KR102351925B1 - Photocurable composition - Google Patents
Photocurable composition Download PDFInfo
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- KR102351925B1 KR102351925B1 KR1020150081204A KR20150081204A KR102351925B1 KR 102351925 B1 KR102351925 B1 KR 102351925B1 KR 1020150081204 A KR1020150081204 A KR 1020150081204A KR 20150081204 A KR20150081204 A KR 20150081204A KR 102351925 B1 KR102351925 B1 KR 102351925B1
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- component
- acrylate
- photocurable composition
- monofunctional
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 75
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 58
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 43
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 phenoxyethyl Chemical group 0.000 claims description 19
- 230000003287 optical effect Effects 0.000 claims description 12
- 125000002723 alicyclic group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 8
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 6
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 18
- 230000000052 comparative effect Effects 0.000 description 27
- 239000000853 adhesive Substances 0.000 description 21
- 230000001070 adhesive effect Effects 0.000 description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000945 filler Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 5
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- VMFJVWPCRCAWBS-UHFFFAOYSA-N (3-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 VMFJVWPCRCAWBS-UHFFFAOYSA-N 0.000 description 1
- ZRIPJJWYODJTLH-UHFFFAOYSA-N (4-benzylphenyl)-(4-chlorophenyl)methanone Chemical compound C1=CC(Cl)=CC=C1C(=O)C(C=C1)=CC=C1CC1=CC=CC=C1 ZRIPJJWYODJTLH-UHFFFAOYSA-N 0.000 description 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- JYAQYXOVOHJRCS-UHFFFAOYSA-N 1-(3-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(Br)=C1 JYAQYXOVOHJRCS-UHFFFAOYSA-N 0.000 description 1
- SKBBQSLSGRSQAJ-UHFFFAOYSA-N 1-(4-acetylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C(C)=O)C=C1 SKBBQSLSGRSQAJ-UHFFFAOYSA-N 0.000 description 1
- HDMHXSCNTJQYOS-UHFFFAOYSA-N 1-(4-prop-2-enylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(CC=C)C=C1 HDMHXSCNTJQYOS-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- KMSYDDGPKBBSNA-UHFFFAOYSA-N 3-ethyl-1-phenylpentan-1-one Chemical compound CCC(CC)CC(=O)C1=CC=CC=C1 KMSYDDGPKBBSNA-UHFFFAOYSA-N 0.000 description 1
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 1
- DLGLWFGFEQRRCP-UHFFFAOYSA-N 6-chloro-1-nonylxanthen-9-one Chemical compound O1C2=CC(Cl)=CC=C2C(=O)C2=C1C=CC=C2CCCCCCCCC DLGLWFGFEQRRCP-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- FPLYNRPOIZEADP-UHFFFAOYSA-N octylsilane Chemical compound CCCCCCCC[SiH3] FPLYNRPOIZEADP-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 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 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000009849 vacuum degassing Methods 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Abstract
접착하기 어려운 재료에 대하여도 안정된 접착성을 갖는 동시에, 신뢰성 시험 후에 있어서도 안정된 접착성을 확보할 수 있는 광경화성 조성물을 제공하는 것을 목적으로 한다.
하기 (A)~(D)성분을 포함하고, (A)성분 100질량부에 대하여, (B)성분, (C)성분, 및, (B)성분과 (C)성분 이외의 (메타)아크릴 단량체의 합계가 50~200질량부인 광경화성 조성물.
(A)성분 : (메타)아크릴기를 갖는 (메타)아크릴 단량체 중합체
(B)성분 : 아크릴로일 모르폴린
(C)성분 : 디사이클로펜타닐(메타)아크릴레이트
(D)성분 : 광개시제 An object of the present invention is to provide a photocurable composition that has stable adhesiveness even to materials that are difficult to adhere and can ensure stable adhesiveness even after a reliability test.
The following (A)-(D)component is included, with respect to 100 mass parts of (A)component, (B)component, (C)component, and (B)component and (meth)acryl other than (C)component The photocurable composition whose total of a monomer is 50-200 mass parts.
(A) component: (meth)acrylic monomer polymer which has (meth)acrylic group
(B) component: acryloyl morpholine
(C)component: dicyclofentanyl (meth)acrylate
(D) component: photoinitiator
Description
본 발명은, 광 픽업의, 포토디텍터나 레이저 다이오드의 조립 또는 액추에이터의 고정에 적합한 광경화성 조성물에 관한 것이다. The present invention relates to a photocurable composition suitable for assembling a photodetector or laser diode of an optical pickup or fixing an actuator.
특허문헌 1(일본특허공개2008-150502호 공보)에는, 아크릴로일기를 양 말단에 갖는 폴리 아크릴 중합체를 포함하는 조성물에 관한 발명이 기재되어 있다. 해당조성물의 경화물에는 유연성이 있으므로, 영구압축변형 등의 시험에 있어서는, 양호한 결과를 갖는다. 그러나, 피착체를 강고히 고정하는 것에는 적합하지 않으며, 해당 문헌에는 접착 용도에 적합하다고 기재되어 있으나, 접착 강도가 어느 정도인지 명확하지 않다. (메타)아크릴 단량체를 이용한 광경화성 조성물은, 흡습되기 쉽고, 신뢰성 시험인 내습성 시험 (60 ℃, 95% RH 등)에서는 경화물과 피착체의 계면에 수분이 침입하여, 박리되기 쉬운 경향을 보이며, 특히 경화물이 연질한 것은 그 경향이 강하다. Patent Document 1 (Japanese Patent Application Laid-Open No. 2008-150502) describes an invention relating to a composition comprising a polyacrylic polymer having acryloyl groups at both terminals. Since the cured product of the composition has flexibility, good results are obtained in tests such as permanent compression set. However, it is not suitable for firmly fixing an adherend, and although it is described in the document that it is suitable for an adhesive use, it is not clear to what extent the adhesive strength is. A photocurable composition using a (meth)acrylic monomer is prone to moisture absorption, and in a moisture resistance test (60 ° C, 95% RH, etc.), which is a reliability test, moisture enters the interface between the cured product and the adherend, and tends to peel off. The tendency is strong, especially when the cured product is soft.
또한, 종래의 치수 정밀도는 양호하나 접착하기 어려운 엔지니어링 플라스틱인 폴리페닐렌 설파이드 등이, 광 픽업의 포토디텍터, 레이저 다이오드, 액추에이터의 부품으로서 사용되어 왔다. 그러나, 해당 재료는 난접착 재료이므로 접착력을 확보하는 동시에, 내습성 시험에 있어서도 그 접착력을 유지하는 것은 곤란하였다. In addition, polyphenylene sulfide, which is an engineering plastic that has good dimensional accuracy but is difficult to adhere, has been used as components of photodetectors, laser diodes, and actuators of optical pickups. However, since the material is a non-adhesive material, it was difficult to secure the adhesive force and maintain the adhesive force also in the moisture resistance test.
본 발명은, 접착하기 어려운 재료에 대해서도 안정된 접착성을 갖는 동시에, 신뢰성 시험 후에 있어서도 안정된 접착성을 확보할 수 있는 광경화성 조성물을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a photocurable composition which has stable adhesiveness even to materials that are difficult to adhere and can ensure stable adhesiveness even after a reliability test.
본 발명자들은, 상기 과제를 달성하기 위해 예의 검토한 결과, 하기의 특정한 성분을 배합하는 것에 의해, 접착하기 어려운 재료에 대하여 접착과 동시에, 내습시험에 있어서도 물리특성을 유지할 수 있는 광경화성 조성물을 얻을 수 있는 것을 발견하여, 본 발명을 완성하기에 이르렀다. As a result of intensive studies to achieve the above object, the present inventors have obtained a photocurable composition capable of maintaining physical properties even in a moisture resistance test while adhering to a material that is difficult to adhere by blending the following specific components Found that it can be done, and came to complete the present invention.
본 발명의 요지를 이하에 설명한다. The gist of the present invention will be described below.
1. 하기 (A)~(D)성분을 포함하고, (A)성분 100질량부에 대하여, (B)성분, (C)성분, 및, (B)성분과 (C)성분 이외의 (메타)아크릴 단량체의 합계가 50~200질량부인 광경화성 조성물. 1. Following (A)-(D)component is included, with respect to 100 mass parts of (A)component, (B)component, (C)component, and (B)component other than (B)component and (C)component (meta ) A photocurable composition in which the total of the acrylic monomer is 50 to 200 parts by mass.
