KR20220020202A - (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
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- KR20220020202A KR20220020202A KR1020210095972A KR20210095972A KR20220020202A KR 20220020202 A KR20220020202 A KR 20220020202A KR 1020210095972 A KR1020210095972 A KR 1020210095972A KR 20210095972 A KR20210095972 A KR 20210095972A KR 20220020202 A KR20220020202 A KR 20220020202A
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- South Korea
- Prior art keywords
- meth
- acrylic resin
- acrylic
- weight
- resin film
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 68
- 229920005989 resin Polymers 0.000 title claims abstract description 68
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 16
- 239000011342 resin composition Substances 0.000 title description 11
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 152
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 152
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 55
- 229920001971 elastomer Polymers 0.000 claims abstract description 53
- 239000005060 rubber Substances 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 44
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 125000000524 functional group Chemical group 0.000 claims abstract description 18
- 229920001519 homopolymer Polymers 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 32
- -1 aziridine compound Chemical class 0.000 claims description 28
- 238000004132 cross linking Methods 0.000 claims description 27
- 238000005452 bending Methods 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000011258 core-shell material Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims description 4
- XFOFBPRPOAWWPA-UHFFFAOYSA-N 6-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCO XFOFBPRPOAWWPA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- FJNCXZZQNBKEJT-UHFFFAOYSA-N 8beta-hydroxymarrubiin Natural products O1C(=O)C2(C)CCCC3(C)C2C1CC(C)(O)C3(O)CCC=1C=COC=1 FJNCXZZQNBKEJT-UHFFFAOYSA-N 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 2
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 abstract description 14
- 239000010408 film Substances 0.000 description 174
- 239000000243 solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 238000001125 extrusion Methods 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 14
- 239000004926 polymethyl methacrylate Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 12
- 239000012788 optical film Substances 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 229920000800 acrylic rubber Polymers 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 3
- YPMOAQISONSSNL-UHFFFAOYSA-N 8-hydroxyoctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCO YPMOAQISONSSNL-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene 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
- 230000001588 bifunctional effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 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
- 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
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101150096839 Fcmr gene Proteins 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 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
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920001400 block copolymer Polymers 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
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 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 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 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
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-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
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-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 compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 description 1
- TUAJZTAVXLCEGA-UHFFFAOYSA-N 1-hydroxyethyl prop-2-enoate Chemical compound CC(O)OC(=O)C=C TUAJZTAVXLCEGA-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
- 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
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
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- FYAMXEPQQLNQDM-UHFFFAOYSA-N Tris(1-aziridinyl)phosphine oxide Chemical compound C1CN1P(N1CC1)(=O)N1CC1 FYAMXEPQQLNQDM-UHFFFAOYSA-N 0.000 description 1
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- General Physics & Mathematics (AREA)
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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 forming a (meth)acrylic resin film and the like, and 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 device parts such as electronic devices, home appliances, automobile interior and exterior parts, and building members, in terms of high transparency, heat workability, weather resistance, and chemical resistance, (meth)acrylic resins film is being used.
또한, 근래에는 고투명성, 내후성 등이 우수한 점에서, (메타)아크릴계 수지 필름이 광학용 필름으로서 사용되고 있다.Moreover, in recent years, since it is excellent in high transparency, weather resistance, etc., the (meth)acrylic-type 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 for producing a (meth)acrylic resin film (PMMA film) made of polymethyl methacrylate (PMMA) resin, a method of forming a PMMA resin by melt extrusion method 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 표면 보호층의 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, 표면 보호층의 형성에 사용하는 도장 대체 아크릴 수지 필름으로서, 바람직하게 사용할 수 있다고 하고 있다.For example, Patent Document 1 discloses an acrylic resin film suitable for use in a member for integrating an acrylic resin film and a molded resin, and particularly a coating replacement acrylic resin film suitable for forming a surface protective layer. The acrylic resin film which concerns on invention described in patent document 1 combines the ultraviolet absorber and lubricant added to an acrylic resin film in a specific kind, and is making these components into specific content further. For this reason, in patent document 1, it is said that it can use suitably as a coating replacement 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 for improving impact resistance, which is an essential defect of acrylic resins, without containing a rubber-containing graft copolymer that causes the uniquely beautiful color tone and transparency to be impaired, which are advantages of acrylic resins. In 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 the melt extrusion method, decomposition gas or bleed-out material generated by thermal decomposition of the graft copolymer, It is said that the problem that cooling rolls, such as a cast roll, are contaminated and productivity falls can be solved.
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 a resin composition melted in a melt extruder The acrylic resin film was formed into a film by the melt extrusion method which extrudes and performs by T-die. Moreover, in Examples 1-6 of patent document 1, the acrylic resin film whose film thickness is 50-125 micrometers is obtained. However, since the acrylic resin film which concerns on invention described in patent document 1 is a resin film formed into a film by the melt-extrusion method, it had the problem that it was difficult to obtain the thin resin film whose film thickness is 40 micrometers 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 in that the process for obtaining the graft copolymer takes a long time because the graft copolymer is gradually completed by performing the graft polymerization reaction in 3 to 4 steps. Moreover, in Examples 6-8 which manufactured the acrylic resin film by the melt-extrusion method of patent document 2, the film thickness of the acrylic resin film obtained without extending|stretching is 80 micrometers, The film thickness of 40 micrometers or less without extending|stretching is a thin resin No 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, the method of forming a PMMA resin into a film by the solution casting method which is a more convenient film forming method of a resin film compared with the melt-extrusion method, and has the advantage of being able to thin film was calculated|required. The present inventors earnestly studied the method of forming a PMMA resin into a film by the solution casting method. As a result, it was found that by using a specific PMMA resin composition, a PMMA resin film having excellent physical properties equal to or higher than that produced by the melt extrusion method can be obtained even when a film is formed by the solution casting method, and the present invention can 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 가능하지만, 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 고점도이고, 제막 공정에서의 작업성이 양호하지 않다는 문제가 있었다.In the case of the method of forming a (meth)acrylic-type resin film into a film by the conventional melt-extrusion method, it was difficult to thin it to the thickness of 40 micrometers or less. On the other hand, in the case of the method of forming a (meth)acrylic resin film by the solution casting method, it is possible to thin it to a thickness of 40 μm or less, but as a physical property of the obtained (meth)acrylic resin film, solvent resistance performance is improved. The problem was that it was difficult. In addition, in the solution casting method, since it is necessary to make the weight average molecular weight of the uncrosslinked PMMA resin contained in the (meth)acrylic resin composition a large value of 1 million or more, the solution of the (meth)acrylic resin composition has a high viscosity and there was a problem that the workability in the film forming process 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, 신장성, 내용제성이 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, wherein a molded article such as a resin film formed into a film is excellent in fold resistance, fracture resistance, extensibility, and solvent resistance (meth) ) It is an object to provide an acrylic resin composition and a (meth)acrylic resin film.
한편, 제막한 (메타)아크릴계 수지 필름의 각종 물성은, 예를 들면, 「내절성」에 대해서는 「내절 횟수」의 측정, 「내파단성」에 대해서는 「인장 파단 강도」의 측정, 「신장성」에 대해서는 「파단 신장률」의 측정, 「내용제성」에 대해서는 「겔분율」의 측정을 각각 행함으로써 판정하는 것이 가능하다.On the other hand, various physical properties of the (meth)acrylic resin film formed into a film are, for example, measurement of "number of times of bending" for "fold resistance", measurement of "tensile breaking strength" for "break resistance", and "extensibility" It is possible to determine by performing the measurement of "elongation at break" and the measurement of "gel fraction" about "solvent resistance", respectively.
본 발명자들은 상기 과제를 해결하기 위해 예의 검토한 결과, (메타)아크릴계 폴리머와, 고무 화합물과, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서, 상기 (메타)아크릴계 폴리머가 MMA(메틸메타크릴레이트)와, 상기 MMA 이외의, 호모 폴리머의 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, 신장성, 내용제성이 우수하며, 특히 내절성, 신장성이 현격히 향상하는 것을 알아내어, 본 발명을 완성시킬 수 있었다. 즉, 본 발명은 특정 (메타)아크릴계 폴리머와, 고무 화합물과, 가교제를 함유하는 (메타)아크릴계 수지 조성물을 가교시킨 수지층으로 이루어지는 (메타)아크릴계 수지 필름을, 용액 캐스트법에 의해 얻는 것을 기술 사상으로 하고 있다.As a result of intensive studies of the present inventors in order to solve the above problems, as a (meth)acrylic resin composition containing a (meth)acrylic polymer, a rubber compound, and a crosslinking agent, the (meth)acrylic polymer is MMA (methyl methacrylate) ), and the Tg of the homopolymer other than MMA is 0 ° C. or higher, and the alkyl (meth)acrylate having C1-C14 carbon atoms in the alkyl group, and at least one copolymerizable monomer having a functional group in a specific ratio By setting it as a (meth)acrylic polymer consisting of a copolymerized copolymer, the (meth)acrylic resin film obtained by the solution casting method using this (meth)acrylic resin composition has fold resistance, fracture resistance, extensibility, and solvent resistance. It was excellent, and it discovered that especially the fold resistance and extensibility improved markedly, and was able to complete this invention. That is, the present invention describes obtaining a (meth)acrylic resin film comprising a resin layer obtained by crosslinking a specific (meth)acrylic polymer, a rubber compound, and a (meth)acrylic resin composition containing a crosslinking agent by a solution casting method I do it with thought.
상기 과제를 해결하기 위해, 본 발명은 (메타)아크릴계 폴리머와, 고무 화합물과, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서, 상기 (메타)아크릴계 폴리머가 (A) 메틸메타크릴레이트 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상과의 합계 100중량부와, (B) 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 폴리머이며, 상기 (A)의 합계 100중량부에 대해, 상기 고무 화합물을 1.0∼25.0중량부의 비율로 함유하여 이루어지는 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, a rubber compound, and a crosslinking agent, wherein the (meth)acrylic polymer is (A) 80 parts by weight of methyl methacrylate A total of 100 parts by weight of at least one or more alkyl (meth)acrylates having a Tg of 0° C. or higher and an alkyl group having C1-C14 carbon atoms, other than methyl methacrylate, ( B) a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of greater than 100,000 and not more than 1,000,000 obtained by copolymerizing 1.0 to 20.0 parts by weight of at least one copolymerizable monomer having a functional group capable of reacting with the crosslinking agent, (A) provides a (meth)acrylic resin composition comprising the rubber compound in a proportion of 1.0 to 25.0 parts by weight with respect to 100 parts by weight in total.
상기 (메타)아크릴계 폴리머가 (A) 메틸메타크릴레이트 80∼99중량부와, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 1∼20중량부의 합계 100중량부와, (B) 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머로서, 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중으로부터 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 contains (A) 80 to 99 parts by weight of methyl methacrylate and an alkyl ( A total of 100 parts by weight of at least one or more 1 to 20 parts by weight of meth) acrylate and (B) a copolymerizable monomer having a functional group capable of reacting with the crosslinking agent, a copolymerizable monomer having a hydroxyl group and a carboxyl group copolymerizable It is preferably a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of more than 100,000 and not more than 1,000,000 obtained by copolymerizing 1.0 to 20.0 parts by weight of a total of at least one or more monomers selected from the group consisting of monomers.
