<4>のいずれかに記載のポリエステル樹脂。
<6>
前記環構造を有するジオールに由来する単位(B)の環構造が多環構造であり、2つの水酸基が各々異なる環に水酸基が結合された、前記<1>~前記<5>のいずれかに記載のポリエステル樹脂。
<7>
前記環構造を有するジオールに由来する単位(B)が、下記一般式(A-1)及び下記一般式(A-2)から選ばれる少なくとも一種で示されるジオールに由来する、前記<6>に記載のポリエステル樹脂。
(一般式(A-1)において、Yは、H、CH3又はC2H5である。)
<8>
前記環構造を有するジオールに由来する単位(B)の環構造が単環構造であり、2つの水酸基が各々隣接しない炭素原子に結合された、前記<1>~前記<5>のいずれかに記載のポリエステル樹脂。
<9>
前記直鎖アルキル構造を有するジオールに由来する単位(C)のアルキル構造が、炭素数2~6の直鎖アルキル構造である、前記<1>~前記<8>のいずれかに記載のポリエステル樹脂。
<10>
下記一般式(1)で示されるジカルボン酸エステル(A1)と、環構造を有するジオール(B1)と、直鎖アルキル構造を有するジオール(C1)と、を用いた、前記<1>~前記<9>のいずれかに記載のポリエステル樹脂の製造方法であって、
前記製造方法は、少なくともエステル交換反応工程と重縮合工程とを含み、前記エステル交換反応工程において、少なくともマンガン化合物とカルシウム化合物とをエステル交換反応触媒として用いる、ポリエステル樹脂の製造方法。
(一般式(1)において、R1は、炭素数1~3のアルキル基を示す。R2は、炭素数1~8のアルキル基を示す。mは、0~8の整数を示す。)
<11>
前記エステル交換反応工程におけるエステル交換反応触媒の総使用量が、130ppm以下である、前記<10>に記載のポリエステル樹脂の製造方法。
<12>
前記重縮合工程において、少なくともゲルマニウム化合物を重縮合反応触媒として用いる、前記<10>又は前記<11>に記載のポリエステル樹脂の製造方法。
<13>
前記一般式(1)で示されるジカルボン酸エステル(A1)と前記環構造を有するジオール(B1)と前記直鎖アルキル構造を有するジオール(C1)との総量に対する、前記直鎖アルキル構造を有するジオール(C1)の含有量が1~20モル%である、前記<10>~前記<12>のいずれかに記載のポリエステル樹脂の製造方法。
<14>
前記<1>~前記<9>のいずれかに記載のポリエステル樹脂を含む樹脂組成物。
<15>
前記<1>~前記<9>のいずれかに記載のポリエステル樹脂を用いて形成された成形体。
<16>
前記<1>~前記<9>のいずれかに記載のポリエステル樹脂を用いて形成された光学部材。
本実施形態のポリエステル樹脂は、下記一般式(1)で示されるジカルボン酸エステルに由来する単位(A)と、環構造を有するジオールに由来する単位(B)と、直鎖アルキル構造を有するジオールに由来する単位(C)と、を含み、分子量分散度(Mw/Mn;Mwは重量平均分子量を示し、Mnは数平均分子量を示す)が2.3~2.5である。以下、上述の各単位を、単に「単位(A)」等と称することがある。
これに対し、本実施形態のポリエステル樹脂は、耐熱性や強度が高く且つ流動性に優れるため、連続成形時の温度や成形速度条件の許容幅が広く連続成形性に優れる。
-一般式(1)で示されるジカルボン酸エステルに由来する単位(A)-
本実施形態のポリエステル樹脂は、ジカルボン酸に由来する単位として、一般式(1)で示されるジカルボン酸エステルに由来する単位(A)を有する。
(一般式(1)において、R1は、炭素数1~3のアルキル基を示す。R2は、炭素数1~8のアルキル基を示す。mは、0~8の整数を示す。)
一般式(1)において、R2は、炭素数1~8のアルキル基を示し、炭素数4~8のアルキル基であることが好ましい。R2が示すアルキル基は、直鎖状、分岐状又は環状のアルキル基のいずれであってもよく、特に限定はないが、例えば、シクロペンタン、シクロヘキサン、ノルボルナン等環状のアルキル基が好ましい例として挙げられる。
一般式(1)において、mは、0~8の整数を示し、反応性の観点から、0~6が好ましい。