(A)성분 : (메타)아크릴기를 갖는 (메타)아크릴 단량체 중합체 (A) component: (meth)acrylic monomer polymer which has (meth)acrylic group
(B)성분 : 아크릴로일 모르폴린 (B) component: acryloyl morpholine
(C)성분 : 디사이클로펜타닐(메타)아크릴레이트 (C)component: dicyclofentanyl (meth)acrylate
(D)성분 : 광개시제 (D) component: photoinitiator
2. (B)성분과 (C)성분 이외의 (메타)아크릴 단량체는, 상기 (B)성분과 상기 (C)성분 이외의 지환식 탄화수소기를 갖는 단관능(메타)아크릴 단량체와, 방향족 구조를 갖는 단관능(메타)아크릴 단량체, 및/또는 탄소원자수 10이하의 알킬기를 갖는 단관능(메타)아크릴레이트를 더욱 포함하는, 상기 1에 기재된 광경화성 조성물. 2. (B) component and (C) component (meth)acryl monomer other than the monofunctional (meth)acryl monomer which has alicyclic hydrocarbon groups other than the said (B) component and said (C)component, and aromatic structure The photocurable composition according to 1, further comprising a monofunctional (meth)acrylic monomer having a monofunctional (meth)acrylic monomer, and/or a monofunctional (meth)acrylate having an alkyl group having 10 or less carbon atoms.
3. 지환식 탄화수소기를 갖는 단관능(메타)아크릴 단량체는 이소보닐(메타)아크릴레이트를 포함하고, 방향족 구조를 갖는 단관능(메타)아크릴 단량체는 페녹시에틸(메타)아크릴레이트를 포함하고, 탄소원자수 10이하의 알킬기를 갖는 단관능(메타)아크릴레이트는 이소노닐(메타)아크릴레이트를 포함하는 상기 2에 기재된 광경화성 조성물. 3. The monofunctional (meth) acrylic monomer having an alicyclic hydrocarbon group includes isobornyl (meth) acrylate, and the monofunctional (meth) acrylic monomer having an aromatic structure includes phenoxyethyl (meth) acrylate, The photocurable composition according to 2 above, wherein the monofunctional (meth)acrylate having an alkyl group having 10 or less carbon atoms includes isononyl (meth)acrylate.
4. 경화물 유리전이 온도가 100 ℃ 이상인 상기 1~3의 어느 것인가에 기재된 광경화성 조성물. 4. The photocurable composition according to any one of 1 to 3 above, wherein the cured product glass transition temperature is 100°C or higher.
5. 광 픽업에 사용되는 상기 1~4의 어느 것인가에 기재된 광경화성 조성물. 5. The photocurable composition as described in any one of said 1-4 used for an optical pickup.
6. 포토디텍터의 조립, 레이저 다이오드의 조립 또는 액추에이터의 고정에 사용 되는, 상기 1~5의 어느 것인가에 기재된 광경화성 조성물. 6. The photocurable composition according to any one of 1 to 5 above, which is used for assembling a photodetector, assembling a laser diode, or fixing an actuator.
7. 폴리페닐렌 설파이드, 폴리카보네이트, 및 액정 폴리머로 이루어지는 군에서선택되는 적어도 1종을 포함하는 피착체를 접착하는 용도로 이용하는, 상기 1~6의 어느 1항에 기재된 광경화성 조성물. 7. The photocurable composition according to any one of 1 to 6 above, which is used for adhering an adherend comprising at least one selected from the group consisting of polyphenylene sulfide, polycarbonate, and liquid crystal polymer.
본 발명의 광경화성 조성물은, 응력 저감이 요구되는 광학부품 용도에 사용되는 접착하기 어려운 재료에 대해서도 안정된 접착성을 갖는 동시에, 신뢰성 시험 후에 있어서도 안정된 접착성을 확보할 수 있다. 따라서, 본 발명의 광경화성 조성물은, 광 픽업의 렌즈 등의 광학부품의 접착에 특히 호적하게 이용된다. The photocurable composition of the present invention has stable adhesion even to materials that are difficult to adhere to materials used for optical component applications requiring stress reduction, and can ensure stable adhesion even after a reliability test. Therefore, the photocurable composition of this invention is used especially suitably for adhesion|attachment of optical components, such as a lens of an optical pickup.
본 발명에 대해 이하에 상세히 설명한다. 본 발명의 광경화성 조성물(이하, 단순히 「조성물」이라고도 칭함)은, 하기 (A)~(D)성분을 포함하고, (A)성분 100질량부에 대하여, (B)성분, (C)성분, 및, (B)성분과 (C)성분 이외의 (메타)아크릴 단량체의 합계가 50~200질량부인 것을 특징으로 한다. The present invention will be described in detail below. The photocurable composition (henceforth simply referred to as "composition") of this invention contains the following (A)-(D)component, (B)component, (C)component with respect to 100 mass parts of (A)components and (B) component and the sum total of (meth)acryl monomers other than (C)component are 50-200 mass parts, It is characterized by the above-mentioned.
(A)성분 : (메타)아크릴기를 갖는 (메타)아크릴 단량체 중합체 (A) component: (meth)acrylic monomer polymer which has (meth)acrylic group
(B)성분 : 아크릴로일 모르폴린 (B) component: acryloyl morpholine
(C)성분 : 디사이클로펜타닐(메타)아크릴레이트 (C)component: dicyclofentanyl (meth)acrylate
(D)성분 : 광개시제. (D) Component: Photoinitiator.
본 발명의 광경화성 조성물은, (A)성분으로서, (메타)아크릴기를 갖는 (메타)아크릴 단량체 중합체 ((메타)아크릴기를 갖는 단량체 성분을 중합하여 이루어지는 중합체)를 필수적으로 포함한다. 여기에서, (메타)아크릴이란 아크릴과 메타크릴의 총칭이다. (A)성분은, 주골격인 (메타)아크릴 단량체 중합체에, 반응성을 갖는 (메타)아크릴기가 도입된 구조를 갖고 있다. 해당(메타)아크릴기는, 분자의 측쇄(側鎖)및/또는 말단의 어느 것인가에 존재할 수 있다. 또한, (메타)아크릴 단량체 중합체는, 분자 내에 1이상의 (메타)아크릴기를 포함하면 되고, 2이상의 (메타)아크릴기를 포함하고 있을 수 있다. The photocurable composition of the present invention essentially contains, as component (A), a (meth)acrylic monomer polymer having a (meth)acryl group (a polymer formed by polymerizing a monomer component having a (meth)acryl group). Here, (meth)acryl is a generic term for acryl and methacryl. (A) Component has the structure in which the (meth)acryl group which has reactivity was introduce|transduced into the (meth)acryl monomer polymer which is a main skeleton. The (meth)acryl group may exist in either the side chain and/or the terminal of the molecule. In addition, the (meth)acryl monomer polymer may contain one or more (meth)acryl groups in the molecule, and may contain two or more (meth)acryl groups.
