KR20210019950A - (meth)acrylic-based resin composition and (meth)acrylic-based resin film - Google Patents
(meth)acrylic-based resin composition and (meth)acrylic-based resin film Download PDFInfo
- Publication number
- KR20210019950A KR20210019950A KR1020200097710A KR20200097710A KR20210019950A KR 20210019950 A KR20210019950 A KR 20210019950A KR 1020200097710 A KR1020200097710 A KR 1020200097710A KR 20200097710 A KR20200097710 A KR 20200097710A KR 20210019950 A KR20210019950 A KR 20210019950A
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylic resin
- weight
- resin composition
- acrylic
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 title claims abstract description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title description 3
- 239000011342 resin composition Substances 0.000 title description 3
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 134
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 134
- 239000000203 mixture Substances 0.000 claims abstract description 60
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 52
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 48
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 32
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920001519 homopolymer Polymers 0.000 claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 125000000524 functional group Chemical group 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000010410 layer Substances 0.000 claims description 23
- -1 aziridine compound Chemical class 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 16
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 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
- 239000002904 solvent Substances 0.000 abstract description 30
- 238000005266 casting Methods 0.000 abstract description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 137
- 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 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 15
- 239000000155 melt Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000012788 optical film Substances 0.000 description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 12
- 239000004926 polymethyl methacrylate Substances 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 229920000578 graft copolymer Polymers 0.000 description 4
- 238000004519 manufacturing process 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
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 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
- 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
- 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 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 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
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 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
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000314 lubricant Substances 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
- 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
- 230000001681 protective effect Effects 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
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-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
- 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 class C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-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
- 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
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-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
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical class CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive 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
- 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
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 238000005452 bending Methods 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
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 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
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine 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
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 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
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 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
- 238000010422 painting Methods 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
- 238000012545 processing 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
- 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
- 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
- 238000005979 thermal decomposition reaction Methods 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
Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
본 발명은 (메타)아크릴계 수지 필름 등의 형성에 바람직하게 사용되는 (메타)아크릴계 수지 조성물, 및 이를 사용한 (메타)아크릴계 수지 필름에 관한 것이다.The present invention relates to a (meth)acrylic resin composition preferably used for formation of a (meth)acrylic resin film and the like, and to a (meth)acrylic resin film using the same.
종래부터 고투명성, 가열 가공성, 내후성, 내약품성이 우수한 점에서, 전자 기기, 가전 제품, 자동차 내외장 부품, 건축 부재 등의 각종 기기 부품의 표면 피복에 사용하는 수지 필름으로서, (메타)아크릴계 수지 필름이 사용되고 있다.Conventionally, as a resin film used for surface coating of various equipment parts such as electronic devices, home appliances, automobile interior and exterior parts, and building members from the viewpoint of high transparency, heat processability, weather resistance, and chemical resistance, (meth)acrylic resin Film is being used.
또한, 근래에는 고투명성, 내후성 등이 우수한 점에서, (메타)아크릴계 수지 필름이 광학용 필름으로서 사용되고 있다.In addition, in recent years, since high transparency, weather resistance, etc. are excellent, a (meth)acrylic resin film is used as an optical film.
종래, 폴리메틸메타크릴레이트(PMMA) 수지로 이루어지는 (메타)아크릴계 수지 필름(PMMA 필름)을 제조하는 방법으로는, 생산성이 높은 점에서, PMMA 수지를 용융 압출법에 의해 제막하는 방법이 채용되고 있었다.Conventionally, as a method of producing a (meth)acrylic resin film (PMMA film) made of a polymethyl methacrylate (PMMA) resin, a method of forming a film by a melt extrusion method of PMMA resin is adopted from the viewpoint of high productivity. there was.
예를 들면, 특허문헌 1에는, 아크릴 수지 필름과 성형 수지를 일체화하는 부재에 바람직하게 사용 가능한 아크릴 수지 필름으로서, 특히 표면의 보호층 형성에 바람직한 도장 대체 아크릴 수지 필름이 개시되어 있다. 특허문헌 1에 기재된 발명에 따른 아크릴 수지 필름은 아크릴 수지 필름에 첨가하는 자외선 흡수제와 윤활제를 특정 종류로 조합하고, 추가로 이들 성분을 특정 함유량으로 하고 있다. 이 때문에, 특허문헌 1에서는, 표면의 보호층 형성에 사용하는 도장 대체 아크릴 수지 필름으로서, 바람직하게 사용할 수 있다고 하고 있다.For example, Patent Literature 1 discloses an acrylic resin film suitable for forming a protective layer on the surface as an acrylic resin film that can be preferably used for a member that integrates an acrylic resin film and a molding resin. The acrylic resin film according to the invention described in Patent Document 1 combines an ultraviolet absorber and a lubricant added to the acrylic resin film in a specific type, and further contains these components as a specific content. For this reason, in patent document 1, it is said that it can be used suitably as a painting substitute acrylic resin film used for formation of a surface protective layer.
또한, 특허문헌 2에는, 아크릴계 수지의 장점인 독특하게 아름다운 색조, 및 투명성이 저해되는 원인이 되는 고무 함유 그래프트 공중합체를 함유시키지 않고, 아크릴계 수지의 본질적인 결점인 내충격성을 개선하는 방법이 개시되어 있다. 특허문헌 2에 기재된 발명에 따른 아크릴계 수지 조성물은, 상기 수지 조성물을 용융 압출법에 의해 필름화할 때 용융 압출 온도를 높게 하면, 상기 그래프트 공중합체가 열분해함으로써 발생하는 분해 가스, 또는 블리드 아웃물에 의해, 캐스트 롤 등의 냉각 롤이 오염되어, 생산성이 떨어진다는 문제를 해결할 수 있다고 하고 있다.In addition, Patent Document 2 discloses a method of improving the impact resistance, which is an essential drawback of acrylic resin, without containing a rubber-containing graft copolymer that causes a uniquely beautiful color tone, which is an advantage of acrylic resin, and transparency is impaired. . The acrylic resin composition according to the invention described in Patent Document 2, when the melt extrusion temperature is increased when the resin composition is formed into a film by a melt extrusion method, is caused by a decomposition gas generated by thermal decomposition of the graft copolymer, or a bleed-out product. It is said that it is possible to solve the problem of poor productivity due to contamination of cooling rolls such as cast rolls.
그런데, 특허문헌 1에 기재된 발명에 따른 아크릴 수지 필름은, 열가소성 중합체를 포함하는 아크릴 수지 조성물의 혼합물을 탈기식 이축 압출기에서 혼련하여, 아크릴 수지 조성물의 펠릿을 얻은 후, 용융 압출기에서 용융한 수지 조성물을 T 다이에 압출하여 행하는 용융 압출법에 의해, 아크릴 수지 필름을 제막한 것이다. 또한, 특허문헌 1에 기재된 실시예 1∼6에서는, 막두께가 50∼125㎛인 아크릴 수지 필름이 얻어지고 있다. 그러나, 특허문헌 1에 기재된 발명에 따른 아크릴 수지 필름은 용융 압출법에 의해 제막한 수지 필름인 점에서, 막두께가 40㎛ 이하인 얇은 수지 필름을 얻는 것이 곤란하다는 문제를 갖고 있었다.By the way, in the acrylic resin film according to the invention described in Patent Document 1, a mixture of an acrylic resin composition containing a thermoplastic polymer is kneaded in a degassing twin-screw extruder to obtain pellets of the acrylic resin composition, and then melted in a melt extruder. The acrylic resin film was formed into a film by a melt extrusion method performed by extruding a T-die. In addition, in Examples 1 to 6 described in Patent Document 1, an acrylic resin film having a film thickness of 50 to 125 µm is obtained. However, since the acrylic resin film according to the invention described in Patent Document 1 is a resin film formed by a melt extrusion method, it has a problem that it is difficult to obtain a thin resin film having a film thickness of 40 μm or less.
또한, 특허문헌 2에 기재된 발명에 따른 아크릴 수지 조성물은, 3∼4단계의 그래프트 중합 반응을 행하여 서서히 그래프트 공중합체를 완성시키기 때문에, 그래프트 공중합체를 얻는 공정에 장시간을 요한다는 문제를 갖고 있었다. 또한, 특허문헌 2의, 용융 압출법에 의해 아크릴 수지 필름을 제조한 실시예 6∼8에서는, 연신하지 않고 얻어진 아크릴 수지 필름의 막두께가 80㎛이며, 연신하지 않고 막두께가 40㎛ 이하인 얇은 수지 필름이 얻어지지 않았다.In addition, the acrylic resin composition according to the invention described in Patent Document 2 has a problem that a long time is required for the step of obtaining the graft copolymer because the graft copolymer is gradually completed by performing the graft polymerization reaction of 3 to 4 steps. In addition, in Examples 6 to 8 in which the acrylic resin film was produced by the melt extrusion method of Patent Document 2, the acrylic resin film obtained without stretching had a film thickness of 80 µm, and a thin film having a film thickness of 40 µm or less without stretching. No resin film was obtained.
이러한 가운데, 용융 압출법에 비해, 보다 간편한 수지 필름의 제막 방법이며, 박막화할 수 있는 이점이 있는 용액 캐스트법에 의해 PMMA 수지를 제막하는 방법이 요구되고 있었다. 본 발명자들은 용액 캐스트법에 의해 PMMA 수지를 제막하는 방법을 예의 검토했다. 그 결과, 특정 PMMA 수지 조성물을 사용함으로써, 용액 캐스트법에 의해 제막한 경우에도, 용융 압출법에 의해 제막한 것과 동등 이상의 우수한 물성을 갖는 PMMA 수지 필름이 얻어지는 것을 알아내어, 본 발명을 완성시킬 수 있었다.Among these, there has been a demand for a method of forming a PMMA resin by a solution casting method, which is a more convenient method for forming a resin film than a melt extrusion method, and has an advantage of being able to form a thin film. The present inventors intensively studied a method of forming a PMMA resin by a solution casting method. As a result, by using a specific PMMA resin composition, it was found that even when the film was formed by the solution casting method, a PMMA resin film having excellent physical properties equal to or higher than that formed by the melt extrusion method was obtained, and the present invention could be completed. there was.
