JP2022072382A - Methacrylic based copolymer, composition, molding, film, method for manufacturing sheet, and laminate - Google Patents
Methacrylic based copolymer, composition, molding, film, method for manufacturing sheet, and laminate Download PDFInfo
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- JP2022072382A JP2022072382A JP2020181775A JP2020181775A JP2022072382A JP 2022072382 A JP2022072382 A JP 2022072382A JP 2020181775 A JP2020181775 A JP 2020181775A JP 2020181775 A JP2020181775 A JP 2020181775A JP 2022072382 A JP2022072382 A JP 2022072382A
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- methacrylic copolymer
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- film
- sheet
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000000465 moulding Methods 0.000 title claims abstract description 19
- 125000005395 methacrylic acid group Chemical group 0.000 title abstract description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 30
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 27
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000009477 glass transition Effects 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical group O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims description 3
- -1 molding Substances 0.000 abstract description 25
- 229920000642 polymer Polymers 0.000 description 63
- 239000010408 film Substances 0.000 description 60
- 239000002243 precursor Substances 0.000 description 41
- 239000011347 resin Substances 0.000 description 36
- 229920005989 resin Polymers 0.000 description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 29
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 28
- 239000003795 chemical substances by application Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 21
- 230000003287 optical effect Effects 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000004898 kneading Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 150000003923 2,5-pyrrolediones Chemical group 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 4
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical group O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229940057054 1,3-dimethylurea Drugs 0.000 description 2
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 2
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 2
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
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- 150000001565 benzotriazoles Chemical class 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 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 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- KUWAAZMPJBFLEO-UHFFFAOYSA-N n,n,2-trichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1Cl KUWAAZMPJBFLEO-UHFFFAOYSA-N 0.000 description 2
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 238000010094 polymer processing Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
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- OXXJEEWPKQNYJK-UHFFFAOYSA-N 1-(2,4,6-trimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC(C)=CC(C)=C1N1C(=O)C=CC1=O OXXJEEWPKQNYJK-UHFFFAOYSA-N 0.000 description 1
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 1
- GZNWHPFWQMQXII-UHFFFAOYSA-N 1-(2-ethylphenyl)pyrrole-2,5-dione Chemical compound CCC1=CC=CC=C1N1C(=O)C=CC1=O GZNWHPFWQMQXII-UHFFFAOYSA-N 0.000 description 1
- LJDGDRYFCIHDPX-UHFFFAOYSA-N 1-(2-methoxyphenyl)pyrrole-2,5-dione Chemical compound COC1=CC=CC=C1N1C(=O)C=CC1=O LJDGDRYFCIHDPX-UHFFFAOYSA-N 0.000 description 1
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- AIMUHNZKNFEZSN-UHFFFAOYSA-M sodium;decane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCS([O-])(=O)=O AIMUHNZKNFEZSN-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- REFMEZARFCPESH-UHFFFAOYSA-M sodium;heptane-1-sulfonate Chemical compound [Na+].CCCCCCCS([O-])(=O)=O REFMEZARFCPESH-UHFFFAOYSA-M 0.000 description 1
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 description 1
- RUYRDULZOKULPK-UHFFFAOYSA-M sodium;nonane-1-sulfonate Chemical compound [Na+].CCCCCCCCCS([O-])(=O)=O RUYRDULZOKULPK-UHFFFAOYSA-M 0.000 description 1
- KBAFDSIZQYCDPK-UHFFFAOYSA-M sodium;octadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O KBAFDSIZQYCDPK-UHFFFAOYSA-M 0.000 description 1
- HRQDCDQDOPSGBR-UHFFFAOYSA-M sodium;octane-1-sulfonate Chemical compound [Na+].CCCCCCCCS([O-])(=O)=O HRQDCDQDOPSGBR-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- QJAVUVZBMMXBRO-UHFFFAOYSA-N tripentyl phosphate Chemical compound CCCCCOP(=O)(OCCCCC)OCCCCC QJAVUVZBMMXBRO-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、メタクリル系共重合体、組成物、成形体、フィルム又はシートの製造方法、および積層体に関する。 The present invention relates to a methacrylic copolymer, a composition, a molded product, a method for producing a film or a sheet, and a laminate.
（メタ）アクリル樹脂は、透明性に優れ光学歪も少ないことからレンズ、プリズム、位相差フィルム、導光板、光拡散フィルム、偏光板保護フィルムなどの光学部材を構成する材料として広く用いられている。これらの用途では、成形品の複屈折がデバイスの性能に影響を与える。たとえば、液晶表示装置や光ディスク装置、プロジェクションスクリーン等のデバイスにおいては、複屈折性を持つフィルム、レンズ等が光路中に存在すると、像質や信号読み取り性能に悪影響を及ぼす。そのため近年では、複屈折性をできるだけ小さく抑えた材料が求められている。 (Meta) Acrylic resin is widely used as a material for constituting optical members such as lenses, prisms, retardation films, light guide plates, light diffusing films, and polarizing plate protective films because of its excellent transparency and low optical distortion. .. In these applications, the birefringence of the part affects the performance of the device. For example, in a device such as a liquid crystal display device, an optical disk device, or a projection screen, the presence of a birefringent film, lens, or the like in the optical path adversely affects the image quality and signal reading performance. Therefore, in recent years, there has been a demand for a material having birefringence as small as possible.
樹脂が示す複屈折には、ポリマー分子の配向に起因する配向複屈折と、応力に起因する光弾性複屈折があり、これらはポリマーの一次構造に由来するポリマー固有の性質である。 The birefringence exhibited by the resin includes orientation birefringence due to the orientation of the polymer molecule and photoelastic birefringence due to stress, which are polymer-specific properties derived from the primary structure of the polymer.
一般的なポリマーの繰り返し単位では、主鎖方向と側鎖方向の分極率が異なり、分極率の異方性を有している。ポリマーに歪みが印加されていない状態では、繰り返し単位がランダムに配向しているため、繰り返し単位の異方性は互いに打ち消しあい、巨視的な屈折率は等方的となる。しかし、一般的なポリマーを成形するプロセス、例えば、ポリマーフィルム製造時の押出成形や延伸のプロセス、または、各種光学部材の製造時に多用されている射出成形プロセスなど、材料の流動を伴うプロセスでは、ポリマー主鎖の配向が生じ、光学部材に配向が固定されて残留する。主鎖が配向した状態では、巨視的な等方性が崩れ、ポリマーの繰り返し単位由来の分極率異方性が主鎖の配向の程度に応じて光学部材に発現することとなる。このような、ポリマー主鎖の配向によって生じる複屈折を配向複屈折と呼ぶ。ここで、主鎖の配向方向に対して平行方向に屈折率が大きくなる場合は、正の配向複屈折、直交方向に屈折率が大きくなる場合は、負の配向複屈折と表現する。 In a general polymer repeating unit, the polarizabilities in the main chain direction and the side chain direction are different, and the polarizability has anisotropy. In the state where the polymer is not strained, the repeating units are randomly oriented, so that the anisotropy of the repeating units cancels each other out and the macroscopic refractive index becomes isotropic. However, in general polymer molding processes, such as extrusion molding and stretching processes during polymer film production, or injection molding processes often used during the production of various optical components, processes involving material flow may occur. Orientation of the polymer backbone occurs, and the orientation is fixed and remains on the optical member. In the state where the main chain is oriented, the microscopic isotropic property is broken, and the polarizability anisotropy derived from the repeating unit of the polymer is developed in the optical member according to the degree of the orientation of the main chain. Such birefringence caused by the orientation of the polymer main chain is called orientation birefringence. Here, when the refractive index increases in the direction parallel to the orientation direction of the main chain, it is expressed as positive orientation birefringence, and when the refractive index increases in the orthogonal direction, it is expressed as negative orientation birefringence.
また、ポリマーが弾性変形することで複屈折が発現することも知られており、光弾性複屈折と呼ばれる。例えば、ポリマーを含む光学部材が機器に固定されている状態で外力を受け、弾性変形している場合、光弾性係数に応じた光弾性複屈折を発現する。また、光学部材の成形時に、ポリマーのガラス転移温度以上の成形温度から冷却する際の体積収縮により、材料中に残留する歪みも、光弾性複屈折を発現する原因となりうる。 It is also known that birefringence occurs when a polymer is elastically deformed, which is called photoelastic birefringence. For example, when an optical member containing a polymer receives an external force while being fixed to an instrument and is elastically deformed, photoelastic birefringence corresponding to the photoelastic coefficient is exhibited. In addition, strain remaining in the material due to volume shrinkage when cooling from a molding temperature equal to or higher than the glass transition temperature of the polymer during molding of the optical member can also cause photoelastic birefringence to occur.
配向複屈折と光弾性複屈折を同時に小さくし、ポリマーの複屈折性を抑制する試みは種々なされている。 Various attempts have been made to suppress the birefringence of the polymer by simultaneously reducing the orientation birefringence and the photoelastic birefringence.
低複屈折性の材料を得る方法として、ホモポリマーとしての固有複屈折及び光弾性係数の各々の符号が異なるモノマーを複数組み合わせて、固有複屈折及び光弾性係数が相殺されるように組成を調整して共重合することにより、共重合体としての配向複屈折と光弾性複屈折を低減する技術が知られている。例えば特許文献１には、メタクリル酸メチル単位、メタクリル酸２，２，２－トリフルオロエチル単位、メタクリル酸ベンジル単位を含む共重合体は、配向複屈折と光弾性複屈折を同時に小さくできることが開示されている。しかし、樹脂のガラス転移温度が低いために耐熱性に劣り、高温条件下での使用が想定される電子機器や車載用途への適用が制限される課題があった。 As a method for obtaining a material having low birefringence, a plurality of monomers having different codes of the intrinsic birefringence and the photoelastic coefficient as a homopolymer are combined, and the composition is adjusted so that the intrinsic birefringence and the photoelastic coefficient are offset. A technique for reducing orientation birefringence and photoelastic birefringence as a copolymer is known. For example, Patent Document 1 discloses that a copolymer containing a methyl methacrylate unit, a methacrylic acid 2,2,2-trifluoroethyl unit, and a benzyl methacrylate unit can simultaneously reduce orientation birefringence and photoelastic birefringence. Has been done. However, since the glass transition temperature of the resin is low, the heat resistance is inferior, and there is a problem that the application to electronic devices and in-vehicle applications that are expected to be used under high temperature conditions is limited.
そのため、耐熱性を具備しつつ複屈折性を低減した樹脂として、特許文献２にはグルタルイミド単位を含む（メタ）アクリル系樹脂が提案されている。しかしこの樹脂は、配向複屈折は低いものの光弾性複屈折を十分に低減できていないため、成形品の残留歪みや光学部材をデバイスに装着した場合に印加される応力によって複屈折が発現するという課題があった。 Therefore, as a resin having heat resistance and reduced birefringence, Patent Document 2 proposes a (meth) acrylic resin containing a glutarimide unit. However, although this resin has low orientation birefringence, it cannot sufficiently reduce photoelastic birefringence, so it is said that birefringence develops due to residual strain of the molded product and stress applied when the optical member is attached to the device. There was a challenge.
これらの要請を受け、耐熱性を具備しつつ、配向複屈折と光弾性複屈折の両方を低減した樹脂として、メタクリレート単量体単位、ビニル芳香族単量体単位、芳香族基を有するメタクリレート単量体単位、環状酸無水物繰り返し単位を含有するアクリル系熱可塑性樹脂（特許文献３）、Ｎ－置換若しくは無置換グルタルイミド単位、（メタ）アクリル酸エステル単量体単位、ビニル芳香族単量体単位を含有するイミド樹脂（特許文献４）が開示されている。しかし、特許文献３および４の樹脂では、筆者らの検討によれば、表面硬度が不十分であり、光学部材としての応用には未だ課題が残されている。 In response to these requests, as a resin having heat resistance and reduced both orientation double refraction and photoelastic double refraction, a methacrylate monomer unit, a vinyl aromatic monomer unit, and a methacrylate monomer having an aromatic group. Acrylic thermoplastic resin containing a weight unit, a cyclic acid anhydride repeating unit (Patent Document 3), an N-substituted or unsubstituted glutalimide unit, a (meth) acrylic acid ester monomer unit, a vinyl aromatic unit. An imide resin containing a body unit (Patent Document 4) is disclosed. However, according to the studies by the authors, the resins of Patent Documents 3 and 4 have insufficient surface hardness, and there are still problems in their application as optical members.
本発明の目的は、耐熱性に優れるとともに、配向複屈折と光弾性複屈折がともに小さく、表面硬度が高いメタクリル系共重合体、および前記共重合体を含む組成物、成形体、フィルム又はシートの製造方法、積層体を提供することである。 An object of the present invention is a methacrylic copolymer having excellent heat resistance, small orientation birefringence and small photoelastic birefringence, and high surface hardness, and a composition, molded product, film or sheet containing the copolymer. Is to provide a manufacturing method of the above, a laminated body.
本発明は、上記目的を達成するために鋭意検討を行った結果、以下の形態を包含する本発明を完成するに至った。
〔１〕
メタクリル酸メチル単位と、α―メチルスチレン単位と、無水マレイン酸単位と、下記式（１）～（３）からなる群より選ばれる少なくともひとつの環構造を主鎖に有する構造単位（Ｒ）とを含有し、光弾性係数の絶対値が３．０×１０－１２Ｐａ－１以下であり、かつ２０ｍｍ×４０ｍｍ×厚さ１．０ｍｍのシートをガラス転移温度より１０℃高い温度にて３ｍｍ／分の速度で一方向に１００％延伸して得られる延伸フィルムの配向複屈折の絶対値が２．５×１０－４以下である、メタクリル系共重合体。
As a result of diligent studies to achieve the above object, the present invention has been completed including the following embodiments.
[1]
A methyl methacrylate unit, an α-methylstyrene unit, a maleic anhydride unit, and a structural unit (R) having at least one ring structure selected from the group consisting of the following formulas (1) to (3) in the main chain. The absolute value of the photoelastic coefficient is 3.0 × 10-12 Pa -1 or less, and a sheet of 20 mm × 40 mm × thickness 1.0 mm is 3 mm / at a temperature 10 ° C higher than the glass transition temperature. A methacrylic copolymer having an absolute value of orientation and double refraction of a stretched film obtained by stretching 100% in one direction at a rate of minutes of 2.5 × 10 -4 or less.
（式（１）中、Ｒ１１とＲ１２はそれぞれ独立に水素原子または炭素数１～５のアルキル基である。） (In formula (1), R 11 and R 12 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, respectively.)
（式（２）中、Ｒ２１とＲ２２はそれぞれ独立に水素原子またはメチル基であり、Ｒ２３は水素原子、炭素数１～１８のアルキル基、炭素数３～１２のシクロアルキル基、または芳香環を含む炭素数６～１５の有機基である。） (In the formula (2), R 21 and R 22 are independently hydrogen atoms or methyl groups, respectively, and R 23 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or It is an organic group having 6 to 15 carbon atoms including an aromatic ring.)
（式（３）中、Ｒ３１とＲ３２はそれぞれ独立に水素原子、炭素数１～１２のアルキル基、または炭素数６～１４のアリール基であり、Ｒ３３は、水素原子、炭素数１～１８のアルキル基、炭素数３～１２のシクロアルキル基、または芳香環を含む炭素数６～１５の有機基である。）
〔２〕
構造単位（Ｒ）が、式（２）で表されるＮ－置換若しくは無置換グルタルイミド単位、または式（３）で表されるＮ－置換若しくは無置換マレイミド単位からなる群より選ばれる少なくともひとつの構造単位である、〔１〕に記載のメタクリル系共重合体。
〔３〕
ガラス転移温度が１２０℃以上である、〔１〕または〔２〕記載のメタクリル系共重合体。
〔４〕
メタクリル酸メチル単位を２２～８７質量％、α－メチルスチレン単位を７～３０質量％、無水マレイン酸単位を１～３０質量％、構造単位（Ｒ）を３～７０質量％含有する、〔１〕～〔３〕のいずれかひとつに記載のメタクリル系共重合体。
〔５〕
〔１〕～〔４〕のいずれかひとつに記載のメタクリル系共重合体を含む樹脂組成物。
〔６〕
〔１〕～〔４〕のいずれかひとつに記載のメタクリル系共重合体または〔５〕に記載の組成物を含む成形体。
〔７〕
前記成形体がフィルム又はシートである、〔６〕に記載の成形体。
〔８〕
〔１〕～〔４〕のいずれかひとつに記載のメタクリル系共重合体または〔５〕に記載の組成物を溶融成形法によりフィルム又はシートに成形する工程を含む、フィルム又はシートの製造方法。
〔９〕
〔１〕～〔４〕のいずれかひとつに記載のメタクリル系共重合体または〔５〕に記載の組成物を溶液キャスト法によりフィルム又はシートに成形する工程を含む、フィルム又はシートの製造方法。
〔１０〕
〔１〕～〔４〕のいずれかひとつに記載のメタクリル系共重合体または〔５〕に記載の組成物を含むフィルム又はシートからなる層を少なくとも１層有する、積層体。
(In the formula (3), R 31 and R 32 are independently hydrogen atoms, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and R 33 is a hydrogen atom and 1 carbon atom. It is an alkyl group of ~ 18, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms including an aromatic ring.)