(A)성분의 (메타)아크릴 단량체 중합체를 구성하는 (메타)아크릴 단량체로는 특별히 한정되지 않고, 다양한 것을 이용할 수 있다. 구체적으로는, (메타)아크릴산, (메타)아크릴산 메틸, (메타)아크릴산 에틸, (메타)아크릴산-n-프로필, (메타)아크릴산 이소프로필, (메타)아크릴산-n-부틸, (메타)아크릴산 이소부틸, (메타)아크릴산-t-부틸, (메타)아크릴산-n-펜틸, (메타)아크릴산-n-헥실, (메타)아크릴산 사이클로헥실, (메타)아크릴산-n-헵틸, (메타)아크릴산-n-옥틸, (메타)아크릴산-2-에틸헥실, (메타)아크릴산 노닐, (메타)아크릴산 데실, (메타)아크릴산 도데실, (메타)아크릴산 페닐, (메타)아크릴산 톨루일, (메타)아크릴산 벤질, (메타)아크릴산 2-메톡시에틸, (메타)아크릴산 3-메톡시부틸, (메타)아크릴산 2-히드록시에틸, (메타)아크릴산 2-하이드록시프로필, (메타)아크릴산 스테아릴, (메타)아크릴산 글리시딜, (메타)아크릴산 2-아미노에틸, γ-(메타크릴로일옥시프로필)트리메톡시실란, (메타)아크릴산의 에틸렌옥사이드 부가물, (메타)아크릴산 트리플루오로메틸, (메타)아크릴산 2-트리플루오로메틸에틸, (메타)아크릴산 2-퍼플루오르에틸에틸, (메타)아크릴산 2-퍼플루오르에틸-2-퍼플루오르부틸에틸, (메타)아크릴산 2-퍼플루오르에틸, (메타)아크릴산퍼플루오르메틸, (메타)아크릴산디퍼플루오르메틸메틸, (메타)아크릴산 2-퍼플루오르메틸-2-퍼플루오르에틸메틸, (메타)아크릴산 2-퍼플루오르헥실에틸, (메타)아크릴산 2-퍼플루오르데실에틸, (메타)아크릴산 2-퍼플루오르헥사데실에틸 등을 들 수 있으나, 이것들에 한정되는 것은 아니다. 본 발명에 있어서는, 상기(메타)아크릴 단량체에서 선택하여 중합시킬 수 있으나, 바람직하게는 탄화수소기를 갖는 (메타)아크릴 단량체를 선택하는 것이 바람직하다. 한편, 상기(메타)아크릴 단량체 중합체를 구성하는 (메타)아크릴 단량체는, 1종만을 단독으로 사용할 수도 있고, 2종 이상을 조합하여 사용할 수도 있다. (A) It does not specifically limit as a (meth)acryl monomer which comprises the (meth)acryl monomer polymer of component, A various thing can be used. Specifically, (meth)acrylic acid, (meth)methyl acrylate, (meth)acrylate, (meth)acrylic acid-n-propyl, (meth)acrylic acid isopropyl, (meth)acrylic acid-n-butyl, (meth)acrylic acid Isobutyl, (meth)acrylic acid-t-butyl, (meth)acrylic acid-n-pentyl, (meth)acrylic acid-n-hexyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid-n-heptyl, (meth)acrylic acid -n-octyl, (meth)acrylic acid-2-ethylhexyl, (meth)acrylic acid nonyl, (meth)acrylic acid decyl, (meth)acrylic acid dodecyl, (meth)acrylic acid phenyl, (meth)acrylic acid toluyl, (meth) Benzyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid glycidyl, (meth)acrylic acid 2-aminoethyl, γ-(methacryloyloxypropyl)trimethoxysilane, (meth)acrylic acid ethylene oxide adduct, (meth)acrylic acid trifluoromethyl , (meth)acrylic acid 2-trifluoromethylethyl, (meth)acrylic acid 2-perfluoroethylethyl, (meth)acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth)acrylic acid 2-perfluoroethyl , (meth)acrylic acid perfluoromethyl, (meth)acrylic acid diperfluoromethylmethyl, (meth)acrylic acid 2-perfluoromethyl-2-perfluoroethylmethyl, (meth)acrylic acid 2-perfluorohexylethyl, (meth)acrylic acid 2-perfluordecylethyl, (meth)acrylic acid 2-perfluorohexadecylethyl, etc. are mentioned, However, It is not limited to these. In the present invention, polymerization can be carried out by selecting from the above (meth)acrylic monomers, but it is preferable to select a (meth)acrylic monomer having a hydrocarbon group. In addition, the (meth)acryl monomer which comprises the said (meth)acryl monomer polymer may be used individually by 1 type, and may be used in combination of 2 or more type.
(A)성분의 중량평균 분자량은, 바람직하게는 10,000~50,000이다. 중량평균 분자량이 10,000 이상이면, 경화물의 탄성이 양호하게 발현되어, 내열성 시험에 있어서 경화물에 깨어짐이 발생하는 것을 억제할 수 있다. 한편, 중량평균 분자량이 50,000 이하이면, 점도가 지나치게 높아져 광경화성 조성물을 도포할 때에 섬유화가 발생하는 것을 억제할 수 있다. (A) The weight average molecular weight of component becomes like this. Preferably it is 10,000-50,000. When the weight average molecular weight is 10,000 or more, elasticity of the cured product is favorably expressed, and cracking of the cured product can be suppressed in the heat resistance test. On the other hand, when the weight average molecular weight is 50,000 or less, the viscosity becomes too high and it can suppress that fiberization occurs when the photocurable composition is applied.
(A)성분은 다양한 중합법에 의해 얻을 수 있고, 그 방법은 특별히 한정되지 않으나, 단량체의 범용성 및 반응 제어의 용이성의 점에서 라디칼 중합법이 바람직하다. 라디칼 중합 중에서도 제어 라디칼 중합이 바람직하고, 리빙 라디칼 중합이 보다 바람직하고, 원자이동 라디칼 중합이 특히 바람직하다. 또한, 주골격인 (메타)아크릴 단량체의 중합체에 대하여, (메타)아크릴기를 도입하는 방법으로는, (1)말단에 수산기를 갖는 비닐계 중합체와, 염소, 브롬, 또는 수산기를 함유하는 (메타)아크릴레이트 화합물을 반응시키는 방법, (2)말단에 할로겐기를 갖는 비닐계 중합체와 알칼리 금속 이온 또는 4급 암모니움 이온을 함유하는 (메타)아크릴레이트 화합물을 반응시키는 방법, (3)말단에 수산기를 갖는 비닐계 중합체에 디이소시아네이트 화합물을 반응시켜, 잔존 이소시아네이트기와 수산기함유(메타)아크릴레이트를 반응시키는 방법 등을 들 수 있다. 이들 방법은 이미 공지되어 있고, 일본특허공개 소61-133201호 공보, 일본특허공개 평11-80250호 공보, 일본특허공개 2000-38404호 공보, 일본특허공개 2001-271055호 공보, 일본특허공개 2002-69121호 공보 등에 기재되어 있다. (A) Component can be obtained by various polymerization methods, The method is although it does not specifically limit, The point of the versatility of a monomer and the easiness of reaction control, the radical polymerization method is preferable. Among the radical polymerizations, controlled radical polymerization is preferable, living radical polymerization is more preferable, and atom transfer radical polymerization is particularly preferable. In addition, as a method of introducing a (meth)acrylic group to the polymer of the (meth)acrylic monomer as the main skeleton, (1) a vinyl polymer having a hydroxyl group at the terminal, chlorine, bromine, or (meth) containing a hydroxyl group ) A method of reacting an acrylate compound, (2) a method of reacting a vinyl polymer having a halogen group at the terminal with a (meth)acrylate compound containing an alkali metal ion or quaternary ammonium ion, (3) a hydroxyl group at the terminal and a method of reacting a diisocyanate compound with a vinyl polymer having These methods are already known. Japanese Patent Laid-Open No. 61-133201, Japanese Patent Laid-Open No. Hei 11-80250, Japanese Unexamined Patent Publication No. 2000-38404, Japanese Patent Application Laid-Open No. 2001-271055, Japanese Patent Laid-Open No. 2002 -69121, etc. are described.
(A)성분은, 시판품을 이용할 수도 있고, 시판품으로는, 주식회사 가네카제의 RC200C, RC100C 등을 들 수 있으나, 이것들에 한정되는 것이 아니다. (A) A commercial item can also be used for (A) component, Although RC200C by Kaneka Corporation, RC100C, etc. are mentioned as a commercial item, It is not limited to these.
본 발명의 광경화성 조성물은, (B)성분으로, 하기 화학식 1에 기재된 아크릴로일 모르폴린을 필수적으로 포함한다. (B)성분의 시판품으로는, 코진필름&케미칼 주식회사제의 ACMO(등록상표) 등을 들 수 있으나, 이것에 한정되는 것이 아니다. The photocurable composition of the present invention essentially contains, as component (B), acryloyl morpholine represented by the following formula (1). (B) Although ACMO (trademark) manufactured by Kojin Film & Chemicals Co., Ltd. etc. are mentioned as a commercial item of (B) component, It is not limited to this.
