JP2016145297A - Photocurable resin composition - Google Patents
Photocurable resin composition Download PDFInfo
- Publication number
- JP2016145297A JP2016145297A JP2015023108A JP2015023108A JP2016145297A JP 2016145297 A JP2016145297 A JP 2016145297A JP 2015023108 A JP2015023108 A JP 2015023108A JP 2015023108 A JP2015023108 A JP 2015023108A JP 2016145297 A JP2016145297 A JP 2016145297A
- Authority
- JP
- Japan
- Prior art keywords
- group
- component
- resin composition
- photocurable resin
- compound
- 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
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 6
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000620 organic polymer Polymers 0.000 claims abstract description 5
- -1 thiazole compound Chemical class 0.000 claims description 60
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000005372 silanol group Chemical group 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 8
- 229920001296 polysiloxane Chemical group 0.000 claims description 8
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 6
- 229920002367 Polyisobutene Polymers 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 14
- 150000003557 thiazoles Chemical class 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 44
- 229910002012 Aerosil® Inorganic materials 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000005266 casting Methods 0.000 description 8
- 229910021485 fumed silica Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 238000007789 sealing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 125000005370 alkoxysilyl group Chemical group 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- HKJNHYJTVPWVGV-UHFFFAOYSA-N n,n-diethyl-4-methylaniline Chemical compound CCN(CC)C1=CC=C(C)C=C1 HKJNHYJTVPWVGV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- UROHSXQUJQQUOO-UHFFFAOYSA-M (4-benzoylphenyl)methyl-trimethylazanium;chloride Chemical compound [Cl-].C1=CC(C[N+](C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 UROHSXQUJQQUOO-UHFFFAOYSA-M 0.000 description 1
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- MPJPKEMZYOAIRN-UHFFFAOYSA-N 1,3,5-tris(2-methylprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CC(=C)CN1C(=O)N(CC(C)=C)C(=O)N(CC(C)=C)C1=O MPJPKEMZYOAIRN-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-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
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- VJKZIQFVKMUTID-UHFFFAOYSA-N 2-diazonio-5-sulfonaphthalen-1-olate Chemical compound N#[N+]C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1[O-] VJKZIQFVKMUTID-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical class OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- IFWSKNUWNMLVQH-UHFFFAOYSA-N 2-phenylsilylethane-1,1-diol Chemical compound C1(=CC=CC=C1)[SiH2]CC(O)O IFWSKNUWNMLVQH-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 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
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-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
- IKVYHNPVKUNCJM-UHFFFAOYSA-N 4-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C(C)C)=CC=C2 IKVYHNPVKUNCJM-UHFFFAOYSA-N 0.000 description 1
- 125000004864 4-thiomethylphenyl group Chemical group 0.000 description 1
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 1
- 229910002015 Aerosil® 150 Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 1
- 229910002019 Aerosil® 380 Inorganic materials 0.000 description 1
- 229910002013 Aerosil® 90 Inorganic materials 0.000 description 1
- 229910002021 Aerosil® TT 600 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- MSCACPYBYUDWML-UHFFFAOYSA-L C(CCCCCCCCCCC)(=[O+][O-])[O-].C(CCC)[Sn+2]CCCC.C(CCCCCCCCCCC)(=[O+][O-])[O-] Chemical compound C(CCCCCCCCCCC)(=[O+][O-])[O-].C(CCC)[Sn+2]CCCC.C(CCCCCCCCCCC)(=[O+][O-])[O-] MSCACPYBYUDWML-UHFFFAOYSA-L 0.000 description 1
- JLTFZOLNJALRLP-UHFFFAOYSA-N C1(C(C=CC2=CC=CC=C12)=O)=O.[Na] Chemical compound C1(C(C=CC2=CC=CC=C12)=O)=O.[Na] JLTFZOLNJALRLP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- YVHDRFKHKGNLNW-UHFFFAOYSA-L [dibutyl(octadecanoyloxy)stannyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCCCCCCCC YVHDRFKHKGNLNW-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 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
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MBPUYGZEDYDAHA-CLFAGFIQSA-N bis[(z)-octadec-9-enyl] 2-hydroxybutanedioate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CC(O)C(=O)OCCCCCCCC\C=C/CCCCCCCC MBPUYGZEDYDAHA-CLFAGFIQSA-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
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000008320 black ointment Substances 0.000 description 1
- 239000007767 bonding agent Substances 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical class CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 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
- CBMQIDZFEYECES-UHFFFAOYSA-N diphenylsilylmethanol Chemical compound C=1C=CC=CC=1[SiH](CO)C1=CC=CC=C1 CBMQIDZFEYECES-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003759 ester based solvent Substances 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 group 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
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UKASIOIEWZDBIT-UHFFFAOYSA-N phenyl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)C1=CC=CC=C1 UKASIOIEWZDBIT-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- VTYAFYZMLWQBHQ-UHFFFAOYSA-N phenylsilylmethanediol Chemical compound OC(O)[SiH2]C1=CC=CC=C1 VTYAFYZMLWQBHQ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 150000004980 phosphorus peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- FCVNATXRSJMIDT-UHFFFAOYSA-N trihydroxy(phenyl)silane Chemical compound O[Si](O)(O)C1=CC=CC=C1 FCVNATXRSJMIDT-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-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
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、紫外線などの活性エネルギー線の照射により速やかに硬化し、且つ貯蔵安定性に優れる光硬化性樹脂組成物に関する。 The present invention relates to a photocurable resin composition that is rapidly cured by irradiation with active energy rays such as ultraviolet rays and that is excellent in storage stability.
従来より、空気中の湿気により硬化可能な硬化性樹脂組成物が知られており、接着剤、シール剤、コーティング剤等に多用されている。しかしながら、上記硬化性樹脂組成物は、空気中の湿気により硬化させるためには１週間程の長時間が必要であり、接着剤、シール剤、コーティング剤等に利用した場合、生産性に劣るという問題があった。 2. Description of the Related Art Conventionally, curable resin compositions that can be cured by moisture in the air are known, and are widely used for adhesives, sealants, coating agents, and the like. However, the curable resin composition requires a long time of about one week in order to be cured by moisture in the air, and is inferior in productivity when used for an adhesive, a sealant, a coating agent, or the like. There was a problem.
そのような背景から特許文献１には、平均して少なくとも１個の架橋性シリル基を末端に有するビニル系重合体、および光照射により酸または塩基を発生する化合物を含有する硬化性組成物が開示され、この硬化性組成物は、紫外線などの活性エネルギー線の照射により速やかに硬化する旨開示されている。 From such a background, Patent Document 1 discloses a curable composition containing, on average, a vinyl polymer having at least one crosslinkable silyl group at its terminal, and a compound that generates an acid or a base upon irradiation with light. It is disclosed that this curable composition cures rapidly upon irradiation with active energy rays such as ultraviolet rays.
しかしながら、特許文献１に記載の硬化性組成物は、本願明細書の比較例１と同じ構成のものであるが、光照射により短時間で硬化はするが、室温での貯蔵安定性が劣るという課題を有していた。 However, although the curable composition described in Patent Document 1 has the same configuration as Comparative Example 1 of the present specification, it is cured in a short time by light irradiation, but is poor in storage stability at room temperature. Had problems.
本発明は、紫外線などの活性エネルギー線の照射により速やかに硬化し、且つ貯蔵安定性に優れる光硬化性樹脂組成物を提供することを目的とする。 An object of this invention is to provide the photocurable resin composition which hardens | cures rapidly by irradiation of active energy rays, such as an ultraviolet-ray, and is excellent in storage stability.
本発明の要旨を次に説明する。本発明は上述した従来の問題点を克服するものである。
下記の（Ａ）〜（Ｃ）成分を含有することを特徴とする光硬化性樹脂組成物。
（Ａ）成分：１分子中に加水分解性シリル基を２以上有する有機重合体
（Ｂ）成分：光照射により酸を発生する化合物
（Ｃ）成分：イソシアヌル環を有する化合物（Ｃ−１）又はチアゾール化合物（Ｃ−２）から選択される化合物
The gist of the present invention will be described next. The present invention overcomes the above-mentioned conventional problems.
A photocurable resin composition comprising the following components (A) to (C):
(A) component: an organic polymer having two or more hydrolyzable silyl groups in the molecule (B) component: a compound that generates an acid by light irradiation (C) component: a compound (C-1) having an isocyanuric ring or Compound selected from thiazole compound (C-2)
本発明の光硬化性樹脂組成物は、紫外線などの活性エネルギー線の照射により速やかに硬化し、且つ貯蔵安定性に優れるものである。 The photocurable resin composition of the present invention is rapidly cured by irradiation with active energy rays such as ultraviolet rays and has excellent storage stability.
