CN112831278A - Photocurable resin composition - Google Patents
Photocurable resin composition Download PDFInfo
- Publication number
- CN112831278A CN112831278A CN202011325667.0A CN202011325667A CN112831278A CN 112831278 A CN112831278 A CN 112831278A CN 202011325667 A CN202011325667 A CN 202011325667A CN 112831278 A CN112831278 A CN 112831278A
- Authority
- CN
- China
- Prior art keywords
- meth
- acrylate
- acrylic monomer
- resin composition
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 142
- 239000000178 monomer Substances 0.000 claims abstract description 52
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 49
- -1 oxime compound Chemical class 0.000 claims abstract description 41
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 23
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 23
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 230000001588 bifunctional effect Effects 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- NQSVZHBORWLSRN-UHFFFAOYSA-N 1-cyclohexyl-1-hydroxy-1-phenylpropan-2-one Chemical compound C=1C=CC=CC=1C(O)(C(=O)C)C1CCCCC1 NQSVZHBORWLSRN-UHFFFAOYSA-N 0.000 description 2
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000006226 butoxyethyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 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
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003190 viscoelastic substance Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical group CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- XDHOEHJVXXTEDV-UHFFFAOYSA-N 1-ethoxyprop-1-ene Chemical group CCOC=CC XDHOEHJVXXTEDV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- QHMVQKOXILNZQR-UHFFFAOYSA-N 1-methoxyprop-1-ene Chemical group COC=CC QHMVQKOXILNZQR-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- BTZDVSBDHTYXIH-UHFFFAOYSA-N 1-phenoxyethenol Chemical group OC(=C)OC1=CC=CC=C1 BTZDVSBDHTYXIH-UHFFFAOYSA-N 0.000 description 1
- SWQVMNMCLOEIHC-UHFFFAOYSA-N 1-phenoxyprop-1-en-1-ol Chemical group CC=C(O)OC1=CC=CC=C1 SWQVMNMCLOEIHC-UHFFFAOYSA-N 0.000 description 1
- NTXOAYYHJHJLCN-UHFFFAOYSA-N 1-prop-1-enoxypropane Chemical group CCCOC=CC NTXOAYYHJHJLCN-UHFFFAOYSA-N 0.000 description 1
- HPQUMJNDQVOTAZ-UHFFFAOYSA-N 2,2-dihydroxypropanoic acid Chemical compound CC(O)(O)C(O)=O HPQUMJNDQVOTAZ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- LDFUDVLWUQLNIS-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1.C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 LDFUDVLWUQLNIS-UHFFFAOYSA-N 0.000 description 1
- ZEERWUUHFUFJJT-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1.CC(C)(O)C(=O)C1=CC=CC=C1 ZEERWUUHFUFJJT-UHFFFAOYSA-N 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- YQLRKXVEALTVCZ-UHFFFAOYSA-N 2-isocyanato-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1N=C=O YQLRKXVEALTVCZ-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- 150000005351 2-phenylphenols Chemical class 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- KRHMGQFGGUBDJI-UHFFFAOYSA-N 4-ethyl-1-(2-hydroxyethoxy)octan-2-ol Chemical compound CCCCC(CC)CC(O)COCCO KRHMGQFGGUBDJI-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- MUARTMHRWRHBAP-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3C12.C1=CC=CC=2C3=CC=CC=C3C12 Chemical group C1=CC=CC=2C3=CC=CC=C3C12.C1=CC=CC=2C3=CC=CC=C3C12 MUARTMHRWRHBAP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BRGQQWJYACAPRA-UHFFFAOYSA-N N=C=O.N=C=O.C1CCC=CC1 Chemical compound N=C=O.N=C=O.C1CCC=CC1 BRGQQWJYACAPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- OQHMGFSAURFQAF-UHFFFAOYSA-N [2-hydroxy-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C(C)=C OQHMGFSAURFQAF-UHFFFAOYSA-N 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- QSACPWSIIRFHHR-UHFFFAOYSA-N dimethylphenyl isocyanide Natural products CC1=CC=CC(C)=C1C#N QSACPWSIIRFHHR-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical group C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical group CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- YOQPJXKVVLAWRU-UHFFFAOYSA-N ethyl carbamate;methyl prop-2-enoate Chemical compound CCOC(N)=O.COC(=O)C=C YOQPJXKVVLAWRU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical group COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OCDPVICYFFZSFE-UHFFFAOYSA-N prop-1-enoxybenzene Chemical group CC=COC1=CC=CC=C1 OCDPVICYFFZSFE-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to a photocurable resin composition comprising an acrylic resin, a polyfunctional urethane (meth) acrylate having 3 or more functional groups in one molecule, an acrylic monomer, and a photoinitiator, wherein the photoinitiator comprises an oxime compound and a ketone compound.