(A)성분 100질량부에 대하여, (B)성분은 1~120질량부 첨가되는 것이 바람직하다. 보다 바람직하게는 50~100질량부이다. (B)성분이 1질량부 이상 첨가되면 경화물이 경질되어 내습성이 향상되고, (B)성분이 120질량부 이하 첨가되면 경화물에 가요성이 발현된다. It is preferable that 1-120 mass parts of (B) components are added with respect to 100 mass parts of (A) component. More preferably, it is 50-100 mass parts. When 1 mass part or more of (B) component is added, hardened|cured material will harden and moisture resistance will improve, and when 120 mass parts or less of (B) component is added, flexibility will express to hardened|cured material.
본 발명의 광경화성 조성물은, (C)성분으로서, 하기 화학식 2에 기재된 디사이클로펜타닐(메타)아크릴레이트를 필수적으로 포함한다. 화학식 2에 있어서, R은 수소원자 또는 메틸기를 나타낸다. (C)성분의 시판품으로는, 히타치카세이 주식회사제의 FA-513AS등을 들 수 있으나, 이것에 한정되는 것이 아니다. The photocurable composition of the present invention essentially contains, as component (C), dicyclofentanyl (meth)acrylate represented by the following formula (2). In formula (2), R represents a hydrogen atom or a methyl group. (C) Although FA-513AS manufactured by Hitachi Kasei Co., Ltd. etc. are mentioned as a commercial item of (C)component, It is not limited to this.
(A)성분 100질량부에 대하여, (C)성분은 1~120질량부 첨가되는 것이 바람직하다. (C)성분이 1질량부 이상 첨가되면 경화물이 경질되어 내습성이 향상되고, (C)성분이 120질량부 이하 첨가되면 접착력이 향상된다. It is preferable that 1-120 mass parts of (C)components are added with respect to 100 mass parts of (A) component. When 1 mass part or more of (C)component is added, hardened|cured material will harden and moisture resistance will improve, and when (C)component is added 120 mass parts or less, adhesive force will improve.
본 발명에서는 신뢰성 시험에 있어서의 성능을 유지할 수 있는 범위에서 (B)성분과 (C)성분 이외의 (메타)아크릴 단량체 (이하, 「다른 (메타)아크릴 단량체」라고도 칭함)를 포함할 수도 있다. 한편, 본 명세서에서는, (A)성분은 분자 내에 (메타)아크릴 단량체 중합체 ((메타)아크릴기를 갖는 단량체 성분이 중합되어 이루어지는 중합체)을 포함하므로, 「(메타)아크릴 단량체」에는 포함하지 않는 것으로 한다. 또한, 본 명세서 내에서, 「(메타)아크릴 단량체」는, (메타)아크릴기를 갖는 인산 에스테르 화합물을 제외하는 것으로 한다. (메타)아크릴기를 갖는 인산 에스테르 화합물은, 점성이 높고 희석 능력이 낮은 경향이 있어, 본 명세서 내에서는, 이것 외의 (메타)아크릴 단량체와 구별하여 취급한다. In the present invention, (meth)acryl monomers other than (B) component and (C) component (hereinafter also referred to as "other (meth)acryl monomer") may be included in the range that can maintain the performance in the reliability test. . On the other hand, in this specification, since component (A) contains a (meth)acrylic monomer polymer (a polymer obtained by polymerization of a monomer component having a (meth)acryl group) in the molecule, it is not included in "(meth)acrylic monomer". do. In addition, in this specification, "(meth)acryl monomer" shall exclude the phosphoric acid ester compound which has a (meth)acryl group. The phosphate ester compound which has a (meth)acryl group has a high viscosity and tends to have low dilution ability, and within this specification, it is handled separately from other (meth)acryl monomers.
다른 (메타)아크릴 단량체는, 분자 내에 (메타)아크릴기를 1개 갖는, 단관능(메타)아크릴 단량체인 것이 바람직하다. 이러한 단관능(메타)아크릴 단량체 중에서도 특히, 지환식 탄화수소기를 갖는 단관능(메타)아크릴 단량체와, 방향족 구조(aromatic structure)을 갖는 단관능(메타)아크릴 단량체 및/또는 탄소원자수 10이하의 알킬기를 갖는 단관능(메타)아크릴레이트를 포함하는 것이 바람직하다. 이것들의 단관능(메타)아크릴 단량체를 첨가하는 것으로, 내습성이 향상되고, 난접착의 피착체에 대하여도 접착력 저하를 억제할 수 있다. It is preferable that another (meth)acryl monomer is a monofunctional (meth)acryl monomer which has one (meth)acryl group in a molecule|numerator. Among these monofunctional (meth)acrylic monomers, in particular, a monofunctional (meth)acrylic monomer having an alicyclic hydrocarbon group, a monofunctional (meth)acrylic monomer having an aromatic structure, and/or an alkyl group having 10 or less carbon atoms It is preferable to contain the monofunctional (meth)acrylate which has. By adding these monofunctional (meth)acryl monomers, moisture resistance can improve and the adhesive force fall can be suppressed also with respect to a to-be-adhered body of hard adhesion.
지환식 탄화수소기를 갖는 단관능(메타)아크릴 단량체의 구체적인 예로는, 이소보닐(메타)아크릴레이트, 사이클로헥실(메타)아크릴레이트, 아다만타닐(메타)아크릴레이트 등을 들 수 있으나, 이것들에 한정되는 것이 아니다. 이것들의 지환식 탄화수소기를 갖는 단관능(메타)아크릴 단량체는, 1종류를 단독으로 사용할 수도 있고 2종류 이상을 혼합하여 사용할 수도 있다. 지환식 탄화수소기를 갖는 단관능(메타)아크릴 단량체는, 시판품을 이용할 수도 있고, 예를 들면, 교에이샤 케미칼 주식회사제의 라이트 아크릴레이트 IBX-A, 라이트 에스테르 IB-X 등, 오사카유기화학공업 주식회사제의 IBXA, V#155 등을 들 수 있으나, 이것들에 한정되는 것은 아니다. Specific examples of the monofunctional (meth)acrylic monomer having an alicyclic hydrocarbon group include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, adamantanyl (meth)acrylate, etc., but limited to these it's not going to be These monofunctional (meth)acryl monomers which have an alicyclic hydrocarbon group may be used individually by 1 type, and may be used in mixture of 2 or more types. As the monofunctional (meth)acrylic monomer having an alicyclic hydrocarbon group, a commercially available product may be used, for example, light acrylate IBX-A, light ester IB-X manufactured by Kyoeisha Chemical Co., Ltd., Osaka Organic Chemical Industry Co., Ltd. Although IBXA, V#155, etc. are mentioned, it is not limited to these.
방향족 구조를 갖는 단관능(메타)아크릴 단량체의 구체적인 예로는, 벤질(메타)아크릴레이트, 페녹시에틸(메타)아크릴레이트, 페녹시폴리에틸렌글리콜(메타)아크릴레이트 등을 들 수 있으나 이것들에 한정되는 것이 아니다. 이것들의 방향족 구조를 갖는 단관능(메타)아크릴 단량체는, 1종류를 단독으로 사용할 수도 있고, 2종류 이상을 혼합하여 사용할 수도 있다. 방향족 구조를 갖는 단관능(메타)아크릴 단량체는, 시판품을 이용할 수도 있고, 예를 들면, 교에이샤 케미칼 주식회사제의 라이트 에스테르 BZ, PO, 라이트 아크릴레이트 PO-A, P-200A 등, 오사카유기화학공업 주식회사제의 V#160, V#192 등을 들 수 있으나, 이것들에 한정되는 것이 아니다. Specific examples of the monofunctional (meth)acrylic monomer having an aromatic structure include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, etc., but are limited to these it is not The monofunctional (meth)acryl monomer which has these aromatic structures may be used individually by 1 type, and may be used in mixture of 2 or more types. As the monofunctional (meth)acrylic monomer having an aromatic structure, a commercially available product may be used, for example, light ester BZ, PO, light acrylate PO-A, P-200A manufactured by Kyoeisha Chemical Co., Ltd., Osaka Organic Co., Ltd. Although V#160, V#192, etc. manufactured by Chemical Industry Co., Ltd. are mentioned, it is not limited to these.