本実施形態のポリエステル樹脂エステルは、単位(A)と併用して他のジカルボン酸に由来する単位を含んでいてもよい。他のジカルボン酸に由来する単位としては、特に限定されないが、テレフタル酸、イソフタル酸、フタル酸、1,3-ナフタレンジカルボン酸、1,4-ナフタレンジカルボン酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、2,7-ナフタレンジカルボン酸、テレフタル酸ジメチル、2-メチルテレフタル酸、ビフェニルジカルボン酸、テトラリンジカルボン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、デカンジカルボン酸、ドデカンジカルボン酸、シクロヘキサンジカルボン酸、デカリンジカルボン酸、ノルボルナンジカルボン酸、トリシクロデカンジカルボン酸、ペンタシクロドデカンジカルボン酸、3,9-ビス(1,1-ジメチル-2-カルボキシエチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカン、5-カルボキシ-5-エチル-2-(1,1-ジメチル-2-カルボキシエチル)-1,3-ジオキサン、ダイマー酸等に由来する構成単位が例示できる。ポリエステル樹脂の機械強度、耐熱性、入手容易性の観点からは、テレフタル酸、イソフタル酸、2,6-ナフタレンジカルボン酸及び1,4-シクロヘキサンジカルボン酸から選ばれる少なくとも一種に由来する構成単位が好ましく、経済性の観点からは、テレフタル酸及びイソフタル酸に由来する構成単位がさらに好ましく、反応性の観点からテレフタル酸ジメチルが特に好ましい。
本実施形態のポリエステル樹脂は、ジオールに由来する単位として、環構造を有するジオールに由来する単位(B)と、直鎖アルキル構造を有するジオールに由来する単位(C)と、を含む。
環構造を有するジオールに由来する単位(B)は特に限定されるものでないか、主骨格に環構造を有するジオール化合物に由来することが好ましい。前記環構造は特に限定はなく、単環構造、多環構造(縮合環を含む)のいずれであってもよく、更に、脂環式、芳香環、複素環のいずれであってもよい。また、単位(B)は、合成効率などの観点から、2つの水酸基が各々隣接しない炭素原子に結合されたジオール化合物に由来する単位であることが好ましい。単位(B)としては、例えば、脂環式及び芳香環を有するジオール類、ビスフェノール類等が挙げられる。
前記単位(B)としては、環構造が多環構造であり、2つの水酸基が各々異なる環に水酸基が結合されたジオール化合物を用いることができる。ここで、「多環構造」は1分子中に2以上の環構造を有することを意味し、例えば、フルオレン環やノルボルネン環などの縮合環を有る化合物も含まれる。また、「2つの水酸基が各々異なる環に水酸基が結合された」とは、ジオール化合物の2つの水酸基が各々異なる環に結合されていることを意味し、縮合環の場合には、縮合環を形成する各々環において別々の環に水酸基が結合していることを意味する。
前記単位(B)としては、単環構造であり、2つの水酸基が各々隣接しない炭素原子に結合されたジオール化合物に由来する単位を用いることができる。ここで、「単環構造」とは1分子中に1つの環構造を有することを意味し、縮合環はこれに含まれない。また、「2つの水酸基が各々隣接しない炭素原子に結合された」とは、2つの水酸基が各々隣接しない炭素原子に結合されたことを意味し、特に環構造上において1つ以上離れた炭素原子に2つの水酸基が結合していることが好ましい。
本実施形態のポリエステル樹脂は、ジオールに由来する単位として、環構造を有するジオールに由来する単位(B)と共に、直鎖アルキル構造を有するジオールに由来する単位(C)と、を含む。単位(C)が有する直鎖アルキル構造は特に限定はないが、沸点の観点から、炭素数2~6の直鎖アルキル構造であることが好ましく、取り扱い性等の観点から、炭素数2~4の直鎖アルキル構造がさらに好ましい。
本実施形態のポリエステル樹脂の総量に対する単位(A)のモル比は、流動性の点から、20モル%以上が好ましく、25モル%以上がさらに好ましく、30モル%以上が特に好ましい。
本実施形態のポリエステル樹脂の総量に対する単位(B)のモル比は、耐熱性の点から、20モル%以上が好ましく、25モル%以上がさらに好ましく、30モル%以上が特に好ましい。
本実施形態のポリエステル樹脂の総量に対する単位(C)のモル比は、反応性の点から、1~20モル%が好ましく、5~20モル%がさらに好ましく、5~15モル%が特に好ましい。
本実施形態のポリエステル樹脂は、本実施形態の目的を損なわない範囲で、単位(A)、単位(B)、単位(C)以外の他の単位を含んでいてもよい。例えば、溶融粘弾性や分子量等を調整するために、他の単位として、モノアルコールに由来する単位、3価以上の多価アルコールに由来する単位、モノカルボン酸に由来する単位、多価カルボン酸に由来する単位、オキシ酸に由来する単位を含むことができる。
