JP2023178316A - (meth)acrylic resin composition and (meth)acrylic resin film - Google Patents
(meth)acrylic resin composition and (meth)acrylic resin film Download PDFInfo
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- JP2023178316A JP2023178316A JP2023167276A JP2023167276A JP2023178316A JP 2023178316 A JP2023178316 A JP 2023178316A JP 2023167276 A JP2023167276 A JP 2023167276A JP 2023167276 A JP2023167276 A JP 2023167276A JP 2023178316 A JP2023178316 A JP 2023178316A
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- Prior art keywords
- meth
- acrylic resin
- resin composition
- weight
- resin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 138
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 138
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 52
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 33
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920001519 homopolymer Polymers 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 17
- -1 methacryloyl Chemical group 0.000 claims description 17
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 4
- 150000001541 aziridines Chemical class 0.000 claims description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims 1
- 239000003085 diluting agent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 30
- 239000002904 solvent Substances 0.000 abstract description 30
- 238000005266 casting Methods 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 133
- 239000000243 solution Substances 0.000 description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001125 extrusion Methods 0.000 description 15
- 239000012788 optical film Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 12
- 239000004926 polymethyl methacrylate Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 239000000155 melt Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004069 aziridinyl group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 description 1
- KQSMCAVKSJWMSI-UHFFFAOYSA-N 2,4-dimethyl-1-n,1-n,3-n,3-n-tetrakis(oxiran-2-ylmethyl)benzene-1,3-diamine Chemical compound CC1=C(N(CC2OC2)CC2OC2)C(C)=CC=C1N(CC1OC1)CC1CO1 KQSMCAVKSJWMSI-UHFFFAOYSA-N 0.000 description 1
- HYFWTAIKSNDMBJ-UHFFFAOYSA-N 2-(aziridin-1-yl)propanoic acid 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound N1(CC1)C(C(=O)O)C.N1(CC1)C(C(=O)O)C.N1(CC1)C(C(=O)O)C.C(O)C(CO)(CO)CO HYFWTAIKSNDMBJ-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-UHFFFAOYSA-N 0.000 description 1
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical compound CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- TZCGFWIYMJNJIO-UHFFFAOYSA-N 4-methylpentyl 2-methylprop-2-enoate Chemical compound CC(C)CCCOC(=O)C(C)=C TZCGFWIYMJNJIO-UHFFFAOYSA-N 0.000 description 1
- JSCDRVVVGGYHSN-UHFFFAOYSA-N 8-hydroxyoctyl prop-2-enoate Chemical compound OCCCCCCCCOC(=O)C=C JSCDRVVVGGYHSN-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- XXGJJYJASLTCBM-UHFFFAOYSA-N CC(N1CC1)C(O)=O.CC(N1CC1)C(O)=O.CC(N1CC1)C(O)=O.CCC(CO)(CO)CO Chemical compound CC(N1CC1)C(O)=O.CC(N1CC1)C(O)=O.CC(N1CC1)C(O)=O.CCC(CO)(CO)CO XXGJJYJASLTCBM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- FOCVUCIESVLUNU-UHFFFAOYSA-N Thiotepa Chemical compound C1CN1P(N1CC1)(=S)N1CC1 FOCVUCIESVLUNU-UHFFFAOYSA-N 0.000 description 1
- FYAMXEPQQLNQDM-UHFFFAOYSA-N Tris(1-aziridinyl)phosphine oxide Chemical compound C1CN1P(N1CC1)(=O)N1CC1 FYAMXEPQQLNQDM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- VXTQKJXIZHSXBY-UHFFFAOYSA-N butan-2-yl 2-methylprop-2-enoate Chemical compound CCC(C)OC(=O)C(C)=C VXTQKJXIZHSXBY-UHFFFAOYSA-N 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- YVOQADGLLJCMOE-UHFFFAOYSA-N n-[6-(aziridine-1-carbonylamino)hexyl]aziridine-1-carboxamide Chemical compound C1CN1C(=O)NCCCCCCNC(=O)N1CC1 YVOQADGLLJCMOE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IUCJMVBFZDHPDX-UHFFFAOYSA-N tretamine Chemical compound C1CN1C1=NC(N2CC2)=NC(N2CC2)=N1 IUCJMVBFZDHPDX-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
本発明は、（メタ）アクリル系樹脂フィルム等の形成に好適に用いられる（メタ）アクリル系樹脂組成物、及びそれを用いた（メタ）アクリル系樹脂フィルムに関する。 The present invention relates to a (meth)acrylic resin composition suitably used for forming a (meth)acrylic resin film and the like, and a (meth)acrylic resin film using the same.
従来から、高透明性、加熱加工性、耐候性、耐薬品性に優れていることから、電子機器、家電製品、自動車内外装部品、建築部材などの各種機器部品の表面被覆に用いる樹脂フィルムとして、（メタ）アクリル系樹脂フィルムが用いられている。
また、近年では、高透明性、耐候性などに優れていることから、（メタ）アクリル系樹脂フィルムが、光学用フィルムとして用いられている。
Due to its high transparency, heat processability, weather resistance, and chemical resistance, it has long been used as a resin film for coating the surface of various equipment parts such as electronic devices, home appliances, automobile interior and exterior parts, and building materials. , (meth)acrylic resin film is used.
In recent years, (meth)acrylic resin films have been used as optical films because of their excellent transparency and weather resistance.
従来、ポリメチルメタクリレート（ＰＭＭＡ）樹脂からなる（メタ）アクリル系樹脂フィルム（ＰＭＭＡフィルム）を製造する方法としては、生産性が高いことから、ＰＭＭＡ樹脂を溶融押出法により製膜する方法が採用されていた。 Conventionally, as a method for manufacturing a (meth)acrylic resin film (PMMA film) made of polymethyl methacrylate (PMMA) resin, a method of forming a PMMA resin film by melt extrusion has been adopted because of its high productivity. was.
例えば、特許文献１には、アクリル樹脂フィルムと成形樹脂とを一体化する部材に好適に使用可能なアクリル樹脂フィルムであって、特に、表面の保護層の形成に好適な塗装代替アクリル樹脂フィルムが開示されている。特許文献１に記載の発明に係わるアクリル樹脂フィルムは、アクリル樹脂フィルムに添加する紫外線吸収剤と滑剤とを特定の種類で組み合わせ、しかもこれらの成分を特定の含有量としている。このため、特許文献１では、表面の保護層の形成に使用する塗装代替アクリル樹脂フィルムとして、好適に使用できるとしている。 For example, Patent Document 1 describes an acrylic resin film that can be suitably used for a member that integrates an acrylic resin film and a molded resin, and that is particularly suitable for forming a protective layer on the surface as a paint substitute acrylic resin film. Disclosed. The acrylic resin film according to the invention described in Patent Document 1 is a combination of a specific type of ultraviolet absorber and a lubricant added to the acrylic resin film, and has a specific content of these components. For this reason, Patent Document 1 states that it can be suitably used as a paint substitute acrylic resin film used to form a surface protective layer.
また、特許文献２には、アクリル系樹脂の長所である独特の美しい色調、及び透明性が損なわれる原因となるゴム含有グラフト共重合体を含有させないで、アクリル系樹脂の本質的な欠点である耐衝撃性を改善する方法が開示されている。特許文献２に記載の発明に係わるアクリル系樹脂組成物は、前記樹脂組成物を溶融押出法によりフィルム化する際に溶融押出温度を高くすると、前記グラフト共重合体が熱分解することにより発生する分解ガス、又はブリードアウト物により、キャストロール等の冷却ロールが汚染されて、生産性が落ちるという問題を解決できるとしている。 In addition, Patent Document 2 discloses that it does not contain rubber-containing graft copolymers that cause loss of unique beautiful color tone, which is an advantage of acrylic resin, and transparency, which is an essential disadvantage of acrylic resin. A method of improving impact resistance is disclosed. In the acrylic resin composition according to the invention described in Patent Document 2, when the resin composition is formed into a film by a melt extrusion method, when the melt extrusion temperature is increased, the graft copolymer is thermally decomposed. The company claims that it can solve the problem of cooling rolls such as cast rolls being contaminated by decomposition gas or bleed-out products, which reduces productivity.
ところで、特許文献１に記載の発明に係わるアクリル樹脂フィルムは、熱可塑性重合体を含むアクリル樹脂組成物の混合物を脱気式二軸押出機にて混練して、アクリル樹脂組成物のペレットを得た後に、溶融押出機にて溶融した樹脂組成物をＴダイに押し出して行う溶融押出法により、アクリル樹脂フィルムを製膜したものである。また、特許文献１に記載の実施例１～６では、膜厚が５０～１２５μｍのアクリル樹脂フィルムが得られている。しかし、特許文献１に記載の発明に係わるアクリル樹脂フィルムは、溶融押出法により製膜した樹脂フィルムであることから、膜厚が４０μｍ以下の薄い樹脂フィルムを得ることが困難であるという問題を有していた。 By the way, the acrylic resin film according to the invention described in Patent Document 1 is produced by kneading a mixture of an acrylic resin composition containing a thermoplastic polymer in a degassing twin-screw extruder to obtain pellets of the acrylic resin composition. After that, an acrylic resin film was formed by a melt extrusion method in which the resin composition melted with a melt extruder was extruded through a T-die. Furthermore, in Examples 1 to 6 described in Patent Document 1, acrylic resin films having a thickness of 50 to 125 μm were obtained. However, since the acrylic resin film according to the invention described in Patent Document 1 is a resin film produced by a melt extrusion method, it has the problem that it is difficult to obtain a thin resin film with a thickness of 40 μm or less. Was.