상기 가교제가 에폭시 화합물, 아지리딘 화합물, 이소시아네이트 화합물로 이루어지는 화합물군으로부터 선택된 1종 이상인 것이 바람직하다.It is preferable that the said crosslinking agent is 1 or more types selected from the compound group which consists of an epoxy compound, an aziridine compound, and an isocyanate compound.
상기 고무 화합물이 코어부에 SBR 또는 부타디엔을 주체로 한 고무층과, 쉘부에 메틸메타크릴레이트를 주체로 한 아크릴층으로 형성된 코어쉘 입자이고, 상기 코어쉘 입자의 체적 기준 평균 입자 직경이 0.05∼2.0㎛인 것이 바람직하다.The rubber compound is a core-shell particle formed of a rubber layer mainly composed of SBR or butadiene in the core portion and an acrylic layer mainly composed of methyl methacrylate in the shell portion, and the volume-based average particle diameter of the core-shell particles is 0.05 to 2.0 It is preferable that it is micrometer.
상기 수산기를 갖는 공중합 가능한 모노머가 8-히드록시옥틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, N-히드록시(메타)아크릴아미드, N-히드록시메틸(메타)아크릴아미드, N-히드록시에틸(메타)아크릴아미드로 이루어지는 화합물군으로부터 선택된 적어도 1종 이상이고, 또한 8-히드록시옥틸메타크릴레이트, 6-히드록시헥실메타크릴레이트, 4-히드록시부틸메타크릴레이트, 2-히드록시에틸메타크릴레이트, 2-히드록시에틸아크릴레이트로 이루어지는 화합물군으로부터 선택된 적어도 1종 이상을 포함하는 것이 바람직하다.The copolymerizable monomer having a hydroxyl group is 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylic It is at least one selected from the group consisting of lactate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide, and 8-hydroxy at least one selected from the group consisting of octyl methacrylate, 6-hydroxyhexyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate; It is preferable to include
또한, 본 발명은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 두께가 10∼50㎛의 (메타)아크릴계 수지 필름으로서, 상기 (메타)아크릴계 수지 필름의 면내 위상차 Re가 1.0㎚ 이하, 헤이즈값이 3.0％ 이하인 것을 특징으로 하는 (메타)아크릴계 수지 필름을 제공한다.In addition, the present invention is a (meth)acrylic resin film having a thickness of 10 to 50 μm, which is a resin layer formed by crosslinking the (meth)acrylic resin composition, wherein the (meth)acrylic resin film has an in-plane retardation Re of 1.0 nm or less, It provides a (meth)acrylic resin film characterized in that the haze value is 3.0% or less.
또한, 본 발명은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 (메타)아크릴계 수지 필름으로서, 상기 (메타)아크릴계 수지 필름의 내용제성으로서의 겔분율이 90％ 이상이며, 또한 내절성으로서의 내절 횟수(JIS P8115)가 100회 이상, 또한 신장성으로서의 파단 신장률이 10％ 이상인 것을 특징으로 하는 (메타)아크릴계 수지 필름을 제공한다.In addition, the present invention is a (meth)acrylic resin film, which is a resin layer formed by crosslinking the (meth)acrylic resin composition, wherein the (meth)acrylic resin film has a gel fraction as solvent resistance of 90% or more, and also has fold resistance. Provided is a (meth)acrylic resin film characterized in that the number of times of bending (JIS P8115) is 100 or more, and the elongation at break as extensibility is 10% or more.
또한, 본 발명은 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 (메타)아크릴계 수지 필름의 편면 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 side or both sides of the (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 편면 또는 양면에 형성하여 이루어지는 것을 특징으로 하는 편광 필름을 제공한다.Further, the present invention provides a polarizing film 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.
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, 신장성, 내용제성이 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 resin film having a thin film thickness, a molded article such as a resin film formed into a film is excellent in fold resistance, fracture resistance, extensibility, and solvent resistance A (meth)acrylic resin composition and a (meth)acrylic resin film can be provided.
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 time, the (meth)acrylic resin remaining as an insoluble content (residue) without eluting into the solvent 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 40 µm or less unless uniaxial or biaxial stretching processing is performed after the resin film is formed. there was no On the other hand, if 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 manufactured using only the solution casting method, and the manufacturing process becomes simpler and , it is possible to reduce the cost of the manufacturing apparatus.
이하, 바람직한 실시형태에 기초하여 본 발명을 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on preferable embodiment.
본 실시형태의 (메타)아크릴계 수지 조성물은 (메타)아크릴계 폴리머와, 고무 화합물과, 가교제를 함유하는 (메타)아크릴계 수지 조성물로서, 상기 (메타)아크릴계 폴리머가 (A) 메틸메타크릴레이트 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상과의 합계 100중량부와, (B) 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 폴리머이며, 상기 (A)의 합계 100중량부에 대해, 상기 고무 화합물을 1.0∼25.0중량부의 비율로 함유하여 이루어지는 것을 특징으로 한다.The (meth)acrylic resin composition of this embodiment is a (meth)acrylic resin composition containing a (meth)acrylic polymer, a rubber compound, and a crosslinking agent, wherein the (meth)acrylic polymer is (A) methyl methacrylate 80 weight 100 parts by weight or more and a total of 100 parts by weight of at least one or more alkyl (meth)acrylates having a Tg of 0° C. or higher and an alkyl group having C1-C14 carbon atoms other than methyl methacrylate; (B) a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of more than 100,000 and 1 million or less obtained by copolymerizing 1.0 to 20.0 parts by weight of at least one copolymerizable monomer having a functional group capable of reacting with the crosslinking agent, It is characterized by containing the said rubber compound in the ratio of 1.0-25.0 weight part with respect to a total of 100 weight part of said (A).
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 호모 폴리머의 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, 호모 폴리머의 Tg를 가리키는 경우가 있다.The (meth)acrylic polymer used in the (meth)acrylic resin composition of this embodiment has an alkyl (meth)acrylate having C1-C14 carbon atoms in the alkyl group as a main component, and in particular, methyl methacrylate (MMA) as a main component It is preferable that it is a (meth)acrylic-type polymer to do. The alkyl group of the alkyl (meth)acrylate may be either acyclic (linear, branched) or cyclic (monocyclic, polycyclic). It is preferable that the said (meth)acrylic-type polymer is a copolymer containing at least 2 or more types of C1-C14 alkyl (meth)acrylate of carbon number of an alkyl group. The (meth)acrylic polymer is preferably a copolymer obtained by copolymerizing at least one alkyl (meth)acrylate having a homopolymer Tg of 0° C. or higher and an alkyl group having C1-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 compound group that accounts for 50% by weight or more of the (meth)acrylic polymer in a total of two or more types means That is, in 100 parts by weight of the (meth)acrylic polymer, the main component occupies a proportion of 50 parts by weight or more. In addition, in the following description, when simply referring to Tg for a monomer, it may refer to Tg of a homopolymer.
상기 (메타)아크릴계 폴리머에 있어서, 호모 폴리머의 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 화합물군으로부터 선택된 1종 이상을 들 수 있다. 여기서, (메타)아크릴레이트는 아크릴레이트 또는 메타크릴레이트의 적어도 한쪽을 의미한다.In the (meth)acrylic polymer, the Tg of the homopolymer is 0° C. or higher, and the alkyl (meth)acrylate having C1-C14 carbon atoms in the alkyl group is 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 One selected from the group of compounds consisting of methacrylate, n-hexyl methacrylate, isohexyl methacrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate more can be mentioned. Here, (meth)acrylate means at least one of an acrylate or a methacrylate.
상기 (메타)아크릴계 폴리머에 있어서, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트로는, 알킬기의 탄소수가 C1∼C6인 알킬(메타)아크릴레이트가 바람직하며, 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 화합물군으로부터 선택된 1종 이상인 것이 특히 바람직하다.In the above (meth)acrylic polymer, the Tg of the homopolymer is 0°C or higher, and the alkyl (meth)acrylate having C1-C14 carbon atoms in the alkyl group is an alkyl (meth)acryl group having C1-C6 carbon atoms. A rate is preferable, and the alkyl (meth)acrylate whose carbon number of an alkyl group is C1-C4 is more preferable. Moreover, in the C1-C4 alkyl (meth)acrylate of C1-C4 alkyl groups other than methyl methacrylate, methyl acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n- At least one selected from the group consisting of butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl acrylate and t-butyl methacrylate is particularly preferable.
또한, 상기 (메타)아크릴계 폴리머에 있어서, (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상과의 합계 100중량부 중, 메틸메타크릴레이트 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이며, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계를 20중량부 이하의 비율로 함유하는 것이 바람직하고, 메틸메타크릴레이트 80∼99중량부와, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이며, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 합계를 1∼20중량부의 비율로 함유하는 것이 보다 바람직하다.Further, in the (meth)acrylic polymer, (A) methyl methacrylate and the homopolymer other than methyl methacrylate have a Tg of 0° C. or higher, and an alkyl (meth) having C1-C14 carbon atoms in the alkyl group. ) In a total of 100 parts by weight of at least one or more acrylates, 80 parts by weight or more of methyl methacrylate and Tg of the homopolymer other than the methyl methacrylate is 0° C. or more, and the number of carbon atoms in the alkyl group is C1 It is preferable to contain the total of at least one or more types of alkyl (meth)acrylate of -C14 in a ratio 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 the total of at least one type of alkyl (meth)acrylate having a Tg of 0° C. or higher and the alkyl group having C1-C14 carbon atoms in a proportion of 1 to 20 parts by weight.
상기 (메타)아크릴계 폴리머가 상기 (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상과의 합계 100중량부에 대해, 상기 (B) 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계를 1.0∼20.0중량부의 비율로 함유하는 것이 바람직하며, 1.0∼12.0중량부의 비율로 함유하는 것이 보다 바람직하고, 1.0∼9.0중량부의 비율로 함유하는 것이 특히 바람직하다.The (meth)acrylic polymer is an alkyl (meth)acrylate in which the Tg of the homopolymer other than the (A) methyl methacrylate and the methyl methacrylate is 0° C. or higher, and the carbon number of the alkyl group is C1-C14. It is preferable to contain the total of at least one type of copolymerizable monomer having a functional group capable of reacting with the (B) crosslinking agent in a ratio of 1.0 to 20.0 parts by weight with respect to 100 parts by weight in total with at least one or more of It is more preferable to contain in the ratio of 1.0-12.0 weight part, and it is especially preferable to contain it in the ratio of 1.0-9.0 weight part.
상기 (B) 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머로는, 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중으로부터 선택된 적어도 1종 이상의 모노머를 들 수 있다. 상기 (B) 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.The copolymerizable monomer having a functional group capable of reacting with the (B) crosslinking agent includes 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. (B) The copolymerizable monomer having a functional group capable of reacting with the crosslinking agent may be only a copolymerizable monomer having a hydroxyl group, may be only a copolymerizable monomer having a carboxyl group, a copolymerizable monomer having a hydroxyl group, and a copolymerizable monomer having a carboxyl group You may use both of them together.