탄소원자수 10이하의 알킬기를 갖는 단관능(메타)아크릴 단량체의 구체적인 예로는, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 이소노닐(메타)아크릴레이트 등을 들 수 있으나, 이것들에 한정되는 것이 아니다. 이것들의 탄소원자수 10이하의 알킬기를 갖는 단관능(메타)아크릴 단량체는, 1종류를 단독으로 사용할 수도 있고, 2종류 이상을 혼합하여 사용할 수도 있다. 탄소원자수 10이하의 알킬기를 갖는 단관능(메타)아크릴 단량체는, 시판품을 이용할 수도 있고, 예를 들면, 교에이샤 케미칼 주식회사제의 라이트 에스테르 M, E, NB, IB, TB, EH, 라이트 아크릴레이트 IAA, L-A, IM-A, S-A등, 오사카유기화학공업 주식회사제의 INAA, AIB, TBA, IOAA 등을 들 수 있으나 이것들에 한정되는 것이 아니다. Specific examples of the monofunctional (meth)acrylic monomer having an alkyl group having 10 or less carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , t-butyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and the like, but is not limited thereto. These monofunctional (meth)acryl monomers which have a C10 or less alkyl group may be used individually by 1 type, and may mix and use 2 or more types. Commercially available monofunctional (meth)acrylic monomers having an alkyl group having 10 or less carbon atoms, for example, light esters M, E, NB, IB, TB, EH, and light acryl manufactured by Kyoeisha Chemical Co., Ltd. Rate IAA, LA, IM-A, SA, and the like, and INAA, AIB, TBA, IOAA manufactured by Osaka Organic Chemical Industry Co., Ltd., but is not limited thereto.
상기 이외에, 다른 (메타)아크릴 단량체로서, 탄소원자수가 11이상의 알킬기를 갖는 단관능(메타)아크릴 단량체인 이소스테아릴아크릴레이트나, 2관능(메타)아크릴 단량체인 디메틸올트리시클로데칸디 아크릴레이트 등을 첨가할 수도 있다. 구체적으로는, 신나카무라화학공업 주식회사제의 S-1800A, 교에이샤 케미칼 주식회사제의 라이트 아크릴레이트 DPM-A 등을 들 수 있으나, 이것들에 한정되는 것은 아니다. In addition to the above, as other (meth)acrylic monomers, isostearyl acrylate, which is a monofunctional (meth)acrylic monomer having an alkyl group having 11 or more carbon atoms, and dimethyloltricyclodecanediacrylate, which is a bifunctional (meth)acrylic monomer etc. may be added. Specific examples thereof include S-1800A manufactured by Shin-Nakamura Chemical Industry Co., Ltd., light acrylate DPM-A manufactured by Kyoeisha Chemical Co., Ltd., and the like, but are not limited thereto.
(A)성분 100질량부에 대하여, (B)성분, (C)성분, 및, (B)성분과 (C)성분 이외의 (메타)아크릴 단량체의 합계가 50~200질량부인 것이 바람직하다. 50질량부 이상이면 광경화성 조성물의 점도가 낮아져 취급성이 향상된다. 한편, 200질량부 이하이면 접착력이 충분히 유지된다. It is preferable that the sum total of (meth)acryl monomers other than (B)component, (C)component, and (B)component and (C)component is 50-200 mass parts with respect to 100 mass parts of (A) component. If it is 50 mass parts or more, the viscosity of a photocurable composition will become low and handleability will improve. On the other hand, if it is 200 mass parts or less, adhesive force is fully maintained.
본 발명의 광경화성 조성물은, (D)성분으로서 광개시제를 필수적으로 포함한다. 광개시제는, 상기의 (메타)아크릴 단량체를 경화시키기 위해, 자외선이나 가시광등의 에너지 선이 조사되었을 때에 분해한다. 이러한 광개시제로서, 특히 바람직하게는, 에너지 선을 조사했을 때에 라디칼종을 발생하는 광개시제가 사용된다. The photocurable composition of this invention contains a photoinitiator essentially as (D)component. The photoinitiator decomposes when irradiated with energy rays such as ultraviolet rays or visible light in order to cure the (meth)acrylic monomer. As such a photoinitiator, particularly preferably, a photoinitiator that generates radical species when irradiated with an energy ray is used.
(D)성분의 구체적인 예로는, 아세토페논, 프로피오페논, 벤조페논, 크산톤, 플루오레논, 벤즈알데히드, 안트라퀴논, 트리페닐아민, 카르바졸, 3-메틸 아세토페논, 4-메틸 아세토페논, 3-펜틸아세토페논, 4-메톡시아세토페논, 3-브로모아세토페논, 2,2-디에톡시아세토페논, p-디아세틸벤젠, 3-메톡시벤조페논, 2,4,6-트리메틸벤조페논, 올리고 (2-하이드록시-2-메틸-1- (4- (1-메틸비닐)페닐)프로파논), 4-알릴아세토페논, 캠퍼퀴논, 2,4,6-트리메틸벤조일디페닐 포스핀옥사이드, 4-메틸 벤조페논, 4-클로로-4'-벤질벤조페논, 2-하이드록시-2-메틸-1-페닐-프로판-1-온 , 1-하이드록시사이클로헥실페닐케톤, 3-클로로크산톤, 3,9-디클로로 크산톤, 3-클로로-8-노닐크산톤, 벤조일, 벤조일메틸에테르, 벤조인부틸에테르, 비스(4-디메틸아미노페닐)케톤, 벤질메톡시케탈, 2-클로로티오잔톤, o-메틸 벤조에이트, 벤질디메틸케탈, 메틸벤조일포르메이트 등을 들 수 있으나, 이것들에 한정되는 것이 아니다. (D) As a specific example of a component, acetophenone, propiophenone, benzophenone, xanthone, fluorenone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3 -Pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 2,2-diethoxyacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 2,4,6-trimethylbenzophenone , oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), 4-allylacetophenone, camphorquinone, 2,4,6-trimethylbenzoyldiphenyl phosphine Oxide, 4-methylbenzophenone, 4-chloro-4'-benzylbenzophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexylphenylketone, 3-chloro Loxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoylmethyl ether, benzoinbutyl ether, bis(4-dimethylaminophenyl)ketone, benzylmethoxyketal, 2-chloro thioxanthone, o-methyl benzoate, benzyl dimethyl ketal, methyl benzoyl formate, and the like, but are not limited thereto.
(A)성분, (B)성분, (C)성분, (B)성분과 (C)성분 이외의 (메타)아크릴 단량체(기타의 (메타)아크릴 단량체)의 합계 100질량부에 대하여, (D)성분이 0.1~10질량부 첨가되는 것이 바람직하다. (D)성분이 0.1질량부 이상이면 표면경화성이 향상되어 턱(tuck)이 없어지고, (D)성분이 10질량부 이하이면 광경화성 조성물의 보존 안정성을 유지할 수 있다. (A) With respect to a total of 100 mass parts of (meth)acryl monomers (other (meth)acryl monomers) other than (A) component, (B)component, (C)component, (B)component, and (C)component, (D ) It is preferable that 0.1-10 mass parts of components are added. When (D)component is 0.1 mass part or more, surface hardening property improves and a tuck disappears, and (D)component is 10 mass parts or less, storage stability of a photocurable composition can be maintained.
본 발명의 광경화성 조성물에는, 무기 충진제나 유기 충진제 등의 충진제를 적당히 첨가할 수 있다. 충진제를 첨가하는 것으로, 점성·요변성(thixotropy)뿐만아니라 경화성, 강인성을 조정할 수 있다. To the photocurable composition of the present invention, a filler such as an inorganic filler or an organic filler may be appropriately added. By adding a filler, not only viscosity and thixotropy but also hardenability and toughness can be adjusted.