以下本発明を詳細に説明する。
＜（Ａ）成分＞
本発明の（Ａ）成分は、湿気により架橋反応が開始される１分子中に加水分解性シリル基を２以上有する有機重合体である。加水分解性シリル基は、有機重合体の末端又は側鎖に結合してよいが、光硬化性樹脂組成物の硬化性に優れるという観点から好ましくは末端に結合しているものがあげられる。
The present invention will be described in detail below.
<(A) component>
The component (A) of the present invention is an organic polymer having two or more hydrolyzable silyl groups in one molecule where a crosslinking reaction is initiated by moisture. The hydrolyzable silyl group may be bonded to the terminal or side chain of the organic polymer, but from the viewpoint of excellent curability of the photo-curable resin composition, those that are bonded to the terminal are preferable.
（Ａ）成分は、取扱いの観点より２５℃において液状であることが好ましい。（Ａ）成分の粘度（２５℃）は、特に限定されないが、好ましくは５〜３０００Ｐａ・ｓであり、更に好ましくは１０〜２０００Ｐａ・ｓであり、特に好ましくは、５０〜１５００Ｐａ・ｓがあげられる。（Ａ）成分の粘度が５Ｐａ・ｓ未満であると、深部硬化性に劣るおそれがあり、（Ａ）成分の粘度が３０００Ｐａ・ｓを超えた（Ａ）成分を用いると高粘度な組成物であることから作業性が劣るおそれがある。 The component (A) is preferably liquid at 25 ° C. from the viewpoint of handling. The viscosity (25 ° C.) of the component (A) is not particularly limited, but is preferably 5 to 3000 Pa · s, more preferably 10 to 2000 Pa · s, and particularly preferably 50 to 1500 Pa · s. . When the viscosity of the component (A) is less than 5 Pa · s, the deep part curability may be inferior, and when the component (A) having the viscosity of the component (A) exceeding 3000 Pa · s is used, the composition has a high viscosity. Therefore, workability may be inferior.
また、（Ａ）成分の分子量は、光硬化性樹脂組成物が低粘度にでき塗布作業が容易にできるという観点から、１０００〜１０００００であるのが好ましく、３０００〜５００００であるのがより好ましい。なお、本発明において（Ａ）成分としてのポリシロキサンの分子量は、クロロホルムを溶媒とするゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）によるポリスチレン換算の重量平均分子量である。 Further, the molecular weight of the component (A) is preferably 1000 to 100,000, more preferably 3000 to 50,000, from the viewpoint that the photocurable resin composition can have a low viscosity and can be easily applied. In the present invention, the molecular weight of the polysiloxane as the component (A) is a weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent.
上記加水分解性シリル基とは、珪素原子に１〜３個の加水分解性官能基が結合したものであり、該加水分解性官能基としては、例えば、ハロゲン原子、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基等のアルコキシ基、アシルオキシド基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシド基などが好ましい例として挙げられ、反応性の観点からアルコキシ基が特に好ましい。 The hydrolyzable silyl group is a group in which 1 to 3 hydrolyzable functional groups are bonded to a silicon atom. Examples of the hydrolyzable functional group include a halogen atom, a methoxy group, an ethoxy group, and a propyl group. Preferred examples include alkoxy groups such as oxy group, isopropyloxy group, butoxy group, acyl oxide group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyl oxide group, and the like. An alkoxy group is particularly preferable from the viewpoint of properties.
上記（Ａ）成分の主鎖構造は特に限定されないが、例えば、ポリエーテル主鎖構造、ポリエステル主鎖構造、ポリカーボネート主鎖構造、ポリウレタン主鎖構造、ポリアミド主鎖構造、ポリウレア主鎖構造、ポリイミド主鎖構造、ビニル系重合体主鎖構造等が挙げられる。これらの中でも、ゴム特性に優れ、ポリマー設計自由度が高いことから、ビニル重合体主鎖構造が好ましく用いられる。また、２種以上の混合物であっても良い。 The main chain structure of the component (A) is not particularly limited, and examples thereof include a polyether main chain structure, a polyester main chain structure, a polycarbonate main chain structure, a polyurethane main chain structure, a polyamide main chain structure, a polyurea main chain structure, and a polyimide main chain structure. Examples thereof include a chain structure and a vinyl polymer main chain structure. Among these, a vinyl polymer main chain structure is preferably used because of excellent rubber characteristics and a high degree of freedom in polymer design. Also, a mixture of two or more kinds may be used.
前記ビニル系重合体主鎖構造としては、エチレン性不飽和基を有する化合物を重合して得られるビニル系重合体構造であれば特に限定されないが、具体的には、ポリエチレン、ポリプロピレン、ポリイソブチレン、ポリ（メタ）アクリレート、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリブタジエン、ポリイソプレン、ポリ酢酸ビニル、ポリビニルブチラール、ポリビニルエーテル等を挙げることができる。これらの中でもガスバリア性に優れた硬化物が得られる観点でポリイソブチレンが好ましく、光硬化性が良好であるという観点からはポリ（メタ）アクリレートが好ましい。 The vinyl polymer main chain structure is not particularly limited as long as it is a vinyl polymer structure obtained by polymerizing a compound having an ethylenically unsaturated group. Specifically, polyethylene, polypropylene, polyisobutylene, Examples include poly (meth) acrylate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl butyral, and polyvinyl ether. Among these, polyisobutylene is preferable from the viewpoint of obtaining a cured product having excellent gas barrier properties, and poly (meth) acrylate is preferable from the viewpoint of good photocurability.
加水分解性シリル基を有するポリイソブチレンの市販品としては、カネカ株式会社製ＥＰ１００Ｓ、ＥＰ１０３Ｓ、ＥＰ３０３Ｓ、ＥＰ５０５Ｓ等が挙げられる。 Examples of commercially available polyisobutylene having a hydrolyzable silyl group include EP100S, EP103S, EP303S and EP505S manufactured by Kaneka Corporation.
加水分解性シリル基を有するポリ（メタ）アクリレートの市販品としては、カネカ株式会社製ＳＡ１００Ｓ、ＳＡ１１０Ｓ、ＳＡ１２０Ｓ、ＯＲ１００Ｓ、ＯＲ１１０Ｓ等が挙げられる。 Examples of the commercially available poly (meth) acrylate having a hydrolyzable silyl group include SA100S, SA110S, SA120S, OR100S, OR110S manufactured by Kaneka Corporation.
＜（Ｂ）成分＞
本発明の（Ｂ）成分の光照射により酸を発生する化合物とは、活性エネルギー線の照射により、（Ａ）成分を架橋させることができる酸性物質を放出することができる化合物である。
<(B) component>
The compound that generates an acid by light irradiation of the component (B) of the present invention is a compound that can release an acidic substance capable of crosslinking the component (A) by irradiation with active energy rays.
（Ｂ）成分の配合割合は、特に限定されないが、（Ａ）成分１００質量部に対して、０．０１〜２０質量部であり、好ましくは０．０３〜１０質量部であり、特に好ましくは０．０５〜５質量部である。０．０１質量部を下回ると、硬化性が低下するおそれがあり、１０質量部を超えると、光硬化性樹脂組成物の硬化物の耐熱性低下するおそれがある。 (B) Although the compounding ratio of a component is not specifically limited, It is 0.01-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.03-10 mass parts, Most preferably 0.05 to 5 parts by mass. If it is less than 0.01 parts by mass, the curability may be reduced, and if it exceeds 10 parts by mass, the heat resistance of the cured product of the photocurable resin composition may be reduced.
本発明の光硬化性樹脂組成物に使用できる光照射により酸発生する化合物としては、光酸発生剤があげられ、このような光酸発生剤としては、例えば、スルホン酸エステル化合物、オニウム塩化合物があげられるが、好ましくは（Ａ）成分との相溶性に優れるという観点からスルホン酸エステル化合物があげられる。これらの化合物の１種のみならず、２種以上を組み合わせて使用することができる。 Examples of the compound capable of generating an acid upon irradiation with light that can be used in the photocurable resin composition of the present invention include a photoacid generator. Examples of such a photoacid generator include a sulfonic acid ester compound and an onium salt compound. Preferably, a sulfonic acid ester compound is used from the viewpoint of excellent compatibility with the component (A). Not only one of these compounds but also two or more can be used in combination.