상기 수산기를 갖는 공중합 가능한 모노머로는, 히드록시알킬(메타)아크릴레이트류 및 수산기 함유 (메타)아크릴아미드류 등으로 이루어지는 화합물군 중으로부터 선택된 적어도 1종 이상인 것이 바람직하다.The copolymerizable monomer having a hydroxyl group is preferably at least one selected from the group consisting of hydroxyalkyl (meth)acrylates and hydroxyl group-containing (meth)acrylamides.
또한, 상기 수산기를 갖는 공중합 가능한 모노머로는 구체적으로는, 8-히드록시옥틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, N-히드록시(메타)아크릴아미드, N-히드록시메틸(메타)아크릴아미드, N-히드록시에틸(메타)아크릴아미드로 이루어지는 화합물군 중으로부터 선택된 적어도 1종 이상인 것이 바람직하다.In addition, as the copolymerizable monomer having a hydroxyl group, specifically, 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- At least one selected from the group consisting of hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide more preferably.
또한, 상기 수산기를 갖는 공중합 가능한 모노머가, 8-히드록시옥틸메타크릴레이트, 6-히드록시헥실메타크릴레이트, 4-히드록시부틸메타크릴레이트, 2-히드록시에틸메타크릴레이트, 2-히드록시에틸아크릴레이트로 이루어지는 화합물군으로부터 선택된 적어도 1종 이상을 포함하는 것이 바람직하다.In addition, the copolymerizable monomer having a hydroxyl group is 8-hydroxyoctyl methacrylate, 6-hydroxyhexyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxy It is preferable to contain at least 1 type or more selected from the compound group which consists of oxyethyl acrylate.
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 중으로부터 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)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl maleic acid, carboxypolycaprolactone It is preferable that it is at least 1 sort(s) or more selected from the compound group which consists of mono(meth)acrylate, 2-(meth)acryloyloxyethyl tetrahydrophthalic acid, etc.
상기 아크릴계 폴리머는 상기 (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상과의 합계 100중량부에 대해, 상기 (B) 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머로서, 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중으로부터 선택된 적어도 1종 이상의 모노머의 합계를 1.0∼20.0중량부의 비율로 함유하는 것이 바람직하며, 1.0∼12.0중량부의 비율로 함유하는 것이 보다 바람직하고, 1.0∼9.0중량부의 비율로 함유하는 것이 특히 바람직하다.In the acrylic polymer, at least one of (A) methyl methacrylate and an alkyl (meth) acrylate having a Tg of 0° C. or higher and a C1-C14 alkyl group other than the methyl methacrylate. With respect to a total of 100 parts by weight with more than one species, at least selected from the group consisting of a copolymerizable monomer having a functional group capable of reacting with the (B) crosslinking agent, a copolymerizable monomer having a hydroxyl group, and a copolymerizable monomer having a carboxyl group It is preferable to contain the total of 1 or more types of monomer in the ratio of 1.0-20.0 weight part, It is more preferable to contain in the ratio of 1.0-12.0 weight part, It is especially preferable to contain in the ratio of 1.0-9.0 weight part.
상기 아크릴계 폴리머의 제조 방법은 특별히 한정되는 것이 아니고, 용액 중합법, 유화 중합법 등, 적절히 공지의 중합 방법이 사용 가능하다. 상기 아크릴계 폴리머는 중량 평균 분자량이 10만 초과 100만 이하의 공중합체인 것이 바람직하고, 중량 평균 분자량이 10만 초과 95만 이하의 공중합체인 것이 보다 바람직하며, 중량 평균 분자량이 10만 초과 90만 이하의 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 manufacturing method of the said acrylic polymer is not specifically limited, Well-known polymerization methods, such as a solution polymerization method and an emulsion polymerization method, can be used suitably. The acrylic polymer is preferably a copolymer having a weight average molecular weight of more than 100,000 and 1 million or less, more preferably a copolymer having a weight average molecular weight of more than 100,000 and 950,000 or less, and a weight average molecular weight of more than 100,000 and 900,000 or less It is especially preferable that it is a copolymer. When the weight average molecular weight of the acrylic polymer is 100,000 or less, it becomes difficult to obtain a molded article such as a (meth)acrylic resin film having excellent physical properties even if the (meth)acrylic resin composition is crosslinked. When the weight average molecular weight of the said acrylic polymer is larger than 1 million, the solution of a (meth)acrylic-type resin composition will become high viscosity, and workability|operativity of a film forming process is not favorable.
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.As said crosslinking agent, the compound which has the functional group which the said (meth)acrylic-type polymer has, and the crosslinkable functional group which can crosslinking-react is mentioned. The crosslinking agent is preferably a compound in which a crosslinking reaction hardly occurs at room temperature (generally 5 to 35° C.) from the viewpoint of storage stability of the (meth)acrylic resin composition, and the crosslinking reaction is initiated when heated to a predetermined temperature or higher. Do.
상기 가교제가 에폭시 화합물, 아지리딘 화합물, 이소시아네이트 화합물로 이루어지는 화합물군으로부터 선택된 1종 이상인 것이 바람직하다. 본 실시형태의 (메타)아크릴계 수지 조성물은 상기 (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상과의 합계 100중량부에 대해, 상기 가교제를 0.01∼10중량부의 비율로 함유하는 것이 바람직하다.It is preferable that the said crosslinking agent is 1 or more types selected from the compound group which consists of an epoxy compound, an aziridine compound, and an isocyanate compound. In the (meth)acrylic resin composition of this embodiment, the Tg of the homopolymer other than the (A) methyl methacrylate and the methyl methacrylate is 0° C. or higher, and the alkyl group having C1-C14 carbon atoms ( It is preferable to contain the said crosslinking agent in the ratio of 0.01-10 weight part with respect to a total of 100 weight part with at least 1 type or more of meth)acrylate.
상기 에폭시 화합물로 이루어지는 가교제(에폭시계 가교제)로는, 2관능 이상의 에폭시 화합물이면 특별히 한정되지 않지만, 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-based 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 1 type or more selected from the compound group which consists of diglycidyl ester of dicarboxylic acid, diglycidyl substituted amines, tetraglycidyl substituted diamine, etc. is mentioned.
상기 에폭시계 가교제 중, 폴리올류의 폴리글리시딜에테르로는 예를 들면, 에틸렌글리콜디글리시딜에테르, 프로필렌글리콜디글리시딜에테르, 네오펜틸글리콜디글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 레조르신디글리시딜에테르, 글리세롤폴리글리시딜에테르, 트리메틸올프로판폴리글리시딜에테르, 펜타에리스리톨폴리글리시딜에테르, 소르비톨폴리글리시딜에테르 등을 들 수 있다.Among the epoxy-based crosslinking agents, polyglycidyl ethers of polyols include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, polyethylene glycol diglycidyl ether, resorcinol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether Cidyl ether etc. are mentioned.
또한, 디카르복실산의 디글리시딜에스테르로는 예를 들면, 아디프산디글리시딜에스테르, 프탈산디글리시딜에스테르 등을 들 수 있다.Moreover, as diglycidyl ester of 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.Moreover, as diglycidyl-substituted amines, N,N- diglycidyl aniline, N,N- diglycidyl toluidine, etc. are mentioned, for example.
또한, 테트라글리시딜 치환 디아민류로는, 1,3-비스(N,N-디글리시딜아미노메틸)시클로헥산, N,N,N',N'-테트라글리시딜-m-자일렌디아민 등을 들 수 있다.Examples of tetraglycidyl-substituted diamines include 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) comprising the aziridine compound is not particularly limited as long as it is a bifunctional or more functional aziridine compound, a compound having two or more aziridine-based functional groups in one molecule, or the like. Examples of the aziridine-based functional group include a substituted aziridinyl group having a substituent such as a 1-aziridinyl group [-N(CH 2 ) 2 ], a 2-aziridinyl group, and a methyl group. Specific examples of the aziridine-based crosslinking agent include, for example, an addition product of a polyisocyanate compound and aziridine as shown in (1) to (2) below, and polyol polyacrylate as shown in (3) to (4) below. The addition product of a compound and aziridine, and other polyacridine compounds like the following (5)-(7) are 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)포스핀설파이드(6) tris(1-aziridinyl)phosphinesulfide
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.As the crosslinking agent (isocyanate-based crosslinking agent) composed of the isocyanate compound, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate ( At least one or more selected from the group consisting of bifunctional isocyanates (diisocyanate compounds) such as XDI) can be heard Here, as for the adduct body more than trifunctional, the adduct body of the polyol more than trivalence, such as a diisocyanate compound and trimethylol propane and glycerol, is mentioned.
상기 (메타)아크릴계 수지 조성물은 (메타)아크릴계 폴리머와, 상기 (메타)아크릴계 폴리머를 가교시키는 가교제에 추가로, 고무 화합물을 필수 성분으로서 함유한다. 본 실시형태의 (메타)아크릴계 수지 조성물은 상기 (A) 메틸메타크릴레이트와, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상과의 합계 100중량부에 대해, 상기 고무 화합물을 1.0∼25.0중량부의 비율로 함유하는 것이 바람직하며, 3.0∼20.0중량부의 비율로 함유하는 것이 보다 바람직하다.The (meth)acrylic resin composition contains a (meth)acrylic polymer and a rubber compound as an essential component in addition to a crosslinking agent for crosslinking the (meth)acrylic polymer. In the (meth)acrylic resin composition of this embodiment, the Tg of the homopolymer other than the (A) methyl methacrylate and the methyl methacrylate is 0° C. or higher, and the alkyl group having C1-C14 carbon atoms ( It is preferable to contain the said rubber compound in the ratio of 1.0-25.0 weight part with respect to a total of 100 weight part with at least 1 or more types of meth)acrylate, It is more preferable to contain in the ratio of 3.0-20.0 weight part.
상기 고무 화합물로는, 고무상의 탄성을 나타내는 중합체(폴리머)이면 특별히 한정되지 않지만, 상기 (메타)아크릴계 폴리머에 대한 분산성 또는 혼화성이 우수한 고무 화합물이 바람직하다. 예를 들면, 올레핀계 엘라스토머, 스티렌계 엘라스토머, 아크릴계 엘라스토머, 아크릴 고무, 니트릴 고무, 부타디엔계 고무, 폴리이소프렌 고무, 천연 고무 등의 비닐계 중합체로 이루어지는 고무 화합물이 바람직하다. 상기 고무 화합물은 하드 세그먼트와 소프트 세그먼트로 이루어지는 공중합체여도 되고, 예를 들면, (하드 세그먼트)-(소프트 세그먼트)-(하드 세그먼트)와 같이, 적어도 3개 이상의 블록을 갖는 블록 공중합체여도 된다.The rubber compound is not particularly limited as long as it is a polymer (polymer) exhibiting rubber-like elasticity, and a rubber compound excellent in dispersibility or miscibility with the (meth)acrylic polymer is preferable. For example, a rubber compound composed of a vinyl polymer such as an olefin elastomer, a styrene elastomer, an acrylic elastomer, an acrylic rubber, a nitrile rubber, a butadiene rubber, a polyisoprene rubber, or a natural rubber is preferable. The rubber compound may be a copolymer composed of a hard segment and a soft segment, or may be a block copolymer having at least three or more blocks such as (hard segment)-(soft segment)-(hard segment).