(分散度(Mw/Mn))
本実施形態のポリエステル樹脂の分子量分散度(Mw/Mn)が2.3~2.5である。前記分散度が2.3~2.5の範囲内にあると、重量平均分子量に対する曲げ強度が高く、優れた流動性と曲げ強度との両立を達成することができる。前記分子量分散度は、特に限定されるものではないが、2.30~2.45がさらに好ましく、2.3~2.4が特に好ましい。
本実施形態のポリエステル樹脂のガラス転移温度(Tg)は、特に限定されるものではないが、PET等と比較した耐熱性の観点から、90℃以上であることが好ましく、140℃以上であることが好ましく、145℃以上であることが特に好ましい。また、ガラス転移温度(Tg)の上限は特に限定はないが、取り扱い性等の観点から、180℃以下であることが好ましく、175℃以下であることが好ましく、170℃以下であることが特に好ましい。
ガラス転移温度は、公知の方法によって適宜測定することができ、例えば、後述する実施例に記載の方法に従って測定することができる。
本実施形態のポリエステル樹脂は、特に限定されるものではないが、成形性の強度の観点から、重量平均分子量(Mw)が45,000~80,000であることが好ましく、48,000~80,000であることがより好ましく、50,000~80,000であることが特に好ましい。
本実施形態のポリエステル樹脂は、特に限定されるものではないが、流動性と強度とを両立させる観点から、数平均分子量(Mn)が18,000~32,000であることが好ましく、20,000~33,000であることがより好ましく、21,000~34,000であることが特に好ましい。
数平均分子量及び重量平均分子量は、公知の方法によって適宜測定することができ、例えば、後述する実施例に記載の方法に従って測定することができる。
本実施形態のポリエステル樹脂は、特に限定されるものではないが、成形性の観点から、MVRが20~60cm3/10minであることが好ましく、25~50cm3/10minであることがより好ましく、30~45cm3/10minであることが特に好ましい。
MVRは、公知の方法によって適宜測定することができ、例えば、後述する実施例に記載の方法に従って測定することができる。
本実施形態のポリエステル樹脂は、特に限定されるものではないが、成形体の強度の観点から、成形体の曲げ弾性率(MPa)が3000MPa以上であることが好ましく、3,100MPa以上であることがより好ましく、3,200MPa以上であることが特に好ましい。また、特に限定されるものではないが、前記曲げ弾性率(MPa)の上限は、フィルム化時の成形性の観点から、4,500MPa以下が好ましく、4,200MPa以下がより好ましい。例えば、成形体の曲げ弾性率(MPa)は、3000MPa以上4500MPa以下、3100MPa以上4200MPa以下、3200MPa以上4200MPa以下とすることができる。
本実施形態のポリエステル樹脂は、特に限定されるものではないが、成形体の強度の観点から、成形体の曲げ強度(MPa)が75MPa以上であることが好ましく、80MPa以上であることがより好ましく、82MPa以上であることが特に好ましい。また、特に限定されるものではないが、前記曲げ強度(MPa)の上限は、150MPa以下が好ましく、120MPa以下がより好ましい。例えば、成形体の曲げ強度(MPa)は、75MPa以上150MPa以下、80MPa以上120MPa以下、82MPa以上120MPa以下とすることができる。
曲げ弾性率及び曲げ強度は、公知の方法によって適宜測定することができ、例えば、後述する実施例に記載の方法に従って測定することができる。
本実施形態のポリエステル樹脂は、特に限定されるものではないが、レンズの曲率を小さくする観点から、成形体の屈折率(nd)が1.53~1.63であることが好ましく、1.53~1.61であることがより好ましく、1.53~1.605であることが特に好ましい。
屈折率は、公知の方法によって適宜測定することができ、例えば、後述する実施例に記載の方法に従って測定することができる。
本実施形態のポリエステル樹脂は、特に限定されるものではないが、レンズユニットの性能の観点から、成形体の複屈折(nm)が100以下であることが好ましく、80以下であることがより好ましく、60以下であることが特に好ましい。