Description
Technical Field
The present invention relates to a photocurable resin composition which can be cured even under low light and has excellent adhesion and weather resistance.
Background
A screen protection window member for protecting a Display Panel is provided on a front surface of the Display Panel such as a Liquid Crystal Display Panel (Liquid Crystal Display Panel), a Plasma Display Panel (Plasma Display Panel), or an Organic Light Emitting Display Panel (Organic Light Emitting Display Panel). The window member is adhered and fixed to a surface of the display panel in order that a user may externally recognize an input of the user or an output of the device. Also, the window member is formed on the surface of the device and directly affects the appearance of the device. Therefore, in addition to the function of protecting the display panel, various design designs have been attempted to be added to the window member.
Specifically, as a method for increasing the design of a window member, a method of laminating a decorative film to a window member has been proposed, in which a layer to which an optical function is imparted by an ultraviolet-curable molding layer and a deposited film using an inorganic material or a metal are applied as the decorative film. In this case, the decorative film generally has a dark color in order to impart various colors to the window member.
For example, korean laid-open patent No. 2012-0040225 (patent document 1) discloses a photocurable resin composition comprising (a) a urethane (meth) acrylate oligomer having a polyoxyalkylene structure; (B) a (meth) acrylic polymer; (C) a (meth) acrylic monomer; and (D) a photopolymerization initiator.
However, in recent years, as the design of window members has become more colorful and diversified, the decorative film is designed to have a dark color, and thus, the transmittance of ultraviolet rays at the time of curing is reduced. As a result, a large amount of curing energy is required or incomplete curing occurs, resulting in a problem that reliability of the product is lowered.
Therefore, development of a photocurable resin composition which can be cured even with a low light amount and has excellent physical properties such as adhesiveness and weather resistance has been demanded.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a photocurable resin composition which can be cured even at a low light amount and has excellent physical properties such as adhesion and weather resistance.
Solving means
The invention provides a photocurable resin composition, which comprises an acrylic resin, polyfunctional urethane (methyl) acrylate with more than 3 functional groups in one molecule, an acrylic monomer and a photoinitiator, wherein the photoinitiator comprises oxime compounds and ketone compounds.
Effects of the invention
The photocurable resin composition according to the present invention, light thereofExcellent in curability and therefore in the range of 1,000 to 2,000mJ/cm2Can be cured at a low light level. Further, a cured product obtained from the photocurable resin composition is excellent in adhesion and weather resistance, and is useful as a material in various fields such as window members because it does not cause a decrease in physical properties under high-temperature and high-humidity conditions and thermal shock conditions.
Detailed Description
In the present specification, "(meth) acrylic acid" means "acrylic acid" and/or "methacrylic acid", and "(meth) acrylate" means "acrylate" and/or "methacrylate".
The "weight average molecular weight" used in the present specification is measured by a conventional method known in the art, for example, by a Gel Permeation Chromatography (GPC) method. In addition, the "glass transition temperature" is measured by a conventional method known in the art, and for example, can be measured by Differential Scanning Calorimetry (DSC).
The photocurable resin composition according to the present invention comprises: an acrylic resin, a polyfunctional urethane (meth) acrylate having 3 or more functional groups in one molecule, an acrylic monomer, and a photoinitiator.
Acrylic resin
The acrylic resin functions to improve the adhesion of the composition.
The acrylic resin may be a resin directly synthesized according to a known method or a commercially available product. For example, the acrylic resin may be a resin that polymerizes more than one acrylic monomer.
The acrylic monomer may be methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate or mixtures of these.
In addition, the weight average molecular weight (Mw) of the acrylic resin may be 30,000 to 80,000g/mol or 40,000 to 60,000 g/mol. When the weight average molecular weight of the acrylic resin is within the above range, there is an effect that the adhesive force with the substrate is excellent.
The acrylic resin may have a glass transition temperature (Tg) of 40 to 80 ℃ or 45 to 70 ℃. When the glass transition temperature of the acrylic resin is within the above range, there is an effect that the adhesive force with the substrate is excellent.