また、特許文献２に記載の発明に係わるアクリル樹脂組成物は、３～４段階のグラフト重合反応を行い徐々にグラフト共重合体を完成させるため、グラフト共重合体を得る工程に長時間を要するという問題を有していた。また、特許文献２の、溶融押出法によりアクリル樹脂フィルムを製造した実施例６～８では、延伸しないで得られたアクリル樹脂フィルムの膜厚が８０μｍであり、延伸しないで膜厚が４０μｍ以下の薄い樹脂フィルムが得られていなかった。 In addition, the acrylic resin composition according to the invention described in Patent Document 2 performs a 3-4 step graft polymerization reaction to gradually complete the graft copolymer, so the process of obtaining the graft copolymer takes a long time. There was a problem. Furthermore, in Examples 6 to 8 of Patent Document 2, in which acrylic resin films were produced by melt extrusion, the thickness of the acrylic resin film obtained without stretching was 80 μm, and the film thickness was 40 μm or less without stretching. A thin resin film was not obtained.
こうしたなか、溶融押出法に比べて、より簡便な樹脂フィルムの製膜方法であり、薄膜化にできる利点がある溶液キャスト法によりＰＭＭＡ樹脂を製膜する方法が求められていた。本発明者らは、溶液キャスト法によりＰＭＭＡ樹脂を製膜する方法を鋭意検討した。その結果、特定のＰＭＭＡ樹脂組成物を用いることにより、溶液キャスト法により製膜した場合でも、溶融押出法により製膜したものと同等以上の優れた物性を有するＰＭＭＡ樹脂フィルムが得られることを見出し、本発明を完成させることができた。 Under these circumstances, there has been a demand for a method of forming a PMMA resin film by a solution casting method, which is a simpler method of forming a resin film than the melt extrusion method and has the advantage of being able to form a thin film. The present inventors have intensively studied a method of forming a PMMA resin film by a solution casting method. As a result, it was discovered that by using a specific PMMA resin composition, a PMMA resin film having excellent physical properties equivalent to or better than those produced by melt extrusion, even when produced by solution casting, was found. , we were able to complete the present invention.
従来の溶融押出法により、（メタ）アクリル系樹脂フィルムを製膜する方法の場合には、４０μｍ以下の厚みに薄膜化することが困難であった。一方、溶液キャスト法により、（メタ）アクリル系樹脂フィルムを製膜する方法の場合には、４０μｍ以下の厚みに薄膜化することが可能であるが、得られた（メタ）アクリル系樹脂フィルムの物性として耐溶剤性の性能を向上させることが難しいという問題があった。また、溶液キャスト法においては、（メタ）アクリル系樹脂組成物に含有する未架橋のＰＭＭＡ樹脂の重量平均分子量を１００万以上の大きな値にする必要があるため、該（メタ）アクリル系樹脂組成物の溶液が高粘度であり、製膜工程での作業性が良くないという問題があった。 In the case of a method of forming a (meth)acrylic resin film by the conventional melt extrusion method, it was difficult to reduce the film thickness to 40 μm or less. On the other hand, in the case of a method of forming a (meth)acrylic resin film by a solution casting method, it is possible to reduce the thickness to 40 μm or less, but the resulting (meth)acrylic resin film There was a problem in that it was difficult to improve solvent resistance as a physical property. In addition, in the solution casting method, since it is necessary to make the weight average molecular weight of the uncrosslinked PMMA resin contained in the (meth)acrylic resin composition a large value of 1 million or more, the (meth)acrylic resin composition There was a problem in that the solution had a high viscosity and the workability in the film forming process was poor.
本発明は、薄い膜厚の樹脂フィルムを得るための溶液キャスト法に使用できる（メタ）アクリル系樹脂組成物であって、製膜した樹脂フィルム等の成形品が耐折性、耐切性（引張破断強度）、破断伸び、耐溶剤性（ゲル分率）に優れている（メタ）アクリル系樹脂組成物、及び（メタ）アクリル系樹脂フィルムを提供することを課題とする。 The present invention is a (meth)acrylic resin composition that can be used in a solution casting method to obtain a thin resin film, and the molded products such as the resin film formed into the film have good bending durability, cut resistance (tensile strength), etc. An object of the present invention is to provide a (meth)acrylic resin composition and a (meth)acrylic resin film that are excellent in breaking strength), breaking elongation, and solvent resistance (gel fraction).
本発明者らは、上記の課題を解決するために鋭意検討した結果、（メタ）アクリル系ポリマーと、架橋剤とを含有する（メタ）アクリル系樹脂組成物であって、前記（メタ）アクリル系ポリマーが、ＭＭＡ（メチルメタクリレート）と、前記ＭＭＡ以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートと、官能基を有する共重合可能なモノマーの少なくとも１種以上とを、特定の割合で共重合させた共重合体からなる（メタ）アクリル系ポリマーとすることにより、このような（メタ）アクリル系樹脂組成物を用いて、溶液キャスト法により得られた（メタ）アクリル系樹脂フィルムは、耐折性、耐切性（引張破断強度）、破断伸び、耐溶剤性（ゲル分率）に優れていることを見出し、本発明を完成させることができた。すなわち、本発明は、特定の（メタ）アクリル系ポリマーと、架橋剤とを含有する（メタ）アクリル系樹脂組成物を架橋させた樹脂層からなる（メタ）アクリル系樹脂フィルムを得ることを技術思想としている。 As a result of intensive studies to solve the above problems, the present inventors have discovered a (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent, the (meth)acrylic The system polymer has MMA (methyl methacrylate), an alkyl (meth)acrylate other than the MMA, the homopolymer of which has a Tg of 0° C. or higher and whose alkyl group has a carbon number of C1 to C14, and a functional group. By forming a (meth)acrylic polymer consisting of a copolymer copolymerized with at least one type of copolymerizable monomer at a specific ratio, such a (meth)acrylic resin composition can be used. We discovered that (meth)acrylic resin films obtained by solution casting have excellent bending durability, cut resistance (tensile strength at break), elongation at break, and solvent resistance (gel fraction). I was able to complete my invention. That is, the present invention provides a technique for obtaining a (meth)acrylic resin film consisting of a resin layer formed by crosslinking a (meth)acrylic resin composition containing a specific (meth)acrylic polymer and a crosslinking agent. It is a thought.
前記課題を解決するため、本発明は、（メタ）アクリル系ポリマーと、架橋剤とを含有する（メタ）アクリル系樹脂組成物であって、前記（メタ）アクリル系ポリマーが、メチルメタクリレートを８０重量部以上と、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上との合計を１００重量部と、前記架橋剤と反応できる官能基を有する共重合可能なモノマーの少なくとも１種以上の合計を１．０～２０．０重量部と、を共重合させた重量平均分子量が１０万超過１００万以下の共重合体からなる（メタ）アクリル系ポリマーであることを特徴とする（メタ）アクリル系樹脂組成物を提供する。 In order to solve the above problems, the present invention provides a (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent, wherein the (meth)acrylic polymer contains 80% of methyl methacrylate. The total of 100 parts by weight or more and at least one alkyl (meth)acrylate other than the above-mentioned methyl methacrylate whose homopolymer Tg is 0 ° C. or more and whose alkyl group has carbon atoms of C1 to C14 and a total of 1.0 to 20.0 parts by weight of at least one copolymerizable monomer having a functional group capable of reacting with the crosslinking agent, the weight average molecular weight of which is over 100,000 100 Provided is a (meth)acrylic resin composition characterized in that it is a (meth)acrylic polymer comprising a copolymer of 10,000 or less.
前記（メタ）アクリル系ポリマーが、（Ａ）メチルメタクリレートを８０～９９重量部と、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上の１～２０重量部との合計を１００重量部と、前記架橋剤と反応できる官能基を有する共重合可能なモノマーとして、（Ｂ）水酸基を有する共重合可能なモノマー、及びカルボキシル基を有する共重合可能なモノマーからなるモノマー群の中から選択した少なくとも１種以上のモノマーの合計を１．０～２０．０重量部と、を共重合させた重量平均分子量が１０万超過１００万以下の共重合体からなる（メタ）アクリル系ポリマーであることが好ましい。 The (meth)acrylic polymer contains 80 to 99 parts by weight of (A) methyl methacrylate, the Tg of the homopolymer other than the methyl methacrylate is 0° C. or higher, and the number of carbon atoms in the alkyl group is C1 to C14. (B) a copolymerizable monomer having a functional group capable of reacting with the crosslinking agent; 1 to 20 parts by weight of at least one alkyl (meth)acrylate; A total of 1.0 to 20.0 parts by weight of at least one monomer selected from the monomer group consisting of a polymerizable monomer and a copolymerizable monomer having a carboxyl group, and the weight of the copolymerized product. A (meth)acrylic polymer comprising a copolymer having an average molecular weight of more than 100,000 and less than 1,000,000 is preferable.
前記架橋剤が、エポキシ化合物、アジリジン化合物、イソシアネート化合物からなる化合物群から選択した１種以上であることが好ましい。 It is preferable that the crosslinking agent is one or more selected from the group of compounds consisting of epoxy compounds, aziridine compounds, and isocyanate compounds.
また、本発明は、前記（メタ）アクリル系樹脂組成物を架橋してなる樹脂層であることを特徴とする（メタ）アクリル系樹脂フィルムを提供する。 The present invention also provides a (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition.
また、本発明は、前記（メタ）アクリル系樹脂組成物を架橋してなる樹脂層である（メタ）アクリル系樹脂フィルムの片面または両面に、粘着層を形成してなることを特徴とする粘着シートを提供する。 The present invention also provides an adhesive characterized in that an adhesive layer is formed on one or both sides of a (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition. Provide sheets.
また、本発明は、前記（メタ）アクリル系樹脂組成物を架橋してなる樹脂層である（メタ）アクリル系樹脂フィルムを、偏光子の片面または両面に形成してなることを特徴とする偏光フィルムを提供する。 Further, the present invention provides polarized light characterized in that a (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition, is formed on one or both sides of a polarizer. Provide film.