複屈折は、公知の方法によって適宜測定することができ、例えば、後述する実施例に記載の方法に従って測定することができる。
本実施形態のポリエステル樹脂は、ペレットをJIS K7103に従って反射法にて測定される3mm厚でのYI値が15以下であることが好ましく、特に良好な色相の樹脂とする観点から、10以下であることがさらに好ましく、8以下であることが特に好ましい。
本実施形態において、ポリエステル樹脂のYI値の調製は特に限定されないが、例えば、上述したエステル交換反応触媒の総使用量やリン化合物の添加量等により適宜調整することができる。
また、YI値は、公知の方法によって適宜測定することができ、例えば、後述する実施例に記載の方法に従って測定することができる。
本実施形態のポリエステル樹脂は、単位(A)~(C)を含み、かつ、本実施形態のポリエステル樹脂の分子量分散度(Mw/Mn;Mwは重量平均分子量を示し、Mnは数平均分子量を示す)が2.3~2.5とすることができれば、製造方法は特に制限はなく、従来公知の方法を適用することができる。例えばエステル交換法、直接エステル化法等の溶融重合法、又は溶液重合法等を挙げることができる。エステル交換触媒、エステル化触媒、エーテル化防止剤、熱安定剤、光安定剤等の各種安定剤、重合調整剤等も従来既知のものを用いることができる。
本実施形態の製造方法は、エステル交換反応工程を含む。エステル交換反応工程は、エステル交換反応触媒下で、一般式(1)で示されるジカルボン酸エステル(A1)と、環構造を有するジオール(B1)と、直鎖アルキル構造を有するジオール(C1)とを、エステル交換させる工程である。
エステル交換反応工程における反応条件は公知ものを適宜採用することができるが、例えば、常圧下で、温度180~260℃(好ましくは200℃~250℃)とすることができる。
また、エステル交換反応工程におけるマンガン化合物(m)とカルシウム化合物(c)とモル比(m/c)は、反応性の観点から、例えば、2/1~4/1が好ましく、3/1~4/1がさらに好ましい。
本実施形態の製造方法は、重縮合工程を含む。重縮合工程は、重縮合触媒減圧下で、エステル交換反応工程で得られたジカルボン酸エステル(A1)、ジオール(B1)及び(C1)の生成物を、減圧、昇温によって、重縮合させる工程である。当該工程においては、重縮合時に生成物中のジオール(C1)に由来する部位がジオール(B1)に由来する部位に置き換わること重合反応が進行する。当該反応によって発生したジオール(C1)に由来するアルキルジオールは、系外に排出される。
重縮合工程における反応条件は公知ものを適宜採用することができる。なお、重縮合工程における反応温度は触媒の種類、その使用量などによるが、通常150℃から300℃の範囲で選ばれ、反応速度及び樹脂の着色を鑑みると180℃~280℃が好ましい。反応槽内の圧力は、大気雰囲気下から最終的には1kPa以下に調節し、最終的には0.5kPa以下とするのが好ましい。
ゲルマニウムを含む触媒としては、二酸化ゲルマニウム、四酸化ゲルマニウム、ゲルマニウムテトラメトキシド、ゲルマニウムテトラエトキシド、ゲルマニウムテトラプロポキシド、ゲルマニウムテトラブトキシド、ゲルマニウムテトラペンタキシド、ゲルマニウム、テトラヘキソキシドが例示され、二酸化ゲルマニウムが好ましい。
アンチモンを含む触媒としては、三酸化アンチモン、酢酸アンチモン、酒石酸アンチモン、酒石酸アンチモンカリ、オキシ塩化アンチモン、アンチモングリコレ-ト、五酸化アンチモン、トリフェニルアンチモンが例示され、三酸化アンチモンが好ましい。
チタンを含む触媒としては、テトラ-n-プロピルチタネート、テトラ-i-プロピルチタネート、テトラ-n-ブチルチタネート、テトラ-n-ブチルチタネートテトラマー、テトラ-t-ブチルチタネート、テトラシクロヘキシルチタネート、テトラフェニルチタネート、及び、テトラベンジルチタネート等のチタンアルコキシド、チタンアルコキシドの加水分解により得られるチタン酸化物、チタンアルコキシドと珪素アルコキシド及び/又はジルコニウムアルコキシドとの混合物の加水分解により得られるチタン-珪素及び/又はジルコニウム複合酸化物、酢酸チタン、シュウ酸チタン、シュウ酸チタンカリウム、シュウ酸チタンナトリウム、チタン酸カリウム、チタン酸ナトリウム、チタン酸-水酸化アルミニウム混合物、塩化チタン、塩化チタン-塩化アルミニウム混合物、臭化チタン、フッ化チタン、六フッ化チタン酸カリウム、六フッ化チタン酸コバルト、六フッ化チタン酸マンガン、六フッ化チタン酸アンモニウム、チタンアセチルアセトナートが例示され、中でも、テトラ-n-ブチルチタネートが好ましい。