상기 고무 화합물은 물리 가교 또는 화학 가교에 의해 가교되어 있는 것이 바람직하다.The rubber compound is preferably crosslinked by physical crosslinking or chemical crosslinking.
물리 가교로는 예를 들면, 수소 결합, 소수 결합 등에 한하지 않고, 공유 결합에 의하지 않는 상호 작용에 의한 가교이면 특별히 한정되지 않는다. 물리 가교의 경우에는, 상온에서는 가교점이 고정되어 고온에서는 결합이 해리되고, 고무 화합물이 열가소성을 나타내는 것도 가능하다.The physical crosslinking is not limited to, for example, a hydrogen bond, a hydrophobic bond, or the like, and is not particularly limited as long as it is a crosslinking by an interaction other than a covalent bond. In the case of physical crosslinking, the crosslinking point is fixed at room temperature, the bond is dissociated at high temperature, and it is possible that the rubber compound exhibits thermoplasticity.
화학 가교로는, 가교성 모노머 또는 가교제와 같이, 비닐기, 에폭시기, 이소시아네이트기 등의 관능기를 갖는 화합물이 사용된다. 가교성 모노머를 비가교성 모노머와 공중합시켜, 가교 폴리머를 합성해도 된다. 비가교성 모노머로부터 얻어진 비가교 폴리머에 가교제를 반응시키고, 가교 폴리머를 합성해도 된다. 비가교 폴리머의 가교는 과산화물 등의 라디칼 발생제, 자외선 등의 에너지선 등을 사용하여, 폴리머 중에 공유 결합을 도입함으로써 행하는 것도 가능하다.As a chemical crosslinking, the compound which has functional groups, such as a vinyl group, an epoxy group, and an isocyanate group, is used like a crosslinking|crosslinked monomer or a crosslinking agent. A crosslinkable monomer may be copolymerized with a non-crosslinkable monomer, and a crosslinked polymer may be synthesize|combined. A crosslinking agent may be made to react with the non-crosslinked polymer obtained from a non-crosslinkable monomer, and you may synthesize|combine a crosslinked polymer. Crosslinking of the non-crosslinked polymer can also be performed by introducing a covalent bond into the polymer using a radical generator such as a peroxide or an energy ray such as ultraviolet light.
상기 올레핀계 엘라스토머로는, 프로필렌-에틸렌 공중합체, 에틸렌-1-부텐 공중합체, 에틸렌-1-헥센 공중합체, 에틸렌-1-옥텐 공중합체, 프로필렌-에틸렌-1-부텐 공중합체, 프로필렌-1-부텐 공중합체 등의 지방족 올레핀의 공중합체를 들 수 있다.Examples of the olefin-based elastomer include propylene-ethylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-ethylene-1-butene copolymer, and propylene-1. Copolymers of aliphatic olefins, such as a butene copolymer, are mentioned.
상기 스티렌계 엘라스토머로는, 스티렌-부타디엔 고무(SBR) 등의 스티렌-부타디엔 공중합체, 스티렌-이소프렌 공중합체, 스티렌-에틸렌 공중합체 등의 방향족 올레핀-지방족 올레핀의 공중합체를 들 수 있다.Examples of the styrene-based elastomer include styrene-butadiene copolymers such as styrene-butadiene rubber (SBR), styrene-isoprene copolymers, and aromatic olefin-aliphatic olefin copolymers such as styrene-ethylene copolymers.
상기 아크릴계 엘라스토머로는, (메타)아크릴산에스테르-아크릴로니트릴 공중합체, (메타)아크릴산에스테르-에틸렌 공중합체, 아크릴산에스테르-메타크릴산 에스테르 블록 공중합체 등을 들 수 있다.Examples of the acrylic elastomer include (meth)acrylic acid ester-acrylonitrile copolymer, (meth)acrylic acid ester-ethylene copolymer, and acrylic acid ester-methacrylic acid ester block copolymer.
상기 아크릴 고무로는, 아크릴산에스테르-아크릴로니트릴 공중합체, 아크릴산에스테르-클로로에틸비닐에테르 공중합체 등을 들 수 있다.As said acrylic rubber, an acrylic acid ester-acrylonitrile copolymer, an acrylic acid ester- chloroethyl vinyl ether copolymer, etc. are mentioned.
상기 니트릴 고무로는, 아크릴로니트릴-부타디엔 공중합체, 아크릴로니트릴-이소프렌 공중합체 등을 들 수 있다.Examples of the nitrile rubber include an acrylonitrile-butadiene copolymer and an acrylonitrile-isoprene copolymer.
상기 부타디엔계 고무로는, 폴리부타디엔, 아크릴로니트릴-부타디엔-스티렌 공중합체, 메틸메타크릴레이트-부타디엔-스티렌 공중합체 등을 들 수 있다.Examples of the butadiene-based rubber include polybutadiene, acrylonitrile-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer.
상기 고무 화합물로서, 아크릴산에스테르를 주성분으로 하고, 알킬렌글리콜디(메타)아크릴레이트, 폴리알킬렌글리콜디(메타)아크릴레이트, 알릴(메타)아크릴레이트 등의 가교성 모노머를 공중합시킨 가교 고무를 사용해도 된다.As the rubber compound, a crosslinked rubber containing an acrylic acid ester as a main component and copolymerized with a crosslinking monomer such as alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, or allyl(meth)acrylate. You may use it.
상기 고무 화합물은 코어부의 고무층과, 쉘부의 아크릴층으로 형성된 코어쉘 입자인 것이 바람직하다. 이에 의해, 상기 (메타)아크릴계 폴리머에 대한 상기 고무 화합물의 상용성, 분산성을 향상할 수 있다. 상기 코어부를 형성하는 고무층의 재료로는, 상술한 각종 고무 화합물을 채용할 수 있다. 고무 화합물이 부타디엔, 이소프렌 등의 공액 디엔을 포함하는 공중합체여도 된다.The rubber compound is preferably a core-shell particle formed of a rubber layer in the core portion and an acrylic layer in the shell portion. Thereby, compatibility and dispersibility of the said rubber compound with respect to the said (meth)acrylic-type polymer can be improved. As a material of the rubber layer forming the core portion, the various rubber compounds described above can be employed. A copolymer containing a conjugated diene such as butadiene and isoprene may be sufficient as the rubber compound.
상기 쉘부의 아크릴층을 형성하는 아크릴계 재료로는, (메타)아크릴산에스테르, (메타)아크릴산, (메타)아크릴로니트릴 등의 적어도 1종을 모노머로서 함유하는 (메타)아크릴계 중합체를 들 수 있다. 상기 아크릴계 재료는 메틸메타크릴레이트(MMA)를 함유하는 메틸메타크릴레이트 공중합체 또는 메틸메타크릴레이트 단독 중합체여도 된다. 상기 (메타)아크릴계 중합체는 에틸렌, 프로필렌, 부타디엔, 이소프렌, 스티렌 등의 올레핀류를 공중합시킨 (메타)아크릴계 공중합체여도 된다. 상기 아크릴계 재료는 수산기, 카르복실기, 비닐기 등의 관능기를 갖는 모노머를 공중합시킨 (메타)아크릴계 공중합체여도 된다.Examples of the acrylic material for forming the acrylic layer of the shell portion include (meth)acrylic polymers containing at least one type of (meth)acrylic acid ester, (meth)acrylic acid, (meth)acrylonitrile, etc. as a monomer. The acrylic material may be a methyl methacrylate copolymer or methyl methacrylate homopolymer containing methyl methacrylate (MMA). The (meth)acrylic polymer may be a (meth)acrylic copolymer obtained by copolymerizing olefins such as ethylene, propylene, butadiene, isoprene and styrene. The acrylic material may be a (meth)acrylic copolymer obtained by copolymerizing a monomer having a functional group such as a hydroxyl group, a carboxyl group or a vinyl group.
상기 코어쉘 입자는 코어부의 주위를 쉘부가 완전히 피복한 구조여도 되고, 코어부 주위의 일부를 쉘부로 피복한 구조여도 된다. 코어부의 주위에서 수지의 도포, 경화 등에 의해 쉘부를 형성해도 된다.The core-shell particles may have a structure in which the shell part completely covers the periphery of the core part, or may have a structure in which the shell part covers the periphery of the core part. You may form a shell part by application|coating of resin, hardening, etc. around the core part.
상기 코어쉘 입자는 코어부와 쉘부 사이에 중간층을 가져도 된다. 중간층이 생략되고, 코어부에 접하여 쉘층이 형성되어 있어도 된다. 중간층이 코어부를 형성하는 고무 화합물과, 쉘층을 형성하는 아크릴층이 혼재한 과도적인 조성을 가져도 된다. 중간층으로서, 코어부와 쉘부의 접착층이 적층되어 있어도 된다.The said core-shell particle|grains may have an intermediate|middle layer between a core part and a shell part. The intermediate layer may be omitted and a shell layer may be formed in contact with the core portion. The intermediate layer may have a transient composition in which the rubber compound forming the core portion and the acrylic layer forming the shell layer are mixed. As an intermediate|middle layer, the adhesive layer of a core part and a shell part may be laminated|stacked.
상기 코어쉘 입자에 있어서, 코어부와 쉘부가 화학 결합을 개재하여 결합되어 있어도 된다. 예를 들면, 코어부를 형성하는 고무 화합물의 입자의 존재하에서, 쉘부를 형성하는 단량체를 중합시킴으로써, 쉘부를 형성하는 수지를 코어부에 그래프트 중합시킨 구조여도 된다. 코어부와 쉘부가 일체의 그래프트 공중합체를 형성하고 있어도 된다.The said core-shell particle WHEREIN: The core part and the shell part may be couple|bonded through a chemical bond. For example, a structure in which resin forming the shell portion is graft polymerized to the core portion may be employed by polymerizing a monomer forming the shell portion in the presence of particles of a rubber compound forming the core portion. The core part and the shell part may form the integral graft copolymer.
상기 코어쉘 입자의 제조 방법은 특별히 한정되지 않지만, 예를 들면, 코어부의 유화 중합 등에 의해, 코어부의 원하는 직경에 도달할 때까지 코어부의 중합을 진행시킴으로써, 형상이나 치수 등의 균일성이 높은 입자상의 코어부를 형성할 수 있다. 또한, 쉘부의 유화 중합 등에 의해, 쉘부의 원하는 직경에 도달할 때까지 쉘부의 중합을 진행시킴으로써, 형상이나 치수 등의 균일성이 높은 입자상의 쉘부를 형성할 수 있다. 코어부와 쉘부가 그래프트 중합에 의해 결합하고 있는 경우에는, 코어부와 쉘부가 화학 결합을 개재하여 강고하게 일체화되므로, 쉘층의 박리를 억제할 수 있다.Although the method for producing the core-shell particles is not particularly limited, for example, by emulsion polymerization of the core part, polymerization of the core part is progressed until the desired diameter of the core part is reached, whereby a particulate form with high uniformity in shape and size, etc. can form a core part of In addition, by advancing polymerization of the shell part by emulsion polymerization of the shell part until a desired diameter of the shell part is reached, a particulate shell part with high uniformity in shape and size can be formed. When the core portion and the shell portion are bonded to each other by graft polymerization, the core portion and the shell portion are firmly integrated through a chemical bond, so that peeling of the shell layer can be suppressed.