Also, the acrylic resin may be included in the composition in an amount of 3 to 38 parts by weight or 5 to 28 parts by weight, relative to 1 to 30 parts by weight of the multifunctional urethane (meth) acrylate. When the content of the acrylic resin is within the above range, there is an effect of excellent adhesion to a substrate.
Polyfunctional urethane (meth) acrylate
The multifunctional urethane (meth) acrylate functions to improve the photocurability of the composition.
The multifunctional urethane (meth) acrylate may be directly synthesized according to a known method or may be a commercially available product.
The multifunctional urethane (meth) acrylate may be prepared by the reaction of one or more compounds including one or more polyisocyanates, one or more (meth) acrylate functional groups including one or more reactive groups that can react with isocyanate groups, and one or more reactive groups including 2 or more reactive groups that can further react with isocyanates. At this time, the reactive group that can react with the isocyanate group may be a hydroxyl group.
For example, the multifunctional urethane (meth) acrylate of the present invention can produce a multifunctional (meth) acrylate containing 3 or more hydroxyl groups in the molecule and a compound having an isocyanate group in the presence of a catalyst.
In this case, the polyfunctional (meth) acrylate having a hydroxyl group in the molecule may be one or more selected from the group consisting of 4-hydroxybutyl (meth) acrylate, pentaerythritol tri/tetra (meth) acrylate mixture, and dipentaerythritol penta/hexa (meth) acrylate mixture.
In addition, the compound having the isocyanate group may be selected from the group consisting of 1, 4-diisocyanatobutane, 1, 6-diisocyanatohexane, 1, 8-diisocyanatooctane, 1, 12-diisocyanatododecane, 1, 5-diisocyanato-2-methylpentane, trimethyl-1, 6-diisocyanatohexane, 1, 3-bis (isocyanatomethyl) cyclohexane, trans-1, 4-cyclohexene diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, xylene-1, 4-diisocyanate, tetramethylxylene-1, 3-diisocyanate, 1-chloromethyl-2, 4-diisocyanate, 4 '-methylenebis (2, 6-dimethylphenyl isocyanate), 4' -oxybis (phenyl isocyanate), trifunctional isocyanate derived from hexamethylene diisocyanate, and a trimethylolpropane adduct of toluene diisocyanate.
On the other hand, commercially available products such as Miramer PU610, Miramer SC2100, Miramer SC2152, and 1290 of SK-Cytec Co., Ltd can be used as the multifunctional urethane (meth) acrylate, but the present invention is not limited thereto.
Specifically, the multifunctional urethane (meth) acrylate of the present invention may include 3 or more functional groups in one molecule, that is, wherein each molecule may have 3 or more or 6 to 15 (meth) acrylate reactive groups.
In addition, the weight average molecular weight (Mw) of the multifunctional urethane (meth) acrylate may be 1,000 to 7,000g/mol or 1,500 to 6,000 g/mol. When the weight average molecular weight of the multifunctional urethane (meth) acrylate is within the above range, there is an effect that curability is excellent.
The multifunctional urethane (meth) acrylate may be included in the composition in an amount of 1 to 30 parts by weight or 3 to 20 parts by weight, relative to 3 to 38 parts by weight of the acrylic resin. When the content of the multifunctional urethane (meth) acrylate is within the above range, there is an effect of satisfying both curability and adhesion.
Acrylic acid monomer
The acrylic monomer of the present invention functions to adjust the viscosity of the photocurable resin composition and to improve the strength of the coating film produced.
The acrylic monomer may be any known (meth) acrylate monomer having one or more photopolymerizable unsaturated groups in the molecule thereof. In addition, the acrylic monomers may be classified into monofunctional acrylic monomers (1), difunctional acrylic monomers (2), and multifunctional acrylic monomers (3 or more) according to the number of polymerizable functional groups, such as (meth) acrylate groups, included in one molecule.
Specifically, the acrylic monomer may include a monofunctional acrylic monomer containing one functional group in one molecule, a bifunctional acrylic monomer containing 2 functional groups in one molecule, and a multifunctional acrylic monomer containing 3 or more functional groups in one molecule.