무기충진제로서는, 알루미나, 실리카, 비정질 실리카 등을 들 수 있으나, 이것들에 한정되는 것이 아니다. 한편, 유기 충진제로는, 스티렌 필러, 고무 필러, 코어쉘아크릴 필러 등을 들 수 있으나, 이것들에 한정되는 것이 아니다. 시판품으로는, 실리카분으로서, 주식회사 타츠모리제의 FUSELEX E-1, 아도마테크 주식회사제의 AO-802, 일본아에로질재팬 주식회사제의 아에로질시리즈로서 R972(디메틸디클로로실란 처리), R976(디메틸디클로로실란 처리), RY200(디메틸실리콘 처리), RX200(헥사메틸다이실라제인 처리), R800(옥틸실란 처리)등 들 수 있으나 이것들에 한정되는 것이 아니다. Examples of the inorganic filler include, but are not limited to, alumina, silica, amorphous silica, and the like. Meanwhile, examples of the organic filler include, but are not limited to, a styrene filler, a rubber filler, and a core-shell acrylic filler. Commercially available products include FUSELEX E-1 manufactured by Tatsumori Co., Ltd. as silica powder, AO-802 manufactured by Adomatech Co., Ltd., and R972 (dimethyldichlorosilane treatment) as aerosil series manufactured by Nippon Aerosil Japan Co., Ltd. , R976 (dimethyldichlorosilane treatment), RY200 (dimethylsilicone treatment), RX200 (hexamethyldisilazane treatment), R800 (octylsilane treatment), and the like, but are not limited thereto.
본 발명의 광경화성 조성물의 성상이나, 경화물의 물성이 손상되지 않을 정도로 그 특성을 조정하기 위해, 라디칼 열경화제, 감광제, 실란계 커플링제, 티타늄계 커플링제, 레벨링제, 중합 금지제, 노화 방지제, 가소제, 요변성 부여제, 충진제, 용제 등의 첨가제를 배합할 수 있다. In order to adjust the properties of the photocurable composition of the present invention and the physical properties of the cured product to the extent that the properties are not impaired, a radical thermosetting agent, a photosensitizer, a silane-based coupling agent, a titanium-based coupling agent, a leveling agent, a polymerization inhibitor, an anti-aging agent , a plasticizer, a thixotropic agent, a filler, and an additive such as a solvent may be blended.
본 발명의 광경화성 조성물은, 해당 조성물을 경화하여 이루어지는 경화물 유리전이 온도가 100?이상인 것이 바람직하다. 유리전이 온도가 100?이상이면, 고습도하에서도 충분한 접착성을 유지할 수 있다. The photocurable composition of the present invention preferably has a glass transition temperature of 100°C or more of a cured product obtained by curing the composition. When the glass transition temperature is 100°C or higher, sufficient adhesiveness can be maintained even under high humidity.
본 발명의 광경화성 조성물은, 응력저감이 요구되는 광학부품 용도에서 사용되는 접착하기 어려운 재료에 대하여도 안정된 접착성을 갖는 동시에, 신뢰성 시험 후에 있어서도 안정된 접착성을 확보할 수 있다. 따라서, 본 발명의 광경화성 조성물은, 광 픽업에 이용할 수 있는 것이 바람직하다. 상세하게는, 본 발명의 광경화성 조성물은, 포토디텍터의 조립, 레이저 다이오드의 조립 또는 액추에이터의 고정에 이용되는 것이 바람직하다. The photocurable composition of the present invention has stable adhesion even to materials that are difficult to adhere to for use in optical component applications requiring stress reduction, and can ensure stable adhesion even after a reliability test. Therefore, it is preferable that the photocurable composition of this invention can be used for an optical pickup. Specifically, the photocurable composition of the present invention is preferably used for assembling a photodetector, assembling a laser diode, or fixing an actuator.
또한, 상술한 바와 같이, 본 발명의 광경화성 조성물은, 접착하기 어려운 재료에 대한 접착성이 우수하다. 접착하기 어려운 재료로는, 예를 들면, 폴리페닐렌 설파이드, 폴리카보네이트, 액정 폴리머 등을 들 수 있다. 따라서, 본 발명의 광경화성 조성물은, 이것들의 재료로 이루어지는 군에서 선택되는 적어도 1종을 포함하는 피착체를 접착하는 용도로 이용되는 것이 바람직하다.
Moreover, as mentioned above, the photocurable composition of this invention is excellent in adhesiveness with respect to the material which is hard to adhere|attach. Examples of the material that are difficult to adhere to include polyphenylene sulfide, polycarbonate, and liquid crystal polymer. Accordingly, the photocurable composition of the present invention is preferably used for adhering an adherend comprising at least one selected from the group consisting of these materials.
[실시예][Example]
다음으로 실시예를 들어 본 발명을 더욱 상세히 설명하나, 본 발명은 이것들의 실시예로만 한정되는 것이 아니다. Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited only to these Examples.
[실시예 1~9, 비교예 1~7] [Examples 1 to 9, Comparative Examples 1 to 7]
조성물을 조제하기 위해 하기 성분을 준비하였다. The following ingredients were prepared to prepare the composition.
(A)성분 : (메타)아크릴기를 갖는 (메타)아크릴 단량체 중합체 (A) component: (meth)acrylic monomer polymer which has (meth)acrylic group
· 양말단에 아크릴기를 갖는 폴리아크릴 단량체 중합체(RC200C 주식회사 가네카제) · Polyacrylic monomer polymer having acrylic groups at both ends (RC200C Kaneka Co., Ltd.)
(A')성분 : (A)성분 이외의 (메타)아크릴기를 갖는 화합물 (A') component: The compound which has (meth)acryl groups other than (A) component
· 폴리부타디엔의 양말단에 우레탄 결합을 통해 아크릴기를 갖는 수지(TE-2000 니혼소다 주식회사제) Resin having acrylic groups through urethane bonds at both ends of polybutadiene (TE-2000 manufactured by Nippon Soda Co., Ltd.)
· 에스테르 타입의 2관능 아크릴올리고머(UV-3000B 일본합성화학공업주식회사제) · Ester-type bifunctional acrylic oligomer (UV-3000B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
(B)성분 : 아크릴로일 모르폴린 (B) component: acryloyl morpholine
· 아크릴로일 모르폴린(ACMO(등록상표) 코진필름&케미칼 주식회사제) · Acryloyl morpholine (ACMO (registered trademark) manufactured by Kojin Film & Chemical Co., Ltd.)
(C)성분 : 디사이클로펜타닐(메타)아크릴레이트 (C)component: dicyclofentanyl (meth)acrylate
· 디사이클로펜타닐 아크릴레이트(FA-513AS 히타치카세이 주식회사제) · Dicyclofentanyl acrylate (FA-513AS manufactured by Hitachi Kasei Co., Ltd.)
(B)성분과 (C)성분 이외의 (메타)아크릴레이트 단량체 (B) (meth)acrylate monomers other than component and (C)component
지환식 탄화수소기를 갖는 단관능(메타)아크릴 단량체 Monofunctional (meth)acrylic monomer having an alicyclic hydrocarbon group
· 이소보닐메타크릴레이트(라이트 에스테르IB-X 교에이샤 케미칼 주식회사제) · Isobornyl methacrylate (Light Ester IB-X, manufactured by Kyoeisha Chemical Co., Ltd.)
방향족 구조를 갖는 단관능(메타)아크릴 단량체 Monofunctional (meth)acrylic monomer having an aromatic structure
· 페녹시에틸 아크릴레이트(V#192 오사카유기화학공업 주식회사제) · Phenoxyethyl acrylate (V#192, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
탄소원자수 10이하의 알킬기를 갖는 단관능(메타)아크릴레이트 Monofunctional (meth)acrylate having an alkyl group having 10 or less carbon atoms
· 이소노닐아크릴레이트(INAA 오사카유기화학공업 주식회사제) · Isononyl acrylate (INAA Osaka Organic Chemical Co., Ltd.)
그 밖의 (메타)아크릴레이트 Other (meth)acrylates
· 이소스테아릴아크릴레이트(S-1800A 신나카무라화학공업 주식회사제) · Isostearyl acrylate (S-1800A manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
· 디메틸올 트리시클로데칸 디아크릴레이트(라이트아크릴레이트DPM-A 교에이샤 케미칼 주식회사제) · Dimethylol tricyclodecane diacrylate (light acrylate DPM-A manufactured by Kyoeisha Chemical Co., Ltd.)
(D)성분 : 광개시제 (D) component: photoinitiator
· 2-하이드록시-2-메틸-1-페닐-프로판-1-온 (DAROCUR1173 BASF사제) · 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR1173 manufactured by BASF)
첨가제 additive
· 2-히드록시에틸메타크릴레이트 애시드 포스페이트(JPA-514 조호쿠화학공업 주식회사제) · 2-hydroxyethyl methacrylate acid phosphate (JPA-514 Johoku Chemical Industry Co., Ltd.)