[2]
At least one structural unit (R) selected from the group consisting of N-substituted or unsubstituted glutarimide units represented by the formula (2) or N-substituted or unsubstituted maleimide units represented by the formula (3). The methacrylic copolymer according to [1], which is the structural unit of.
[3]
The methacrylic copolymer according to [1] or [2], wherein the glass transition temperature is 120 ° C. or higher.
[4]
It contains 22 to 87% by mass of methyl methacrylate unit, 7 to 30% by mass of α-methylstyrene unit, 1 to 30% by mass of maleic anhydride unit, and 3 to 70% by mass of structural unit (R) [1]. ] To [3]. The methacrylic copolymer according to any one of.
[5]
A resin composition containing the methacrylic copolymer according to any one of [1] to [4].
[6]
A molded product containing the methacrylic copolymer according to any one of [1] to [4] or the composition according to [5].
[7]
The molded product according to [6], wherein the molded product is a film or a sheet.
[8]
A method for producing a film or sheet, which comprises a step of molding the methacrylic copolymer according to any one of [1] to [4] or the composition according to [5] into a film or sheet by a melt molding method.
[9]
A method for producing a film or sheet, which comprises a step of molding the methacrylic copolymer according to any one of [1] to [4] or the composition according to [5] into a film or sheet by a solution casting method.
[10]
A laminate having at least one layer composed of the methacrylic copolymer according to any one of [1] to [4] or the film or sheet containing the composition according to [5].
本発明によれば、耐熱性に優れるとともに、配向複屈折と光弾性複屈折がともに小さく、表面硬度が高いメタクリル系共重合体、および前記共重合体を含む組成物、成形体、フィルム又はシートの製造方法、積層体を得ることができる。 According to the present invention, a methacrylic copolymer having excellent heat resistance, small orientation birefringence and small photoelastic birefringence, and high surface hardness, and a composition, molded product, film or sheet containing the copolymer. The manufacturing method and laminate can be obtained.
（メタクリル系共重合体）
本発明のメタクリル系共重合体は、メタクリル酸メチル単位と、α－メチルスチレン単位と、無水マレイン酸単位と、構造単位（Ｒ）とを含有する。
(Metal-based copolymer)
The methacrylic copolymer of the present invention contains a methyl methacrylate unit, an α-methylstyrene unit, a maleic anhydride unit, and a structural unit (R).
本発明のメタクリル系共重合体は、メタクリル酸メチル単位の割合が、全構造単位に対して、好ましくは２２～８７質量％、より好ましくは２７～８５質量％、さらに好ましくは３２～８０質量％である。メタクリル酸メチル単位の割合がこの範囲よりも少ないと、得られるメタクリル系共重合体の全光線透過率が悪化し、メタクリル酸メチル単位の割合がこの範囲よりも多いと、得られるメタクリル系共重合体の耐熱性は低くなる。 In the methacrylic copolymer of the present invention, the ratio of the methyl methacrylate unit is preferably 22 to 87% by mass, more preferably 27 to 85% by mass, still more preferably 32 to 80% by mass with respect to the total structural units. Is. If the proportion of methyl methacrylate units is less than this range, the total light transmittance of the obtained methacrylic acid copolymer deteriorates, and if the proportion of methyl methacrylate units is higher than this range, the obtained methacrylic acid copolymer weight is deteriorated. The heat resistance of the coalescence is low.
本発明のメタクリル系共重合体は、α－メチルスチレン単位の割合が、全構造単位に対して、好ましくは７～３０質量％、より好ましくは８～２７質量％、さらに好ましくは１１～２５質量％である。α－メチルスチレン単位の割合がこの範囲よりも少ないと、得られるメタクリル系共重合体の表面硬度が低くなる。また、α－メチルスチレン単位の割合がこの範囲よりも多いと、得られるメタクリル系共重合体の重合性が低く、生産性が低下する。 In the methacrylic copolymer of the present invention, the ratio of α-methylstyrene units is preferably 7 to 30% by mass, more preferably 8 to 27% by mass, still more preferably 11 to 25% by mass with respect to the total structural units. %. If the proportion of α-methylstyrene units is less than this range, the surface hardness of the obtained methacrylic copolymer will be low. Further, when the ratio of the α-methylstyrene unit is larger than this range, the polymerizability of the obtained methacrylic copolymer is low, and the productivity is lowered.
本発明のメタクリル系共重合体は、無水マレイン酸単位の割合が、全構造単位に対して、好ましくは１～２９．５質量％、より好ましくは２～２７質量％、さらに好ましくは３～２５質量％である。無水マレイン酸単位の割合がこの範囲よりも少ないと、得られるメタクリル系共重合体の複屈折が高くなり、無水マレイン酸単位の割合がこの範囲よりも多いと、得られるメタクリル系共重合体の耐熱性、溶融粘度が不必要に上がり、成形加工性が悪くなる。構造単位（Ｒ）が式（２）で表されるグルタルイミド単位と式（３）で表されるマレイミド単位（Ｒ３１＝Ｒ３２＝Ｈ、かつ、Ｒ３３＝Ｒ２３）を含む場合、本発明のメタクリル系共重合体は、無水マレイン酸単位の割合が、全構造単位に対して、好ましくは０．５～２７質量％、より好ましくは１～２５質量％、さらに好ましくは２ ～２３質量％である。 In the methacrylic copolymer of the present invention, the ratio of maleic anhydride units is preferably 1 to 29.5% by mass, more preferably 2 to 27% by mass, and further preferably 3 to 25 with respect to all structural units. It is mass%. If the proportion of maleic anhydride units is less than this range, the compound refraction of the obtained methacrylic acid copolymer will be high, and if the proportion of maleic anhydride units is more than this range, the obtained methacrylic acid copolymer will have a higher compound refraction. Heat resistance and melt viscosity increase unnecessarily, and molding processability deteriorates. When the structural unit (R) includes a glutarimide unit represented by the formula (2) and a maleimide unit represented by the formula (3) (R 31 = R 32 = H and R 33 = R 23 ), this In the methacrylic copolymer of the present invention, the ratio of the maleic anhydride unit is preferably 0.5 to 27% by mass, more preferably 1 to 25% by mass, and further preferably 2 with respect to the total structural units. It is ~ 23% by mass.
構造単位（Ｒ）は、無水グルタル酸単位、Ｎ－置換若しくは無置換グルタルイミド単位、Ｎ－置換若しくは無置換マレイミド単位からなる群より選ばれる少なくともひとつの環構造を主鎖に有する構造単位である。 The structural unit (R) is a structural unit having at least one ring structure selected from the group consisting of an anhydrous glutaric acid unit, an N-substituted or unsubstituted glutarimide unit, and an N-substituted or unsubstituted maleimide unit in the main chain. ..
無水グルタル酸単位は、２，６－ジオキソジヒドロピランジイル構造を有する単位である。２，６－ジオキソジヒドロピランジイル構造を有する単位としては、式（１）で表される構造単位を挙げることができる。 The glutaric anhydride unit is a unit having a 2,6-dioxodihydropyrandiyl structure. Examples of the unit having a 2,6-dioxodihydropyranziyl structure include a structural unit represented by the formula (1).
式（１）中、Ｒ１１とＲ１２はそれぞれ独立に水素原子または炭素数１～５のアルキル基であり、メチル基であるのが好ましい。 In the formula (1), R 11 and R 12 are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and are preferably methyl groups.
２，６－ジオキソジヒドロピランジイル構造を有する単位は、特開２００７－１９７７０３号公報、特開２０１０－９６９１９号公報などに記載の方法、例えば、隣り合う二つの（メタ）アクリル酸に由来する構造単位の分子内環化、（メタ）アクリル酸に由来する構造単位と（メタ）アクリル酸メチルに由来する構造単位との分子内環化などによって、メタクリル系共重合体に含有させることができる。 The unit having a 2,6-dioxodihydropyranjiyl structure is derived from the methods described in JP-A-2007-197703, JP-A-2010-96919, etc., for example, two adjacent (meth) acrylic acids. It can be contained in a methacrylic copolymer by intramolecular cyclization of structural units, intramolecular cyclization of structural units derived from (meth) acrylic acid and structural units derived from methyl (meth) acrylate. ..
Ｎ－置換若しくは無置換グルタルイミド単位は、Ｎ－置換若しくは無置換２，６－ジオキソピペリジンジイル構造を有する単位である。 An N-substituted or unsubstituted glutarimide unit is a unit having an N-substituted or unsubstituted 2,6-dioxopiperidinediyl structure.
Ｎ－置換若しくは無置換２，６－ジオキソピペリジンジイル構造を有する単位としては、式（２）で表される構造単位を挙げることができる。 Examples of the unit having an N-substituted or unsubstituted 2,6-dioxopiperidinediyl structure include a structural unit represented by the formula (2).
式（２）中、Ｒ２１とＲ２２はそれぞれ独立に水素原子またはメチル基であり、メチル基であるのが好ましい。Ｒ２３は水素原子、炭素数１～１８のアルキル基、炭素数３～１２のシクロアルキル基、または芳香環を含む炭素数６～１５の有機基であり、好ましくは水素原子、メチル基、ｎ－ブチル基、シクロヘキシル基またはベンジル基であり、より好ましくはメチル基、ｎ－ブチル基、またはシクロヘキシル基である。 In the formula (2), R 21 and R 22 are independently hydrogen atoms or methyl groups, and are preferably methyl groups. R 23 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms including an aromatic ring, preferably a hydrogen atom, a methyl group, or n. -A butyl group, a cyclohexyl group or a benzyl group, more preferably a methyl group, an n-butyl group or a cyclohexyl group.
式（２）で表される構造単位は、例えばスキーム（ｉ）で示されるように対応する酸無水物（1a）とＲ２３－ＮＨ２で表されるイミド化剤の反応により生成してもよく、式（4）の部分構造を有する共重合体の分子内環化反応により生成してもよい。分子内環化反応により式（4）で表される構造単位を式（2）で表される構造単位に変換するために加熱することが好ましい。
スキーム（ｉ）
The structural unit represented by the formula (2) may be produced, for example, by the reaction of the corresponding acid anhydride (1a) and the imidizing agent represented by R 23 -NH 2 as shown in the scheme (i). Often, it may be produced by an intramolecular cyclization reaction of a copolymer having a partial structure of the formula (4). It is preferable to heat the structural unit represented by the formula (4) in order to convert it into the structural unit represented by the formula (2) by an intramolecular cyclization reaction.
Scheme (i)
（式中、Ｒ２１、Ｒ２２、Ｒ２３は前記に定義される通りである。）
Ｎ－置換若しくは無置換グルタルイミド単位は、ＷＯ２００５／１０８３８Ａ１、特開２０１０－２５４７４２号公報、特開２００８－２７３１４０号公報、特開２００８－２７４１８７号公報などに記載の方法、具体的には、隣り合う二つのメタクリル酸メチルに由来する構造単位または無水グルタル酸単位に、アンモニア、メチルアミン、エチルアミン、ｎ－プロピルアミン、イソプロピルアミン、ｎ－ブチルアミン、イソブチルアミン、ｔｅｒｔ－ブチルアミン、ｎ－ヘキシルアミン等の脂肪族炭化水素基含有アミン、アニリン、トルイジン、トリクロロアニリン等の芳香族炭化水素基含有アミン、シクロヘキシルアミン等などの脂環式炭化水素基含有アミン、尿素、１，３－ジメチル尿素、１，３－ジエチル尿素、１，３－ジプロピル尿素などのイミド化剤を反応させることによって得ることができる。これらの中で、メチルアミンが好ましい。
(In the formula, R 21 , R 22 , and R 23 are as defined above.)
The N-substituted or unsubstituted glutarimide unit is the method described in WO2005 / 10838A1, JP-A-2010-254742, JP-A-2008-273140, JP-A-2008-274187, and the like, specifically, adjacent to each other. Structural units or glutaric acid anhydride units derived from two matching methyl methacrylates include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, n-hexylamine and the like. Arophilic hydrocarbon group-containing amines such as aliphatic hydrocarbon group-containing amines, aniline, toluidine, and trichloroaniline, alicyclic hydrocarbon group-containing amines such as cyclohexylamine, urea, 1,3-dimethylurea, 1,3. -It can be obtained by reacting with an imidizing agent such as diethylurea and 1,3-dipropylurea. Of these, methylamine is preferred.
Ｎ－置換若しくは無置換マレイミド単位は、Ｎ－置換若しくは無置換２，５－ジオキソ－２，５－ジヒドロピロール－３，４－ジイル構造を有する単位である。 The N-substituted or unsubstituted maleimide unit is a unit having an N-substituted or unsubstituted 2,5-dioxo-2,5-dihydropyrrole-3,4-diyl structure.
Ｎ－置換若しくは無置換２，５－ジオキソ－２，５－ジヒドロピロール－３，４－ジイル構造を有する単位としては、式（３）で表される構造単位を挙げることができる。 Examples of the unit having an N-substituted or unsubstituted 2,5-dioxo-2,5-dihydropyrrole-3,4-diyl structure include a structural unit represented by the formula (3).
式（３）中、Ｒ３１とＲ３２はそれぞれ独立に水素原子、炭素数１～１２のアルキル基、または炭素数６～１４のアリール基であり、Ｒ３３は、水素原子、炭素数１～１８のアルキル基、炭素数３～１２のシクロアルキル基、または芳香環を含む炭素数６～１５の有機基である。 In the formula (3), R 31 and R 32 are independently hydrogen atoms, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and R 33 is a hydrogen atom and 1 to 12 carbon atoms. It is an alkyl group having 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms containing an aromatic ring.
Ｎ－置換若しくは無置換マレイミド単位を形成する方法は、特に限定されず、対応するＮ－置換若しくは無置換マレイミド単量体を共重合する方法により形成してもよい。Ｎ－置換若しくは無置換マレイミド単量体としては、マレイミド；Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、Ｎ－ｎ－プロピルマレイミド、Ｎ－イソプロピルマレイミド、Ｎ－ｎ－ブチルマレイミド、Ｎ－イソブチルマレイミド、Ｎ－ｓ－ブチルマレイミド、Ｎ－ｔ－ブチルマレイミド、Ｎ－ｎ－ペンチルマレイミド、Ｎ－ｎ－ヘキシルマレイミド、Ｎ－ｎ－ヘプチルマレイミド、Ｎ－ｎ－オクチルマレイミド、Ｎ－ラウリルマレイミド、Ｎ－ステアリルマレイミド等のＮ－アルキルマレイミド；Ｎ－シクロペンチルマレイミド、Ｎ－シクロヘキシルマレイミド、１－シクロヘキシル－３－メチル－１－フェニル－１Ｈ－ピロール－２，５－ジオン、１－シクロヘキシル－３，４－ジメチル－１－フェニル－１Ｈ－ピロール－２，５－ジオン、１－シクロヘキシル－３－フェニル－１Ｈ－ピロール－２，５－ジオン、１－シクロヘキシル－３，４－ジフェニル－１Ｈ－ピロール－２，５－ジオン等のＮ－シクロアルキルマレイミド；Ｎ－フェニルマレイミド、Ｎ－（２－クロロフェニル）マレイミド、Ｎ－（４－クロロフェニル）マレイミド、Ｎ－（４－ブロモフェニル）マレイミド、Ｎ－（２－メチルフェニル）マレイミド、Ｎ－（２－エチルフェニル）マレイミド、Ｎ－（２－メトキシフェニル）マレイミド、Ｎ－（２－ニトロフェニル）マレイミド、Ｎ－（２、４、６－トリメチルフェニル）マレイミド、Ｎ－（４－ベンジルフェニル）マレイミド、Ｎ－（２、４、６－トリブロモフェニル）マレイミド、Ｎ－ナフチルマレイミド、Ｎ－アントラセニルマレイミド、３－メチル－１－フェニル－１Ｈ－ピロール－２，５－ジオン、３，４－ジメチル－１－フェニル－１Ｈ－ピロール－２，５－ジオン、１，３－ジフェニル－１Ｈ－ピロール－２，５－ジオン、１，３，４－トリフェニル－１Ｈ－ピロール－２，５－ジオン等のＮ－アリールマレイミド；Ｎ－ベンジルマレイミド等が挙げられる。これらの単量体のうち、メタクリル系共重合体の耐候性の観点から、Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、Ｎ－イソプロピルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミド、Ｎ－ベンジルマレイミドが好ましく、Ｎ－メチルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミドが特に好ましい。 The method for forming the N-substituted or unsubstituted maleimide unit is not particularly limited, and may be formed by a method of copolymerizing the corresponding N-substituted or unsubstituted maleimide monomer. Examples of the N-substituted or unsubstituted maleimide monomer include maleimide; N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N. -S-butylmaleimide, Nt-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide N-alkylmaleimide such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, 1-cyclohexyl-3-methyl-1-phenyl-1H-pyrrole-2,5-dione, 1-cyclohexyl-3,4-dimethyl-1 -Phenyl-1H-pyrol-2,5-dione, 1-cyclohexyl-3-phenyl-1H-pyrol-2,5-dione, 1-cyclohexyl-3,4-diphenyl-1H-pyrol-2,5-dione N-Cycloalkylmaleimide, etc .; N-phenylmaleimide, N- (2-chlorophenyl) maleimide, N- (4-chlorophenyl) maleimide, N- (4-bromophenyl) maleimide, N- (2-methylphenyl) maleimide, etc. , N- (2-ethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N- (2-nitrophenyl) maleimide, N- (2,4,6-trimethylphenyl) maleimide, N- (4-) Benzylphenyl) maleimide, N- (2,4,6-tribromophenyl) maleimide, N-naphthylmaleimide, N-anthrasenylmaleimide, 3-methyl-1-phenyl-1H-pyrrole-2,5-dione, 3,4-dimethyl-1-phenyl-1H-pyrrole-2,5-dione, 1,3-diphenyl-1H-pyrrole-2,5-dione, 1,3,4-triphenyl-1H-pyrrole-2 , 5-Dione and the like N-arylmaleimide; N-benzylmaleimide and the like. Among these monomers, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide are selected from the viewpoint of weather resistance of methacrylic copolymers. Preferably, N-methylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide are particularly preferable.
