CN112391022A - (meth) acrylic resin composition and (meth) acrylic resin film - Google Patents
(meth) acrylic resin composition and (meth) acrylic resin film Download PDFInfo
- Publication number
- CN112391022A CN112391022A CN202010782838.6A CN202010782838A CN112391022A CN 112391022 A CN112391022 A CN 112391022A CN 202010782838 A CN202010782838 A CN 202010782838A CN 112391022 A CN112391022 A CN 112391022A
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- Prior art keywords
- meth
- acrylic resin
- film
- 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 144
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 144
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 48
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 48
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 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
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 229920001519 homopolymer Polymers 0.000 claims abstract description 18
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 17
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 19
- -1 aziridine compound Chemical class 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 15
- 239000012790 adhesive layer Substances 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000010408 film Substances 0.000 abstract description 156
- 239000002904 solvent Substances 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 30
- 238000005266 casting Methods 0.000 abstract description 15
- 239000010409 thin film Substances 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 238000001125 extrusion Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 239000012788 optical film Substances 0.000 description 13
- 239000000155 melt Substances 0.000 description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 11
- 239000004926 polymethyl methacrylate Substances 0.000 description 11
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000011248 coating agent Substances 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
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 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
- 150000001541 aziridines Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 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
- 230000001681 protective effect Effects 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 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
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 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
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 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
- 230000008901 benefit Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters 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
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 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
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 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
- 150000005846 sugar alcohols Polymers 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
- MMEJYPZZFYTVLJ-WAYWQWQTSA-N (z)-2-(2-prop-2-enoyloxyethyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\CCOC(=O)C=C MMEJYPZZFYTVLJ-WAYWQWQTSA-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
- NQUXRXBRYDZZDL-UHFFFAOYSA-N 1-(2-prop-2-enoyloxyethyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCOC(=O)C=C)C(O)=O NQUXRXBRYDZZDL-UHFFFAOYSA-N 0.000 description 1
- PWMLMBQHHBLIQM-UHFFFAOYSA-N 1-(3-prop-2-enoyloxypropyl)cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1(CCCOC(=O)C=C)C(O)=O PWMLMBQHHBLIQM-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
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- YDRQKFSCVSLQKI-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1(CCOC(=O)C=C)C(O)=O YDRQKFSCVSLQKI-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
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-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
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-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
- UXTGJIIBLZIQPK-UHFFFAOYSA-N 3-(2-prop-2-enoyloxyethyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(CCOC(=O)C=C)=C1C(O)=O UXTGJIIBLZIQPK-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- LUUDMRYCMSHDDD-UHFFFAOYSA-N O=C(NC(C1=CC=CC=C1)C1=CC=CC=C1)N1CC1 Chemical compound O=C(NC(C1=CC=CC=C1)C1=CC=CC=C1)N1CC1 LUUDMRYCMSHDDD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- FOCVUCIESVLUNU-UHFFFAOYSA-N Thiotepa Chemical group C1CN1P(N1CC1)(=S)N1CC1 FOCVUCIESVLUNU-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- FYAMXEPQQLNQDM-UHFFFAOYSA-N Tris(1-aziridinyl)phosphine oxide Chemical class 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
- 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
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 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
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- 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
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- 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
- KWNUZMYDZGSFJN-UHFFFAOYSA-N n-hexylaziridine-1-carboxamide Chemical compound CCCCCCNC(=O)N1CC1 KWNUZMYDZGSFJN-UHFFFAOYSA-N 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
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- 238000003860 storage Methods 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
- 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
- IUCJMVBFZDHPDX-UHFFFAOYSA-N tretamine Chemical compound C1CN1C1=NC(N2CC2)=NC(N2CC2)=N1 IUCJMVBFZDHPDX-UHFFFAOYSA-N 0.000 description 1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C09J2433/00—Presence of (meth)acrylic polymer
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Abstract
The present invention provides a (meth) acrylic resin composition and a (meth) acrylic resin film which can be used in a solution casting method for obtaining a resin film having a thin film thickness and which are excellent in folding resistance, shear resistance (tensile breaking strength), elongation at break and solvent resistance (gel fraction). The (meth) acrylic resin composition comprises a (meth) acrylic polymer and a crosslinking agent, wherein the (meth) acrylic polymer is composed of a copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 100 ten thousand, and the copolymer is obtained by copolymerizing 100 parts by weight in total of at least 80 parts by weight of methyl methacrylate and at least one or more selected from alkyl (meth) acrylates other than the methyl methacrylate, wherein the homopolymers have a Tg of not less than 0 ℃ and the alkyl group has a carbon number of C1-C14, and at least one or more selected from copolymerizable monomers having a functional group reactive with the crosslinking agent in total of 1.0-20.0 parts by weight.
Description
Technical Field
The present invention relates to a (meth) acrylic resin composition suitable for forming a (meth) acrylic resin film or the like, and a (meth) acrylic resin film using the (meth) acrylic resin composition.
Background
Conventionally, a (meth) acrylic resin film has been used as a resin film for surface coating of various device parts such as electronic devices, household electrical appliances, interior and exterior parts of automobiles, and building members because of its high transparency, excellent hot workability, weather resistance, and excellent chemical resistance.