本実施形態のポリエステル樹脂は、種々の目的に応じてポリエステル樹脂を含む樹脂組成物として使用することができる。本実施形態のポリエステル樹脂を含む樹脂組成物は、本実施形態のポリエステル樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。
前記樹脂組成物には、本実施形態のポリエステル樹脂の効果を損なわない範囲で、酸化防止剤、光安定剤、紫外線吸収剤、可塑剤、増量剤、艶消し剤、乾燥調節剤、帯電防止剤、沈降防止剤、界面活性剤、流れ改良剤、乾燥油、ワックス類、フィラー、着色剤、補強剤、表面平滑剤、レベリング剤、硬化反応促進剤などの各種添加剤、成形助剤を添加することができる。各種添加剤等は、1種のみ含んでいてもよいし、2種以上含んでいてもよい。
また、前記樹脂組成物には、本実施形態のポリエステル樹脂の効果を損なわない範囲で、他のポリエステル樹脂、ポリオレフィン樹脂、ポリアミド樹脂、ポリカーボネート樹脂、アクリロニトリル樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、ポリアクリル酸樹脂、ポリメタクリル酸樹脂、ポリスチレン、ABS樹脂(アクリロニトリル(Acrylonitrile)、ブタジエン(Butadiene)、スチレン(Styrene)共重合樹脂)、ポリイミド樹脂、AS樹脂(アクリロニトリル(Acrylonitrile)、スチレン (Styrene)の共重合樹脂)等の樹脂、オリゴマーを添加することもできる。前記他のポリエステル樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート等が例示される。
本実施形態のポリエステル樹脂、ポリエステル樹脂を含む組成物種々の形態で、種々の用途に用いることができ、例えば、成形体としての使用が可能である。前記成形体は部品や部材であってもよい。
例えば、本実施形態のポリエステル樹脂の用途としては、射出成形体、押し出し成形体、プレス成形体、シート、フィルム、パイプ等の押出成形体、ボトル、発泡体、粘着材、接着剤、塗料等に用いることができる。具体的には、射出成形体はインサート成形でも二色成形でもよい。シートは単層でも多層でもよく、フィルムも単層でも多層でもよく、また未延伸のものでも、一方向、又は二方向に延伸されたものでもよく、鋼板などに積層してもよい。フィルムはインフレーション成形したものでもよい。ボトルはダイレクトブローボトルでもインジェクションブローボトルでもよく、射出成形されたものでもよい。発泡体は、ビーズ発泡体でも押し出し発泡体でもよい。
本実施形態のポリエステル樹脂を用いた成形体は、特に屈折率及び複屈折が小さく、また、着色(黄色)が抑制されており透明性に優れることから、光学部材として好適に用いることができる。前記光学部材としては、例えば、レンズ、フィルム、シート、自動車ヘッドランプ等が挙げられる。
ポリエステル樹脂のガラス転移温度は、示差走査熱量計((株)島津製作所製、商品名:DSC/TA-60WS)を使用し、ポリエステル樹脂約10mgをアルミニウム製非密封容器に入れ、窒素ガス(50ml/分)気流中、昇温速度20℃/分で280℃まで加熱、溶融したものを急冷して測定用試料とした。該試料を同条件で測定し、DSC曲線の転移前後における基線の差の1/2だけ変化した温度をガラス転移温度とした。
得られたポリエステル樹脂のMw及びMnは、ゲル浸透クロマトグラフィー(GPC;東ソー(株)製「HLC8320GPC」)を用い、テトラヒドロフランを展開溶媒として、既知の分子量(分子量分布=1)の標準ポリスチレンを用いて検量線を作成した。この検量線に基づいてGPCのリテンションタイムから算出した。
東洋精機製の「MELT INDEXER T-111」を使用し、260℃、2.16kg荷重をかけて測定した。
樹脂を直径40mm、厚さ3mmの大きさの円板に、プレス成形(成形条件:200℃、100kgf/cm2、2分間)し、直角に切り出した試験片に対して、精密屈折率計(カルニュー製、製品名「KPR-200」)を用いて測定した。
得られたポリエステル樹脂を厚さ100μmのフィルムとし、樹脂のガラス転移温度(Tg)+20℃で、一軸1.5倍延伸を行った。延伸後のフィルムにつき、600nmにおける位相差を、エリプソメータ(日本分光(株)製、製品名「M-220」)を用いて測定した。