상기 고무 화합물은 상기 (메타)아크릴계 수지 조성물에 있어서, 입자상인 것이 바람직하다. 상기 (메타)아크릴계 수지 조성물을 가열 성형할 때, 상기 고무 화합물이 입자의 형상을 유지해도 되고, 혹은 상기 고무 화합물이 용융되어, 상기 (메타)아크릴계 수지 조성물 중에 분산되어도 된다. 상기 고무 화합물의 입자 직경의 종류로는, 레이저 회절법 등으로 측정 가능한 체적 기준 평균 입자 직경을 들 수 있다. 상기 고무 화합물의 체적 기준 평균 입자 직경은 예를 들면, 0.05∼2.0㎛가 바람직하고, 0.05∼1.0㎛가 보다 바람직하다. 상기 고무 화합물이 상기 코어쉘 입자인 경우에는, 상기 코어쉘 입자의 입자 직경에는 쉘부의 범위도 포함된다.It is preferable that the said rubber compound is particulate in the said (meth)acrylic-type resin composition. When heat-molding the (meth)acrylic resin composition, the rubber compound may maintain the shape of the particles, or the rubber compound may be melted and dispersed in the (meth)acrylic resin composition. As a kind of the particle diameter of the said rubber compound, the volume-based average particle diameter measurable by a laser diffraction method etc. is mentioned. The volume-based average particle diameter of the rubber compound is, for example, preferably 0.05 to 2.0 µm, more preferably 0.05 to 1.0 µm. When the rubber compound is the core-shell particle, the particle diameter of the core-shell particle includes the range of the shell part.
상기 고무 화합물로는, 코어부에 스티렌-부타디엔 고무(SBR) 또는 부타디엔을 주체로 한 고무층과, 쉘부에 메틸메타크릴레이트(MMA)를 주체로 한 아크릴층으로 형성된 코어쉘 입자인 것이 바람직하고, 상기 코어쉘 입자의 체적 기준 평균 입자 직경은 0.05∼2.0㎛가 바람직하며, 0.05∼1.0㎛가 보다 바람직하다.The rubber compound is preferably a core-shell particle formed of a rubber layer mainly composed of styrene-butadiene rubber (SBR) or butadiene in the core portion and an acrylic layer mainly composed of methyl methacrylate (MMA) in the shell portion, The volume-based average particle diameter of the core-shell particles is preferably 0.05 to 2.0 μm, more preferably 0.05 to 1.0 μm.
상기 (메타)아크릴계 수지 조성물은 상술한 첨가제에 한하지 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 above additives, 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 colorant, a ultraviolet absorber, and an infrared absorber, may be mix|blended suitably. These additives are independent or can use 2 or more types together.
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 않지만, 필름, 판(시트), 봉(로드), 섬유(파이버) 등을 들 수 있다. 상기 성형품의 성형 방법은 특별히 한정되지 않지만, 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 않지만, 수지 필름, 이형 필름, 종이 기재, 금속박, 적층체 등을 들 수 있다.The (meth)acrylic resin composition may be molded or coated in a predetermined shape, and then cured by reacting the (meth)acrylic polymer with the crosslinking agent. Although it does not specifically limit as a molded article obtained from the said (meth)acrylic-type resin composition, A film, a board (sheet), a rod (rod), a fiber (fiber), etc. are mentioned. Although the molding method of the said molded article is not specifically limited, Cast molding, lamination molding, extrusion molding, etc. are mentioned. When the (meth)acrylic resin composition is applied on a substrate, a resin film may be formed on the substrate by, for example, solution coating. Although it does not specifically limit as said base material, A resin film, a release film, a paper base material, 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 (meth) It is preferable to make it fluidize as a solution of an 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 inhibiting the reactivity of the functional group of the acrylic polymer and 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 and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone (MEK), and acetic acid Ester solvents, such as ethyl, etc. are mentioned. When the said acrylic polymer is manufactured by the solution polymerization method, at least a part of the solvent used for superposition|polymerization may become at least a part of the solvent of the said (meth)acrylic-type 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 한하지 않고, 수지 필름의 롤체로부터 되감긴 수지 필름, 가동 벨트, 드럼 등을 들 수 있다. 상기 기재의 표면 성상은 평활면이 바람직하지만, 기재에 소정의 요철을 형성함으로써, 얻어지는 상기 (메타)아크릴계 수지 필름의 표면에 요철을 전사하는 것도 가능하다.The (meth)acrylic resin film of this embodiment is a resin layer formed by bridge|crosslinking the said (meth)acrylic resin composition, It is characterized by the above-mentioned. The (meth)acrylic resin film is, for example, by using a solution casting method, by applying a solution of the (meth)acrylic resin composition on a predetermined substrate to form a thin film, then heat-drying to remove the solvent from the thin film It can manufacture by crosslinking with volatilization. As said base material, it is not limited to a fixed plane, The resin film rewound from the roll body of a resin film, a movable belt, a drum, etc. are mentioned. Although a smooth surface is preferable for the surface property of the said base material, it is also possible to transcribe|transfer the unevenness|corrugation on the surface of the said (meth)acrylic-type resin film obtained by forming predetermined unevenness|corrugation on a 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 한하지 않고, 「복굴절률」 등의 광학 이방성도 들 수 있다.The said (meth)acrylic-type resin film obtained by the said solution casting method may be extended|stretched in predetermined directions, such as a longitudinal direction and a width direction, and it is good also as a non-stretched state. The use of the optical film WHEREIN: When it is necessary to reduce anisotropy, it is preferable to use the said (meth)acrylic-type resin film as a non-stretched film. You may process into a biaxially stretched film by adding operation of extending|stretching in the longitudinal direction and the width direction of the said (meth)acrylic-type resin film. On the other hand, as anisotropy of a film, not only the anisotropy of mechanical properties, such as "elongation at break", but optical anisotropy, such as a "birefringence," is also mentioned.
상기 (메타)아크릴계 수지 필름의 기계적 특성은 용도에도 의존하지만, 점착 시트, 광학용 필름, 표면 보호 필름, 공정 필름 등에 사용하는 경우나, 길이 방향의 반송, 롤로부터 풀어냄, 롤로의 권취 등을 행하는 경우에는, 내절성으로서의 내절 횟수가 많은 것, 및 내파단성으로서의 인장 파단 강도가 높은 것에 추가로, 피착체 등에 대한 추종성이 얻어지도록 신장성으로서의 적절한 파단 신장률을 갖는 것이 바람직하다.The mechanical properties of the (meth)acrylic resin film depend on the use, but when used in an adhesive sheet, an optical film, a surface protection film, a process film, etc., conveying in the longitudinal direction, unwinding from a roll, winding into a roll In the case of carrying out, it is preferable to have an appropriate elongation at break as extensibility so that followability to an adherend or the like can be obtained in addition to a thing having a large number of times of bending resistance as a fold resistance and a high tensile breaking strength as a breaking resistance.
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 필름이 필요로 하는 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 is 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 physical property required for the (meth)acrylic resin film, can be improved.
상기 (메타)아크릴계 수지 필름의 두께는 특별히 한정되지 않지만, 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 편면 또는 양면에 다른 재료를 적층하는 경우에는, 필요에 따라, 코로나 방전에 의한 표면 개질, 앵커 코트제 도포 등의 이접착 처리를 실시해도 된다.Although 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, and a thickness of 10 to 50 μm is more preferable, and the thickness is It is especially preferable that it is 10-40 micrometers, and thickness can also be made into the thin film of 40 micrometers or less. When laminating another material on one side or both surfaces of the (meth)acrylic resin film, if necessary, an easily adhesive treatment such as surface modification by corona discharge or application of an anchor coat agent may be performed.
상기 (메타)아크릴계 수지 필름은 상기 (메타)아크릴계 수지 조성물에 고무 화합물을 함유하기 때문에, 내굴곡성을 향상할 수 있다. 상기 (메타)아크릴계 수지 필름은 JIS P8115(종이 및 판지-내절 강도 시험 방법-MIT 시험기법)에 준거하여 측정했을 때, 내절성으로서의 내절 횟수가 100회 이상인 것이 바람직하고, 200회 이상인 것이 보다 바람직하다. 내절 횟수의 통상의 측정 조건으로는, 폭 15.0±0.1㎜, 길이 약 110㎜의 시험편에 대해, 하중 9.8N으로 매분 175±10회의 속도로 왕복 절곡을 반복하는 방법을 들 수 있다. 시험편이 파단할 때까지의 왕복 절곡 횟수가 내절 횟수로서 측정된다.Since the (meth)acrylic resin film contains a rubber compound in the (meth)acrylic resin composition, bending resistance can be improved. As for the (meth)acrylic resin film, when measured in accordance with JIS P8115 (paper and paperboard-Bending strength test method-MIT test method), the number of bending resistance as fold resistance is preferably 100 or more, and more preferably 200 or more Do. A method of repeating reciprocating bending at a rate of 175±10 times per minute with a load of 9.8N for a test piece having a width of 15.0±0.1 mm and a length of about 110 mm as a normal measurement condition for the number of bending resistance. The number of reciprocating bending until the specimen fractures is measured as the number of internal bending.
상기 (메타)아크릴계 수지 필름은 상기 (메타)아크릴계 수지 조성물에 고무 화합물을 함유하기 때문에, 변형성을 향상할 수 있다. 상기 (메타)아크릴계 수지 필름의 신장성으로서의 파단 신장률이 10％ 이상인 것이 바람직하고, 20％ 이상인 것이 보다 바람직하다. 필름류의 파단 신장률은 예를 들면, JIS K7161(플라스틱-인장 특성의 구하는 방법), JIS K7127(플라스틱-인장 특성의 시험 방법) 등의 규격에 준거하여 측정할 수 있다.Since the (meth)acrylic resin film contains a rubber compound in the (meth)acrylic resin composition, deformability can be improved. It is preferable that the breaking elongation as extensibility of the said (meth)acrylic-type resin film is 10 % or more, and it is more preferable that it is 20 % or more. The elongation at break of films can be measured, for example, in accordance with standards such as JIS K7161 (method for determining plastic-tensile properties) and JIS K7127 (testing method for plastic-tensile properties).
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 필름으로서 사용하는 경우에는 무색 투명인 것이 바람직하다.You may use the said (meth)acrylic-type resin film for the base material of the film for optics. As an optical film, a polarizing film, retardation film, an antireflection film, an anti-glare (anti-glare) film, a ultraviolet-absorbing film, an infrared-absorbing film, an optical compensation film, a brightness improving film, etc. are mentioned. As an apparatus to which the member for optics is applied, a liquid crystal panel, organic electroluminescent panel, a touch panel, etc. are mentioned. When using the said (meth)acrylic-type resin film as an optical film, it is preferable that it is colorless and transparent.