Ｎ－置換若しくは無置換マレイミド単位は、特開２００６－１２４５９２号公報に記載の方法、具体的には、無水マレイン酸単位にイミド化剤を反応させることによっても得ることができる。イミド化剤としては、例えば、アンモニア、メチルアミン、エチルアミン、ｎ－プロピルアミン、イソプロピルアミン、ｎ－ブチルアミン、イソブチルアミン、ｔｅｒｔ－ブチルアミン、ｎ－ヘキシルアミン等の脂肪族炭化水素基含有アミン、アニリン、トルイジン、トリクロロアニリン、ベンジルアミン等の芳香族炭化水素基含有アミン、シクロヘキシルアミン等の脂環式炭化水素基含有アミン、尿素、１，３－ジメチル尿素、１，３－ジエチル尿素、１，３－ジプロピル尿素などが挙げられ、これらイミド化剤のうち、メチルアミンが好ましい。 The N-substituted or unsubstituted maleimide unit can also be obtained by reacting an imidizing agent with the method described in JP-A-2006-124592, specifically, a maleic anhydride unit. Examples of the imidizing agent include aliphatic hydrocarbon group-containing amines such as ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine and n-hexylamine, and aniline. Aromatic hydrocarbon group-containing amines such as toluidine, trichloroaniline, benzylamine, alicyclic hydrocarbon group-containing amines such as cyclohexylamine, urea, 1,3-dimethylurea, 1,3-diethylurea, 1,3- Examples thereof include dipropylurea, and among these imidizing agents, methylamine is preferable.
本発明のメタクリル系共重合体は、構造単位（Ｒ）の割合が、全構造単位に対して、好ましくは３～７０質量％、より好ましくは５～６５質量％、さらに好ましくは８～６０質量％である。構造単位（Ｒ）の割合が全構造単位に対して上記の範囲内であれば、耐熱性が高く、樹脂の複屈折を好適に制御しつつ、成形加工性に優れたメタクリル系共重合体が得られるので、好ましい。 In the methacrylic copolymer of the present invention, the ratio of the structural unit (R) is preferably 3 to 70% by mass, more preferably 5 to 65% by mass, and further preferably 8 to 60% by mass with respect to all the structural units. %. When the ratio of the structural unit (R) is within the above range with respect to all the structural units, a methacrylic copolymer having high heat resistance, suitable control of birefringence of the resin, and excellent molding processability can be obtained. It is preferable because it can be obtained.
本発明のメタクリル系共重合体は、メタクリル酸メチル単位、α－メチルスチレン単位、無水マレイン酸単位、構造単位（Ｒ）の他に、共重合可能なその他のビニル系単量体単位を任意に含んでもよい。共重合可能なその他のビニル系単量体としては、メタクリル酸エチル、メタクリル酸ブチルなどのメタクリル酸メチル以外のメタクリル酸アルキルエステル；メタクリル酸フェニルなどのメタクリル酸アリールエステル；メタクリル酸シクロへキシル、メタクリル酸ノルボルネニルなどのメタクリル酸シクロアルキルエステル；アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチルなどのアクリル酸アルキルエステル；アクリル酸フェニルなどのアクリル酸アリールエステル；アクリル酸シクロへキシル、アクリル酸ノルボルネニルなどのアクリル酸シクロアルキルエステル；スチレンなどα－メチルスチレン以外の芳香族ビニル単量体；アクリルアミド；メタクリルアミド；アクリロニトリル、メタクリロニトリルなどのシアン化ビニル単量体；などの一分子中に重合性アルケニル基を一つだけ有するビニル単量体が挙げられる。これら単量体のうち、メタクリル共重合体の複屈折を高度に制御する観点から、アクリル酸アルキルエステル、α－メチルスチレン以外の芳香族ビニル単量体、シアン化ビニル単量体が好ましく、アクリル酸メチル、スチレン、アクリロニトリルがより好ましく、スチレンがさらに好ましい。 The methacrylic copolymer of the present invention may optionally contain other copolymerizable vinyl-based monomer units in addition to the methyl methacrylate unit, α-methylstyrene unit, maleic anhydride unit, and structural unit (R). It may be included. Other copolymerizable vinyl-based monomers include methacrylic acid alkyl esters other than methyl methacrylate such as ethyl methacrylate and butyl methacrylate; methacrylic acid aryl esters such as phenyl methacrylate; cyclohexyl methacrylate and methacrylic acid. Methacrylic acid cycloalkyl ester such as norbornenyl acid; Acrylic acid alkyl ester such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate; Acrylic acid aryl ester such as phenyl acrylate; Cyclohexyl acrylate, acrylate Acrylic acid cycloalkyl ester such as norbornenyl; aromatic vinyl monomer other than α-methylstyrene such as styrene; acrylamide; methacrylicamide; vinyl cyanide monomer such as acrylonitrile and methacrylic nitrile; Examples thereof include vinyl monomers having only one sex alkenyl group. Of these monomers, acrylic acid alkyl esters, aromatic vinyl monomers other than α-methylstyrene, and vinyl cyanide monomers are preferable, from the viewpoint of highly controlling the double refraction of the methacrylic copolymer. Methyl acid, styrene and acrylonitrile are more preferred, and styrene is even more preferred.
本発明のメタクリル系共重合体は、共重合可能なその他のビニル系単量体単位の割合が、全構造単位に対して、好ましくは３０質量％以下である。 In the methacrylic copolymer of the present invention, the proportion of other copolymerizable vinyl-based monomer units is preferably 30% by mass or less with respect to the total structural units.
本発明のメタクリル系共重合体は、重量平均分子量（Ｍｗ）が、好ましくは４００００～２０００００、より好ましくは５００００～１８００００、さらに好ましくは５５０００～１６００００である。Ｍｗが４００００以上であると、本発明の成形体の強度および靭性等が向上する。Ｍｗが２０００００以下であると、本発明のメタクリル系共重合体の流動性が向上し、成形加工性が向上する。 The methacrylic copolymer of the present invention has a weight average molecular weight (Mw) of preferably 40,000 to 200,000, more preferably 50,000 to 1,800,000, still more preferably 55,000 to 1,600,000. When Mw is 40,000 or more, the strength and toughness of the molded product of the present invention are improved. When Mw is 200,000 or less, the fluidity of the methacrylic copolymer of the present invention is improved, and the molding processability is improved.
重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定されるクロマトグラムを標準ポリスチレンの分子量に換算して算出される値である。 The weight average molecular weight (Mw) is a value calculated by converting a chromatogram measured by gel permeation chromatography (GPC) into a molecular weight of standard polystyrene.
本発明のメタクリル系共重合体は、酸価が、好ましくは０．０１～０．３０ｍｍｏｌ／ｇ、より好ましくは０．０５～０．２８ｍｍｏｌ／ｇである。酸価は、メタクリル系共重合体中のカルボン酸単位、カルボン酸無水物単位の含有量に比例する値である。酸価は、例えば、特開２００５－２３２７２号公報に記載の方法によって算出することができる。酸価が上記範囲内にあると、耐熱性、機械物性、成形加工性のバランスに優れる。 The methacrylic copolymer of the present invention has an acid value of preferably 0.01 to 0.30 mmol / g, more preferably 0.05 to 0.28 mmol / g. The acid value is a value proportional to the content of the carboxylic acid unit and the carboxylic acid anhydride unit in the methacrylic copolymer. The acid value can be calculated, for example, by the method described in JP-A-2005-23272. When the acid value is within the above range, the balance between heat resistance, mechanical properties, and molding processability is excellent.
本発明のメタクリル系共重合体は、ガラス転移温度が、下限として、好ましくは１２０℃、より好ましくは１２１℃、さらに好ましくは１２２℃であり、上限として、特に制限されないが、好ましくは２００℃である。メタクリル系共重合体のガラス転移温度が高くなるほど、メタクリル系共重合体を含む成形体は熱による変形や収縮を起こしにくく、すなわち耐熱性が高い。 The methacrylic copolymer of the present invention has a glass transition temperature of preferably 120 ° C., more preferably 121 ° C., still more preferably 122 ° C. as a lower limit, and the upper limit is not particularly limited, but is preferably 200 ° C. be. The higher the glass transition temperature of the methacrylic copolymer, the less likely the molded body containing the methacrylic copolymer to be deformed or shrunk due to heat, that is, the higher the heat resistance.
本明細書において、「ガラス転移温度（Ｔｇ）」は、ＪＩＳ Ｋ７１２１に準拠して測定する。具体的には、２３０℃まで一度昇温し、次いで室温まで冷却し、その後、室温から２３０℃までを１０℃／分で昇温させる条件にてＤＳＣ曲線を測定する。２回目の昇温時に測定されるＤＳＣ曲線から求められる中間点を「ガラス転移温度（Ｔｇ）」として求める。 In the present specification, the "glass transition temperature (Tg)" is measured according to JIS K7121. Specifically, the DSC curve is measured under the condition that the temperature is raised to 230 ° C., then cooled to room temperature, and then the temperature is raised from room temperature to 230 ° C. at 10 ° C./min. The intermediate point obtained from the DSC curve measured at the time of the second temperature rise is obtained as the "glass transition temperature (Tg)".
本発明のメタクリル系共重合体は、後述する方法により測定した光弾性係数の絶対値が、３．０×１０－１２Ｐａ－１以下であることが好ましい。より好ましくは、２．５×１０－１２Ｐａ－１以下、さらに好ましくは、２．０×１０－１２Ｐａ－１以下である。 In the methacrylic copolymer of the present invention, the absolute value of the photoelastic coefficient measured by the method described later is preferably 3.0 × 10-12 Pa -1 or less. More preferably, it is 2.5 × 10 -12 Pa -1 or less, and even more preferably 2.0 × 10 -12 Pa -1 or less.
光弾性係数は、メタクリル系共重合体からなる幅１５ｍｍ×長さ６０ｍｍ×厚さ１．０ｍｍのプレス成形シートに、チャック間距離４５ｍｍ、温度２３℃にて、張力を０Ｎから１０Ｎずつ増して１００Ｎまで付与し、張力増加の都度に、シートの中央部分を、温度２３℃、ＮａのＤ線波長にて、複屈折を測定し、測定された応力と複屈折との関係を最小二乗法で一次関数に近似したときに算出される傾きである。なお、応力は、張力をシート断面積で除した値である。シート断面積はシート幅１５ｍｍとシートの中央部分の測定点における厚さとの積として算出した。複屈折は、引張方向に平行な偏光面を持つ光の屈折率ｎpと引張方向に垂直な偏光面を持つ光の屈折率ｎoとの差（Δｎ＝ｎp－ｎo）として定義される。 The photoelastic coefficient is 100 N on a press-formed sheet made of a methacrylic copolymer having a width of 15 mm, a length of 60 mm, and a thickness of 1.0 mm, and the tension is increased by 10 N from 0 N at a chuck distance of 45 mm and a temperature of 23 ° C. When the tension is increased, the central part of the sheet is measured for double refraction at a temperature of 23 ° C and a D-line wavelength of Na, and the relationship between the measured stress and double refraction is first-ordered by the minimum square method. It is the slope calculated when it approximates the function. The stress is a value obtained by dividing the tension by the cross-sectional area of the sheet. The sheet cross-sectional area was calculated as the product of the sheet width of 15 mm and the thickness at the measurement point of the central portion of the sheet. Birefringence is defined as the difference ( Δn = n p − no) between the refractive index n p of light having a polarization plane parallel to the tensile direction and the refractive index no of light having a polarizing plane perpendicular to the tensile direction. Ru.
本発明のメタクリル系共重合体は、後述する方法により測定した配向複屈折の絶対値が、２．５×１０－４以下であることが好ましい。より好ましくは、２．３×１０－４以下、さらに好ましくは、２．２×１０－４以下、よりさらに好ましくは、２．０×１０－４以下である。 In the methacrylic copolymer of the present invention, the absolute value of the orientation birefringence measured by the method described later is preferably 2.5 × 10 -4 or less. It is more preferably 2.3 × 10 -4 or less, further preferably 2.2 × 10 -4 or less, and even more preferably 2.0 × 10 -4 or less.
配向複屈折は、メタクリル系共重合体からなる幅２０ｍｍ×長さ４０ｍｍ×厚さ１．０ｍｍのプレス成形シートをガラス転移温度より１０℃高い温度にて３ｍｍ／分の速度で一方向に１００％延伸して得られる延伸フィルムの中央部分を、温度２３℃、ＮａのＤ線波長にて、張力を掛けずに、計測された複屈折である。
（メタクリル系共重合体の製造方法）
本発明のメタクリル系共重合体は、例えば、メタクリル酸メチル、α－メチルスチレン、無水マレイン酸、及び任意に選択される共重合可能なその他のビニル系単量体の共重合体（以下、前駆体ポリマーということがある）を環構造形成反応させることを含む方法によって得ることができる。
Orientation double refraction is 100% in one direction at a rate of 3 mm / min at a temperature 10 ° C higher than the glass transition temperature of a press-formed sheet made of a methacrylic copolymer having a width of 20 mm, a length of 40 mm, and a thickness of 1.0 mm. The central portion of the stretched film obtained by stretching is a double refraction measured at a temperature of 23 ° C. and a D-line wavelength of Na without applying tension.
(Manufacturing method of methacrylic copolymer)
The methacrylic copolymer of the present invention is, for example, a copolymer of methyl methacrylate, α-methylstyrene, maleic anhydride, and an arbitrarily selected copolymerizable other vinyl-based monomer (hereinafter, precursor). It can be obtained by a method including a ring structure forming reaction (sometimes referred to as a body polymer).
すなわち本発明のメタクリル系共重合体の製造方法は、メタクリル酸メチル５１～９４質量％、α－メチルスチレン５～３０質量％、無水マレイン酸１～３０質量％、共重合可能なその他のビニル系単量体０～３０質量％を含む単量体混合物と、ラジカル重合開始剤と、必要に応じ連鎖移動剤とを含んでなる反応原料を、槽型反応器に連続的に供給する工程、
槽型反応器内で前記単量体混合物を重合転化率３０～６０質量％まで塊状重合して反応生成物を得る工程、および
反応生成物中の単量体混合物を除去して前駆体ポリマーを得る工程、
得られた前駆体ポリマーに環構造形成反応をさせる工程
を含み、各工程は公知の技術によって実施することができる。
That is, the method for producing a methacrylic copolymer of the present invention is 51 to 94% by mass of methyl methacrylate, 5 to 30% by mass of α-methylstyrene, 1 to 30% by mass of maleic anhydride, and other copolymerizable vinyl-based copolymers. A step of continuously supplying a reaction raw material containing a monomer mixture containing 0 to 30% by mass of a monomer, a radical polymerization initiator, and, if necessary, a chain transfer agent, to a tank-type reactor.
A step of bulk polymerization of the monomer mixture to a polymerization conversion rate of 30 to 60% by mass in a tank-type reactor to obtain a reaction product, and removal of the monomer mixture in the reaction product to obtain a precursor polymer. Getting process,
Each step can be carried out by a known technique, including a step of allowing the obtained precursor polymer to undergo a ring structure forming reaction.
前駆体ポリマーは、単量体混合物とラジカル重合開始剤と必要に応じて連鎖移動剤とを含む反応原料から重合して製造されるものであり、単量体混合物はメタクリル酸メチルを単量体混合物の中に５１～９４質量％、好ましくは５５～８５質量％含むものである。α－メチルスチレンは、５～３０質量％、好ましくは７～２５質量％含むものである。無水マレイン酸は、１～３０質量％、好ましくは、３～２５質量％含むものである。共重合可能なその他のビニル系単量体は０～３０質量％、好ましくは、３～２５質量％含むものである。 The precursor polymer is produced by polymerizing from a reaction raw material containing a monomer mixture, a radical polymerization initiator and, if necessary, a chain transfer agent, and the monomer mixture contains methyl methacrylate as a monomer. The mixture contains 51 to 94% by mass, preferably 55 to 85% by mass. α-Methylstyrene is contained in an amount of 5 to 30% by mass, preferably 7 to 25% by mass. Maleic anhydride is contained in an amount of 1 to 30% by mass, preferably 3 to 25% by mass. The other copolymerizable vinyl-based monomer contains 0 to 30% by mass, preferably 3 to 25% by mass.
単量体混合物は、メタクリル酸メチル、α－メチルスチレン、無水マレイン酸以外の共重合可能なその他のビニル系単量体を含んでいてもよく、具体的には、上記で例示した単量体が挙げられ、好ましい例も同様である。 The monomer mixture may contain other copolymerizable vinyl-based monomers other than methyl methacrylate, α-methylstyrene and maleic anhydride, and specifically, the monomers exemplified above. The same applies to preferred examples.
単量体混合物は、ｂ*が－１～２であることが好ましく、－０．５～１．５であることがより好ましい。ｂ*がこの範囲にあると、得られるメタクリル系共重合体組成物を成形した場合に、着色が殆んどない成形品を、高い生産効率で得る上で有利となる。なお、ｂ*は国際照明委員会（ＣＩＥ）規格（１９７６年）またはＪＩＳ Ｚ－８７２２に準拠して測定した値である。 The monomer mixture preferably has b * of -1 to 2, more preferably -0.5 to 1.5. When b * is in this range, it is advantageous to obtain a molded product having almost no coloring when the obtained methacrylic copolymer composition is molded with high production efficiency. Note that b * is a value measured in accordance with the International Commission on Illumination (CIE) standard (1976) or JIS Z-8722.
用いられる重合開始剤は、反応性ラジカルを発生するものであれば特に限定されない。例えば、ジイソプロピルベンゼンヒドロペルオキシド、ｔ－ブチルヒドロペルオキシドなどのペルオキシド系開始剤、２，２’－アゾビス（２－メチルプロピオニトリル）などのアゾ系開始剤が挙げられる。 The polymerization initiator used is not particularly limited as long as it generates a reactive radical. Examples thereof include a peroxide-based initiator such as diisopropylbenzene hydroperoxide and t-butyl hydroperoxide, and an azo-based initiator such as 2,2'-azobis (2-methylpropionitrile).
用いられる重合開始剤は、後述する槽型反応器内の重合温度における未開裂の平均開始剤濃度が５．１×１０－５～２．４×１０－４（ｍｏｌ／Ｌ）の範囲であることが望ましい。 The polymerization initiator used has an uncracked average initiator concentration in the range of 5.1 × 10-5 to 2.4 × 10 -4 (mol / L) at the polymerization temperature in the tank reactor described later. Is desirable.
重合開始剤の使用量は、重合温度に合わせ、上記開始剤濃度となる様に、単量体混合物に添加する。 The amount of the polymerization initiator used is adjusted to the polymerization temperature and added to the monomer mixture so as to have the above-mentioned initiator concentration.
用いられる連鎖移動剤としては、ｎ－オクチルメルカプタン、ｎ－ドデシルメルカプタンなどの単官能アルキルメルカプタンが好ましい。これら連鎖移動剤は１種単独でまたは２種以上を組み合わせて用いることができる。連鎖移動剤の使用量は、単量体混合物１００質量部に対して、好ましくは０～１質量部、より好ましくは０．０１～０．８質量部、さらに好ましくは０．０２～０．６質量部である。 As the chain transfer agent used, monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan are preferable. These chain transfer agents can be used alone or in combination of two or more. The amount of the chain transfer agent used is preferably 0 to 1 part by mass, more preferably 0.01 to 0.8 part by mass, and further preferably 0.02 to 0.6 part by mass with respect to 100 parts by mass of the monomer mixture. It is a mass part.
塊状重合においては溶剤を原則使用しないが、重合反応速度や反応液の粘度を調整するなどの目的において、必要に応じて有機溶剤を反応原料に含めることができる。有機溶剤としては、ベンゼン、トルエン、キシレンなどの芳香族炭化水素、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセトフェノン等のケトン類、テトラヒドロフラン、１、４－ジオキサン等のエーテル類などが挙げられるが、単量体や共重合体の溶解度、溶剤回収のし易さの観点から、メチルエチルケトン、メチルイソブチルケトン、トルエンが好ましい。有機溶剤は１種単独でまたは２種以上を組み合わせて用いることができる。有機溶剤の使用量の上限は、単量体混合物１００質量部に対して、好ましくは３０質量部、より好ましくは２５質量部、さらに好ましくは２０質量部である。有機溶剤の使用量の下限は、通常、０質量部、好ましくは１質量部である。 In bulk polymerization, a solvent is not used in principle, but an organic solvent can be included in the reaction raw material as needed for the purpose of adjusting the polymerization reaction rate and the viscosity of the reaction solution. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetophenone, and ethers such as tetrahydrofuran and 1,4-dioxane. Methyl ethyl ketone, methyl isobutyl ketone, and toluene are preferable from the viewpoints of solubility of the body and copolymer and ease of solvent recovery. The organic solvent may be used alone or in combination of two or more. The upper limit of the amount of the organic solvent used is preferably 30 parts by mass, more preferably 25 parts by mass, and further preferably 20 parts by mass with respect to 100 parts by mass of the monomer mixture. The lower limit of the amount of the organic solvent used is usually 0 parts by mass, preferably 1 part by mass.
槽型反応器内の温度、すなわち反応槽内にある液の温度は、好ましくは１１０～１４０℃、より好ましくは１１４～１３５℃である。温度がこの範囲よりも高いと、α-メチルスチレンを含む高分子量体が生成しづらく、耐熱性の低下の原因となる。 The temperature in the tank reactor, that is, the temperature of the liquid in the reaction tank is preferably 110 to 140 ° C, more preferably 114 to 135 ° C. If the temperature is higher than this range, it is difficult to form a high molecular weight substance containing α-methylstyrene, which causes a decrease in heat resistance.
槽型反応器においては塊状重合を、重合転化率が３０～６５質量％となるまで、好ましくは３５～６０質量％となるまで行うことが好ましい。 In the tank reactor, bulk polymerization is preferably carried out until the polymerization conversion is 30 to 65% by mass, preferably 35 to 60% by mass.
また、槽型反応器における反応原料の平均滞留時間（θ）は、好ましくは１．５～５時間、より好ましくは２～４．５時間、さらに好ましくは２．５～４時間である。平均滞留時間が短すぎると重合開始剤の必要量が増える。また重合開始剤の増量により重合反応の制御が難しくなるとともに、分子量の制御が困難になる傾向がある。一方、平均滞留時間が長すぎると反応が定常状態になるまでに時間を要し、生産性が低下する傾向がある。平均滞留時間は槽型反応器の容量と反応原料の供給量によって調整することができる。 The average residence time (θ) of the reaction raw material in the tank reactor is preferably 1.5 to 5 hours, more preferably 2 to 4.5 hours, and further preferably 2.5 to 4 hours. If the average residence time is too short, the required amount of polymerization initiator will increase. Further, increasing the amount of the polymerization initiator makes it difficult to control the polymerization reaction and tends to make it difficult to control the molecular weight. On the other hand, if the average residence time is too long, it takes time for the reaction to reach a steady state, and the productivity tends to decrease. The average residence time can be adjusted by the capacity of the tank reactor and the supply amount of the reaction raw material.
塊状重合は窒素ガスなど不活性ガス雰囲気で行うことが好ましい。 Bulk polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen gas.
本発明に関わる好ましい製造方法は、反応生成物中の単量体混合物を除去する工程を有する。除去方法は特に制限されないが、加熱脱揮法が好ましい。単量体混合物を除去した後、メタクリル系共重合体組成物は、成形材料としての扱い易さを容易にするために、公知の方法に従って、ペレットや粉粒にすることができる。得られるメタクリル系樹脂組成物中の単量体混合物の含有量は、１質量％以下であることが好ましく、０．５質量％以下であることがより好ましい。 The preferred production method according to the present invention comprises the step of removing the monomer mixture in the reaction product. The removal method is not particularly limited, but a heat volatilization method is preferable. After removing the monomer mixture, the methacrylic copolymer composition can be pelletized or powdered according to a known method in order to facilitate handling as a molding material. The content of the monomer mixture in the obtained methacrylic resin composition is preferably 1% by mass or less, more preferably 0.5% by mass or less.
前駆体ポリマーは、ガラス転移温度が、下限として好ましくは１１４℃、より好ましくは１１５℃、さらに好ましくは１１７℃である。ガラス転移温度は、分子量やα-メチルスチレン共重合量などを調節することによって変えることができる。前駆体ポリマーのガラス転移温度が高いほど耐熱性が向上する。ガラス転移温度の高い前駆体ポリマーを用いて得られるメタクリル系共重合体は、構造単位（Ｒ）の量が少なくても高い耐熱性を有するので、飽和吸水率の悪化等を引き起し難い。 The precursor polymer has a glass transition temperature of preferably 114 ° C., more preferably 115 ° C., and even more preferably 117 ° C. as the lower limit. The glass transition temperature can be changed by adjusting the molecular weight, the amount of α-methylstyrene copolymerization, and the like. The higher the glass transition temperature of the precursor polymer, the better the heat resistance. Since the methacrylic copolymer obtained by using the precursor polymer having a high glass transition temperature has high heat resistance even if the amount of the structural unit (R) is small, it is unlikely to cause deterioration of the saturated water absorption rate.
前駆体ポリマーは、メタクリル酸メチルに由来する構造単位の総含有量が５１～９２質量％、α－メチルスチレンに由来する構造単位の総含有量が５～３０質量％、無水マレイン酸に由来する構造単位の総含有量が１～３０質量％のものであれば、特に制限されない。重合性、透明性などの観点から、前駆体ポリマーのメタクリル酸メチルに由来する構造単位の総含有量は、好ましくは５１質量％以上９２質量％以下、より好ましくは５５質量％以上９２質量％以下、最も好ましくは６０質量％以上９２質量％以下である。 The precursor polymer has a total content of 51 to 92% by mass of structural units derived from methyl methacrylate, a total content of 5 to 30% by mass of structural units derived from α-methylstyrene, and is derived from maleic anhydride. The total content of the structural unit is not particularly limited as long as it is 1 to 30% by mass. From the viewpoint of polymerizable property, transparency, etc., the total content of structural units derived from methyl methacrylate of the precursor polymer is preferably 51% by mass or more and 92% by mass or less, more preferably 55% by mass or more and 92% by mass or less. Most preferably, it is 60% by mass or more and 92% by mass or less.
耐熱性、重合性、吸水率などの観点から、前駆体ポリマーのα－メチルスチレンに由来する構造単位の総含有量は、好ましくは７～３０質量％、より好ましくは８～２７質量％、さらに好ましくは１１～２５質量％である。α－メチルスチレンに由来する構造単位がこの範囲よりも少ないと、十分な耐熱性が得られず、この範囲よりも多いと、重合性が著しく低下する。 From the viewpoint of heat resistance, polymerizability, water absorption, etc., the total content of structural units derived from α-methylstyrene of the precursor polymer is preferably 7 to 30% by mass, more preferably 8 to 27% by mass, and further. It is preferably 11 to 25% by mass. If the number of structural units derived from α-methylstyrene is less than this range, sufficient heat resistance cannot be obtained, and if it is more than this range, the polymerizable property is significantly lowered.
耐熱性、光学物性（特に複屈折性）の制御性の観点から、前駆体ポリマーの無水マレイン酸に由来する構造単位の総含有量は、好ましくは１～３０質量％、より好ましくは２～２７質量％、さらに好ましくは３～２７質量％である。無水マレイン酸に由来する構造単位がこの範囲よりも少ないと、複屈折が高くなり、この範囲よりも多いと、前駆体ポリマーの耐熱性、溶融粘度が不必要に上がり、後述する環構造形成反応における生産性が低下する。 From the viewpoint of heat resistance and controllability of optical properties (particularly birefringence), the total content of structural units derived from maleic anhydride of the precursor polymer is preferably 1 to 30% by mass, more preferably 2 to 27. It is by mass, more preferably 3 to 27% by mass. If the number of structural units derived from maleic anhydride is less than this range, birefringence will be high, and if it is more than this range, the heat resistance and melt viscosity of the precursor polymer will be unnecessarily increased, and the ring structure formation reaction described later will be performed. Productivity is reduced.
前駆体ポリマーは、ゲルパーミエーションクロマトグラフィーで得られるクロマトグラムにおいて、ポリスチレン換算の重量平均分子量Ｍwが、好ましくは４００００以上２０００００以下、より好ましくは４００００以上１８００００以下、さらに好ましくは５００００以上１６００００以下である。重量平均分子量Ｍwがこの範囲よりも小さいと、得られる成形体が脆くなり、この範囲よりも高いと生産性が悪化する。Ｍｗは、前駆体ポリマーの製造の際に使用する重合開始剤や連鎖移動剤（任意成分）の種類、量、添加時期などを調整することによって制御できる。 The precursor polymer has a polystyrene-equivalent weight average molecular weight Mw of preferably 40,000 or more and 200,000 or less, more preferably 40,000 or more and 180,000 or less, and further preferably 50,000 or more and 160000 or less in a chromatogram obtained by gel permeation chromatography. .. If the weight average molecular weight Mw is smaller than this range, the obtained molded product becomes brittle, and if it is higher than this range, the productivity deteriorates. Mw can be controlled by adjusting the type, amount, addition timing, etc. of the polymerization initiator and chain transfer agent (arbitrary component) used in the production of the precursor polymer.
環構造形成反応は、例えば、押出機を用いて、行うことができる。押出機として例えば単軸押出機、二軸押出機、多軸押出機などが挙げられる。混合性能の点から、二軸押出機が好ましい。二軸押出機には非噛合い型同方向回転式、噛合い型同方向回転式、非噛合い型異方向回転式、噛合い型異方向回転式が含まれる。噛合い型同方向回転式は、高速回転が可能であり、混合を効率的に促進できるので好ましい。これらの押出機は、単独で用いても、直列に繋いで用いてもよい。 The ring structure forming reaction can be carried out using, for example, an extruder. Examples of the extruder include a single-screw extruder, a twin-screw extruder, a multi-screw extruder and the like. A twin-screw extruder is preferable from the viewpoint of mixing performance. The twin-screw extruder includes a non-meshing type same-direction rotation type, a meshing type same-direction rotation type, a non-meshing type different-direction rotation type, and a meshing type different-direction rotation type. The meshing type co-rotation type is preferable because it can rotate at high speed and can efficiently promote mixing. These extruders may be used alone or in series.
押出機を用いての環構造形成反応では、例えば、原料である前駆体ポリマーを押出機の原料投入部から投入し、該前駆体ポリマーを溶融させ、シリンダ内に充満させた後、添加ポンプを用いてイミド化剤（任意成分）などを押出機中に注入することにより、押出機中で環構造形成反応を進行させることができる。イミド化剤を用いると、構造単位（Ｒ）は、Ｎ－置換若しくは無置換グルタルイミド単位、Ｎ－置換若しくは無置換マレイミド単位のうち少なくとも一つを含み、必要に応じてラクトン環単位及び/又は無水グルタル酸単位を含んでいてもよい。好ましいイミド化剤はＲ２３－ＮＨ２（Ｒ２３は前記に定義される通りである）、または、Ｒ３３－ＮＨ２（Ｒ３３は前記に定義される通りである）で表される。イミド化剤は、メタクリル系共重合体１００質量部に対し好ましくは１．６～２０質量部使用される。イミド化剤が上記範囲内の使用量であると、メタクリル酸アミド単位の副生を抑制できる。なお、イミド化剤Ｒ３３－ＮＨ２（Ｒ３３は前記に定義される通りである）を使用すると、前駆体ポリマーの無水マレイン酸単位の一部が式（３）で表されるマレイミド単位（Ｒ３１＝Ｒ３２＝Ｈ）に変換される。本発明の１つの実施形態において、イミド化剤Ｒ２３－ＮＨ２（Ｒ２３は前記に定義される通りである）を使用して式（２）で表される構造単位（Ｒ）を生成させると、同時に式（３）で表されるマレイミド単位（Ｒ３１＝Ｒ３２＝Ｈ）が生成し、構造単位（Ｒ）は式（２）と式（３）の構造単位を含み、かつ、Ｒ２３＝Ｒ３３となる。 In the ring structure formation reaction using an extruder, for example, a precursor polymer as a raw material is charged from the raw material charging section of the extruder, the precursor polymer is melted, filled in a cylinder, and then an addition pump is used. By injecting an imidizing agent (arbitrary component) or the like into the extruder, the ring structure forming reaction can be allowed to proceed in the extruder. With an imidizing agent, the structural unit (R) comprises at least one of N-substituted or unsubstituted glutarimide units, N-substituted or unsubstituted maleimide units, and optionally lactone ring units and / or. It may contain glutaric anhydride units. Preferred imidizing agents are represented by R 23 -NH 2 (R 23 is as defined above) or R 33 -NH 2 (R 33 is as defined above). The imidizing agent is preferably used in an amount of 1.6 to 20 parts by mass with respect to 100 parts by mass of the methacrylic copolymer. When the amount of the imidizing agent used is within the above range, the by-product of the methacrylic acid amide unit can be suppressed. When the imidizing agent R 33 -NH 2 (R 33 is as defined above) is used, a part of the maleic anhydride unit of the precursor polymer is represented by the formula (3) (maleimide unit). It is converted to R 31 = R 32 = H). In one embodiment of the invention, the imidizing agent R 23 -NH 2 (R 23 is as defined above) is used to generate the structural unit (R) represented by formula (2). At the same time, a maleimide unit (R 31 = R 32 = H) represented by the formula (3) is generated, and the structural unit (R) includes the structural units of the formulas (2) and (3), and is R. 23 = R 33 .