In addition, the monofunctional acrylic monomer may include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isoamyl (meth) acrylate, isomyristyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, long-chain alkyl (meth) acrylate, n-butoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl-diethylene glycol (meth) acrylate, n-butyl (meth) acrylate, butoxyethyl (meth) acrylate, n-butyl (meth) acrylate, butoxy, Dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, methoxy ethylene glycol-modified (meth) acrylate, ethoxy ethylene glycol-modified (meth) acrylate, propoxy ethylene glycol-modified (meth) acrylate, methoxy propylene glycol-modified (meth) acrylate, ethoxy propylene glycol-modified (meth) acrylate, propoxy propylene glycol-modified (meth) acrylate, and mixtures thereof, Aliphatic monofunctional acrylic monomers such as tetrahydrofuran (meth) acrylate and acryloylmorpholine; and at least one aromatic monofunctional acrylic monomer such as phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethylene glycol-modified (meth) acrylate, phenoxypropylene glycol-modified (meth) acrylate, hydroxyphenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, hydroxyphenoxyethylene glycol-modified (meth) acrylate, hydroxyphenoxypropylene glycol-modified (meth) acrylate, alkylphenol ethylene glycol-modified (meth) acrylate, alkylphenol propylene glycol-modified (meth) acrylate, ethoxylated orthophenyl phenol (meth) acrylate, isobornyl (meth) acrylate, or the like.
On the other hand, the bifunctional acrylic monomer may include one or more monomers selected from the group consisting of ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyolefin glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, 2-hydroxy-1, 3-dimethacryloxypropane, dioxane glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, glycerol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, and mixtures thereof, Aliphatic bifunctional acrylic monomers such as neopentyl glycol di (meth) acrylate, 2-methyl-1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, butylethylpropanediol di (meth) acrylate, and 3-methyl-1, 5-pentanediol di (meth) acrylate; and at least one aromatic bifunctional acrylic monomer such as ethoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and ethoxylated bisphenol F di (meth) acrylate.
On the other hand, the multifunctional acrylic monomer may include: trifunctional monomers such as ethoxylated glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate or pentaerythritol tri (meth) acrylate; tetrafunctional group monomers such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and ethoxylated pentaerythritol tetra (meth) acrylate; and monomers having five or more functional groups such as dipentaerythritol hexa (meth) acrylate and dipentaerythritol polyacrylate.
The acrylic monomer may be present in an amount of 0.1 to 3: 0.1 to 3: 1 or 0.5 to 2: 0.5 to 2: the weight ratio of 1 comprises a monofunctional acrylic monomer, a difunctional acrylic monomer and a polyfunctional acrylic monomer. When the acrylic monomer contains the monofunctional acrylic monomer, the difunctional acrylic monomer and the polyfunctional acrylic monomer in the above weight ratio, the effect of satisfying both curability and adhesiveness is obtained.
In addition, the acrylic monomer may be included in the composition in a content of 20 to 70 parts by weight or 25 to 55 parts by weight with respect to 3 to 38 parts by weight of the acrylic resin. When the content of the acrylic monomer is within the above range, the composition may have characteristics of a visco-elastic material (visco-elastic material) in which viscosity and elasticity coexist.
Photoinitiator
The photoinitiator functions to initiate the curing reaction in the composition.
The photoinitiator comprises oxime compounds and ketone compounds. Specifically, the photoinitiator may be present in a ratio of 1: 0.1 to 5 or 1: oxime compounds and ketone compounds are mixed in a weight ratio of 1 to 4.
The oxime compound can be a ketoxime ester compound. For example, the oxime compound may be represented by the following formula 1.
[ chemical formula 1 ]
In chemical formula 1, R1To R3Each independently is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms. Specifically, R1To R3May be each independently an alkyl group having a carbon number of 1 to 8 or an aryl group having a carbon number of 6 to 12.
In this case, the alkyl group may be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, or the like, and specifically, may be a methyl group. In addition, the alkyl group may be linear or branched.
The aryl group may be, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenylene (biphenylene) group, or the like, and specifically, may be a phenyl group.
Examples of the ketone compound include Benzophenone (Benzophenone), hydroxycyclohexylphenylacetone (Hydroxycyclohexylphenylacetone), Chloroacetophenone (Chloroacetophenone), 1, 1-dichloroacetophenone (1, 1-dichloroacetophenone), diethoxyacetophenone (Diethoxyacetophenone), HydroxyAcetophenone (Hydroxyacetophenone), 2-chlorothioxanthone (2-Chlorothioxanthone), 1-Hydroxy-cyclohexyl-phenyl-ketone (1-Hydroxy-cyclohexyl-phenyl-ketone), 2-Hydroxy-2-methyl-1-phenyl-1-propanone (2-Hydroxy-2-methyl-1-phenyl-1-propanone), 2-Hydroxy-2-methoxy-2-methyl-1-propanone (2-Hydroxy-2-methyl-1-Hydroxy-1-propanone), 2-Hydroxy-1-Hydroxy-2-Hydroxy-1- (2-Hydroxy-1-Hydroxy-2-Hydroxy-1-propanone (2-Hydroxy-1-2-Hydroxy-2-ethoxy-1-2-Hydroxy-1-propanone), and 2-Hydroxy-2- (2-Hydroxy-2-ethoxy) -1-2-Hydroxy-1-phenyl-propanone (1-Hydroxy-2-ethoxy-1-2- [4- (2-hydroxyethoxy) phenyl ] -2-methyl-1-propanone), and the like.