本発明で使用できるスルホン酸エステル化合物としては、特に限定されないが、例えば、トリフルオロメタンスルホン酸−１、８−ナフタルイミド、ノナフルオロブタンスルホン酸−１、８−ナフタルイミド、パーフルオロオクタンスルホン酸−１、８−ナフタルイミド、ペンタフルオロベンゼンスルホン酸−１、８−ナフタルイミド、ノナフルオロブタンスルホン酸１、３、６−トリオキソ−３、６−ジヒドロ−１Ｈ−１１−チア−アザシクロペンタアントラセン−２イルエステル、ノナフルオロブタンスルホン酸８−イソプロピル−１、３、６− トリオキソ−３、６−ジヒドロ−１Ｈ−１１−チア−２−アザシクロペンタアントラセン−２−イル エステル、１，２−ナフトキノン−２−ジアジド−５−スルホン酸クロリド、１，２−ナフトキノン−２−ジアジド−４−スルホン酸クロリド、１，２−ベンゾキノン−２−ジアジド−４−スルホン酸クロリド、１，２−ナフトキノン−２−ジアジド−５−スルホン酸ナトリウム、１，２−ナフトキノン−２−ジアジド−４−スルホン酸ナトリウム、１，２−ベンゾキノン−２−ジアジド−４−スルホン酸ナトリウム、１，２−ナフトキノン−２−ジアジド−５−スルホン酸カリウム、１，２−ナフトキノン−２−ジアジド−４−スルホン酸カリウム、１，２−ベンゾキノン−２−ジアジド−４−スルホン酸カリウム、１，２−ナフトキノン−２−ジアジド−５−スルホン酸メチル、１，２−ベンゾキノン−２−ジアジド−４−スルホン酸メチル等を挙げることができる。市販品としては例えばＳＩＮ−１１（株式会社三宝化学研究所製）、ＮＴ−１ＴＦ（サンアプロ株式会社製）等があげられる。 The sulfonic acid ester compound that can be used in the present invention is not particularly limited. For example, trifluoromethanesulfonic acid-1,8-naphthalimide, nonafluorobutanesulfonic acid-1,8-naphthalimide, perfluorooctanesulfonic acid- 1,8-naphthalimide, pentafluorobenzenesulfonic acid-1,8-naphthalimide, nonafluorobutanesulfonic acid 1,3,6-trioxo-3,6-dihydro-1H-11-thia-azacyclopentanthracene- 2-yl ester, nonafluorobutanesulfonic acid 8-isopropyl-1,3,6-trioxo-3,6-dihydro-1H-11-thia-2-azacyclopentanthracen-2-yl ester, 1,2-naphthoquinone -2-diazide-5-sulfonic acid chloride, 1,2-na Phtoquinone-2-diazide-4-sulfonic acid chloride, 1,2-benzoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-5-sulfonic acid sodium salt, 1,2-naphthoquinone- Sodium 2-diazide-4-sulfonate, sodium 1,2-benzoquinone-2-diazide-4-sulfonate, potassium 1,2-naphthoquinone-2-diazide-5-sulfonate, 1,2-naphthoquinone-2- Potassium diazide-4-sulfonate, potassium 1,2-benzoquinone-2-diazide-4-sulfonate, methyl 1,2-naphthoquinone-2-diazide-5-sulfonate, 1,2-benzoquinone-2-diazide- Examples include methyl 4-sulfonate. Examples of commercially available products include SIN-11 (manufactured by Sanpo Chemical Laboratory Co., Ltd.), NT-1TF (manufactured by San Apro Co., Ltd.), and the like.
本発明で使用できるオニウム塩化合物としては、特に限定されないが、例えばヘキサフルオロアンチモネート、テトラフルオロボレート、ヘキサフルオロホスフェート、ヘキサフルオロアルセネート、ヘキサクロルアンチモネート、トリフルオロメタンスルフォン酸イオン、フルオロスルフォン酸イオン等のアニオンを有するヨードニウム塩又はスルホニウム塩が挙げられる。市販品のオニウム塩化合物としては、ＣＰＩ−１００Ｐ、ＣＰＩ−１０１Ｐ、ＣＰＩ−２００Ｋ、ＣＰＩ−２１０Ｓ（サンアプロ株式会社製）、ＷＰＩ−１１３、ＷＰＩ−１１６、ＷＰＩ−１６９、ＷＰＩ−１７０，ＷＰＡＧ−３３６、ＷＰＡＧ−３６７、ＷＰＡＧ−３７０、ＷＰＡＧ−４６９、ＷＰＡＧ−６３８ （和光純薬工業株式会社製）アデカオプトマーＳＰ−１５０、ＳＰ−１５１、ＳＰ−１７０、ＳＰ−１７１、ＳＰ−１７２（旭電化工業株式会社製）、イルガキュアー２５０（ＢＡＳＦ社製）、ＣＤ−１０１０、ＣＤ−１０１１、ＣＤ−１０１２（サートマー社製）、サンエイドＳＩ−６０、ＳＩ−８０、ＳＩ−１００、ＳＩ−６０Ｌ、ＳＩ−８０Ｌ、ＳＩ−１００Ｌ、ＳＩ−Ｌ１４５、ＳＩ−Ｌ１５０、ＳＩ−Ｌ１６０、ＳＩ−Ｌ１１０、ＳＩ−Ｌ１４７（三新化学工業株式会社製）等を挙げることができる。 The onium salt compound that can be used in the present invention is not particularly limited. For example, hexafluoroantimonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexachloroantimonate, trifluoromethanesulfonate ion, fluorosulfonate ion Iodonium salts or sulfonium salts having anions such as Commercially available onium salt compounds include CPI-100P, CPI-101P, CPI-200K, CPI-210S (manufactured by San Apro Co., Ltd.), WPI-113, WPI-116, WPI-169, WPI-170, WPAG-336. , WPAG-367, WPAG-370, WPAG-469, WPAG-638 (manufactured by Wako Pure Chemical Industries, Ltd.) Adekaoptomer SP-150, SP-151, SP-170, SP-171, SP-172 (Asahi Denka) Manufactured by Kogyo Co., Ltd.), Irgacure 250 (manufactured by BASF), CD-1010, CD-1011, CD-1012 (manufactured by Sartomer), Sun-Aid SI-60, SI-80, SI-100, SI-60L, SI -80L, SI-100L, SI-L145, SI-L150, SI-L160, S -L110, SI-L147 (Sanshin Chemical Industry Co., Ltd.), and the like.
本発明の（Ｃ）成分は、本発明の光硬化性樹脂組成物に貯蔵安定性を付与するもので、イソシアヌル環を有する化合物（Ｃ−１）およびチアゾール化合物（Ｃ−２）から少なくとも１種類選択される化合物である。 Component (C) of the present invention imparts storage stability to the photocurable resin composition of the present invention, and is at least one kind from compound (C-1) and thiazole compound (C-2) having an isocyanuric ring. The selected compound.
前記イソシアヌル環を有する化合物（Ｃ−１）は、特に制限されない。例えば、トリス（２−アクリロイルオキシエチル）イソシアヌレート、ビス（２−アクリロイルオキシエチル）−２− ヒドロキシエチルイソシアヌレート、ε−カプロラクトン変性トリス−（２−アクリロキシエチル）イソシアヌレート、トリアリルイソシアヌレート、ジアリルモノグリシジルイソシアヌレート、ジアリルモノメチルイソシアヌレート、モノアリルジグリシジルイソシアヌレート、モノアリルジメチルイソシアヌレート、トリス−（トリメトキシシリルプロピル）イソシアヌレートが挙げられる。中でも、貯蔵安定性が優れるという観点から、トリス（２−アクリロイルオキシエチル）イソシアヌレート、ビス（２−アクリロイルオキシエチル）−２− ヒドロキシエチルイソシアヌレートが好ましい。また、（Ｃ−１）の市販品としては、Ｍ−３１３、Ｍ−３１５（東亜合成株式会社製）、ＦＡ−７３１Ａ（日立化成株式会社製）Ａ−９３００、Ａ−９３００−１ＣＬ（新中村化学工業株式会社製）、ＴＡＩＣ、ＴＭＡＩＣ（日本化成株式会社製）等が挙げられる。 The compound (C-1) having the isocyanuric ring is not particularly limited. For example, tris (2-acryloyloxyethyl) isocyanurate, bis (2-acryloyloxyethyl) -2-hydroxyethyl isocyanurate, ε-caprolactone modified tris- (2-acryloxyethyl) isocyanurate, triallyl isocyanurate, Examples include diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl dimethyl isocyanurate, and tris- (trimethoxysilylpropyl) isocyanurate. Among these, tris (2-acryloyloxyethyl) isocyanurate and bis (2-acryloyloxyethyl) -2-hydroxyethyl isocyanurate are preferable from the viewpoint of excellent storage stability. Moreover, as a commercial item of (C-1), M-313, M-315 (made by Toagosei Co., Ltd.), FA-731A (made by Hitachi Chemical Co., Ltd.) A-9300, A-9300-1CL (Shin Nakamura) Chemical Industry Co., Ltd.), TAIC, TMAIC (Nippon Kasei Co., Ltd.) and the like.