충진제 filler
· 실리카분 (FUSELEX E-1 주식회사 타츠모리제) Silica powder (FUSELEX E-1 manufactured by Tatsumori Co., Ltd.)
실시예 1~9과 비교예 1~7의 조성물을 조제하였다. (A)성분 (또는 (A')성분), (B)성분, (C)성분, (B)성분과 (C)성분 이외의 (메타)아크릴 단량체 및 첨가제를 칭량하여 교반솥에 투입하고, 교반기에서 30분간 교반하여 균일하게 하였다. 그 후, 다시 (D)성분을 칭량하여 교반솥에 투입한 후에 30분간 교반하였다. 마지막으로, 충진제를 칭량하여 교반솥에 투입하고, 30분간 감압탈포 교반을 하였다. 각 성분의 배합량은 표1에 따르고, 수치는 모두 질량부로 표기한다. 또한, 표 1에는, (B)성분, (C)성분, 및, (B)성분과 (C)성분 이외의 (메타)아크릴 단량체의 합계를 「전(全)(메타)아크릴 단량체의 합계」로 기재하였다. The compositions of Examples 1 to 9 and Comparative Examples 1 to 7 were prepared. (A) component (or (A') component), (B) component, (C) component, (B) component, and (meth)acrylic monomers and additives other than (C) component are weighed and put into a stirring pot, It was stirred for 30 minutes on a stirrer to make it uniform. Then, (D)component was again weighed, and after injecting|throwing-in to the stirring pot, it stirred for 30 minutes. Finally, the filler was weighed and put in a stirring pot, followed by vacuum degassing and stirring for 30 minutes. The mixing amount of each component is according to Table 1, and all numerical values are expressed in parts by mass. In addition, in Table 1, (B) component, (C)component, and the sum total of (meth)acryl monomers other than (B)component and (C)component "the sum total of all (meth)acryl monomers" was described as
2comparative example
2
3comparative example
3
4comparative example
4
5comparative example
5
6comparative example
6
7comparative example
7
실시예 1~9, 비교예 1~7에 대하여, 하기의 내습시험을 실시하고, 결과를 표 2에 정리하였다. Examples 1 to 9 and Comparative Examples 1 to 7 were subjected to the following moisture resistance test, and the results are summarized in Table 2.
[접착력 측정] [Adhesive force measurement]
폴리페닐렌 설파이드(PPS)제의 기재(基材)상에, 외경 7.6mm/내경 3.0mm의 두께 0.5mm의 금속제 워셔(단위:N)를 두었다. 내경을 조성물로 채우기 위해, 조성물을 10mg 적하 하였다. 적산 광량 30kJ/m2로 자외선 조사하여 조성물을 광경화시켜 테스트 피스를 작성하였다. 실온으로 되돌린 후, 디지털 포스 게이지의 헤드를 50mm/min으로 슬라이드 시키고, 워셔 측면에서 전단방향으로 워셔를 튀게하여, 「강도(N)」을 측정하였다. 내경으로 환산하여 「접착력 (MPa)」을 구하였다. 접착력은, 바람직하게는 4MPa이상이며, 보다 바람직하게는 6MPa이상이다. A metal washer (unit: N) having an outer diameter of 7.6 mm/internal diameter of 3.0 mm and a thickness of 0.5 mm was placed on a polyphenylene sulfide (PPS) base material. To fill the inner diameter with the composition, 10 mg of the composition was added dropwise. The composition was photocured by UV irradiation at an accumulated light amount of 30 kJ/m 2 to prepare a test piece. After returning to room temperature, the head of the digital force gauge was slid at 50 mm/min, the washer was bounced from the side of the washer in the shear direction, and "strength (N)" was measured. "Adhesive force (MPa)" was calculated|required by converting into inner diameter. Adhesive force becomes like this. Preferably it is 4 MPa or more, More preferably, it is 6 MPa or more.
[내습시험] [Moisture Resistance Test]
상기의 접착력 측정에 있어서의 테스트 피스 작성방법과 같이 테스트 피스를 작성하였다. 초기의 접착력을 측정하고, 이것을 「초기 접착력」으로 하였다. 그 후, 다른 테스트 피스를 60 ℃, 95% RH의 분위기하에서 144시간 방치하였다. 내습시험 종료 후에 테스트 피스를 꺼내, 테스트 피스의 온도를 실온으로 되돌린 후, 상기와 같은 방법으로 「접착력 (MPa)」을 측정하였다. 또한, 초기의 접착력을 기준으로 한 내습성 시험 후의 접착력의 변화의 비율을 「변화율(%)」로 하였다. 「변화율」은 -40~0%인 것이 바람직하고, 더욱 바람직하게는 -30~0%이며, 가장 바람직하게는 -25~0%이다. A test piece was prepared in the same manner as in the method for preparing the test piece for measuring the adhesive force described above. The initial adhesive force was measured, and this was made into "initial adhesive force". After that, the other test piece was left to stand for 144 hours in an atmosphere of 60 DEG C and 95% RH. After completion of the moisture resistance test, the test piece was taken out, the temperature of the test piece was returned to room temperature, and "adhesive force (MPa)" was measured in the same manner as above. In addition, the ratio of the change of the adhesive force after the moisture resistance test on the basis of the initial adhesive force was made into "change rate (%)". The "change rate" is preferably -40 to 0%, more preferably -30 to 0%, and most preferably -25 to 0%.
실시예와 비교예를 비교하면 변화율에 큰 차이가 있었다. 비교예 1~4는 (C)성분을 포함하지 않는 조성물, 비교예 5과 6에 있어서는 (A)성분을 포함하지 않는 조성물이다. 내습시험을 실시하면 접착력이 떨어지는 경향이 보이지만, 접착력의 변화율은 실시예에 있어서는 -40~0%의 범위내이며, 비교예에서는, 비교예 5를 제외하고, -60이상~-40%미만의 범위였다. 한편, 비교예 5에서는 변화율이 18%이며, 내습 시험후의 접착력이 상승하였으나, 초기의 경화가 불충분하여 내습 시험시의 열로 경화가 진행한 것이라 추측되었다. There was a large difference in the rate of change when the Example and Comparative Example were compared. Comparative Examples 1-4 are the composition which does not contain (C)component, and the composition which does not contain (A)component in Comparative Examples 5 and 6. When the moisture resistance test is carried out, the adhesive strength tends to decrease, but the change rate of the adhesive strength is in the range of -40 to 0% in Examples, and in Comparative Examples, except for Comparative Example 5, -60 or more and less than -40% was the range. On the other hand, in Comparative Example 5, the rate of change was 18%, and the adhesive strength after the moisture resistance test was increased, but initial curing was insufficient, and it was assumed that curing proceeded due to heat during the moisture resistance test.
실시예 4, 5, 8, 비교예 5, 6에 대하여, 하기의 DMA(동적 점탄성)측정을 실시하고, 그 결과를 표 3에 정리하였다. Examples 4, 5, 8 and Comparative Examples 5 and 6 were subjected to the following DMA (dynamic viscoelasticity) measurements, and the results are summarized in Table 3.