In recent years, a (meth) acrylic resin film has been used as an optical film because of its high transparency, excellent weather resistance, and the like.
Conventionally, as a method for producing a (meth) acrylic resin film (PMMA film) made of a polymethyl methacrylate (PMMA) resin, a method of forming a PMMA resin film by a melt extrusion method has been adopted because of high productivity.
For example, patent document 1 discloses an acrylic resin film which can be applied to a member in which an acrylic resin film and a molding resin are integrated, and which is particularly suitable for forming an alternative coating layer of a protective layer on a surface. The acrylic resin film of the invention described in patent document 1 is obtained by combining an ultraviolet absorber and a lubricant added to the acrylic resin film in a specific type, and setting the above components to specific contents. Therefore, patent document 1 can be applied to an acrylic resin film used as an alternative coating layer for forming a protective layer on the surface.
Further, patent document 2 discloses a method for improving impact resistance, which is an essential disadvantage of acrylic resins, by not containing a rubber-containing graft copolymer that causes impairment of unique beautiful color tone and transparency, which are advantages of acrylic resins. The acrylic resin composition of the invention described in patent document 2 solves the following problems: when the melt extrusion temperature is increased in the case of forming a film from the resin composition by the melt extrusion method, the graft copolymer is thermally decomposed, and the decomposed gas or exudate generated thereby contaminates cooling rolls such as casting rolls, and the productivity is lowered.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-286960
Patent document 2: international publication No. 2016/139927
Disclosure of Invention
Technical problem to be solved by the invention
Therefore, the acrylic resin film of the invention described in patent document 1 is formed into a film by a melt extrusion method in which a mixture of an acrylic resin composition containing a thermoplastic polymer is kneaded by a degassing twin-screw extruder to obtain pellets of the acrylic resin composition, and then the molten resin composition is extruded to a T-die by a melt extruder. In addition, in examples 1 to 6 described in patent document 1, acrylic resin films having a film thickness of 50 to 125 μm were obtained. However, the acrylic resin film of the invention described in patent document 1 is a resin film obtained by film formation by a melt extrusion method, and therefore, there is a problem that it is difficult to obtain a thin resin film having a film thickness of 40 μm or less.
Further, the acrylic resin composition of the invention described in patent document 2 has a problem that the graft copolymer is gradually completed by performing 3 to 4 stages of graft polymerization reaction, and thus the process for obtaining the graft copolymer requires a long time. In examples 6 to 8 of patent document 2, in which an acrylic resin film was produced by melt extrusion, the film thickness of the acrylic resin film obtained without stretching was 80 μm, and a thin resin film having a film thickness of 40 μm or less could not be obtained without stretching.
Under the circumstances, a method for forming a resin film by a solution casting method, which is more convenient than a melt extrusion method and has an advantage of being capable of being made thinner, is desired. The present inventors have earnestly studied a method for forming a film of PMMA resin by a solution casting method. As a result, they have found that a PMMA resin film having excellent physical properties equal to or higher than those of a film formed by a melt extrusion method can be obtained by using a specific PMMA resin composition even when the film is formed by a solution casting method, and have completed the present invention.
In a conventional method for forming a (meth) acrylic resin film by melt extrusion, it is difficult to reduce the film thickness to 40 μm or less. On the other hand, in the method of forming a (meth) acrylic resin film by the solution casting method, the film can be formed to a thickness of 40 μm or less, but there is a problem that it is difficult to improve the performance of solvent resistance, which is the physical property of the obtained (meth) acrylic resin film. In addition, in the solution casting method, the weight average molecular weight of the uncrosslinked PMMA resin contained in the (meth) acrylic resin composition needs to be a large value of 100 ten thousand or more, and therefore the solution of the (meth) acrylic resin composition has a high viscosity, and there is a problem that workability in a film forming process is poor.
The present invention addresses the problem of providing a (meth) acrylic resin composition that can be used in a solution casting method for obtaining a thin resin film, and that gives a molded article such as a resin film obtained by film formation that has excellent folding resistance, cut resistance (tensile breaking strength), elongation at break, and solvent resistance (gel fraction), and a (meth) acrylic resin film.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that by preparing a (meth) acrylic resin composition containing a (meth) acrylic polymer and a crosslinking agent, and a (meth) acrylic resin film obtained by a solution casting method using such a (meth) acrylic resin composition is excellent in folding resistance, cutting resistance (tensile breaking strength), elongation at break, and solvent resistance (gel fraction), wherein the (meth) acrylic polymer is composed of a copolymer obtained by copolymerizing MMA (methyl methacrylate), at least one or more of an alkyl (meth) acrylate other than MMA, the homopolymer of which has a Tg of 0 ℃ or higher and the alkyl group has from C1 to C14, and a copolymerizable monomer having a functional group at a specific ratio. That is, the technical idea of the present invention is to obtain a (meth) acrylic resin film composed of a resin layer obtained by crosslinking a (meth) acrylic resin composition containing a specific (meth) acrylic polymer and a crosslinking agent.