前記チアゾール化合物（Ｃ−２）は、チアゾール骨格を有する化合物であれば特に制限されない。例えば、ベンゾチアゾール、２−メルカプトベンゾチアゾール、２−（４−チオシアノメチルチオ）ベンゾチアゾールが挙げられる。中でも、貯蔵安定性が優れるという観点から、ベンゾチアゾール、２−メルカプトベンゾチアゾールが好ましい。また、（Ｃ−２）の市販品としては、サンスラーＭ（三新化学工業株式会社製）が挙げられる。 The thiazole compound (C-2) is not particularly limited as long as it is a compound having a thiazole skeleton. Examples thereof include benzothiazole, 2-mercaptobenzothiazole, and 2- (4-thiocyanomethylthio) benzothiazole. Among these, benzothiazole and 2-mercaptobenzothiazole are preferable from the viewpoint of excellent storage stability. Moreover, as a commercial item of (C-2), Sunsler M (made by Sanshin Chemical Industry Co., Ltd.) is mentioned.
（Ｃ）成分の配合割合は、前記（Ａ）成分１００質量部に対して、０．１〜５０質量部であり、好ましくは、０．５〜２０質量部である。上記の範囲内であることで、光硬化性と鋳造安定性を両立させることが可能である。 (C) The mixture ratio of a component is 0.1-50 mass parts with respect to 100 mass parts of said (A) component, Preferably, it is 0.5-20 mass parts. By being within the above range, it is possible to achieve both photocurability and casting stability.
＜（Ｄ）成分＞
本発明の（Ｄ）成分は、本発明の光硬化性樹脂組成物に深部硬化性を付与するもので、ケイ素原子に、アリール基又は複素環が１以上且つ１以上の水酸基が直接結合している化合物（但し、ポリシロキサンではない）及び少なくとも２以上のシラノール基を有するポリシロキサンからなる群から選択される化合物である。なお、前記アリール基とは、例えば炭素数６〜１２の芳香族環構造の官能基などがあげられ、より具体的には、フェニル基、ベンジル基、トリル基、キシリル基などが挙げられる。また、前記複素環としては、硫黄原子、窒素原子、酸素原子のいずれかを少なくとも有する三員環から十員環までの環構造等があげられる。
<(D) component>
The component (D) of the present invention imparts deep curability to the photocurable resin composition of the present invention, and one or more aryl groups or heterocyclic rings and one or more hydroxyl groups are directly bonded to a silicon atom. And a compound selected from the group consisting of a polysiloxane having at least two or more silanol groups. The aryl group includes, for example, a functional group having an aromatic ring structure having 6 to 12 carbon atoms, and more specifically includes a phenyl group, a benzyl group, a tolyl group, a xylyl group, and the like. Examples of the heterocyclic ring include a ring structure from a three-membered ring to a ten-membered ring having at least one of a sulfur atom, a nitrogen atom, and an oxygen atom.
（Ｄ）成分により、本発明の光硬化性樹脂組成物に深部硬化性を付与するメカニズムについては、不明であるが、以下のように推測している。すなわち、活性エネルギー線により（Ｂ）成分から酸性物質が発生し、（Ｄ）成分のシラノール基同士の脱水反応を促進し、水分が発生するので、光硬化性樹脂組成物に深部硬化を付与するものと推察される。 About the mechanism which provides deep part sclerosis | hardenability to the photocurable resin composition of this invention by (D) component, although it is unknown, it estimates as follows. That is, an active energy ray generates an acidic substance from the component (B), promotes a dehydration reaction between the silanol groups of the component (D), and generates moisture, thereby imparting deep curing to the photocurable resin composition. Inferred.
また、（Ｄ）成分の分子量は、光硬化性樹脂組成物が低粘度にでき塗布作業が容易にできるという観点から、Ｍｗ＝７０〜３００００であるのが好ましく、更に好ましくは９０〜１００００であるのがより好ましい。１２０〜３０００であるのがより好ましい。なお、本発明において（Ｄ）成分としてのポリシロキサンの分子量は、クロロホルムを溶媒とするゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）によるポリスチレン換算の重量平均分子量である。 The molecular weight of the component (D) is preferably Mw = 70 to 30000, more preferably 90 to 10000, from the viewpoint that the photocurable resin composition can have a low viscosity and can be easily applied. Is more preferable. More preferably, it is 120-3000. In the present invention, the molecular weight of the polysiloxane as the component (D) is a weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent.
前記（Ｄ）成分のケイ素原子に、アリール基又は複素環が１以上且つ１以上の水酸基が直接結合している化合物としては、例えば一般式（１）で表される化合物があげられる。 Examples of the compound in which one or more aryl groups or heterocyclic rings and one or more hydroxyl groups are directly bonded to the silicon atom of the component (D) include compounds represented by the general formula (1).
前記一般式（１）のＲにおける置換基は、水素原子、炭素数１〜１２の直鎖状又は分岐状のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン原子、炭素数３〜１２のシクロアルキル基、エポキシ基、ビニル基、（メタ）アクリロイル基、アミノ基、ニトロ基、チオール基、イソシアネート基、スルフィド基、スチリル基など挙げられるがこの限りではない。この中でも好ましくは、炭素数１〜１２の直鎖状又は分岐状のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン原子、炭素数３〜１２のシクロアルキル基であり、特に好ましくは、炭素数１〜１２の直鎖状又は分岐状のアルキル基、炭素数１〜８のアルコキシ基、炭素数３〜１２のシクロアルキル基である。 The substituent in R of the general formula (1) is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, or 3 to 12 carbon atoms. Examples thereof include, but are not limited to, a cycloalkyl group, an epoxy group, a vinyl group, a (meth) acryloyl group, an amino group, a nitro group, a thiol group, an isocyanate group, a sulfide group, and a styryl group. Among these, a linear or branched alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, and a cycloalkyl group having 3 to 12 carbon atoms are preferable, and carbon is particularly preferable. A linear or branched alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms.
前記（Ｄ）成分のケイ素原子に、アリール基又は複素環が１以上且つ１以上の水酸基が直接結合している化合物の具体例としては例えばトリフェニルシラノール、ジメチル−２−チオフェンシラノール、ジフェニルジヒドロキシシラン、ジメチルフェニルシラノール、フェニルトリヒドロキシシラン、フェニルジヒドロキシメチルシラン、ジフェニルヒドロキシメチルシラン、フェニルジヒドロキシエチルシランなどがあげられる。これらは単独で用いられてもよく、２種以上が併用されてもよい。 Specific examples of the compound in which one or more aryl groups or heterocycles and one or more hydroxyl groups are directly bonded to the silicon atom of the component (D) include, for example, triphenylsilanol, dimethyl-2-thiophensilanol, diphenyldihydroxysilane Dimethylphenylsilanol, phenyltrihydroxysilane, phenyldihydroxymethylsilane, diphenylhydroxymethylsilane, phenyldihydroxyethylsilane, and the like. These may be used independently and 2 or more types may be used together.
前記（Ｄ）成分に該当する１分子中に少なくとも２以上のシラノール基を有するポリシロキサンについて説明する。シラノール基は、シロキサン分子鎖の末端又は側鎖に結合してよいが、硬化性が優れるという観点から好ましくは末端に結合しているものである。また、ポリシロキサンの主鎖は直鎖、分岐のいずれであってもよい。更に、ポリシロキサンが有する炭化水素基は特に制限されないが、例えば、フェニル基等の芳香族基、メチル基、エチル基、プロピル基等のアルキル基、アルケニル基があげられる。また、１分子中に少なくとも２以上のシラノール基を有するポリシロキサンの２５℃における粘度は、特に限定されないが、硬化性及び取扱いの観点より好ましくは１〜１００００ｃｓｔであり、更に好ましくは、２〜５０００ｃｓｔであり、特に好ましくは、３〜１０００ｃｓｔであることがあげられる。 The polysiloxane having at least two or more silanol groups in one molecule corresponding to the component (D) will be described. The silanol group may be bonded to the terminal or side chain of the siloxane molecular chain, but is preferably bonded to the terminal from the viewpoint of excellent curability. The main chain of the polysiloxane may be either linear or branched. Further, the hydrocarbon group of the polysiloxane is not particularly limited, and examples thereof include aromatic groups such as phenyl groups, alkyl groups such as methyl groups, ethyl groups, and propyl groups, and alkenyl groups. The viscosity at 25 ° C. of the polysiloxane having at least two or more silanol groups in one molecule is not particularly limited, but is preferably 1 to 10,000 cst, more preferably 2 to 5000 cst from the viewpoint of curability and handling. Particularly preferred is 3 to 1000 cst.
