JP2018168271A - Polyketone resin composition, polyketone cured product, optical element, image display device, coating material and molding - Google Patents
Polyketone resin composition, polyketone cured product, optical element, image display device, coating material and molding Download PDFInfo
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- JP2018168271A JP2018168271A JP2017066347A JP2017066347A JP2018168271A JP 2018168271 A JP2018168271 A JP 2018168271A JP 2017066347 A JP2017066347 A JP 2017066347A JP 2017066347 A JP2017066347 A JP 2017066347A JP 2018168271 A JP2018168271 A JP 2018168271A
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- Prior art keywords
- polyketone
- group
- general formula
- resin composition
- hydrocarbon group
- Prior art date
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- 229920001470 polyketone Polymers 0.000 title claims abstract description 228
- 239000011342 resin composition Substances 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims description 30
- 239000011248 coating agent Substances 0.000 title claims description 16
- 238000000576 coating method Methods 0.000 title claims description 16
- 230000003287 optical effect Effects 0.000 title claims description 15
- 238000000465 moulding Methods 0.000 title description 9
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 106
- 239000010954 inorganic particle Substances 0.000 claims abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 125000004849 alkoxymethyl group Chemical group 0.000 claims abstract description 13
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 68
- 125000001424 substituent group Chemical group 0.000 claims description 48
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- 125000002723 alicyclic group Chemical group 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002834 transmittance Methods 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 230000004888 barrier function Effects 0.000 abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 150000002430 hydrocarbons Chemical group 0.000 description 67
- 239000000047 product Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 36
- 239000000758 substrate Substances 0.000 description 34
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 23
- 239000011521 glass Substances 0.000 description 19
- 125000001931 aliphatic group Chemical group 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000178 monomer Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000004642 Polyimide Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- VGMKUVCDINAAFC-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyphenyl)benzene Chemical group COC1=CC=CC=C1C1=CC=CC=C1OC VGMKUVCDINAAFC-UHFFFAOYSA-N 0.000 description 9
- 101100459319 Arabidopsis thaliana VIII-2 gene Proteins 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- UTENGZNBNPABQE-UHFFFAOYSA-N 2-[3-(carboxymethyl)-1-adamantyl]acetic acid Chemical compound C1C(C2)CC3CC1(CC(=O)O)CC2(CC(O)=O)C3 UTENGZNBNPABQE-UHFFFAOYSA-N 0.000 description 8
- 238000007611 bar coating method Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 7
- 101100132433 Arabidopsis thaliana VIII-1 gene Proteins 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 101710148171 Pyrokinin-4 Proteins 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000004814 1,1-dimethylethylene group Chemical group [H]C([H])([H])C([*:1])(C([H])([H])[H])C([H])([H])[*:2] 0.000 description 2
- 125000004815 1,2-dimethylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([*:2])C([H])([H])[H] 0.000 description 2
- 125000004837 1-methylpentylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical group CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- 125000004838 2-methylpentylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000004839 3-methylpentylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])C([H])([H])[*:1])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- PAVQGHWQOQZQEH-UHFFFAOYSA-N adamantane-1,3-dicarboxylic acid Chemical compound C1C(C2)CC3CC1(C(=O)O)CC2(C(O)=O)C3 PAVQGHWQOQZQEH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229960000250 adipic acid Drugs 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- GPRLTFBKWDERLU-UHFFFAOYSA-N bicyclo[2.2.2]octane Chemical group C1CC2CCC1CC2 GPRLTFBKWDERLU-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- TXWRERCHRDBNLG-UHFFFAOYSA-N cubane Chemical group C12C3C4C1C1C4C3C12 TXWRERCHRDBNLG-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 2
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical group C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000001227 electron beam curing Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000011415 microwave curing Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000004043 oxo group Chemical group O=* 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
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- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
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- 238000004528 spin coating Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
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- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- GLCPRUJXNXWSRF-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene-2,6-dicarboxylic acid Chemical compound C1C(C(O)=O)CCC2CC(C(=O)O)CCC21 GLCPRUJXNXWSRF-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- GVSTYPOYHNVKHY-UHFFFAOYSA-N 2-methoxybutanoic acid Chemical compound CCC(OC)C(O)=O GVSTYPOYHNVKHY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
本発明は、ポリケトン樹脂組成物、ポリケトン硬化物、光学素子、画像表示装置、被覆材料及び成形体に関する。 The present invention relates to a polyketone resin composition, a polyketone cured product, an optical element, an image display device, a coating material, and a molded article.
主鎖に芳香環とカルボニル基とを有する芳香族ポリケトンは、優れた耐熱性と機械特性とを有しており、エンジニアリングプラスチックとして利用されている。芳香族ポリケトンに属する高分子のほとんどは、求核芳香族置換反応を利用して重合された芳香族ポリエーテルケトンであり、主鎖にエーテル結合も有している。これに対し、主鎖にエーテル結合を有していない芳香族ポリケトンは、芳香族ポリエーテルケトンよりもさらに耐熱性及び耐薬品性に優れることが知られている（例えば、特許文献１及び特許文献２参照）。 An aromatic polyketone having an aromatic ring and a carbonyl group in the main chain has excellent heat resistance and mechanical properties, and is used as an engineering plastic. Most of the polymers belonging to the aromatic polyketone are aromatic polyether ketones polymerized using a nucleophilic aromatic substitution reaction, and have an ether bond in the main chain. On the other hand, it is known that an aromatic polyketone having no ether bond in the main chain is more excellent in heat resistance and chemical resistance than aromatic polyether ketone (for example, Patent Document 1 and Patent Document). 2).
近年、脂環式ジカルボン酸と２，２’−ジアルコキシビフェニル化合物とをＦｒｉｅｄｅｌ−Ｃｒａｆｔｓアシル化により直接重合することで、高い透明性と耐熱性とを両立した芳香族ポリケトンが得られることが報告され（例えば、特許文献３参照）、光学部品への応用が期待されている。 In recent years, it has been reported that an aromatic polyketone having both high transparency and heat resistance can be obtained by directly polymerizing an alicyclic dicarboxylic acid and a 2,2′-dialkoxybiphenyl compound by Friedel-Crafts acylation. (See, for example, Patent Document 3), and application to optical components is expected.
芳香族ポリケトン等の樹脂材料を光学部品に応用する場合には、無機材料では得られない特性を発揮できることが望ましく、そのような特性としては、例えば、軽量性及び柔軟性が挙げられる。軽量性を活かした適用例としては、例えば、ポータブルデバイスのガラス代替材及びコート材が挙げられ、柔軟さを活かした適用例としては、フレキシブルディスプレイ及び有機ＥＬ（有機エレクトロルミネッセンス）ディスプレイが挙げられる。なかでも、有機ＥＬディスプレイへの樹脂材料の適用は、近年特に注目されている。 When a resin material such as an aromatic polyketone is applied to an optical component, it is desirable to exhibit characteristics that cannot be obtained with an inorganic material. Examples of such characteristics include lightness and flexibility. Examples of applications that take advantage of lightness include glass substitutes and coating materials for portable devices, and examples of applications that take advantage of flexibility include flexible displays and organic EL (organic electroluminescence) displays. Among these, application of resin materials to organic EL displays has attracted particular attention in recent years.
有機ＥＬディスプレイ等の材料には、高い透明性と耐熱性の他に、高い表面硬度並びに酸素及び水蒸気に対する高いバリア性も求められる。しかし、上記特許文献に記載されている芳香族ポリケトンから形成される膜は、透明性及び耐熱性に優れるが、表面硬度並びに酸素及び水蒸気に対するバリア性に改善の余地がある。したがって、高い透明性と耐熱性を維持しつつ、良好な表面硬度並びに酸素及び水蒸気に対する高いバリア性を有する芳香族ポリケトンの開発が望まれている。 In addition to high transparency and heat resistance, materials such as organic EL displays are required to have high surface hardness and high barrier properties against oxygen and water vapor. However, the film formed from the aromatic polyketone described in the above patent document is excellent in transparency and heat resistance, but there is room for improvement in surface hardness and barrier properties against oxygen and water vapor. Therefore, development of an aromatic polyketone having good surface hardness and high barrier property against oxygen and water vapor while maintaining high transparency and heat resistance is desired.
本発明の一形態は、上記現状に鑑みなされたものであり、硬化膜としたときに、透明性及び耐熱性に優れ、高い表面硬度並びに酸素及び水蒸気に対する高いバリア性を示すポリケトン樹脂組成物を提供することを目的とする。さらに、本発明の一形態は、透明性及び耐熱性に優れ、高い表面硬度並びに酸素及び水蒸気に対する高いバリア性を示すポリケトン硬化物並びにポリケトン硬化物を有する光学素子、画像表示装置、被覆材料及び成形体を提供することを目的とする。 One aspect of the present invention has been made in view of the above-described present situation. When a cured film is used, a polyketone resin composition having excellent transparency and heat resistance, high surface hardness, and high barrier properties against oxygen and water vapor is provided. The purpose is to provide. Furthermore, one embodiment of the present invention is a polyketone cured product that exhibits excellent transparency and heat resistance, high surface hardness, and high barrier properties against oxygen and water vapor, and an optical element, image display device, coating material, and molding having the polyketone cured product. The purpose is to provide a body.
上記課題を解決するための手段には、以下の実施態様が含まれる。
＜１＞ 下記一般式（Ｉ）で表される構造単位を主鎖に含むポリケトン、窒素原子と、前記窒素原子と結合するヒドロキシメチル基及びアルコキシメチル基からなる群より選択される少なくとも１種の基と、を有する含窒素化合物、並びに、無機粒子を含有し、
前記ポリケトン、前記含窒素化合物及び前記無機粒子の合計量１００質量部に対して、前記無機粒子の含有量が、１０質量部〜７０質量部である、ポリケトン樹脂組成物。
Means for solving the above problems include the following embodiments.
<1> At least one selected from the group consisting of a polyketone containing a structural unit represented by the following general formula (I) in the main chain, a nitrogen atom, and a hydroxymethyl group and an alkoxymethyl group bonded to the nitrogen atom A nitrogen-containing compound having a group, and inorganic particles,
The polyketone resin composition whose content of the said inorganic particle is 10 mass parts-70 mass parts with respect to 100 mass parts of total amounts of the said polyketone, the said nitrogen-containing compound, and the said inorganic particle.
〔一般式（Ｉ）中、Ｘは、置換基を有していてもよい炭素数１〜５０の２価の基を表し、Ｙは、置換基を有していてもよい炭素数１〜３０の２価の炭化水素基を表し、ｎは１〜１５００の整数を表す。〕
＜２＞ 前記無機粒子の平均粒子径が、１０ｎｍ〜２００ｎｍである、＜１＞に記載のポリケトン樹脂組成物。
＜３＞ 前記一般式（Ｉ）において、Ｘが、芳香環を含む炭素数６〜５０の２価の基である、＜１＞又は＜２＞に記載のポリケトン樹脂組成物。
＜４＞ 前記一般式（Ｉ）において、Ｘが、下記一般式（ＩＩ−１）〜下記一般式（ＩＩ−３）からなる群より選択される少なくとも１種で表される２価の基である、＜１＞〜＜３＞のいずれか１項に記載のポリケトン樹脂組成物。
[In General Formula (I), X represents a divalent group having 1 to 50 carbon atoms which may have a substituent, and Y represents 1 to 30 carbon atoms which may have a substituent. In the formula, n represents an integer of 1 to 1500. ]
<2> The polyketone resin composition according to <1>, wherein the inorganic particles have an average particle diameter of 10 nm to 200 nm.
<3> The polyketone resin composition according to <1> or <2>, wherein, in the general formula (I), X is a divalent group having 6 to 50 carbon atoms including an aromatic ring.
<4> In the general formula (I), X is a divalent group represented by at least one selected from the group consisting of the following general formula (II-1) to the following general formula (II-3). The polyketone resin composition according to any one of <1> to <3>.
〔一般式（ＩＩ−１）中、Ｒ１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｍは、それぞれ独立に、０〜３の整数を表す。〕 [In General Formula (II-1), each R 1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and each R 2 independently represents The C1-C30 hydrocarbon group which may have a substituent is represented, m represents the integer of 0-3 each independently. ]
〔一般式（ＩＩ−２）中、Ｒ１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｍは、それぞれ独立に、０〜３の整数を表し、Ｚは、酸素原子又は下記一般式（ＩＩＩ−１）〜下記一般式（ＩＩＩ−７）のいずれかで表される２価の基を表す。〕 [In General Formula (II-2), each R 1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and each R 2 independently represents Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, m represents an integer of 0 to 3 independently, and Z represents an oxygen atom or the following general formula (III-1) -The bivalent group represented by either of the following general formula (III-7) is represented. ]
〔一般式（ＩＩＩ−１）〜一般式（ＩＩＩ−７）中、Ｒ１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ３及びＲ４は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｍは、それぞれ独立に、０〜３の整数を表し、ｎは、それぞれ独立に、０〜４の整数を表し、ｐは、それぞれ独立に、０〜２の整数を表す。〕 [In General Formula (III-1) to General Formula (III-7), each R 1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, R 2 represents each independently a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R 3 and R 4 each independently have a hydrogen atom or a substituent. Each represents an integer of 0 to 3, n is independently an integer of 0 to 4, and p is independently of each other. , Represents an integer of 0-2. ]
〔一般式（ＩＩ−３）中、Ｒ５は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｎは、それぞれ独立に、０〜４の整数を表す。〕
＜５＞ 前記一般式（Ｉ）において、Ｙが、２価の飽和炭化水素基である、＜１＞〜＜４＞のいずれか１項に記載のポリケトン樹脂組成物。
＜６＞ 前記一般式（Ｉ）において、Ｙが、２価の飽和脂環式炭化水素基である、＜１＞〜＜５＞のいずれか１項に記載のポリケトン樹脂組成物。
＜７＞ 前記一般式（Ｉ）において、Ｙの炭素数が、６〜３０である、＜１＞〜＜６＞のいずれか１項に記載のポリケトン樹脂組成物。
＜８＞ 前記無機粒子が、シリカ粒子である、＜１＞〜＜７＞のいずれか１項に記載のポリケトン樹脂組成物。
＜９＞ 前記含窒素化合物の分子中に含まれる前記ヒドロキシメチル基及び前記アルコキシメチル基の総数が、２個〜６個である、＜１＞〜＜８＞のいずれか１項に記載のポリケトン樹脂組成物。
＜１０＞ 熱潜在酸発生剤をさらに含有する、＜１＞〜＜９＞のいずれか１項に記載のポリケトン樹脂組成物。
＜１１＞ 溶媒をさらに含有する、＜１＞〜＜１０＞のいずれか１項に記載のポリケトン樹脂組成物。
＜１２＞ ＜１＞〜＜１１＞のいずれか１項に記載のポリケトン樹脂組成物の硬化物である、ポリケトン硬化物。
＜１３＞ 厚さ１０μｍとしたときのヘイズが、１％未満である、＜１２＞に記載のポリケトン硬化物。
＜１４＞ ４００ｎｍの透過率が、膜厚１μｍ換算で８５％以上である、＜１２＞又は＜１３＞に記載のポリケトン硬化物。
＜１５＞ ＜１２＞〜＜１４＞のいずれか１項に記載のポリケトン硬化物を有する光学素子。
＜１６＞ ＜１２＞〜＜１４＞のいずれか１項に記載のポリケトン硬化物を有する画像表示装置。
＜１７＞ ＜１２＞〜＜１４＞のいずれか１項に記載のポリケトン硬化物を有する被覆材料。
＜１８＞ ＜１２＞〜＜１４＞のいずれか１項に記載のポリケトン硬化物を有する成形体。
[In General Formula (II-3), each R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n is each independently 0 to 4 Represents an integer. ]
<5> The polyketone resin composition according to any one of <1> to <4>, wherein Y is a divalent saturated hydrocarbon group in the general formula (I).