[DMA(동적 점탄성)측정] [Dynamic Viscoelasticity (DMA) Measurement]
조성물의 두께를 1mm로 설정하고, 적산광량 30kJ/m2을 자외선 조사하여 시트형상의 경화물을 작성하였다. 경화물을 폭 10mm로 구멍을 내고, 테스트 피스를 제작하였다. DMA장치에 장착하여 -40~200?의 온도범위에서 측정하였다. -20 ℃에 있어서의 저장 탄성율, 손실 탄성율의 극대값(유리전이 온도)을 확인하고, 각각 「E'(×108Pa)」, 「E"(℃)」로 하였다. 내습시험에 있어서, 열팽창에 대한 추종과 함께 흡습을 억제하기 위해서는, 저장 탄성율 E'이 10.0 ×108Pa 미만인 것이 바람직하다. 또한, 손실 탄성율의 극대값(유리전이 온도)E"으로는 80 ℃ 이상인 것이 바람직하고, 100 ℃이상인 것이 더욱 바람직하다. The thickness of the composition was set to 1 mm, and the accumulated light amount of 30 kJ/m 2 was irradiated with ultraviolet rays to prepare a sheet-like cured product. The hardened|cured material was punched out to a width of 10 mm, and the test piece was produced. It was mounted on a DMA device and measured in a temperature range of -40 to 200 °C. The maximum values (glass transition temperature) of the storage modulus and loss modulus at -20°C were confirmed, and they were set as “E' (×10 8 Pa)” and “E” (°C), respectively. In the moisture resistance test, thermal expansion in order to suppress the moisture absorption with a follow-on, the storage modulus E 'is 10.0 × 10 8 to Pa is less than is desirable. in addition, the E peak value of the loss elastic modulus (glass transition temperature) "is to be not less than 80 ℃ preferably, 100 ℃ It is more preferable that it is more than that.
실시예 4, 5, 8과 비교예 5, 6을 비교하면, (A)성분을 포함하는지 아닌지가 다르다. 실시예에서는 E'이 10.0 ×108Pa미만이며 경화물에 가요성이 있으므로, 팽창 수축에 대하여 어느 정도 추종할 수 있다고 생각할 수 있고, 상술한 접착력 변화율이 낮게 억제되어 있다고 생각할 수 있다. When Examples 4, 5, 8 and Comparative Examples 5 and 6 are compared, it is different whether or not (A) component is included. In the embodiment, E' is less than 10.0 x 10 8 Pa, and since the cured product is flexible, it can be considered that expansion and contraction can be followed to some extent, and the above-mentioned rate of change of adhesive force is considered to be low.
또한, 실시예 4, 5에서는, 조성물을 경화하여 이루어지는 경화물 유리전이 온도가 100 ℃ 이상인 것이 확인되었다. 유리전이 온도가 100 ℃이상이면, 고습도하에서도 충분한 접착성을 유지할 수 있다. Moreover, in Examples 4 and 5, it was confirmed that the glass transition temperature of the hardened|cured material formed by hardening|curing a composition was 100 degreeC or more. When the glass transition temperature is 100°C or higher, sufficient adhesiveness can be maintained even under high humidity.
본 발명의 광경화성 조성물은, 응력저감이 요구되는 광학부품 용도에서 사용되는 접착하기 어려운 재료에 대해서도 안정된 접착성을 갖는 동시에, 신뢰성 시험 후에 있어서도 안정된 접착성을 확보할 수 있다. 따라서, 본 발명의 광경화성 조성물은, 광 픽업의 렌즈 등의 광학부품의 접착에 특히 호적하게 이용할 수 있다. The photocurable composition of the present invention has stable adhesion to materials that are difficult to adhere to for use in optical component applications requiring stress reduction, and can ensure stable adhesion even after a reliability test. Therefore, the photocurable composition of this invention can be used especially suitably for adhesion|attachment of optical components, such as a lens of an optical pickup.
Claims (7)
(B)성분, (C)성분, 및, 상기 (B)성분과 (C)성분 이외의 (메타)아크릴 단량체의 합계가 50~200질량부이고,
상기 (B)성분과 (C)성분 이외의 (메타)아크릴 단량체는,
상기 (B)성분과 상기 (C)성분 이외의 지환식 탄화수소기를 갖는 단관능(메타)아크릴 단량체, 및 방향족 구조를 갖는 단관능(메타)아크릴 단량체, 또는 지환식 탄화수소기를 갖는 단관능(메타)아크릴 단량체 및 탄소원자수 10이하의 알킬기를 갖는 단관능(메타)아크릴레이트를 포함하고,
상기 지환식 탄화수소기를 갖는 단관능(메타)아크릴 단량체는 이소보닐(메타)아크릴레이트를 포함하는 광경화성 조성물.
(A)성분 : 양 말단에 (메타)아크릴기를 갖는 (메타)아크릴 단량체 중합체
(B)성분 : 아크릴로일 모르폴린
(C)성분 : 디사이클로펜타닐(메타)아크릴레이트
(D)성분 : 광개시제 Following (A)-(D)component and (B)component, including (meth)acryl monomers other than (C)component, with respect to 100 mass parts of (A)component,
(B) component, (C)component, and the sum total of (meth)acryl monomers other than the said (B)component and (C)component is 50-200 mass parts,
The (meth)acryl monomers other than the said (B) component and (C)component,
The monofunctional (meth)acrylic monomer having an alicyclic hydrocarbon group other than the component (B) and the component (C), and a monofunctional (meth)acrylic monomer having an aromatic structure, or a monofunctional (meth) having an alicyclic hydrocarbon group It contains an acrylic monomer and a monofunctional (meth)acrylate having an alkyl group having 10 or less carbon atoms,
The monofunctional (meth)acrylic monomer having an alicyclic hydrocarbon group is a photocurable composition comprising isobornyl (meth)acrylate.
(A) Component: (meth)acrylic monomer polymer having (meth)acrylic groups at both terminals
(B) component: acryloyl morpholine
(C) Component: Dicyclofentanyl (meth)acrylate
(D) component: photoinitiator
상기 방향족 구조를 갖는 단관능(메타)아크릴 단량체는 페녹시에틸(메타)아크릴레이트를 포함하고,
상기 탄소원자수 10이하의 알킬기를 갖는 단관능(메타)아크릴레이트는 이소노닐(메타)아크릴레이트를 포함하는, 광경화성 조성물. According to claim 1,
The monofunctional (meth)acrylic monomer having the aromatic structure includes phenoxyethyl (meth)acrylate,
The monofunctional (meth) acrylate having an alkyl group having 10 or less carbon atoms includes isononyl (meth) acrylate, the photocurable composition.
경화물 유리전이 온도가 100 ℃이상인 광경화성 조성물. 3. The method of claim 1 or 2,
A photocurable composition having a cured product glass transition temperature of 100° C. or higher.
광 픽업에 사용되는 광경화성 조성물. According to claim 1,
A photocurable composition used in an optical pickup.
포토디텍터의 조립, 레이저 다이오드의 조립 또는 액추에이터의 고정에 사용 되는, 광경화성 조성물. According to claim 1,
A photocurable composition used for assembling a photodetector, assembling a laser diode or fixing an actuator.
폴리페닐렌 설파이드, 폴리카보네이트, 및 액정 폴리머로 이루어지는 군에서 선택되는 적어도 1종을 포함하는 피착체를 접착하는 용도로 이용하는, 광경화성 조성물.According to claim 1,
A photocurable composition used for adhering an adherend comprising at least one selected from the group consisting of polyphenylene sulfide, polycarbonate, and liquid crystal polymer.
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| JPJP-P-2014-120356 | 2014-06-11 | ||
| JP2014120356A JP6327518B2 (en) | 2014-06-11 | 2014-06-11 | Photocurable composition |
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| KR20150143325A KR20150143325A (en) | 2015-12-23 |
| KR102351925B1 true KR102351925B1 (en) | 2022-01-14 |
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| JP6913273B2 (en) * | 2016-04-05 | 2021-08-04 | 株式会社スリーボンド | Radical curable resin composition, adhesive composition for motors |
| JP2020007449A (en) * | 2018-07-06 | 2020-01-16 | 株式会社コバヤシ | Photocurable composition |
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| JP3605848B2 (en) * | 1994-05-17 | 2004-12-22 | Ｊｓｒ株式会社 | Liquid curable adhesive / adhesive composition |
| JP3751753B2 (en) | 1998-07-23 | 2006-03-01 | 株式会社カネカ | Method for producing polymer having alkenyl group at terminal and curable composition using the polymer |
| JP2001271055A (en) | 2000-03-27 | 2001-10-02 | Kanegafuchi Chem Ind Co Ltd | Sealing material composition |
| JP4499260B2 (en) | 2000-08-25 | 2010-07-07 | 株式会社カネカ | Method for purifying vinyl polymer |
| JP2014162852A (en) * | 2013-02-25 | 2014-09-08 | Hitachi Chemical Co Ltd | Photocurable resin composition and laminated sheet using same |
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| JP2016000766A (en) | 2016-01-07 |
| KR20150143325A (en) | 2015-12-23 |
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