本発明によれば、薄い膜厚の樹脂フィルムを得るための溶液キャスト法に使用できる（メタ）アクリル系樹脂組成物であって、製膜した樹脂フィルム等の成形品が耐折性、耐切性（引張破断強度）、破断伸び、耐溶剤性（ゲル分率）に優れている（メタ）アクリル系樹脂組成物、及び（メタ）アクリル系樹脂フィルムを提供することができる。
なお、本発明では、耐溶剤性の試験方法として、（メタ）アクリル系樹脂フィルムの試験片を、溶剤の液中に所定時間に渡り浸漬した後、前記溶剤に溶出しないで不溶分（残渣）として残った（メタ）アクリル系樹脂フィルムの割合（いわゆる、ゲル分率）を測定し、耐溶剤性を試験した。
また、従来技術の溶融押出法により（メタ）アクリル系樹脂フィルムを製膜する場合は、樹脂フィルムを製膜した後に、１軸又は２軸の延伸加工を施さない限り膜厚を４０μｍ以下とすることができなかった。一方、本発明の（メタ）アクリル系樹脂組成物を用いれば、溶液キャスト法のみを用いて、膜厚が４０μｍ以下である薄膜の（メタ）アクリル系樹脂フィルムを製造することができ、製造工程がより簡便になると共に、製造装置の費用低減を図ることができる。
According to the present invention, there is provided a (meth)acrylic resin composition that can be used in a solution casting method to obtain a thin resin film, and the molded product such as the resin film produced has good bending durability and cut resistance. It is possible to provide a (meth)acrylic resin composition and a (meth)acrylic resin film that are excellent in (tensile strength at break), elongation at break, and solvent resistance (gel fraction).
In addition, in the present invention, as a test method for solvent resistance, a test piece of a (meth)acrylic resin film is immersed in a solvent solution for a predetermined period of time, and then the insoluble content (residue) is determined without being eluted into the solvent. The proportion of the (meth)acrylic resin film remaining (so-called gel fraction) was measured, and the solvent resistance was tested.
In addition, when forming a (meth)acrylic resin film by the conventional melt extrusion method, the film thickness should be 40 μm or less unless uniaxial or biaxial stretching is performed after forming the resin film. I couldn't do that. On the other hand, if the (meth)acrylic resin composition of the present invention is used, a thin (meth)acrylic resin film with a thickness of 40 μm or less can be produced using only a solution casting method, and the manufacturing process In addition to being simpler, it is possible to reduce the cost of manufacturing equipment.
以下、好適な実施形態に基づいて、本発明を説明する。
本実施形態の（メタ）アクリル系樹脂組成物は、（メタ）アクリル系ポリマーと、架橋剤とを含有する（メタ）アクリル系樹脂組成物であって、前記（メタ）アクリル系ポリマーが、メチルメタクリレートを８０重量部以上と、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上との合計を１００重量部と、前記架橋剤と反応できる官能基を有する共重合可能なモノマーの少なくとも１種以上の合計を１．０～２０．０重量部と、を共重合させた重量平均分子量が１０万超過１００万以下の共重合体からなる（メタ）アクリル系ポリマーであることを特徴とする。
The present invention will be described below based on preferred embodiments.
The (meth)acrylic resin composition of the present embodiment is a (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent, wherein the (meth)acrylic polymer is methyl A total of 80 parts by weight or more of methacrylate and at least one alkyl (meth)acrylate other than the above-mentioned methyl methacrylate, the homopolymer of which has a Tg of 0° C. or more and whose alkyl group has a carbon number of C1 to C14. and a total of 1.0 to 20.0 parts by weight of at least one copolymerizable monomer having a functional group that can react with the crosslinking agent, and the weight average molecular weight is 10. It is characterized by being a (meth)acrylic polymer consisting of a copolymer of more than 10,000 and less than 1,000,000.
本実施形態の（メタ）アクリル系樹脂組成物に用いられる（メタ）アクリル系ポリマーは、アルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートを主成分とし、特にメチルメタクリレート（ＭＭＡ）を主成分とする（メタ）アクリル系ポリマーであることが好ましい。前記アルキル（メタ）アクリレートのアルキル基は、非環状（直鎖、分枝状）、環状（単環、多環）のいずれでもよい。前記（メタ）アクリル系ポリマーは、アルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも２種以上を含有する共重合体であることが好ましい。前記（メタ）アクリル系ポリマーは、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上を共重合させた共重合体であることが好ましい。ここで、（メタ）アクリル系ポリマーの主成分とは、１種類で（メタ）アクリル系ポリマーの５０重量％以上の割合を占める化合物、又は２種類以上の合計で（メタ）アクリル系ポリマーの５０重量％以上の割合を占める化合物群を意味する。つまり、（メタ）アクリル系ポリマーの１００重量部のうち、主成分が５０重量部以上の割合を占める場合である。なお、以下の説明において、モノマーについて、単にＴｇという場合は、ホモポリマーのＴｇを指す場合がある。 The (meth)acrylic polymer used in the (meth)acrylic resin composition of this embodiment is mainly composed of alkyl (meth)acrylates in which the number of carbon atoms in the alkyl group is C1 to C14, particularly methyl methacrylate (MMA). A (meth)acrylic polymer containing as a main component is preferable. The alkyl group of the alkyl (meth)acrylate may be either acyclic (linear, branched) or cyclic (monocyclic, polycyclic). The (meth)acrylic polymer is preferably a copolymer containing at least two or more alkyl (meth)acrylates whose alkyl groups have carbon atoms of C1 to C14. The (meth)acrylic polymer is a copolymer obtained by copolymerizing at least one alkyl (meth)acrylate whose homopolymer Tg is 0° C. or higher and whose alkyl group has carbon atoms of C1 to C14. It is preferable that Here, the main component of the (meth)acrylic polymer is a compound that accounts for 50% by weight or more of the (meth)acrylic polymer in one type, or a compound that accounts for 50% by weight or more of the (meth)acrylic polymer in total of two or more types. It means a group of compounds that account for more than % by weight. In other words, the main component accounts for 50 parts by weight or more out of 100 parts by weight of the (meth)acrylic polymer. In addition, in the following description, when a monomer is simply referred to as Tg, it may refer to the Tg of a homopolymer.
前記（メタ）アクリル系ポリマーにおいて、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチルメタクリレート、ｎ－プロピルメタクリレート、イソプロピルメタクリレート、ｎ－ブチルメタクリレート、イソブチルメタクリレート、ｓ－ブチルメタクリレート、ｔ－ブチル（メタ）アクリレート、ｎ－ペンチルメタクリレート、イソペンチルメタクリレート、ｎ－ヘキシルメタクリレート、イソヘキシルメタクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレートからなる化合物群から選択した１種以上が挙げられる。ここで、（メタ）アクリレートは、アクリレート又はメタクリレートの少なくとも一方を意味する。 In the (meth)acrylic polymer, the alkyl (meth)acrylate whose homopolymer has a Tg of 0° C. or higher and whose alkyl group has carbon atoms of C1 to C14 includes methyl (meth)acrylate, ethyl methacrylate, n -Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl (meth)acrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, cyclohexyl (meth) One or more types selected from the group of compounds consisting of acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate can be mentioned. Here, (meth)acrylate means at least one of acrylate and methacrylate.
前記（メタ）アクリル系ポリマーにおいて、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートとしては、アルキル基の炭素数がＣ１～Ｃ６であるアルキル（メタ）アクリレートが好ましく、アルキル基の炭素数がＣ１～Ｃ４であるアルキル（メタ）アクリレートがより好ましい。また、メチルメタクリレート以外の、アルキル基の炭素数がＣ１～Ｃ４であるアルキル（メタ）アクリレートの中では、メチルアクリレート、エチルメタクリレート、ｎ－プロピルメタクリレート、イソプロピルメタクリレート、ｎ－ブチルメタクリレート、イソブチルメタクリレート、ｓ－ブチルメタクリレート、ｔ－ブチルアクリレート、ｔ－ブチルメタクリレートからなる化合物群から選択した１種以上であることが特に好ましい。 In the above (meth)acrylic polymer, the alkyl (meth)acrylate whose homopolymer has a Tg of 0°C or more and whose alkyl group has carbon atoms of C1 to C14 is an alkyl (meth)acrylate whose homopolymer has a carbon number of C1 to C6. Certain alkyl (meth)acrylates are preferred, and alkyl (meth)acrylates in which the number of carbon atoms in the alkyl group is C1 to C4 are more preferred. In addition, among alkyl (meth)acrylates other than methyl methacrylate, in which the alkyl group has a carbon number of C1 to C4, methyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s Particularly preferred is one or more selected from the group of compounds consisting of -butyl methacrylate, t-butyl acrylate, and t-butyl methacrylate.
また、前記（メタ）アクリル系ポリマーにおいて、（Ａ）メチルメタクリレートと、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上との合計の１００重量部のうち、メチルメタクリレートを８０重量部以上と、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上の合計を、２０重量部以下との割合で含有することが好ましく、メチルメタクリレートを８０～９９重量部と、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上の合計を、１～２０重量部との割合で含有することがより好ましい。 Further, in the (meth)acrylic polymer, (A) methyl methacrylate and a homopolymer other than the methyl methacrylate have a Tg of 0°C or higher, and the alkyl group has a carbon number of C1 to C14. ) Out of the total 100 parts by weight of at least one acrylate, 80 parts by weight or more of methyl methacrylate, the Tg of the homopolymer other than the methyl methacrylate is 0°C or more, and the number of carbon atoms in the alkyl group is It is preferable to contain a total of at least one kind of alkyl (meth)acrylates which are C1 to C14 in a ratio of 20 parts by weight or less, and 80 to 99 parts by weight of methyl methacrylate and a homogeneous material other than the above methyl methacrylate. It is preferable that the polymer has a Tg of 0° C. or higher and contains at least one alkyl (meth)acrylate whose alkyl group has carbon atoms of C1 to C14 in a proportion of 1 to 20 parts by weight. preferable.