射出成形により80mm×10mm×3.2mmの試験片を作製し、オートグラフAGS-X((株)島津製作所製)を使用して、温度23℃、相対湿度50%、試験速度2mm/分の条件で試験片の曲げ弾性率及び曲げ強度を測定した。
得られたポリエステル樹脂を用いて射出成形により3mm厚のプレートを成形した。各サンプルのYI値は、一測色色差計(日本電色工業(株)製、商品名:カラーメーターZE-2000)を用いて行った。
FANUC社製の射出成形機を用いて、シリンダ温度280℃、金型温度130℃としサイクルタイム30秒に設定し連続成形を行った。
型開き時に破断していたり、突き出し時に離型しない場合は“成形不良”とみなし、成形不良が発生するまでに連続で成形できる回数を測定した。
連続成形性に関し、以下の基準に従って評価した。
A:連続成形できた回数が100回以上
B:連続成形できた回数が21~99回
C:連続成形できた回数が20回以下
モノマーとして以下の化合物を使用した。
・NBDM(ジカルボン酸エステル(A1)):
NBDMは、公知の手法に従って、シクロペンタジエンとマレイン酸ジメチルとを200℃でディールスアルダー反応を行い、水素化触媒としてニッケルを用いることで不飽和部を還元し下記化合物を合成した。
D-NDM:(環構造を有するジオール(B1))
下記式(1a)で示される化合物を国際公開WO2016/052370A1号公報の「モノマー合成例1」に従って合成した。得られた化合物は、2,6位の異性体(76質量%)と2,7位の異性体(24質量%)との異性体混合物であった。
9,9-ビス[4-(2-ヒドロキシエトキシ)フェニル]フルオレン(東京化成工業(株)製)
・DMT:テレフタル酸ジメチル(東京化成工業(株)製)
・EG:エチレングリコール
NBDM:203.20g(0.730モル)、D-NDM:136.33g(0.613モル)、EG:61.62g(0.993モル)及び酢酸マンガン四水和物:0.114g(4.6×10-4モル)、酢酸カルシウム:0.020g(1.1×10-4モル)を攪拌機及び留出装置付きの500mL反応器に入れ、大気圧(760torr)、窒素雰囲気下で撹拌しながら3時間かけて250℃まで昇温し、反応で発生するメタノールを留出させながら250℃で2時間保持し保持し、エステル交換反応を行った。エステル交換後、リン酸:0.081g(8.2×10-4モル)、二酸化ゲルマニウム:0.302g(2.9×10-3モル)を投入し、投入後に昇温と減圧とを開始した。EGを留去しながら1時間半かけて275℃まで昇温し、1Torrまで減圧した後、180分間保持して重縮合反応を行い、ポリエステル樹脂を得た。
各実施例及び比較例において、樹脂種及びその使用量を下記表1に従って変更した以外は実施例1と同様にして、ポリエステル樹脂を得た。得られたポリエステル樹脂に対し実施例1と同様の評価を行った。また、参考例1としてポリカーボネート(PC)のデータを示す。
NBDM:241.81g(0.869モル)、CHDM(1,4-シクロヘキサンジメタノール):105.23g(0.730モル)、EG:73.33g(1.182モル)および酢酸マンガン四水和物:0.114g(4.6×10-4モル)、酢酸カルシウム:0.040g(2.3×10-4モル)を攪拌機および留出装置付きの500mL反応器に入れ、大気圧、窒素雰囲気下で撹拌しながら3時間かけて250℃まで昇温し、反応で発生するメタノールを留出させながらエステル交換を行った。エステル交換後、リン酸:0.085g(8.2×10-4モル)、二酸化ゲルマニウム:0.302g(2.9×10-3モル)を投入した。投入後に昇温と減圧とを開始し、1時間半かけ275℃、1Torrまで減圧したのち180分間保持し、ポリエステル樹脂を得た。
得られたポリエステル樹脂のMw=78,000、Tg=115℃であった。Mw/Mn=2.38、MVR=50、屈折率=1.522、曲げ弾性率2,800MPa、曲げ強度110MPaであった。また3mm厚でのYIは13であった。
NBDM:214.62g(0.771モル)、TCDDM(トリシクロデカンジメタノール):127.13g(0.645モル)、EG:65.09g(1.049モル)および酢酸マンガン四水和物:0.100g(4.1×10-4モル)、酢酸カルシウム:0.020g(1.1×10-4モル)を攪拌機および留出装置付きの500mL反応器に入れ、大気圧、窒素雰囲気下で撹拌しながら3時間かけて250℃まで昇温し、反応で発生するメタノールを留出させながらエステル交換を行った。エステル交換後、リン酸:0.071g(7.3×10-4モル)、二酸化ゲルマニウム:0.302g(2.9×10-3モル)を投入した。投入後に昇温と減圧を開始し、1時間半かけ275℃、1Torrまで減圧したのち180分間保持し、ポリエステル樹脂を得た。
得られたポリエステル樹脂のMw=66,000、Tg=125℃であった。Mw/Mn=2.36、MVR=46、屈折率=1.526、曲げ弾性率3,000MPa、曲げ強度90MPaであった。また3mm厚でのYIは12であった。
NBDM:174.01g(0.625モル)、SPG(スピログリコール:(2,2’-(2,4,8,10-テトラオキサスピロ[5.5]ウンデカン-3,9-ジイル)ビス(2,2-ジメチルエタノール)):159.84g(0.525モル)、EG:52.77g(0.850モル)および酢酸マンガン四水和物:0.107g(4.4×10-4モル)、酢酸カルシウム:0.026g(1.5×10-4モル)を攪拌機および留出装置付きの500mL反応器に入れ、大気圧、窒素雰囲気下で撹拌しながら3時間かけて250℃まで昇温し、反応で発生するメタノールを留出させながらエステル交換を行った。エステル交換後、リン酸:0.076g(7.8×10-4モル)、二酸化ゲルマニウム:0.302g(2.9×10-3モル)を投入した。投入後に昇温と減圧を開始し、1時間半かけ275℃、1Torrまで減圧したのち180分間保持し、ポリエステル樹脂を得た。
得られたポリエステル樹脂のMw=55,000、Tg=131℃であった。Mw/Mn=2.38、MVR=45、屈折率=1.518、曲げ弾性率3,100MPa、曲げ強度80MPaであった。また3mm厚でのYIは9であった。
NBDM:202.09g(0.726モル)、D-NDM:135.59g(0.610モル)、PG(プロピレングリコール):75.14g(0.987モル)および酢酸マンガン四水和物:0.100g(4.1×10-4モル)、酢酸カルシウム:0.020g(1.1×10-4モル)を攪拌機および留出装置付きの500mL反応器に入れ、大気圧、窒素雰囲気下で撹拌しながら3時間かけて250℃まで昇温し、反応で発生するメタノールを留出させながらエステル交換を行った。エステル交換後、リン酸:0.071g(7.3×10-4モル)、二酸化ゲルマニウム:0.303g(2.9×10-3モル)を投入した。投入後に昇温と減圧を開始し、1時間半かけ275℃、1Torrまで減圧したのち180分間保持し、ポリエステル樹脂を得た。
得られたポリエステル樹脂のMw=56,000、Tg=146℃であった。Mw/Mn=2.32、MVR=45、屈折率=1.533、曲げ弾性率2,950MPa、曲げ強度95MPaであった。また3mm厚でのYIは11であった。
これに対し、エステル交換反応触媒としてMnのみを使用し、分子量分散度が2.64であった比較例1は、流動性(NVR)に優れるものの、分子量に対し曲げ弾性率及び曲げ強度が低いことがわかる。なお、環構造を有するジオールを用いなかった比較例2は重合体を合成できなかった。
また、分子量に対し曲げ弾性率及び曲げ強度が劣っていた比較例1は、連続性生産性に劣り、また、YI値も高いものとなった。
また、明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (16)
- 重量平均分子量(Mw)が、45,000~80,000である、請求項1に記載のポリエステル樹脂。
- メルトボリュームフローレイト(MVR)が20~60cm3/10minである、請求項1に記載のポリエステル樹脂。
- 曲げ強度が75MPa以上である、請求項1に記載のポリエステル樹脂。
- 曲げ弾性率が3000MPa以上である、請求項1に記載のポリエステル樹脂。
- 前記環構造を有するジオールに由来する単位(B)の環構造が多環構造であり、2つの水酸基が各々異なる環に水酸基が結合された、請求項1に記載のポリエステル樹脂。
- 前記環構造を有するジオールに由来する単位(B)の環構造が単環構造であり、2つの水酸基が各々隣接しない炭素原子に結合された、請求項1に記載のポリエステル樹脂。
- 前記直鎖アルキル構造を有するジオールに由来する単位(C)のアルキル構造が、炭素数2~6の直鎖アルキル構造である、請求項1に記載のポリエステル樹脂。
- 前記エステル交換反応工程におけるエステル交換反応触媒の総使用量が、130ppm以下である、請求項10に記載のポリエステル樹脂の製造方法。
- 前記重縮合工程において、少なくともゲルマニウム化合物を重縮合反応触媒として用いる、請求項10に記載のポリエステル樹脂の製造方法。
- 前記一般式(1)で示されるジカルボン酸エステル(A1)と前記環構造を有するジオール(B1)と前記直鎖アルキル構造を有するジオール(C1)との総量に対する、前記直鎖アルキル構造を有するジオール(C1)の含有量が1~20モル%である、請求項10に記載のポリエステル樹脂の製造方法。
- 請求項1~請求項9のいずれか一項に記載のポリエステル樹脂を含む樹脂組成物。
- 請求項1~請求項9のいずれか一項に記載のポリエステル樹脂を用いて形成された成形体。
- 請求項1~請求項9のいずれか一項に記載のポリエステル樹脂を用いて形成された光学部材。
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CN202280066979.5A CN118055963A (zh) | 2021-10-05 | 2022-10-04 | 聚酯树脂及其制造方法、以及树脂组合物、成型体、光学部件 |
EP22878501.0A EP4414406A1 (en) | 2021-10-05 | 2022-10-04 | Polyester resin and method for producing same, and resin composition, molded body, and optical member |
KR1020247012146A KR20240065277A (ko) | 2021-10-05 | 2022-10-04 | 폴리에스터 수지 및 그의 제조 방법, 및 수지 조성물, 성형체, 광학 부재 |
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JP2021164109A (ja) | 2020-04-02 | 2021-10-11 | アルプスアルパイン株式会社 | 音場補正方法、音場補正プログラムおよび音場補正システム |
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2022
- 2022-10-04 EP EP22878501.0A patent/EP4414406A1/en active Pending
- 2022-10-04 CN CN202280066979.5A patent/CN118055963A/zh active Pending
- 2022-10-04 JP JP2023552886A patent/JPWO2023058632A1/ja active Pending
- 2022-10-04 WO PCT/JP2022/037066 patent/WO2023058632A1/ja active Application Filing
- 2022-10-04 KR KR1020247012146A patent/KR20240065277A/ko unknown
- 2022-10-05 TW TW111137767A patent/TW202330711A/zh unknown
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JPH02253201A (ja) | 1989-03-27 | 1990-10-12 | Kuraray Co Ltd | 光学用成形品 |
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JPH0517560A (ja) | 1991-07-10 | 1993-01-26 | Arakawa Chem Ind Co Ltd | 新規ポリエステル樹脂 |
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TW202330711A (zh) | 2023-08-01 |
CN118055963A (zh) | 2024-05-17 |
JPWO2023058632A1 (ja) | 2023-04-13 |
KR20240065277A (ko) | 2024-05-14 |
EP4414406A1 (en) | 2024-08-14 |
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