In addition, the photoinitiator may be included in the composition in a content of 0.1 to 12 parts by weight or 0.5 to 10 parts by weight with respect to 3 to 38 parts by weight of the acrylic resin. Specifically, the photoinitiator may include 0.1 to 5 parts by weight or 0.5 to 3 parts by weight of an oxime compound and 0.1 to 8 parts by weight or 1 to 5 parts by weight of a ketone compound, relative to 3 to 38 parts by weight of the acrylic resin. When the content of the photoinitiator is within the above range, the effect of facilitating processability and curability is obtained, and when the content of the oxime compound and the ketone compound is within the above range, the effect of excellent curability at a low light amount is obtained.
Additive agent
The photocurable resin composition may further include one or more additives selected from the group consisting of leveling agents and coupling agents.
At this time, the additive may be included in a content of 0.1 to 30 parts by weight or 0.5 to 20 parts by weight with respect to 3 to 38 parts by weight of the acrylic resin.
The adhesive force in the photocurable resin composition can be further improved by including the leveling agent, which performs leveling so as to be applied evenly and smoothly when the photocurable resin composition is applied. As the leveling agent, acrylic, silicon, or the like may be used alone or in combination of 2 or more. Specifically, the leveling agent may include polyether-modified polydimethylsiloxane, and may include, for example, (meth) acryl groups added in a polyether chain. The leveling agent may be included in a content of 0.1 to 5 parts by weight or 0.2 to 2 parts by weight with respect to 3 to 38 parts by weight of the acrylic resin.
The coupling agent functions to improve adhesion. The coupling agent may be, for example, gamma-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (beta-methoxyethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-ureidopropyltrimethoxysilane, gamma-N-beta- (ethoxyethyl) -gamma-N-aminopropylmethyldimethoxysilane, gamma-N-ureidopropyltrimethoxysilane, gamma-N-t-butoxysilane, gamma-N, Phenyltrimethoxysilane, phenyltriethoxysilane, rho-styryltrimethoxysilane, and the like. The coupling agent may be included in a content of 0.1 to 5 parts by weight or 0.2 to 2 parts by weight with respect to 3 to 38 parts by weight of the acrylic resin.
Can be irradiated with light having a wavelength of 310 to 400nm and a light amount of 1000 to 2000mJ/cm2The photocurable resin composition is cured.
The photocurable resin composition according to the present invention as described above is in the range of 1,000 to 2,000mJ/cm2Can be cured rapidly even at a low light amount, and therefore, when applied to various printing methods (gradation printing, etc.) or decorative films of various designs, also exhibits excellent photocurability.
In addition, a cured product prepared from the photocurable resin composition has excellent adhesiveness and weather resistance, and does not suffer from a decrease in physical properties under high-temperature and high-humidity conditions and thermal shock conditions, and thus, can be used as a material in various fields such as window members.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following description of the examples is intended only to specifically illustrate the specific embodiments of the present invention, and is not intended to limit the scope of the claims of the present invention to be interpreted or limited to what is described in the examples.
[ examples ]
Examples 1 to 8 and comparative examples 1 to 8. Preparation of Photocurable resin composition
The components were mixed to prepare a photocurable resin composition according to the compositions described in tables 1 and 2 below.
[ TABLE 1 ]
[ TABLE 2 ]
Table 3 below shows the components and product names of the respective constituent elements used in the following examples and comparative examples.
[ TABLE 3 ]
Test example: evaluation of physical Properties
The physical properties of the compositions of examples and comparative examples or samples manufactured therefrom were measured by the following methods and are shown in table 4.
Specifically, the photocurable resin compositions of examples and comparative examples were applied to a dry film thickness of 10 μm and then irradiated with a light amount of 1000mJ/cm2Ultraviolet (UV) at UV wavelengths.
(1) Speed of curing
For the samples produced, at 810cm by FT-IR-1The percentage of decrease in the double bond peak of the acrylate was measured.