前記（Ｄ）成分の配合量は、特に限定されないが、（Ａ）成分１００質量部に対して、０．１〜３００質量部であり、更に好ましくは０．３〜１００質量部であり、特に好ましくは０．５〜７０質量部である。０．１質量部を下回ると、光硬化性が低下するおそれがあり、３００質量部を超えると、硬化物のゴム特性が低下するおそれがある。 Although the compounding quantity of the said (D) component is not specifically limited, It is 0.1-300 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 0.3-100 mass parts, Especially Preferably it is 0.5-70 mass parts. If the amount is less than 0.1 parts by mass, the photocurability may be reduced, and if it exceeds 300 parts by mass, the rubber properties of the cured product may be reduced.
さらに本発明の光硬化性樹脂組成物には、本発明の特性を損なわない範囲において、種々の添加剤を添加してもよい。添加剤としては、例えば、充填材、光ラジカル重合開始剤、増感剤、溶剤、可塑剤、硬化触媒、シランカップリング剤、保存安定剤、酸化防止剤、紫外線吸収剤乳化剤、界面活性剤、分散剤、消泡剤、防曇剤、増粘剤、難燃剤、金属不活性化剤、オゾン劣化防止剤、リン系過酸化物分解剤、滑剤、発泡剤、顔料、染料等の着色剤等があげられる。 Furthermore, you may add various additives to the photocurable resin composition of this invention in the range which does not impair the characteristic of this invention. Examples of additives include fillers, radical photopolymerization initiators, sensitizers, solvents, plasticizers, curing catalysts, silane coupling agents, storage stabilizers, antioxidants, UV absorber emulsifiers, surfactants, Dispersants, antifoaming agents, antifogging agents, thickeners, flame retardants, metal deactivators, antiozonants, phosphorus peroxide decomposers, lubricants, foaming agents, colorants such as pigments, dyes, etc. Can be given.
前記充填剤としては、ヒュームドシリカ、沈降性シリカ、結晶性シリカ、溶融シリカ、ドロマイト、カーボンブラック、炭酸カルシウム、酸化チタン、タルク、クレー、ガラスバルーンがあげられ、なかでも補強性及び透明性に優れることからヒュームドシリカが好ましい。またその表面が、オルガノシランやオルガノシラザン等の有機ケイ素化合物で予め疎水処理されたシリカを用いてもよい。充填剤を添加する場合の配合量は、本発明の（Ａ）成分１００質量部に対して０．１〜３００質量部であり、更に好ましくは０．３〜１００質量部であり、特に好ましくは、０．５〜５０質量部である。 Examples of the filler include fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc, clay, and glass balloon. Fumed silica is preferred because of its superiority. Further, silica whose surface is previously hydrophobically treated with an organosilicon compound such as organosilane or organosilazane may be used. The compounding amount in the case of adding a filler is 0.1 to 300 parts by mass, more preferably 0.3 to 100 parts by mass, particularly preferably 100 parts by mass of the component (A) of the present invention. 0.5 to 50 parts by mass.
前記ヒュームドシリカの市販品としては、特に限定されないが、日本アエロジル株式会社の無処理のヒュームドシリカとしては例えば、ＡＥＲＯＳＩＬ ９０、ＡＥＲＯＳＩＬ １３０、ＡＥＲＯＳＩＬ １５０、ＡＥＲＯＳＩＬ ２００、ＡＥＲＯＳＩＬ ３００、ＡＥＲＯＳＩＬ ３８０、ＡＥＲＯＳＩＬＯＸ５０、ＡＥＲＯＳＩＬ ＥＧ５０、ＡＥＲＯＳＩＬ ＴＴ６００などが挙げられ、疎水処理されたヒュームドシリカとしては例えばＡＥＲＯＳＩＬ Ｒ９７２、ＡＥＲＯＳＩＬ Ｒ９７４、ＡＥＲＯＳＩＬ Ｒ９７６、ＡＥＲＯＳＩＬ Ｒ１０４、ＡＥＲＯＳＩＬ Ｒ１０６、ＡＥＲＯＳＩＬ Ｒ２０２、ＡＥＲＯＳＩＬ Ｒ８０５、ＡＥＲＯＳＩＬ Ｒ８１２、ＡＥＲＯＳＩＬ Ｒ８１２Ｓ、ＡＥＲＯＳＩＬ Ｒ８１６、ＡＥＲＯＳＩＬ Ｒ７２００、ＡＥＲＯＳＩＬ Ｒ８２００、ＡＥＲＯＳＩＬ Ｒ９２００、ＡＥＲＯＳＩＬ ＲＹ５０、ＡＥＲＯＳＩＬ ＮＹ５０、ＡＥＲＯＳＩＬ ＲＹ３００、ＡＥＲＯＳＩＬ ＲＹ２００、ＡＥＲＯＳＩＬ ＲＹ２００Ｓなどが挙げられる。 Although it does not specifically limit as a commercial item of the said fumed silica, As an untreated fumed silica of Nippon Aerosil Co., Ltd., for example, AEROSIL 90, AEROSIL 130, AEROSIL 150, AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSILOX50, AEROSIL EG50, AEROSIL TT600 etc. are mentioned, and examples of the hydrotreated fumed silica include AEROSIL R972, AEROSIL R974, AEROSIL R976, AEROSIL R104, AEROSIL R106, AEROSIL R202, AEROSIL R812, AEROSIL R812, AEROSIL R812, AEROSIL R812, AEROSIL R812, AEROSIL R812, AEROSIL 7200, AEROSIL R8200, AEROSIL R9200, AEROSIL RY50, AEROSIL NY50, AEROSIL RY300, AEROSIL RY200, etc. AEROSIL RY200S and the like.
前記ヒュームドシリカの平均粒径は１ｎｍ以上３０μ以下のシリカが好ましく用いられる。ヒュームドシリカについては、一次粒子の平均粒径１ｎｍ以上５０ｎｍ以下のヒュームドシリカを用いると、補強効果が特に高いのでより好ましい。 Silica having an average particle diameter of fumed silica of 1 nm to 30 μm is preferably used. As for fumed silica, it is more preferable to use fumed silica having an average primary particle diameter of 1 nm to 50 nm because the reinforcing effect is particularly high.
前記光ラジカル重合開始剤としては、例えば、本発明の（Ｂ）成分と併用することにより硬化性を向上させることができる。具体例としては、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−２−モルホリノ（４−チオメチルフェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタノン、２−ヒドロキシ−２−メチル−１−［４−（１−メチルビニル）フェニル］プロパノンオリゴマー等のアセトフェノン類；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン類；ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、４−ベンゾイル−４′−メチル−ジフェニルサルファイド、３，３′，４，４′−テトラ（ｔ−ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６−トリメチルベンゾフェノン、４−ベンゾイル−Ｎ，Ｎ−ジメチル−Ｎ−［２−（１−オキソ−２−プロペニルオキシ）エチル］ベンゼンメタナミニウムブロミド、（４−ベンゾイルベンジル）トリメチルアンモニウムクロリド等のベンゾフェノン類；２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジクロロチオキサントン、１−クロロ−４−プロポキシチオキサントン、２−（３−ジメチルアミノ−２−ヒドロキシ）−３，４−ジメチル−９Ｈ−チオキサントン−９−オンメソクロリド等のチオキサントン類、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイドなどのアシルホスフィンオキサイド化合物等などが挙げられる。これらのうち、アセトフェノン類、アシルホスフィンオキサイド化合物が好ましい。これらは単独で用いられてもよく、２種以上が併用されてもよい。ラジカル重合開始剤を添加する場合の配合量は、本発明の（Ａ）成分１００質量部に対して０．１〜２０質量部であることが好ましい。 As said radical photopolymerization initiator, sclerosis | hardenability can be improved by using together with (B) component of this invention, for example. Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone. 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy Acetophenones such as 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, -Methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6- Benzophenones such as trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4- Dimethyl-9H-thio Sandton 9 thioxanthones such Onmesokurorido, such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide acylphosphine oxide compounds such as and the like. Of these, acetophenones and acylphosphine oxide compounds are preferred. These may be used independently and 2 or more types may be used together. The amount of the radical polymerization initiator added is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A) of the present invention.