In order to solve the above-mentioned problems, the present invention provides a (meth) acrylic resin composition comprising a (meth) acrylic polymer and a crosslinking agent, wherein the (meth) acrylic polymer is composed of a copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 100 ten thousand, and the copolymer is obtained by copolymerizing 100 parts by weight in total of at least 80 parts by weight of methyl methacrylate and at least one or more selected from alkyl (meth) acrylates other than the methyl methacrylate, the homopolymers of which have a Tg of not less than 0 ℃ and the alkyl group has a carbon number of C1 to C14, and 1.0 to 20.0 parts by weight in total of at least one or more copolymerizable monomers having a functional group reactive with the crosslinking agent.
Preferably, the (meth) acrylic polymer is composed of a copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 100 ten thousand, and the copolymer is obtained by copolymerizing 100 parts by weight in total of at least one selected from the group consisting of (a)80 to 99 parts by weight of methyl methacrylate, 1 to 20 parts by weight of at least one selected from the group consisting of alkyl (meth) acrylates other than the methyl methacrylate, the homopolymers of which have a Tg of 0 ℃ or more and the alkyl groups have carbon atoms of C1 to C14, and 1.0 to 20.0 parts by weight in total of at least one selected from the group consisting of a copolymerizable monomer having a functional group reactive with the crosslinking agent and a copolymerizable monomer having a carboxyl group.
Preferably, the crosslinking agent is one or more selected from the group consisting of epoxy compounds, aziridine compounds, and isocyanate compounds.
The present invention also provides a (meth) acrylic resin film obtained by crosslinking the (meth) acrylic resin composition.
The present invention also provides an adhesive sheet comprising a (meth) acrylic resin film and an adhesive layer formed on one or both surfaces of the (meth) acrylic resin film, wherein the (meth) acrylic resin film is a resin layer obtained by crosslinking the (meth) acrylic resin composition.
The present invention also provides a polarizing film comprising a polarizer and a (meth) acrylic resin film formed on one or both surfaces of the polarizer, wherein the (meth) acrylic resin film is a resin layer obtained by crosslinking the (meth) acrylic resin composition.
Effects of the invention
According to the present invention, a (meth) acrylic resin composition which can be used in a solution casting method for obtaining a resin film having a thin film thickness and which is excellent in folding resistance, cutting resistance (tensile breaking strength), elongation at break and solvent resistance (gel fraction) of a molded article such as a resin film obtained by film formation, and a (meth) acrylic resin film can be provided.
In the present invention, as a method for testing solvent resistance, a test piece of a (meth) acrylic resin film is immersed in a solvent liquid for a predetermined time, and then the ratio of the (meth) acrylic resin film remaining as insoluble matter (residue) without being eluted into the solvent (so-called gel fraction) is measured to test solvent resistance.
Further, when a (meth) acrylic resin film is formed by a melt extrusion method according to the related art, the film thickness cannot be made 40 μm or less unless uniaxial or biaxial stretching processing is performed after the film is formed into a resin film. On the other hand, when the (meth) acrylic resin composition of the present invention is used, a (meth) acrylic resin film having a film thickness of 40 μm or less can be produced by a solution casting method alone, the production process is simplified, and the production equipment cost can be reduced.
Detailed Description
The present invention will be described below based on preferred embodiments.
The (meth) acrylic resin composition of the present embodiment contains a (meth) acrylic polymer and a crosslinking agent, and is characterized in that the (meth) acrylic polymer is composed of a copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 100 ten thousand, and the copolymer is obtained by copolymerizing 100 parts by weight in total of at least 80 parts by weight of methyl methacrylate and at least one or more selected from alkyl (meth) acrylates other than the methyl methacrylate, the homopolymers of which have a Tg of not less than 0 ℃ and the alkyl group has carbon atoms of from C1 to C14, and at least one or more selected from copolymerizable monomers having a functional group reactive with the crosslinking agent in total of 1.0 to 20.0 parts by weight.
The (meth) acrylic polymer used in the (meth) acrylic resin composition of the present embodiment is preferably a (meth) acrylic polymer containing an alkyl (meth) acrylate having an alkyl group having from C1 to C14 as a main component, and particularly preferably a (meth) acrylic polymer containing Methyl Methacrylate (MMA) as a main component. The alkyl group of the alkyl (meth) acrylate may be any of acyclic (linear, branched), cyclic (monocyclic, polycyclic). The (meth) acrylic polymer is preferably a copolymer of at least two or more kinds of alkyl (meth) acrylates having C1-C14 alkyl groups. The (meth) acrylic polymer is preferably a copolymer obtained by copolymerizing at least one or more alkyl (meth) acrylates having a homopolymer Tg of 0 ℃ or higher and an alkyl group having C1 to C14 carbon atoms. The main component of the (meth) acrylic polymer is a compound in which 1 species accounts for 50 wt% or more of the (meth) acrylic polymer, or a group of compounds in which 2 or more species accounts for 50 wt% or more of the (meth) acrylic polymer in total. That is, the amount of the main component is 50 parts by weight or more per 100 parts by weight of the (meth) acrylic polymer. In the following description, the monomer is referred to as Tg alone, which is a homopolymer Tg.
In the (meth) acrylic polymer, as the alkyl (meth) acrylate having a homopolymer Tg of 0 ℃ or higher and an alkyl group having a carbon number of C1 to C14, one or more compounds selected from the group consisting of methyl (meth) acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl (meth) acrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate can be mentioned. Here, the (meth) acrylate refers to at least one of acrylate and methacrylate.