(2) Adhesion Property
On the surface of the sample, 100 squares (width × length) of 1mm × 1mm were drawn with a knife, removed with a Nichiban tape (JIS Z1522), and the number of peels from the squares was measured to evaluate the adhesiveness. At this time, peeling was repeated 3 times using a tape, and if the number of remaining squares was less than 100, NG was evaluated.
(3) Adhesiveness to heat-resistant liquid
After the sample was left to stand in distilled water at 100 ℃ for 30 minutes, the adhesiveness was evaluated by the same method and standard as in item (2).
(4) Adhesion after photocuring
In addition, the light dosage is 4,000mJ/cm2After the sample was irradiated with ultraviolet rays, the adhesiveness was evaluated by the same method and standard as in item (2).
(5) Weather resistance
After the sheet was left to stand in ultraviolet light of UV A wavelength (340nm) for 72 hours using an ultraviolet irradiation (QUV) apparatus of Atlas, adhesiveness was evaluated by the same method and criteria as in item (2).
(6) High temperature and high humidity (50/95)
After the sample was left to stand in a high temperature and high humidity apparatus at 50 ℃ and 95% relative humidity for 72 hours, the adhesion was evaluated by the same method and standard as in item (2).
(7) High temperature and high humidity (85/85)
After the sample was left to stand in a high temperature and high humidity apparatus at 85 ℃ and 85% relative humidity for 72 hours, the adhesiveness was evaluated by the same method and standard as in item (2).
[ TABLE 4 ]
As shown in Table 4, it was confirmed that the composition of the examples was 1,000mJ/cm2Has excellent UV curing properties at a low light intensity, i.e., a curing rate of 85% or more. In addition, it was confirmed that the adhesive properties and weather resistance in a high-temperature and high-humidity environment were excellent in addition to UV curability.
In addition, it was confirmed that the compositions of comparative examples 1 to 4, which did not contain an oxime photoinitiator, were 1,000mJ/cm2Is 75% or less, is not sufficiently cured, and a sample made from the composition not containing a multifunctional urethane (meth) acrylate, a monofunctional acrylic monomer, a difunctional acrylic monomer, or a multifunctional acrylic monomer lacks adhesiveness and/or weather resistance.
Claims (6)
1. A photocurable resin composition comprising an acrylic resin, a polyfunctional urethane (meth) acrylate having 3 or more functional groups in one molecule, an acrylic monomer and a photoinitiator,
wherein, the photoinitiator comprises oxime compounds and ketone compounds.
2. The photocurable resin composition according to claim 1, wherein the weight average molecular weight of the acrylic resin is 30,000 to 80,000g/mol, and the glass transition temperature is 40 to 80 ℃.
3. The photocurable resin composition according to claim 1, wherein the multifunctional urethane (meth) acrylate has a weight average molecular weight of 1,000 to 7,000 g/mol.
4. The photocurable resin composition according to claim 1, wherein the acrylic monomer comprises: a monofunctional acrylic monomer having one functional group in one molecule, a bifunctional acrylic monomer having 2 functional groups in one molecule, and a polyfunctional acrylic monomer having more than 3 functional groups in one molecule,
the acrylic monomer is present in an amount of 0.1 to 3: 0.1 to 3: the weight ratio of 1 comprises the monofunctional acrylic monomer, the difunctional acrylic monomer and the polyfunctional acrylic monomer.
5. The photocurable resin composition according to claim 1, wherein the photocurable resin composition comprises: 3 to 38 parts by weight of an acrylic resin, 1 to 30 parts by weight of a multifunctional urethane (meth) acrylate, 20 to 70 parts by weight of an acrylic monomer, and 0.1 to 12 parts by weight of a photoinitiator.
6. The photocurable resin composition according to claim 1, wherein the photocurable resin composition is irradiated with light having a wavelength of 310 to 400nm and a light amount of 1,000 to 2,000mJ/cm2Is cured.
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| CN114032038A (en) * | 2021-12-09 | 2022-02-11 | 泉州利萨奇新材料科技有限公司 | Anti-ultraviolet anti-yellowing resin composition and preparation process thereof |
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| KR102594277B1 (en) * | 2021-12-02 | 2023-10-26 | 주식회사 한솔케미칼 | Uv curable resin composition containing pigment having low hardness |
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| US20140329927A1 (en) * | 2011-12-07 | 2014-11-06 | Kyoung Jin Ha | Photocurable adhesive composition and display device comprising same |
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