押出機中の反応ゾーンの樹脂温度は１８０～３００℃の範囲にすることが好ましく、２００～３００℃の範囲にすることがより好ましい。反応ゾーンの樹脂温度が１８０℃未満だと環構造形成反応の反応効率の低下、メタクリル酸アミド単位の副生、等によりメタクリル系共重合体の耐熱性が低下する傾向となる。反応ゾーンの樹脂温度が３００℃を超えると樹脂の分解が著しくなり得られるメタクリル系共重合体からなる成形体およびフィルムの引張り破断強度等の機械的強度が低下する傾向となる。なお、押出機中の反応ゾーンとは、押出機のシリンダにおいてイミド化剤などの注入位置から樹脂吐出口（ダイス部）までの間の領域をいう。 The resin temperature of the reaction zone in the extruder is preferably in the range of 180 to 300 ° C, more preferably in the range of 200 to 300 ° C. If the resin temperature in the reaction zone is less than 180 ° C., the heat resistance of the methacrylic copolymer tends to decrease due to a decrease in the reaction efficiency of the ring structure forming reaction, a by-product of the methacrylic acid amide unit, and the like. When the resin temperature in the reaction zone exceeds 300 ° C., the resin is significantly decomposed, and the mechanical strength such as the tensile breaking strength of the molded body and the film made of the methacrylic copolymer tends to decrease. The reaction zone in the extruder is a region in the cylinder of the extruder from the injection position of the imidizing agent or the like to the resin discharge port (die portion).
押出機の反応ゾーン内での反応時間を長くすることにより、環構造形成反応をより進行させることができる。押出機の反応ゾーン内の反応時間は１０秒より長くすることが好ましく、さらには３０秒より長くすることがより好ましい。１０秒以下の反応時間では環構造形成反応がほとんど進行しない可能性がある。 By lengthening the reaction time in the reaction zone of the extruder, the ring structure forming reaction can be further promoted. The reaction time in the reaction zone of the extruder is preferably longer than 10 seconds, more preferably longer than 30 seconds. If the reaction time is 10 seconds or less, the ring structure formation reaction may hardly proceed.
押出機での樹脂圧力は、大気圧～５０ＭＰａの範囲内とすることが好ましく、さらには１～３０ＭＰａの範囲内とすることがより好ましい。５０ＭＰａ以上では通常の押出機の機械耐圧の限界を越え、特殊な装置が必要となりコスト的に好ましくない。 The resin pressure in the extruder is preferably in the range of atmospheric pressure to 50 MPa, more preferably in the range of 1 to 30 MPa. If it is 50 MPa or more, the limit of the mechanical pressure resistance of a normal extruder is exceeded, and a special device is required, which is not preferable in terms of cost.
大気圧以下に減圧可能なベント孔を有する押出機を使用することが好ましい。このような構成によれば、未反応物、もしくはメタノール等の副生物やモノマー類を除去することができ、本発明のアクリル系樹脂組成物を含む成形体の破断強度が向上する傾向となる。 It is preferable to use an extruder having a vent hole capable of reducing the pressure below atmospheric pressure. According to such a configuration, unreacted substances, by-products such as methanol and monomers can be removed, and the breaking strength of the molded product containing the acrylic resin composition of the present invention tends to be improved.
環構造形成反応には、押出機の代わりに、例えば、住友重機械工業（株）製のバイボラックのような横型二軸反応装置やスーパーブレンドのような竪型二軸攪拌槽などの高粘度対応の反応装置も好適に使用できる。 For the ring structure formation reaction, instead of the extruder, for example, a horizontal twin-screw reactor such as Vivolac manufactured by Sumitomo Heavy Industries, Ltd. or a vertical twin-screw tank such as Super Blend can be used for high viscosity. The reaction device of the above can also be preferably used.
環構造形成反応時にメタクリル系共重合体中にカルボキシ基が副生することがある。このカルボキシ基は、必要に応じてエステル化剤や触媒などによりエステル基に変換してもよい。これにより光学フィルムを製造する際の樹脂の発泡が低減できる。かかるエステル基は、使用するエステル化剤や触媒により異なるが、溶融成形時の樹脂溶融粘度の低減およびエステル化の反応性、エステル化後の樹脂の耐熱性の観点から、メタクリル酸メチル単位を含むことが好ましく、メタクリル酸メチル単位とメタクリル酸エチル単位を共に含むことがより好ましい。 A carboxy group may be produced as a by-product in the methacrylic copolymer during the ring structure formation reaction. This carboxy group may be converted into an ester group by an esterifying agent, a catalyst or the like, if necessary. This can reduce the foaming of the resin when manufacturing the optical film. Such an ester group contains a methyl methacrylate unit from the viewpoint of reducing the melt viscosity of the resin during melt molding, the reactivity of esterification, and the heat resistance of the resin after esterification, although it varies depending on the esterifying agent and the catalyst used. It is preferable, and it is more preferable to contain both the methyl methacrylate unit and the ethyl methacrylate unit.
エステル化剤としては、コスト、反応性などの観点から、ジメチルカーボネートが好ましい。 As the esterifying agent, dimethyl carbonate is preferable from the viewpoint of cost, reactivity and the like.
エステル化剤の添加量は、例えば、メタクリル系共重合体の酸価が所望の値になるように設定することができる。 The amount of the esterifying agent added can be set, for example, so that the acid value of the methacrylic copolymer becomes a desired value.
上記エステル化剤に加え、触媒を併用することもできる。触媒の種類は特に限定されるものではないが、例えば、トリメチルアミン、トリエチルアミン、モノメチルジエチルアミン、ジメチルモノエチルアミン等のアミン系化合物が挙げられる。これらの中でもコスト、反応性などの観点からトリエチルアミンが好ましい。 In addition to the above esterifying agent, a catalyst can also be used in combination. The type of catalyst is not particularly limited, and examples thereof include amine compounds such as trimethylamine, triethylamine, monomethyldiethylamine, and dimethylmonoethylamine. Among these, triethylamine is preferable from the viewpoint of cost, reactivity and the like.
（樹脂組成物）
一般的に樹脂組成物に用いられる添加剤を、本発明の目的が損なわれない範囲で含んでいてもよい。添加剤としては、フィラー、酸化防止剤、熱劣化防止剤、紫外線吸収剤、光安定剤、滑剤、離型剤、高分子加工助剤、帯電防止剤、難燃剤、着色剤、染料、顔料、光拡散剤、有機色素、艶消し剤、耐衝撃性改質剤、蛍光体などが挙げられる。フィラー以外のかかる添加剤の合計量は、好ましくは７質量％以下、より好ましくは５質量％以下、さらに好ましくは４質量％以下である。
(Resin composition)
Additives generally used in resin compositions may be included as long as the object of the present invention is not impaired. Additives include fillers, antioxidants, thermal degradation inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, colorants, dyes, pigments, Examples thereof include light diffusing agents, organic dyes, matting agents, impact resistance modifiers, and phosphors. The total amount of such additives other than the filler is preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less.
フィラーとしては、炭酸カルシウム、タルク、カーボンブラック、酸化チタン、シリカ、クレー、硫酸バリウム、炭酸マグネシウムなどを挙げることができる。本発明のメタクリル系共重合体組成物に含有し得るフィラーの量は、好ましくは３質量％以下、より好ましくは１．５質量％以下である。 Examples of the filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate and the like. The amount of the filler that can be contained in the methacrylic copolymer composition of the present invention is preferably 3% by mass or less, more preferably 1.5% by mass or less.
酸化防止剤は、酸素存在下においてそれ単体で樹脂の酸化劣化防止に効果を有するものである。例えば、リン系酸化防止剤、ヒンダードフェノール系酸化防止剤、チオエーテル系酸化防止剤などを挙げることができる。これらの酸化防止剤は１種を単独で用いても、２種以上を併用してもよい。 The antioxidant is effective in preventing oxidative deterioration of the resin by itself in the presence of oxygen. For example, phosphorus-based antioxidants, hindered phenol-based antioxidants, thioether-based antioxidants, and the like can be mentioned. These antioxidants may be used alone or in combination of two or more.
熱劣化防止剤は、実質上無酸素の状態下で高熱にさらされたときに生じるポリマーラジカルを捕捉することによって樹脂の熱劣化を防止できるものである。 The heat deterioration inhibitor can prevent the heat deterioration of the resin by capturing the polymer radicals generated when exposed to high heat under a substantially oxygen-free state.
該熱劣化防止剤としては、２－ｔｅｒｔ－ブチル－６－（３’－ｔｅｒｔ－ブチル－５’－メチル－ヒドロキシベンジル）－４－メチルフェニルアクリレート（住友化学社製；商品名スミライザーＧＭ）、２，４－ジ－ｔｅｒｔ－アミル－６－（３’，５’－ジ－ｔｅｒｔ－アミル－２’－ヒドロキシ－α－メチルベンジル）フェニルアクリレート（住友化学社製；商品名スミライザーＧＳ）などを挙げることができる。 Examples of the heat deterioration inhibitor include 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-hydroxybenzyl) -4-methylphenylacrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: Smilizer GM). 2,4-Di-tert-amyl-6- (3', 5'-di-tert-amyl-2'-hydroxy-α-methylbenzyl) phenylacrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name Smilizer GS), etc. Can be mentioned.
紫外線吸収剤は、紫外線を吸収する能力を有する化合物である。紫外線吸収剤は、主に光エネルギーを熱エネルギーに変換する機能を有すると言われる化合物である。 An ultraviolet absorber is a compound having the ability to absorb ultraviolet rays. The ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy.
紫外線吸収剤としては、ベンゾフェノン類、ベンゾトリアゾール類、トリアジン類、ベンゾエート類、サリシレート類、シアノアクリレート類、蓚酸アニリド類、マロン酸エステル類、ホルムアミジン類などを挙げることができる。これらは１種を単独で用いても、２種以上を併用してもよい。これらの中でも、ベンゾトリアゾール類、トリアジン類、または波長３８０～４５０ｎｍにおけるモル吸光係数の最大値εｍａｘが１２００ｄｍ３・ｍｏｌ－１ｃｍ－１以下である紫外線吸収剤が好ましい。 Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, malonic acid anilides, malonic acid esters, formamidines and the like. These may be used alone or in combination of two or more. Among these, benzotriazoles, triazines, or an ultraviolet absorber having a maximum molar extinction coefficient ε max of 1200 dm 3 · mol -1 cm -1 or less at a wavelength of 380 to 450 nm is preferable.
光安定剤は、主に光による酸化で生成するラジカルを捕捉する機能を有すると言われる化合物である。好適な光安定剤としては、２，２，６，６－テトラアルキルピペリジン骨格を持つ化合物などのヒンダードアミン類を挙げることができる。 The light stabilizer is a compound that is said to have a function of capturing radicals mainly generated by oxidation by light. Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.
滑剤としては、例えば、ステアリン酸、ベヘニン酸、ステアロアミド酸、メチレンビスステアロアミド、ヒドロキシステアリン酸トリグリセリド、パラフィンワックス、ケトンワックス、オクチルアルコール、硬化油などを挙げることができる。 Examples of the lubricant include stearic acid, behenic acid, stearoamic acid, methylenebisstearoamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, hydrogenated oil and the like.
離型剤としては、セチルアルコール、ステアリルアルコールなどの高級アルコール類；ステアリン酸モノグリセライド、ステアリン酸ジグリセライドなどのグリセリン高級脂肪酸エステルなどを挙げることができる。本発明においては、離型剤として、高級アルコール類とグリセリン脂肪酸モノエステルとを併用することが好ましい。高級アルコール類とグリセリン脂肪酸モノエステルとを併用する場合、その割合は特に制限されないが、高級アルコール類の使用量：グリセリン脂肪酸モノエステルの使用量は、質量比で、２．５：１～３．５：１が好ましく、２．８：１～３．２：１がより好ましい。 Examples of the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride. In the present invention, it is preferable to use higher alcohols and glycerin fatty acid monoester in combination as a release agent. When the higher alcohols and the glycerin fatty acid monoester are used in combination, the ratio is not particularly limited, but the amount of the higher alcohols used: the amount of the glycerin fatty acid monoester used is 2.5: 1 to 3. 5: 1 is preferable, and 2.8: 1 to 3.2: 1 are more preferable.
高分子加工助剤としては、通常、乳化重合法によって製造できる、０．０５～０．５μｍの粒子径を有する重合体粒子（非架橋ゴム粒子）を用いる。該重合体粒子は、単一組成比および単一極限粘度の重合体からなる単層粒子であってもよいし、また組成比または極限粘度の異なる２種以上の重合体からなる多層粒子であってもよい。 As the polymer processing aid, polymer particles (non-crosslinked rubber particles) having a particle size of 0.05 to 0.5 μm, which can be usually produced by an emulsion polymerization method, are used. The polymer particles may be single-layer particles made of a polymer having a single composition ratio and a single extreme viscosity, or may be multilayer particles made of two or more kinds of polymers having different composition ratios or extreme viscosities. You may.
帯電防止剤としては、ヘプチルスルホン酸ナトリウム、オクチルスルホン酸ナトリウム、ノニルスルホン酸ナトリウム、デシルスルホン酸ナトリウム、ドデシルスルホン酸ナトリウム、セチルスルホン酸ナトリウム、オクタデシルスルホン酸ナトリウム、ジヘプチルスルホン酸ナトリウム、ヘプチルスルホン酸カリウム、オクチルスルホン酸カリウム、ノニルスルホン酸カリウム、デシルスルホン酸カリウム、ドデシルスルホン酸カリウム、セチルスルホン酸カリウム、オクタデシルスルホン酸カリウム、ジヘプチルスルホン酸カリウム、ヘプチルスルホン酸リチウム、オクチルスルホン酸リチウム、ノニルスルホン酸リチウム、デシルスルホン酸リチウム、ドデシルスルホン酸リチウム、セチルスルホン酸リチウム、オクタデシルスルホン酸リチウム、ジヘプチルスルホン酸リチウム等のアルキルスルホン酸塩等が挙げられる。 Antistatic agents include sodium heptyl sulfonate, sodium octyl sulfonate, sodium nonyl sulfonate, sodium decyl sulfonate, sodium dodecyl sulfonate, sodium cetyl sulfonate, sodium octadecyl sulfonate, sodium diheptyl sulfonate, heptyl sulfonic acid. Potassium, potassium octyl sulfonate, potassium nonyl sulfonate, potassium decyl sulfonate, potassium dodecyl sulfonate, potassium cetyl sulfonate, potassium octadecyl sulfonate, potassium diheptyl sulfonate, lithium heptyl sulfonate, lithium octyl sulfonate, nonyl sulfonate Examples thereof include alkyl sulfonates such as lithium acid, lithium decyl sulfonate, lithium dodecyl sulfonate, lithium cetyl sulfonate, lithium octadecyl sulfonate, and lithium diheptyl sulfonate.
難燃剤としては、水酸化マグネシウム、水酸化アルミニウム、水和珪酸アルミニウム、水和珪酸マグネシウム、ハイドロタルサイト等の水酸基または結晶水を有する金属水和物、ポリリン酸アミン、リン酸エステル等のリン酸化合物、シリコン化合物等が挙げられ、トリメチルホスフェート、トリエチルホスフェート、トリプロピルホスフェート、トリブチルホスフェート、トリペンチルホスフェート、トリヘキシルホスフェート、トリシクロヘキシルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、ジメチルエチルホスフェート、メチルジブチルホスフェート、エチルジプロピルホスフェート、ヒドロキシフェニルジフェニルホスフェートなどのリン酸エステル系難燃剤が好ましい。 Examples of the flame retardant include magnesium hydroxide, aluminum hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, metal hydrate having a hydroxyl group or crystalline water such as hydrotalcite, and phosphoric acid such as polyphosphate amine and phosphate ester. Examples thereof include compounds, silicon compounds and the like, such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate and dimethyl ethyl. Phosphate-based flame retardants such as phosphate, methyldibutyl phosphate, ethyldipropyl phosphate, hydroxyphenyldiphenyl phosphate and the like are preferred.
染料・顔料としては、パラレッド、ファイヤーレッド、ピラゾロンレッド、チオインジコレッド、ペリレンレッドなどの赤色有機顔料、としてシアニンブルー、インダンスレンブルーなどの青色有機顔料、シアニングリーン、ナフトールグリーンなどの緑色有機顔料が挙げられ、これらの１種又は２種以上を使用することができる。 Dyes / pigments include red organic pigments such as parared, fire red, pyrazolone red, thioindico red, and perylene red, blue organic pigments such as cyanine blue and indanslen blue, and green organic pigments such as cyanine green and naphthol green. Pigments are mentioned, and one or more of these can be used.
有機色素としては、紫外線を可視光線に変換する機能を有する化合物が好ましく用いられる。 As the organic dye, a compound having a function of converting ultraviolet rays into visible light is preferably used.
光拡散剤や艶消し剤としては、ガラス微粒子、ポリシロキサン系架橋微粒子、架橋ポリマー微粒子、タルク、炭酸カルシウム、硫酸バリウムなどを挙げることができる。 Examples of the light diffusing agent and the matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, barium sulfate and the like.
蛍光体としては、蛍光顔料、蛍光染料、蛍光白色染料、蛍光増白剤、蛍光漂白剤などを挙げることができる。 Examples of the fluorescent substance include fluorescent pigments, fluorescent dyes, fluorescent white dyes, fluorescent whitening agents, and fluorescent bleaching agents.
本発明のメタクリル系共重合体組成物は、その製造方法によって特に限定されず、例えば、本発明のメタクリル系共重合体と紫外線吸収剤などの添加剤と必要に応じて他の重合体とを溶融混練することによって、製造することができる。溶融混練は、例えば、ニーダールーダー、押出機、ミキシングロール、バンバリーミキサーなどの溶融混練装置を用いて行うことができる。混練時の温度は、メタクリル系共重合体および他の重合体の軟化温度に応じて適宜設定でき、例えば１５０～３００℃に設定することができる。また、混練時の剪断速度は、例えば、１０～５０００ｓｅｃ－１に設定することができる。 The methacrylic copolymer composition of the present invention is not particularly limited depending on the production method thereof, and for example, the methacrylic copolymer of the present invention, an additive such as an ultraviolet absorber, and other polymers as needed. It can be manufactured by melt-kneading. The melt-kneading can be performed using, for example, a melt-kneading device such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer. The temperature at the time of kneading can be appropriately set according to the softening temperature of the methacrylic copolymer and other polymers, and can be set to, for example, 150 to 300 ° C. Further, the shear rate at the time of kneading can be set to, for example, 10 to 5000 sec -1 .
本発明のメタクリル系共重合体組成物は、保存、運搬、または成形時の利便性を高めるために、ペレットなどの形態にすることができる。
（成形体）
本発明の成形体は本発明のメタクリル系共重合体またはメタクリル系共重合体組成物を含む。本発明の成形体の製造法は特に限定されない。例えばＴダイ法（ラミネート法、共押出法など）、インフレーション法（共押出法など）、圧縮成形法、ブロー成形法、カレンダー成形法、真空成形法、射出成形法（インサート法、二色法、プレス法、コアバック法、サンドイッチ法など）などの溶融成形法ならびに溶液キャスト法などを挙げることができる。これらのうち、生産性の高さ、コストなどの点から、Ｔダイ法、インフレーション法、射出成形法または溶液キャスト法が好ましい。成形体の種類に制限はないが、フィルム（厚さ５μｍ以上２５０μｍ以下の平面状成形体）やシート（２５０μｍより厚い平面状成形体）が好ましいものとして挙げられる。
The methacrylic copolymer composition of the present invention can be in the form of pellets or the like in order to enhance convenience during storage, transportation, or molding.
(Molded body)
The molded product of the present invention contains the methacrylic copolymer or the methacrylic copolymer composition of the present invention. The method for producing the molded product of the present invention is not particularly limited. For example, T-die method (lamination method, coextrusion method, etc.), inflation method (coextrusion method, etc.), compression molding method, blow molding method, calendar forming method, vacuum forming method, injection molding method (insert method, two-color method, etc.) A melt molding method such as a press method, a core back method, a sandwich method, etc., and a solution casting method can be mentioned. Of these, the T-die method, the inflation method, the injection molding method, or the solution casting method is preferable from the viewpoint of high productivity, cost, and the like. The type of the molded body is not limited, but a film (a planar molded body having a thickness of 5 μm or more and 250 μm or less) or a sheet (a planar molded body thicker than 250 μm) is preferable.
本発明の成形体は、成形体の面内位相差（Ｒｅ）の絶対値の平均値が、厚み１ｍｍあたりの値として、好ましくは１０．０ｎｍ以下であり、より好ましくは、６．０ｎｍ以下であり、さらに好ましくは５．０ｎｍ以下であり、さらにより好ましくは３．０ｎｍ以下である。 In the molded product of the present invention, the average value of the absolute values of the in-plane phase difference (Re) of the molded product is preferably 10.0 nm or less, more preferably 6.0 nm or less as a value per 1 mm of thickness. Yes, more preferably 5.0 nm or less, and even more preferably 3.0 nm or less.
本発明の成形体の一形態であるフィルムは、溶液キャスト法、溶融流延法、押出成形法、インフレーション成形法、ブロー成形法などによって製造することができる。これらのうち、透明性に優れ、改善された靭性を持ち、取扱い性に優れ、靭性と表面硬度および剛性とのバランスに優れたフィルムを得ることができるという観点から、押出成形法または溶液キャスト法が好ましい。押出機から吐出される溶融樹脂の温度は好ましくは１６０～２７０℃、より好ましくは２２０～２６０℃に設定する。 The film, which is one form of the molded product of the present invention, can be produced by a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, a blow molding method, or the like. Of these, the extrusion molding method or the solution casting method can be used from the viewpoint of obtaining a film having excellent transparency, improved toughness, excellent handleability, and an excellent balance between toughness and surface hardness and rigidity. Is preferable. The temperature of the molten resin discharged from the extruder is preferably set to 160 to 270 ° C, more preferably 220 to 260 ° C.
押出成形法のうち、良好な表面平滑性、良好な鏡面光沢、低ヘイズのフィルムが得られるという観点からＴダイ法が好ましい。このＴダイ法では、押出機、ギアポンプ、ポリマーフィルター、ミキサーを経てＴダイから吐出される溶融樹脂を、２本以上の鏡面ロールもしくは鏡面ベルトに挟み込んでフィルムに成形することが好ましい。鏡面ロールもしくは鏡面ベルトに挟み込む際にバンクを形成させてもよいし、形成させなくてもよい。ダイは、リップ開度の自動調整機能を有したものであり、エアギャップは１００ｍｍ以下が好ましい。 Of the extrusion molding methods, the T-die method is preferable from the viewpoint of obtaining a film having good surface smoothness, good mirror gloss, and low haze. In this T-die method, it is preferable that the molten resin discharged from the T-die via an extruder, a gear pump, a polymer filter, and a mixer is sandwiched between two or more mirror rolls or a mirror belt to form a film. Banks may or may not be formed when sandwiched between mirror rolls or mirror belts. The die has a function of automatically adjusting the lip opening, and the air gap is preferably 100 mm or less.
鏡面ロールまたは鏡面ベルトは金属製であることが好ましい。鏡面ロールとしては金属剛体ロール、金属弾性体ロールなどを用いることができ、金弾弾性体ロールと金属剛体ロールとを組み合わせて用いることが好ましい。また、鏡面ロールまたは鏡面ベルトの表面温度は共に１３０℃以下であることが好ましい。また、一対の鏡面ロール若しくは鏡面ベルトは、少なくとも一方の表面温度が６０℃以上であることが好ましい。このような表面温度に設定すると、押出機から吐出される溶融樹脂を自然放冷よりも速い速度で冷却することができ、表面平滑性に優れ且つヘイズの低いフィルムを製造し易い。一対のロールまたはベルトの間の線圧は好ましくは１０Ｎ／ｍｍ以上、より好ましくは３０Ｎ／ｍｍ以上である。押出成形で得られる未延伸フィルムの厚さは、１０～３００μｍであることが好ましい。フィルムのヘイズは、厚さ１００μｍにおいて、好ましくは０．７％以下、より好ましくは０．５％以下、さらに好ましくは０．３％以下である。 The mirror roll or mirror belt is preferably made of metal. As the mirror surface roll, a metal rigid body roll, a metal elastic body roll, or the like can be used, and it is preferable to use a metal bullet elastic body roll and a metal rigid body roll in combination. Further, it is preferable that the surface temperature of the mirror surface roll or the mirror surface belt is 130 ° C. or lower. Further, it is preferable that the surface temperature of at least one of the pair of mirror rolls or mirror belts is 60 ° C. or higher. When the surface temperature is set to such a value, the molten resin discharged from the extruder can be cooled at a speed higher than that of natural cooling, and it is easy to produce a film having excellent surface smoothness and low haze. The linear pressure between the pair of rolls or belts is preferably 10 N / mm or more, more preferably 30 N / mm or more. The thickness of the unstretched film obtained by extrusion molding is preferably 10 to 300 μm. The haze of the film is preferably 0.7% or less, more preferably 0.5% or less, still more preferably 0.3% or less at a thickness of 100 μm.
上記のようにして得られる未延伸フィルムに延伸処理を施してもよい。延伸処理によって機械的強度が高まり、ひび割れし難いフィルムを得ることができる。延伸方法は特に限定されず、同時二軸延伸法、逐次二軸延伸法、チュブラー延伸法などを挙げることができる。均一に延伸でき高い強度のフィルムが得られるという観点から、延伸時の温度の下限はメタクリル系共重合体またはメタクリル系共重合体組成物のガラス転移温度より１０℃高い温度であり、延伸時の温度の上限はメタクリル系共重合体またはメタクリル系共重合体組成物のガラス転移温度より４０℃高い温度である。延伸は通常１００～５０００％／分で行われる。延伸の後、熱固定を行うことによって、熱収縮の少ないフィルムを得ることができる。延伸後のフィルムの厚さは１０～２００μｍであることが好ましい。 The unstretched film obtained as described above may be subjected to a stretching treatment. By the stretching treatment, the mechanical strength is increased, and a film that is not easily cracked can be obtained. The stretching method is not particularly limited, and examples thereof include a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tuber stretching method. From the viewpoint of being able to be uniformly stretched and obtaining a high-strength film, the lower limit of the temperature at the time of stretching is a temperature 10 ° C. higher than the glass transition temperature of the methacrylic copolymer or the methacrylic copolymer composition, and is at the time of stretching. The upper limit of the temperature is a temperature 40 ° C. higher than the glass transition temperature of the methacrylic copolymer or the methacrylic copolymer composition. Stretching is usually performed at 100-5000% / min. By performing heat fixation after stretching, a film having less heat shrinkage can be obtained. The thickness of the stretched film is preferably 10 to 200 μm.
本発明の成形体の一形態であるフィルムの表面に機能層を設けてもよい。機能層としては、ハードコート層、アンチグレア層、反射防止層、スティッキング防止層、拡散層、防眩層、静電気防止層、防汚層、微粒子などの易滑性層を挙げることができる。 A functional layer may be provided on the surface of a film which is a form of a molded product of the present invention. Examples of the functional layer include a hard coat layer, an anti-glare layer, an anti-reflection layer, an anti-sticking layer, a diffusion layer, an anti-glare layer, an anti-static layer, an anti-fouling layer, and an easy-to-slip layer such as fine particles.
また、本発明のフィルムの少なくとも片面に、上記機能層との密着強度を向上させたり、他のフィルムとの接着剤もしくは粘着剤を介しての積層における接着強度を向上させたりするために、アンダーコート層を設けることが好ましい。 Further, in order to improve the adhesive strength with the functional layer on at least one side of the film of the present invention, or to improve the adhesive strength in laminating with another film via an adhesive or an adhesive, under. It is preferable to provide a coat layer.
本発明のメタクリル系共重合体またはメタクリル系共重合体組成物は、成形材料として好適である。本発明の成形体は、各種用途の部材にすることができる。具体的な用途としては、例えば、広告塔、スタンド看板、袖看板、欄間看板、屋上看板等の看板部品やマーキングフィルム；ショーケース、仕切板、店舗ディスプレイ等のディスプレイ部品；蛍光灯カバー、ムード照明カバー、ランプシェード、光天井、光壁、シャンデリア等の照明部品；家具、ペンダント、ミラー等のインテリア部品；ドア、ドーム、安全窓ガラス、間仕切り、階段腰板、バルコニー腰板、レジャー用建築物の屋根等の建築用部品；航空機風防、パイロット用バイザー、オートバイ、モーターボート風防、バス用遮光板、自動車用サイドバイザー、リアバイザー、ヘッドウィング、ヘッドライトカバー、自動車内装部材、バンパーなどの自動車外装部材等の輸送機関係部品；音響映像用銘板、ステレオカバー、テレビ保護マスク、自動販売機、携帯電話、パソコン等の電子機器部品；保育器、レントゲン部品等の医療機器部品；機械カバー、計器カバー、実験装置、定規、文字盤、観察窓等の機器関係部品；液晶保護板、導光板、導光フィルム、フレネルレンズ、レンチキュラーレンズ、各種ディスプレイの前面板、拡散板等の光学関係部品；道路標識、案内板、カーブミラー、防音壁等の交通関係部品；その他、温室、大型水槽、箱水槽、浴室部材、時計パネル、バスタブ、サニタリー、デスクマット、遊技部品、玩具、楽器、熔接時の顔面保護用マスク、太陽電池のバックシート、フレキシブル太陽電池用フロントシート、加飾フィルム；パソコン、携帯電話、家具、自動販売機、浴室部材などに用いる表面材料等を挙げることができる。 The methacrylic copolymer or the methacrylic copolymer composition of the present invention is suitable as a molding material. The molded product of the present invention can be used as a member for various purposes. Specific uses include, for example, signboard parts and marking films such as advertising towers, stand signs, sleeve signs, column signs, roof signs; display parts such as showcases, dividers, and store displays; fluorescent lamp covers, mood lighting. Lighting parts such as covers, lamp shades, light ceilings, light walls, chandeliers; interior parts such as furniture, pendants, mirrors; doors, dome, safety window glass, partitions, staircase wainscots, balcony wainscots, roofs of leisure buildings, etc. Building parts; aircraft windshields, pilot visors, motorcycles, motor boat windshields, bus shading plates, automobile side visors, rear visors, head wings, headlight covers, automobile interior parts, automobile exterior parts such as bumpers, etc. Related parts; Electronic equipment parts such as audiovisual name plates, stereo covers, TV protective masks, vending machines, mobile phones, personal computers; Medical equipment parts such as incubators and roentgen parts; Machine covers, instrument covers, experimental equipment, rulers , Equipment-related parts such as dials and observation windows; Optical-related parts such as liquid crystal protective plates, light guide plates, light guide films, frennel lenses, lenticular lenses, front plates of various displays, diffuser plates; road signs, guide plates, curves Traffic-related parts such as mirrors and soundproof walls; Others, greenhouses, large water tanks, box water tanks, bathroom parts, watch panels, bathtubs, sanitary, desk mats, game parts, toys, musical instruments, face protection masks during welding, solar cells Back sheets, front sheets for flexible solar cells, decorative films; surface materials used for personal computers, mobile phones, furniture, vending machines, bathroom materials, and the like.
本発明のメタクリル系共重合体またはメタクリル系共重合体組成物を含有する層と、他の材料（例えば、他の熱可塑性共重合体を含有する層）とを積層することによって、積層体を得ることができる。積層体に用いられる他の材料としては、鋼材、プラスチック（例えば、熱可塑性樹脂）、木材、ガラス等を挙げることができる。本発明によって得られる積層体は、壁紙；自動車内装部材表面；バンパーなどの自動車外装部材表面；携帯電話表面；家具表面；パソコン表面；自動販売機表面；浴槽などの浴室部材表面等に好適に用いることができる。 By laminating a layer containing the methacrylic copolymer or the methacrylic copolymer composition of the present invention with another material (for example, a layer containing another thermoplastic copolymer), the laminated body is formed. Obtainable. Examples of other materials used for the laminate include steel, plastic (for example, thermoplastic resin), wood, glass and the like. The laminate obtained by the present invention is suitably used for wallpaper; the surface of an automobile interior member; the surface of an automobile exterior member such as a bumper; the surface of a mobile phone; the surface of furniture; the surface of a personal computer; the surface of a vending machine; the surface of a bathroom member such as a bathtub. be able to.
本発明の成形体の一形態であるフィルムは透明性、耐熱性が高いため、光学用途に好適であり、偏光子保護フィルム、液晶保護板、携帯型情報端末の表面材、携帯型情報端末の表示窓保護フィルム、導光フィルム、銀ナノワイヤーやカーボンナノチューブを表面に塗布した透明導電フィルム、各種ディスプレイの前面板用途に特に好適である。本発明のフィルムは透明性、耐熱性が高いため、光学用途以外の用途として、赤外線カットフィルムや、防犯フィルム、飛散防止フィルム、加飾フィルム、金属加飾フィルム、シュリンクフィルム、インモールドラベル用フィルムに使用することができる。 The film, which is a form of the molded body of the present invention, has high transparency and heat resistance, and is therefore suitable for optical applications. It is particularly suitable for display window protective films, light guide films, transparent conductive films coated with silver nanowires and carbon nanotubes on the surface, and front panel applications of various displays. Since the film of the present invention has high transparency and heat resistance, it is used as an infrared cut film, a security film, a shatterproof film, a decorative film, a metal decorative film, a shrink film, and an in-mold label film for applications other than optical applications. Can be used for.
本発明の成形体の一形態であるフィルムを偏光子保護フィルムや位相差フィルムとして用いる場合、偏光子フィルムの片面だけに積層してもよいし、両面に積層してもよい。偏光子フィルムと積層する際は、接着層や粘着層を介して積層することができる。偏光子フィルムとしては、ポリビニルアルコール系樹脂とヨウ素からなる延伸フィルムを用いることができ、その膜厚は１～１００μｍであることが好ましい。 When the film which is one form of the molded product of the present invention is used as a polarizing element protective film or a retardation film, it may be laminated on only one side of the polarizing element film or may be laminated on both sides. When laminated with the polarizing film, it can be laminated via an adhesive layer or an adhesive layer. As the polarizing film, a stretched film made of a polyvinyl alcohol-based resin and iodine can be used, and the film thickness is preferably 1 to 100 μm.
次に実施例を示して本発明をより具体的に説明する。なお、本発明は実施例によって制限されるものではない。 Next, the present invention will be described in more detail with reference to examples. The present invention is not limited to the examples.
物性等の測定は以下の方法によって実施した。
（重合転化率）
島津製作所社製ガスクロマトグラフＧＣ－１４Ａに、カラムとしてＧＬ Ｓｃｉｅｎｃｅｓ Ｉｎｃ．製ＩＮＥＲＴＣＡＰ１（ｄｆ＝０．４μｍ、０．２５ｍｍＩ．Ｄ．×６０ｍ）を繋ぎ、下記の条件にて分析を行い、それに基づいて算出した。
The physical properties were measured by the following method.
(Polymerization conversion rate)
A gas chromatograph GC-14A manufactured by Shimadzu Corporation was used as a column on GL Sciences Inc. INERTCAP 1 (df = 0.4 μm, 0.25 mm ID × 60 m) manufactured by INERTCAP 1 was connected, and analysis was performed under the following conditions, and calculation was performed based on the analysis.
ｉｎｊｅｃｔｉｏｎ温度＝２５０℃
ｄｅｔｅｃｔｏｒ温度＝２５０℃
温度条件：６０℃で５分間保持→１０℃／分で２５０℃まで昇温→２５０℃で１０分間保持
Injection temperature = 250 ° C
detector temperature = 250 ° C
Temperature conditions: Hold at 60 ° C for 5 minutes → Raise to 250 ° C at 10 ° C / min → Hold at 250 ° C for 10 minutes
（分子量）
樹脂の重量平均分子量（Ｍｗ）は、ＧＰＣ法（ゲル浸透クロマトグラフィ法）により求めた。測定対象樹脂４ｍｇをテトラヒドロフラン５ｍｌに溶解させて試料溶液を調整した。カラムオーブンの温度を４０℃に設定し、溶離液流量０．３５ｍｌ／分で、試料溶液２０μｌを装置内に注入して、クロマトグラムを測定した。分子量が４００～５，０００，０００の範囲内にある標準ポリスチレン１０点をＧＰＣ測定し、保持時間と分子量との関係を示す検量線を作成した。この検量線に基づいて測定対象樹脂のＭｗを決定した 。
(Molecular weight)
The weight average molecular weight (Mw) of the resin was determined by the GPC method (gel permeation chromatography method). A sample solution was prepared by dissolving 4 mg of the resin to be measured in 5 ml of tetrahydrofuran. The temperature of the column oven was set to 40 ° C., the eluent flow rate was 0.35 ml / min, 20 μl of the sample solution was injected into the apparatus, and the chromatogram was measured. 10 points of standard polystyrene having a molecular weight in the range of 400 to 5,000,000 were measured by GPC, and a calibration curve showing the relationship between the retention time and the molecular weight was prepared. The Mw of the resin to be measured was determined based on this calibration curve.
装置：東ソー社製ＧＰＣ装置ＨＬＣ－８３２０
分離カラム：東ソー社製のＴＳＫｇｕａｒｄｃｏＩｕｍＳｕｐｅｒＨＺ－ＨとＴＳＫｇｅＩＨＺＭ－ＭとＴＳＫｇｅＩＳｕｐｅｒＨＺ４０００とを直列に連結
溶離剤：テトラヒドロフラン
溶離剤流量：０．３５ｍＩ／分
カラム温度：４０℃
検出方法：示差屈折率（ＲＩ）
Equipment: Tosoh GPC equipment HLC-8320
Separation column: TSKguardcoIumSuperHZ-H, TSKgeIHZM-M and TSKgeISuperHZ4000 manufactured by Tosoh Co., Ltd. are connected in series. Eluent: Tetrahydrofuran Eluent flow rate: 0.35 mI / min Column temperature: 40 ° C.
Detection method: Differential refractometer (RI)
（前駆体ポリマー中の各単位組成）
インバースゲートデカップリング法１３Ｃ－ＮＭＲによりメタクリル酸メチル単位のカルボニル炭素と、α－メチルスチレン単位の１位の芳香族炭素と、スチレン単位の１位の芳香族炭素と、無水マレイン酸単位のカルボニル炭素の積分値比を求め、これによって前駆体ポリマー中の各単位組成を算出した。
(Composition of each unit in the precursor polymer)
Inverse gate decoupling method 13 By C-NMR, carbonyl carbon of methyl methacrylate unit, 1-position aromatic carbon of α-methylstyrene unit, 1-position aromatic carbon of styrene unit, and carbonyl of maleic anhydride unit. The integrated value ratio of carbon was obtained, and the composition of each unit in the precursor polymer was calculated by this.
（ガラス転移温度Ｔｇ）
製造例及び実施例で得られたメタクリル系共重合体を、ＪＩＳ Ｋ７１２１に準拠して、示差走査熱量測定装置（島津製作所製、ＤＳＣ－５０（品番））を用いて、２５０℃まで一度昇温し、次いで室温まで冷却し、その後、室温から２３０℃までを１０℃／分で昇温させる条件にてＤＳＣ曲線を測定した。２回目の昇温時に測定されるＤＳＣ曲線から求められる中間点ガラス転移温度を本発明におけるガラス転移温度とした。
(Glass transition temperature Tg)
The methacrylic copolymer obtained in the production examples and the examples was once heated to 250 ° C. using a differential scanning calorimetry device (manufactured by Shimadzu Corporation, DSC-50 (product number)) in accordance with JIS K7121. Then, the DSC curve was measured under the condition of cooling to room temperature and then raising the temperature from room temperature to 230 ° C. at 10 ° C./min. The midpoint glass transition temperature obtained from the DSC curve measured at the time of the second temperature rise was defined as the glass transition temperature in the present invention.
（イミド化率）
１Ｈ－ＮＭＲ（Ｂｒｕｋｅｒ社製；商品名ＵＬＴＲＡ ＳＨＩＥＬＤ ４００ ＰＬＵＳ）を用いて、共重合体の１Ｈ－ＮＭＲ測定を行い、３．５～３．８ｐｐｍ付近のメタクリル酸メチルのＯ－ＣＨ３基に由来するピークの面積Ａと、３．０～３．３ｐｐｍ付近のグルタルイミド、マレイミドのＮ－ＣＨ３基に由来するピークの面積Ｂより、次式で求めた値をイミド化率（Ｉｍ）とした。
イミド化率（Ｒ）（％）＝［Ｂ／（Ａ＋Ｂ）］×１００
(Imidization rate)
1 H-NMR measurement of the copolymer was performed using 1 H-NMR (manufactured by Bruker; trade name ULTRA SHIELD 400 PLUS), and 3 O-CH groups of methyl methacrylate in the vicinity of 3.5 to 3.8 ppm. The imidization rate (Im) is the value obtained by the following equation from the peak area A derived from the above and the peak area B derived from the three N-CH groups of glutarimide and maleimide in the vicinity of 3.0 to 3.3 ppm. And said.
Imidization rate (R) (%) = [B / (A + B)] × 100
（メタクリル系共重合体中の無水マレイン酸単位量）
実施例で得られたメタクリル系共重合体を、ＴｈｅｒｍｏＳｃｉｅｎｔｉｆｉｃ社製Ｎｉｃｏｌｅｔ ｉＮ１０ＭＸを用いて、室温にてＩＲスペクトルを測定した。得られたスペクトルより、１７８０ｃｍ－１付近の無水マレイン酸のカルボニルに由来するピークの吸収強度と、１６８５ｃｍ－１付近のマレイミドのカルボニルに由来するピークの吸収強度から無水マレイン酸のイミド化率（Ｉｍ’；モル％）を求めた。１３Ｃ－ＮＭＲで求めた前駆体ポリマーの無水マレイン酸単位量（ｍ；質量％）とイミド化率より、次式で求めた値を実施例、比較例で得られた樹脂中の無水マレイン酸単位量（Ｒ-ｍ；質量％）とした。
無水マレイン酸単位量（Ｒ-ｍ）＝ｍ×（１００－Ｉｍ’´）／１００
(Amount of maleic anhydride unit in methacrylic copolymer)
The IR spectrum of the methacrylic copolymer obtained in the examples was measured at room temperature using Nicolet iN10MX manufactured by Thermo Scientific. From the obtained spectrum, the absorption intensity of the peak derived from the carbonyl of maleic anhydride near 1780 cm -1 and the absorption intensity of the peak derived from the carbonyl of maleimide near 1685 cm -1 indicate the imidization rate of maleic anhydride (Im). '; Mol%) was calculated. 13 Maleic anhydride in the resin obtained in Examples and Comparative Examples is the value obtained by the following formula from the unit amount (m; mass%) of maleic anhydride of the precursor polymer obtained by C-NMR and the imidization rate. The unit amount ( RM ; mass%) was used.
Maleic anhydride Unit amount (R- m ) = m × (100-Im'') / 100
（表面硬度）
射出成形機（株式会社名機製作所製、Ｍ－１００Ｃ）を用いて、シリンダ温度２６０℃、金型温度５０℃、射出速度５０ｍｍ／秒の条件で実施例および比較例で得られたアクリル系樹脂組成物を射出成形して、厚さ３ｍｍ、一辺５０ｍｍの正方形の試験片を得た。
また、軸径２０ｍの単軸押出機を用いて、樹脂温度２６０℃にて、実施例および比較例で得られたアクリル系樹脂組成物を１５０ｍｍ幅のＴダイから押出し、幅１００ｍｍ、厚さ８０μｍの単層フィルムを得た。
各試験片および単層フィルムをＪＩＳ Ｋ５６００－５－４に準拠して、０．７５Ｋｇ荷重で、鉛筆硬度を測定した。
○：試験片および単層フィルムの鉛筆硬度がＨ以上
×：試験片または単層フィルムの鉛筆硬度がＦ以下
(surface hardness)
Acrylic resin obtained in Examples and Comparative Examples using an injection molding machine (M-100C manufactured by Meiki Co., Ltd.) under the conditions of a cylinder temperature of 260 ° C., a mold temperature of 50 ° C., and an injection speed of 50 mm / sec. The composition was injection molded to obtain a square test piece having a thickness of 3 mm and a side of 50 mm.
Further, using a single-screw extruder having a shaft diameter of 20 m, the acrylic resin compositions obtained in Examples and Comparative Examples were extruded from a T-die having a width of 150 mm at a resin temperature of 260 ° C., and the width was 100 mm and the thickness was 80 μm. Single layer film was obtained.
The pencil hardness of each test piece and single-layer film was measured according to JIS K5600-5-4 under a load of 0.75 kg.
◯: Pencil hardness of test piece or single layer film is H or more ×: Pencil hardness of test piece or single layer film is F or less
（光弾性係数）
メタクリル系共重合体をプレス成形により、１．０ｍｍのシートを得た。得られたプレス成形シートの中央部から、１５ｍｍ×６０ｍｍの試験片を切り出した。切り出したシートの長辺方向両端をチャック間距離が４５ｍｍとなるように固定し、駿河精機製Ｘ軸アリ式ステージＢ０５－１１ＢＭを用いてシートに、０Ｎから１００Ｎまで１０Ｎ毎に段階的に張力を付与した。張力Ｔは株式会社イマダ製センサーセパレート型デジタルフォースゲージＺＰＳ－ＤＰＵ－５０Ｎによりモニターした。各張力を付与した状態での位相差ＰＤを王子計測機器製ＫＯＢＲＡ－ＷＲを用いてＮａのＤ線波長にて測定した。位相差測定後シートを治具より外し、位相差測定部分の厚さｄを測定した。測定値から、シートの断面積Ｓ＝１５ｍｍ×ｄ、応力σ（＝Ｔ／Ｓ）および複屈折Δｎ（＝ＰＤ／ｄ）を算出し、横軸に応力σ、縦軸に複屈折Δｎをプロットし、最小自乗法により求め得られた直線の傾きを光弾性係数とした。
(Photoelastic coefficient)
The methacrylic copolymer was press-molded to obtain a 1.0 mm sheet. A 15 mm × 60 mm test piece was cut out from the central portion of the obtained press-formed sheet. Both ends of the cut sheet in the long side direction are fixed so that the distance between the chucks is 45 mm, and tension is applied to the sheet step by step from 0N to 100N using the X-axis dovetail stage B05-11BM manufactured by Suruga Seiki. Granted. The tension T was monitored by a sensor separate type digital force gauge ZPS-DPU-50N manufactured by Imada Co., Ltd. The phase difference PD with each tension applied was measured at the D-line wavelength of Na using KOBRA-WR manufactured by Oji Measuring Instruments. After the phase difference measurement, the sheet was removed from the jig, and the thickness d of the phase difference measurement portion was measured. From the measured values, the cross-sectional area S of the sheet S = 15 mm × d, stress σ (= T / S) and birefringence Δn (= PD / d) are calculated, and stress σ is plotted on the horizontal axis and birefringence Δn is plotted on the vertical axis. Then, the slope of a straight line obtained by the minimum self-squared method was used as the photoelastic coefficient.
（配向複屈折）
メタクリル系共重合体をプレス成形により、１．０ｍｍのシートを得た。得られたプレス成形シートの中央部から、２０ｍｍ×４０ｍｍの試験片を切り出し、加熱チャンバー付きオートグラフ（ＳＨＩＭＡＤＺＵ社製）に試験片を設置した。オートグラフでのつかみ間距離を２０ｍｍとし、ガラス転移温度＋１０℃にて３分間保持した。その後、３ｍｍ／分の速度で一方向に１００％延伸（つかみ間距離が４０ｍｍになる）した。得られた延伸フィルムを２３℃に冷却し、オートグラフから取外し、延伸フィルム中央部分の位相差ＰＤを王子計測機器製ＫＯＢＲＡ－ＷＲを用いてＮａのＤ線波長にて測定した。位相差測定部分の厚さｄを測定した。測定値から、複屈折Δｎ（＝ＰＤ／ｄ）を算出し、これを配向複屈折とした。
(Orientation birefringence)
The methacrylic copolymer was press-molded to obtain a 1.0 mm sheet. A 20 mm × 40 mm test piece was cut out from the central portion of the obtained press-molded sheet, and the test piece was placed in an autograph with a heating chamber (manufactured by SHIMADZU). The gripping distance in the autograph was set to 20 mm, and the glass transition temperature was maintained at + 10 ° C. for 3 minutes. Then, it was stretched 100% in one direction at a speed of 3 mm / min (the distance between grips became 40 mm). The obtained stretched film was cooled to 23 ° C., removed from the autograph, and the phase difference PD at the center of the stretched film was measured at the D-line wavelength of Na using KOBRA-WR manufactured by Oji Measuring Instruments. The thickness d of the phase difference measuring portion was measured. The birefringence Δn (= PD / d) was calculated from the measured value, and this was defined as the orientation birefringence.
製造例１
撹拌機付オートクレーブＡに、精製されたメタクリル酸メチル（ＭＭＡ）、α－メチルスチレン、無水マレイン酸、２，２’－アゾビス（２－メチルプロピオニトリル）（ＡＩＢＮ）およびｎ－オクチルメルカプタン（ｎ－ＯＭ）を表１に記載の割合で仕込み、均一に溶解させて重合原料を得た。
Production Example 1
Purified methyl methacrylate (MMA), α-methylstyrene, maleic anhydride, 2,2'-azobis (2-methylpropionitrile) (AIBN) and n-octyl mercaptan (n) in an autoclave A with a stirrer. -OM) was charged at the ratio shown in Table 1 and uniformly dissolved to obtain a polymerization raw material.
重合原料を、オートクレーブＡから１．５ｋｇ／ｈｒで、重合温度１２０℃に制御された槽型反応器に連続的に供給し、平均滞留時間２．５時間で塊状重合法によって重合反応させ、槽型反応器からメタクリル系共重合体を含む液を連続的に排出した。重合転化率は表１に記載の値になった。次いで、反応器から排出された液を２３０℃に加温し、２４０℃に制御された二軸押出機に供給した。該二軸押出機において未反応単量体を主成分とする揮発分を分離除去して、メタクリル系共重合体をストランドにして押出した。該ストランドをペレタイザーでカットし、前駆体ポリマーＡ－ａを得た。得られた前駆体ポリマーＡ－ａの重量平均分子量Ｍｗ、共重合体の各単位組成、ガラス転移温度Ｔｇを測定した。その結果を表１に示す。なお、本製造例において、ＭＭＡに由来する単位の量は、α-メチルスチレン単位、スチレン単位、無水マレイン酸単位以外の単位の量であるので、表への記載を省略した。 The polymerization raw material is continuously supplied from the autoclave A to a tank reactor controlled at a polymerization temperature of 120 ° C. at 1.5 kg / hr, and the polymerization reaction is carried out by a massive polymerization method with an average residence time of 2.5 hours. The liquid containing the methacrylic copolymer was continuously discharged from the mold reactor. The polymerization conversion rate was the value shown in Table 1. Then, the liquid discharged from the reactor was heated to 230 ° C. and supplied to a twin-screw extruder controlled to 240 ° C. In the twin-screw extruder, the volatile matter containing the unreacted monomer as a main component was separated and removed, and the methacrylic copolymer was extruded into strands. The strands were cut with a pelletizer to give the precursor polymer A-a. The weight average molecular weight Mw of the obtained precursor polymer Aa, each unit composition of the copolymer, and the glass transition temperature Tg were measured. The results are shown in Table 1. In this production example, the amount of the unit derived from MMA is the amount of the unit other than the α-methylstyrene unit, the styrene unit, and the maleic anhydride unit, so the description in the table is omitted.
製造例２～７
重合原料中のモノマー組成、連鎖移動剤の使用量を表１に示す通り変更した以外は、製造例１と同様にして前駆体ポリマーＡ－ｂ～Ａ－ｇを得た。
Production Examples 2 to 7
Precursor polymers AB to Ag were obtained in the same manner as in Production Example 1 except that the monomer composition in the polymerization raw material and the amount of the chain transfer agent used were changed as shown in Table 1.
製造例８
特開２００３－２３１７８５号公報の［実施例］の項に記載の共重合体（Ａ）の製造方法に従って、ＭＳ樹脂（メタクリル酸メチル（ＭＭＡ）とスチレン（Ｓｔ）との共重合体）を製造した。オートクレーブ内に仕込むＭＭＡとＳｔとｔ－ドデシルメルカプタン（ｔ－ＤＭ）の質量比を変えて、前駆体ポリマーＡ－ｈ；Mw=９５０００、Ｔｇ＝１１３℃、スチレン単量体単位の含有量２０質量％を得た。
Production Example 8
MS resin (copolymer of methyl methacrylate (MMA) and styrene (St)) is produced according to the method for producing a copolymer (A) described in the section of [Example] of JP-A-2003-231785. bottom. By changing the mass ratio of MMA, St and t-dodecyl mercaptan (t-DM) charged in the autoclave, the precursor polymer Ah; Mw = 95000, Tg = 113 ° C., content of styrene monomer unit 20 mass. % Was obtained.
＜実施例１＞
輸送部、溶融混練部、脱揮部および排出部からなり且つスクリュー回転数１２０ｒｐｍおよび温度２８０℃に設定された二軸押出機（テクノベル社製；商品名ＫＺＷ２０ＴＷ－４５ＭＧ－ＮＨ－６００）の輸送部に製造例１で示した前駆体ポリマー〔Ａ－ａ〕を２ｋｇ／ｈｒで供給し、ニーディングブロックの設置された溶融混練部においてモノメチルアミンを０．４１ｋｇ／ｈｒで二軸押出機の添加剤供給口から注入し、前駆体ポリマー〔A-a〕とモノメチルアミンとを反応させた。なお、反応ゾーンの末端のスクリューにリバースフライトを設置した。
<Example 1>
Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 120 rpm and a temperature of 280 ° C. The precursor polymer [Aa] shown in Production Example 1 was supplied at 2 kg / hr, and monomethylamine was added at 0.41 kg / hr in a melt-kneaded portion in which a kneading block was installed as an additive for a twin-screw extruder. It was injected from the supply port to react the precursor polymer [Aa] with monomethylamine. A reverse flight was installed on the screw at the end of the reaction zone.
２０Ｔｏｒｒ（約２．７ｋＰａ）に設定された脱揮部において、副生成物および過剰のモノメチルアミンを、溶融混練部を通過した溶融樹脂から揮発させ、ベントを通して排出した。 In the devolatilization section set to 20 Torr (about 2.7 kPa), by-products and excess monomethylamine were volatilized from the molten resin that had passed through the melt kneading section and discharged through the vent.
二軸押出機の排出部の末端に設けられたダイスからストランドとして押出された溶融樹脂を、水槽で冷却し、その後、ペレタイザでカットしてペレット状のメタクリル系共重合体（Ａ－ａ－１）を得た。 The molten resin extruded as a strand from a die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to form a pellet-shaped methacrylic copolymer (A-a-1). ) Was obtained.
輸送部、溶融混練部、脱揮部および排出部からなり且つスクリュー回転数１００ｒｐｍおよび温度２８０℃に設定された二軸押出機（テクノベル社製；商品名ＫＺＷ２０ＴＷ－４５ＭＧ－ＮＨ－６００）の輸送部に共重合体（Ａ－ａ－１）を１ｋｇ／ｈｒで供給し、ニーディングブロックの設置された溶融混練部において、炭酸ジメチル０．８質量部およびトリエチルアミン０．２質量部からなる液を０．１１２ｋｇ／ｈｒで注入し、メタクリル系共重合体（Ａ－ａ－１）中のカルボキシ基に炭酸ジメチルを反応させた。なお、反応ゾーンの末端のスクリューにリバースフライトを設置した。 Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt-kneading section, a volatilization section, and a discharge section and set to a screw rotation speed of 100 rpm and a temperature of 280 ° C. The copolymer (A-a-1) was supplied at 1 kg / hr, and in the melt-kneaded portion in which the kneading block was installed, a liquid consisting of 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine was added to 0. The mixture was injected at 112 kg / hr, and the carboxy group in the methacrylic copolymer (A-a-1) was reacted with dimethyl carbonate. A reverse flight was installed on the screw at the end of the reaction zone.
２０Ｔｏｒｒ（約２．７ｋＰａ）に設定された脱揮部において、副生成物および過剰の炭酸ジメチルを、溶融混練部を通過した溶融樹脂から揮発させ、ベントを通して排出した。 In the devolatilization section set to 20 Torr (about 2.7 kPa), by-products and excess dimethyl carbonate were volatilized from the molten resin that had passed through the melt kneading section and discharged through the vent.
二軸押出機の排出部の末端に設けられたダイスからストランドとして押出された溶融樹脂を、水槽で冷却し、その後、ペレタイザでカットしてペレット状のメタクリル系共重合体（Ａ－ａ－２）を得た。 The molten resin extruded as a strand from a die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to form a pellet-shaped methacrylic copolymer (A-a-2). ) Was obtained.
輸送部、溶融混練部、脱揮部および排出部からなり且つスクリュー回転数１００ｒｐｍおよび温度２８０℃に設定された二軸押出機（テクノベル社製；商品名ＫＺＷ２０ＴＷ－４５ＭＧ－ＮＨ－６００）の輸送部にメタクリル系共重合体（Ａ－ａ－２）を１ｋｇ／ｈｒで供給した。 Transport section of a twin-screw extruder (manufactured by Technobel Co., Ltd .; trade name KZW20TW-45MG-NH-600) consisting of a transport section, a melt-kneading section, a devolatilization section, and a discharge section and set to a screw rotation speed of 100 rpm and a temperature of 280 ° C. A methacrylic copolymer (A-a-2) was supplied at 1 kg / hr.
２０Ｔｏｒｒ（約２．７ｋＰａ）に設定された脱揮部において、未反応物などの揮発分を、溶融混練部を通過した溶融樹脂から揮発させ、ベントを通して排出した。 In the devolatilization section set to 20 Torr (about 2.7 kPa), volatile components such as unreacted substances were volatilized from the molten resin that had passed through the melt-kneading section and discharged through the vent.
二軸押出機の排出部の末端に設けられたダイスからストランドとして押出された溶融樹脂を、水槽で冷却し、その後、ペレタイザでカットしてペレット状のメタクリル系共重合体（Ａ－１）を得た。メタクリル系共重合体（Ａ－１）は、イミド化率Ｉｍが６２ｗｔ％、無水マレイン酸単位量Ｍが２ｗｔ％、ガラス転移温度が１８６℃、配向複屈折が０．１０×１０－４、光弾性係数が０．２１×１０－１２Ｐａ－１であった。メタクリル系共重合体（Ａ－１）の物性を表２に示す。 The molten resin extruded as a strand from a die provided at the end of the discharge section of the twin-screw extruder is cooled in a water tank and then cut with a pelletizer to obtain a pellet-shaped methacrylic copolymer (A-1). Obtained. The methacrylic copolymer (A-1) has an imidization ratio of 62 wt%, a maleic anhydride unit amount of M of 2 wt%, a glass transition temperature of 186 ° C., an orientation birefringence of 0.10 × 10 -4 , and light. The elastic coefficient was 0.21 × 10-12 Pa -1 . Table 2 shows the physical characteristics of the methacrylic copolymer (A-1).
＜実施例２＞
前駆体ポリマー〔Ａ－ａ〕の替わりに、前駆体ポリマー〔Ａ－ｂ〕を用い、モノメチルアミンの添加量を０．２９ｋｇ／ｈｒ、炭酸ジメチル０．８質量部およびトリエチルアミン０．２質量部からなる液を０．０７７ｋｇ／ｈｒで注入した以外は、実施例１と同じ方法で、メタクリル系共重合体（Ａ－２）を得た。メタクリル系共重合体（Ａ－２）の物性を表２に示す。
<Example 2>
Using the precursor polymer [Ab] instead of the precursor polymer [Aa], the amount of monomethylamine added is 0.29 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine. A methacrylic copolymer (A-2) was obtained by the same method as in Example 1 except that the solution was injected at 0.077 kg / hr. Table 2 shows the physical characteristics of the methacrylic copolymer (A-2).
＜実施例３＞
前駆体ポリマー〔Ａ－ａ〕の替わりに、前駆体ポリマー〔Ａ－ｃ〕を用い、モノメチルアミンの添加量を０．３２ｋｇ／ｈｒ、炭酸ジメチル０．８質量部およびトリエチルアミン０．２質量部からなる液を０．０８６ｋｇ／ｈｒで注入した以外は、実施例１と同じ方法で、メタクリル系共重合体（Ａ－３）を得た。メタクリル系共重合体（Ａ－３）の物性を表２に示す。
<Example 3>
Using the precursor polymer [A-c] instead of the precursor polymer [A-a], the amount of monomethylamine added is 0.32 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine. A methacrylic copolymer (A-3) was obtained by the same method as in Example 1 except that the solution was injected at 0.086 kg / hr. Table 2 shows the physical characteristics of the methacrylic copolymer (A-3).
＜実施例４＞
前駆体ポリマー〔Ａ－ａ〕の替わりに、前駆体ポリマー〔Ａ－ｄ〕を用い、モノメチルアミンの添加量を０．３８ｋｇ／ｈｒ、炭酸ジメチル０．８質量部およびトリエチルアミン０．２質量部からなる液を０．１０３ｋｇ／ｈｒで注入した以外は、実施例１と同じ方法で、メタクリル系共重合体（Ａ－４）を得た。メタクリル系共重合体（Ａ－４）の物性を表２に示す。
<Example 4>
Instead of the precursor polymer [AA], the precursor polymer [Ad] was used, and the amount of monomethylamine added was 0.38 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine. A methacrylic copolymer (A-4) was obtained by the same method as in Example 1 except that the solution was injected at 0.103 kg / hr. Table 2 shows the physical characteristics of the methacrylic copolymer (A-4).
＜実施例５＞
前駆体ポリマー〔Ａ－ａ〕の替わりに、前駆体ポリマー〔Ａ－ｅ〕を用い、モノメチルアミンの添加量を０．３３ｋｇ／ｈｒ、炭酸ジメチル０．８質量部およびトリエチルアミン０．２質量部からなる液を０．０８８ｋｇ／ｈｒで注入した以外は、実施例１と同じ方法で、メタクリル系共重合体（Ａ－５）を得た。メタクリル系共重合体（Ａ－５）の物性を表２に示す。
<Example 5>
Instead of the precursor polymer [Aa], the precursor polymer [Ae] was used, and the amount of monomethylamine added was 0.33 kg / hr, from 0.8 parts by mass of dimethyl carbonate and 0.2 parts by mass of triethylamine. A methacrylic copolymer (A-5) was obtained by the same method as in Example 1 except that the solution was injected at 0.088 kg / hr. Table 2 shows the physical characteristics of the methacrylic copolymer (A-5).
＜比較例１＞
前駆体ポリマー〔Ａ－ａ〕の替わりに、前駆体ポリマー〔Ａ－ｆ〕を用い、二軸押出機の温度を２５０℃に設定し、モノメチルアミンの添加量を０．０３ｋｇ／ｈｒ、炭酸ジメチル０．８質量部およびトリエチルアミン０．２質量部からなる液を０．００９ｋｇ／ｈｒで注入した以外は、実施例１と同じ方法で、メタクリル系共重合体（Ａ－６）を得た。メタクリル系共重合体（Ａ－６）の物性を表２に示す。
<Comparative Example 1>
Using the precursor polymer [AF] instead of the precursor polymer [AA], the temperature of the twin-screw extruder was set to 250 ° C., the amount of monomethylamine added was 0.03 kg / hr, and dimethyl carbonate was used. A methacrylic copolymer (A-6) was obtained by the same method as in Example 1 except that a liquid consisting of 0.8 parts by mass and 0.2 parts by mass of triethylamine was injected at 0.009 kg / hr. Table 2 shows the physical characteristics of the methacrylic copolymer (A-6).
＜比較例２＞
前駆体ポリマー〔Ａ－ａ〕の替わりに、前駆体ポリマー〔Ａ－ｇ〕を用い、二軸押出機の温度を２５０℃に設定し、モノメチルアミンの添加量を０．１５ｋｇ／ｈｒ、炭酸ジメチル０．８質量部およびトリエチルアミン０．２質量部からなる液を０．０４ｋｇ／ｈｒで注入した以外は、実施例１と同じ方法で、メタクリル系共重合体（Ａ－７）を得た。メタクリル系共重合体（Ａ－７）の物性を表２に示す。
<Comparative Example 2>
Using the precursor polymer [Ag] instead of the precursor polymer [Aa], the temperature of the twin-screw extruder was set to 250 ° C., the amount of monomethylamine added was 0.15 kg / hr, and dimethyl carbonate. A methacrylic copolymer (A-7) was obtained by the same method as in Example 1 except that a liquid consisting of 0.8 parts by mass and 0.2 parts by mass of triethylamine was injected at 0.04 kg / hr. Table 2 shows the physical characteristics of the methacrylic copolymer (A-7).
＜比較例３＞
前駆体ポリマー〔Ａ－ａ〕の替わりに、前駆体ポリマー〔Ａ－ｈ〕を用い、二軸押出機の温度を２５０℃に設定し、モノメチルアミンの添加量を０．２６ｋｇ／ｈｒ、炭酸ジメチル０．８質量部およびトリエチルアミン０．２質量部からなる液を０．０７ｋｇ／ｈｒで注入した以外は、実施例１と同じ方法で、メタクリル系共重合体（Ａ－８）を得た。メタクリル系共重合体（Ａ－８）の物性を表２に示す。
<Comparative Example 3>
Using the precursor polymer [Ah] instead of the precursor polymer [A-a], the temperature of the twin-screw extruder was set to 250 ° C., the amount of monomethylamine added was 0.26 kg / hr, and dimethyl carbonate. A methacrylic copolymer (A-8) was obtained by the same method as in Example 1 except that a liquid consisting of 0.8 parts by mass and 0.2 parts by mass of triethylamine was injected at 0.07 kg / hr. Table 2 shows the physical characteristics of the methacrylic copolymer (A-8).
＜比較例４＞
前駆体ポリマー〔Ａ－ａ〕を用い、添加剤を加えず、押出機を素通しした以外は、実施例１と同じ方法で、アクリル系共重合体（Ａ－９）を得た。アクリル系共重合体（Ａ－９）の物性を表２に示す。
<Comparative Example 4>
An acrylic copolymer (A-9) was obtained by the same method as in Example 1 except that the precursor polymer [Aa] was used, no additives were added, and the extruder was passed through. Table 2 shows the physical characteristics of the acrylic copolymer (A-9).
実施例１～５で得られたメタクリル系重合体は、耐熱性が高く、高い光学的等方性（極めて小さな配向複屈折および極めて小さな光弾性係数）を有しており、表面硬度が高いため、光学部材を構成する材料として好適に使用することができる。一方、比較例１～４で得られたメタクリル系共重合体は、本発明の範囲にないため、光学的等方性が低い、または表面硬度が低いため、本発明と比べて劣るものであった。 The methacrylic polymers obtained in Examples 1 to 5 have high heat resistance, high optical isotropic properties (extremely small orientation birefringence and extremely small photoelastic coefficient), and have high surface hardness. , Can be suitably used as a material constituting an optical member. On the other hand, the methacrylic copolymers obtained in Comparative Examples 1 to 4 are inferior to the present invention because they are not within the scope of the present invention and therefore have low optical isotropic properties or low surface hardness. rice field.
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