Among the (meth) acrylic polymers, the homopolymer of the (meth) acrylic polymer is an alkyl (meth) acrylate having a Tg of 0 ℃ or higher and an alkyl group having from C1 to C14, preferably an alkyl (meth) acrylate having a C1 to C6, and more preferably an alkyl (meth) acrylate having a C1 to C4. Among the alkyl (meth) acrylates other than methyl methacrylate having an alkyl group with a carbon number of C1 to C4, one or more compounds selected from the group consisting of methyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl acrylate and tert-butyl methacrylate are particularly preferable.
In the (meth) acrylic polymer, it is preferable that the methyl methacrylate is contained in a proportion of 80 parts by weight or more to 100 parts by weight in total of the methyl methacrylate (A) and at least one or more selected from alkyl (meth) acrylates other than the methyl methacrylate, the homopolymers of which have a Tg of 0 ℃ or more and an alkyl group having a carbon number of C1 to C14, at least one or more selected from alkyl (meth) acrylates other than the methyl methacrylate, wherein the homopolymer has a Tg of 0 ℃ or higher and the alkyl group has a carbon number of from C1 to C14, is contained in a total amount of 20 parts by weight or less, more preferably 80 to 99 parts by weight, at least one or more selected from alkyl (meth) acrylates other than the methyl methacrylate, wherein the homopolymers have a Tg of 0 ℃ or higher and the alkyl group has a carbon number of C1-C14, in a total amount of 1 to 20 parts by weight.
The (meth) acrylic polymer preferably contains at least one or more copolymerizable monomers having a functional group reactive with the crosslinking agent in a total amount of 1.0 to 20.0 parts by weight, more preferably 1.0 to 12.0 parts by weight, and particularly preferably 1.0 to 9.0 parts by weight, based on 100 parts by weight in total of the (A) methyl methacrylate and at least one or more selected from alkyl (meth) acrylates other than the methyl methacrylate, the homopolymers of which have a Tg of 0 ℃ or higher and alkyl groups having carbon atoms ranging from C1 to C14.
Examples of the copolymerizable monomer having a functional group reactive with the crosslinking agent include (B) at least one monomer selected from the group consisting of a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group. The copolymerizable monomer having a functional group reactive with the crosslinking agent may be only a copolymerizable monomer having a hydroxyl group, may be only a copolymerizable monomer having a carboxyl group, or may be both a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group.
The copolymerizable monomer having a hydroxyl group is preferably at least one selected from the group consisting of hydroxyalkyl (meth) acrylates such as 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate, and hydroxyl-containing (meth) acrylamides such as N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide.
The copolymerizable monomer having a carboxyl group is preferably at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyltetrahydrophthalic acid and the like.
The acrylic polymer preferably contains the (B) at least one monomer selected from the group consisting of a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group in a proportion of 1.0 to 20.0 parts by weight in total, based on 100 parts by weight in total of the (A) methyl methacrylate and at least one or more selected from alkyl (meth) acrylates other than the methyl methacrylate, the homopolymers of which have a Tg of 0 ℃ or higher and the alkyl group has a carbon number of C1 to C14.
The method for producing the acrylic polymer is not particularly limited, and a known polymerization method such as a solution polymerization method or an emulsion polymerization method can be appropriately used. The acrylic polymer is preferably a copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 100 ten thousand, more preferably a copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 95 ten thousand, and particularly preferably a copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 90 ten thousand. When the weight average molecular weight of the acrylic polymer is 10 ten thousand or less, it is difficult to obtain a molded article such as a (meth) acrylic resin film having excellent physical properties even when the (meth) acrylic resin composition is crosslinked. If the weight average molecular weight of the acrylic polymer is more than 100 ten thousand, the solution of the (meth) acrylic resin composition becomes high in viscosity, and the workability in the film-forming step is poor.
Examples of the crosslinking agent include compounds having a crosslinkable functional group capable of crosslinking 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 preferably a compound which is less likely to undergo a crosslinking reaction at normal temperature (usually 5 to 35 ℃) and which starts the crosslinking reaction when heated to a predetermined temperature or higher.
Preferably, the crosslinking agent is one or more selected from the group consisting of epoxy compounds, aziridine compounds, and isocyanate compounds. The (meth) acrylic resin composition of the present embodiment preferably contains the crosslinking agent in an amount of 0.01 to 10 parts by weight based on 100 parts by weight in total of the methyl methacrylate (a) and at least one or more selected from alkyl (meth) acrylates other than the methyl methacrylate, the homopolymers of which have a Tg of 0 ℃ or higher and the alkyl group has a carbon number of C1 to C14.
The crosslinking agent (epoxy crosslinking agent) composed of the epoxy compound is not particularly limited as long as it is an epoxy compound having a bifunctional or higher, and examples thereof include at least one compound selected from the group consisting of polyglycidyl ethers of polyhydric alcohols (including glycols, bisphenols), diglycidyl esters of dicarboxylic acids, diglycidyl-substituted amines, tetraglycidyl-substituted diamines, and the like.
Examples of the polyhydric alcohol-based polyglycidyl ether in the epoxy-based crosslinking agent include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, resorcinol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether (pentaerythrityl polyglycidyl ether), and sorbitol polyglycidyl ether.
Examples of the diglycidyl ester of the dicarboxylic acid include diglycidyl adipate and diglycidyl phthalate.
Examples of the diglycidyl-substituted amines include N, N-diglycidylaniline and N, N-diglycidyltoluidine.
Examples of the tetraglycidyl-substituted diamines include 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N' -tetraglycidyl-m-xylylenediamine, and the like.
The crosslinking agent (aziridine-based crosslinking agent) comprising the aziridine compound may be a bifunctional or higher aziridineThe pyridine compound, the compound having 2 or more aziridine functional groups in 1 molecule, and the like are not particularly limited. Examples of the aziridine functional group include 1-aziridinyl [ -N (CH)2)2]2-aziridinyl, substituted aziridinyl having a substituent such as methyl, and the like. Specific examples of the aziridine-based crosslinking agent include addition products of the polyisocyanate compounds and aziridines as described in the following (1) to (2), addition products of the polyol polyacrylate compounds and aziridines as described in the following (3) to (4), and other polyaziridine compounds as described in the following (5) to (7).
(1)4, 4' -bis [ (1-aziridinyl) carbonylamino ] diphenylmethane
(CH2)2NCONH-C6H4CH2C6H4-NHCON(CH2)2
(2)1, 6-bis [ (1-aziridinyl) carbonylamino ] hexane
(CH2)2NCONH-(CH2)6-NHCON(CH2)2
(3) Trimethylolpropane-tris [2- (1-aziridinyl) propionate ]
CH3CH2C[CH2O-COCH2CH2N(CH2)2]3
(4) Tetrakishydroxymethylmethane-tris [2- (1-aziridinyl) propionate ]
HOCH2C[CH2O-COCH2CH2N(CH2)2]3
(5) Tris (1-aziridinyl) phosphine oxides
O＝P[N(CH2)2]3
(6) Tris (1-aziridinyl) thiophosphoryl group
S＝P[N(CH2)2]3
(7)2,4, 6-tris (1-aziridinyl) -1,3, 5-triazine
(C3N3)[N(CH2)2]3
Examples of the crosslinking agent (isocyanate-based crosslinking agent) composed of the isocyanate compound include at least one compound selected from the group consisting of bifunctional isocyanates (diisocyanate compounds) such as Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), and Xylylene Diisocyanate (XDI), and trifunctional or higher polyisocyanate compounds such as biuret modified products, isocyanurate modified products, and adducts thereof. Examples of the trifunctional or higher adduct include adducts of a diisocyanate compound and a trihydric or higher polyol such as trimethylolpropane and glycerol.
The (meth) acrylic resin composition is not limited to the above-mentioned additives, and known additives such as a surfactant, a curing accelerator, a curing retarder, a plasticizer, a filler, a lubricant, a processing aid, an anti-aging agent, a heat stabilizer, a light stabilizer, an antioxidant, an antistatic agent, a colorant, an ultraviolet absorber, and an infrared absorber may be appropriately blended. These additives may be used alone or in combination of two or more.
The (meth) acrylic resin composition can be cured by forming or coating the composition into a predetermined shape and then reacting the (meth) acrylic polymer with the crosslinking agent. The molded article obtained from the (meth) acrylic resin composition is not particularly limited, and examples thereof include a film, a sheet, a rod, and a fiber. The method for molding the molded article is not particularly limited, and examples thereof include casting molding, lamination molding, extrusion molding, and the like. When the (meth) acrylic resin composition is coated on a substrate, for example, a resin film can be formed on the substrate by coating a solution. The substrate is not particularly limited, and examples thereof include a resin film, a release film, a paper substrate, a metal foil, and a laminate.
When the crosslinking agent contained in the (meth) acrylic resin composition is a thermal crosslinking agent which starts a crosslinking reaction by heating, it is preferable that the solution of the (meth) acrylic resin composition is prepared and fluidized, rather than the acrylic polymer is heated and melted to fluidize, when the molded article is molded. The solvent used for obtaining the solution of the (meth) acrylic resin composition is not particularly limited as long as the acrylic polymer is soluble and the reactivity of the functional group of the acrylic polymer and the crosslinking agent is not impaired. Examples of the solvent include hydrocarbon solvents such as toluene; alcohol solvents such as ethanol and isopropanol, ether solvents such as diethyl ether and tetrahydrofuran, ketone solvents such as acetone and Methyl Ethyl Ketone (MEK), and ester solvents such as ethyl acetate. In the case of producing the acrylic polymer by a solution polymerization method, at least a part of a solvent used in the polymerization may be at least a part of a solvent of the (meth) acrylic resin composition.
The (meth) acrylic resin film according to the present embodiment is a resin layer obtained by crosslinking the (meth) acrylic resin composition. The (meth) acrylic resin film can be produced by: for example, a solution of the (meth) acrylic resin composition is applied to a predetermined substrate by a solution casting method to form a film, and then the film is heated and dried to volatilize the solvent from the film and crosslink the film at the same time. The substrate is not limited to a fixed plane, and examples thereof include a resin film unwound from a roll of the resin film, a movable tape (belt), and a drum (drum). The surface texture of the substrate is preferably a smooth surface, but the surface texture of the (meth) acrylic resin film obtained can be transferred with irregularities by providing the substrate with predetermined irregularities.
The (meth) acrylic resin film obtained by the solution casting method may or may not be stretched in a predetermined direction such as a longitudinal direction and a width direction. When it is necessary to reduce the anisotropy in the use of an optical film, it is preferable to use the (meth) acrylic resin film as a non-stretched film. The (meth) acrylic resin film may be processed into a biaxially oriented film, in addition to the operation of stretching the film in the longitudinal direction and the width direction. The anisotropy of the film is not limited to the anisotropy of mechanical properties such as "elongation at break", but may be optical anisotropy such as "birefringence".
The mechanical properties of the (meth) acrylic resin film also depend on the application, but when used in an adhesive sheet, an optical film, a surface protective film, a process film, or the like, or when transported in the longitudinal direction, unwound from a roll, wound on a roll, or the like, it is preferable that the (meth) acrylic resin film has a suitable elongation at break in addition to high folding resistance and shear resistance (tensile breaking strength) so that the (meth) acrylic resin film can have conformability to an adherend or the like.
The gel fraction of the resin layer obtained by crosslinking the (meth) acrylic resin composition constituting the (meth) acrylic resin film is preferably 50% or more, more preferably 70% or more, even more preferably 90 to 100%, and particularly preferably 93 to 100%. In this way, the gel fraction of the resin layer is high, and thus the solvent resistance, which is the physical property required for the (meth) acrylic resin film, can be improved.
The thickness of the (meth) acrylic resin film is not particularly limited, and for example, in the case of an optical film, the film is preferably about 10 to 200 μm, more preferably 10 to 50 μm, particularly preferably 10 to 40 μm, and can be a thin film having a thickness of 40 μm or less. When another material is laminated on one surface or both surfaces of the (meth) acrylic resin film, an easy adhesion treatment such as surface modification by corona discharge, or application of a primer (anchor coat agent) may be performed as needed.
The (meth) acrylic resin film can also be used as a base material for an optical film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an anti-glare (anti-glare) film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, and a brightness enhancement film. Examples of devices to which the optical member is applied include a liquid crystal panel, an organic EL panel, and a touch panel. When the (meth) acrylic resin film is used as an optical film, the film is preferably colorless and transparent.
One or more of a hard coat layer, an antistatic layer, an antireflection layer, an antifouling layer, an antiglare layer, a low refractive index layer, an adhesive layer, a mold release layer, and the like may be laminated on one surface or both surfaces of the (meth) acrylic resin film. Examples of the fluorine compound used in the composition for forming a low refractive index layer include a fluorine-containing copolymer of one or two or more kinds of polymers selected from fluorinated olefins, fluorinated vinyl ethers, fluorinated alkyl (meth) acrylates, and the like, and a condensate of a silane compound containing a fluorinated alkyl group. In addition to the fluorinated monomer, the fluorinated copolymer may be copolymerized with an unfluorinated monomer such as an olefin, a vinyl ether, or a (meth) acrylate. The low refractive index layer may be combined with a high refractive index layer or the like to constitute an antireflection layer.
The pressure-sensitive adhesive sheet of the present embodiment is characterized by being obtained by forming a pressure-sensitive adhesive layer on one surface or both surfaces of the (meth) acrylic resin film as a resin layer obtained by crosslinking the (meth) acrylic resin composition. The adhesive layer is preferably an adhesive layer made of a (meth) acrylic adhesive. The method for forming the adhesive layer on the (meth) acrylic resin film may be performed by a known method. Specifically, known coating methods such as reverse coating, comma coating (comma coating), gravure coating, nip extrusion coating, meyer rod coating, and air knife coating can be used.
The pressure-sensitive adhesive sheet may be an optical film with a pressure-sensitive adhesive layer formed by laminating a pressure-sensitive adhesive layer on at least one surface of an optical film comprising the (meth) acrylic resin film as a base. The optical film with an adhesive layer can be used for bonding optical films in various display devices such as liquid crystal display devices, touch panels, electronic paper, and organic EL. The pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer used for bonding the optical film may be protected by a release film. The surface of the release film on the side opposite to the adhesive surface of the adhesive layer may be subjected to release treatment using a silicone-based or fluorine-based release agent.
The pressure-sensitive adhesive sheet may be a surface protective film which is bonded via the pressure-sensitive adhesive layer and protects the surface of an adherend such as glass, an optical film, or an optical member. The optical properties of the adherend, the presence or absence of foreign matter, and the like can be optically inspected in a state where the surface protective film is bonded to the adherend. In addition, the surface protective film can be peeled off from the adherend and removed at the stage of assembling the adherend into a product.
The polarizing film of the present embodiment is characterized by having the (meth) acrylic resin film as a resin layer obtained by crosslinking the (meth) acrylic resin composition formed on one surface or both surfaces of a polarizer. The surface treatment applied to the surface of the protective layer of the polarizer may be at least one selected from the group consisting of an untreated surface, an AG treatment, an LR treatment, an AR treatment, an AG-LR treatment, and an AG-AR treatment. Here, AG means Anti-Glare (Anti Glare), LR means Low Reflection (Low Reflection), and AR means Anti-Reflection (Anti Reflection).
Examples
The present invention will be specifically described below with reference to examples.
< (meth) acrylic polymer and production of (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 gas introduction tube, thereby replacing the air in the reaction apparatus with nitrogen gas. Then, 95 parts by weight of methyl methacrylate, 5 parts by weight of methyl acrylate, 3.0 parts by weight of 8-hydroxyoctyl acrylate and a solvent (ethyl acetate) were simultaneously added to the reaction apparatus. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise, heated to 65 ℃ and reacted for a predetermined time to obtain a (meth) acrylic polymer solution of example 1. The weight average molecular weight (Mw) of the (meth) acrylic polymer contained in the (meth) acrylic polymer solution was measured, and it was 20 ten thousand. 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.
Examples 2 to 5 and comparative examples 1 to 2
(meth) acrylic polymers and (meth) acrylic resin compositions of examples 2 to 5 and comparative examples 1 to 2 were obtained in the same manner as in example 1, except that the compositions of the (meth) acrylic polymer and the (meth) acrylic resin composition of example 1 were each adjusted to the composition described in table 1. The weight average molecular weights (Mw) of the (meth) acrylic polymers of examples 2 to 5 and comparative examples 1 to 2 are shown in Table 1.
Comparative example 3
A commercially available PMMA film (thickness: 80 μm) produced by a melt extrusion method 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 was 30 ten thousand.
[ Table 1]
In addition, the compound names of the abbreviations of the components (a) to (C) used in table 1 are shown in table 2. In the crosslinking agent of group (C), CORONATE (registered trademark) HX and CORONATE HL are trade names of TOSOH CORPORATION, TAKENATE (registered trademark) D-140N is a trade name of Mitsui Chemicals, Inc., and TETRAD (registered trademark) -X is a trade name of MITSUBISHI GAS CHEMICAL COMPANY, INC.
[ Table 2]
Production of (meth) acrylic resin film
The (meth) acrylic resin compositions of examples 1 to 5 and comparative examples 1 to 2 were formed into a resin film by a solution casting method, and heated, dried and crosslinked under temperature conditions suitable for drying of the solvent and curing of the crosslinking agent, to obtain (meth) acrylic resin films of examples 1 to 5 and comparative examples 1 to 2. The thickness of each film is shown in table 3.
Further, as the (meth) acrylic resin film of comparative example 3, a commercially available PMMA film (thickness: 80 μm) produced by a melt extrusion method was used as described above.
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 methods.
< folding resistance >
After preparing test pieces from the (meth) acrylic resin films of examples 1 to 5 and comparative examples 1 to 3, the folding endurance test was carried out according to JIS P8115 (paper and paperboard-folding endurance test method-MIT TESTER method) using a folding endurance TESTER (manufacturer: TESTER SANGYO CO, LTD., model: MIT folding endurance TESTER BE-201), and the number of reciprocal folding until the test pieces broke (folding endurance) was measured.
< solvent resistance (gel fraction) >
As a method for testing solvent resistance, a test piece of a (meth) acrylic resin film was immersed in a solvent liquid for a predetermined time, and then the ratio of the (meth) acrylic resin film remaining as insoluble matter (residue) without being eluted into the solvent (so-called gel fraction) was measured to test solvent resistance.
Test pieces were produced 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 the test pieces were immersed in Methyl Ethyl Ketone (MEK) for 24 hours and then filtered through a 200-mesh wire. Then, the mass of the residue obtained by drying the filtrate at a temperature of 100 ℃ for 1 hour was accurately measured, and the gel fraction (%) in the case of the solvent resistance test method by immersing the residue in a solvent was measured by the following equation.
Gel fraction (%) (% insoluble matter (residue) mass (g)/film (test piece) mass (g) × 100
< cut resistance (tensile breaking strength) and 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 the cut resistance (tensile breaking strength (MPa)) and elongation at break (%) of the test pieces at break were measured using a tensile tester (manufactured by Shimadzu Corporation, model: AGS-X).
< phase difference >
The in-plane retardation values (Re) (nm) of the (meth) acrylic resin films of examples 1 to 5 and comparative examples 1 to 3 were measured using a phase difference measuring apparatus (manufactured by Oji Scientific Instruments, model: KOBRA-HBPR/SPC). The wavelength for measuring the retardation can be selected appropriately from the visible light range such as 450 to 550 nm. The value of Re can be expressed by the following formula, where the refractive index n in the x-axis direction is defined as the x-axis (slow axis) where the in-plane refractive index is the maximum and the y-axis (fast axis) is defined as the direction orthogonal to the x-axisxRefractive index n in y-axis directionyAnd the film thickness d of the film.
In-plane retardation value Re ═ nx-ny)×d
The film thickness d of the film here is 1000 times the film thickness (μm) since it is in nm units as the in-plane retardation value Re.
Table 3 shows the evaluation results of the (meth) acrylic resin films of examples 1 to 5 and comparative examples 1 to 3.
[ Table 3]
The (meth) acrylic resin films of examples 1 to 5 were each a film having a thickness of 40 μm or less, and were excellent in all of folding endurance of 50 times or more, shear resistance (tensile breaking strength) of 50MPa or more, elongation at break of 9 to 12%, and solvent resistance (gel fraction) of 93% or more.
Thus, it was confirmed that the (meth) acrylic resin films of examples 1 to 5 can solve the technical problems of the present invention.
The (meth) acrylic resin film of comparative example 1 had a low folding resistance and a low elongation at break, because the (meth) acrylic polymer was copolymerized only with MMA, which is an alkyl (meth) acrylate having an alkyl group of C1 to C14, and no alkyl (meth) acrylate other than MMA, which is a homopolymer having a Tg of 0 ℃ or higher and an alkyl group having a C1 to C14 was copolymerized.
The (meth) acrylic resin film of comparative example 2 had extremely low folding resistance and solvent resistance (gel fraction) because the (meth) acrylic resin composition contained no crosslinking agent.
The (meth) acrylic resin film of comparative example 3 was produced by a melt extrusion method, but it was confirmed that the folding resistance and the solvent resistance (gel fraction) were extremely low as compared with the (meth) acrylic resin films of examples 1 to 5. When the thickness of the (meth) acrylic resin film of comparative example 3 was 20 μm, the value of Re was 1/4 in terms of the thickness ratio (20/80), but even though the value of Re was large, it was considered that the birefringence (n) was large (n)x-ny) The value of (a) is itself large.
As described above, the (meth) acrylic resin films of comparative examples 1 to 3 failed to solve the technical problem of the present invention and provided a (meth) acrylic resin film having excellent folding endurance, cut endurance (tensile breaking strength), elongation at break, and solvent resistance (gel fraction).
Industrial applicability
The (meth) acrylic resin composition of the present invention and the (meth) acrylic resin film using the (meth) acrylic resin composition have excellent properties particularly in terms of the reduction in thickness, folding resistance, and solvent resistance (gel fraction) as compared with those of conventional (meth) acrylic resin films obtained by melt extrusion methods, and therefore, the (meth) acrylic resin composition and the (meth) acrylic resin film can be expected to have effects of reducing the thickness and improving the durability of various optical devices such as displays, and therefore, have a great industrial value.
Claims (6)
1. A (meth) acrylic resin composition comprising a (meth) acrylic polymer and a crosslinking agent, characterized in that,
the (meth) acrylic polymer is composed of a copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 100 ten thousand, and is obtained by copolymerizing 100 parts by weight in total of at least 80 parts by weight of methyl methacrylate and at least one or more selected from alkyl (meth) acrylates other than the methyl methacrylate, the homopolymers of which have a Tg of not less than 0 ℃ and an alkyl group having a carbon number of C1 to C14, and at least one or more selected from copolymerizable monomers having a functional group reactive with the crosslinking agent in total of 1.0 to 20.0 parts by weight.
2. The (meth) acrylic resin composition according to claim 1,
the (meth) acrylic polymer is composed of a copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 100 ten thousand, and is obtained by copolymerizing 100 parts by weight in total of at least one selected from the group consisting of (A)80 to 99 parts by weight of methyl methacrylate, 1 to 20 parts by weight of at least one selected from the group consisting of alkyl (meth) acrylates other than the methyl methacrylate, the homopolymers of which have a Tg of 0 ℃ or more and an alkyl group having a carbon number of C1 to C14, and 1.0 to 20.0 parts by weight in total of at least one selected from the group consisting of a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group, the copolymerizable monomer being a copolymerizable monomer having a functional group reactive with the crosslinking agent.
3. The (meth) acrylic resin composition according to claim 1 or 2, wherein the crosslinking agent is one or more selected from the group consisting of an epoxy compound, an aziridine compound and an isocyanate compound.
4. A (meth) acrylic resin film characterized by being a resin layer obtained by crosslinking the (meth) acrylic resin composition according to claim 1 or 2.
5. An adhesive sheet comprising a (meth) acrylic resin film and an adhesive layer formed on one or both surfaces of the (meth) acrylic resin film, wherein the (meth) acrylic resin film is a resin layer obtained by crosslinking the (meth) acrylic resin composition according to any one of claims 1 to 3.
6. A polarizing film comprising a polarizer and a (meth) acrylic resin film formed on one or both surfaces of the polarizer, wherein the (meth) acrylic resin film is a resin layer obtained by crosslinking the (meth) acrylic resin composition according to any one of claims 1 to 3.
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| JP2009034846A (en) * | 2007-07-31 | 2009-02-19 | Chisso Corp | Transfer film |
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| JP2011255534A (en) * | 2010-06-07 | 2011-12-22 | Dic Corp | Transfer sheet |
| JP6104588B2 (en) * | 2012-12-11 | 2017-03-29 | 日本写真印刷株式会社 | Three-dimensional decorative molded product and manufacturing method thereof |
| JP6342791B2 (en) * | 2013-12-27 | 2018-06-13 | 住友化学株式会社 | Protective film for polarizing plate and polarizing plate using the same |
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| JP2009286960A (en) * | 2008-05-30 | 2009-12-10 | Mitsubishi Rayon Co Ltd | Acrylic resin film composition and molded article using the same |
| WO2016139927A1 (en) * | 2015-03-02 | 2016-09-09 | 株式会社カネカ | Acrylic resin composition, and molded product and film made from same |
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| KR20230149802A (en) | 2023-10-27 |
| JP7360842B2 (en) | 2023-10-13 |
| TW202112951A (en) | 2021-04-01 |
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