前記の増感剤としては、例えば、アントラセン化合物、ピレン化合物、アントラキノン化合物、チオキサントン化合物、フルオレノン化合物、色素などが挙げられる。増感剤を添加する場合の配合量は、本発明の（Ａ）成分１００質量部に対して０．１〜５０質量部であり、好ましくは０．３〜２０質量部であり、更に好ましくは、０．５〜１０質量部である。 Examples of the sensitizer include anthracene compounds, pyrene compounds, anthraquinone compounds, thioxanthone compounds, fluorenone compounds, and dyes. The compounding amount in the case of adding a sensitizer is 0.1 to 50 parts by mass, preferably 0.3 to 20 parts by mass, more preferably 100 parts by mass of the component (A) of the present invention. 0.5 to 10 parts by mass.
前記溶剤としては、脂肪族炭化水素系溶剤、芳香族炭化水素系溶剤、脂環式炭化水素系溶剤、アルコール系溶剤、アルデヒド系溶剤、ケトン系溶剤、エステル系溶剤、エーテル系溶剤、石油系溶剤などが挙げられ、これらは、単独或いは二種類以上を混合して用いてもよい。 Examples of the solvent include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, alicyclic hydrocarbon solvents, alcohol solvents, aldehyde solvents, ketone solvents, ester solvents, ether solvents, petroleum solvents. These may be used, and these may be used alone or in admixture of two or more.
前記可塑剤としては、例えば、プロセスオイル、ポリαオレフィン等の液状炭化水素化合物、リン酸エステル化合物、フタル酸エステル化合物、ポリエーテル化合物等が挙げられ、これらは単独又は２種以上を併用出来る。 Examples of the plasticizer include process oils, liquid hydrocarbon compounds such as poly-α-olefins, phosphate ester compounds, phthalate ester compounds, polyether compounds, and the like, and these can be used alone or in combination of two or more.
前記硬化触媒としては、（Ａ）成分を架橋させる触媒であれば特に限定されない。具体的には、ジブチル錫ジラウレート、ジブチル錫オキサイド、ジブチル錫ジアセテート、ジブチル錫ジステアレート、ジブチル錫ラウレートオキサイド、ジブチル錫ジアセチルアセトナート、ジブチル錫ジオレイルマレート、ジブチル錫オクトエート、ジオクチル錫オキサイド、ジオクチル錫ジラウレート等の錫化合物；金属錯体としてはテトラ−ｎ−ブトキシチタネート、テトライソプロポキシチタネート等のチタネート系化合物；オクチル酸鉛、ナフテン酸鉛、ナフテン酸ニッケル、ナフテン酸コバルト、亜鉛系化合物、鉄系化合物、ビスマス等のカルボン酸金属塩；アルミニウムアセチルアセトナート錯体、バナジウムアセチルアセトナート錯体等の金属アセチルアセトナート錯体が挙げられる。またジブチルアミン−２−エチルヘキソエート等のアミン塩や、モノメチル燐酸、ジ−ｎ−ブチル燐酸などの有機燐酸化合物や他の酸性触媒及び塩基性触媒等も使用することができる。これらは単独で用いられてもよく、２種類以上が併用されてもよい。 The curing catalyst is not particularly limited as long as it is a catalyst that crosslinks the component (A). Specifically, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin distearate, dibutyltin laurate oxide, dibutyltin diacetylacetonate, dibutyltin dioleyl malate, dibutyltin octoate, dioctyltin oxide, dioctyl Tin compounds such as tin dilaurate; Titanate compounds such as tetra-n-butoxy titanate and tetraisopropoxy titanate as metal complexes; lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, zinc-based compounds, iron-based compounds Compound, carboxylic acid metal salt such as bismuth; metal acetylacetonate complex such as aluminum acetylacetonate complex and vanadium acetylacetonate complex. Also, amine salts such as dibutylamine-2-ethylhexoate, organic phosphoric acid compounds such as monomethyl phosphoric acid and di-n-butyl phosphoric acid, other acidic catalysts and basic catalysts, and the like can be used. These may be used alone or in combination of two or more.
前記保存安定剤としては、光硬化性樹脂組成物の水分を吸収したり、水分と反応するものであれば特に限定されない。例えば、テトラメトキシシラン、テトラエトキシシラン等の４官能アルコキシシラン及びそれらの加水分解物、メチルトリメトキシシラン、メチルトリエトキシシラン及びこれらの加水分解物メチルシリケート、エチルシリケート、プロピルシリケート、ブチルシリケートに代表されるシリケート化合物類およびそのオリゴマー類などが挙げられる。これらは単独で用いられてもよく、２種以上が併用されてもよい。 The storage stabilizer is not particularly limited as long as it absorbs moisture of the photocurable resin composition or reacts with moisture. For example, tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane and their hydrolysates, methyltrimethoxysilane, methyltriethoxysilane and their hydrolysates methyl silicate, ethyl silicate, propyl silicate and butyl silicate. Silicate compounds and oligomers thereof. These may be used independently and 2 or more types may be used together.
前記シランカップリング剤としては、例えば、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン等のグリシジル基含有シランカップリング剤、ビニルトリス（β−メトキシエトキシ）シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン等のビニル基含有シランカップリング剤、γ−メタクリロキシプロピルトリメトキシシラン等の（メタ）アクリル基含有シランカップリング剤、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤、その他γ−メルカプトプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、スチリルシラン、ウレイドシラン、スルフィドシラン、イソシアネートシラン等が挙げられる。これらは単独で用いられてもよく、２種以上が併用されてもよい。なお、シランカップリング剤を添加する場合の配合量は、本発明の（Ａ）成分１００質量部に対して０．１〜２０質量部であることが好ましい。 Examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxy. Glycidyl group-containing silane coupling agents such as propyltrimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane, vinyl group-containing silane cups such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane and vinyltrimethoxysilane Ring agent, (meth) acryl group-containing silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Phenyl- Examples include amino group-containing silane coupling agents such as γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, styrylsilane, ureidosilane, sulfide silane, isocyanate silane, and the like. These may be used independently and 2 or more types may be used together. In addition, it is preferable that the compounding quantity in the case of adding a silane coupling agent is 0.1-20 mass parts with respect to 100 mass parts of (A) component of this invention.
本発明の光硬化性樹脂組成物を硬化させる活性エネルギーとは、例えば紫外線、可視光線、レーザー光が挙げられ、その積算光量は５〜５００ｋＪ／ｃｍ２であり、好ましくは１０〜３００ｋＪ／ｃｍ２の範囲である。活性エネルギーの波長は、１５０〜７５０ｎｍが好ましい。また、活性エネルギー線の照射源としては、例えば高圧水銀灯、無電極ランプ、キセノン灯、メタルハライド灯、太陽光等が挙げられる。 Examples of the active energy for curing the photocurable resin composition of the present invention include ultraviolet light, visible light, and laser light. The accumulated light amount is 5 to 500 kJ / cm 2 , preferably 10 to 300 kJ / cm 2. Range. The wavelength of the active energy is preferably 150 to 750 nm. Examples of the active energy ray irradiation source include a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, a metal halide lamp, and sunlight.
また、本発明の光硬化性樹脂組成物は、エネルギー照射後速やかに硬化することも、エネルギー照射直後は硬化せず、その後短時間の室温での放置により硬化することも可能であり、後者のような性質は、接着部材が光等のエネルギーを透過しない場合でも、組成物にエネルギーを照射した後、塗布貼り合わせすることにより接着が可能である。 In addition, the photocurable resin composition of the present invention can be cured immediately after energy irradiation, or can be cured by leaving at room temperature for a short period of time without being cured immediately after energy irradiation. Even if the adhesive member does not transmit energy such as light, such properties can be adhered by irradiating the composition with energy and then applying and bonding.
本発明によれば、本発明の光硬化性樹脂組成物を硬化して得られる硬化物（樹脂硬化物）も提供される。 According to this invention, the hardened | cured material (resin hardened | cured material) obtained by hardening | curing the photocurable resin composition of this invention is also provided.