前記（メタ）アクリル系ポリマーが、前記（Ａ）メチルメタクリレートと、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上との合計の１００重量部に対して、前記架橋剤と反応できる官能基を有する共重合可能なモノマーの少なくとも１種以上の合計を１．０～２０．０重量部の割合で含有することが好ましく、１．０～１２．０重量部の割合で含有することがより好ましく、１．０～９．０重量部の割合で含有することが特に好ましい。 The (meth)acrylic polymer is an alkyl (meth) in which the (A) methyl methacrylate and a homopolymer other than the methyl methacrylate have a Tg of 0° C. or higher, and the number of carbon atoms in the alkyl group is C1 to C14. A total of 1.0 to 20.0 parts by weight of at least one copolymerizable monomer having a functional group capable of reacting with the crosslinking agent is added to 100 parts by weight of the total of at least one acrylate. It is preferably contained in a proportion of 1.0 to 12.0 parts by weight, more preferably 1.0 to 12.0 parts by weight, and particularly preferably contained in a proportion of 1.0 to 9.0 parts by weight.
前記架橋剤と反応できる官能基を有する共重合可能なモノマーとしては、（Ｂ）水酸基を有する共重合可能なモノマー、及びカルボキシル基を有する共重合可能なモノマーからなるモノマー群の中から選択した少なくとも１種以上のモノマーが挙げられる。前記架橋剤と反応できる官能基を有する共重合可能なモノマーは、水酸基を有する共重合可能なモノマーのみでもよく、カルボキシル基を有する共重合可能なモノマーのみでもよく、水酸基を有する共重合可能なモノマー及びカルボキシル基を有する共重合可能なモノマーの両方を併用してもよい。 The copolymerizable monomer having a functional group capable of reacting with the crosslinking agent is at least selected from the monomer group consisting of (B) a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group. One or more monomers may be mentioned. The copolymerizable monomer having a functional group that can react with the crosslinking agent may be only a copolymerizable monomer having a hydroxyl group, or may be only a copolymerizable monomer having a carboxyl group, or a copolymerizable monomer having a hydroxyl group. and a copolymerizable monomer having a carboxyl group may be used in combination.
前記水酸基を有する共重合可能なモノマーとしては、８－ヒドロキシオクチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類や、Ｎ－ヒドロキシ（メタ）アクリルアミド、Ｎ－ヒドロキシメチル（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミド等の水酸基含有（メタ）アクリルアミド類などからなる化合物群の中から選択された、少なくとも１種以上であることが好ましい。 Examples of the copolymerizable monomer having a hydroxyl group include hydroxyl groups such as 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. From a group of compounds consisting of alkyl (meth)acrylates and hydroxyl group-containing (meth)acrylamides such as N-hydroxy (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, and N-hydroxyethyl (meth)acrylamide. It is preferable that at least one kind is selected.
前記カルボキシル基を有する共重合可能なモノマーとしては、（メタ）アクリル酸、カルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシプロピルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルマレイン酸、カルボキシポリカプロラクトンモノ（メタ）アクリレート、２－（メタ）アクリロイロキシエチルテトラヒドロフタル酸などからなる化合物群の中から選択された、少なくとも１種以上であることが好ましい。 Examples of the copolymerizable monomer having a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-( meth)acryloyloxypropylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylmaleic acid, carboxypolycaprolactone Preferably, it is at least one selected from the group of compounds consisting of mono(meth)acrylate, 2-(meth)acryloyloxyethyltetrahydrophthalic acid, and the like.
前記アクリル系ポリマーは、前記（Ａ）メチルメタクリレートと、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上との合計の１００重量部に対して、前記（Ｂ）水酸基を有する共重合可能なモノマー、及びカルボキシル基を有する共重合可能なモノマーからなるモノマー群の中から選択した少なくとも１種以上のモノマーの合計を１．０～２０．０重量部の割合で含有することが好ましい。 The acrylic polymer includes at least the (A) methyl methacrylate and an alkyl (meth)acrylate other than the methyl methacrylate, the homopolymer of which has a Tg of 0° C. or higher and whose alkyl group has carbon atoms of C1 to C14. At least one type selected from the monomer group consisting of (B) a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group, relative to 100 parts by weight of the total of one or more types. The total amount of monomers is preferably 1.0 to 20.0 parts by weight.
前記アクリル系ポリマーの製造方法は、特に限定されるものではなく、溶液重合法、乳化重合法等、適宜、公知の重合方法が使用可能である。前記アクリル系ポリマーは、重量平均分子量が１０万超過１００万以下の共重合体であることが好ましく、重量平均分子量が１０万超過９５万以下の共重合体であることがより好ましく、重量平均分子量が１０万超過９０万以下の共重合体であることが特に好ましい。前記アクリル系ポリマーの重量平均分子量が１０万以下であると、（メタ）アクリル系樹脂組成物を架橋しても優れた物性を有する（メタ）アクリル系樹脂フィルム等の成形品が得られ難くなる。前記アクリル系ポリマーの重量平均分子量が１００万より大きいと、（メタ）アクリル系樹脂組成物の溶液が高粘度となり、製膜工程の作業性が良くない。 The method for producing the acrylic polymer is not particularly limited, and any known polymerization method such as a solution polymerization method or an emulsion polymerization method can be used as appropriate. The acrylic polymer is preferably a copolymer with a weight average molecular weight of more than 100,000 and less than 1 million, more preferably a copolymer with a weight average molecular weight of more than 100,000 and less than 950,000. It is particularly preferable that the copolymer has a molecular weight of more than 100,000 and less than 900,000. If the weight average molecular weight of the acrylic polymer is 100,000 or less, it becomes difficult to obtain a molded article such as a (meth)acrylic resin film having excellent physical properties even if the (meth)acrylic resin composition is crosslinked. . If the weight average molecular weight of the acrylic polymer is greater than 1 million, the solution of the (meth)acrylic resin composition will have a high viscosity, resulting in poor workability in the film forming process.
前記架橋剤としては、前記（メタ）アクリル系ポリマーの有する官能基と、架橋反応することができる架橋性官能基を有する化合物が挙げられる。前記架橋剤は、前記（メタ）アクリル系樹脂組成物の保存安定性等の観点から、常温（一般には５～３５℃）では架橋反応が起こり難く、所定の温度以上に加熱すると架橋反応が開始する化合物であることが好ましい。 Examples of the crosslinking agent include compounds having a crosslinkable functional group that can undergo a crosslinking reaction with the functional group of the (meth)acrylic polymer. From the viewpoint of storage stability of the (meth)acrylic resin composition, the crosslinking agent is difficult to cause a crosslinking reaction at room temperature (generally 5 to 35°C), and the crosslinking reaction starts when heated to a predetermined temperature or higher. Preferably, it is a compound that
前記架橋剤が、エポキシ化合物、アジリジン化合物、イソシアネート化合物からなる化合物群から選択した１種以上であることが好ましい。本実施形態の（メタ）アクリル系樹脂組成物は、前記（Ａ）メチルメタクリレートと、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上との合計の１００重量部に対して、前記架橋剤を０．０１～１０重量部の割合で含有することが好ましい。 It is preferable that the crosslinking agent is one or more selected from the group of compounds consisting of epoxy compounds, aziridine compounds, and isocyanate compounds. The (meth)acrylic resin composition of the present embodiment is characterized in that the (A) methyl methacrylate and the homopolymer other than the methyl methacrylate have a Tg of 0°C or higher, and the number of carbon atoms in the alkyl group is C1 to C14. The crosslinking agent is preferably contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of at least one alkyl (meth)acrylate.
前記エポキシ化合物からなる架橋剤（エポキシ系架橋剤）としては、２官能以上のエポキシ化合物であれば特に限定されないが、例えば、ポリオール類（ジオール類、グリコール類、ビスフェノール類を含む。）のポリグリシジルエーテル、ジカルボン酸のジグリシジルエステル、ジグリシジル置換のアミン類、テトラグリシジル置換のジアミン類などからなる化合物群から選択される少なくとも１種以上が挙げられる。 The crosslinking agent (epoxy crosslinking agent) made of the epoxy compound is not particularly limited as long as it is a difunctional or higher functional epoxy compound, but for example, polyglycidyl of polyols (including diols, glycols, and bisphenols). At least one kind selected from the group of compounds consisting of ethers, diglycidyl esters of dicarboxylic acids, diglycidyl-substituted amines, tetraglycidyl-substituted diamines, etc. can be mentioned.
前記エポキシ系架橋剤のうち、ポリオール類のポリグリシジルエーテルとしては、例えば、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、レゾルシンジグリシジルエーテル、グリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル等が挙げられる。
また、ジカルボン酸のジグリシジルエステルとしては、例えば、アジピン酸ジグリシジルエステル、フタル酸ジグリシジルエステル等が挙げられる。
また、ジグリシジル置換のアミン類としては、例えば、Ｎ，Ｎ－ジグリシジルアニリン、Ｎ，Ｎ－ジグリシジルトルイジン等が挙げられる。
また、テトラグリシジル置換のジアミン類としては、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ′，Ｎ′－テトラグリシジル－ｍ－キシレンジアミン等が挙げられる。
Among the epoxy crosslinking agents, examples of polyglycidyl ethers of polyols include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polyethylene glycol. Examples include diglycidyl ether, resorcin diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and sorbitol polyglycidyl ether.
Furthermore, examples of diglycidyl esters of dicarboxylic acids include adipic acid diglycidyl ester and phthalic acid diglycidyl ester.
Examples of diglycidyl-substituted amines include N,N-diglycidylaniline and N,N-diglycidyltoluidine.
Examples of tetraglycidyl-substituted diamines include 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-m-xylene diamine, and the like.
前記アジリジン化合物からなる架橋剤（アジリジン系架橋剤）としては、２官能以上のアジリジン化合物、１分子中に２個以上のアジリジン系官能基を有する化合物等であれば特に限定されない。アジリジン系官能基としては、１－アジリジニル基〔－Ｎ（ＣＨ２）２〕、２－アジリジニル基、メチル基等の置換基を有する置換アジリジニル基等が挙げられる。アジリジン系架橋剤の具体例としては、例えば、次の（１）～（２）のような、ポリイソシアネート化合物とアジリジンとの付加生成物、次の（３）～（４）のような、ポリオールポリアクリレート化合物とアジリジンとの付加生成物、次の（５）～（７）のような、その他のポリアクリジン化合物が挙げられる。 The crosslinking agent made of the aziridine compound (aziridine crosslinking agent) is not particularly limited as long as it is a bifunctional or more functional aziridine compound, a compound having two or more aziridine functional groups in one molecule, or the like. Examples of the aziridine functional group include a 1-aziridinyl group [-N(CH 2 ) 2 ], a 2-aziridinyl group, and a substituted aziridinyl group having a substituent such as a methyl group. Specific examples of aziridine-based crosslinking agents include addition products of polyisocyanate compounds and aziridine as shown in (1) to (2) below, and polyols as shown in (3) to (4) below. Examples include addition products of polyacrylate compounds and aziridine, and other polyacridine compounds such as the following (5) to (7).
（１）４，４′－ビス［（１－アジリジニル）カルボニルアミノ］ジフェニルメタン
（ＣＨ２）２ＮＣＯＮＨ－Ｃ６Ｈ４ＣＨ２Ｃ６Ｈ４－ＮＨＣＯＮ（ＣＨ２）２
（２）１，６－ビス［（１－アジリジニル）カルボニルアミノ］ヘキサン
（ＣＨ２）２ＮＣＯＮＨ－（ＣＨ２）６－ＮＨＣＯＮ（ＣＨ２）２
（３）トリメチロールプロパン－トリス［２－（１－アジリジニル）プロピオネート］
ＣＨ３ＣＨ２Ｃ［ＣＨ２Ｏ－ＣＯＣＨ２ＣＨ２Ｎ（ＣＨ２）２］３
（４）テトラメチロールメタン－トリス［２－（１－アジリジニル）プロピオネート］
ＨＯＣＨ２Ｃ［ＣＨ２Ｏ－ＣＯＣＨ２ＣＨ２Ｎ（ＣＨ２）２］３
（５）トリス（１－アジリジニル）ホスフィンオキサイド
Ｏ＝Ｐ［Ｎ（ＣＨ２）２］３
（６）トリス（１－アジリジニル）ホスフィンスルフィド
Ｓ＝Ｐ［Ｎ（ＣＨ２）２］３
（７）２，４，６－トリス（１－アジリジニル）－１，３，５－トリアジン
（Ｃ３Ｎ３）［Ｎ（ＣＨ２）２］３
(1) 4,4'-bis[(1-aziridinyl)carbonylamino]diphenylmethane (CH 2 ) 2 NCONH-C 6 H 4 CH 2 C 6 H 4 -NHCON(CH 2 ) 2
(2) 1,6-bis[(1-aziridinyl)carbonylamino]hexane (CH 2 ) 2 NCONH-(CH 2 ) 6 -NHCON(CH 2 ) 2
(3) Trimethylolpropane-tris[2-(1-aziridinyl)propionate]
CH 3 CH 2 C[CH 2 O-COCH 2 CH 2 N(CH 2 ) 2 ] 3
(4) Tetramethylolmethane-tris[2-(1-aziridinyl)propionate]
HOCH 2 C[CH 2 O-COCH 2 CH 2 N(CH 2 ) 2 ] 3
(5) Tris(1-aziridinyl)phosphine oxide O=P[N(CH 2 ) 2 ] 3
(6) Tris(1-aziridinyl)phosphine sulfide S=P[N(CH 2 ) 2 ] 3
(7) 2,4,6-tris(1-aziridinyl)-1,3,5-triazine (C 3 N 3 ) [N(CH 2 ) 2 ] 3
前記イソシアネート化合物からなる架橋剤（イソシアネート系架橋剤）としては、ヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、トリレンジイソシアネート（ＴＤＩ）、キシリレンジイソシアネート（ＸＤＩ）等の２官能イソシアネート（ジイソシアネート化合物）や、これらのビュレット変性体、イソシアヌレート変性体、アダクト体等の３官能以上のポリイソシアネート化合物からなる化合物群から選択される少なくとも１種以上が挙げられる。ここで、３官能以上のアダクト体は、ジイソシアネート化合物と、トリメチロールプロパン、グリセリン等の３価以上のポリオールとのアダクト体が挙げられる。 Examples of the crosslinking agent (isocyanate crosslinking agent) made of the isocyanate compound include hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), etc. At least one kind selected from the group consisting of bifunctional isocyanates (diisocyanate compounds) and trifunctional or higher functional polyisocyanate compounds such as biuret-modified products, isocyanurate-modified products, and adducts thereof. Here, the trifunctional or higher functional adduct includes an adduct of a diisocyanate compound and a trivalent or higher functional polyol such as trimethylolpropane or glycerin.
前記（メタ）アクリル系樹脂組成物は、上述の添加剤に限らず、界面活性剤、硬化促進剤、硬化遅延剤、可塑剤、充填剤、滑剤、加工助剤、老化防止剤、熱安定剤、光安定剤、酸化防止剤、帯電防止剤、着色剤、紫外線吸収剤、赤外線吸収剤などの公知の添加剤が適宜に配合されてもよい。これらの添加剤は、単独で、もしくは２種以上を併せて用いることができる。 The (meth)acrylic resin composition is not limited to the additives mentioned above, but also includes surfactants, curing accelerators, curing retarders, plasticizers, fillers, lubricants, processing aids, anti-aging agents, and heat stabilizers. , a light stabilizer, an antioxidant, an antistatic agent, a coloring agent, an ultraviolet absorber, an infrared absorber, and other known additives may be appropriately blended. These additives can be used alone or in combination of two or more.
前記（メタ）アクリル系樹脂組成物は、所定の形状に成形又は塗布した後で前記（メタ）アクリル系ポリマーと前記架橋剤とを反応させることにより、硬化させることができる。前記（メタ）アクリル系樹脂組成物から得られる成形品としては、特に限定されないが、フィルム、板（シート）、棒（ロッド）、繊維（ファイバー）などが挙げられる。前記成形品の成形方法は、特に限定されないが、キャスト成形、積層成形、押出成形などが挙げられる。前記（メタ）アクリル系樹脂組成物を、基材上に塗布する場合は、例えば、溶液コーティングにより該基材上に樹脂膜を形成することができる。該基材としては、特に限定されないが、樹脂フィルム、離型フィルム、紙基材、金属箔、積層体等が挙げられる。 The (meth)acrylic resin composition can be cured by reacting the (meth)acrylic polymer and the crosslinking agent after being molded or coated into a predetermined shape. Molded products obtained from the (meth)acrylic resin composition include, but are not particularly limited to, films, sheets, rods, fibers, and the like. The molding method for the molded article is not particularly limited, and examples thereof include cast molding, lamination molding, extrusion molding, and the like. When applying the (meth)acrylic resin composition onto a base material, a resin film can be formed on the base material, for example, by solution coating. The base material includes, but is not particularly limited to, a resin film, a release film, a paper base material, a metal foil, a laminate, and the like.
前記（メタ）アクリル系樹脂組成物に含有されている前記架橋剤が、加熱により架橋反応を開始する熱架橋剤である場合、前記成形品の成形時において前記アクリル系ポリマーを加熱溶融させて流動化させるのではなく、前記（メタ）アクリル系樹脂組成物の溶液として流動化させるのが好ましい。前記（メタ）アクリル系樹脂組成物の溶液を得るための溶剤としては、前記アクリル系ポリマーの官能基及び前記架橋剤の反応性を損なうことなく、前記アクリル系ポリマーを溶解させることができれば特に限定されない。前記溶剤としては、トルエン等の炭化水素系溶剤、エタノールやイソプロピルアルコール等のアルコール系溶剤、ジエチルエーテルやテトラヒドロフラン等のエーテル系溶剤、アセトンやメチルエチルケトン（ＭＥＫ）等のケトン系溶剤、酢酸エチル等のエステル系溶剤などが挙げられる。前記アクリル系ポリマーを溶液重合法により製造した場合、重合に用いた溶剤の少なくとも一部が、前記（メタ）アクリル系樹脂組成物の溶剤の少なくとも一部となってもよい。 When the crosslinking agent contained in the (meth)acrylic resin composition is a thermal crosslinking agent that starts a crosslinking reaction by heating, the acrylic polymer is heated and melted to flow during molding of the molded article. It is preferable to fluidize the (meth)acrylic resin composition as a solution instead of converting it into a liquid. The solvent for obtaining the solution of the (meth)acrylic resin composition is particularly limited as long as it can dissolve the acrylic polymer without impairing the functional groups of the acrylic polymer and the reactivity of the crosslinking agent. Not done. Examples of the solvent include hydrocarbon solvents such as toluene, alcohol solvents such as ethanol and isopropyl alcohol, ether solvents such as diethyl ether and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone (MEK), and esters such as ethyl acetate. Examples include solvents. When the acrylic polymer is produced by a solution polymerization method, at least a part of the solvent used for polymerization may become at least a part of the solvent of the (meth)acrylic resin composition.
本実施形態の（メタ）アクリル系樹脂フィルムは、前記（メタ）アクリル系樹脂組成物を架橋してなる樹脂層であることを特徴とする。前記（メタ）アクリル系樹脂フィルムは、例えば、溶液キャスト法を用いることにより、前記（メタ）アクリル系樹脂組成物の溶液を所定の基材上に塗布して薄膜を形成した後、加熱乾燥させて前記薄膜から溶剤を揮発させると共に架橋させることにより、製造することができる。前記基材としては、固定された平面に限らず、樹脂フィルムのロール体から巻き戻された樹脂フィルム、可動のベルト、ドラムなどが挙げられる。前記基材の表面性状は、平滑面が好ましいが、基材に所定の凹凸を設けることにより、得られる前記（メタ）アクリル系樹脂フィルムの表面に凹凸を転写することも可能である。 The (meth)acrylic resin film of this embodiment is characterized by being a resin layer formed by crosslinking the (meth)acrylic resin composition. The (meth)acrylic resin film is produced by, for example, applying a solution of the (meth)acrylic resin composition onto a predetermined base material to form a thin film by using a solution casting method, and then heating and drying the film. It can be produced by volatilizing the solvent from the thin film and crosslinking it. The base material is not limited to a fixed plane, but includes a resin film unwound from a resin film roll, a movable belt, a drum, and the like. The surface of the base material is preferably a smooth surface, but by providing the base material with predetermined irregularities, it is also possible to transfer the irregularities to the surface of the resulting (meth)acrylic resin film.
上記の、溶液キャスト法により得られた前記（メタ）アクリル系樹脂フィルムは、長手方向、幅方向等の所定の方向に延伸してもよく、無延伸のままとしてもよい。光学用フィルムの用途において、異方性を低減する必要がある場合は、前記（メタ）アクリル系樹脂フィルムを無延伸フィルムとすることが好ましい。前記（メタ）アクリル系樹脂フィルムの長手方向及び幅方向に延伸する操作を加えて、二軸延伸フィルムに加工してもよい。なお、フィルムの異方性としては、「破断伸び」などの機械的特性の異方性に限らず、「複屈折率」などの光学異方性も挙げられる。
前記（メタ）アクリル系樹脂フィルムの機械的特性は、用途にも依存するが、粘着シート、光学用フィルム、表面保護フィルム、工程フィルム等に用いる場合や、長手方向の搬送、ロールからの繰り出し、ロールへの巻き取りなどを行う場合は、耐折性及び耐切性（引張破断強度）が高いことに加えて、被着体等に対する追従性が得られるよう、適度な破断伸びを有することが好ましい。
The (meth)acrylic resin film obtained by the solution casting method may be stretched in a predetermined direction such as the longitudinal direction or the width direction, or may be left unstretched. In applications of optical films, if it is necessary to reduce anisotropy, the (meth)acrylic resin film is preferably a non-stretched film. The (meth)acrylic resin film may be processed into a biaxially stretched film by stretching it in the longitudinal direction and the width direction. Note that the anisotropy of the film is not limited to anisotropy of mechanical properties such as "elongation at break", but also includes optical anisotropy such as "birefringence".
The mechanical properties of the (meth)acrylic resin film depend on the application, but it may be used for adhesive sheets, optical films, surface protection films, process films, etc., or when it is transported in the longitudinal direction, unrolled from a roll, When winding into a roll, in addition to having high folding and cut resistance (tensile strength at break), it is preferable to have appropriate elongation at break so that it can conform to adherends, etc. .
前記（メタ）アクリル系樹脂フィルムを構成する、前記（メタ）アクリル系樹脂組成物を架橋してなる樹脂層のゲル分率は、５０％以上であることが好ましく、７０％以上であることがより好ましく、９０～１００％であることがさらに好ましく、９３～１００％であることが特に好ましい。このように前記樹脂層のゲル分率が高いことにより、前記（メタ）アクリル系樹脂フィルムの必要とされる物性である耐溶剤性を改善することができる。 The gel fraction of the resin layer formed by crosslinking the (meth)acrylic resin composition constituting the (meth)acrylic resin film is preferably 50% or more, and preferably 70% or more. It is more preferably 90 to 100%, and particularly preferably 93 to 100%. Since the gel fraction of the resin layer is thus high, solvent resistance, which is a required physical property of the (meth)acrylic resin film, can be improved.
前記（メタ）アクリル系樹脂フィルムの厚みは、特に限定されないが、例えば、光学用フィルムの場合は、１０～２００μｍ程度の厚みが好ましく、厚みが１０～５０μｍであることがより好ましく、厚みが１０～４０μｍであることが特に好ましく、厚みを４０μｍ以下の薄膜にすることもできる。前記（メタ）アクリル系樹脂フィルムの片面または両面に他の材料を積層する場合は、必要に応じて、コロナ放電による表面改質、アンカーコート剤の塗付などの易接着処理を施してもよい。 The thickness of the (meth)acrylic resin film is not particularly limited, but for example, in the case of an optical film, the thickness is preferably about 10 to 200 μm, more preferably the thickness is 10 to 50 μm, and the thickness is about 10 μm. It is particularly preferable that the thickness is 40 μm or less, and it is also possible to form a thin film with a thickness of 40 μm or less. When laminating other materials on one or both sides of the (meth)acrylic resin film, adhesion-facilitating treatment such as surface modification by corona discharge or application of an anchor coating agent may be performed as necessary. .
前記（メタ）アクリル系樹脂フィルムは、光学用フィルムの基材に用いてもよい。光学用フィルムとしては、偏光フィルム、位相差フィルム、反射防止フィルム、防眩（アンチグレア）フィルム、紫外線吸収フィルム、赤外線吸収フィルム、光学補償フィルム、輝度向上フィルムなどが挙げられる。光学用部材が適用される機器としては、液晶パネル、有機ＥＬパネル、タッチパネルなどが挙げられる。前記（メタ）アクリル系樹脂フィルムを光学用フィルムとして用いる場合は、無色透明であることが好ましい。 The (meth)acrylic resin film may be used as a base material for an optical film. Examples of optical films include polarizing films, retardation films, antireflection films, antiglare films, ultraviolet absorbing films, infrared absorbing films, optical compensation films, and brightness enhancement films. Devices to which the optical member is applied include liquid crystal panels, organic EL panels, touch panels, and the like. When the (meth)acrylic resin film is used as an optical film, it is preferably colorless and transparent.
前記（メタ）アクリル系樹脂フィルムの片面または両面には、ハードコート層、帯電防止層、反射防止層、防汚層、防眩層、低屈折率層、粘着層、離型層などの１種又は２種以上を積層してもよい。低屈折率層形成用の組成物に用いられるフッ素化合物としては、フッ素化オレフィン類、フッ素化ビニルエーテル類、フッ素化アルキル（メタ）アクリレート等の１種又は２種以上の重合物である含フッ素共重合体、フッ素化アルキル基含有シラン化合物などの縮合物が挙げられる。含フッ素共重合体は、フッ素化されたモノマーに加えて、オレフィン類、ビニルエーテル類、（メタ）アクリレートなどの、フッ素化されていないモノマーが共重合されていてもよい。低屈折率層は、高屈折率層等と組み合わせて反射防止層を構成してもよい。 On one or both sides of the (meth)acrylic resin film, one type of hard coat layer, antistatic layer, antireflection layer, antifouling layer, antiglare layer, low refractive index layer, adhesive layer, release layer, etc. Alternatively, two or more types may be laminated. Fluorine compounds used in the composition for forming a low refractive index layer include fluorine-containing compounds that are polymers of one or more of fluorinated olefins, fluorinated vinyl ethers, fluorinated alkyl (meth)acrylates, etc. Examples include condensates such as polymers and fluorinated alkyl group-containing silane compounds. In addition to the fluorinated monomer, the fluorine-containing copolymer may be copolymerized with non-fluorinated monomers such as olefins, vinyl ethers, and (meth)acrylates. The low refractive index layer may be combined with a high refractive index layer to form an antireflection layer.
本実施形態の粘着シートは、前記（メタ）アクリル系樹脂組成物を架橋してなる樹脂層である前記（メタ）アクリル系樹脂フィルムの片面または両面に、粘着層を形成してなることを特徴とする。前記粘着層としては、（メタ）アクリル系粘着剤からなる粘着剤層が好ましい。前記（メタ）アクリル系樹脂フィルムに粘着層を形成する方法は、公知の方法で行えばよい。具体的には、リバースコーティング、コンマコーティング、グラビアコーティング、スロットダイコーティング、メイヤーバーコーティング、エアーナイフコーティングなどの、公知の塗工方法を使用することができる。 The adhesive sheet of this embodiment is characterized in that an adhesive layer is formed on one or both sides of the (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition. shall be. As the adhesive layer, an adhesive layer made of a (meth)acrylic adhesive is preferable. The adhesive layer may be formed on the (meth)acrylic resin film by any known method. Specifically, known coating methods such as reverse coating, comma coating, gravure coating, slot die coating, Meyer bar coating, and air knife coating can be used.
前記粘着シートは、前記（メタ）アクリル系樹脂フィルムを基材としてなる光学用フィルムの少なくとも一方の面に、粘着層が積層されてなる粘着層付き光学用フィルムとしてもよい。粘着層付き光学用フィルムは、液晶表示装置、タッチパネル、電子ペーパー、有機ＥＬ等の各種表示装置における光学用フィルムの貼り合せに用いることができる。光学用フィルムの貼り合せに用いられる粘着層の粘着面は、離型フィルムを用いて保護してもよい。離型フィルムには、粘着層の粘着面と合わされる側の面に、シリコーン系、フッ素系の離型剤などにより離型処理が施されてもよい。 The adhesive sheet may be an optical film with an adhesive layer, in which an adhesive layer is laminated on at least one surface of an optical film made of the (meth)acrylic resin film as a base material. The optical film with an adhesive layer can be used for laminating optical films in various display devices such as liquid crystal display devices, touch panels, electronic paper, and organic EL devices. The adhesive surface of the adhesive layer used for laminating optical films may be protected using a release film. The release film may be subjected to a release treatment using a silicone-based, fluorine-based release agent, or the like on the side that is to be combined with the adhesive surface of the adhesive layer.
前記粘着シートは、ガラス、光学用フィルム、光学用部材等の被着体の表面を保護するために前記粘着層を介して貼り合される表面保護フィルムを構成してもよい。表面保護フィルムを被着体に貼り合わせた状態で、被着体の光学特性、異物の有無等を光学的に検査することができる。また、被着体を製品に組み込む段階では、表面保護フィルムを被着体から剥離して除去することができる。 The adhesive sheet may constitute a surface protection film that is bonded via the adhesive layer to protect the surface of an adherend such as glass, an optical film, or an optical member. With the surface protection film attached to the adherend, it is possible to optically inspect the optical properties of the adherend, the presence or absence of foreign matter, and the like. Further, at the stage of incorporating the adherend into a product, the surface protection film can be peeled off and removed from the adherend.
本実施形態の偏光フィルムは、前記（メタ）アクリル系樹脂組成物を架橋してなる樹脂層である前記（メタ）アクリル系樹脂フィルムを、偏光子の片面または両面に形成してなることを特徴とする。前記偏光子の保護層の表面に施されている表面処理が、未処理、ＡＧ処理、ＬＲ処理、ＡＲ処理、ＡＧ－ＬＲ処理、ＡＧ－ＡＲ処理からなる群より選択された少なくとも１種以上であってもよい。ここで、ＡＧとはアンチグレア（Ａｎｔｉ Ｇｌａｒｅ）、ＬＲとはローリフレクション（Ｌｏｗ Ｒｅｆｌｅｃｔｉｏｎ）、ＡＲとはアンチリフレクション（Ａｎｔｉ Ｒｅｆｌｅｃｔｉｏｎ）である。 The polarizing film of this embodiment is characterized in that the (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition, is formed on one or both sides of a polarizer. shall be. The surface treatment applied to the surface of the protective layer of the polarizer is at least one type selected from the group consisting of untreated, AG treatment, LR treatment, AR treatment, AG-LR treatment, and AG-AR treatment. There may be. Here, AG stands for anti-glare, LR stands for low reflection, and AR stands for anti-reflection.
以下、実施例をもって本発明を具体的に説明する。 The present invention will be specifically explained below with reference to Examples.
＜（メタ）アクリル系ポリマー及び（メタ）アクリル系樹脂組成物の製造＞
［実施例１］
撹拌機、温度計、還流冷却器及び窒素導入管を備えた反応装置に、窒素ガスを導入して、反応装置内の空気を窒素ガスで置換した。その後、反応装置に、メチルメタクリレート９５重量部、メチルアクリレート５重量部、８－ヒドロキシオクチルアクリレート３．０重量部とともに溶剤（酢酸エチル）を加えた。その後、重合開始剤としてアゾビスイソブチロニトリル０．１重量部を滴下させ、６５℃に加熱して所定の時間反応させ、実施例１の（メタ）アクリル系ポリマー溶液を得た。この（メタ）アクリル系ポリマー溶液に含まれる（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）を測定したところ、２０万であった。実施例１の（メタ）アクリル系ポリマー溶液に対して、コロネートＨＸ（ヘキサメチレンジイソシアネート化合物のイソシアヌレート体）３．０重量部を加えて撹拌混合して実施例１の（メタ）アクリル系樹脂組成物を得た。
<Production of (meth)acrylic polymer and (meth)acrylic resin composition>
[Example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the air in the reaction apparatus was replaced with nitrogen gas. Thereafter, a solvent (ethyl acetate) was added to the reactor along with 95 parts by weight of methyl methacrylate, 5 parts by weight of methyl acrylate, and 3.0 parts by weight of 8-hydroxyoctyl acrylate. Thereafter, 0.1 part by weight of azobisisobutyronitrile was added dropwise as a polymerization initiator, heated to 65° C., and reacted for a predetermined time to obtain the (meth)acrylic polymer solution of Example 1. The weight average molecular weight (Mw) of the (meth)acrylic polymer contained in this (meth)acrylic polymer solution was measured and found to be 200,000. To the (meth)acrylic polymer solution of Example 1, 3.0 parts by weight of Coronate HX (isocyanurate of hexamethylene diisocyanate compound) was added and mixed with stirring to obtain the (meth)acrylic resin composition of Example 1. I got something.
［実施例２～５及び比較例１～２］
実施例１の（メタ）アクリル系ポリマー及び（メタ）アクリル系樹脂組成物の組成を各々、表１の記載のようにした以外は、実施例１と同様にして、実施例２～５及び比較例１～２の（メタ）アクリル系ポリマー及び（メタ）アクリル系樹脂組成物を得た。実施例２～５及び比較例１～２の（メタ）アクリル系ポリマーの重量平均分子量（Ｍｗ）は、表１に示すとおりであった。
[Examples 2 to 5 and Comparative Examples 1 to 2]
Examples 2 to 5 and comparison were prepared in the same manner as in Example 1, except that the compositions of the (meth)acrylic polymer and (meth)acrylic resin composition of Example 1 were changed as shown in Table 1. (Meth)acrylic polymer and (meth)acrylic resin compositions of Examples 1 and 2 were obtained. The weight average molecular weights (Mw) of the (meth)acrylic polymers of Examples 2 to 5 and Comparative Examples 1 to 2 were as shown in Table 1.
［比較例３］
溶融押出法により製造された市販のＰＭＭＡフィルム（厚み：８０μｍ）を溶剤としてメチルエチルケトン（ＭＥＫ）に溶解して、ＰＭＭＡフィルムに含まれるポリマーの重量平均分子量（Ｍｗ）を測定したところ、３０万であった。
[Comparative example 3]
A commercially available PMMA film (thickness: 80 μm) produced by melt extrusion was dissolved in methyl ethyl ketone (MEK) as a solvent, and the weight average molecular weight (Mw) of the polymer contained in the PMMA film was measured and found to be 300,000. Ta.
また、表１に用いた（Ａ）～（Ｃ）の各成分の略記号の化合物名を、表２に示す。なお、（Ｃ）群の架橋剤において、コロネート（登録商標）ＨＸ及び同ＨＬは東ソー株式会社の商品名であり、タケネート（登録商標）Ｄ－１４０Ｎは三井化学株式会社の商品名であり、ＴＥＴＲＡＤ（登録商標）－Ｘは三菱ガス化学株式会社の商品名である。 Further, the compound names of the abbreviations for each of the components (A) to (C) used in Table 1 are shown in Table 2. Regarding the cross-linking agents of group (C), Coronate (registered trademark) HX and Coronate HL are the trade names of Tosoh Corporation, Takenate (registered trademark) D-140N is the trade name of Mitsui Chemicals Co., Ltd., and TETRAD (Registered Trademark) -X is a product name of Mitsubishi Gas Chemical Co., Ltd.
＜（メタ）アクリル系樹脂フィルムの作製＞
実施例１～５及び比較例１～２の（メタ）アクリル系樹脂組成物を溶液キャスト法により、樹脂フィルム状に製膜し、溶剤の乾燥及び架橋剤の硬化に適した温度条件にして加熱乾燥、及び架橋させて、実施例１～５及び比較例１～２の（メタ）アクリル系樹脂フィルムを得た。各フィルムの厚みを表３に示す。
また、比較例３の（メタ）アクリル系樹脂フィルムとしては、上記のとおり、溶融押出法により製造された市販のＰＭＭＡフィルム（厚み：８０μｍ）を用いた。
<Preparation of (meth)acrylic resin film>
The (meth)acrylic resin compositions of Examples 1 to 5 and Comparative Examples 1 to 2 were formed into resin films by a solution casting method, and heated under temperature conditions suitable for drying the solvent and curing the crosslinking agent. By drying and crosslinking, (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 2 were obtained. Table 3 shows the thickness of each film.
Moreover, as the (meth)acrylic resin film of Comparative Example 3, a commercially available PMMA film (thickness: 80 μm) manufactured by the melt extrusion method was used as described above.
＜（メタ）アクリル系樹脂フィルムの試験方法及び評価＞
実施例１～５及び比較例１～３の（メタ）アクリル系樹脂フィルムを、以下の試験方法により評価した。
<Test method and evaluation of (meth)acrylic resin film>
The (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated by the following test method.
＜耐折性＞
実施例１～５及び比較例１～３の（メタ）アクリル系樹脂フィルムから試験片を作製した後、ＪＩＳ Ｐ８１１５（紙及び板紙－耐折強さ試験方法－ＭＩＴ試験機法）に準拠して、耐折度試験装置（メーカ：テスター産業株式会社、型式：ＭＩＴ耐折度試験装置ＢＥ－２０１）を用いて耐折性の試験を行い、試験片が破断するまでの往復折曲げ回数（耐折回数）を測定した。
<Bending durability>
After preparing test pieces from the (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 3, they were tested in accordance with JIS P8115 (Paper and Paperboard - Folding strength test method - MIT tester method). , the folding durability was tested using a folding durability tester (manufacturer: Tester Sangyo Co., Ltd., model: MIT folding durability tester BE-201), and the number of reciprocating bends (resistance) until the test piece broke was determined. The number of folds) was measured.
＜耐溶剤性（ゲル分率）＞
耐溶剤性の試験方法として、下記のように（メタ）アクリル系樹脂フィルムの試験片を、溶剤の液中に所定時間に渡り浸漬した後、前記溶剤に溶出しないで不溶分（残渣）として残った（メタ）アクリル系樹脂フィルムの割合（いわゆる、ゲル分率）を測定し、耐溶剤性を試験した。
実施例１～５及び比較例１～３の（メタ）アクリル系樹脂フィルムから試験片を作製し、試験片の質量を正確に測定し、メチルエチルケトン（ＭＥＫ）中に２４ｈｒ浸漬した後、２００メッシュの金網で濾過した。その後、濾過物を、温度１００℃で、１ｈｒ乾燥して得られた残渣の質量を正確に測定して、以下の式から耐溶剤性の試験方法として、溶剤への浸漬によるゲル分率（％）を測定した。
ゲル分率（％）＝不溶分（残渣）質量（ｇ）／フィルム（試験片）質量（ｇ）×１００
<Solvent resistance (gel fraction)>
As a test method for solvent resistance, a test piece of (meth)acrylic resin film is immersed in a solvent solution for a predetermined period of time as shown below, and then an insoluble matter (residue) remains without being eluted into the solvent. The ratio of the (meth)acrylic resin film (so-called gel fraction) was measured, and the solvent resistance was tested.
Test pieces were prepared from the (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 3, the mass of the test pieces was accurately measured, and after being immersed in methyl ethyl ketone (MEK) for 24 hours, 200 mesh It was filtered through a wire mesh. Thereafter, the mass of the residue obtained by drying the filtrate for 1 hour at a temperature of 100°C was accurately measured, and the gel fraction (% ) was measured.
Gel fraction (%) = insoluble matter (residue) mass (g) / film (test piece) mass (g) x 100
＜耐切性（引張破断強度）、破断伸び率＞
実施例１～５及び比較例１～３の（メタ）アクリル系樹脂フィルムから試験片を作製し、引張試験装置（メーカ：株式会社島津製作所、型式：ＡＧＳ－Ｘ）を用いて測定し、試験片が破断するまでの耐切性（引張破断強度（ＭＰａ））、及び破断伸び率（％）の値を求めた。
<Cut resistance (tensile strength at break), elongation at break>
Test pieces were prepared from the (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 3, and measured and tested using a tensile test device (manufacturer: Shimadzu Corporation, model: AGS-X). The values of cut resistance (tensile strength at break (MPa)) and elongation at break (%) until the piece broke were determined.
＜位相差＞
実施例１～５及び比較例１～３の（メタ）アクリル系樹脂フィルムの面内位相差（Ｒｅ）値（ｎｍ）を、位相差測定装置（メーカ：王子計測機器株式会社、型式：ＫＯＢＲＡ－ＨＢＰＲ／ＳＰＣ）を用いて測定した。位相差の測定波長は、例えば４５０～５５０ｎｍ等の可視領域から適宜選択することができる。Ｒｅ値は、面内の屈折率が最大になる方向をｘ軸（遅相軸）、これと直交する方向をｙ軸（進相軸）とするとき、ｘ軸方向の屈折率ｎｘと、ｙ軸方向の屈折率ｎｙと、フィルムの膜厚ｄとから、次の式により算出される。
面内位相差Ｒｅ＝（ｎｘ－ｎｙ）×ｄ
ここで、フィルムの膜厚ｄは、面内位相差Ｒｅと同じくｎｍ単位であるから、フィルムの厚み（μｍ）の１０００倍である。
<Phase difference>
The in-plane retardation (Re) values (nm) of the (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 3 were measured using a retardation measuring device (manufacturer: Oji Scientific Instruments Co., Ltd., model: KOBRA-). HBPR/SPC). The measurement wavelength of the phase difference can be appropriately selected from the visible range, for example, from 450 to 550 nm. The Re value is defined as the refractive index n It is calculated from the refractive index n y in the y-axis direction and the thickness d of the film using the following formula.
In-plane phase difference Re = (n x - n y ) x d
Here, the thickness d of the film is in nm units like the in-plane retardation Re, so it is 1000 times the thickness (μm) of the film.
表３に、実施例１～５及び比較例１～３の（メタ）アクリル系樹脂フィルムについての評価結果を示す。 Table 3 shows the evaluation results for the (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 3.
実施例１～５の（メタ）アクリル系樹脂フィルムは、厚みが４０μｍ以下の薄膜に製膜されたものであり、耐折性が５０回以上、耐切性（引張破断強度）が５０ＭＰａ以上、破断伸び率が９～１２％、耐溶剤性（ゲル分率）が９３％以上であり、いずれの特性にも優れているものであった。
このように、実施例１～５の（メタ）アクリル系樹脂フィルムでは、本発明の課題を解決できることが実証されている。
The (meth)acrylic resin films of Examples 1 to 5 were formed into thin films with a thickness of 40 μm or less, and had a folding resistance of 50 times or more, a cut resistance (tensile strength at break) of 50 MPa or more, and a breakage resistance of 50 MPa or more. The elongation rate was 9 to 12%, and the solvent resistance (gel fraction) was 93% or more, and it was excellent in all properties.
As described above, it has been demonstrated that the (meth)acrylic resin films of Examples 1 to 5 can solve the problems of the present invention.
比較例１の（メタ）アクリル系樹脂フィルムは、（メタ）アクリル系ポリマーが、アルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートとしてＭＭＡのみを共重合したものであり、ＭＭＡ以外の、ホモポリマーのＴｇが０℃以上であり、アルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートを共重合していないためか、耐折性が極めて低く、破断伸び率が低かった。
比較例２の（メタ）アクリル系樹脂フィルムは、（メタ）アクリル系樹脂組成物が、架橋剤を含有していないためか、耐折性及び耐溶剤性（ゲル分率）が極めて低かった。
The (meth)acrylic resin film of Comparative Example 1 is a (meth)acrylic polymer copolymerized with only MMA as an alkyl (meth)acrylate whose alkyl group has carbon atoms of C1 to C14, and other than MMA. The Tg of the homopolymer is 0°C or higher, and the folding durability is extremely low and the elongation at break is low, probably because the alkyl (meth)acrylate whose alkyl group has carbon atoms of C1 to C14 is not copolymerized. Ta.
The (meth)acrylic resin film of Comparative Example 2 had extremely low bending durability and solvent resistance (gel fraction), probably because the (meth)acrylic resin composition did not contain a crosslinking agent.
比較例３の（メタ）アクリル系樹脂フィルムは、溶融押出法により製造された樹脂フィルムであるが、耐折性及び耐溶剤性（ゲル分率）が、実施例１～５による（メタ）アクリル系樹脂フィルムに比べて極めて低いことが判明した。なお、比較例３の（メタ）アクリル系樹脂フィルムの厚みが２０μｍと仮定すると、Ｒｅの値は厚みの比率（２０／８０）に応じて、１／４の値となるが、それでもＲｅ値が大きいことから、複屈折率（ｎｘ－ｎｙ）の値自体が大きいと考えられる。 The (meth)acrylic resin film of Comparative Example 3 is a resin film manufactured by a melt extrusion method, but the folding durability and solvent resistance (gel fraction) are different from that of the (meth)acrylic resin film of Examples 1 to 5. It was found that this was extremely low compared to other resin films. Assuming that the thickness of the (meth)acrylic resin film of Comparative Example 3 is 20 μm, the Re value will be 1/4 according to the thickness ratio (20/80), but the Re value will still be Since it is large, it is considered that the value of the birefringence index (n x −n y ) itself is large.
以上のように、比較例１～３の（メタ）アクリル系樹脂フィルムでは、本発明の課題である、耐折性、耐切性（引張破断強度）、破断伸び率、耐溶剤性（ゲル分率）に優れている（メタ）アクリル系樹脂フィルムを提供することを解決することができなかった。 As described above, the (meth)acrylic resin films of Comparative Examples 1 to 3 have good bending durability, cut resistance (tensile strength at break), elongation at break, and solvent resistance (gel fraction ) It has not been possible to solve the problem of providing a (meth)acrylic resin film that has excellent properties.
本発明の（メタ）アクリル系樹脂組成物、及びそれを用いた（メタ）アクリル系樹脂フィルムは、従来の溶融押出法により得られた（メタ）アクリル系樹脂フィルムと比較すると、特に、薄膜化、耐折性、耐溶剤性（ゲル分率）の点において優れた特性を有することから、ディスプレイなどの各種光学機器の薄型化、及び耐久性の向上に効果を発揮することが期待できるため、産業上の利用価値が大である。 The (meth)acrylic resin composition of the present invention and the (meth)acrylic resin film using the same are particularly advantageous when compared with (meth)acrylic resin films obtained by conventional melt extrusion methods. It has excellent properties in terms of bending durability and solvent resistance (gel fraction), so it is expected to be effective in making various optical devices such as displays thinner and improving durability. It has great industrial utility value.
Claims (6)
前記（メタ）アクリル系ポリマーが、
メチルメタクリレートを８０重量部以上と、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上との合計を１００重量部と、
前記架橋剤と反応できる官能基を有する共重合可能なモノマーの少なくとも１種以上の合計を１．０～２０．０重量部と、
を共重合させた重量平均分子量が１０万超過１００万以下の共重合体からなる（メタ）アクリル系ポリマーであることを特徴とする（メタ）アクリル系樹脂組成物。 A (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent (excluding a photocurable composition containing a reactive diluent having a photopolymerizable functional group, and Excluding resin compositions containing prepolymers having three or more acryloyl groups or methacryloyl groups),
The (meth)acrylic polymer is
80 parts by weight or more of methyl methacrylate and at least one alkyl (meth)acrylate other than the methyl methacrylate, the homopolymer of which has a Tg of 0° C. or more and whose alkyl group has carbon atoms of C1 to C14. The total is 100 parts by weight,
A total of 1.0 to 20.0 parts by weight of at least one copolymerizable monomer having a functional group that can react with the crosslinking agent,
A (meth)acrylic resin composition comprising a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of more than 100,000 and less than 1,000,000.
（Ａ）メチルメタクリレートを８０～９９重量部と、前記メチルメタクリレート以外の、ホモポリマーのＴｇが０℃以上であり、且つアルキル基の炭素数がＣ１～Ｃ１４であるアルキル（メタ）アクリレートの少なくとも１種以上の１～２０重量部との合計を１００重量部と、
前記架橋剤と反応できる官能基を有する共重合可能なモノマーとして、（Ｂ）水酸基を有する共重合可能なモノマー、及びカルボキシル基を有する共重合可能なモノマーからなるモノマー群の中から選択した少なくとも１種以上のモノマーの合計を１．０～２０．０重量部と、
を共重合させた重量平均分子量が１０万超過１００万以下の共重合体からなる（メタ）アクリル系ポリマーであることを特徴とする請求項１に記載の（メタ）アクリル系樹脂組成物。 The (meth)acrylic polymer is
(A) 80 to 99 parts by weight of methyl methacrylate and at least one alkyl (meth)acrylate other than the methyl methacrylate, the homopolymer of which has a Tg of 0° C. or higher and whose alkyl group has carbon atoms of C1 to C14; The total of 1 to 20 parts by weight of seeds or more is 100 parts by weight,
As the copolymerizable monomer having a functional group capable of reacting with the crosslinking agent, at least one selected from the monomer group consisting of (B) a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group. The total amount of monomers of the species or more is 1.0 to 20.0 parts by weight,
The (meth)acrylic resin composition according to claim 1, wherein the (meth)acrylic resin composition is a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of more than 100,000 and less than 1,000,000.
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