종래의 용융 압출법에 의해, (메타)아크릴계 수지 필름을 제막하는 방법의 경우에는, 40㎛ 이하의 두께로 박막화하는 것이 곤란했다. 한편, 용액 캐스트법에 의해, (메타)아크릴계 수지 필름을 제막하는 방법의 경우에는, 40㎛ 이하의 두께로 박막화하는 것이 가능하나, 얻어진 (메타)아크릴계 수지 필름의 물성으로서 내용제성 성능을 향상시키는 것이 어렵다는 문제가 있었다. 또한, 용액 캐스트법에 있어서는, (메타)아크릴계 수지 조성물에 함유하는 미가교된 PMMA 수지의 중량 평균 분자량을 100만 이상의 큰 값으로 할 필요가 있기 때문에, 당해 (메타)아크릴계 수지 조성물의 용액이 고점도여서, 제막 공정에서의 작업성이 양호하지 않다는 문제가 있었다.In the case of a method of forming a (meth)acrylic resin film into a film by a conventional melt extrusion method, it was difficult to form a thin film to a thickness of 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 make a thin film to a thickness of 40 μm or less, but as a physical property of the obtained (meth)acrylic resin film, the solvent resistance performance is improved. There was a problem that it was difficult. In addition, in the solution casting method, since it is necessary to set the weight average molecular weight of the uncrosslinked PMMA resin contained in the (meth)acrylic resin composition to a large value of 1 million or more, the solution of the (meth)acrylic resin composition has a high viscosity. Therefore, there was a problem that the workability in the film forming step was not good.
본 발명은 얇은 막두께의 수지 필름을 얻기 위한 용액 캐스트법에 사용할 수 있는 (메타)아크릴계 수지 조성물로서, 제막한 수지 필름 등의 성형품이 내절성, 내파단성(인장 파단 강도), 파단 신도, 내용제성(겔분율)이 우수한 (메타)아크릴계 수지 조성물, 및 (메타)아크릴계 수지 필름을 제공하는 것을 과제로 한다.The present invention is a (meth)acrylic resin composition that can be used in a solution casting method for obtaining a thin resin film, and a molded article such as a formed resin film has cut resistance, break resistance (tensile breaking strength), breaking elongation, and contents. It is an object to provide a (meth)acrylic resin composition excellent in forming properties (gel fraction), and a (meth)acrylic resin film.
본 발명자들은 상기 과제를 해결하기 위해 예의 검토한 결과, (메타)아크릴계 폴리머와, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서, 상기 (메타)아크릴계 폴리머가 MMA(메틸메타크릴레이트)와, 상기 MMA 이외의 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트와, 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상을 특정 비율로 공중합시킨 공중합체로 이루어지는 (메타)아크릴계 폴리머로 함으로써, 이러한 (메타)아크릴계 수지 조성물을 사용하여 용액 캐스트법에 의해 얻어진 (메타)아크릴계 수지 필름은, 내절성, 내파단성(인장 파단 강도), 파단 신도, 내용제성(겔분율)이 우수한 것을 알아내어, 본 발명을 완성시킬 수 있었다. 즉, 본 발명은 특정 (메타)아크릴계 폴리머와, 가교제를 함유하는 (메타)아크릴계 수지 조성물을 가교시킨 수지층으로 이루어지는 (메타)아크릴계 수지 필름을 얻는 것을 기술 사상으로 하고 있다.The inventors of the present invention intensively studied in order to solve the above problems, as a result of the (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent, wherein the (meth)acrylic polymer is MMA (methyl methacrylate), A copolymer obtained by copolymerizing an alkyl (meth)acrylate having a homopolymer other than MMA having a Tg of 0°C or higher and having a C1 to C14 alkyl group and at least one copolymerizable monomer having a functional group in a specific ratio. The (meth)acrylic resin film obtained by the solution casting method using such a (meth)acrylic resin composition by using the (meth)acrylic polymer is cut resistance, fracture resistance (tensile fracture strength), elongation at break, and solvent resistance ( The gel fraction) was found to be excellent, and the present invention could be completed. That is, the present invention makes it a technical idea to obtain a (meth)acrylic resin film comprising a resin layer obtained by crosslinking a specific (meth)acrylic polymer and a (meth)acrylic resin composition containing a crosslinking agent.
상기 과제를 해결하기 위해, 본 발명은 (메타)아크릴계 폴리머와, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서, 상기 (메타)아크릴계 폴리머가 메틸메타크릴레이트 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부와, 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계 1.0∼20.0중량부를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머인 것을 특징으로 하는 (메타)아크릴계 수지 조성물을 제공한다.In order to solve the above problems, the present invention is a (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent, wherein the (meth)acrylic polymer is at least 80 parts by weight of methyl methacrylate, and the methylmethacryl In addition to the rate, the homopolymer has a Tg of 0°C or higher, and a total of 100 parts by weight of at least one or more alkyl (meth)acrylates having C1-C14 carbon atoms in the alkyl group, and a functional group capable of reacting with the crosslinking agent. Provided is a (meth)acrylic resin composition characterized in that it is a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of more than 100,000 and less than 1 million by copolymerizing 1.0 to 20.0 parts by weight of at least one copolymerizable monomer in total.
상기 (메타)아크릴계 폴리머가 (A) 메틸메타크릴레이트 80∼99중량부와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 1∼20중량부의 합계 100중량부와, 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머로서, (B) 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중에서 선택된 적어도 1종 이상의 모노머의 합계 1.0∼20.0중량부를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머인 것이 바람직하다.The (meth)acrylic polymer is (A) 80 to 99 parts by weight of methyl methacrylate, and the Tg of a homopolymer other than the methyl methacrylate is 0° C. or higher, and the alkyl group has C1-C14 alkyl ( As a copolymerizable monomer having a total of 1 to 20 parts by weight of at least one meth) acrylate and a functional group capable of reacting with the crosslinking agent, (B) a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group It is preferable that it is a (meth)acrylic polymer composed of a copolymer having a weight average molecular weight of more than 100,000 and not more than 1 million by copolymerizing 1.0 to 20.0 parts by weight of at least one monomer selected from the group of monomers.
상기 가교제가 에폭시 화합물, 아지리딘 화합물, 이소시아네이트 화합물로 이루어지는 화합물군에서 선택된 1종 이상인 것이 바람직하다.It is preferable that the crosslinking agent is at least one selected from the group of compounds consisting of an epoxy compound, an aziridine compound, and an isocyanate compound.
또한, 본 발명은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 것을 특징으로 하는 (메타)아크릴계 수지 필름을 제공한다.In addition, the present invention provides a (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition.
또한, 본 발명은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 (메타)아크릴계 수지 필름의 한쪽 면 또는 양면에 점착층을 형성하여 이루어지는 것을 특징으로 하는 점착 시트를 제공한다.In addition, the present invention provides an adhesive sheet, characterized in that the adhesive layer is formed on one or both surfaces of a (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition.
또한, 본 발명은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 (메타)아크릴계 수지 필름을, 편광자의 한쪽 면 또는 양면에 형성하여 이루어지는 것을 특징으로 하는 편광 필름을 제공한다.Further, the present invention provides a polarizing film, 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.
본 발명에 의하면, 얇은 막두께의 수지 필름을 얻기 위한 용액 캐스트법에 사용할 수 있는 (메타)아크릴계 수지 조성물로서, 제막한 수지 필름 등의 성형품이 내절성, 내파단성(인장 파단 강도), 파단 신도, 내용제성(겔분율)이 우수한 (메타)아크릴계 수지 조성물, 및 (메타)아크릴계 수지 필름을 제공할 수 있다. According to the present invention, as a (meth)acrylic resin composition that can be used in a solution casting method for obtaining a thin resin film, a molded article such as a formed resin film has cutting resistance, fracture resistance (tensile breaking strength), and breaking elongation. , It is possible to provide a (meth)acrylic resin composition having excellent solvent resistance (gel fraction), and a (meth)acrylic resin film.
한편, 본 발명에서는, 내용제성 시험 방법으로서, (메타)아크릴계 수지 필름의 시험편을 용제의 액 중에 소정 시간에 걸쳐 침지한 후, 상기 용제에 용출하지 않고 불용분(잔사)으로서 남은 (메타)아크릴계 수지 필름의 비율(이른바, 겔분율)을 측정하여, 내용제성을 시험했다. On the other hand, in the present invention, as a solvent resistance test method, after immersing a test piece of a (meth)acrylic resin film in a solution of a solvent for a predetermined period of time, it is not eluted in the solvent and remains as an insoluble matter (residue). The ratio (so-called gel fraction) of the resin film was measured, and solvent resistance was tested.
또한, 종래 기술의 용융 압출법에 의해 (메타)아크릴계 수지 필름을 제막하는 경우에는, 수지 필름을 제막한 후, 1축 또는 2축 연신 가공을 실시하지 않는 한 막두께를 40㎛ 이하로 할 수 없었다. 한편, 본 발명의 (메타)아크릴계 수지 조성물을 사용하면, 용액 캐스트법만을 이용하여, 막두께가 40㎛ 이하인 박막의 (메타)아크릴계 수지 필름을 제조할 수 있어, 제조 공정이 보다 간편해짐과 함께, 제조 장치의 비용 저감을 도모할 수 있다.In addition, in the case of forming a (meth)acrylic resin film by the melt extrusion method of the prior art, the film thickness can be set to 40 μm or less unless uniaxial or biaxial stretching processing is performed after forming the resin film. There was no. On the other hand, when the (meth)acrylic resin composition of the present invention is used, a thin (meth)acrylic resin film having a film thickness of 40 μm or less can be produced by using only the solution casting method, thus simplifying the manufacturing process. , It is possible to reduce the cost of the manufacturing device.
이하, 바람직한 실시형태에 기초하여 본 발명을 설명한다.Hereinafter, the present invention will be described based on preferred embodiments.
본 실시형태의 (메타)아크릴계 수지 조성물은 (메타)아크릴계 폴리머와, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서, 상기 (메타)아크릴계 폴리머가 메틸메타크릴레이트 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부와, 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계 1.0∼20.0중량부를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머인 것을 특징으로 한다.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 at least 80 parts by weight of methyl methacrylate, and the methylmethacrylate A total of 100 parts by weight of at least one or more alkyl (meth)acrylates having a homopolymer other than acrylate having a Tg of 0°C or higher and having C1 to C14 carbon atoms in the alkyl group, and a functional group capable of reacting with the crosslinking agent It is characterized in that it is a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of more than 100,000 and less than 1 million by copolymerizing 1.0 to 20.0 parts by weight of at least one copolymerizable monomer.
본 실시형태의 (메타)아크릴계 수지 조성물에 사용되는 (메타)아크릴계 폴리머는 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트를 주성분으로 하고, 특히 메틸메타크릴레이트(MMA)를 주성분으로 하는 (메타)아크릴계 폴리머인 것이 바람직하다. 상기 알킬(메타)아크릴레이트의 알킬기는 비고리형(직쇄, 분지형), 고리형(단환, 다환) 중 어느 하나여도 된다. 상기 (메타)아크릴계 폴리머는 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 2종 이상을 함유하는 공중합체인 것이 바람직하다. 상기 (메타)아크릴계 폴리머는 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상을 공중합시킨 공중합체인 것이 바람직하다. 여기서, (메타)아크릴계 폴리머의 주성분이란, 1종류로 (메타)아크릴계 폴리머의 50중량％ 이상의 비율을 차지하는 화합물, 또는 2종류 이상의 합계로 (메타)아크릴계 폴리머의 50중량％ 이상의 비율을 차지하는 화합물군을 의미한다. 즉, (메타)아크릴계 폴리머의 100중량부 중, 주성분이 50중량부 이상인 비율을 차지하는 경우이다. 한편, 이하의 설명에 있어서, 모노머에 대해, 단순히 Tg라고 하는 경우에는, 호모폴리머의 Tg를 가리키는 경우가 있다.The (meth)acrylic polymer used in the (meth)acrylic resin composition of the present embodiment is mainly composed of an alkyl (meth)acrylate having C1 to C14 carbon atoms in the alkyl group, and in particular, methyl methacrylate (MMA) as a main component. It is preferably a (meth)acrylic polymer. The alkyl group of the alkyl (meth)acrylate may be acyclic (linear or branched) or cyclic (monocyclic or polycyclic). The (meth)acrylic polymer is preferably a copolymer containing at least two or more of alkyl (meth)acrylates having C1 to C14 in the alkyl group. It is preferable that the (meth)acrylic polymer is a copolymer obtained by copolymerizing at least one or more alkyl (meth)acrylates having a homopolymer having a Tg of 0°C or higher and an alkyl group having C1 to C14 carbon atoms. 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 group of compounds that accounts for 50% by weight or more of the (meth)acrylic polymer as a sum of two or more types. Means. That is, in 100 parts by weight of the (meth)acrylic polymer, the main component occupies a ratio of 50 parts by weight or more. On the other hand, in the following description, in the case of simply referring to Tg for a monomer, there may be a case where Tg of a homopolymer is indicated.
상기 (메타)아크릴계 폴리머에 있어서, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트로는, 메틸(메타)아크릴레이트, 에틸메타크릴레이트, n-프로필메타크릴레이트, 이소프로필메타크릴레이트, n-부틸메타크릴레이트, 이소부틸메타크릴레이트, s-부틸메타크릴레이트, t-부틸(메타)아크릴레이트, n-펜틸메타크릴레이트, 이소펜틸메타크릴레이트, n-헥실메타크릴레이트, 이소헥실메타크릴레이트, 시클로헥실(메타)아크릴레이트, 이소보르닐(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트로 이루어지는 화합물군에서 선택된 1종 이상을 들 수 있다. 여기서, (메타)아크릴레이트는 아크릴레이트 또는 메타크릴레이트의 적어도 한쪽을 의미한다.In the above (meth)acrylic polymer, examples of the alkyl (meth)acrylate having a homopolymer having a Tg of 0°C or higher and having C1 to C14 carbon atoms in the alkyl group include 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) acrylate, isobornyl (meth) acrylate, one selected from the compound group consisting of dicyclopentanyl (meth) acrylate The above can be mentioned. Here, (meth)acrylate means at least one of acrylate or methacrylate.
상기 (메타)아크릴계 폴리머에 있어서, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트로는, 알킬기의 탄소수가 C1∼C6인 알킬(메타)아크릴레이트가 바람직하고, 알킬기의 탄소수가 C1∼C4인 알킬(메타)아크릴레이트가 보다 바람직하다. 또한, 메틸메타크릴레이트 이외의, 알킬기의 탄소수가 C1∼C4인 알킬(메타)아크릴레이트 중에서는, 메틸아크릴레이트, 에틸메타크릴레이트, n-프로필메타크릴레이트, 이소프로필메타크릴레이트, n-부틸메타크릴레이트, 이소부틸메타크릴레이트, s-부틸메타크릴레이트, t-부틸아크릴레이트, t-부틸메타크릴레이트로 이루어지는 화합물군에서 선택된 1종 이상인 것이 특히 바람직하다.In the above (meth)acrylic polymer, the Tg of the homopolymer is 0°C or higher, and as an alkyl (meth)acrylate having C1 to C14 carbon atoms in the alkyl group, the alkyl (meth)acrylic having C1 to C6 carbon atoms in the alkyl group A rate is preferred, and an alkyl (meth)acrylate having C1-C4 carbon atoms in the alkyl group is more preferred. In addition, among alkyl (meth)acrylates having C1-C4 carbon atoms in the alkyl group other than methyl methacrylate, methyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n- It is particularly preferably at least one selected from the group of compounds consisting of butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl acrylate and t-butyl methacrylate.
또한, 상기 (메타)아크릴계 폴리머에 있어서, (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부 중, 메틸메타크릴레이트를 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 20중량부 이하의 비율로 함유하는 것이 바람직하고, 메틸메타크릴레이트를 80∼99중량부와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 1∼20중량부의 비율로 함유하는 것이 보다 바람직하다.In addition, 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 an alkyl group having C1 to C14 (meth) ) Of the total 100 parts by weight of at least one acrylate, 80 parts by weight or more of methyl methacrylate, the Tg of a homopolymer other than the methyl methacrylate is 0° C. or more, and the number of carbon atoms of the alkyl group is C1 to It is preferable to contain at least one C14 alkyl (meth)acrylate in a total of 20 parts by weight or less, and 80 to 99 parts by weight of methyl methacrylate and a homopolymer other than the methyl methacrylate. It is more preferable to contain Tg in a ratio of 1 to 20 parts by weight in total of at least one or more alkyl (meth)acrylates having 0°C or higher and having C1 to C14 carbon atoms in the alkyl group.
상기 (메타)아크릴계 폴리머가 상기 (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부에 대해, 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계 1.0∼20.0중량부의 비율로 함유하는 것이 바람직하고, 1.0∼12.0중량부의 비율로 함유하는 것이 보다 바람직하며, 1.0∼9.0중량부의 비율로 함유하는 것이 특히 바람직하다.The (meth)acrylic polymer is an alkyl (meth)acrylate in which Tg of a homopolymer other than the (A) methyl methacrylate and the methyl methacrylate is 0°C or higher and the alkyl group has C1 to C14 carbon atoms It is preferable to contain in a ratio of 1.0 to 20.0 parts by weight of a total of at least one copolymerizable monomer having a functional group capable of reacting with the crosslinking agent, based on 100 parts by weight of the total of at least one or more types, 1.0 to 12.0 parts by weight It is more preferable to contain it, and it is especially preferable to contain it in 1.0 to 9.0 weight part ratio.
상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머로는, (B) 수산기를 갖는 공중합 가능한 모노머, 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중에서 선택된 적어도 1종 이상의 모노머를 들 수 있다. 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머는 수산기를 갖는 공중합 가능한 모노머만이어도 되고, 카르복실기를 갖는 공중합 가능한 모노머만이어도 되며, 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머의 양쪽을 병용해도 된다.Examples of the copolymerizable monomer having a functional group capable of reacting with the crosslinking agent include at least one or more monomers selected from the group consisting of (B) a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group. The copolymerizable monomer having a functional group capable of reacting with the crosslinking agent may be only a copolymerizable monomer having a hydroxyl group, or only a copolymerizable monomer having a carboxyl group, and both a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group You may use it together.
상기 수산기를 갖는 공중합 가능한 모노머로는, 8-히드록시옥틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트 등의 히드록시알킬(메타)아크릴레이트류나, N-히드록시(메타)아크릴아미드, N-히드록시메틸(메타)아크릴아미드, N-히드록시에틸(메타)아크릴아미드 등의 수산기 함유 (메타)아크릴아미드류 등으로 이루어지는 화합물군 중에서 선택된 적어도 1종 이상인 것이 바람직하다.Examples of the copolymerizable monomer having a hydroxyl group include 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. )Hydroxyalkyl (meth)acrylates such as acrylates, and hydroxyl groups such as N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and N-hydroxyethyl(meth)acrylamide It is preferable that it is at least 1 type or more selected from the compound group consisting of (meth)acrylamides etc.
상기 카르복실기를 갖는 공중합 가능한 모노머로는, (메타)아크릴산, 카르복시에틸(메타)아크릴레이트, 카르복시펜틸(메타)아크릴레이트, 2-(메타)아크릴로일옥시에틸헥사히드로프탈산, 2-(메타)아크릴로일옥시프로필헥사히드로프탈산, 2-(메타)아크릴로일옥시에틸프탈산, 2-(메타)아크릴로일옥시에틸숙신산, 2-(메타)아크릴로일옥시에틸말레산, 카르복시폴리카프로락톤모노(메타)아크릴레이트, 2-(메타)아크릴로일옥시에틸테트라히드로프탈산 등으로 이루어지는 화합물군 중에서 선택된 적어도 1종 이상인 것이 바람직하다.Examples of the copolymerizable monomer having a carboxyl group include (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 It is preferably at least one or more selected from the group of compounds consisting of mono(meth)acrylate, 2-(meth)acryloyloxyethyltetrahydrophthalic acid, and the like.
상기 아크릴계 폴리머는 상기 (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부에 대해, 상기 (B) 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중에서 선택된 적어도 1종 이상의 모노머의 합계 1.0∼20.0중량부의 비율로 함유하는 것이 바람직하다.The acrylic polymer is at least one of the above (A) methyl methacrylate and an alkyl (meth)acrylate having a homopolymer Tg of 0° C. or higher, and the alkyl group having C1 to C14 carbon atoms other than the methyl methacrylate. It is preferable to contain in a ratio of 1.0 to 20.0 parts by weight of the total of at least one or more monomers selected from the monomer group consisting of (B) a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group based on 100 parts by weight of the total Do.
상기 아크릴계 폴리머의 제조 방법은 특별히 한정되는 것이 아니며, 용액 중합법, 유화 중합법 등, 적절히 공지의 중합 방법이 사용 가능하다. 상기 아크릴계 폴리머는 중량 평균 분자량이 10만 초과 100만 이하인 공중합체인 것이 바람직하고, 중량 평균 분자량이 10만 초과 95만 이하인 공중합체인 것이 보다 바람직하며, 중량 평균 분자량이 10만 초과 90만 이하인 공중합체인 것이 특히 바람직하다. 상기 아크릴계 폴리머의 중량 평균 분자량이 10만 이하이면, (메타)아크릴계 수지 조성물을 가교해도 우수한 물성을 갖는 (메타)아크릴계 수지 필름 등의 성형품이 얻어지기 어려워진다. 상기 아크릴계 폴리머의 중량 평균 분자량이 100만보다 크면, (메타)아크릴계 수지 조성물의 용액이 고점도가 되어, 제막 공정의 작업성이 양호하지 않다.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 may be appropriately used. The acrylic polymer is preferably a copolymer having a weight average molecular weight of more than 100,000 and not more than 1 million, more preferably a copolymer having a weight average molecular weight of more than 100,000 and not more than 950,000, and a copolymer having a weight average molecular weight of more than 100,000 and not more than 900,000. It is particularly preferred. If the weight average molecular weight of the acrylic polymer is 100,000 or less, even if the (meth)acrylic resin composition is crosslinked, it becomes difficult to obtain a molded article such as a (meth)acrylic resin film having excellent physical properties. If the weight average molecular weight of the acrylic polymer is more than 1 million, the solution of the (meth)acrylic resin composition becomes high viscosity, and the workability of the film forming step is not good.
상기 가교제로는, 상기 (메타)아크릴계 폴리머가 갖는 관능기와, 가교 반응할 수 있는 가교성 관능기를 갖는 화합물을 들 수 있다. 상기 가교제는 상기 (메타)아크릴계 수지 조성물의 보존 안정성 등의 관점에서, 상온(일반적으로는 5∼35℃)에서는 가교 반응이 일어나기 어렵고, 소정 온도 이상으로 가열하면 가교 반응이 개시되는 화합물인 것이 바람직하다.Examples of the crosslinking agent include a compound having a functional group of the (meth)acrylic polymer and a crosslinkable functional group capable of crosslinking reaction. 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 is preferably a compound that initiates a crosslinking reaction when heated to a predetermined temperature or higher. Do.
상기 가교제가 에폭시 화합물, 아지리딘 화합물, 이소시아네이트 화합물로 이루어지는 화합물군에서 선택된 1종 이상인 것이 바람직하다. 본 실시형태의 (메타)아크릴계 수지 조성물은 상기 (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부에 대해, 상기 가교제를 0.01∼10중량부의 비율로 함유하는 것이 바람직하다.It is preferable that the crosslinking agent is at least one selected from the group of compounds consisting of an epoxy compound, an aziridine compound, and an isocyanate compound. In the (meth)acrylic resin composition of the present embodiment, the Tg of the homopolymer other than the above (A) methyl methacrylate and the methyl methacrylate is 0°C or higher, and the alkyl group has a C1 to C14 alkyl ( It is preferable to contain the crosslinking agent in a ratio of 0.01 to 10 parts by weight with respect to 100 parts by weight in total of at least one meth)acrylate.
상기 에폭시 화합물로 이루어지는 가교제(에폭시계 가교제)로는, 2관능 이상의 에폭시 화합물이면 특별히 한정되지 않으나, 예를 들면, 폴리올류(디올류, 글리콜류, 비스페놀류를 포함한다)의 폴리글리시딜에테르, 디카르복실산의 디글리시딜에스테르, 디글리시딜 치환 아민류, 테트라글리시딜 치환 디아민류 등으로 이루어지는 화합물군으로부터 선택되는 적어도 1종 이상을 들 수 있다.The crosslinking agent (epoxy crosslinking agent) made of the above epoxy compound is not particularly limited as long as it is a bifunctional or higher epoxy compound. For example, polyglycidyl ether of polyols (including diols, glycols, and bisphenols), At least one or more selected from the group of compounds consisting of diglycidyl esters of dicarboxylic acids, diglycidyl substituted amines, tetraglycidyl substituted diamines, and the like can be mentioned.
상기 에폭시계 가교제 중, 폴리올류 폴리글리시딜에테르로는 예를 들면, 에틸렌글리콜디글리시딜에테르, 프로필렌글리콜디글리시딜에테르, 네오펜틸글리콜디글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 레조르신디글리시딜에테르, 글리세롤폴리글리시딜에테르, 트리메틸올프로판폴리글리시딜에테르, 펜타에리트리톨폴리글리시딜에테르, 소르비톨폴리글리시딜에테르 등을 들 수 있다.Among the epoxy-based crosslinking agents, polyols polyglycidyl ether include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol Diglycidyl ether, polyethylene glycol diglycidyl ether, resorcin diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polygly Cidyl ether, etc. are mentioned.
또한, 디카르복실산의 디글리시딜에스테르로는 예를 들면, 아디프산디글리시딜에스테르, 프탈산디글리시딜에스테르 등을 들 수 있다.Moreover, as a diglycidyl ester of a dicarboxylic acid, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, etc. are mentioned, for example.
또한, 디글리시딜 치환 아민류로는 예를 들면, N,N-디글리시딜아닐린, N,N-디글리시딜톨루이딘 등을 들 수 있다.Further, examples of diglycidyl substituted amines include N,N-diglycidylaniline, N,N-diglycidyltoluidine, and the like.
또한, 테트라글리시딜 치환 디아민류로는, 1,3-비스(N,N-디글리시딜아미노메틸)시클로헥산, N,N,N',N'-테트라글리시딜-m-자일렌디아민 등을 들 수 있다.In addition, as tetraglycidyl substituted diamines, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-m-xyl Rendiamine, etc. are mentioned.
상기 아지리딘 화합물로 이루어지는 가교제(아지리딘계 가교제)로는, 2관능 이상의 아지리딘 화합물, 1분자 중에 2개 이상의 아지리딘계 관능기를 갖는 화합물 등이면 특별히 한정되지 않는다. 아지리딘계 관능기로는, 1-아지리디닐기[-N(CH2)2], 2-아지리디닐기, 메틸기 등의 치환기를 갖는 치환 아지리디닐기 등을 들 수 있다. 아지리딘계 가교제의 구체예로는 예를 들면, 다음의 (1)∼(2)와 같은, 폴리이소시아네이트 화합물과 아지리딘의 부가 생성물, 다음의 (3)∼(4)와 같은, 폴리올폴리아크릴레이트 화합물과 아지리딘의 부가 생성물, 다음의 (5)∼(7)과 같은. 그 외의 폴리아크리딘 화합물을 들 수 있다.The crosslinking agent (aziridine-based crosslinking agent) made of the aziridine compound is not particularly limited as long as it is a bifunctional or more aziridine compound, a compound having two or more aziridine-based functional groups in one molecule. Examples of the aziridine-based functional group include a substituted aziridinyl group having a substituent such as 1-aziridinyl group [-N(CH 2 ) 2 ], 2-aziridinyl group, and methyl group. Specific examples of the aziridine crosslinking agent include, for example, the addition product of a polyisocyanate compound and aziridine, such as the following (1) to (2), and a polyol polyacrylate such as the following (3) to (4). Compound and aziridine addition product, such as the following (5) to (7). Other polyacridine compounds can be mentioned.
(1) 4,4'-비스[(1-아지리디닐)카르보닐아미노]디페닐메탄(1) 4,4'-bis[(1-aziridinyl)carbonylamino]diphenylmethane
(CH2)2NCONH-C6H4CH2C6H4-NHCON(CH2)2 (CH 2 ) 2 NCONH-C 6 H 4 CH 2 C 6 H 4 -NHCON(CH 2 ) 2
(2) 1,6-비스[(1-아지리디닐)카르보닐아미노]헥산(2) 1,6-bis[(1-aziridinyl)carbonylamino]hexane
(CH2)2NCONH-(CH2)6-NHCON(CH2)2 (CH 2 ) 2 NCONH-(CH 2 ) 6 -NHCON(CH 2 ) 2
(3) 트리메틸올프로판-트리스[2-(1-아지리디닐)프로피오네이트](3) Trimethylolpropane-tris[2-(1-aziridinyl)propionate]
CH3CH2C[CH2O-COCH2CH2N(CH2)2]3 CH 3 CH 2 C[CH 2 O-COCH 2 CH 2 N(CH 2 ) 2 ] 3
(4) 테트라메틸올메탄-트리스[2-(1-아지리디닐)프로피오네이트](4) Tetramethylolmethane-tris[2-(1-aziridinyl)propionate]
HOCH2C[CH2O-COCH2CH2N(CH2)2]3 HOCH 2 C[CH 2 O-COCH 2 CH 2 N(CH 2 ) 2 ] 3
(5) 트리스(1-아지리디닐)포스핀옥사이드(5) tris(1-aziridinyl)phosphine oxide
O=P[N(CH2)2]3 O=P[N(CH 2 ) 2 ] 3
(6) 트리스(1-아지리디닐)포스핀설피드(6) tris(1-aziridinyl)phosphine sulfide
S=P[N(CH2)2]3 S=P[N(CH 2 ) 2 ] 3
(7) 2,4,6-트리스(1-아지리디닐)-1,3,5-트리아진(7) 2,4,6-tris(1-aziridinyl)-1,3,5-triazine
(C3N3)[N(CH2)2]3 (C 3 N 3 )[N(CH 2 ) 2 ] 3
상기 이소시아네이트 화합물로 이루어지는 가교제(이소시아네이트계 가교제)로는, 헥사메틸렌디이소시아네이트(HDI), 이소포론디이소시아네이트(IPDI), 디페닐메탄디이소시아네이트(MDI), 톨릴렌디이소시아네이트(TDI), 자일릴렌디이소시아네이트(XDI) 등의 2관능 이소시아네이트(디이소시아네이트 화합물)나, 이들의 뷰렛 변성체, 이소시아누레이트 변성체, 어덕트체 등의 3관능 이상의 폴리이소시아네이트 화합물로 이루어지는 화합물군으로부터 선택되는 적어도 1종 이상을 들 수 있다. 여기서, 3관능 이상의 어덕트체는 디이소시아네이트 화합물과, 트리메틸올프로판, 글리세린 등의 3가 이상의 폴리올의 어덕트체를 들 수 있다.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), and xylylene diisocyanate ( XDI) or the like, and at least one selected from the group consisting of trifunctional or higher polyisocyanate compounds such as bifunctional isocyanates (diisocyanate compounds), biuret modified products, isocyanurate modified products, and adducts. Can be lifted. Here, the adduct body of a diisocyanate compound and trivalent or more polyols, such as trimethylolpropane and glycerin, can be mentioned as an adduct body of trifunctional or more.
상기 (메타)아크릴계 수지 조성물은 상술한 첨가제에 한정하지 않고, 계면 활성제, 경화 촉진제, 경화 지연제, 가소제, 충전제, 윤활제, 가공 보조제, 노화 방지제, 열안정제, 광안정제, 산화 방지제, 대전 방지제, 착색제, 자외선 흡수제, 적외선 흡수제 등의 공지의 첨가제가 적절히 배합되어도 된다. 이들 첨가제는 단독으로, 또는 2종 이상을 병용할 수 있다.The (meth)acrylic resin composition is not limited to the additives described above, but a surfactant, a curing accelerator, a curing retardant, a plasticizer, a filler, a lubricant, a processing aid, an anti-aging agent, a heat stabilizer, a light stabilizer, an antioxidant, an antistatic agent, Well-known additives, such as a coloring agent, an ultraviolet absorber, and an infrared absorber, may be blended suitably. These additives may be used alone or in combination of two or more.
상기 (메타)아크릴계 수지 조성물은 소정 형상으로 성형 또는 도포한 후, 상기 (메타)아크릴계 폴리머와 상기 가교제를 반응시킴으로써 경화시킬 수 있다. 상기 (메타)아크릴계 수지 조성물로부터 얻어지는 성형품으로는, 특별히 한정되지 않으나, 필름, 판(시트), 봉(로드), 섬유(파이버) 등을 들 수 있다. 상기 성형품의 성형 방법은 특별히 한정되지 않으나, 캐스트 성형, 적층 성형, 압출 성형 등을 들 수 있다. 상기 (메타)아크릴계 수지 조성물을 기재 상에 도포하는 경우에는 예를 들면, 용액 코팅에 의해 당해 기재 상에 수지막을 형성할 수 있다. 당해 기재로는, 특별히 한정되지 않으나, 수지 필름, 이형 필름, 종이 기재, 금속박, 적층체 등을 들 수 있다.The (meth)acrylic resin composition can be cured by reacting the (meth)acrylic polymer and the crosslinking agent after molding or coating into a predetermined shape. Although it does not specifically limit as a molded article obtained from the said (meth)acrylic resin composition, A film, a plate (sheet), a rod (rod), a fiber (fiber), etc. are mentioned. The molding method of the molded article is not particularly limited, but may include cast molding, lamination molding, and extrusion molding. When the (meth)acrylic resin composition is applied on a substrate, a resin film may be formed on the substrate by solution coating, for example. Although it does not specifically limit as said base material, A resin film, a release film, a paper base material, a metal foil, a laminated body, etc. are mentioned.
상기 (메타)아크릴계 수지 조성물에 함유되어 있는 상기 가교제가 가열에 의해 가교 반응을 개시하는 열 가교제인 경우, 상기 성형품의 성형시에 있어서 상기 아크릴계 폴리머를 가열 용융시켜 유동화시키는 것이 아니라, 상기 (메타)아크릴계 수지 조성물의 용액으로서 유동화시키는 것이 바람직하다. 상기 (메타)아크릴계 수지 조성물의 용액을 얻기 위한 용제로는, 상기 아크릴계 폴리머의 관능기 및 상기 가교제의 반응성을 저해하지 않고, 상기 아크릴계 폴리머를 용해시킬 수 있으면 특별히 한정되지 않는다. 상기 용제로는 톨루엔 등의 탄화수소계 용제, 에탄올이나 이소프로필알코올 등의 알코올계 용제, 디에틸에테르나 테트라히드로푸란 등의 에테르계 용제, 아세톤이나 메틸에틸케톤(MEK) 등의 케톤계 용제, 초산에틸 등의 에스테르계 용제 등을 들 수 있다. 상기 아크릴계 폴리머를 용액 중합법에 의해 제조한 경우, 중합에 사용한 용제의 적어도 일부가 상기 (메타)아크릴계 수지 조성물의 용제의 적어도 일부가 되어도 된다.When the crosslinking agent contained in the (meth)acrylic resin composition is a thermal crosslinking agent that initiates a crosslinking reaction by heating, the acrylic polymer is not heated and melted to fluidize the molded article, but the (meth) It is preferable to fluidize as a solution of the acrylic resin composition. The solvent for obtaining the solution of the (meth)acrylic resin composition is not particularly limited as long as it can dissolve the acrylic polymer without impairing the functional group of the acrylic polymer and the reactivity of the crosslinking agent. Examples of the solvent include hydrocarbon solvents such as toluene, alcohol solvents such as ethanol and isopropyl alcohol, ether solvents such as diethyl ether or tetrahydrofuran, ketone solvents such as acetone or methyl ethyl ketone (MEK), and acetic acid. Ester solvents, such as ethyl, etc. are mentioned. When the acrylic polymer is produced by a solution polymerization method, at least a part of the solvent used for polymerization may be at least a part of the solvent of the (meth)acrylic resin composition.
본 실시형태의 (메타)아크릴계 수지 필름은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 것을 특징으로 한다. 상기 (메타)아크릴계 수지 필름은 예를 들면, 용액 캐스트법을 사용함으로써, 상기 (메타)아크릴계 수지 조성물의 용액을 소정의 기재 상에 도포하여 박막을 형성한 후, 가열 건조시켜 상기 박막으로부터 용제를 휘발시킴과 함께 가교시킴으로써 제조할 수 있다. 상기 기재로는, 고정된 평면에 한정하지 않고, 수지 필름의 롤체로부터 되감긴 수지 필름, 가동 벨트, 드럼 등을 들 수 있다. 상기 기재의 표면 성상은 평활면이 바람직하나, 기재에 소정의 요철을 형성함으로써, 얻어지는 상기 (메타)아크릴계 수지 필름의 표면에 요철을 전사하는 것도 가능하다.The (meth)acrylic resin film of the present embodiment is characterized in that it is a resin layer formed by crosslinking the (meth)acrylic resin composition. For the (meth)acrylic resin film, for example, by using a solution casting method, a solution of the (meth)acrylic resin composition is applied on a predetermined substrate to form a thin film, followed by heating and drying to remove a solvent from the thin film. It can be produced by volatilizing and crosslinking. The base material is not limited to a fixed flat surface, and includes a resin film, a movable belt, a drum, and the like that are rewound from a roll body of a resin film. The surface property of the substrate is preferably a smooth surface, but it is also possible to transfer the irregularities to the surface of the obtained (meth)acrylic resin film by forming predetermined irregularities on the base material.
상기 용액 캐스트법에 의해 얻어진 상기 (메타)아크릴계 수지 필름은 길이 방향, 폭 방향 등의 소정 방향으로 연신해도 되고, 무연신인 상태로 해도 된다. 광학용 필름의 용도에 있어서, 이방성을 저감할 필요가 있는 경우에는 상기 (메타)아크릴계 수지 필름을 무연신 필름으로 하는 것이 바람직하다. 상기 (메타)아크릴계 수지 필름의 길이 방향 및 폭 방향으로 연신하는 조작을 추가하여, 이축 연신 필름으로 가공해도 된다. 한편, 필름의 이방성으로는, 「파단 신도」 등의 기계적 특성의 이방성에 한정하지 않고, 「복굴절률」 등의 광학 이방성도 들 수 있다.The (meth)acrylic resin film obtained by the solution casting method may be stretched in a predetermined direction such as a longitudinal direction and a width direction, or may be in a state of non-stretching. In the use of an optical film, when it is necessary to reduce anisotropy, it is preferable to use the (meth)acrylic resin film as a non-stretched film. You may process into a biaxially stretched film by adding the operation of extending|stretching in the longitudinal direction and the width direction of the said (meth)acrylic resin film. On the other hand, the anisotropy of the film is not limited to anisotropy of mechanical properties such as "breaking elongation", and optical anisotropy such as "birefringence" is also mentioned.
상기 (메타)아크릴계 수지 필름의 기계적 특성은 용도에도 의존하나, 점착 시트, 광학용 필름, 표면 보호 필름, 공정 필름 등에 사용하는 경우나, 길이 방향의 반송, 롤로부터 풀어내기, 롤에 권취하기 등을 행하는 경우에는, 내절성 및 내파단성(인장 파단 강도)이 높은 것에 추가로, 피착체 등에 대한 추종성이 얻어지도록, 적절한 파단 신도를 갖는 것이 바람직하다.The mechanical properties of the (meth)acrylic resin film depend on the application, but are used for adhesive sheets, optical films, surface protective films, process films, etc., conveyed in the longitudinal direction, unrolled from a roll, wound on a roll, etc. In the case of performing, in addition to having high cutting resistance and breaking resistance (tensile breaking strength), it is preferable to have an appropriate breaking elongation so that followability to an adherend or the like can be obtained.
상기 (메타)아크릴계 수지 필름을 구성하는, 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층의 겔분율은 50％ 이상인 것이 바람직하고, 70％ 이상인 것이 보다 바람직하며, 90∼100％인 것이 더욱 바람직하고, 93∼100％인 것이 특히 바람직하다. 이와 같이 상기 수지층의 겔분율이 높음으로써, 상기 (메타)아크릴계 수지 필름의 필요한 물성인 내용제성을 개선할 수 있다.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, more preferably 70% or more, and furthermore 90 to 100%. It is preferable, and it is especially preferable that it is 93-100%. As described above, when the gel fraction of the resin layer is high, solvent resistance, which is a necessary physical property of the (meth)acrylic resin film, can be improved.
상기 (메타)아크릴계 수지 필름의 두께는 특별히 한정되지 않으나, 예를 들면, 광학용 필름의 경우에는 10∼200㎛ 정도의 두께가 바람직하고, 두께가 10∼50㎛인 것이 보다 바람직하며, 두께가 10∼40㎛인 것이 특히 바람직하고, 두께를 40㎛ 이하의 박막으로 할 수도 있다. 상기 (메타)아크릴계 수지 필름의 한쪽 면 또는 양면에 다른 재료를 적층하는 경우에는 필요에 따라, 코로나 방전에 의한 표면 개질, 앵커 코트제 도포 등의 이(易)접착 처리를 실시해도 된다.The thickness of the (meth)acrylic resin film is not particularly limited. For example, in the case of an optical film, a thickness of about 10 to 200 µm is preferable, more preferably 10 to 50 µm, and the thickness is It is particularly preferably 10 to 40 µm, and a thin film having a thickness of 40 µm or less can also be used. In the case of laminating another material on one side or both sides of the (meth)acrylic resin film, if necessary, easily bonding treatment such as surface modification by corona discharge and application of an anchor coat agent may be performed.
상기 (메타)아크릴계 수지 필름은 광학용 필름의 기재에 사용해도 된다. 광학용 필름으로는, 편광 필름, 위상차 필름, 반사 방지 필름, 방현(안티 글레어) 필름, 자외선 흡수 필름, 적외선 흡수 필름, 광학 보상 필름, 휘도 향상 필름 등을 들 수 있다. 광학용 부재가 적용되는 기기로는, 액정 패널, 유기 EL 패널, 터치 패널 등을 들 수 있다. 상기 (메타)아크릴계 수지 필름을 광학용 필름으로 사용하는 경우에는 무색 투명인 것이 바람직하다.The (meth)acrylic resin film may be used for a base material of an optical film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an antiglare (anti-glare) film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, and a brightness improving 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, it is preferably colorless and transparent.
상기 (메타)아크릴계 수지 필름의 한쪽 면 또는 양면에는, 하드 코트층, 대전 방지층, 반사 방지층, 방오층, 방현층, 저굴절률층, 점착층, 이형층 등의 1종 또는 2종 이상을 적층해도 된다. 저굴절률층 형성용 조성물에 사용되는 불소 화합물로는, 불소화 올레핀류, 불소화 비닐에테르류, 불소화 알킬(메타)아크릴레이트 등의 1종 또는 2종 이상의 중합물인 함불소 공중합체, 불소화 알킬기 함유 실란 화합물 등의 축합물을 들 수 있다. 함불소 공중합체는 불소화된 모노머에 추가로, 올레핀류, 비닐에테르류, (메타)아크릴레이트 등의 불소화되어 있지 않은 모노머가 공중합되어도 된다. 저굴절률층은 고굴절률층 등과 조합하여 반사 방지층을 구성해도 된다.One or two or more of a hard coat layer, an antistatic layer, an antireflection layer, an antifouling layer, an anti-glare layer, a low refractive index layer, an adhesive layer, and a release layer may be laminated on one or both sides of the (meth)acrylic resin film. do. As a fluorine compound used in the composition for forming a low refractive index layer, a fluorinated copolymer such as one or two or more polymers such as fluorinated olefins, fluorinated vinyl ethers, and fluorinated alkyl (meth)acrylates, and silane compounds containing fluorinated alkyl groups Condensation products, such as are mentioned. In the fluorinated copolymer, in addition to the fluorinated monomer, a non-fluorinated monomer such as olefins, vinyl ethers, and (meth)acrylates may be copolymerized. The low refractive index layer may be combined with a high refractive index layer or the like to form an antireflection layer.
본 실시형태의 점착 시트는, 상기 (메타)아크릴계 수지 조성물을 가교해서 이루어지는 수지층인 상기 (메타)아크릴계 수지 필름의 한쪽 면 또는 양면에 점착층을 형성하여 이루어지는 것을 특징으로 한다. 상기 점착층으로는, (메타)아크릴계 점착제로 이루어지는 점착제층이 바람직하다. 상기 (메타)아크릴계 수지 필름에 점착층을 형성하는 방법은 공지의 방법으로 행하면 된다. 구체적으로는, 리버스 코팅, 콤마 코팅, 그라비아 코팅, 슬롯 다이 코팅, 메이어 바 코팅, 에어 나이프 코팅 등의 공지의 도공 방법을 사용할 수 있다.The adhesive sheet of the present embodiment is characterized by forming an adhesive layer on one or both surfaces of the (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition. As the adhesive layer, an adhesive layer made of a (meth)acrylic adhesive is preferable. The method of 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, gravure coating, slot die coating, Mayer bar coating, and air knife coating can be used.
상기 점착 시트는 상기 (메타)아크릴계 수지 필름을 기재로 하여 이루어지는 광학용 필름의 적어도 한쪽 면에 점착층이 적층되어 이루어지는 점착층 형성 광학용 필름으로 해도 된다. 점착층 형성 광학용 필름은 액정 표시 장치, 터치 패널, 전자 종이, 유기 EL 등의 각종 표시 장치에 있어서의 광학용 필름의 첩합에 사용할 수 있다. 광학용 필름의 첩합에 사용되는 점착층의 점착면은 이형 필름을 사용하여 보호해도 된다. 이형 필름에는, 점착층의 점착면과 합쳐지는 측의 면에 실리콘계, 불소계 이형제 등에 의해 이형 처리가 실시되어도 된다.The pressure-sensitive adhesive sheet may be an optical film for forming 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 film for adhesive layer formation optics can be used for bonding of optical films in various display devices, such as a liquid crystal display device, a touch panel, electronic paper, and organic EL. The adhesive surface of the adhesive layer used for bonding of the optical film may be protected using a release film. The release film may be subjected to a release treatment with a silicone-based or fluorine-based releasing agent or the like on the side of the adhesive layer on the side to be joined with the adhesive surface.
상기 점착 시트는 유리, 광학용 필름, 광학용 부재 등의 피착체의 표면을 보호하기 위해, 상기 점착층을 개재하여 첩합되는 표면 보호 필름을 구성해도 된다. 표면 보호 필름을 피착체에 첩합한 상태에서 피착체의 광학 특성, 이물질의 유무 등을 광학적으로 검사할 수 있다. 또한, 피착체를 제품에 탑재하는 단계에서는, 표면 보호 필름을 피착체로부터 박리하여 제거할 수 있다.In order to protect the surface of an adherend, such as glass, an optical film, and an optical member, the said adhesive sheet may comprise a surface protection film bonded through the said adhesive layer. In the state where the surface protection film is adhered to the adherend, optical properties of the adherend, the presence or absence of foreign substances, and the like can be optically inspected. In addition, in the step of mounting the adherend on the product, the surface protective film can be peeled off and removed from the adherend.
본 실시형태의 편광 필름은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 상기 (메타)아크릴계 수지 필름을, 편광자의 한쪽 면 또는 양면에 형성하여 이루어지는 것을 특징으로 한다. 상기 편광자의 보호층의 표면에 실시되어 있는 표면 처리가, 미처리, AG 처리, LR 처리, AR 처리, AG-LR 처리, AG-AR 처리로 이루어지는 군으로부터 선택되는 적어도 1종 이상이어도 된다. 여기서, AG는 안티 글레어(Anti Glare), LR은 로우 리플렉션(Low Reflection), AR은 안티 리플렉션(Anti Reflection)이다.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 surfaces of a polarizer. The surface treatment applied to the surface of the protective layer of the polarizer may be at least one or more selected from the group consisting of untreated, AG treatment, LR treatment, AR treatment, AG-LR treatment, and AG-AR treatment. Here, AG stands for Anti Glare, LR stands for Low Reflection, and AR stands for Anti Reflection.
실시예Example
이하, 실시예에 의해 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be described in detail by examples.
＜(메타)아크릴계 폴리머 및 (메타)아크릴계 수지 조성물의 제조＞<Preparation of (meth)acrylic polymer and (meth)acrylic resin composition>
[실시예 1][Example 1]
교반기, 온도계, 환류 냉각기, 및 질소 도입관을 구비한 반응 장치에 질소 가스를 도입하여, 반응 장치 내의 공기를 질소 가스로 치환했다. 그 후, 반응 장치에 메틸메타크릴레이트 95중량부, 메틸아크릴레이트 5중량부, 8-히드록시옥틸아크릴레이트 3.0중량부와 함께 용제(초산에틸)를 첨가했다. 그 후, 중합 개시제로서 아조비스이소부티로니트릴 0.1중량부를 적하시키고, 65℃로 가열하여 소정 시간 반응시켜, 실시예 1의 (메타)아크릴계 폴리머 용액을 얻었다. 이 (메타)아크릴계 폴리머 용액에 포함되는 (메타)아크릴계 폴리머의 중량 평균 분자량(Mw)을 측정한 결과, 20만이었다. 실시예 1의 (메타)아크릴계 폴리머 용액에 대해, 코로네이트 HX(헥사메틸렌디이소시아네이트 화합물의 이소시아누레이트체) 3.0중량부를 첨가하고 교반 혼합하여, 실시예 1의 (메타)아크릴계 수지 조성물을 얻었다.Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and air in the reaction apparatus was replaced with nitrogen gas. Then, a solvent (ethyl acetate) was added to the reaction apparatus together 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 parts by weight of azobisisobutyronitrile was added dropwise as a polymerization initiator, heated to 65° C., and reacted for a predetermined time to obtain a (meth)acrylic polymer solution of Example 1. When the weight average molecular weight (Mw) of the (meth)acrylic polymer contained in this (meth)acrylic polymer solution was measured, it was 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 stirred and mixed to obtain a (meth)acrylic resin composition of Example 1. .
[실시예 2∼5 및 비교예 1∼2][Examples 2 to 5 and Comparative Examples 1 to 2]
실시예 1의 (메타)아크릴계 폴리머 및 (메타)아크릴계 수지 조성물의 조성을 각각, 표 1의 기재와 같게 한 것 이외에는, 실시예 1과 동일하게 하여, 실시예 2∼5 및 비교예 1∼2의 (메타)아크릴계 폴리머 및 (메타)아크릴계 수지 조성물을 얻었다. 실시예 2∼5 및 비교예 1∼2의 (메타)아크릴계 폴리머의 중량 평균 분자량(Mw)은 표 1에 나타내는 바와 같다.In the same manner as in Example 1, except that the composition of the (meth)acrylic polymer and the (meth)acrylic resin composition of Example 1 was the same as described in Table 1, respectively, Examples 2 to 5 and Comparative Examples 1 to 2 A (meth)acrylic polymer and a (meth)acrylic resin composition were obtained. The weight average molecular weight (Mw) of the (meth)acrylic polymer of Examples 2 to 5 and Comparative Examples 1 to 2 is as shown in Table 1.
[비교예 3][Comparative Example 3]
용융 압출법에 의해 제조된 시판의 PMMA 필름(두께: 80㎛)을 용제로서 메틸에틸케톤(MEK)에 용해하고, PMMA 필름에 포함되는 폴리머의 중량 평균 분자량(Mw)을 측정한 결과, 30만이었다.A commercially available PMMA film (thickness: 80 µm) prepared by the 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. Done.
또한, 표 1에 사용한 (A)∼(C)의 각 성분의 약기호 화합물명을 표 2에 나타낸다. 한편, (C)군의 가교제에 있어서, 코로네이트(등록상표) HX 및 동 HL은 토소 주식회사의 상품명이고, 타케네이트(등록상표) D-140N은 미츠이 화학 주식회사의 상품명이며, TETRAD(등록상표)-X는 미츠비시 가스 화학 주식회사의 상품명이다.In addition, the abbreviated symbol compound name of each component of (A)-(C) used in Table 1 is shown in Table 2. On the other hand, in the crosslinking agent of group (C), Coronate (registered trademark) HX and the same HL are brand names of Tosoh Corporation, and Takenate (registered trademark) D-140N is a brand name of Mitsui Chemicals Corporation, and TETRAD (registered trademark) -X is a brand name of Mitsubishi Gas Chemical Co., Ltd.
＜(메타)아크릴계 수지 필름의 제작＞<Production of (meth)acrylic resin film>
실시예 1∼5 및 비교예 1∼2의 (메타)아크릴계 수지 조성물을 용액 캐스트법에 따라 수지 필름상으로 제막하고, 용제의 건조 및 가교제의 경화에 적합한 온도 조건으로 하여 가열 건조 및 가교시켜, 실시예 1∼5 및 비교예 1∼2의 (메타)아크릴계 수지 필름을 얻었다. 각 필름의 두께를 표 3에 나타낸다.The (meth)acrylic resin composition of Examples 1 to 5 and Comparative Examples 1 to 2 was formed into a resin film according to the solution casting method, and heated and dried and crosslinked under temperature conditions suitable for drying of the solvent and curing of the crosslinking agent, The (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.
또한, 비교예 3의 (메타)아크릴계 수지 필름으로는, 상기와 같이, 용융 압출법에 의해 제조된 시판의 PMMA 필름(두께: 80㎛)을 사용했다.In addition, as the (meth)acrylic resin film of Comparative Example 3, a commercially available PMMA film (thickness: 80 µm) manufactured by the melt extrusion method as described above was used.
＜(메타)아크릴계 수지 필름의 시험 방법 및 평가＞<Test method and evaluation of (meth)acrylic resin film>
실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름을 이하의 시험 방법에 따라 평가했다.The (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated according to the following test methods.
＜내절성＞<heat resistance>
실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름으로부터 시험편을 제작한 후, JIS P8115(종이 및 판지-내절 강도 시험 방법-MIT 시험기법)에 준거하고, 내절도 시험 장치(제조사: 테스터 산업 주식회사, 형식: MIT 내절도 시험 장치 BE-201)를 이용하여 내절성 시험을 행하고, 시험편이 파단될 때까지의 왕복 절곡 횟수(내절 횟수)를 측정했다.After preparing a test piece from the (meth)acrylic resin film of Examples 1 to 5 and Comparative Examples 1 to 3, in conformity with JIS P8115 (paper and cardboard-resistance strength test method-MIT test method), a cut resistance test apparatus ( Manufacturer: Tester Industrial Co., Ltd., model: MIT cut resistance test apparatus BE-201) was used to perform a cut resistance test, and the number of reciprocating bendings (number of cuts) until the test piece was broken was measured.
＜내용제성(겔분율)＞＜solvent resistance (gel fraction)＞
내용제성 시험 방법으로서, 하기와 같이 (메타)아크릴계 수지 필름의 시험편을 용제의 액 중에 소정 시간에 걸쳐 침지한 후, 상기 용제에 용출하지 않고 불용분(잔사)으로서 남은 (메타)아크릴계 수지 필름의 비율(이른바, 겔분율)을 측정하여, 내용제성을 시험했다.As a solvent resistance test method, after immersing a test piece of a (meth)acrylic resin film in a solution of a solvent for a predetermined period of time as follows, the (meth)acrylic resin film remaining as an insoluble matter (residue) without eluting in the solvent The ratio (so-called gel fraction) was measured and tested for solvent resistance.
실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름으로부터 시험편을 제작하고, 시험편의 질량을 정확하게 측정하고, 메틸에틸케톤(MEK) 중에 24hr 침지한 후, 200메시의 철망으로 여과했다. 그 후, 여과물을 온도 100℃에서 1hr 건조하여 얻어지는 잔사의 질량을 정확하게 측정하고, 이하의 식으로부터 내용제성 시험 방법으로서, 용제에 대한 침지에 의한 겔분율(％)을 측정했다.A test piece was prepared from the (meth)acrylic resin film of Examples 1 to 5 and Comparative Examples 1 to 3, the mass of the test piece was accurately measured, immersed in methyl ethyl ketone (MEK) for 24 hours, and then filtered through a 200 mesh wire mesh. did. Thereafter, the mass of the residue obtained by drying the filtrate at a temperature of 100° C. for 1 hour was accurately measured, and the gel fraction (%) by immersion in a solvent was measured as a solvent resistance test method from the following equation.