상기 (메타)아크릴계 수지 필름의 면내 위상차 Re가 1.0㎚ 이하인 것이 바람직하다. 면내 위상차 Re가 작을수록, 상기 (메타)아크릴계 수지 필름이 광학적으로 등방적이 되고, 광학 장치에 첩부하거나, 상기 (메타)아크릴계 수지 필름을 광학적 검사의 용도로 제공했을 때, 색조의 변화를 억제할 수 있다.It is preferable that the in-plane retardation Re of the said (meth)acrylic-type resin film is 1.0 nm or less. As the in-plane retardation Re is small, the (meth)acrylic resin film becomes optically isotropic, and when affixed to an optical device, or when the (meth)acrylic resin film is provided for optical inspection, the change in color tone is suppressed. can
상기 (메타)아크릴계 수지 필름의 헤이즈값이 3.0％ 이하인 것이 바람직하다. 헤이즈값이 낮을수록, 상기 (메타)아크릴계 수지 필름을 투과할 때의 광산란이 감소한다. 예를 들면, 상기 (메타)아크릴계 수지 필름을 디스플레이 등의 광학 장치에 탑재할 때, 산란광에 의한 누광을 억제할 수 있다.It is preferable that the haze value of the said (meth)acrylic-type resin film is 3.0 % or less. The light scattering at the time of permeate|transmitting the said (meth)acrylic-type resin film reduces, so that a haze value is low. For example, when the (meth)acrylic resin film is mounted on an optical device such as a display, light leakage due to scattered light can be suppressed.
상기 (메타)아크릴계 수지 조성물의 광학 특성을 비교하는 목적으로, 면내 위상차 Re, 헤이즈값 등의 광학 특성을 측정할 때에는, 측정에 사용하는 상기 (메타)아크릴계 수지 필름의 두께가 제품으로 하는 상기 (메타)아크릴계 수지 필름의 두께와 상이해도 된다. 광학 특성의 기준으로 할 때의 상기 (메타)아크릴계 수지 필름의 두께는 예를 들면, 20∼30㎛로 해도 되고, 보다 구체적으로는, 25㎛로 해도 된다.For the purpose of comparing the optical properties of the (meth)acrylic resin composition, when measuring optical properties such as in-plane retardation Re and haze value, the thickness of the (meth)acrylic resin film used for measurement is the above ( It may differ from the thickness of a meth)acrylic-type resin film. The thickness of the said (meth)acrylic-type resin film at the time of setting it as the reference|standard of an optical characteristic is good also as 20-30 micrometers, for example, and is good also as 25 micrometers more specifically.
상기 (메타)아크릴계 수지 필름의 편면 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 antiglare layer, a low refractive index layer, an adhesive layer, and a release layer, etc. may be laminated on one side or both sides of the (meth)acrylic resin film. . Examples of the fluorine compound used in the composition for forming a low refractive index layer include a fluorinated copolymer which is one or two or more polymers such as fluorinated olefins, fluorinated vinyl ethers, and fluorinated alkyl (meth) acrylates, and fluorinated alkyl group-containing silane compounds. Condensates, such as these are mentioned. The fluorinated copolymer may be copolymerized with non-fluorinated monomers such as olefins, vinyl ethers and (meth)acrylates in addition to the fluorinated monomers. The low-refractive-index layer may be combined with a high-refractive-index layer or the like to constitute an antireflection layer.
본 실시형태의 점착 시트는 상기 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 상기 (메타)아크릴계 수지 필름의 편면 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 pressure-sensitive adhesive sheet of the present embodiment is characterized in that the pressure-sensitive adhesive layer is formed 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 said adhesive layer, the adhesive layer which consists of a (meth)acrylic adhesive is preferable. What is necessary is just to perform the method of forming an adhesion layer in the said (meth)acrylic-type resin film by a well-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, 점착층이 형성된 광학용 필름으로 해도 된다. 점착층이 형성된 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 said adhesive sheet is good also as an optical film with an adhesive layer in which the adhesive layer is laminated|stacked on at least one surface of the optical film which uses the said (meth)acrylic-type resin film as a base material. The optical film with an adhesion layer can be used for bonding of the optical film in various display apparatuses, such as a liquid crystal display device, a touchscreen, electronic paper, and organic electroluminescent. You may protect the adhesion surface of the adhesion layer used for bonding of the film for optics using a release film. The release film may be subjected to a mold release treatment with a silicone-based, fluorine-based mold release agent, or the like, to the surface on the side that is combined with the adhesive surface of the pressure-sensitive adhesive layer.
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.The said adhesive sheet may comprise the surface protection film bonded together through the said adhesive layer in order to protect the surface of to-be-adhered objects, such as glass, an optical film, and an optics member. In a state where the surface protection film is pasted to the adherend, the 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 protection 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 편면 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 formed by forming the said (meth)acrylic-type resin film which is a resin layer formed by bridge|crosslinking the said (meth)acrylic-type resin composition on one side or both surfaces of a polarizer, It is characterized by the above-mentioned. 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 untreated, AG treatment, LR treatment, AR treatment, AG-LR treatment, and AG-AR treatment. Here, AG is anti-glare, LR is low reflection, and AR is anti-reflection.
상기 편광자의 보호층으로는, 트리아세틸셀룰로오스(TAC), 폴리메틸메타크릴레이트(PMMA) 등의 아크릴계 수지, 폴리에틸렌테레프탈레이트(PET) 등의 폴리에스테르계 수지, 고리형 올레핀계 폴리머, 폴리카보네이트 등을 들 수 있다. 상기 편광자의 보호층에 대해, 상기 점착 시트의 점착층을 개재하여, 상기 (메타)아크릴계 수지 필름을 첩합해도 된다. 또한, 본 실시형태의 (메타)아크릴계 수지 조성물을 가교하여 이루어지는 수지층인 상기 (메타)아크릴계 수지 필름을 상기 편광자의 보호층으로 하는 것도 가능하다.As the protective layer of the polarizer, acrylic resin such as triacetyl cellulose (TAC) and polymethyl methacrylate (PMMA), polyester resin such as polyethylene terephthalate (PET), cyclic olefin polymer, polycarbonate, etc. can be heard With respect to the protective layer of the said polarizer, you may bond the said (meth)acrylic-type resin film through the adhesion layer of the said adhesive sheet. Moreover, it is also possible to use the said (meth)acrylic-type resin film which is a resin layer formed by bridge|crosslinking the (meth)acrylic-type resin composition of this embodiment as a protective layer of the said polarizer.
실시예Example
이하, 실시예에 의해 본 발명을 구체적으로 설명한다.Hereinafter, the present invention will be specifically described by way of Examples.
＜(메타)아크릴계 폴리머 및 (메타)아크릴계 수지 조성물의 제조＞<Production 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-히드록시옥틸메타크릴레이트 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, 고무 화합물로서 카네에이스(등록상표) M-230 10중량부와, 가교제로서 코로네이트(등록상표) HX 3.0중량부의 비율로 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 the air in the reaction apparatus was replaced with nitrogen gas. Then, the solvent (ethyl acetate) was added to the reaction apparatus with 95 weight part of methyl methacrylate, 5 weight part of methyl acrylates, and 3.0 weight part of 8-hydroxyoctyl methacrylate. Then, 0.1 weight part of azobisisobutyronitrile was dripped as a polymerization initiator, it was made to react by heating at 65 degreeC for predetermined time, and the (meth)acrylic-type polymer solution of Example 1 was obtained. It was 200,000 as a result of measuring the weight average molecular weight (Mw) of the (meth)acrylic-type polymer contained in this (meth)acrylic-type polymer solution. To the (meth)acrylic polymer solution of Example 1, 10 parts by weight of Carneace (registered trademark) M-230 as a rubber compound and 3.0 parts by weight of Coronate (registered trademark) HX as a crosslinking agent were added and mixed with stirring, A (meth)acrylic resin composition of Example 1 was obtained.
[실시예 2∼7 및 비교예 1∼3][Examples 2 to 7 and Comparative Examples 1 to 3]
실시예 1의 (메타)아크릴계 폴리머 및 (메타)아크릴계 수지 조성물의 조성을 각각, 표 1의 기재와 같이 한 것 이외에는, 실시예 1과 동일하게 하여, 실시예 2∼7 및 비교예 1∼3의 (메타)아크릴계 폴리머 및 (메타)아크릴계 수지 조성물을 얻었다. 실시예 2∼7 및 비교예 1∼3의 (메타)아크릴계 폴리머의 중량 평균 분자량(Mw)은 표 1에 나타내는 바와 같다.Except that the composition of the (meth)acrylic polymer and the (meth)acrylic resin composition of Example 1 was as described in Table 1, respectively, in the same manner as in Example 1, Examples 2 to 7 and Comparative Examples 1 to 3 A (meth)acrylic polymer and a (meth)acrylic resin composition were obtained. The weight average molecular weights (Mw) of the (meth)acrylic polymers of Examples 2 to 7 and Comparative Examples 1 to 3 are as shown in Table 1.
[비교예 4][Comparative Example 4]
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 melt extrusion was dissolved in methyl ethyl ketone (MEK) as a solvent, and the weight average molecular weight (Mw) of the polymer contained in the PMMA film was measured. As a result, 300,000 it was
표 1에 있어서, (A)군의 모노머의 합계를 100중량부로 하여 구한 중량부의 값을 화합물명에 대응하는 약기호와 함께 나타낸다.In Table 1, the value of parts by weight obtained by setting the total of the monomers of group (A) to be 100 parts by weight is shown together with the abbreviation corresponding to the compound name.
한편, 표 1에서 사용한 약기호의 의미(화합물명 등)는 다음과 같다.Meanwhile, the meanings (compound names, etc.) of the abbreviations used in Table 1 are as follows.
［(A)군의 모노머］[Monomer of group (A)]
「MMA」: 메틸메타크릴레이트"MMA": methyl methacrylate
「MA」: 메틸아크릴레이트"MA": methyl acrylate
「TBA」: t-부틸아크릴레이트"TBA": t-butyl acrylate
「BMA」: n-부틸메타크릴레이트"BMA": n-butyl methacrylate
「EMA」: 에틸메타크릴레이트"EMA": ethyl methacrylate
「IBMA」: 이소부틸메타크릴레이트"IBMA": isobutyl methacrylate
［(B)군의 모노머］[Monomer of group (B)]
「8HOA」: 8-히드록시옥틸아크릴레이트"8HOA": 8-hydroxyoctyl acrylate
「8HOMA」: 8-히드록시옥틸메타크릴레이트"8HOMA": 8-hydroxyoctyl methacrylate
「6HHA」: 6-히드록시헥실아크릴레이트"6HHA": 6-hydroxyhexyl acrylate
「6HHMA」: 6-히드록시헥실메타크릴레이트"6HHMA": 6-hydroxyhexyl methacrylate
「4HBMA」: 4-히드록시부틸메타크릴레이트"4HBMA": 4-hydroxybutyl methacrylate
「HEA」: 2-히드록시에틸아크릴레이트"HEA": 2-hydroxyethyl acrylate
「HEMA」: 2-히드록시에틸메타크릴레이트"HEMA": 2-hydroxyethyl methacrylate
「Aac」: 아크릴산 「Aac」: acrylic acid
［고무 화합물］[Rubber compound]
한편, 이하에 나타내는 입자 직경은 모두 체적 기준 평균 입자 직경이다.In addition, all particle diameters shown below are volume-based average particle diameters.
「M-230」: 카네에이스(등록상표) M-230(코어쉘 입자, 입자 직경: 0.1㎛, 코어부: SBR, 쉘부: MMA, 가부시키가이샤 카네카의 상품명)"M-230": Kaneace (registered trademark) M-230 (core shell particles, particle diameter: 0.1 µm, core part: SBR, shell part: MMA, trade name of Kaneka Corporation)
「M-210」: 카네에이스(등록상표) M-210(코어쉘 입자, 입자 직경: 0.2㎛, 코어부: SBR, 쉘부: MMA, 가부시키가이샤 카네카의 상품명)"M-210": Kaneace (registered trademark) M-210 (core shell particles, particle diameter: 0.2 µm, core part: SBR, shell part: MMA, trade name of Kaneka Corporation)
「B-513」: 카네에이스(등록상표) B-513(코어쉘 입자, 입자 직경: 0.2㎛, 코어부: 부타디엔, 쉘부: MMA, 가부시키가이샤 카네카의 상품명)"B-513": Kaneace (registered trademark) B-513 (core shell particles, particle diameter: 0.2 μm, core portion: butadiene, shell portion: MMA, trade name of Kaneka Corporation)
「LP-4100」: 메타브렌(등록상표) LP-4100(아크릴 고무 입자, 입자 직경: 1㎛, 미츠비시 케미컬 가부시키가이샤의 상품명) "LP-4100": Metabrene (registered trademark) LP-4100 (acrylic rubber particles, particle diameter: 1 μm, trade name of Mitsubishi Chemical Corporation)
［가교제］[crosslinking agent]
「HX」: 코로네이트(등록상표) HX(HDI 이소시아누레이트체, 토소 가부시키가이샤의 상품명)"HX": Coronate (registered trademark) HX (HDI isocyanurate, trade name of Toso Corporation)
「HL」: 코로네이트(등록상표) HL(HDI 어덕트체, 토소 가부시키가이샤의 상품명)"HL": Coronate (registered trademark) HL (HDI Adduct, trade name of Toso Corporation)
「D-140N」: 타케네이트(등록상표) D-140N(IPDI 어덕트체, 미츠이 카가쿠 가부시키가이샤의 상품명)"D-140N": Takenate (registered trademark) D-140N (IPDI adduct, trade name of Mitsui Chemicals Co., Ltd.)
「T-X」: TETRAD(등록상표)-X(4관능 에폭시 화합물, 미츠비시 가스 카가쿠 가부시키가이샤의 상품명) "T-X": TETRAD (registered trademark)-X (tetrafunctional epoxy compound, Mitsubishi Gas Chemical Co., Ltd. trade name)
＜(메타)아크릴계 수지 필름의 제작＞<Production of (meth)acrylic resin film>
실시예 1∼7 및 비교예 1∼3의 (메타)아크릴계 수지 조성물을 용액 캐스트법에 의해 수지 필름상으로 제막하고, 용제의 건조 및 가교제의 경화에 적합한 온도 조건으로 하여 가열 건조 및 가교시켜, 실시예 1∼7 및 비교예 1∼3의 (메타)아크릴계 수지 필름을 얻었다. 각 필름의 두께(㎛)를 표 2에 나타낸다.The (meth)acrylic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were formed into a resin film by a solution casting method, dried by heating and crosslinked under a temperature condition suitable for drying the solvent and curing the crosslinking agent, Examples 1-7 and the (meth)acrylic-type resin film of Comparative Examples 1-3 were obtained. Table 2 shows the thickness (µm) of each film.
또한, 비교예 4의 (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 4, a commercially available PMMA film (thickness: 80 µm) produced 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∼7 및 비교예 1∼4의 (메타)아크릴계 수지 필름을 이하의 시험 방법에 따라 평가했다.The (meth)acrylic resin films of Examples 1-7 and Comparative Examples 1-4 were evaluated according to the following test methods.
＜헤이즈값＞<Haze value>
실시예 1∼7 및 비교예 1∼4의 (메타)아크릴계 수지 필름으로부터 시험편을 제작하고, 헤이즈미터(제조자: 니혼 덴쇼쿠 가부시키가이샤, 형식: Haze Meter, NDH2000)를 이용하여, 헤이즈값(％)을 측정했다.A test piece was prepared from the (meth)acrylic resin film of Examples 1 to 7 and Comparative Examples 1 to 4, and a haze value ( %) was measured.
＜내절성으로서의 내절 횟수＞<Number of folds as fold resistance>
실시예 1∼7 및 비교예 1∼4의 (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 산교 가부시키가이샤, 형식: MIT 내절도 시험 장치 BE-201)를 이용하여 내절성 시험을 행하여, 시험편이 파단될 때까지의 왕복 절곡 횟수(내절 횟수)를 측정했다.After preparing test pieces from the (meth)acrylic resin films of Examples 1 to 7 and Comparative Examples 1 to 4, in accordance with JIS P8115 (paper and paperboard-Bending strength test method-MIT test method), a cut-resistance test apparatus ( Manufacturer: Tester Sangyo Co., Ltd., Model: MIT A bending resistance test was performed using a BE-201 cut-resistance tester), and the number of reciprocating bending (number of bending resistance) until the test piece fractured|ruptured was measured.
＜내용제성으로서의 겔분율＞<Gel fraction as solvent resistance>
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 time as follows, the (meth)acrylic resin film remaining as an insoluble content (residue) without eluting into the solvent The ratio (so-called gel fraction) was measured and solvent resistance was tested.
실시예 1∼7 및 비교예 1∼4의 (메타)아크릴계 수지 필름으로부터 시험편을 제작하고, 시험편의 질량을 정확하게 측정하여, 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, 용제로의 침지에 의한 겔분율(％)을 측정했다.A test piece was prepared from the (meth)acrylic resin film of Examples 1 to 7 and Comparative Examples 1 to 4, 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 hr was accurately measured, and the gel fraction (%) by immersion in a solvent was measured as a solvent resistance test method from the following formula.
겔분율(％)＝불용분(잔사)질량(g)／필름(시험편)질량(g)×100 Gel fraction (%) = insoluble content (residue) mass (g) / film (test piece) mass (g) x 100
＜내파단성으로서의 인장 파단 강도, 신장성으로서의 파단 신장률＞<Tensile rupture strength as fracture resistance, elongation at break as elongation>
실시예 1∼7 및 비교예 1∼4의 (메타)아크릴계 수지 필름으로부터 시험편을 제작하고, 인장 시험 장치(제조사: 가부시키가이샤 시마즈 세이사쿠쇼, 형식: AGS-X)를 이용하여 측정하여, 시험편이 파단될 때까지의 내파단성으로서의 인장 파단 강도(MPa) 및 신장성으로서의 파단 신장률(％)의 값을 구했다.Test pieces were prepared from the (meth)acrylic resin films of Examples 1 to 7 and Comparative Examples 1 to 4, and measured using a tensile tester (manufacturer: Shimadzu Corporation, model: AGS-X), The values of tensile strength at break (MPa) as fracture resistance and elongation at break (%) as extensibility until the specimen fractured were determined.
＜위상차(면내 위상차 Re값)＞<Phase difference (in-plane retardation Re value)>
실시예 1∼7 및 비교예 1∼4의 (메타)아크릴계 수지 필름의 면내 위상차(Re) 값(㎚)을, 위상차 측정 장치(제조사: 오지 케이소쿠 키키 가부시키가이샤, 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) values (nm) of the (meth)acrylic resin films of Examples 1 to 7 and Comparative Examples 1 to 4 were measured with a retardation measuring device (manufacturer: Oji Keisoku Kiki Co., Ltd., model: KOBRA-HBPR/ SPC) was used. The measurement wavelength of the phase difference can be appropriately selected from a visible region of, for example, 450 to 550 nm. The 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 direction in which the in-plane refractive index is maximum is the x-axis (slow axis), and the direction orthogonal thereto is the y-axis (fast axis). and from the film thickness d of the film, it is computed by the following formula.
면내 위상차 Re＝(nx－ny)×d In-plane phase difference 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 as large as the in-plane retardation Re, in terms of the unit of nm, the film thickness (μm).
표 2에 실시예 1∼7 및 비교예 1∼4의 (메타)아크릴계 수지 필름에 대한 평가 결과를 나타낸다.In Table 2, the evaluation result about the (meth)acrylic-type resin film of Examples 1-7 and Comparative Examples 1-4 is shown.
실시예 1∼5의 (메타)아크릴계 수지 필름은 두께가 40㎛ 이하인 박막에 제막된 것이고, 헤이즈값이 3.0％ 이하, 내절성으로서 내절 횟수가 200회 이상, 내용제성으로서 겔분율이 90％ 이상, 내파단성으로서 인장 파단 강도가 40MPa 이상(약 50MPa 이상), 신장성으로서 파단 신장률이 20％ 이상, 면내 위상차 Re가 1.0㎚ 이하였다. 이와 같이, 실시예 1∼5의 (메타)아크릴계 수지 필름은 어느 물성도 우수했다.The (meth)acrylic resin film of Examples 1 to 5 was formed on a thin film having a thickness of 40 µm or less, and had a haze value of 3.0% or less, the number of times of folding as a fold resistance as 200 or more, and a gel fraction as 90% or more as a solvent resistance. , the tensile breaking strength was 40 MPa or more (about 50 MPa or more) as the breaking resistance, the breaking elongation was 20% or more, and the in-plane retardation Re was 1.0 nm or less. Thus, the (meth)acrylic-type resin film of Examples 1-5 was excellent also in any physical property.
실시예 6의 (메타)아크릴계 수지 필름은 두께가 40㎛ 이하인 박막에 제막된 것이고, 헤이즈값이 약간 높지만, 내절성으로서 내절 횟수가 200회 이상, 내용제성으로서 겔분율이 90％ 이상, 내파단성으로서 인장 파단 강도가 50MPa 이상, 신장성으로서 파단 신장률이 20％ 이상, 면내 위상차 Re가 1.0㎚ 이하였다. 이와 같이, 실시예 6의 (메타)아크릴계 수지 필름은 어느 물성도 우수했다.The (meth)acrylic resin film of Example 6 was formed on a thin film having a thickness of 40 μm or less, and although the haze value was slightly high, the number of times of bending resistance was 200 or more, the gel fraction was 90% or more as the solvent resistance, and the fracture resistance was high. The tensile strength at break was 50 MPa or more, the elongation at break was 20% or more in terms of elongation, and the in-plane retardation Re was 1.0 nm or less. Thus, the (meth)acrylic-type resin film of Example 6 was excellent in any physical property.
실시예 7의 (메타)아크릴계 수지 필름은 두께가 40㎛ 이하인 박막에 제막된 것이고, 헤이즈값이 높지만, 내절성으로서 내절 횟수가 100회 이상, 내용제성으로서 겔분율이 90％ 이상, 내파단성으로서 인장 파단 강도가 50MPa 이상, 신장성으로서 파단 신장률이 10％ 이상, 면내 위상차 Re가 1.0㎚ 이하였다. 이와 같이, 실시예 7의 (메타)아크릴계 수지 필름은 어느 물성도 우수했다.The (meth)acrylic resin film of Example 7 was formed on a thin film having a thickness of 40 µm or less, and had a high haze value, but had a folding resistance of 100 or more, a solvent resistance of 90% or more, and a breaking resistance. The tensile strength at break was 50 MPa or more, the elongation at break was 10% or more as extensibility, and the in-plane retardation Re was 1.0 nm or less. Thus, the (meth)acrylic resin film of Example 7 was excellent in any physical property.
이와 같이, 실시예 1∼7의 (메타)아크릴계 수지 필름에서는, 본 발명의 과제를 해결할 수 있는 것이 실증되고 있다.Thus, in the (meth)acrylic-type resin film of Examples 1-7, it is demonstrated that the subject of this invention can be solved.
비교예 1의 (메타)아크릴계 수지 필름은 (메타)아크릴계 수지 조성물이 고무 화합물을 함유하지 않았기 때문인지, 내절성으로서의 내절 횟수가 적었다. 고무 화합물의 유무에 관해, 실시예 7과 비교예 1을 비교하면, 신장성으로서의 파단 신장률에 대해서는, 비교예 1과 실시예 7이 대략 동등하다고 해도, 내절성으로서의 내절 횟수에 대해서는, 비교예 1보다 실시예 7이 2배 이상 우수하다.The (meth)acrylic resin film of Comparative Example 1 had a small number of fold resistance as the fold resistance, probably because the (meth)acrylic resin composition did not contain a rubber compound. Comparing Example 7 and Comparative Example 1 with respect to the presence or absence of the rubber compound, even if Comparative Example 1 and Example 7 were approximately equal to each other in terms of elongation at break as extensibility, Comparative Example 1 as to the number of bending resistance as fold resistance Further, Example 7 is superior to two or more times.
비교예 2의 (메타)아크릴계 수지 필름은 (메타)아크릴계 폴리머가 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트로서 MMA만을 공중합한 것이며, MMA 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트를 공중합하지 않았기 때문인지, 내절성으로서의 내절 횟수가 적고, 신장성으로서의 파단 신장률이 매우 낮았다.The (meth)acrylic resin film of Comparative Example 2 is an alkyl (meth)acrylate in which the (meth)acrylic polymer has C1-C14 carbon atoms in the alkyl group, and only MMA is copolymerized, and the Tg of the homopolymer other than MMA is 0 ° C. or higher and, perhaps because the alkyl (meth)acrylate having C1-C14 carbon atoms in the alkyl group was not copolymerized, the number of times of bending resistance as a bending resistance was small, and the elongation at break as an extensibility was very low.
비교예 3의 (메타)아크릴계 수지 필름은 (메타)아크릴계 수지 조성물이 고무 화합물 및 가교제를 함유하지 않았기 때문인지, 내절성으로서의 내절 횟수가 적고, 내용제성으로서의 겔분율이 매우 낮았다. 내용제성으로서의 겔분율이 매우 낮은 것은, 상기 (메타)아크릴계 수지 조성물이 가교제에 의해 가교되지 않았기 때문이라고 생각된다.Perhaps because the (meth)acrylic resin film of Comparative Example 3 did not contain a rubber compound and a crosslinking agent, the (meth)acrylic resin film had a small number of fold resistance as fold resistance and a very low gel fraction as solvent resistance. The very low gel fraction as solvent resistance is thought to be because the said (meth)acrylic-type resin composition was not crosslinked with a crosslinking agent.
비교예 4의 (메타)아크릴계 수지 필름은 용융 압출법에 의해 제조된 수지 필름이지만, 내절성으로서의 내절 횟수가 적고, 내용제성으로서의 겔분율이 매우 낮으며, 면내 위상차 Re가 컸다. 내용제성으로서의 겔분율이 매우 낮은 것은, 용융 압출법에 의해 제조된 수지 필름이 가교제에 의해 가교되지 않았기 때문이라고 생각된다.Although the (meth)acrylic resin film of Comparative Example 4 was a resin film produced by melt extrusion, the number of fold resistance as fold resistance was small, the gel fraction as solvent resistance was very low, and the in-plane retardation Re was large. It is considered that the very low gel fraction as solvent resistance is because the resin film manufactured by the melt-extrusion method was not crosslinked with a crosslinking agent.
한편, 비교예 4의 (메타)아크릴계 수지 필름의 두께가 20㎛라고 가정하면, Re의 값은 두께의 비율(20/80)에 따라, 1/4의 값이 되지만, 그럼에도 Re값이 큰 점에서, 복굴절률(nx－ny)의 값 자체가 크다고 생각된다.On the other hand, assuming that the thickness of the (meth)acrylic resin film of Comparative Example 4 is 20 μm, the value of Re becomes 1/4 according to the ratio of thickness (20/80), but the Re value is still large , it is considered that the value of the birefringence (n x - n y ) itself is large.
이상과 같이, 비교예 1∼4의 (메타)아크릴계 수지 필름에서는, 본 발명의 과제인 내절성, 내파단성, 신장률, 내용제성이 우수한 (메타)아크릴계 수지 필름을 제공하는 것을 해결할 수 없었다.As described above, in the (meth)acrylic resin films of Comparative Examples 1 to 4, it was not possible to solve the problems of the present invention to provide a (meth)acrylic resin film excellent in fold resistance, fracture resistance, elongation rate, and solvent resistance.
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, 내용제성의 점에 있어서 우수한 물성을 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, in terms of thinning, folding resistance, and solvent resistance. In view of having excellent physical properties in the present invention, it can be expected to exhibit an effect in reducing the thickness and improving durability of various optical devices such as displays, and thus has great industrial utility value.
Claims (9)
상기 (메타)아크릴계 폴리머가
(A) 메틸메타크릴레이트 80중량부 이상과, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상과의 합계 100중량부와,
(B) 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머의 적어도 1종 이상의 합계 1.0∼20.0중량부
를 공중합시킨 중량 평균 분자량이 10만 초과 100만 이하인 공중합체로 이루어지는 (메타)아크릴계 폴리머이며,
상기 (A)의 합계 100중량부에 대해, 상기 고무 화합물을 1.0∼25.0중량부의 비율로 함유하여 이루어지는 것을 특징으로 하는 (메타)아크릴계 수지 조성물.As a (meth)acrylic resin composition containing a (meth)acrylic polymer, a rubber compound, and a crosslinking agent,
The (meth)acrylic polymer is
(A) 80 parts by weight or more of methyl methacrylate, and at least one type of alkyl (meth) acrylate other than the methyl methacrylate, wherein the homopolymer has a Tg of 0° C. or more and the alkyl group has C1-C14 carbon atoms. A total of 100 parts by weight of the above,
(B) 1.0 to 20.0 parts by weight in total of at least one copolymerizable monomer having a functional group capable of reacting with the crosslinking agent
It is a (meth)acrylic polymer consisting of a copolymer having a weight average molecular weight of more than 100,000 and 1 million or less,
A (meth)acrylic resin composition comprising the rubber compound in a ratio of 1.0 to 25.0 parts by weight with respect to 100 parts by weight in total of (A).
상기 (메타)아크릴계 폴리머가
(A) 메틸메타크릴레이트 80∼99중량부와, 상기 메틸메타크릴레이트 이외의, 호모 폴리머의 Tg가 0℃ 이상이고, 또한 알킬기의 탄소수가 C1∼C14인 알킬(메타)아크릴레이트의 적어도 1종 이상의 1∼20중량부의 합계 100중량부와,
(B) 상기 가교제와 반응할 수 있는 관능기를 갖는 공중합 가능한 모노머로서, 수산기를 갖는 공중합 가능한 모노머 및 카르복실기를 갖는 공중합 가능한 모노머로 이루어지는 모노머군 중으로부터 선택된 적어도 1종 이상의 모노머의 합계 1.0∼20.0중량부
를 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 having a Tg of 0° C. or higher and a C1-C14 alkyl group other than the methyl methacrylate. A total of 100 parts by weight of 1 to 20 parts by weight of more than one species,
(B) 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 or more monomers selected from the group consisting of a copolymerizable monomer having a hydroxyl group and a copolymerizable monomer having a carboxyl group
A (meth)acrylic resin composition, characterized in that it is a (meth)acrylic polymer comprising a copolymer having a weight average molecular weight of greater than 100,000 and not more than 1,000,000.
상기 가교제가 에폭시 화합물, 아지리딘 화합물, 이소시아네이트 화합물로 이루어지는 화합물군으로부터 선택된 1종 이상인 것을 특징으로 하는 (메타)아크릴계 수지 조성물.3. The method of claim 1 or 2,
The (meth)acrylic resin composition, characterized in that the crosslinking agent is at least one selected from the group consisting of an epoxy compound, an aziridine compound, and an isocyanate compound.
상기 고무 화합물이 코어부에 SBR 또는 부타디엔을 주체로 한 고무층과, 쉘부에 메틸메타크릴레이트를 주체로 한 아크릴층으로 형성된 코어쉘 입자이고, 상기 코어쉘 입자의 체적 기준 평균 입자 직경이 0.05∼2.0㎛인 것을 특징으로 하는 (메타)아크릴계 수지 조성물.3. The method of claim 1 or 2,
The rubber compound is a core-shell particle formed of a rubber layer mainly composed of SBR or butadiene in the core portion and an acrylic layer mainly composed of methyl methacrylate in the shell portion, and the average particle diameter based on the volume of the core-shell particles is 0.05 to 2.0 A (meth)acrylic resin composition, characterized in that μm.
상기 수산기를 갖는 공중합 가능한 모노머가 8-히드록시옥틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, N-히드록시(메타)아크릴아미드, N-히드록시메틸(메타)아크릴아미드, N-히드록시에틸(메타)아크릴아미드로 이루어지는 화합물군으로부터 선택된 적어도 1종 이상이고, 또한 8-히드록시옥틸메타크릴레이트, 6-히드록시헥실메타크릴레이트, 4-히드록시부틸메타크릴레이트, 2-히드록시에틸메타크릴레이트, 2-히드록시에틸아크릴레이트로 이루어지는 화합물군으로부터 선택된 적어도 1종 이상을 포함하는 것을 특징으로 하는 (메타)아크릴계 수지 조성물.3. The method of claim 2,
The copolymerizable monomer having a hydroxyl group is 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acryl at least one selected from the group consisting of lactate, N-hydroxy(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and N-hydroxyethyl(meth)acrylamide, and 8-hydroxy At least one selected from the group consisting of octyl methacrylate, 6-hydroxyhexyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate A (meth)acrylic resin composition comprising:
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