<6> The polyketone resin composition according to any one of <1> to <5>, wherein Y is a divalent saturated alicyclic hydrocarbon group in the general formula (I).
<7> The polyketone resin composition according to any one of <1> to <6>, wherein in general formula (I), Y has 6 to 30 carbon atoms.
<8> The polyketone resin composition according to any one of <1> to <7>, wherein the inorganic particles are silica particles.
<9> The polyketone according to any one of <1> to <8>, wherein the total number of the hydroxymethyl group and the alkoxymethyl group contained in the molecule of the nitrogen-containing compound is 2 to 6. Resin composition.
<10> The polyketone resin composition according to any one of <1> to <9>, further including a thermal latent acid generator.
<11> The polyketone resin composition according to any one of <1> to <10>, further containing a solvent.
<12> A cured polyketone, which is a cured product of the polyketone resin composition according to any one of <1> to <11>.
<13> The cured polyketone according to <12>, having a haze of less than 1% when the thickness is 10 μm.
<14> The cured polyketone according to <12> or <13>, wherein the transmittance at 400 nm is 85% or more in terms of a film thickness of 1 μm.
<15> An optical element having the cured polyketone according to any one of <12> to <14>.
<16> An image display device having the cured polyketone according to any one of <12> to <14>.
<17> A coating material having the cured polyketone according to any one of <12> to <14>.
<18> A molded article having the polyketone cured product according to any one of <12> to <14>.
本発明の一形態によれば、硬化膜としたときに、透明性及び耐熱性に優れ、高い表面硬度並びに酸素及び水蒸気に対する高いバリア性を示すポリケトン樹脂組成物を提供することができる。さらに、本発明の一形態によれば、透明性及び耐熱性に優れ、高い表面硬度並びに酸素及び水蒸気に対する高いバリア性を示すポリケトン硬化物並びにポリケトン硬化物を有する光学素子、画像表示装置、被覆材料及び成形体を提供することができる。 According to one embodiment of the present invention, it is possible to provide a polyketone resin composition that is excellent in transparency and heat resistance, and has high surface hardness and high barrier properties against oxygen and water vapor when used as a cured film. Furthermore, according to one embodiment of the present invention, a polyketone cured product that is excellent in transparency and heat resistance, exhibits high surface hardness, and a high barrier property against oxygen and water vapor, and an optical element, a display device, and a coating material having the polyketone cured product. And a molded object can be provided.
以下、本発明について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。 Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and the present invention is not limited thereto.
本開示において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
本開示に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において組成物中の各成分の含有率又は含有量は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において「層」又は「膜」との語には、当該層又は膜が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
本開示において「積層」との語は、層を積み重ねることを示し、二以上の層が結合されていてもよく、二以上の層が着脱可能であってもよい。
本開示において「平均粒子径」とは、特に断りのない場合、「平均一次粒子径」と同義である。
本開示においてポリケトン樹脂組成物の硬化物を、硬化物又はポリケトン硬化物ともいう。
本開示においてポリケトン樹脂組成物の硬化物の一形態である膜を、硬化膜又はポリケトン膜ともいう。
In the present disclosure, numerical ranges indicated using “to” indicate ranges including numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present disclosure, the content rate or content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of substances present in the composition unless otherwise specified. Means the total content or content.
In the present disclosure, the term “layer” or “film” includes only a part of the region in addition to the case where the layer or film is formed over the entire region. The case where it is formed is also included.
In the present disclosure, the term “lamination” indicates that layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.
In the present disclosure, the “average particle size” has the same meaning as the “average primary particle size” unless otherwise specified.
In the present disclosure, the cured product of the polyketone resin composition is also referred to as a cured product or a polyketone cured product.
In the present disclosure, a film that is one form of a cured product of the polyketone resin composition is also referred to as a cured film or a polyketone film.
本明細書において「複数の芳香環は相互に非共役であるか、又は相互の共役関係が弱い」とは、２つの芳香環がエーテル結合若しくはメチレン結合を介していること、又は２，２’−置換ビフェニルのように置換基による立体障害により、芳香環どうしの共役が抑えられることをいう。 In the present specification, “a plurality of aromatic rings are non-conjugated to each other or weakly conjugated to each other” means that two aromatic rings are via an ether bond or a methylene bond, or 2,2 ′ -It means that conjugation between aromatic rings is suppressed by steric hindrance by a substituent such as substituted biphenyl.
本明細書において「透明性に優れる」とは、可視光の透過性（少なくとも波長４００ｎｍの可視光の透過性）が８５％以上（膜厚１μｍ換算）であることを意味する。 In this specification, “excellent in transparency” means that the visible light transmission (at least the transmission of visible light having a wavelength of 400 nm) is 85% or more (in terms of a film thickness of 1 μm).
本明細書において「耐熱性」とは、ポリケトンを含む部材においてガラス転移温度（Ｔｇ）が少なくとも１８０℃より高いことを意味する。 In this specification, “heat resistance” means that the glass transition temperature (Tg) of the member containing polyketone is higher than at least 180 ° C.
本明細書において「高い表面硬度」とは、硬化膜の鉛筆硬度が２Ｈ以上であることを意味する。 In this specification, “high surface hardness” means that the pencil hardness of the cured film is 2H or more.
本明細書において「高いバリア性」とは、硬化膜の水蒸気透過率が５ｇ／ｍ２／ｄａｙ以下であること及び硬化膜の酸素透過率が５ｃｃ／ｍ２／ｄａｙ以下であることを意味する。 In this specification, “high barrier property” means that the water vapor permeability of the cured film is 5 g / m 2 / day or less and the oxygen permeability of the cured film is 5 cc / m 2 / day or less. .
＜ポリケトン樹脂組成物＞
本開示のポリケトン樹脂組成物は、下記一般式（Ｉ）で表される構造単位を主鎖に含むポリケトン（以下、「特定ポリケトン」ともいう）、窒素原子と、前記窒素原子と結合するヒドロキシメチル基及びアルコキシメチル基からなる群より選択される少なくとも１種の基と、を有する含窒素化合物（以下、「特定含窒素化合物」ともいう）、並びに、無機粒子を含有する。
<Polyketone resin composition>
The polyketone resin composition of the present disclosure includes a polyketone containing a structural unit represented by the following general formula (I) in the main chain (hereinafter, also referred to as “specific polyketone”), a nitrogen atom, and hydroxymethyl bonded to the nitrogen atom. A nitrogen-containing compound having at least one group selected from the group consisting of a group and an alkoxymethyl group (hereinafter also referred to as “specific nitrogen-containing compound”), and inorganic particles.
一般式（Ｉ）中、Ｘは、置換基を有していてもよい炭素数１〜５０の２価の基を表し、Ｙは、置換基を有していてもよい炭素数１〜３０の２価の炭化水素基を表し、ｎは１〜１５００の整数を表す。 In general formula (I), X represents a C1-C50 bivalent group which may have a substituent, and Y has C1-C30 which may have a substituent. A divalent hydrocarbon group is represented, and n represents an integer of 1 to 1500.
本開示のポリケトン樹脂組成物は、上記構成とすることで、硬化膜としたときに、透明性及び耐熱性に優れ、高い表面硬度並びに酸素及び水蒸気に対する高いバリア性を示す。その理由は、明らかではないが以下のように推測される。
特定ポリケトンは、主鎖にカルボニル基を含むため、耐熱性及び透明性に優れる。また、特定含窒素化合物が架橋剤として機能する場合には、ポリケトン主鎖どうしが架橋し、その結果、特定ポリケトンどうしの絡み合いが多くなり構造が密になることから、硬化膜としたとき酸素及び水蒸気に対する高いバリア性が発現すると考えられる。
The polyketone resin composition of the present disclosure is excellent in transparency and heat resistance when it is formed into a cured film, and exhibits high surface hardness and high barrier properties against oxygen and water vapor. The reason is not clear, but is presumed as follows.
Since the specific polyketone contains a carbonyl group in the main chain, it is excellent in heat resistance and transparency. Further, when the specific nitrogen-containing compound functions as a crosslinking agent, the polyketone main chains are cross-linked, and as a result, the entanglement between the specific polyketones increases and the structure becomes dense. It is considered that a high barrier property against water vapor appears.
以下、各成分について説明する。 Hereinafter, each component will be described.
（Ａ）特定ポリケトン
ポリケトン樹脂組成物は、特定ポリケトンを含有する。特定ポリケトンは、下記一般式（Ｉ）で表される構造単位を主鎖に含む。
(A) Specific polyketone The polyketone resin composition contains a specific polyketone. The specific polyketone contains a structural unit represented by the following general formula (I) in the main chain.
一般式（Ｉ）中、Ｘは、置換基を有していてもよい炭素数１〜５０の２価の基を表す。Ｙは、置換基を有していてもよい炭素数１〜３０の２価の基を表す。ｎは１〜１５００の整数を表し、２〜１０００であることが好ましく、５〜５００であることがより好ましい。なお、２価の基が置換基を有する場合、２価の基の炭素数には、置換基の炭素数を含めないものとする。以降、同様である。
ｎが２以上の場合、複数のＸ及びＹは、同じであっても異なっていてもよい。
In general formula (I), X represents a C1-C50 bivalent group which may have a substituent. Y represents a C1-C30 divalent group which may have a substituent. n represents an integer of 1 to 1500, preferably 2 to 1000, and more preferably 5 to 500. When the divalent group has a substituent, the carbon number of the divalent group does not include the carbon number of the substituent. The same applies thereafter.
When n is 2 or more, the plurality of X and Y may be the same or different.
Ｘで表される２価の基の炭素数は、１〜５０であり、１〜３０であることが好ましく、１〜２４であることがより好ましい。 The divalent group represented by X has 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, and more preferably 1 to 24 carbon atoms.
Ｘが有し得る置換基は、特に限定されず、具体的には、ハロゲン原子、炭素数１〜５のアルコキシ基、炭素数２〜５のアシル基等が挙げられる。 The substituent that X may have is not particularly limited, and specific examples include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.
Ｘで表される２価の基は、炭化水素基であることが好ましく、芳香環を含むことがより好ましい。Ｘが芳香環を有すると、より耐熱性が向上する傾向にある。 The divalent group represented by X is preferably a hydrocarbon group, and more preferably contains an aromatic ring. When X has an aromatic ring, the heat resistance tends to be further improved.
Ｘは、耐熱性が向上する観点から、芳香環を含む炭素数６〜５０の２価の基であることが好ましい。芳香環としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ナフタセン環、クリセン環、ピレン環、トリフェニレン環、ペンタセン環、ベンゾピレン環等が挙げられる。 X is preferably a C 6-50 divalent group containing an aromatic ring from the viewpoint of improving heat resistance. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a naphthacene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a pentacene ring, and a benzopyrene ring.
さらに、Ｘで表される２価の基は、複数の芳香環を含むことが好ましく、複数の芳香環は相互に非共役であるか、又は相互の共役関係が弱い２価の基（以下、「特定芳香環基」ともいう）であることがより好ましい。これにより、ポリケトン合成時に低い反応温度で良好なジアシル化を実現することができ、分子量が高く耐熱性に優れるポリケトンとなる傾向にある。特定芳香環基は、炭素数が１２〜５０であることが好ましい。 Furthermore, the divalent group represented by X preferably includes a plurality of aromatic rings, and the plurality of aromatic rings are non-conjugated to each other or have a weak conjugated relationship with each other (hereinafter, More preferably, it is also referred to as “specific aromatic ring group”. As a result, good diacylation can be realized at a low reaction temperature during the synthesis of the polyketone, and the polyketone tends to have a high molecular weight and excellent heat resistance. The specific aromatic ring group preferably has 12 to 50 carbon atoms.
Ｘとしては、下記一般式（ＩＩ−１）〜下記一般式（ＩＩ−３）からなる群より選択される少なくとも１種で表される２価の基であることが好ましい。 X is preferably a divalent group represented by at least one selected from the group consisting of the following general formula (II-1) to general formula (II-3).
一般式（ＩＩ−１）中、Ｒ１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｍは、それぞれ独立に、０〜３の整数を表す。波線を付した部分は、結合手を意味する。以降、同様である。 In General Formula (II-1), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 is independently substituted. A hydrocarbon group having 1 to 30 carbon atoms which may have a group is represented, and m independently represents an integer of 0 to 3. The part with a wavy line means a bond. The same applies thereafter.
耐熱性の観点から、Ｒ１で表される炭化水素基の炭素数は、１〜３０であり、１〜１０であることが好ましく、１〜６であることがより好ましい。なお、炭化水素基が置換基を有する場合、炭化水素基の炭素数には、置換基の炭素数を含めないものとする。以降、同様である。 From the viewpoint of heat resistance, the hydrocarbon group represented by R 1 has 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. When the hydrocarbon group has a substituent, the carbon number of the hydrocarbon group does not include the carbon number of the substituent. The same applies thereafter.
Ｒ１で表される炭化水素基としては、飽和脂肪族炭化水素基、不飽和脂肪族炭化水素基、脂環式炭化水素基等が挙げられる。 Examples of the hydrocarbon group represented by R 1 include a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, and an alicyclic hydrocarbon group.
Ｒ１で表される飽和脂肪族炭化水素基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ｓｅｃ−ペンチル基、ｎｅｏ−ペンチル基、ｔ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−イコサニル基、ｎ−トリアコンタニル基等が挙げられる。また、飽和脂肪族炭化水素基の末端部分に後述の脂環式炭化水素基を有するものであってもよい。 Examples of the saturated aliphatic hydrocarbon group represented by R 1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and n-pentyl. Group, isopentyl group, sec-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-icosanyl group, An n-triacontanyl group etc. are mentioned. Moreover, you may have the below-mentioned alicyclic hydrocarbon group in the terminal part of a saturated aliphatic hydrocarbon group.
Ｒ１で表される不飽和脂肪族炭化水素基としては、ビニル基、アリル基等のアルケニル基、エチニル基等のアルキニル基などが挙げられる。また、不飽和脂肪族炭化水素基の末端部分に後述の脂環式炭化水素基を有するものであってもよい。 Examples of the unsaturated aliphatic hydrocarbon group represented by R 1 include an alkenyl group such as a vinyl group and an allyl group, and an alkynyl group such as an ethynyl group. Moreover, you may have the below-mentioned alicyclic hydrocarbon group in the terminal part of an unsaturated aliphatic hydrocarbon group.