겔분율(％)＝불용분(잔사)질량(g)／필름(시험편)질량(g)×100 Gel fraction (%) = Insoluble content (residue) mass (g) / Film (test piece) mass (g) × 100
＜내파단성(인장 파단 강도), 파단 신장률＞<Break resistance (tensile breaking strength), breaking elongation>
실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름으로부터 시험편을 제작하고, 인장 시험 장치(제조사: 주식회사 시마즈 제작소, 형식: AGS-X)를 이용하여 측정하고, 시험편이 파단될 때까지의 내파단성(인장 파단 강도(MPa)) 및 파단 신장률(％)의 값을 구했다.A test piece was prepared from the (meth)acrylic resin film of Examples 1 to 5 and Comparative Examples 1 to 3, and measured using a tensile test apparatus (manufacturer: Shimadzu Corporation, type: AGS-X), and the test piece was broken. The values of fracture resistance (tensile fracture strength (MPa)) and elongation at fracture (%) were determined.
＜위상차＞<Phase difference>
실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름의 면내 위상차(Re) 값(㎚)을, 위상차 측정 장치(제조사: 오지 계측 기기 주식회사, 형식: KOBRA-HBPR/SPC)를 이용하여 측정했다. 위상차의 측정 파장은 예를 들면, 450∼550㎚ 등의 가시 영역에서 적절히 선택할 수 있다. Re값은 면내의 굴절률이 최대가 되는 방향을 x축(지상축), 이와 직교하는 방향을 y축(진상축)으로 할 때, x축 방향의 굴절률 nx와, y축 방향의 굴절률 ny와, 필름의 막두께 d로부터, 다음의 식에 의해 산출된다.The in-plane retardation (Re) value (nm) of the (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 3 was measured using a retardation measuring device (manufacturer: Oji Measuring Instruments Co., Ltd., format: KOBRA-HBPR/SPC). It was measured using. The measurement wavelength of the phase difference can be appropriately selected in a visible region such as 450 to 550 nm, for example. Re value is the refractive index n x in the x-axis direction and the refractive index n y in the y-axis direction when the x-axis (ground axis) is the direction in which the in-plane refractive index is maximum, and the y-axis (fast axis) is the direction orthogonal thereto. And, from the film thickness d of the film, it is calculated by the following equation.
면내 위상차 Re＝(nx－ny)×d In-plane retardation Re=(n x- n y )×d
여기서, 필름의 막두께 d는 면내 위상차 Re와 동일하게 ㎚ 단위인 점에서, 필름 두께(㎛)의 1000배이다.Here, the film thickness d of the film is 1000 times the film thickness (µm) in terms of the unit of nm as in the in-plane retardation Re.
표 3에 실시예 1∼5 및 비교예 1∼3의 (메타)아크릴계 수지 필름에 대한 평가 결과를 나타낸다.Table 3 shows the evaluation results for the (meth)acrylic resin films of Examples 1 to 5 and Comparative Examples 1 to 3.
실시예 1∼5의 (메타)아크릴계 수지 필름은 두께가 40㎛ 이하인 박막으로 제막된 것이며, 내절성이 50회 이상, 내파단성(인장 파단 강도)이 50MPa 이상, 파단 신장률이 9∼12％, 내용제성(겔분율)이 93％ 이상이며, 어느 특성도 우수한 것이었다.The (meth)acrylic resin film of Examples 1 to 5 was formed into a thin film having a thickness of 40 μm or less, has a cutting resistance of 50 or more times, a breaking resistance (tensile breaking strength) of 50 MPa or more, and a breaking elongation of 9 to 12%, Solvent resistance (gel fraction) was 93% or more, and all properties were excellent.
이와 같이, 실시예 1∼5의 (메타)아크릴계 수지 필름에서는, 본 발명의 과제를 해결할 수 있음이 실증되었다.Thus, in the (meth)acrylic resin film of Examples 1-5, it was demonstrated that the subject of this invention can be solved.
비교예 1의 (메타)아크릴계 수지 필름은 (메타)아크릴계 폴리머가 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트로서 MMA만을 공중합한 것이며, MMA 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트를 공중합하지 않기 때문인지, 내절성이 매우 낮고, 파단 신장률이 낮았다.In the (meth)acrylic resin film of Comparative Example 1, the (meth)acrylic polymer is an alkyl (meth)acrylate having an alkyl group having C1 to C14 carbon atoms, and is copolymerized with only MMA, and the Tg of a homopolymer other than MMA is 0°C or higher. And the C1-C14 alkyl (meth)acrylate of the alkyl group was not copolymerized, or the cutting resistance was very low and the elongation at break was low.
비교예 2의 (메타)아크릴계 수지 필름은 (메타)아크릴계 수지 조성물이 가교제를 함유하지 않기 때문인지, 내절성 및 내용제성(겔분율)이 매우 낮았다.The (meth)acrylic resin film of Comparative Example 2 was because the (meth)acrylic resin composition did not contain a crosslinking agent, and had very low cutting resistance and solvent resistance (gel fraction).
비교예 3의 (메타)아크릴계 수지 필름은 용융 압출법에 의해 제조된 수지 필름이나, 내절성 및 내용제성(겔분율)이 실시예 1∼5에 의한 (메타)아크릴계 수지 필름에 비해 매우 낮은 것이 판명되었다. 한편, 비교예 3의 (메타)아크릴계 수지 필름의 두께가 20㎛라고 가정하면, Re의 값은 두께의 비율(20/80)에 따라, 1/4의 값이 되나, 그럼에도 Re값이 큰 점에서, 복굴절률(nx－ny)의 값 자체가 큰 것으로 생각된다.The (meth)acrylic resin film of Comparative Example 3 is a resin film prepared by the melt extrusion method, but the cutting resistance and solvent resistance (gel fraction) are very low compared to the (meth)acrylic resin film of Examples 1-5. It turned out. On the other hand, assuming that the thickness of the (meth)acrylic resin film of Comparative Example 3 is 20 μm, the value of Re becomes a value of 1/4 according to the ratio of the thickness (20/80), but the Re value is still large. In, it is considered that the value of the birefringence (n x- n y) itself is large.
이상과 같이, 비교예 1∼3의 (메타)아크릴계 수지 필름에서는, 본 발명의 과제인 내절성, 내파단성(인장 파단 강도), 파단 신장률, 내용제성(겔분율)이 우수한 (메타)아크릴계 수지 필름을 제공하는 것을 해결할 수 없었다.As described above, in the (meth)acrylic resin film of Comparative Examples 1 to 3, the (meth)acrylic resin having excellent cutting resistance, fracture resistance (tensile breaking strength), breaking elongation, and solvent resistance (gel fraction), which are the subject of the present invention. Couldn't solve the provision of the film.
본 발명의 (메타)아크릴계 수지 조성물 및 이를 사용한 (메타)아크릴계 수지 필름은 종래의 용융 압출법에 의해 얻어진 (메타)아크릴계 수지 필름과 비교하면, 특히, 박막화, 내절성, 내용제성(겔분율)의 점에 있어서 우수한 특성을 갖는 점에서, 디스플레이 등 각종 광학 기기의 박형화 및 내구성 향상에 효과를 발휘하는 것을 기대할 수 있기 때문에, 산업상의 이용 가치가 크다.The (meth)acrylic resin composition of the present invention and the (meth)acrylic resin film using the same are compared with the (meth)acrylic resin film obtained by the conventional melt extrusion method, in particular, thinning, cutting resistance, solvent resistance (gel fraction) Since it has excellent properties in terms of, it can be expected to exert an effect on reducing the thickness and improving the durability of various optical devices such as displays, and thus has great industrial use value.
Claims (6)
상기 (메타)아크릴계 폴리머가
메틸메타크릴레이트 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계 100중량부와,
상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계 1.0∼20.0중량부를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머인 것을 특징으로 하는 (메타)아크릴계 수지 조성물.As a (meth)acrylic resin composition containing a (meth)acrylic polymer and a crosslinking agent,
The (meth)acrylic polymer is
A total of 80 parts by weight or more of methyl methacrylate and at least one or more types of alkyl (meth)acrylates other than the methyl methacrylate, wherein the homopolymer has a Tg of 0° C. or more and the alkyl group has C1 to C14 carbon atoms. With parts by weight,
It is characterized in that it is a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of more than 100,000 and not more than 1 million by copolymerizing at least one type of copolymerizable monomer having a functional group capable of reacting with the crosslinking agent. (Meth)acrylic resin composition.
상기 (메타)아크릴계 폴리머가
(A) 메틸메타크릴레이트 80∼99중량부와, 상기 메틸메타크릴레이트 이외의, 호모폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 1∼20중량부의 합계 100중량부와,
상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머로서, (B) 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중에서 선택된 적어도 1종 이상의 모노머의 합계 1.0∼20.0중량부를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머인 것을 특징으로 하는 (메타)아크릴계 수지 조성물.The method of claim 1,
The (meth)acrylic polymer is
(A) 80 to 99 parts by weight of methyl methacrylate and at least 1 of an alkyl (meth)acrylate other than the methyl methacrylate, wherein the homopolymer has a Tg of 0° C. or higher and the alkyl group has C1 to C14 carbon atoms 100 parts by weight in total of 1 to 20 parts by weight or more,
As a copolymerizable monomer having a functional group capable of reacting with the crosslinking agent, a total of 1.0 to 20.0 parts by weight of at least one monomer selected from the monomer group consisting of (B) a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group is copolymerized. A (meth)acrylic resin composition, which is a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of more than 100,000 and 1 million or less.
상기 가교제가 에폭시 화합물, 아지리딘 화합물, 이소시아네이트 화합물로 이루어지는 화합물군에서 선택된 1종 이상인 것을 특징으로 하는 (메타)아크릴계 수지 조성물.The method according to claim 1 or 2,
The crosslinking agent (meth)acrylic resin composition, characterized in that at least one selected from the group of compounds consisting of an epoxy compound, an aziridine compound, and an isocyanate compound.
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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 |
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