本発明の光硬化性樹脂組成物を硬化処理して得られる樹脂硬化物は、強靱で高い接着力を持つなど優れた特性を有し、接着、封止、注型、塗装、コーティング剤、光学部品の成形等様々な用途に使用が可能である。具体的な用途としては、自動車・輸送機分野では、自動車用のスイッチ部分、ヘッドランプ、エンジン内部品、電装部品、駆動エンジン、ブレーキオイルタンク等の接着、封止、注型、成形、コーティング剤等に使用が可能である。また、フラットパネルディスプレイでは、液晶ディスプレイ、有機エレクトロルミネッセンス、発光ダイオード表示装置、フィールドエミッションディスプレイの接着、封止、注型、成形、コーティング剤等に使用が可能である。記録分野では、ビデオディスク、ＣＤ、ＤＶＤ、ＭＤ、ピックアップレンズ、ハードディスク周辺（スピンドルモータ用部材、磁気ヘッドアクチュエータ用部材など）、ブルーレイディスク等の接着、封止、注型、成形、コーティング剤等に使用が可能である。電子材料分野では、電子部品、電気回路、電気接点あるいは半導体素子等の封止材料、ダイボンド剤、導電性接着剤、異方性導電性接着剤、ビルドアップ基板を含む多層基板の層間接着剤、ソルダーレジスト等を挙げることができる。電池分野では、リチウム電池、マンガン電池、アルカリ電池、ニッケル系電池、燃料電池、シリコン系太陽電池、色素増感型太陽電池、有機太陽電池等の接着、封止、注型、成形、コーティング剤等に使用が可能である。光部品分野では、光通信システムでの光スイッチ周辺、光コネクタ周辺の光ファイバー材料、光受動部品、光回路部品、光電子集積回路周辺の等の接着、封止、注型、成形、コーティング剤等に使用が可能である。光学機器分野では、スチールカメラのレンズ用材料、ファインダプリズム、ターゲットプリズム、ファインダーカバー、受光センサー部、撮影レンズ、プロジェクションテレビの投射レンズ等の接着、封止、注型、成形、コーティング等に使用が可能である。また、本発明の光硬化性樹脂組成物は、液晶やタッチパネル等の画像表示装置において、ガラス等の保護部と画像表示部との間に隙間が設けられているが、この隙間を埋める用途で用いてもよい。 The cured resin obtained by curing the photocurable resin composition of the present invention has excellent properties such as toughness and high adhesive strength, and is excellent in adhesion, sealing, casting, coating, coating agent, optical It can be used for various purposes such as forming parts. Specifically, in the field of automobiles and transport equipment, bonding, sealing, casting, molding, coating agents for automotive switch parts, headlamps, engine internal parts, electrical components, drive engines, brake oil tanks, etc. Etc. can be used. Further, the flat panel display can be used for adhesion, sealing, casting, molding, coating agent and the like of a liquid crystal display, organic electroluminescence, light emitting diode display device, and field emission display. In the recording field, for video discs, CDs, DVDs, MDs, pickup lenses, hard disk peripherals (spindle motor members, magnetic head actuator members, etc.), Blu-ray discs, etc., sealing, casting, molding, coating agents, etc. Can be used. In the field of electronic materials, sealing materials for electronic components, electrical circuits, electrical contacts or semiconductor elements, die bonding agents, conductive adhesives, anisotropic conductive adhesives, interlayer adhesives for multilayer substrates including build-up substrates, A solder resist etc. can be mentioned. In the battery field, lithium batteries, manganese batteries, alkaline batteries, nickel-based batteries, fuel cells, silicon-based solar cells, dye-sensitized solar cells, organic solar cells, etc., sealing, casting, molding, coating agents, etc. Can be used. In the field of optical components, for optical switch peripherals, optical connector peripherals, optical passive components, optical circuit components, optoelectronic integrated circuit peripherals, etc. in optical communication systems, adhesives, sealing, casting, molding, coating agents, etc. Can be used. In the field of optical equipment, it is used for bonding, sealing, casting, molding, coating, etc. of lens materials for steel cameras, finder prisms, target prisms, finder covers, light receiving sensor parts, photographic lenses, projection TV projection lenses, etc. Is possible. In addition, the photocurable resin composition of the present invention has a gap provided between a protective part such as glass and the image display part in an image display device such as a liquid crystal or a touch panel. It may be used.
以下に実施例をあげて本発明を更に詳細説明をするが、本発明はこれら実施例に限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
＜光硬化性樹脂組成物の調製＞
各成分を表１に示す質量部で採取し、常温にてミキサーで６０分混合し、光硬化性樹脂を調製し、各種物性に関して次のようにして測定した。数値は全て質量部で標記する。
<Preparation of photocurable resin composition>
Each component was sampled in parts by mass shown in Table 1, mixed with a mixer at room temperature for 60 minutes to prepare a photocurable resin, and various physical properties were measured as follows. All numerical values are expressed in parts by mass.
表１に示されている成分の詳細は、次のとおりである。
＜（Ａ）成分＞
ａ−１：粘度（２５℃）が７００Ｐａ・ｓである両末端アルコキシシリル基含有ポリイソブチレン樹脂（製品名ＥＰＩＯＮ ＥＰ１００Ｓ、株式会社カネカ製）
ａ−２：粘度（２５℃）が２３０Ｐａ．ｓである両末端アルコキシシリル基含有アクリル共重合体（製品名ＳＡ１００Ｓ、株式会社カネカ製）
＜（Ｂ）成分＞
ｂ−１：スルホン酸エステル系光酸発生剤（製品名ＮＴ−１ＴＦ、サンアプロ株式会社製）
＜（Ｃ）成分＞
ｃ−１：トリス（２−アクリロイルオキシエチル）イソシアヌレートとビス（２−アクリロイルオキシエチル）−２−ヒドロキシエチルイソシアヌレートの混合物（Ｍ−３１３、東亜合成株式会社製）
ｃ−２：ベンゾチアゾール（試薬）
＜（Ｃ）成分の比較＞
ｃ’−１：Ｎ，Ｎ−ジメチルＰトルイジン（試薬）
ｃ’−２：Ｎ，Ｎ−ジエチルＰトルイジン（試薬）
ｃ’−３：１，２，３，４−テトラヒドロキノリン（試薬）
＜（Ｄ）成分＞
ｄ−１：ジフェニルジヒドロキシシラン（ＳＩＤ ４５６０．０、ゲレスト製）
ｄ−２：シラノール基を両末端に有するポリジメチルシロキサン：２５℃における粘度１６〜３２ｃＳｔ、分子量５５０、製品名ＤＭＳ−Ｓ１２、Ｇｅｌｅｓｔ，Ｌｎｃ．製
The details of the components shown in Table 1 are as follows.
<(A) component>
a-1: Polyisobutylene resin containing alkoxysilyl groups at both ends having a viscosity (25 ° C.) of 700 Pa · s (product name EPION EP100S, manufactured by Kaneka Corporation)
a-2: Viscosity (25 ° C.) is 230 Pa. s-terminated alkoxysilyl group-containing acrylic copolymer (product name: SA100S, manufactured by Kaneka Corporation)
<(B) component>
b-1: Sulfonate ester photoacid generator (product name NT-1TF, manufactured by San Apro Co., Ltd.)
<(C) component>
c-1: Mixture of tris (2-acryloyloxyethyl) isocyanurate and bis (2-acryloyloxyethyl) -2-hydroxyethyl isocyanurate (M-313, manufactured by Toa Gosei Co., Ltd.)
c-2: benzothiazole (reagent)
<Comparison of component (C)>
c′-1: N, N-dimethyl P toluidine (reagent)
c′-2: N, N-diethyl P toluidine (reagent)
c′-3: 1,2,3,4-tetrahydroquinoline (reagent)
<(D) component>
d-1: Diphenyldihydroxysilane (SID 4560.0, manufactured by Gerest)
d-2: polydimethylsiloxane having silanol groups at both ends: viscosity 16-32 cSt at 25 ° C., molecular weight 550, product name DMS-S12, Gelest, Lnc. Made
表１の実施例及び比較例において使用した試験法は下記の通りである。 The test methods used in the examples and comparative examples in Table 1 are as follows.
＜タックフリータイム試験＞
１０ｍｍ×１０ｍｍのガラス板に各光硬化性樹脂組成物を５００μｍの厚みになるように塗布する。次に、紫外線照射機を用いて６０ｋＪ／ｃｍ２の積算光量の光を照射した。その後、試験片表面のべたつきがなくなるまでの時間を確認し、評価した。なお、べたつきがなくなったかどうかの判断は、指による接触試験で判断した。なお、タックフリータイムは、１５分未満が好ましい。
<Tack free time test>
Each photocurable resin composition is apply | coated so that it may become a thickness of 500 micrometers on a 10 mm x 10 mm glass plate. Next, the light of the integrated light quantity of 60 kJ / cm < 2 > was irradiated using the ultraviolet irradiation machine. Then, the time until the stickiness of the test piece surface disappeared was confirmed and evaluated. Note that whether or not the stickiness disappeared was determined by a finger contact test. The tack free time is preferably less than 15 minutes.