Ｒ１で表される脂環式炭化水素基としては、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基等のシクロアルキル基、シクロヘキセニル基等のシクロアルケニル基などが挙げられる。また、脂環式炭化水素基の環に、飽和脂肪族炭化水素基及び不飽和脂肪族炭化水素基からなる群より選択される少なくとも１種を有するものであってもよい。 Examples of the alicyclic hydrocarbon group represented by R 1 include cycloalkyl groups such as cyclohexyl group, cycloheptyl group, cyclooctyl group and norbornyl group, and cycloalkenyl groups such as cyclohexenyl group. Further, the ring of the alicyclic hydrocarbon group may have at least one selected from the group consisting of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group.
Ｒ１で表される炭化水素基が有し得る置換基は、特に限定されず、ハロゲン原子、炭素数１〜５のアルコキシ基、炭素数２〜５のアシル基等が挙げられる。 The substituent that the hydrocarbon group represented by R 1 may have is not particularly limited, and examples thereof include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms.
一般式（ＩＩ−１）中、Ｒ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表す。耐熱性の観点から、Ｒ２で表される炭化水素基の炭素数は、１〜１０であることが好ましく、１〜５であることがより好ましい。 In General Formula (II-1), each R 2 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. From the viewpoint of heat resistance, the hydrocarbon group represented by R 2 preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
Ｒ２で表される炭素数１〜３０の炭化水素基としては、Ｒ１で例示した炭素数１〜３０の炭化水素基と同様のものが挙げられる。また、Ｒ２で表される炭化水素基が有し得る置換基としては、ハロゲン原子、炭素数１〜５のアルコキシ基、炭素数２〜５のアシル基等が挙げられる。 Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 2, include the same hydrocarbon group having 1 to 30 carbon atoms exemplified for R 1. Examples of the substituent may have a hydrocarbon group represented by R 2, a halogen atom, an alkoxy group having 1 to 5 carbon atoms and an acyl group having 2 to 5 carbon atoms.
一般式（ＩＩ−１）中、ｍは、それぞれ独立に、０〜３の整数を表し、０〜２の整数であることが好ましく、０又は１であることがより好ましい。 In general formula (II-1), m represents the integer of 0-3 each independently, It is preferable that it is an integer of 0-2, and it is more preferable that it is 0 or 1.
一般式（ＩＩ−２）中、Ｒ１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｍは、それぞれ独立に、０〜３の整数を表し、Ｚは酸素原子又は下記一般式（ＩＩＩ−１）〜下記一般式（ＩＩＩ−７）のいずれかで表される２価の基を表す。 In General Formula (II-2), each R 1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and each R 2 is independently substituted. Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a group, each m independently represents an integer of 0 to 3, and Z represents an oxygen atom or the following general formula (III-1) to the following A divalent group represented by any one of the general formula (III-7) is represented.
一般式（ＩＩＩ−１）〜一般式（ＩＩＩ−７）中、Ｒ１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ３及びＲ４は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表す。
ｍは、それぞれ独立に、０〜３の整数を表し、ｎは、それぞれ独立に、０〜４の整数を表し、ｐは、それぞれ独立に、０〜２の整数を表す。
In General Formula (III-1) to General Formula (III-7), each R 1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, R 2 each independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R 3 and R 4 may each independently have a hydrogen atom or a substituent. It represents a good hydrocarbon group having 1 to 30 carbon atoms.
Each m independently represents an integer of 0 to 3, n independently represents an integer of 0 to 4, and p independently represents an integer of 0 to 2, respectively.
一般式（ＩＩＩ−１）におけるＲ３及びＲ４は、耐熱性の観点から、置換基を有していてもよい炭素数１〜５の炭化水素基であることが好ましい。Ｒ３及びＲ４で表される炭素数１〜３０の炭化水素基としては、一般式（ＩＩ−１）中のＲ１で例示した炭素数１〜３０の炭化水素基と同様のものが挙げられる。また、Ｒ３及びＲ４が有し得る置換基としては、ハロゲン原子、炭素数１〜５のアルコキシ基、炭素数２〜５のアシル基等が挙げられる。 R 3 and R 4 in the general formula (III-1) are preferably a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent from the viewpoint of heat resistance. Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 3 and R 4 include the same as the hydrocarbon group having 1 to 30 carbon atoms exemplified by R 1 in the general formula (II-1). It is done. Examples of the substituent R 3 and R 4 may have, a halogen atom, an alkoxy group having 1 to 5 carbon atoms and an acyl group having 2 to 5 carbon atoms.
一般式（ＩＩＩ−２）及び一般式（ＩＩＩ−３）におけるｎは、それぞれ独立に、０〜４の整数を表し、０〜２の整数であることが好ましく、０又は１であることがより好ましい。
一般式（ＩＩＩ−４）、一般式（ＩＩＩ−５）及び一般式（ＩＩＩ−７）におけるｐは、それぞれ独立に、０〜２の整数を表し、０又は１であることが好ましい。
N in the general formula (III-2) and the general formula (III-3) each independently represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1. preferable.
P in general formula (III-4), general formula (III-5), and general formula (III-7) represents the integer of 0-2 each independently, and it is preferable that it is 0 or 1.
一般式（ＩＩ−２）、一般式（ＩＩＩ−２）〜一般式（ＩＩＩ−７）中のＲ１、Ｒ２、及びｍのそれぞれの詳細は、一般式（ＩＩ−１）中のＲ１、Ｒ２、及びｍと同様である。 The details of each of R 1 , R 2 , and m in General Formula (II-2) and General Formula (III-2) to General Formula (III-7) are as follows: R 1 in General Formula (II-1) , R 2 and m.
一般式（ＩＩ−３）中、Ｒ５は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｎは、それぞれ独立に、０〜４の整数を表す。
耐熱性の観点から、Ｒ５で表される炭化水素基の炭素数は、１〜１０であることが好ましく、１〜５であることがより好ましい。
Ｒ５で表される炭素数１〜３０の炭化水素基としては、一般式（ＩＩ−１）中のＲ１で例示した炭素数１〜３０の炭化水素基と同様のものが挙げられる。また、Ｒ５が有し得る置換基としては、ハロゲン原子、炭素数１〜５のアルコキシ基、炭素数２〜５のアシル基等が挙げられる。
In General Formula (II-3), each R 5 independently represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, and n is each independently an integer of 0 to 4 Represents.
From the viewpoint of heat resistance, the hydrocarbon group represented by R 5 preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 5, include the same hydrocarbon groups exemplified C1-30 by formula (II-1) R 1 in. Examples of the substituent R 5 may have, a halogen atom, an alkoxy group having 1 to 5 carbon atoms and an acyl group having 2 to 5 carbon atoms.
一般式（ＩＩ−３）中、ｎは、それぞれ独立に、０〜４の整数を表し、０〜３の整数であることが好ましく、０〜２の整数であることがより好ましく、０又は１であることがさらに好ましい。 In general formula (II-3), n represents the integer of 0-4 each independently, It is preferable that it is an integer of 0-3, It is more preferable that it is an integer of 0-2, 0 or 1 More preferably.
一般式（Ｉ）において、Ｙは、置換基を有していてもよい炭素数１〜３０の２価の炭化水素基を表す。Ｙで表される２価の炭化水素基の炭素数は、４〜３０であることが好ましく、耐熱性の観点からは、６〜３０であることがより好ましい。 In general formula (I), Y represents a C1-C30 bivalent hydrocarbon group which may have a substituent. The carbon number of the divalent hydrocarbon group represented by Y is preferably 4 to 30, and more preferably 6 to 30 from the viewpoint of heat resistance.
Ｙで表される２価の炭化水素基は、透明性の観点から、２価の飽和炭化水素基を含むことが好ましい。２価の飽和炭化水素基は、２価の飽和脂肪族炭化水素基であっても、２価の飽和脂環式炭化水素基であってもよい。より高い耐熱性と透明性の両立の観点から、Ｙで表される２価の炭化水素基は、２価の飽和脂環式炭化水素基を含むことが好ましい。２価の脂環式炭化水素基は、炭素数が同じ２価の脂肪族炭化水素基に比べて嵩高いため、高い耐熱性と透明性を維持したまま、溶媒への溶解性に優れる傾向にある。
また、Ｙで表される２価の炭化水素基は、複数種の２価の飽和脂肪族炭化水素基、又は、複数種の２価の飽和脂環式炭化水素基を含んでいてもよい。また、Ｙは、２価の飽和脂肪族炭化水素基と、２価の飽和脂環式炭化水素基と、を組み合わせて含んでいてもよい。
The divalent hydrocarbon group represented by Y preferably contains a divalent saturated hydrocarbon group from the viewpoint of transparency. The divalent saturated hydrocarbon group may be a divalent saturated aliphatic hydrocarbon group or a divalent saturated alicyclic hydrocarbon group. From the viewpoint of achieving both higher heat resistance and transparency, the divalent hydrocarbon group represented by Y preferably includes a divalent saturated alicyclic hydrocarbon group. Since the divalent alicyclic hydrocarbon group is bulkier than the divalent aliphatic hydrocarbon group having the same carbon number, it tends to be excellent in solubility in a solvent while maintaining high heat resistance and transparency. is there.
The divalent hydrocarbon group represented by Y may include a plurality of types of divalent saturated aliphatic hydrocarbon groups or a plurality of types of divalent saturated alicyclic hydrocarbon groups. Y may contain a combination of a divalent saturated aliphatic hydrocarbon group and a divalent saturated alicyclic hydrocarbon group.
Ｙで表される２価の飽和脂肪族炭化水素基の炭素数は、１〜３０であり、３〜３０であることが好ましい。
２価の飽和脂肪族炭化水素基としては、メチレン基、エチレン基、トリメチレン基、メチルエチレン基、テトラメチレン基、１−メチルトリメチレン基、２−メチルトリメチレン基、エチルエチレン基、１，１−ジメチルエチレン基、１，２−ジメチルエチレン基、ペンチレン基、１−メチルテトラメチレン基、２−メチルテトラメチレン基、１−エチルトリメチレン基、２−エチルトリメチレン基、１，１−ジメチルトリメチレン基、２，２−ジメチルトリメチレン基、１，２−ジメチルトリメチレン基、プロピルエチレン基、エチルメチルエチレン基、ヘキシレン基、１−メチルペンチレン基、２−メチルペンチレン基、３−メチルペンチレン基、１−エチルテトラメチレン基、２−エチルテトラメチレン基、１−プロピルトリメチレン基、２−プロピルトリメチレン基、ブチルエチレン基、１，１−ジメチルテトラメチレン基、２，２−ジメチルテトラメチレン基、１，２−ジメチルテトラメチレン基、１，３−ジメチルテトラメチレン基、１，４−ジメチルテトラメチレン基、１，２，３−トリメチルトリメチレン基、１，１，２−トリメチルトリメチレン基、１，１，３−トリメチルトリメチレン基、１，２，２−トリメチルトリメチレン基、１−エチル−１−メチルトリメチレン基、２−エチル−２−メチルトリメチレン基、１−エチル−２−メチルトリメチレン基、２−エチル−１−メチルトリメチレン基、２，２−エチルメチルトリメチレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、イコサニレン基、トリアコンタニレン基等が挙げられる。
The divalent saturated aliphatic hydrocarbon group represented by Y has 1 to 30 carbon atoms, preferably 3 to 30 carbon atoms.
Examples of the divalent saturated aliphatic hydrocarbon group include methylene group, ethylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1,1 -Dimethylethylene group, 1,2-dimethylethylene group, pentylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethyl group Methylene group, 2,2-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, propylethylene group, ethylmethylethylene group, hexylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methyl Pentylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1-propyltrimethylene 2-propyltrimethylene group, butylethylene group, 1,1-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1, 4-dimethyltetramethylene group, 1,2,3-trimethyltrimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,3-trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group 1-ethyl-1-methyltrimethylene group, 2-ethyl-2-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 2-ethyl-1-methyltrimethylene group, 2,2-ethyl Examples thereof include a methyltrimethylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an icosanylene group and a triacontanilene group.
耐熱性の観点から、２価の飽和脂肪族炭化水素基としては、好ましくは、ヘキシレン基、メチルペンチレン基、エチルテトラメチレン基、プロピルトリメチレン基、ブチルエチレン基、ジメチルテトラメチレン基、トリメチルトリメチレン基、エチルメチルトリメチレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、イコサニレン基、トリアコンタニレン基等が挙げられる。 From the viewpoint of heat resistance, the divalent saturated aliphatic hydrocarbon group is preferably a hexylene group, methylpentylene group, ethyltetramethylene group, propyltrimethylene group, butylethylene group, dimethyltetramethylene group, trimethyltrimethyl group. Examples include a methylene group, an ethylmethyltrimethylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an icosanylene group, and a triacontanilene group.
Ｙで表される２価の飽和脂環式炭化水素基の炭素数は、３〜３０であり、４〜３０であることが好ましく、６〜３０であることがより好ましい。
２価の飽和脂環式炭化水素基としては、シクロプロパン骨格、シクロブタン骨格、シクロペンタン骨格、シクロヘキサン骨格、シクロヘプタン骨格、シクロオクタン骨格、キュバン骨格、ノルボルナン骨格、トリシクロ［５．２．１．０］デカン骨格、アダマンタン骨格、ジアダマンタン骨格、ビシクロ［２．２．２］オクタン骨格、デカヒドロナフタレン骨格等を有する２価の基が挙げられる。
Carbon number of the bivalent saturated alicyclic hydrocarbon group represented by Y is 3-30, it is preferable that it is 4-30, and it is more preferable that it is 6-30.
Examples of the divalent saturated alicyclic hydrocarbon group include cyclopropane skeleton, cyclobutane skeleton, cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cubane skeleton, norbornane skeleton, and tricyclo [5.2.1.0. And a divalent group having a decane skeleton, an adamantane skeleton, a diadamantane skeleton, a bicyclo [2.2.2] octane skeleton, a decahydronaphthalene skeleton and the like.
耐熱性の観点から、２価の飽和脂環式炭化水素基として、好ましくは、シクロヘキサン骨格、シクロヘプタン骨格、シクロオクタン骨格、キュバン骨格、ノルボルナン骨格、トリシクロ［５．２．１．０］デカン骨格、アダマンタン骨格、ジアダマンタン骨格、ビシクロ［２．２．２］オクタン骨格、デカヒドロナフタレン骨格等を有する２価の炭化水素基が挙げられる。 From the viewpoint of heat resistance, the divalent saturated alicyclic hydrocarbon group is preferably a cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cubane skeleton, norbornane skeleton, tricyclo [5.2.1.0] decane skeleton. , Divalent hydrocarbon groups having an adamantane skeleton, a diadamantane skeleton, a bicyclo [2.2.2] octane skeleton, a decahydronaphthalene skeleton, and the like.
Ｙで表される２価の炭化水素基が有し得る置換基としては、アミノ基、オキソ基、水酸基又はハロゲン原子等が挙げられる。 Examples of the substituent that the divalent hydrocarbon group represented by Y may have include an amino group, an oxo group, a hydroxyl group, and a halogen atom.
Ｙは、下記一般式（ＩＶ）及び下記一般式（Ｖ−１）〜下記一般式（Ｖ−３）からなる群より選択される少なくとも１種で表される２価の炭化水素基を少なくとも含むことが好ましく、下記一般式（ＩＶ）で表される２価の炭化水素基を少なくとも含むことがより好ましい。
一般式（ＩＶ）中、アダマンタン骨格の水素原子は、炭化水素基、アミノ基、オキソ基、水酸基又はハロゲン原子で置換されていてもよい。また、一般式（ＩＶ）中、Ｚは、それぞれ独立に、単結合、又は、置換基を有していてもよい炭素数１〜１０の２価の飽和炭化水素基を表す。
柔軟な膜が得られる観点からは、Ｚは、それぞれ独立に、置換基を有していてもよい炭素数１〜１０の２価の飽和炭化水素基であることが好ましく、耐熱性の観点から、Ｚは炭素数１〜５の２価の飽和炭化水素基であることがより好ましい。
In general formula (IV), the hydrogen atom of the adamantane skeleton may be substituted with a hydrocarbon group, an amino group, an oxo group, a hydroxyl group or a halogen atom. Moreover, in general formula (IV), Z represents a C1-C10 bivalent saturated hydrocarbon group which may have a single bond or a substituent each independently.
From the viewpoint of obtaining a flexible film, each Z is preferably independently a divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, from the viewpoint of heat resistance. , Z is more preferably a C1-C5 divalent saturated hydrocarbon group.
Ｚで表される２価の飽和炭化水素基としては、メチレン基、エチレン基、トリメチレン基、メチルエチレン基、テトラメチレン基、１−メチルトリメチレン基、２−メチルトリメチレン基、エチルエチレン基、１，１−ジメチルエチレン基、１，２−ジメチルエチレン基、ペンチレン基、１−メチルテトラメチレン基、２−メチルテトラメチレン基、１−エチルトリメチレン基、２−エチルトリメチレン基、１，１−ジメチルトリメチレン基、２，２−ジメチルトリメチレン基、１，２−ジメチルトリメチレン基、プロピルエチレン基、エチルメチルエチレン基、ヘキシレン基、１−メチルペンチレン基、２−メチルペンチレン基、３−メチルペンチレン基、１−エチルテトラメチレン基、２−エチルテトラメチレン基、１−プロピルトリメチレン基、２−プロピルトリメチレン基、ブチルエチレン基、１，１−ジメチルテトラメチレン基、２，２−ジメチルテトラメチレン基、１，２−ジメチルテトラメチレン基、１，３−ジメチルテトラメチレン基、１，４−ジメチルテトラメチレン基、１，２，３−トリメチルトリメチレン基、１，１，２−トリメチルトリメチレン基、１，１，３−トリメチルトリメチレン基、１，２，２−トリメチルトリメチレン基、１−エチル−１−メチルトリメチレン基、２−エチル−２−メチルトリメチレン基、１−エチル−２−メチルトリメチレン基、２−エチル−１−メチルトリメチレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基等が挙げられる。 Examples of the divalent saturated hydrocarbon group represented by Z include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, pentylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1 -Dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, propylethylene group, ethylmethylethylene group, hexylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1-propyltrimethyl Len group, 2-propyltrimethylene group, butylethylene group, 1,1-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group, 1,2,3-trimethyltrimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,3-trimethyltrimethylene group, 1,2,2-trimethyltrimethyl group Methylene group, 1-ethyl-1-methyltrimethylene group, 2-ethyl-2-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 2-ethyl-1-methyltrimethylene group, heptylene group, Examples include octylene group, nonylene group, decylene group and the like.
Ｚで表される２価の飽和炭化水素基が有し得る置換基としては、ハロゲン原子、炭素数１〜５のアルコキシ基、炭素数２〜５のアシル基等が挙げられる。なお、Ｚで表される２価の飽和炭化水素基が置換基を有する場合、２価の飽和炭化水素基の炭素数には置換基の炭素数を含めないものとする。以下同様である。 Examples of the substituent that the divalent saturated hydrocarbon group represented by Z may have include a halogen atom, an alkoxy group having 1 to 5 carbon atoms, and an acyl group having 2 to 5 carbon atoms. When the divalent saturated hydrocarbon group represented by Z has a substituent, the carbon number of the divalent saturated hydrocarbon group does not include the carbon number of the substituent. The same applies hereinafter.
一般式（ＩＶ）で表される２価の炭化水素基は、下記一般式（ＩＶ−１）で表される２価の炭化水素基であってもよい。
一般式（Ｖ−１）で表される２価の炭化水素基は、下記一般式（ＶＩ−１）で表される２価の炭化水素基であってもよい。
一般式（Ｖ−２）で表される２価の炭化水素基は、下記一般式（ＶＩ−２）で表される２価の炭化水素基であってもよい。
一般式（Ｖ−３）で表される２価の炭化水素基は、下記一般式（ＶＩ−３）で表される２価の炭化水素基であってもよい。
The divalent hydrocarbon group represented by the general formula (IV) may be a divalent hydrocarbon group represented by the following general formula (IV-1).
The divalent hydrocarbon group represented by the general formula (V-1) may be a divalent hydrocarbon group represented by the following general formula (VI-1).
The divalent hydrocarbon group represented by the general formula (V-2) may be a divalent hydrocarbon group represented by the following general formula (VI-2).
The divalent hydrocarbon group represented by the general formula (V-3) may be a divalent hydrocarbon group represented by the following general formula (VI-3).
一般式（ＩＶ−１）、一般式（ＶＩ−１）、一般式（ＶＩ−２）及び一般式（ＶＩ−３）におけるＺは、一般式（ＩＶ）、一般式（Ｖ−１）、一般式（Ｖ−２）及び一般式（Ｖ−３）におけるＺと同様のものが挙げられる。 Z in general formula (IV-1), general formula (VI-1), general formula (VI-2), and general formula (VI-3) represents general formula (IV), general formula (V-1), general The thing similar to Z in Formula (V-2) and General formula (V-3) is mentioned.
特定ポリケトンは、Ｙとして、上記一般式（ＩＶ）で表される２価の炭化水素基を含む一般式（Ｉ）で表される構造単位と、上記一般式（Ｖ−１）〜上記一般式（Ｖ−３）からなる群より選択される少なくとも１種で表される２価の炭化水素基を含む一般式（Ｉ）で表される構造単位と、の両方を含むポリケトンであってもよい。上記一般式（ＩＶ）で表される２価の炭化水素基と、上記一般式（Ｖ−１）〜上記一般式（Ｖ−３）からなる群より選択される少なくとも１種で表される２価の炭化水素基との両方を含むとき、一般式（ＩＶ）で表される２価の炭化水素基の含有量と、一般式（Ｖ−１）〜一般式（Ｖ−３）で表される２価の炭化水素基の総含有量との質量比（（ＩＶ）：（Ｖ−１）〜（Ｖ−３））は特に限定されない。耐熱性及び伸び率の観点から、質量比は５：９５〜９５：５であることが好ましく、耐熱性及び溶解性の観点から、５：９５〜９０：１０であることがより好ましい。 The specific polyketone is represented by the structural unit represented by the general formula (I) containing a divalent hydrocarbon group represented by the above general formula (IV) as Y, and the above general formula (V-1) to the above general formula. It may be a polyketone containing both a structural unit represented by the general formula (I) containing a divalent hydrocarbon group represented by at least one selected from the group consisting of (V-3). . 2 represented by at least one selected from the group consisting of the divalent hydrocarbon group represented by the general formula (IV) and the general formula (V-1) to the general formula (V-3). When both the valent hydrocarbon group is contained, the content of the divalent hydrocarbon group represented by the general formula (IV) and the general formula (V-1) to the general formula (V-3) The mass ratio ((IV) :( V-1) to (V-3)) with respect to the total content of divalent hydrocarbon groups is not particularly limited. From the viewpoints of heat resistance and elongation, the mass ratio is preferably 5:95 to 95: 5, and more preferably 5:95 to 90:10 from the viewpoint of heat resistance and solubility.
特定ポリケトンの重量平均分子量（Ｍｗ）は、耐熱性を維持する観点から、ポリスチレン換算の標準ＧＰＣ（ゲル浸透クロマトグラフィー、ｇｅｌ ｐｅｒｍｅａｔｉｏｎ ｃｈｒｏｍａｔｏｇｒａｐｈｙ）で５００以上であることが好ましく、より高い耐熱性と、溶媒への溶解性の観点から、１０，０００〜１，０００，０００であることがより好ましい。さらに高い耐熱性が必要な場合には、重量平均分子量（Ｍｗ）は、２０，０００〜１，０００，０００であることがさらに好ましい。特定ポリケトンの重量平均分子量（Ｍｗ）は、実施例に記載の方法で測定した値をいう。 The weight average molecular weight (Mw) of the specific polyketone is preferably 500 or more in terms of polystyrene standard GPC (gel permeation chromatography) from the viewpoint of maintaining heat resistance. From the viewpoint of solubility in water, it is more preferably 10,000 to 1,000,000. When higher heat resistance is required, the weight average molecular weight (Mw) is more preferably 20,000 to 1,000,000. The weight average molecular weight (Mw) of the specific polyketone refers to a value measured by the method described in Examples.
特定ポリケトンは、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
また、ポリケトン樹脂組成物は、特定ポリケトン以外の他のポリケトンを含んでいてもよい。以降、特定ポリケトンと他のポリケトンを総称して「ポリケトン」という場合がある。硬化膜としたときの耐熱性及び透明性の観点からは、ポリケトンの総量に対する、特定ポリケトンの含有率は、５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％以上であることがさらに好ましい。
Specific polyketone may be used individually by 1 type, and may be used in combination of 2 or more type.
Moreover, the polyketone resin composition may contain other polyketones other than the specific polyketone. Hereinafter, the specific polyketone and other polyketones may be collectively referred to as “polyketone”. From the viewpoint of heat resistance and transparency when a cured film is used, the content of the specific polyketone relative to the total amount of polyketone is preferably 50% by mass or more, more preferably 60% by mass or more, and 70 More preferably, it is at least mass%.
硬化膜としたときの透明性の観点から、ポリケトンの総含有量は、ポリケトン、特定含窒素化合物及び無機粒子の合計量１００質量部に対して、３０質量部〜９０質量部であることが好ましく、４０質量部〜８０質量部であることがより好ましい。 From the viewpoint of transparency when used as a cured film, the total content of the polyketone is preferably 30 parts by mass to 90 parts by mass with respect to 100 parts by mass of the total amount of the polyketone, the specific nitrogen-containing compound, and the inorganic particles. 40 parts by weight to 80 parts by weight is more preferable.
＜特定含窒素化合物＞
本開示のポリケトン樹脂組成物は、窒素原子と、前記窒素原子と結合するヒドロキシメチル基及びアルコキシメチル基からなる群より選択される少なくとも１種の基と、を有する含窒素化合物（特定含窒素化合物）を含有する。
特定含窒素化合物を用いると硬化物の優れた耐熱性並びに酸素及び水蒸気に対する高いバリア性の点で好ましい。特定含窒素化合物は、ヒドロキシメチル基とアルコキシメチル基の両方を有する化合物又はヒドロキシメチル基を有さずアルコキシメチル基を有する化合物が好ましく、ヒドロキシメチル基を有さずアルコキシメチル基を有する化合物がより好ましい。
<Specific nitrogen-containing compounds>
The polyketone resin composition of the present disclosure includes a nitrogen-containing compound (specific nitrogen-containing compound) having a nitrogen atom and at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group bonded to the nitrogen atom. ).
Use of a specific nitrogen-containing compound is preferable in terms of excellent heat resistance of the cured product and high barrier properties against oxygen and water vapor. The specific nitrogen-containing compound is preferably a compound having both a hydroxymethyl group and an alkoxymethyl group, or a compound having no hydroxymethyl group and having an alkoxymethyl group, more preferably a compound having no hydroxymethyl group and having an alkoxymethyl group. preferable.
特定含窒素化合物の分子中に含まれるヒドロキシメチル基及びアルコキシメチル基の総数は、１個以上であれば特に制限されない。特定含窒素化合物の分子中に含まれるヒドロキシメチル基及びアルコキシメチル基の総数は、２個〜６個であることが好ましく、硬化膜のバリア性の点から、４個〜６個であることがより好ましい。 The total number of hydroxymethyl groups and alkoxymethyl groups contained in the molecule of the specific nitrogen-containing compound is not particularly limited as long as it is 1 or more. The total number of hydroxymethyl groups and alkoxymethyl groups contained in the molecule of the specific nitrogen-containing compound is preferably 2 to 6, and 4 to 6 from the viewpoint of the barrier property of the cured film. More preferred.
アルコキシメチル基におけるアルコキシ基の炭素数は、１〜３０であることが好ましく、１〜１５であることがより好ましく、１〜１０であることがさらに好ましく、１〜３であることが特に好ましく、炭素数１であることが極めて好ましい。 The number of carbon atoms of the alkoxy group in the alkoxymethyl group is preferably 1-30, more preferably 1-15, still more preferably 1-10, and particularly preferably 1-3. It is very preferable that the number of carbon atoms is 1.
特定含窒素化合物としては、下記一般式（ＶＩＩ−１）及び下記一般式（ＶＩＩ−２）で表される化合物が挙げられる。
一般式（ＶＩＩ−１）中、Ａはｎ価の有機基を表し、Ｗ１及びＷ２は、それぞれ独立に、水素原子、下記一般式（ＶＩＩＩ−１）又は下記一般式（ＶＩＩＩ−２）で表される基であり、ｎは２又は３を表す。但し、複数のＷ１及びＷ２のうち、少なくとも１つは、下記一般式（ＶＩＩＩ−１）又は下記一般式（ＶＩＩＩ−２）で表される基であり、複数のＷ１及びＷ２のうちの２以上が、下記一般式（ＶＩＩＩ−１）又は下記一般式（ＶＩＩＩ−２）で表される基であることが好ましい。 In General Formula (VII-1), A represents an n-valent organic group, and W 1 and W 2 each independently represent a hydrogen atom, the following General Formula (VIII-1), or the following General Formula (VIII-2). And n represents 2 or 3. However, among the plurality of W 1 and W 2, at least one is a group represented by the following general formula (VIII-1) or the following general formula (VIII-2), a plurality of W 1 and W 2 Two or more of them are preferably groups represented by the following general formula (VIII-1) or the following general formula (VIII-2).
一般式（ＶＩＩＩ−２）中、Ｒ１は置換基を有していてもよい炭素数１〜３０のアルキル基を表す。Ｒ１で表されるアルキル基の炭素数は、１〜１５であることが好ましく、１〜１０であることがより好ましく、１〜３であることがさらに好ましく、１であることが特に好ましい。一般式（ＶＩＩＩ−２）中のＲ１の詳細は、一般式（ＩＩ−１）中のＲ１と同様である。 In General Formula (VIII-2), R 1 represents an alkyl group having 1 to 30 carbon atoms which may have a substituent. The number of carbon atoms of the alkyl group represented by R 1 is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 3, and particularly preferably 1. The general formula (VIII-2) of R 1 in detail, the same as R 1 in Formula (II-1).
一般式（ＶＩＩ−１）中、Ａで表される有機基としては、例えば、下記一般式（ＩＸ−１）及び下記一般式（ＩＸ−２）で表される基が挙げられる。 In the general formula (VII-1), examples of the organic group represented by A include groups represented by the following general formula (IX-1) and the following general formula (IX-2).
一般式（ＶＩＩ−２）中、Ｗ３〜Ｗ６は、それぞれ独立に、水素原子又は一般式（ＶＩＩＩ−１）又は一般式（ＶＩＩＩ−２）で表される基である。但し、Ｗ３〜Ｗ６のうち、少なくとも１つは、一般式（ＶＩＩＩ−１）又は一般式（ＶＩＩＩ−２）で表される基であり、Ｗ３〜Ｗ６のうちの２以上が、一般式（ＶＩＩＩ−１）又は一般式（ＶＩＩＩ−２）で表される基であることが好ましい。 In General Formula (VII-2), W 3 to W 6 are each independently a hydrogen atom or a group represented by General Formula (VIII-1) or General Formula (VIII-2). However, of W 3 to W-6, at least one is a group represented by the general formula (VIII-1) or general formula (VIII-2), 2 or more of W 3 to W-6 is, A group represented by general formula (VIII-1) or general formula (VIII-2) is preferable.
特定含窒素化合物としては、下記一般式（Ｘ−１）〜下記一般式（Ｘ−３）で表される化合物を例示することができる。 Examples of the specific nitrogen-containing compound include compounds represented by the following general formula (X-1) to the following general formula (X-3).
一般式（Ｘ−１）〜一般式（Ｘ−３）中、Ｒ１は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０のアルキル基を表す。Ｒ１の詳細は、一般式（ＶＩＩＩ−２）におけるＲ１と同様である。 In General Formula (X-1) to General Formula (X-3), R 1 independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent. Details of R 1, is the same as R 1 in the general formula (VIII-2).
特定含窒素化合物は、単量体又はオリゴマーであってもよく、単量体とオリゴマーの混合物であってもよい。オリゴマーとしては、例えば、一般式（Ｘ−１）〜一般式（Ｘ−３）で表される化合物（単量体）が自己反応して形成されるものが挙げられる。 The specific nitrogen-containing compound may be a monomer or an oligomer, or a mixture of a monomer and an oligomer. Examples of the oligomer include those formed by self-reaction of compounds (monomers) represented by general formula (X-1) to general formula (X-3).
特定含窒素化合物は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。特定含窒素化合物の含有量は、硬化膜としたときの耐熱性及びバリア性の観点から、特定ポリケトン、特定含窒素化合物及び無機粒子の合計量１００質量部に対して、１質量部〜５０質量部であることが好ましく、５質量部〜５０質量部であることがより好ましく、５質量部〜２０質量部であることがさらに好ましい。 A specific nitrogen-containing compound may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the specific nitrogen-containing compound is 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the specific polyketone, the specific nitrogen-containing compound and the inorganic particles from the viewpoint of heat resistance and barrier properties when used as a cured film. Part, preferably 5 parts by weight to 50 parts by weight, more preferably 5 parts by weight to 20 parts by weight.
＜熱潜在酸発生剤＞
ポリケトン樹脂組成物は、さらに熱潜在酸発生剤を含有してもよい。熱潜在酸発生剤は、加熱により酸を発生する化合物である。ポリケトン樹脂組成物が熱潜在酸発生剤を含有すると、特定含窒素化合物の架橋反応が促進され、より強固な硬化物を得ることが可能となるため、硬化膜のバリア性が向上する傾向にある。
<Heat latent acid generator>
The polyketone resin composition may further contain a thermal latent acid generator. The thermal latent acid generator is a compound that generates an acid by heating. When the polyketone resin composition contains a thermal latent acid generator, the crosslinking reaction of the specific nitrogen-containing compound is promoted, and a harder cured product can be obtained, so that the barrier property of the cured film tends to be improved. .
熱潜在酸発生剤から発生する酸としては、ｐ−トルエンスルホン酸、ベンゼンスルホン酸等のアリールスルホン酸、（±）−１０−カンファースルホン酸、トリフルオロメタンスルホン酸、ノナフルオロブタンスルホン酸等のパーフルオロアルキルスルホン酸、メタンスルホン酸、エタンスルホン酸、ブタンスルホン酸等のアルキルスルホン酸などが挙げられる。 Examples of acids generated from the thermal latent acid generator include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, and (±) -10-camphorsulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid. Examples thereof include alkyl sulfonic acids such as fluoroalkyl sulfonic acid, methane sulfonic acid, ethane sulfonic acid, and butane sulfonic acid.
熱潜在酸発生剤は、１種を単独で使用してもよく、２種以上を組み合わせて用いてもよい。熱潜在酸発生剤の含有量は、特定ポリケトン、特定含窒素化合物及び熱潜在酸発生剤の合計量１００質量部に対して、０．０５質量部〜３０質量部であることが好ましく、０．１質量部〜２０質量部であることがより好ましく、０．２質量部〜１０質量部であることがさらに好ましい。 A thermal latent acid generator may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the thermal latent acid generator is preferably 0.05 parts by mass to 30 parts by mass with respect to 100 parts by mass of the total amount of the specific polyketone, the specific nitrogen-containing compound, and the thermal latent acid generator. It is more preferably 1 part by mass to 20 parts by mass, and further preferably 0.2 part by mass to 10 parts by mass.
＜無機粒子＞
ポリケトン樹脂組成物は、無機粒子を含有する。
無機粒子としては、例えば、シリカ、アルミナ、天然マイカ、合成マイカ、タルク、酸化カルシウム、炭酸カルシウム、酸化ジルコニウム、酸化チタン、酸化アンチモン、チタン酸バリウム、カオリン、ベントナイト、珪藻土、窒化ホウ素、窒化アルミニウム、炭化ケイ素、酸化亜鉛、酸化セリウム、酸化セシウム、酸化マグネシウム、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、及びグラファイトの粒子が挙げられる。透明性の観点からは、シリカ粒子を用いることが好ましい。
無機粒子は１種を単独で使用することもできるし、２種以上を組み合わせて使用することもできる。
<Inorganic particles>
The polyketone resin composition contains inorganic particles.
Examples of inorganic particles include silica, alumina, natural mica, synthetic mica, talc, calcium oxide, calcium carbonate, zirconium oxide, titanium oxide, antimony oxide, barium titanate, kaolin, bentonite, diatomaceous earth, boron nitride, aluminum nitride, Examples include silicon carbide, zinc oxide, cerium oxide, cesium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and graphite particles. From the viewpoint of transparency, it is preferable to use silica particles.
An inorganic particle can also be used individually by 1 type, and can also be used in combination of 2 or more type.
無機粒子の形状は、特に限定されないが、ポリケトン樹脂組成物の透明性の観点から、球状が好ましい。 The shape of the inorganic particles is not particularly limited, but is preferably spherical from the viewpoint of the transparency of the polyketone resin composition.
無機粒子は、例えば、国際公開第９６／３１５７２号に記載されている火炎加水分解法、火炎熱分解法、プラズマ法等の公知の方法で製造することができる。無機粒子としては、安定化されたコロイド状無機粒子のナノ分散ゾル等を好ましく用いることができ、株式会社アドマテックス製のコロイダルシリカ、メルク社製のＴｉＯ２ゾル、日産化学工業株式会社製のＳｉＯ２、ＺｒＯ２、Ａｌ２Ｏ３及びＳｂ２Ｏ３ゾル、日本アエロジル株式会社製のシリカ（製品名、アエロジル）等の市販品が入手可能である。 The inorganic particles can be produced by a known method such as a flame hydrolysis method, a flame pyrolysis method, or a plasma method described in International Publication No. 96/31572, for example. As the inorganic particles, nano colloidal sols of stabilized colloidal inorganic particles can be preferably used, colloidal silica manufactured by Admatechs Co., Ltd., TiO 2 sol manufactured by Merck Co., Ltd., SiO manufactured by Nissan Chemical Industries, Ltd. Commercial products such as 2 , ZrO 2 , Al 2 O 3 and Sb 2 O 3 sol, and silica (product name, Aerosil) manufactured by Nippon Aerosil Co., Ltd. are available.
無機粒子は、その表面が改質されたものであってもよい。無機粒子の表面改質は、公知の表面改質剤を用いて行うことができる。このような表面改質剤としては、例えば、無機粒子の表面に存在する官能基と共有結合、錯形成等の相互作用が可能な化合物などを用いることができる。このような表面改質剤としては、例えば、分子内にカルボキシ基、（第１級、第２級又は第３級）アミノ基、４級アンモニウム基、カルボニル基、グリシジル基、ビニル基、（メタ）アクリロキシ基、メルカプト基等の官能基を有する化合物などを用いることができる。表面改質剤は、通常、標準温度及び圧力条件下で液体のものが好ましい。 The inorganic particles may have modified surfaces. The surface modification of the inorganic particles can be performed using a known surface modifier. As such a surface modifier, for example, a compound capable of interacting with a functional group present on the surface of the inorganic particles, such as a covalent bond or complex formation, can be used. Examples of such surface modifiers include carboxy groups, (primary, secondary or tertiary) amino groups, quaternary ammonium groups, carbonyl groups, glycidyl groups, vinyl groups, ) A compound having a functional group such as acryloxy group or mercapto group can be used. Usually, the surface modifier is preferably liquid under standard temperature and pressure conditions.
表面改質剤としては、ギ酸、酢酸、プロピオン酸、酪酸、ペンタン酸、ヘキサン酸、アクリル酸、メタクリル酸、クロトン酸、クエン酸、アジピン酸、コハク酸、グルタル酸、シュウ酸、マレイン酸、フマル酸等の炭素数１〜１２の飽和又は不飽和モノ及びポリカルボン酸類（好ましくは、モノカルボン酸類）；これらのエステル類（好ましくはメタクリル酸メチル等の炭素数１〜４のアルキルエステル類）；アミド類；アセチルアセトン、２，４−ヘキサンジオン、３，５−ヘプタンジオン、アセト酢酸、炭素数１〜４のアルキルアセト酢酸類等のβ−ジカルボニル化合物；シランカップリング剤などが挙げられる。 Surface modifiers include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipic acid, succinic acid, glutaric acid, oxalic acid, maleic acid, fumaric acid Saturated or unsaturated mono- and polycarboxylic acids having 1 to 12 carbon atoms such as acids (preferably monocarboxylic acids); esters thereof (preferably alkyl esters having 1 to 4 carbon atoms such as methyl methacrylate); Amides; β-dicarbonyl compounds such as acetylacetone, 2,4-hexanedione, 3,5-heptanedione, acetoacetic acid, alkyl acetoacetates having 1 to 4 carbon atoms; silane coupling agents and the like.
無機粒子の平均粒子径は特に制限されないが、１０ｎｍ〜２００ｎｍであることが好ましく、１０ｎｍ〜１５０ｎｍであることがより好ましく、１０ｎｍ〜１００ｎｍであることがさらに好ましい。１０ｎｍ以上であると所望の表面硬度が得られやすくなり、２００ｎｍ以下であるとヘイズの上昇が抑えられる傾向がある。平均粒子径が１０ｎｍ未満の無機粒子は、分散安定性上、製造が困難であり入手し難い。 The average particle diameter of the inorganic particles is not particularly limited, but is preferably 10 nm to 200 nm, more preferably 10 nm to 150 nm, and further preferably 10 nm to 100 nm. If it is 10 nm or more, a desired surface hardness can be easily obtained, and if it is 200 nm or less, an increase in haze tends to be suppressed. Inorganic particles having an average particle diameter of less than 10 nm are difficult to produce due to dispersion stability and are difficult to obtain.
本開示において、無機粒子の平均粒子径は、実施例に記載の方法を用いて、成膜した後に測定された値とする。 In the present disclosure, the average particle diameter of the inorganic particles is a value measured after film formation using the method described in the examples.
無機粒子の含有量は、特定ポリケトン、特定含窒素化合物及び無機粒子の合計量１００質量部に対して、１０質量部〜７０質量部であり、２０質量部〜６０質量部であることが好ましく、３０質量部〜６０質量部であることがより好ましい。無機粒子の含有量が１０質量部以上であるとポリケトン膜の表面硬度が効果的に向上する傾向があり、７０質量部以下であるとポリケトン膜の透明性に優れ、ヘイズの上昇が抑えられ、靭性に優れる傾向がある。 The content of the inorganic particles is 10 parts by mass to 70 parts by mass and preferably 20 parts by mass to 60 parts by mass with respect to 100 parts by mass of the total amount of the specific polyketone, the specific nitrogen-containing compound and the inorganic particles. It is more preferable that it is 30 mass parts-60 mass parts. If the content of the inorganic particles is 10 parts by mass or more, the surface hardness of the polyketone film tends to be effectively improved, and if it is 70 parts by mass or less, the polyketone film is excellent in transparency and haze increase is suppressed. There is a tendency to be excellent in toughness.
無機粒子として、安定化されたコロイド状無機粒子のナノ分散ゾル等を用いる場合、無機粒子を含む分散液をそのまま用いてもよい。 When a nano-dispersed sol of stabilized colloidal inorganic particles or the like is used as the inorganic particles, a dispersion containing inorganic particles may be used as it is.
＜溶媒＞
ポリケトン樹脂組成物は、さらに溶媒を含有してもよい。溶媒は、各成分を溶解又は分散するものであれば特に制限されない。溶媒としては、γ−ブチロラクトン、乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、酢酸ブチル、酢酸ベンジル、ｎ−ブチルアセテート、エトキシエチルプロピオネート、３−メチルメトキシプロピオネート、Ｎ−メチル−２−ピロリドン、Ｎ−シクロヘキシル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ヘキサメチルホスホリルアミド、テトラメチレンスルホン、ジエチルケトン、ジイソブチルケトン、メチルアミルケトン、シクロペンタノン、シクロヘキサノン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、キシレン、メシチレン、エチルベンゼン、プロピルベンゼン、クメン、ジイソプロピルベンゼン、ヘキシルベンゼン、アニソール、ジグライム、ジメチルスルホキシド、クロロホルム、ジクロロメタン、ジクロロエタン、クロロベンゼン等が挙げられる。これらの溶媒は１種を単独で使用してもよく、又は２種以上を組み合わせて使用してもよい。
<Solvent>
The polyketone resin composition may further contain a solvent. The solvent is not particularly limited as long as it dissolves or disperses each component. As the solvent, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, butyl acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, propylene glycol monomethyl Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, xylene, mesitylene, ether Rubenzen, propylbenzene, cumene, diisopropylbenzene, hexyl benzene, anisole, diglyme, dimethyl sulfoxide, chloroform, dichloromethane, dichloroethane, chlorobenzene and the like. These solvent may be used individually by 1 type, or may be used in combination of 2 or more type.
ポリケトン樹脂組成物が溶媒を含有する場合、溶媒の含有量は、ポリケトン、含窒素化合物、無機粒子、並びに、必要に応じて含有する熱潜在酸発生剤、後述のその他の添加剤及び溶媒の合計量１００質量部に対して、５質量部〜９５質量部であることが好ましく、１０質量部〜９０質量部であることがより好ましい。 When the polyketone resin composition contains a solvent, the content of the solvent is the total of the polyketone, the nitrogen-containing compound, the inorganic particles, and the thermal latent acid generator, if necessary, the other additives described later and the solvent. The amount is preferably 5 parts by mass to 95 parts by mass and more preferably 10 parts by mass to 90 parts by mass with respect to 100 parts by mass.
＜その他の添加剤＞
ポリケトン樹脂組成物は、さらにその他の添加剤を含有してもよい。その他の添加剤としては、接着助剤、界面活性剤、レベリング剤、酸化防止剤、紫外線劣化防止剤、摺動剤（ポリテトラフルオロエチレン粒子等）、光拡散剤（アクリル架橋粒子、シリコーン架橋粒子、極薄ガラスフレーク、炭酸カルシウム粒子等）、蛍光染料、無機系蛍光体（アルミン酸塩を母結晶とする蛍光体等）、帯電防止剤、結晶核剤、無機抗菌剤、有機抗菌剤、光触媒系防汚剤（酸化チタン粒子、酸化亜鉛粒子等）、架橋剤、硬化剤、反応促進剤、赤外線吸収剤（熱線吸収剤）、フォトクロミック剤などが挙げられる。
<Other additives>
The polyketone resin composition may further contain other additives. Other additives include adhesion aids, surfactants, leveling agents, antioxidants, UV degradation inhibitors, sliding agents (polytetrafluoroethylene particles, etc.), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles) , Ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent dyes, inorganic phosphors (phosphors with aluminate as a base crystal), antistatic agents, crystal nucleating agents, inorganic antibacterial agents, organic antibacterial agents, photocatalysts Examples include antifouling agents (titanium oxide particles, zinc oxide particles, etc.), crosslinking agents, curing agents, reaction accelerators, infrared absorbers (heat ray absorbers), photochromic agents, and the like.
＜ポリケトン硬化物＞
本開示のポリケトン硬化物は、本開示のポリケトン樹脂組成物の硬化物である。
本開示のポリケトン硬化物の製造方法は、特に限定されない。例えば、溶媒を含む本開示のポリケトン樹脂組成物を基材の少なくとも一部の表面に付与して組成物層を形成し、乾燥して組成物層から溶媒を除去した後又は溶媒の除去と共に硬化することで、本開示のポリケトン硬化物を製造することができる。
ポリケトン樹脂組成物を基材に付与する方法としては、組成物層を基材上の任意の場所に任意の形状で形成可能な手法であれば特に限定されない。ポリケトン樹脂組成物を基材に付与する方法としては、例えば、浸漬法、スプレー法、スクリーン印刷法、回転塗布法、スピンコート法、及びバーコート法が挙げられる。
<Polyketone cured product>
The polyketone cured product of the present disclosure is a cured product of the polyketone resin composition of the present disclosure.
The manufacturing method of the polyketone hardened | cured material of this indication is not specifically limited. For example, a polyketone resin composition of the present disclosure containing a solvent is applied to at least a part of the surface of the substrate to form a composition layer, and after drying to remove the solvent from the composition layer or curing with removal of the solvent By doing so, the polyketone cured product of the present disclosure can be produced.
The method for applying the polyketone resin composition to the substrate is not particularly limited as long as the method can form the composition layer in an arbitrary shape on an arbitrary location on the substrate. Examples of the method for applying the polyketone resin composition to the substrate include an immersion method, a spray method, a screen printing method, a spin coating method, a spin coating method, and a bar coating method.
ポリケトン樹脂組成物を付与する基材は特に限定されず、ガラス、半導体、金属酸化物絶縁体（酸化チタン、酸化ケイ素等）、窒化ケイ素等の無機材料、トリアセチルセルロース、透明ポリイミド、ポリカルボナート、アクリル系ポリマー、シクロオレフィン樹脂などの透明樹脂で構成される透明基材を例示することができる。基材の形状は特に限定されず、板状又はフィルム状であってもよい。本開示のポリケトン樹脂組成物は、基材のコート材、成形品等として好適に用いることができる。 The base material to which the polyketone resin composition is applied is not particularly limited, and glass, semiconductor, metal oxide insulator (titanium oxide, silicon oxide, etc.), inorganic materials such as silicon nitride, triacetyl cellulose, transparent polyimide, polycarbonate And a transparent substrate composed of a transparent resin such as an acrylic polymer or a cycloolefin resin. The shape of the substrate is not particularly limited, and may be a plate shape or a film shape. The polyketone resin composition of the present disclosure can be suitably used as a coating material for a substrate, a molded product, and the like.
ポリケトン樹脂組成物が溶媒を含有する場合には、乾燥を行ってもよい。乾燥方法は特に限定されず、例えば、ホットプレート、オーブン等の装置を用いて熱処理する方法、自然乾燥する方法などが挙げられる。熱処理することで乾燥を行う条件は、ポリケトン樹脂組成物中の溶媒が充分に揮散する条件であれば特に制限はなく、通常、５０℃〜１５０℃で、１分間〜９０分間程度である。 When the polyketone resin composition contains a solvent, it may be dried. The drying method is not particularly limited, and examples thereof include a heat treatment method using an apparatus such as a hot plate and an oven, and a natural drying method. The conditions for drying by heat treatment are not particularly limited as long as the solvent in the polyketone resin composition is sufficiently volatilized, and is usually about 50 to 150 ° C. for about 1 minute to 90 minutes.
ポリケトン樹脂組成物を硬化する方法は特に制限されず、熱処理等により硬化することができる。熱処理による硬化は、箱型乾燥機、熱風式コンベアー型乾燥機、石英チューブ炉、ホットプレート、ラピッドサーマルアニール、縦型拡散炉、赤外線硬化炉、電子線硬化炉、マイクロ波硬化炉等を用いて行なうことができる。 The method for curing the polyketone resin composition is not particularly limited, and can be cured by heat treatment or the like. Curing by heat treatment uses a box dryer, hot air conveyor dryer, quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, microwave curing furnace, etc. Can be done.
硬化する際の雰囲気は、大気中、窒素等の不活性雰囲気中などのいずれを選択してもよく、ポリケトン樹脂組成物の酸化を防ぐ観点から、窒素雰囲気下で行なうことが好ましい。
硬化のための熱処理の温度及び時間は、組成条件、作業効率等を鑑みて、任意に設定でき、６０℃〜２００℃で３０分〜２時間程度であってもよい。
The atmosphere for curing may be selected from the air, an inert atmosphere such as nitrogen, and the like, and is preferably performed in a nitrogen atmosphere from the viewpoint of preventing oxidation of the polyketone resin composition.
The temperature and time of the heat treatment for curing can be arbitrarily set in view of composition conditions, work efficiency, and the like, and may be about 60 minutes to 200 ° C. for about 30 minutes to 2 hours.
必要に応じて、乾燥した本開示のポリケトン硬化物は、残存溶媒を飛ばし切るために、さらに熱処理してもよい。熱処理の方法は特に限定されず、箱型乾燥機、熱風式コンベアー型乾燥機、石英チューブ炉、ホットプレート、ラピッドサーマルアニール、縦型拡散炉、赤外線硬化炉、電子線硬化炉、マイクロ波硬化炉、真空乾燥機等を用いて行なうことができる。また、熱処理工程における雰囲気としては特に限定されず、大気中、窒素等の不活性雰囲気中などが挙げられる。熱処理を行う条件は、特に制限はなく、１５０℃〜２５０℃で、１分間〜９０分間程度であってもよい。さらに熱処理を行うことで、得られるポリケトン硬化物の密度が高くなる傾向にある。 If necessary, the dried polyketone cured product of the present disclosure may be further heat-treated in order to drive off the remaining solvent. The heat treatment method is not particularly limited, and is a box dryer, hot air conveyor dryer, quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, microwave curing furnace. It can be carried out using a vacuum dryer or the like. In addition, the atmosphere in the heat treatment step is not particularly limited, and examples thereof include air and an inert atmosphere such as nitrogen. The conditions for performing the heat treatment are not particularly limited, and may be 150 to 250 ° C. for 1 to 90 minutes. Furthermore, the density of the resulting polyketone cured product tends to increase by performing heat treatment.
ポリケトン硬化物を厚さ１０μｍとしたときのヘイズは、１％未満であることが好ましい。
また、ポリケトン硬化物の４００ｎｍの透過率は、膜厚１μｍ換算で８５％以上であることが好ましい。
When the polyketone cured product has a thickness of 10 μm, the haze is preferably less than 1%.
Moreover, it is preferable that the transmittance | permeability of 400 nm of polyketone hardened | cured material is 85% or more in conversion of a film thickness of 1 micrometer.
得られたポリケトン硬化物は、基材を付けたままポリケトン硬化物付基材として用いることもでき、必要に応じて、基材から剥がして用いることもできる。
ポリケトン硬化物付基材において、ポリケトン硬化物は、基材の表面の少なくとも一部に設けられていればよく、基材の一方の面のみに設けられても、両面に設けられてもよい。また、ポリケトン硬化物は、一層でも、二層以上が積層された複数層構造であってもよい。
The obtained polyketone cured product can be used as a substrate with a polyketone cured product with the substrate attached, and can be used after being peeled off from the substrate, if necessary.
In the base material with a polyketone cured product, the polyketone cured product may be provided on at least a part of the surface of the base material, and may be provided on only one surface of the base material or on both surfaces. The polyketone cured product may be a single layer or a multi-layer structure in which two or more layers are laminated.
＜光学素子及び画像表示装置＞
本開示の光学素子及び画像表示装置は、それぞれ本開示のポリケトン硬化物を有する。光学素子及び画像表示装置に適用されるポリケトン硬化物は、上述のポリケトン硬化物付基材であってもよい。また、基材が透明基材であれば、光学素子に好適に用いることができる。透明基材としては、ポリケトン硬化物の製造で例示したものが挙げられる。
<Optical element and image display device>
The optical element and the image display device of the present disclosure each have the polyketone cured product of the present disclosure. The polyketone cured product applied to the optical element and the image display device may be the above-described base material with a polyketone cured product. Moreover, if a base material is a transparent base material, it can use suitably for an optical element. Examples of the transparent substrate include those exemplified in the production of the polyketone cured product.
光学素子及び画像表示装置は、例えば、ポリケトン硬化物付基材における基材側を、粘着剤、接着剤等を介してＬＣＤ（液晶ディスプレイ）、ＥＬＤ（エレクトロルミネッセンスディスプレイ）、有機ＥＬディスプレイ等の適用箇所に貼り付けて得ることができる。 The optical element and the image display device are applied to the substrate side of the substrate with a polyketone cured product, such as an LCD (liquid crystal display), an ELD (electroluminescence display), an organic EL display, etc. via an adhesive, an adhesive, etc. It can be obtained by pasting it to the place.
ポリケトン硬化物及びこれを用いた偏光板等の各種光学素子は、液晶表示装置等の各種画像表示装置に好ましく用いることができる。画像表示装置は、本開示のポリケトン硬化物を用いる以外は、従来の画像表示装置と同様の構成であってよい。画像表示装置が液晶表示装置である場合は、液晶セル、偏光板等の光学素子、及び必要に応じ照明システム（バックライト等）等の各構成部品を適宜に組み立てて駆動回路を組み込むことなどにより製造できる。液晶セルとしては、特に制限されず、ＴＮ型、ＳＴＮ型、π型等の様々なタイプを使用できる。 Various optical elements such as a cured polyketone and a polarizing plate using the polyketone can be preferably used for various image display devices such as a liquid crystal display device. The image display device may have the same configuration as the conventional image display device except that the polyketone cured product of the present disclosure is used. When the image display device is a liquid crystal display device, by appropriately assembling each component such as a liquid crystal cell, an optical element such as a polarizing plate, and an illumination system (backlight, etc.) as necessary, and incorporating a drive circuit, etc. Can be manufactured. The liquid crystal cell is not particularly limited, and various types such as a TN type, an STN type, and a π type can be used.
画像表示装置の用途としては、デスクトップパソコン、ノートパソコン、コピー機等のＯＡ機器、携帯電話、時計、デジタルカメラ、携帯情報端末（ＰＤＡ）、携帯ゲーム機等の携帯機器、ビデオカメラ、テレビ、電子レンジ等の家庭用電気機器、バックモニター、カーナビゲーションシステム用モニター、カーオーディオ等の車載用機器、商業店舗用インフォメーション用モニター等の展示機器、監視用モニター等の警備機器、介護用モニター等の介護機器、医療用モニター等の医療機器などが挙げられる。 Applications of image display devices include OA equipment such as desktop personal computers, notebook personal computers, and copiers, mobile phones, watches, digital cameras, personal digital assistants (PDAs), portable devices such as portable game machines, video cameras, televisions, and electronic devices. Household electrical equipment such as a range, back monitor, car navigation system monitor, in-vehicle equipment such as car audio, display equipment such as an information monitor for commercial stores, security equipment such as a monitoring monitor, nursing care such as a care monitor Examples thereof include medical devices such as devices and medical monitors.
＜被覆材料＞
本開示の被覆材料は、本開示のポリケトン樹脂組成物の硬化物を含む。被覆材料で被覆される対象は特に制限されず、デスクトップパソコン、ノートパソコン、コピー機等のＯＡ機器、携帯電話、デジタルカメラ、携帯情報端末（ＰＤＡ）、携帯ゲーム機等の携帯機器、ビデオカメラ、テレビ、各種ディスプレイ、窓ガラス、車載ガラス、カメラレンズなどが挙げられる。本開示のポリケトン樹脂組成物を用いて被覆を形成する方法は特に制限されず、例えば、膜状とした本開示のポリケトン樹脂組成物をラミネート等の方法で被覆対象に接着し、硬化することで被覆を形成してもよく、液状とした本開示のポリケトン樹脂組成物を被覆対象に塗布してから乾燥させ硬化して被覆を形成してもよい。
<Coating material>
The coating material of the present disclosure includes a cured product of the polyketone resin composition of the present disclosure. The object to be coated with the coating material is not particularly limited, and is an OA device such as a desktop personal computer, a notebook personal computer, a copy machine, a mobile phone, a digital camera, a personal digital assistant (PDA), a portable device such as a portable game machine, a video camera, TV, various displays, window glass, in-vehicle glass, camera lens, and the like. The method for forming the coating using the polyketone resin composition of the present disclosure is not particularly limited. For example, the polyketone resin composition of the present disclosure in a film form is bonded to a coating target by a method such as laminating and cured. A coating may be formed, and the polyketone resin composition of the present disclosure in liquid form may be applied to a coating target and then dried and cured to form the coating.
＜成形体＞
本開示の成形体は、本開示のポリケトン樹脂組成物の硬化物を含む。成形体の製造方法は特に制限されず、当該技術分野で既知の方法を用いることができる。例えば、押出成形法、射出成形法、カレンダー成形法、ブロー成形法、ＦＲＰ（Ｆｉｂｅｒ Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃ）成形法、積層成形法、注型法、粉末成形法、溶液流延法、真空成形法、圧空成形法、押出複合成形法、延伸成形法及び発泡成形法により硬化前の成形体を得た後に硬化する方法が挙げられる。
<Molded body>
The molded article of the present disclosure includes a cured product of the polyketone resin composition of the present disclosure. The method for producing the molded body is not particularly limited, and a method known in the technical field can be used. For example, extrusion molding method, injection molding method, calendar molding method, blow molding method, FRP (Fiber Reinforced Plastic) molding method, laminate molding method, casting method, powder molding method, solution casting method, vacuum molding method, pressure forming method And a method of curing after obtaining a molded body before curing by a method, an extrusion composite molding method, a stretch molding method and a foam molding method.
以下、実施例及び比較例に基づいて本発明をより具体的に説明する。ただし、本発明は以下の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described more specifically based on examples and comparative examples. However, the present invention is not limited to the following examples.
＜ポリケトンの分子量測定＞
ポリケトンの分子量（重量平均分子量及び数平均分子量）は、溶離液としてテトラヒドロフラン（ＴＨＦ）を用いて、ＧＰＣ法によって測定し、標準ポリスチレン換算にて求めた。詳細は次のとおりである。
・装置名：Ｅｃｏｓｅｃ ＨＬＣ−８３２０ＧＰＣ（東ソー（株））
・カラム：ＴＳＫｇｅｌ Ｓｕｐｅｒｍｕｌｔｉｐｏｒｅ ＨＺ−Ｍ（東ソー（株））
・検出器：ＵＶ検出器、ＲＩ検出器併用
・流速：０．４ｍｌ／ｍｉｎ
<Measurement of molecular weight of polyketone>
The molecular weight (weight average molecular weight and number average molecular weight) of the polyketone was measured by GPC method using tetrahydrofuran (THF) as an eluent, and was determined in terms of standard polystyrene. Details are as follows.
-Device name: Ecosec HLC-8320GPC (Tosoh Corporation)
Column: TSKgel Supermultipore HZ-M (Tosoh Corporation)
・ Detector: UV detector and RI detector combined ・ Flow rate: 0.4 ml / min
＜ポリケトン樹脂組成物＞
（Ａ）成分〜（Ｄ）成分を、表１又は表２に示した固形分の質量比率となるように配合し、攪拌し、ＰＴＦＥ（ポリテトラフルオロエチレン）製のフィルター（孔径５μｍ）で濾過し、実施例及び比較例のポリケトン樹脂組成物を得た。「−」はその成分を含有しないことを表す。表１又は表２中の各成分は、以下に示すものである。なお、表１及び表２の数値は、各成分の配合比（質量基準）を表す。また、固形分とは、各成分の溶剤を除いた残部をいう。
<Polyketone resin composition>
Ingredients (A) to (D) were mixed so as to have a mass ratio of solids shown in Table 1 or 2, stirred, and filtered with a PTFE (polytetrafluoroethylene) filter (pore diameter 5 μm). Thus, polyketone resin compositions of Examples and Comparative Examples were obtained. "-" Represents that the component is not contained. Each component in Table 1 or Table 2 is shown below. In addition, the numerical value of Table 1 and Table 2 represents the compounding ratio (mass basis) of each component. Moreover, solid content means the remainder except the solvent of each component.
（Ａ）成分［特定ポリケトン］
（合成例１）ポリケトンＰＫ−１の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタンジカルボン酸１０ｍｍｏｌが入ったフラスコに、五酸化二リン及びメタンスルホン酸の混合液（質量比１：１０）を３０ｍｌ加え、６０℃で撹拌した。反応後、内容物をメタノール５００ｍｌ中に投じ、生成した析出物を濾取した。得られた固体を蒸留水とメタノールで洗浄した後、乾燥し、ポリケトンＰＫ−１を得た。
得られたポリケトンＰＫ−１の重量平均分子量は２０，０００、数平均分子量は８，０００であった。
ポリケトンＰＫ−１をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
Component (A) [specific polyketone]
Synthesis Example 1 Synthesis of Polyketone PK-1 As a monomer, a mixture of diphosphorus pentoxide and methanesulfonic acid (mass) in a flask containing 10 mmol of 2,2′-dimethoxybiphenyl and 10 mmol of 1,3-adamantanedicarboxylic acid. 30 ml of the ratio 1:10) was added and stirred at 60 ° C. After the reaction, the content was poured into 500 ml of methanol, and the produced precipitate was collected by filtration. The obtained solid was washed with distilled water and methanol and then dried to obtain polyketone PK-1.
The resulting polyketone PK-1 had a weight average molecular weight of 20,000 and a number average molecular weight of 8,000.
Polyketone PK-1 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution, which was used for the experiment.
（合成例２）ポリケトンＰＫ−２の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，４−シクロヘキサンジカルボン酸（ｃｉｓとｔｒａｎｓの混合体、ｃｉｓ：ｔｒａｎｓ（モル比）＝７：３）１０ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ−２を得た。得られたポリケトンＰＫ−２の重量平均分子量は２５，０００であり、数平均分子量は９，０００であった。
ポリケトンＰＫ−２をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
(Synthesis Example 2) Synthesis of Polyketone PK-2 As monomers, 2,2′-dimethoxybiphenyl 10 mmol and 1,4-cyclohexanedicarboxylic acid (mixture of cis and trans, cis: trans (molar ratio) = 7: 3) A polyketone PK-2 was obtained in the same manner as in Example 1 except that 10 mmol was used. The resulting polyketone PK-2 had a weight average molecular weight of 25,000 and a number average molecular weight of 9,000.
Polyketone PK-2 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution and used for the experiment.
（合成例３）ポリケトンＰＫ−３の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタン二酢酸１０ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ−３を得た。得られたポリケトンＰＫ−３の重量平均分子量は４２，０００であり、数平均分子量は１２，０００であった。
ポリケトンＰＫ−３をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
(Synthesis Example 3) Synthesis of Polyketone PK-3 Polyketone PK-3 was obtained in the same manner as in Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl and 10 mmol of 1,3-adamantanediacetic acid were used as monomers. It was. The resulting polyketone PK-3 had a weight average molecular weight of 42,000 and a number average molecular weight of 12,000.
Polyketone PK-3 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution and used for the experiment.
（合成例４）ポリケトンＰＫ−４の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタンジカルボン酸５ｍｍｏｌとドデカン二酸５ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ−４を得た。得られたポリケトンＰＫ−４の重量平均分子量は３６，０００であり、数平均分子量は１３，０００であった。
ポリケトンＰＫ−４をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
(Synthesis Example 4) Synthesis of Polyketone PK-4 Polyketone was obtained in the same manner as in Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantane dicarboxylic acid and 5 mmol of dodecanedioic acid were used as monomers. PK-4 was obtained. The resulting polyketone PK-4 had a weight average molecular weight of 36,000 and a number average molecular weight of 13,000.
Polyketone PK-4 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution and used for the experiment.
（合成例５）ポリケトンＰＫ−５の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタン二酢酸５ｍｍｏｌとドデカン二酸５ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ−５を得た。得られたポリケトンＰＫ−５の重量平均分子量は３９，０００であり、数平均分子量は１２，０００であった。
ポリケトンＰＫ−５をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
Synthesis Example 5 Synthesis of Polyketone PK-5 The polyketone was obtained in the same manner as in Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid, and 5 mmol of dodecanedioic acid were used as monomers. PK-5 was obtained. The resulting polyketone PK-5 had a weight average molecular weight of 39,000 and a number average molecular weight of 12,000.
Polyketone PK-5 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution and used for the experiment.
（合成例６）ポリケトンＰＫ−６の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタン二酢酸５ｍｍｏｌとヘキサン二酸５ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ−６を得た。得られたポリケトンＰＫ−６の重量平均分子量は３９，０００であり、数平均分子量は１２，０００であった。
ポリケトンＰＫ−６をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
(Synthesis Example 6) Synthesis of Polyketone PK-6 Polyketone was obtained in the same manner as in Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid and 5 mmol of hexanedioic acid were used as monomers. PK-6 was obtained. The resulting polyketone PK-6 had a weight average molecular weight of 39,000 and a number average molecular weight of 12,000.
Polyketone PK-6 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution and used for the experiment.
（合成例７）ポリケトンＰＫ−７の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタン二酢酸５ｍｍｏｌとｃｉｓ−１，４−シクロヘキサンジカルボン酸５ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ−７を得た。得られたポリケトンＰＫ−７の重量平均分子量は４５，０００であり、数平均分子量は１１，０００であった。
ポリケトンＰＫ−７をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
Synthesis Example 7 Synthesis of Polyketone PK-7 Example 1 except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid, and 5 mmol of cis-1,4-cyclohexanedicarboxylic acid were used as monomers. In the same manner as above, polyketone PK-7 was obtained. The resulting polyketone PK-7 had a weight average molecular weight of 45,000 and a number average molecular weight of 11,000.
Polyketone PK-7 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution and used for the experiment.
（合成例８）ポリケトンＰＫ−８の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタン二酢酸５ｍｍｏｌとデカリン−２，６−ジカルボン酸５ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ−８を得た。得られたポリケトンＰＫ−８の重量平均分子量は３３，０００であり、数平均分子量は１０，０００であった。
ポリケトンＰＫ−８をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
(Synthesis Example 8) Synthesis of Polyketone PK-8 Example 1 was used except that 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid, and 5 mmol of decalin-2,6-dicarboxylic acid were used as monomers. Similarly, polyketone PK-8 was obtained. The resulting polyketone PK-8 had a weight average molecular weight of 33,000 and a number average molecular weight of 10,000.
Polyketone PK-8 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution and used for the experiment.
（合成例９）ポリケトンＰＫ−９の合成
モノマとして、２，２’−ジメトキシビフェニル１０ｍｍｏｌと１，３−アダマンタン二酢酸５ｍｍｏｌとノルボルナンジカルボン酸（２，４−、２，５−混合体）５ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ−９を得た。得られたポリケトンＰＫ−９の重量平均分子量は２７，０００であり、数平均分子量は９，２００であった。
ポリケトンＰＫ−９をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
(Synthesis Example 9) Synthesis of polyketone PK-9 As monomers, 10 mmol of 2,2′-dimethoxybiphenyl, 5 mmol of 1,3-adamantanediacetic acid, and 5 mmol of norbornane dicarboxylic acid (2,4-, 2,5-mixture) A polyketone PK-9 was obtained in the same manner as in Example 1 except that it was used. The resulting polyketone PK-9 had a weight average molecular weight of 27,000 and a number average molecular weight of 9,200.
Polyketone PK-9 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution and used for the experiment.
（合成例１０）ポリケトンＰＫ−１０の合成
モノマとして、２，２’−ビス（２−メトキシフェニル）プロパン１０ｍｍｏｌと１，３−アダマンタン二酢酸５ｍｍｏｌと１，４−シクロヘキサンジカルボン酸（ｃｉｓとｔｒａｎｓの混合体、ｃｉｓ：ｔｒａｎｓ（モル比）＝７：３）５ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ−１０を得た。得られたポリケトンＰＫ−１０の重量平均分子量は２８，０００であり、数平均分子量は８，３００であった。
ポリケトンＰＫ−１０をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
Synthesis Example 10 Synthesis of Polyketone PK-10 As monomers, 2,2′-bis (2-methoxyphenyl) propane 10 mmol, 1,3-adamantanediacetic acid 5 mmol and 1,4-cyclohexanedicarboxylic acid (of cis and trans) Polyketone PK-10 was obtained in the same manner as in Example 1 except that 5 mmol of the mixture, cis: trans (molar ratio) = 7: 3) was used. The resulting polyketone PK-10 had a weight average molecular weight of 28,000 and a number average molecular weight of 8,300.
Polyketone PK-10 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution and used for the experiment.
（合成例１１）ポリケトンＰＫ−１１の合成
モノマとして、ジフェニルエーテル１０ｍｍｏｌと１，３−アダマンタン二酢酸５ｍｍｏｌと１，４−シクロヘキサンジカルボン酸（ｃｉｓとｔｒａｎｓの混合体、ｃｉｓ：ｔｒａｎｓ（モル比）＝７：３）５ｍｍｏｌを用いた以外は実施例１と同様にして、ポリケトンＰＫ−１１を得た。得られたポリケトンＰＫ−１１の重量平均分子量は２７，０００であり、数平均分子量は８，０００であった。
ポリケトンＰＫ−１１をＮ−メチル−２−ピロリドンに溶解して２０質量％溶液とし、実験に供した。
(Synthesis Example 11) Synthesis of polyketone PK-11 As monomers, 10 mmol of diphenyl ether, 5 mmol of 1,3-adamantanediacetic acid and 1,4-cyclohexanedicarboxylic acid (mixture of cis and trans, cis: trans (molar ratio) = 7) : 3) A polyketone PK-11 was obtained in the same manner as in Example 1 except that 5 mmol was used. The resulting polyketone PK-11 had a weight average molecular weight of 27,000 and a number average molecular weight of 8,000.
Polyketone PK-11 was dissolved in N-methyl-2-pyrrolidone to give a 20% by mass solution and used for the experiment.
（Ｂ）成分［特定含窒素化合物］
Ｂ１：下記式（ＸＩＩ）で表される化合物（Ｍｅはメチル基を表す）
Component (B) [specific nitrogen-containing compound]
B1: Compound represented by the following formula (XII) (Me represents a methyl group)
Ｂ２：下記式（ＸＩＩＩ）で表される化合物 B2: Compound represented by the following formula (XIII)
Ｂ３：下記式（ＸＩＶ）で表される化合物（Ｍｅはメチル基を表す） B3: Compound represented by the following formula (XIV) (Me represents a methyl group)
Ｂ４：下記式（ＸＶ）で表される化合物（Ｂｕはブチル基を表す） B4: Compound represented by the following formula (XV) (Bu represents a butyl group)
（Ｃ）成分［熱潜在酸発生剤］
Ｃ１：下記式（ＸＶＩ）で表される化合物
Component (C) [thermal latent acid generator]
C1: Compound represented by the following formula (XVI)
（Ｄ）成分［無機粒子］
粒子Ａ：シリカ粒子のシクロヘキサノン分散液（日産化学工業株式会社製 ＣＨＯ−ＳＴ−Ｍ、シリカ粒子の固形分は３０質量％）
粒子Ｂ：シリカ粒子（株式会社アドマテックス製 ＳＣ１０５０−ＳＸＴ）
粒子Ｃ：酸化チタン粒子（Ｓｉｇｍａ−Ａｌｄｒｉｃｈ社製 ６３７２５４）
Component (D) [inorganic particles]
Particle A: Cyclohexanone dispersion of silica particles (CHO-ST-M manufactured by Nissan Chemical Industries, Ltd., solid content of silica particles is 30% by mass)
Particle B: Silica particle (manufactured by ADMATEX SC1050-SXT)
Particle C: Titanium oxide particle (manufactured by Sigma-Aldrich, 633254)
＜評価用サンプルの作製及び評価＞
得られたポリケトン樹脂組成物を用いて、以下の方法により硬化膜を作製し、後述の評価用のサンプルを準備し、下記評価を行った。
<Preparation and Evaluation of Evaluation Sample>
A cured film was prepared by the following method using the obtained polyketone resin composition, a sample for evaluation described later was prepared, and the following evaluation was performed.
（１）平均粒子径の測定
得られたポリケトン樹脂組成物を、バーコート法によりガラス基板の上に塗布し、１２０℃に加熱したホットプレート上で３分間乾燥して、厚さ１０μｍのポリケトン膜を有するポリケトン膜付ガラス基板を作製した。このポリケトン膜付ガラス基板を、窒素置換したイナートガスオーブンを用い２００℃で１時間熱処理した後、ダイヤモンドカッターを用いて切断し、切断面（膜断面）を、走査型電子顕微鏡（株式会社Ｐｈｉｌｉｐｓ製、ＸＬ−３０）を用いて観察を行った。得られた観察画像から、無機粒子の一次粒子５０個について長径を測定し、その平均値を平均粒子径とした。得られた結果を表３に示す。
(1) Measurement of average particle diameter The obtained polyketone resin composition was coated on a glass substrate by a bar coating method and dried on a hot plate heated to 120 ° C. for 3 minutes to obtain a polyketone film having a thickness of 10 μm. A glass substrate with a polyketone film was prepared. This glass substrate with a polyketone film was heat-treated at 200 ° C. for 1 hour using an inert gas oven substituted with nitrogen, then cut using a diamond cutter, and the cut surface (film cross section) was scanned using a scanning electron microscope (manufactured by Philips, Observation was performed using XL-30). From the obtained observation image, the major axis was measured for 50 primary particles of the inorganic particles, and the average value was taken as the average particle size. The obtained results are shown in Table 3.
ここで、長径とは、前記切断面に現れる粒子について、その粒子の外側に接する二つの平行線の組み合わせを、粒子を挟むように選択し、それらの組み合わせのうち最長間隔になる二つの平行線の距離である。 Here, the major axis is a combination of two parallel lines in contact with the outside of the particles appearing on the cut surface, so as to sandwich the particles, and two parallel lines having the longest interval among the combinations. Is the distance.
（１）ヘイズ測定
得られたポリケトン樹脂組成物を、バーコート法によりガラス基板の上に塗布し、１２０℃に加熱したホットプレート上で３分間乾燥して、厚さ１０μｍのポリケトン膜を有するポリケトン膜付ガラス基板を作製した。このポリケトン膜付ガラス基板を、窒素置換したイナートガスオーブンを用い２００℃で１時間熱処理した後、ヘイズメーター（ＮＤＨ ２０００ 日本電色工業（株）製）を用い、ガラス基板をブランクとしてヘイズを測定した。膜の付いていないガラス基板をリファレンスとして、膜厚１μｍに換算した透過率（％）を表３に示す。膜厚は、触針式段差計（「Ｄｅｋｔａｋ３ ＳＴ」、アルバック株式会社（Ｖｅｅｃｏ））を用いて３点測定した値の数平均値とした。
(1) Haze measurement The obtained polyketone resin composition was applied onto a glass substrate by a bar coating method, dried on a hot plate heated to 120 ° C. for 3 minutes, and a polyketone having a polyketone film having a thickness of 10 μm. A glass substrate with a film was prepared. This glass substrate with a polyketone film was heat-treated at 200 ° C. for 1 hour using an inert gas oven substituted with nitrogen, and then the haze was measured using a haze meter (NDH 2000 manufactured by Nippon Denshoku Industries Co., Ltd.) with the glass substrate as a blank. . Table 3 shows transmittance (%) converted to a film thickness of 1 μm using a glass substrate without a film as a reference. The film thickness was the number average value of the values measured at three points using a stylus profilometer ("Dektak 3 ST", ULVAC, Inc. (Veeco)).
（２）透明性の評価
得られたポリケトン樹脂組成物を、バーコート法によりガラス基板の上に塗布し、１２０℃に加熱したホットプレート上で３分間乾燥して、厚さ１０μｍのポリケトン膜を有するポリケトン膜付ガラス基板を作製した。このポリケトン膜付ガラス基板を、窒素置換したイナートガスオーブンを用い２００℃で１時間熱処理した後、波長４００ｎｍにおける透過率を、紫外可視分光光度計（「Ｕ−３３１０ Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ」日立ハイテク株式会社）を用いた紫外可視吸収スペクトル法によって測定した。膜の付いていないガラス基板をリファレンスとして、膜厚１μｍに換算した透過率（％）を表３に示す。膜厚は、触針式段差計（「Ｄｅｋｔａｋ３ ＳＴ」、アルバック株式会社（Ｖｅｅｃｏ））を用いて３点測定した値の数平均値とした。
(2) Evaluation of transparency The obtained polyketone resin composition was applied onto a glass substrate by a bar coating method and dried on a hot plate heated to 120 ° C. for 3 minutes to form a polyketone film having a thickness of 10 μm. A glass substrate with a polyketone film was prepared. This glass substrate with a polyketone film was heat-treated at 200 ° C. for 1 hour using an inert gas oven substituted with nitrogen, and then the transmittance at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer (“U-3310 Spectrophotometer”, Hitachi High-Tech Co., Ltd.). It was measured by the UV-visible absorption spectrum method. Table 3 shows transmittance (%) converted to a film thickness of 1 μm using a glass substrate without a film as a reference. The film thickness was the number average value of the values measured at three points using a stylus profilometer ("Dektak 3 ST", ULVAC, Inc. (Veeco)).
（３）耐熱性の評価
得られたポリケトン樹脂組成物を、バーコート法によりポリイミド（カプトン）フィルムの上に塗布し、１２０℃に加熱したホットプレート上で３分間乾燥して、厚さ１０μｍのポリケトン膜を有するポリケトン膜付ポリイミド基材を作製した。ポリイミド基材からポリケトン膜を剥がし、窒素置換したイナートガスオーブンで、２００℃で１時間熱処理した。その後、膜のガラス転移温度（Ｔｇ）を、動的粘弾性測定装置（「ＲＳＡ−ＩＩ」Ｒｈｅｏｍｅｔｒｉｃｓ社）を用いた動的粘弾性測定法（引張りモード）によって測定した。得られたガラス転移温度の値（℃）を表３に示す。
(3) Evaluation of heat resistance The obtained polyketone resin composition was applied onto a polyimide (Kapton) film by a bar coating method, dried on a hot plate heated to 120 ° C. for 3 minutes, and a thickness of 10 μm. A polyimide substrate with a polyketone film having a polyketone film was prepared. The polyketone film was peeled off from the polyimide substrate and heat treated at 200 ° C. for 1 hour in an inert gas oven substituted with nitrogen. Thereafter, the glass transition temperature (Tg) of the film was measured by a dynamic viscoelasticity measurement method (tensile mode) using a dynamic viscoelasticity measurement apparatus (“RSA-II” Rheometrics). Table 3 shows the glass transition temperature values (° C) obtained.
（４）鉛筆硬度の評価
得られたポリケトン樹脂組成物を、バーコート法によりガラス基板の上に塗布し、１２０℃に加熱したホットプレート上で３分間乾燥して、厚さ１０μｍのポリケトン膜を有するポリケトン膜付ガラス基板を作製した。この膜付ガラス基板を、窒素置換したイナートガスオーブンを用い２００℃で１時間熱処理した後、鉛筆硬度試験により評価した。試験は ＪＩＳ Ｋ５６００−５−４：１９９９に従って行った。試験結果を表３に示す。
(4) Evaluation of pencil hardness The obtained polyketone resin composition was applied onto a glass substrate by a bar coating method and dried on a hot plate heated to 120 ° C. for 3 minutes to form a polyketone film having a thickness of 10 μm. A glass substrate with a polyketone film was prepared. This film-coated glass substrate was heat-treated at 200 ° C. for 1 hour using an inert gas oven substituted with nitrogen, and then evaluated by a pencil hardness test. The test was conducted according to JIS K5600-5-4: 1999. The test results are shown in Table 3.
（５）水蒸気透過率の測定
得られたポリケトン樹脂組成物を、バーコート法によりポリイミド（カプトン）フィルムの上に塗布し、１２０℃に加熱したホットプレート上で３分間乾燥して、ポリケトン膜を有するポリケトン膜付ポリイミド基材を作製した。ポリイミド基材からポリケトン膜を剥がし、窒素置換したイナートガスオーブンで、２００℃で１時間熱処理した。得られたポリケトン膜の水蒸気透過率［ｇ／ｍ２／ｄａｙ］を、ＪＩＳ Ｋ７１２９：２００８に従い測定した。なお、膜厚は５０μｍで、恒温恒湿処理の条件は、温度４０℃、湿度９０％ＲＨとした。試験結果を表３に示す。
(5) Measurement of water vapor transmission rate The obtained polyketone resin composition was applied onto a polyimide (Kapton) film by a bar coating method and dried on a hot plate heated to 120 ° C. for 3 minutes to form a polyketone film. A polyimide substrate with a polyketone film was prepared. The polyketone film was peeled off from the polyimide substrate and heat treated at 200 ° C. for 1 hour in an inert gas oven substituted with nitrogen. The water vapor permeability [g / m 2 / day] of the obtained polyketone membrane was measured according to JIS K7129: 2008. The film thickness was 50 μm, and the conditions of the constant temperature and humidity treatment were a temperature of 40 ° C. and a humidity of 90% RH. The test results are shown in Table 3.
（６）酸素透過率の測定
得られたポリケトン樹脂組成物を、バーコート法によりポリイミド（カプトン）フィルムの上に塗布し、１２０℃に加熱したホットプレート上で３分間乾燥して、ポリケトン膜を有するポリケトン膜付ポリイミド基材を作製した。ポリイミド基材からポリケトン膜を剥がし、窒素置換したイナートガスオーブンで、２００℃で１時間熱処理した。得られたポリケトン膜の酸素透過率［ｃｃ／ｍ２／ｄａｙ］をＪＩＳ Ｋ７１２６−２：２００６に従い測定した。なお、膜厚は５０μｍにした。試験結果を表３に示す。
(6) Measurement of oxygen permeability The obtained polyketone resin composition was applied onto a polyimide (Kapton) film by a bar coating method and dried on a hot plate heated to 120 ° C. for 3 minutes to form a polyketone film. A polyimide substrate with a polyketone film was prepared. The polyketone film was peeled off from the polyimide substrate and heat treated at 200 ° C. for 1 hour in an inert gas oven substituted with nitrogen. The oxygen permeability [cc / m 2 / day] of the obtained polyketone film was measured according to JIS K7126-2: 2006. The film thickness was 50 μm. The test results are shown in Table 3.
実施例のポリケトン樹脂組成物の硬化物は、耐熱性及び透明性に優れ、さらに高い表面硬度及び酸素及び水蒸気に対する高いバリア性を有することわかる。
表３において「単膜不可」とは、ポリイミド基材からポリケトン膜を剥がすことができなかったことを示す。
It can be seen that the cured products of the polyketone resin compositions of the examples are excellent in heat resistance and transparency, and have a high surface hardness and a high barrier property against oxygen and water vapor.
In Table 3, “No single film” indicates that the polyketone film could not be peeled from the polyimide base material.
Claims (18)
前記ポリケトン、前記含窒素化合物及び前記無機粒子の合計量１００質量部に対して、前記無機粒子の含有量が、１０質量部〜７０質量部である、ポリケトン樹脂組成物。
〔一般式（Ｉ）中、Ｘは、置換基を有していてもよい炭素数１〜５０の２価の基を表し、Ｙは、置換基を有していてもよい炭素数１〜３０の２価の炭化水素基を表し、ｎは１〜１５００の整数を表す。〕 A polyketone containing a structural unit represented by the following general formula (I) in the main chain, a nitrogen atom, and at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group bonded to the nitrogen atom; Containing nitrogen-containing compounds having, and inorganic particles,
The polyketone resin composition whose content of the said inorganic particle is 10 mass parts-70 mass parts with respect to 100 mass parts of total amounts of the said polyketone, the said nitrogen-containing compound, and the said inorganic particle.
[In General Formula (I), X represents a divalent group having 1 to 50 carbon atoms which may have a substituent, and Y represents 1 to 30 carbon atoms which may have a substituent. In the formula, n represents an integer of 1 to 1500. ]
〔一般式（ＩＩ−１）中、Ｒ１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｍは、それぞれ独立に、０〜３の整数を表す。〕
〔一般式（ＩＩ−２）中、Ｒ１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｍは、それぞれ独立に、０〜３の整数を表し、Ｚは、酸素原子又は下記一般式（ＩＩＩ−１）〜下記一般式（ＩＩＩ−７）のいずれかで表される２価の基を表す。〕
〔一般式（ＩＩＩ−１）〜一般式（ＩＩＩ−７）中、Ｒ１は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ２は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、Ｒ３及びＲ４は、それぞれ独立に、水素原子又は置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｍは、それぞれ独立に、０〜３の整数を表し、ｎは、それぞれ独立に、０〜４の整数を表し、ｐは、それぞれ独立に、０〜２の整数を表す。〕
〔一般式（ＩＩ−３）中、Ｒ５は、それぞれ独立に、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、ｎは、それぞれ独立に、０〜４の整数を表す。〕 In the general formula (I), X is a divalent group represented by at least one selected from the group consisting of the following general formula (II-1) to the following general formula (II-3). The polyketone resin composition according to any one of claims 1 to 3.
[In General Formula (II-1), each R 1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and each R 2 independently represents The C1-C30 hydrocarbon group which may have a substituent is represented, m represents the integer of 0-3 each independently. ]
[In General Formula (II-2), each R 1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and each R 2 independently represents Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, m represents an integer of 0 to 3 independently, Z represents an oxygen atom or the following general formula (III-1) -The bivalent group represented by either of the following general formula (III-7) is represented. ]
[In General Formula (III-1) to General Formula (III-7), each R 1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, R 2 represents each independently a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R 3 and R 4 each independently have a hydrogen atom or a substituent. Each represents an integer of 0 to 3, n is independently an integer of 0 to 4, and p is independently of each other. , Represents an integer of 0-2. ]
[In General Formula (II-3), each R 5 independently represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and n is each independently 0 to 4 Represents an integer. ]
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