＜貯蔵安定性試験＞
各光硬化性樹脂組成物を黒色軟膏容器に充填し、２５℃環境下で４日間密閉保存する。その後、容器を開封し、下記基準に基づき目視で評価し、その結果を表１に示す。
＜評価基準＞
○：光硬化性樹脂組成物の流動性が確認できた。
×：光硬化性樹脂組成物がゲル化して流動しなくなっていた。
<Storage stability test>
Each photocurable resin composition is filled in a black ointment container and stored in a sealed state in a 25 ° C. environment for 4 days. Thereafter, the container was opened and visually evaluated based on the following criteria, and the results are shown in Table 1.
<Evaluation criteria>
○: The fluidity of the photocurable resin composition was confirmed.
X: The photocurable resin composition gelled and stopped flowing.
表１の本発明に該当する実施例１〜４から、本発明の（Ｃ）成分を選択し、本発明のその他成分と組み合わせることにより、紫外線などの活性エネルギー線の照射により速やかに硬化し、且つ貯蔵安定性に優れることがわかる。また、実施例５、６より、両末端アルコキシシリル基含有ポリイソブチレン樹脂から両末端アルコキシシリル基含有アクリル共重合体に代えても、同様の効果が得られた。また、実施例７より、ジフェニルジヒドロキシシランからシラノール基を両末端に有するポリジメチルシロキサンに代えても、同様の効果が得られた。 By selecting the component (C) of the present invention from Examples 1 to 4 corresponding to the present invention in Table 1, and combining with other components of the present invention, it is quickly cured by irradiation with active energy rays such as ultraviolet rays, And it turns out that it is excellent in storage stability. Further, from Examples 5 and 6, the same effect was obtained even when the both-end alkoxysilyl group-containing polyisobutylene resin was replaced with the both-end alkoxysilyl group-containing acrylic copolymer. Moreover, even if it replaced with the polydimethylsiloxane which has a silanol group from both ends from Example 7 from a diphenyl dihydroxysilane, the same effect was acquired.
また、比較例１は、本発明の（Ｃ）成分が非含有である光硬化性樹脂組成物であるが、本発明の実施例と比較して、貯蔵安定性が劣ることが確認された。また、比較例２〜７は、本発明の（Ｃ）成分の代わりに、
弱塩基性化合物（Ｎ，Ｎ−ジメチルＰトルイジン、Ｎ，Ｎ−ジエチルＰトルイジン、１，２，３，４−テトラヒドロキノリン）を用いたものであるが、タックフリーが遅く、光硬化性が劣ることが確認された。
Moreover, although the comparative example 1 is a photocurable resin composition which does not contain the (C) component of this invention, it was confirmed that storage stability is inferior compared with the Example of this invention. Further, Comparative Examples 2 to 7 instead of the component (C) of the present invention,
Weakly basic compounds (N, N-dimethyl P toluidine, N, N-diethyl P toluidine, 1,2,3,4-tetrahydroquinoline) are used, but tack-free is slow and photocurability is poor. It was confirmed.
本発明は、紫外線などの活性エネルギー線の照射により速やかに硬化し、且つ貯蔵安定性に優れる光硬化性樹脂組成物に関するものであり、広く応用することができるものである。 The present invention relates to a photocurable resin composition that is rapidly cured by irradiation with active energy rays such as ultraviolet rays and that is excellent in storage stability, and can be widely applied.
Claims (8)
（Ａ）成分：１分子中に加水分解性シリル基を２以上有する有機重合体
（Ｂ）成分：光照射により酸を発生する化合物
（Ｃ）成分：イソシアヌル環を有する化合物（Ｃ−１）およびチアゾール化合物（Ｃ−２）から少なくとも１種類選択される化合物 A photocurable resin composition comprising the following components (A) to (C):
(A) Component: Organic polymer having 2 or more hydrolyzable silyl groups in the molecule (B) Component: Compound that generates an acid by light irradiation (C) Component: Compound (C-1) having an isocyanuric ring and Compound selected from at least one kind from thiazole compound (C-2)
且つ、前記（Ｃ−２）成分が、ベンゾチアゾール、２−メルカプトベンゾチアゾール、２−（４−チオシアノメチルチオ）ベンゾチアゾールからなる群から１以上選択されるものであることを特徴とする請求項１に記載の光硬化性樹脂組成物。 The component (C-1) is tris (2-acryloyloxyethyl) isocyanurate, bis (2-acryloyloxyethyl) -2-hydroxyethyl isocyanurate, ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanate. One or more selected from the group consisting of nurate, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, monoallyl diglycidyl isocyanurate, monoallyl dimethyl isocyanurate, tris- (trimethoxysilylpropyl) isocyanurate Is,
The component (C-2) is one or more selected from the group consisting of benzothiazole, 2-mercaptobenzothiazole, and 2- (4-thiocyanomethylthio) benzothiazole. 1. The photocurable resin composition according to 1.
前記（Ｃ）成分を０．１〜５０質量部含有することを特徴とする請求項１〜６のいずれか１項に記載の光硬化性樹脂組成物。 The component (B) is contained in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the component (A)
The photocurable resin composition according to any one of claims 1 to 6, comprising 0.1 to 50 parts by mass of the component (C).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015023108A JP6460324B2 (en) | 2015-02-09 | 2015-02-09 | Photocurable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015023108A JP6460324B2 (en) | 2015-02-09 | 2015-02-09 | Photocurable resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016145297A true JP2016145297A (en) | 2016-08-12 |
| JP6460324B2 JP6460324B2 (en) | 2019-01-30 |
Family
ID=56685392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015023108A Active JP6460324B2 (en) | 2015-02-09 | 2015-02-09 | Photocurable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6460324B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6460658A (en) * | 1987-08-28 | 1989-03-07 | Toshiba Silicone | Primer composition for electric and electronic component |
| JP2015021103A (en) * | 2013-07-23 | 2015-02-02 | スリーボンドファインケミカル株式会社 | Photocurable resin composition |
-
2015
- 2015-02-09 JP JP2015023108A patent/JP6460324B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6460658A (en) * | 1987-08-28 | 1989-03-07 | Toshiba Silicone | Primer composition for electric and electronic component |
| JP2015021103A (en) * | 2013-07-23 | 2015-02-02 | スリーボンドファインケミカル株式会社 | Photocurable resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6460324B2 (en) | 2019-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6213717B2 (en) | Photocurable resin composition | |
| JP6683133B2 (en) | Photocurable composition | |
| JP4860831B2 (en) | Photo-curable epoxy resin composition and photo-curable display element sealing agent | |
| JP7252467B2 (en) | Surface modifier composition and bonding method | |
| JP2010018797A (en) | Curable composition for optical parts, adhesive agent for optical parts, and sealing agent for organic electroluminescence element | |
| US10844251B2 (en) | Pressure-sensitive adhesive | |
| JPWO2008153076A1 (en) | Optical adhesive for substrate bonding, and cured optical adhesive for substrate bonding | |
| CN114761460B (en) | Cation-curable composition, cured product, and joined body | |
| JP6460324B2 (en) | Photocurable resin composition | |
| JP2018062590A (en) | Photocurable composition | |
| JP2018030989A (en) | Photocurable composition, cured composition-containing product, sticking method, and method for producing product | |
| JP6273759B2 (en) | Photocurable composition | |
| WO2024127822A1 (en) | Photocurable resin composition | |
| WO2024116877A1 (en) | Photocurable resin composition | |
| JP2015078314A (en) | Photocurable composition | |
| JP2005187636A (en) | Photo-curable resin composition, adhesive for display device, method of bonding and display device | |
| JP6259657B2 (en) | Sealant for liquid crystal display elements | |
| WO2016167303A1 (en) | Photocurable composition, bonding adhesive using same, cured product, curing method and reworking method | |
| JP7481011B2 (en) | Thermally cationic polymerizable resin composition | |
| JP2008024804A (en) | New thermosetting composition and its cured product | |
| JP2003096185A (en) | Photocurable resin composition | |
| WO2022202683A1 (en) | Thermosetting composition, electronic device, and method for producing electronic device | |
| JP2004259875A (en) | Method for sealing electric/electronic part and electric/electronic part sealed by this sealing method | |
| JP2022112555A (en) | Curable composition | |
| TW202340267A (en) | Resin composition and curable resin composition using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171204 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180801 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180725 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180827 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20181205 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20181218 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6460324 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |