JP7474007B2 - Photocurable silicone resin composition - Google Patents
Photocurable silicone resin composition Download PDFInfo
- Publication number
- JP7474007B2 JP7474007B2 JP2023574574A JP2023574574A JP7474007B2 JP 7474007 B2 JP7474007 B2 JP 7474007B2 JP 2023574574 A JP2023574574 A JP 2023574574A JP 2023574574 A JP2023574574 A JP 2023574574A JP 7474007 B2 JP7474007 B2 JP 7474007B2
- Authority
- JP
- Japan
- Prior art keywords
- organopolysiloxane
- silicone resin
- resin composition
- photocurable silicone
- ratio
- 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.)
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- 229920002050 silicone resin Polymers 0.000 title claims description 108
- 239000011342 resin composition Substances 0.000 title claims description 103
- 229920001296 polysiloxane Polymers 0.000 claims description 157
- 125000005358 mercaptoalkyl group Chemical group 0.000 claims description 50
- 125000001931 aliphatic group Chemical group 0.000 claims description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 61
- 238000013016 damping Methods 0.000 description 58
- 239000000047 product Substances 0.000 description 48
- 238000011156 evaluation Methods 0.000 description 38
- 239000000203 mixture Substances 0.000 description 33
- 239000000463 material Substances 0.000 description 26
- 238000000691 measurement method Methods 0.000 description 25
- 238000009472 formulation Methods 0.000 description 17
- 238000005259 measurement Methods 0.000 description 17
- -1 siloxane chain Chemical group 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 239000006096 absorbing agent Substances 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 description 9
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 8
- 238000006596 Alder-ene reaction Methods 0.000 description 8
- 239000004611 light stabiliser Substances 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229910002012 Aerosil® Inorganic materials 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000004382 potting Methods 0.000 description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- ZIFLDVXQTMSDJE-UHFFFAOYSA-N 3-[[dimethyl-[3-(2-methylprop-2-enoyloxy)propyl]silyl]oxy-dimethylsilyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)O[Si](C)(C)CCCOC(=O)C(C)=C ZIFLDVXQTMSDJE-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 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 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000010894 electron beam technology Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 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
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- KJYSXRBJOSZLEL-UHFFFAOYSA-N (2,4-ditert-butylphenyl) 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 KJYSXRBJOSZLEL-UHFFFAOYSA-N 0.000 description 1
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- OTCWVYFQGYOYJO-UHFFFAOYSA-N 1-o-methyl 10-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound COC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 OTCWVYFQGYOYJO-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- SKMNWICOBCDSSQ-UHFFFAOYSA-N 2-[4-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2,6,6-tetramethylpiperidin-1-yl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCN2C(CC(CC2(C)C)OC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(C)C)=C1 SKMNWICOBCDSSQ-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
- 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
- TVWGHFVGFWIHFN-UHFFFAOYSA-N 2-hexadecan-2-yl-4,6-dimethylphenol Chemical compound CCCCCCCCCCCCCCC(C)C1=CC(C)=CC(C)=C1O TVWGHFVGFWIHFN-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
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- UWRXMIQVSKQAIJ-UHFFFAOYSA-N 2-n-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1h-triazin-2-yl]-[2-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1h-triazin-2-yl]-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1h-triazin-2-yl]amino]propyl Chemical compound C=1C(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NN(NCCCN(CCN(CCCNN2N=C(C=C(N2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N2N=C(C=C(N2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N2N=C(C=C(N2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 UWRXMIQVSKQAIJ-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
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-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
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- RAZWNFJQEZAVOT-UHFFFAOYSA-N 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound O=C1N(CCCCCCCCCCCC)C(=O)NC11CC(C)(C)N(C(C)=O)C(C)(C)C1 RAZWNFJQEZAVOT-UHFFFAOYSA-N 0.000 description 1
- 229920006310 Asahi-Kasei Polymers 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 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
- 125000003277 amino group Chemical group 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
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- RFVHVYKVRGKLNK-UHFFFAOYSA-N bis(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1 RFVHVYKVRGKLNK-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
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- SJEZDMHBMZPMME-UHFFFAOYSA-L calcium;(3,5-ditert-butyl-4-hydroxyphenyl)methyl-ethoxyphosphinate Chemical compound [Ca+2].CCOP([O-])(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.CCOP([O-])(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SJEZDMHBMZPMME-UHFFFAOYSA-L 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-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
- 150000004662 dithiols Chemical class 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000001288 lysyl group Chemical group 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229950002083 octabenzone Drugs 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical group CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-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
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
Description
本発明は、光硬化性シリコーン樹脂組成物に関し、より詳しくは、設計可能な弾性率の範囲が広く、高減衰性でありながら、せん断伸びに優れた硬化物（シリコーンゲル）を形成することのできる光硬化性シリコーン樹脂組成物に関する。The present invention relates to a photocurable silicone resin composition, and more specifically to a photocurable silicone resin composition that can form a cured product (silicone gel) that has a wide range of designable elastic modulus, high damping properties, and excellent shear elongation.
シリコーンゲルは、優れた耐熱性、電気絶縁性および柔軟性を有することから、電気・電子部品のシール材、センサー類などのコーティング材、ポッティング材、ダンピング材として使用されている。なかでも、昨今の生産自動化に伴い、光重合性官能基を有し、紫外線などの光により硬化してシリコーンゲルを形成するチオール－エン反応系の光硬化性シリコーン樹脂組成物が電子機器を中心に用いられている。 Silicone gel has excellent heat resistance, electrical insulation and flexibility, and is therefore used as a sealing material for electrical and electronic components, a coating material for sensors, a potting material and a damping material. In particular, with the recent trend towards automated production, photocurable silicone resin compositions based on thiol-ene reactions, which have photopolymerizable functional groups and cure when exposed to ultraviolet light or other light to form silicone gel, are being used primarily in electronic devices.
そして近年においては、使用用途の多様化に伴い、硬さや減衰性能、粘度といった基本物性に加えて、優れた伸び性を併せ持つ硬化物（シリコーンゲル）を形成することができる光硬化性シリコーン樹脂組成物のニーズがシール材、コーティング材、ポッティング材、防振材、制振材、光学接着剤（ＯＣＲ、ＯＣＡ）などの用途で高まっている。この理由としては、シリコーンゲルの減衰性能を高めると柔軟性が増す傾向にあるため、衝撃や振動が印加された場合に、シリコーンゲルの変形が容易となり、このときに伸び性が乏しいとシリコーンゲルが破損しやすくなることから、高い減衰性能を維持しながらも、伸び性に優れることがこの種の用途において重要なためである。特に制振材用途としての利用などを想定した場合、せん断伸びが重要となり、せん断ひずみ（伸び）が１００％を超える場合でも破断しない材料が求められている。このシリコーンゲルが有する基本物性の設計は、光硬化性シリコーン樹脂組成物中にシリカやレジン等の固形充填剤を含有させることで調整する手法が一般的であるが、この手法では減衰性能と伸び性との両立が困難であり、課題となっていた。そこで、特許文献１では、光硬化性シリコーン樹脂組成物の伸び性の改善のために、脂肪族不飽和基を含有する特定の直鎖状オルガノポリシロキサン（Ｂ）と、ケイ素原子に結合するメルカプトアルキル基を２個超含有するオルガノポリシロキサン（Ａ２）と、両末端ジチオールを含有する特定のオルガノポリシロキサン（Ａ１）とを含み、成分（Ｂ）中の脂肪族不飽和基の個数に対する、成分（Ａ１＋Ａ２）中のチオール基の個数の比が１～３である紫外線硬化型シリコーン樹脂組成物が提案されている。In recent years, with the diversification of applications, the need for photocurable silicone resin compositions capable of forming a cured product (silicone gel) with excellent elongation in addition to basic physical properties such as hardness, damping performance, and viscosity is increasing in applications such as sealing materials, coating materials, potting materials, vibration-proofing materials, vibration-damping materials, and optical adhesives (OCR, OCA). The reason for this is that when the damping performance of silicone gel is increased, its flexibility tends to increase, so that when shock or vibration is applied, the silicone gel becomes easily deformed, and if the elongation is poor at this time, the silicone gel becomes easily damaged. Therefore, it is important for this type of application to have excellent elongation while maintaining high damping performance. In particular, when assuming use as a vibration-damping material, shear elongation is important, and a material that does not break even when the shear strain (elongation) exceeds 100% is required. The design of the basic physical properties of this silicone gel is generally adjusted by adding solid fillers such as silica and resin to the photocurable silicone resin composition, but this method makes it difficult to achieve both damping performance and elongation, which has been a problem. Thus, in order to improve the extensibility of a photocurable silicone resin composition, Patent Document 1 proposes an ultraviolet-curable silicone resin composition that contains a specific linear organopolysiloxane (B) that contains an aliphatic unsaturated group, an organopolysiloxane (A2) that contains more than two mercaptoalkyl groups bonded to a silicon atom, and a specific organopolysiloxane (A1) that contains dithiols at both ends, wherein the ratio of the number of thiol groups in components (A1+A2) to the number of aliphatic unsaturated groups in component (B) is 1 to 3.
しかし、特許文献１の光硬化性シリコーン樹脂組成物では、硬化物の伸び性は改善するものの、複素弾性率が高くなり過ぎたり、減衰性に劣るという課題があった。また、コーティング材、ポッティング材、ダンピング材などの用途においては、未硬化状態での粘度を調整するために、光硬化性シリコーン樹脂組成物中にシリカやレジン等の固形充填剤を含有させた場合には、硬化物の複素弾性率がさらに高くなるため、光硬化性シリコーン樹脂組成物の硬化物（シリコーンゲル）の弾性率について、設計可能な範囲が狭くなる点でも改良の余地があった。However, the photocurable silicone resin composition of Patent Document 1 has problems such as an excessively high complex modulus and poor damping, although it improves the elongation of the cured product. In addition, in applications such as coating materials, potting materials, and damping materials, when a solid filler such as silica or resin is added to the photocurable silicone resin composition to adjust the viscosity in the uncured state, the complex modulus of the cured product becomes even higher, so there is room for improvement in that the designable range of the elastic modulus of the cured product (silicone gel) of the photocurable silicone resin composition becomes narrow.
よって、本発明は従来技術の上述した問題点を解消するものであり、その目的は、複素弾性率の設計可能な範囲が広く、高減衰性でありながら、せん断伸びに優れた硬化物を形成することのできる光硬化性シリコーン樹脂組成物を提供することにある。Therefore, the present invention aims to solve the above-mentioned problems of the prior art, and its object is to provide a photocurable silicone resin composition that has a wide designable range for the complex elastic modulus, has high damping properties, and is capable of forming a cured product with excellent shear elongation.
本発明の光硬化性シリコーン樹脂組成物は、メルカプトアルキル基を含有するオルガノポリシロキサン（Ａ）と、少なくとも両末端に脂肪族不飽和基を含有する直鎖状のオルガノポリシロキサン（Ｂ）と、光重合開始剤（Ｃ）と、を含んでなる光硬化性シリコーン樹脂組成物であって、オルガノポリシロキサン（Ａ）は、両末端にメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ１）と、ケイ素原子に結合するメルカプトアルキル基を１分子当たり２個以上含有するオルガノポリシロキサン（Ａ２）とからなり、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数の比が、０．７０以上１．００未満、かつ、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ１）中のメルカプトアルキル基の個数の比が、０．０６以上であることを特徴とする。なお、本明細書中において、メルカプトアルキル基を含有するオルガノポリシロキサン（Ａ）をオルガノポリシロキサン（Ａ）または成分（Ａ）、両末端にメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ１）をオルガノポリシロキサン（Ａ１）または成分（Ａ１）、ケイ素原子に結合するメルカプトアルキル基を１分子当たり２個以上含有するオルガノポリシロキサン（Ａ２）をオルガノポリシロキサン（Ａ２）または成分（Ａ２）、少なくとも両末端に脂肪族不飽和基を含有する直鎖状のオルガノポリシロキサン（Ｂ）をオルガノポリシロキサン（Ｂ）または成分（Ｂ）、光重合開始剤（Ｃ）を成分（Ｃ）とも称する。The photocurable silicone resin composition of the present invention is a photocurable silicone resin composition comprising an organopolysiloxane (A) containing a mercaptoalkyl group, a linear organopolysiloxane (B) containing aliphatic unsaturated groups at at least both ends, and a photopolymerization initiator (C), wherein the organopolysiloxane (A) is composed of an organopolysiloxane (A1) containing mercaptoalkyl groups at both ends and an organopolysiloxane (A2) containing two or more mercaptoalkyl groups bonded to silicon atoms per molecule, and wherein the ratio of the number of mercaptoalkyl groups in the organopolysiloxane (A) to the number of aliphatic unsaturated groups in the organopolysiloxane (B) is 0.70 or more and less than 1.00, and the ratio of the number of mercaptoalkyl groups in the organopolysiloxane (A1) to the number of aliphatic unsaturated groups in the organopolysiloxane (B) is 0.06 or more. [0023] In this specification, organopolysiloxane (A) containing a mercaptoalkyl group is also referred to as organopolysiloxane (A) or component (A), organopolysiloxane (A1) containing mercaptoalkyl groups at both terminals is also referred to as organopolysiloxane (A1) or component (A1), organopolysiloxane (A2) containing two or more mercaptoalkyl groups bonded to silicon atoms per molecule is also referred to as organopolysiloxane (A2) or component (A2), linear organopolysiloxane (B) containing aliphatic unsaturated groups at least at both terminals is also referred to as organopolysiloxane (B) or component (B), and photopolymerization initiator (C) is also referred to as component (C).
本発明の光硬化性シリコーン樹脂組成物は、両末端にメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ１）と、両末端に脂肪族不飽和基を含有する直鎖状のオルガノポリシロキサン（Ｂ）とが架橋して、オルガノポリシロキサン（Ｂ）が鎖長延長されるように構成され、ケイ素原子に結合するメルカプトアルキル基を１分子中に２個以上含有するオルガノポリシロキサン（Ａ２）と、上記の鎖長延長されたオルガノポリシロキサン分子に残存した脂肪族不飽和基とが架橋することにより、架橋点間のシロキサン鎖が長くなるように構成されている。このとき、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数の比を０．７０以上１．００未満とし、かつ、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ１）中のメルカプトアルキル基の個数の比を０．０６以上とすることによって、光硬化性シリコーン樹脂組成物の硬化物（シリコーンゲル）の粘弾性特性が制御されるため、複素弾性率の設計可能な範囲が広く、高減衰性でありながら、せん断伸びに優れた硬化物特性を有する光硬化性シリコーン樹脂組成物が得られる。The photocurable silicone resin composition of the present invention is configured such that an organopolysiloxane (A1) containing mercaptoalkyl groups at both ends is crosslinked with a linear organopolysiloxane (B) containing aliphatic unsaturated groups at both ends, thereby extending the chain length of the organopolysiloxane (B), and an organopolysiloxane (A2) containing two or more mercaptoalkyl groups bonded to silicon atoms per molecule is crosslinked with the aliphatic unsaturated groups remaining in the chain-extended organopolysiloxane molecule, thereby lengthening the siloxane chain between the crosslinking points. In this case, by setting the ratio of the number of mercaptoalkyl groups in organo polysiloxane (A) to the number of aliphatic unsaturated groups in organo polysiloxane (B) to 0.70 or more and less than 1.00, and by setting the ratio of the number of mercaptoalkyl groups in organo polysiloxane (A1) to the number of aliphatic unsaturated groups in organo polysiloxane (B) to 0.06 or more, the viscoelastic properties of the cured product (silicone gel) of the photocurable silicone resin composition can be controlled, and therefore a photocurable silicone resin composition can be obtained that has a wide designable range for the complex modulus and has cured product properties that are excellent in shear elongation while having high damping properties.
また、本発明の光硬化性シリコーン樹脂組成物は、光重合開始剤（Ｃ）の含有量が、オルガノポリシロキサン（Ｂ）１００質量部に対して、０．０５～５０質量部であることも好ましい。これにより、上記作用に基づく作用効果が良好な光硬化性シリコーン樹脂組成物を得ることができる。また、本発明の光硬化性シリコーン樹脂組成物におけるオルガノポリシロキサン（Ｂ）中の脂肪族不飽和基は、ビニル基であることも好ましい。これにより、上記作用に基づく作用効果が良好な光硬化性シリコーン樹脂組成物を得ることができる。In addition, it is also preferable that the content of the photopolymerization initiator (C) in the photocurable silicone resin composition of the present invention is 0.05 to 50 parts by mass per 100 parts by mass of the organopolysiloxane (B). This makes it possible to obtain a photocurable silicone resin composition having good functional effects based on the above-mentioned action. It is also preferable that the aliphatic unsaturated group in the organopolysiloxane (B) in the photocurable silicone resin composition of the present invention is a vinyl group. This makes it possible to obtain a photocurable silicone resin composition having good functional effects based on the above-mentioned action.
また、本発明の光硬化性シリコーン樹脂組成物は、さらに充填剤（Ｄ）を含むことも好ましい。これにより上記作用効果に加えて、所望の粘弾性特性や機能性が付与された硬化物を形成することができる光硬化性シリコーン樹脂組成物を得ることができる。It is also preferable that the photocurable silicone resin composition of the present invention further contains a filler (D). This makes it possible to obtain a photocurable silicone resin composition that can form a cured product having the desired viscoelastic properties and functionality in addition to the above-mentioned effects.
また、本発明の光硬化性シリコーン樹脂組成物は、充填剤（Ｄ）が、シリカ、シリコーンレジン、固形樹脂、繊維状化合物及び金属酸化物からなる群から選択される少なくとも１種の物質であることも好ましい。これによって、多様な粘弾性特性や機能性が付与された硬化物を形成できる光硬化性シリコーン樹脂組成物の好適な構成成分が選択される。In addition, in the photocurable silicone resin composition of the present invention, it is also preferable that the filler (D) is at least one substance selected from the group consisting of silica, silicone resin, solid resin, fibrous compound, and metal oxide. This allows the selection of suitable components for the photocurable silicone resin composition that can form a cured product with a variety of viscoelastic properties and functionality.
本発明の光硬化性シリコーン樹脂組成物は、両末端にメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ１）とケイ素原子に結合するメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ２）とからなるオルガノポリシロキサン（Ａ）と、両末端に脂肪族不飽和基を含有する直鎖状のオルガノポリシロキサン（Ｂ）と、光重合開始剤（Ｃ）とを含んでなり、オルガノポリシロキサン（Ａ１）によって鎖長延長されたオルガノポリシロキサン（Ｂ）が、オルガノポリシロキサン（Ａ２）と架橋するように構成されているとともに、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ１）中のメルカプトアルキル基の個数の比と、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数の比を特定の範囲としたことによって、複素弾性率の設計可能範囲が広く、高減衰性でありながら、せん断伸びに優れた硬化物を形成することのできる光硬化性シリコーン樹脂組成物を提供することができる。これにより、せん断伸びが１００％を超える場合であっても破損せずに、高減衰性を発揮するシール材、コーティング材、ポッティング材、防振材、制振材、光学接着剤（ＯＣＲ、ＯＣＡ）などを提供することができる。The photocurable silicone resin composition of the present invention comprises organopolysiloxane (A) consisting of organopolysiloxane (A1) containing mercaptoalkyl groups at both ends and organopolysiloxane (A2) containing mercaptoalkyl groups bonded to silicon atoms, linear organopolysiloxane (B) containing aliphatic unsaturated groups at both ends, and photopolymerization initiator (C), and the organopolysiloxane (B) whose chain length has been extended by organopolysiloxane (A1) is crosslinked with organopolysiloxane (A2). In addition, by setting the ratio of the number of mercaptoalkyl groups in the organopolysiloxane (A1) to the number of aliphatic unsaturated groups in the organopolysiloxane (B) and the ratio of the number of mercaptoalkyl groups in the organopolysiloxane (A) to the number of aliphatic unsaturated groups in the organopolysiloxane (B) within a specific range, it is possible to provide a photocurable silicone resin composition capable of forming a cured product having a wide designable range of complex elastic modulus, high damping properties, and excellent shear elongation. This makes it possible to provide a sealing material, coating material, potting material, vibration-proof material, vibration-damping material, optical adhesive (OCR, OCA), etc. that does not break even when the shear elongation exceeds 100% and exhibits high damping properties.
本発明の光硬化性シリコーン樹脂組成物は、メルカプトアルキル基を含有するオルガノポリシロキサン（Ａ）と、少なくとも両末端に脂肪族不飽和基を含有する直鎖状のオルガノポリシロキサン（Ｂ）と、光重合開始剤（Ｃ）と、を含んでなる光硬化性シリコーン樹脂組成物であって、オルガノポリシロキサン（Ａ）は、両末端にメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ１）と、ケイ素原子に結合するメルカプトアルキル基を１分子当たり２個以上含有するオルガノポリシロキサン（Ａ２）とからなり、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数の比が０．７０以上１．００未満、かつ、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ１）中のメルカプトアルキル基の個数の比が０．０６以上である。以下、詳細に説明する。The photocurable silicone resin composition of the present invention is a photocurable silicone resin composition comprising an organopolysiloxane (A) containing a mercaptoalkyl group, a linear organopolysiloxane (B) containing aliphatic unsaturated groups at at least both ends, and a photopolymerization initiator (C), in which the organopolysiloxane (A) is composed of an organopolysiloxane (A1) containing mercaptoalkyl groups at both ends and an organopolysiloxane (A2) containing two or more mercaptoalkyl groups bonded to silicon atoms per molecule, and the ratio of the number of mercaptoalkyl groups in the organopolysiloxane (A) to the number of aliphatic unsaturated groups in the organopolysiloxane (B) is 0.70 or more and less than 1.00, and the ratio of the number of mercaptoalkyl groups in the organopolysiloxane (A1) to the number of aliphatic unsaturated groups in the organopolysiloxane (B) is 0.06 or more. The details will be explained below.
（オルガノポリシロキサン（Ａ））
本発明の光硬化性シリコーン樹脂組成物を構成するメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ）は、両末端にメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ１）と、ケイ素原子に結合するメルカプトアルキル基を１分子当たり２個以上含有するオルガノポリシロキサン（Ａ２）とから構成されている。
(Organopolysiloxane (A))
The mercaptoalkyl group-containing organopolysiloxane (A) that constitutes the photocurable silicone resin composition of the present invention is composed of an organopolysiloxane (A1) that contains mercaptoalkyl groups at both terminals, and an organopolysiloxane (A2) that contains two or more mercaptoalkyl groups bonded to silicon atoms per molecule.
（オルガノポリシロキサン（Ａ１））
オルガノポリシロキサン（Ａ）を構成するオルガノポリシロキサン（Ａ１）は、両末端にメルカプトアルキル基を有する直鎖状のオルガノポリシロキサンであり、両末端のメルカプトアルキル基と、オルガノポリシロキサン（Ｂ）の脂肪族不飽和基とがチオール－エン反応して、オルガノポリシロキサン（Ｂ）の鎖長を延長するための鎖長延長剤として機能する成分である。具体的な好ましい例としては、以下式１の構造（式中Ｒａは、独立して、Ｃ１～Ｃ６のアルキル基、Ｃ６～Ｃ１２のアリール基又は－Ｓｉ（ＯＸ）３（ここで、Ｘは、独立して、Ｃ１～Ｃ６のアルキル基である）であり、Ｒｂは、独立して、Ｃ１～Ｃ６のアルキル基又はＣ６～Ｃ１２のアリール基であり、Ｒｃは、独立して、Ｃ１～Ｃ６のアルキレン基である）で示されるオルガノポリシロキサンである。ｐは、３以上の整数であり、２３℃におけるオルガノポリシロキサン（Ａ１）の粘度を１～２００ｃＰとする数であることが好ましい。なお、本明細書において、本発明に係る組成物又はその構成材料が呈する粘度は、回転粘度計にて、ローターＮｏ．２～４を使用し、３０～６０ｒｐｍ、２３℃で測定した値をいう。このオルガノポリシロキサン（Ａ１）として具体的には、特に限定されないが、例えば、信越化学工業社製品の型番「Ｘ－２２－１６７Ｃ」（メルカプト基当量：０．４３４８ｍｍｏｌ／ｇ）等を用いることができる。
(Organopolysiloxane (A1))
The organopolysiloxane (A1) constituting the organopolysiloxane (A) is a linear organopolysiloxane having mercaptoalkyl groups at both ends, and is a component that functions as a chain extender for extending the chain length of the organopolysiloxane (B) by a thiol-ene reaction between the mercaptoalkyl groups at both ends and the aliphatic unsaturated groups of the organopolysiloxane (B). A specific preferred example is an organopolysiloxane represented by the structure of the following formula 1 (wherein Ra is independently a C1-C6 alkyl group, a C6-C12 aryl group, or -Si(OX) 3 (wherein X is independently a C1-C6 alkyl group), Rb is independently a C1-C6 alkyl group or a C6-C12 aryl group, and Rc is independently a C1-C6 alkylene group). p is an integer of 3 or more, and is preferably a number that makes the viscosity of the organopolysiloxane (A1) at 23° C. 1 to 200 cP. In this specification, the viscosity exhibited by the composition according to the present invention or its constituent materials refers to a value measured with a rotational viscometer using a rotor No. 2 to 4 at 30 to 60 rpm and 23° C. Specifically, the organopolysiloxane (A1) is not particularly limited, but for example, a product of Shin-Etsu Chemical Co., Ltd., model number "X-22-167C" (mercapto group equivalent: 0.4348 mmol/g) can be used.
また、光硬化性シリコーン樹脂組成物の他の実施形態の例として、シリコーンゲルが高い耐熱性が求められない用途に適用される場合には、オルガノポリシロキサン（Ａ１）はシロキサン鎖の一部を炭化水素鎖に置き換えた構造としてもよい。また、オルガノポリシロキサン（Ａ１）の配合量の一部または全部を両末端にメルカプト基を有する直鎖炭化水素構造からなる鎖長延長剤に置き換えてもよい。As another example of an embodiment of the photocurable silicone resin composition, when the silicone gel is used in an application that does not require high heat resistance, the organopolysiloxane (A1) may have a structure in which part of the siloxane chain is replaced with a hydrocarbon chain. Also, part or all of the amount of the organopolysiloxane (A1) may be replaced with a chain extender having a linear hydrocarbon structure with mercapto groups at both ends.
（オルガノポリシロキサン（Ａ２））
オルガノポリシロキサン（Ａ）を構成するオルガノポリシロキサン（Ａ２）は、ケイ素原子に結合するメルカプトアルキル基を１分子当たり２個以上含有するオルガノポリシロキサンであり、ケイ素原子に結合するメルカプトアルキル基と、オルガノポリシロキサン（Ｂ）の脂肪族不飽和基とがチオール－エン反応してオルガノポリシロキサン（Ｂ）を架橋させて、光硬化性シリコーン樹脂組成物を硬化させるための架橋剤成分である。オルガノポリシロキサン（Ａ２）の主鎖の構造は、直鎖状、分岐状、環状のいずれでもよく、三次元的に架橋させる観点から主鎖の側鎖にメルカプトアルキル基が置換したオルガノポリシロキサンであることが好ましい。このオルガノポリシロキサン（Ａ２）として具体的には、特に限定されないが、例えば、信越化学工業社製品の型番「ＫＦ－２００１」（メルカプト基当量：０．５２６３ｍｍｏｌ／ｇ）、Ｇｅｌｅｓｔ社製品の型番「ＳＭＳ－０２２」（メルカプト基当量：０．３２８６ｍｍｏｌ／ｇ）等を用いることができる。
(Organopolysiloxane (A2))
The organopolysiloxane (A2) constituting the organopolysiloxane (A) is an organopolysiloxane containing two or more mercaptoalkyl groups bonded to silicon atoms per molecule, and is a crosslinking agent component for crosslinking the organopolysiloxane (B) by a thiol-ene reaction between the mercaptoalkyl groups bonded to silicon atoms and the aliphatic unsaturated groups of the organopolysiloxane (B) to cure the photocurable silicone resin composition. The main chain structure of the organopolysiloxane (A2) may be linear, branched, or cyclic, and from the viewpoint of three-dimensional crosslinking, it is preferable that the organopolysiloxane is an organopolysiloxane in which a mercaptoalkyl group is substituted on the side chain of the main chain. Organopolysiloxane (A2) is not particularly limited, but examples thereof include Shin-Etsu Chemical Co., Ltd. product model number "KF-2001" (mercapto group equivalent: 0.5263 mmol/g) and Gelest Inc. product model number "SMS-022" (mercapto group equivalent: 0.3286 mmol/g).
（オルガノポリシロキサン（Ｂ））
本発明の光硬化性シリコーン樹脂組成物を構成するオルガノポリシロキサン（Ｂ）は、少なくとも両末端に脂肪族不飽和基を含有する直鎖状オルガノポリシロキサンであり、例えば、以下式２の構造（式中Ｒは脂肪族不飽和基であり、Ｒ１～Ｒ４は同一または異種の非置換もしくは置換の一価炭化水素基である。また、ｑは１０以上の整数であり、好ましくは２３℃におけるオルガノポリシロキサン（Ｂ）の粘度を１００～２５０００ｃＰとする数である）からなる直鎖状オルガノポリシロキサンから選択できる。脂肪族不飽和基としては、例えば、ビニル基、プロペニル基、ブテニル基、ヘキセニル基等が挙げられ、合成の容易さ等の点から、ビニル基が好ましい。Ｒ１～Ｒ４の具体例としては、Ｃ１～Ｃ６のアルキル基（例えば、メチル基、エチル基、プロピル基等）又はＣ６～Ｃ１２のアリール基（例えば、フェニル基、トリル基、キシリル基等）が挙げられ、合成の容易さ等の観点から、Ｃ１～Ｃ６のアルキル基としては、メチル基が好ましく、Ｃ６～Ｃ１２のアリール基としては、フェニル基が好ましい。このオルガノポリシロキサン（Ｂ）として具体的には、特に限定されないが、例えば、Ｇｅｌｅｓｔ社製品の型番「ＤＭＳ－Ｖ３３」（ビニル基当量：０．０４６５ｍｍｏｌ／ｇ）、Ｇｅｌｅｓｔ社製品の型番「ＤＭＳ－Ｖ２２」（ビニル基当量：０．２２２２ｍｍｏｌ／ｇ）等を用いることができる。
(Organopolysiloxane (B))
The organopolysiloxane (B) constituting the photocurable silicone resin composition of the present invention is a linear organopolysiloxane containing aliphatic unsaturated groups at least at both ends, and can be selected, for example, from linear organopolysiloxanes having a structure of the following formula 2 (wherein R is an aliphatic unsaturated group, and R 1 to R 4 are the same or different unsubstituted or substituted monovalent hydrocarbon groups, and q is an integer of 10 or more, preferably a number that provides a viscosity of organopolysiloxane (B) of 100 to 25,000 cP at 23° C.). Examples of the aliphatic unsaturated group include vinyl groups, propenyl groups, butenyl groups, and hexenyl groups, with vinyl groups being preferred from the standpoint of ease of synthesis, etc. Specific examples of R 1 to R 4 include C1 to C6 alkyl groups (e.g., methyl, ethyl, propyl, etc.) and C6 to C12 aryl groups (e.g., phenyl, tolyl, xylyl, etc.), and from the viewpoint of ease of synthesis, etc., the C1 to C6 alkyl group is preferably a methyl group, and the C6 to C12 aryl group is preferably a phenyl group. Specific examples of this organopolysiloxane (B) are not particularly limited, but examples that can be used include Gelest's product model number "DMS-V33" (vinyl group equivalent: 0.0465 mmol/g) and Gelest's product model number "DMS-V22" (vinyl group equivalent: 0.2222 mmol/g).
オルガノポリシロキサン（Ａ１）とオルガノポリシロキサン（Ａ２）とからなるオルガノポリシロキサン（Ａ）と、オルガノポリシロキサン（Ｂ）の配合割合は、設計調整可能な弾性率の範囲が広く、高減衰性でありながら、せん断伸びに優れた硬化物を得る観点から、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数の比が０．７０以上１．００未満、かつオルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ１）中のメルカプトアルキル基の個数の比が、０．０６以上の範囲である。オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数の比が、０．７０未満の場合にはチオール－エン反応による架橋が不十分となって光硬化性シリコーン樹脂組成物が硬化せず、１．００以上の場合には硬化物の弾性率が高くなり過ぎたり、良好な減衰性が得られない。そのため、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数の比は、０．７０以上１．００未満が好ましく、０．７０以上０．９５以下がより好ましく、０．７０以上０．９０以下がさらに好ましい。また、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ１）中のメルカプトアルキル基の個数の比が０．０６未満の場合には、硬化物の良好なせん断伸びが得られない。そのため、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ１）中のメルカプトアルキル基の個数の比は、０．０６以上が好ましく、０．０６以上０．５以下がより好ましく、０．１以上０．５以下がさらに好ましい。The blending ratio of organopolysiloxane (A), which is composed of organopolysiloxane (A1) and organopolysiloxane (A2), and organopolysiloxane (B), from the viewpoint of obtaining a cured product having a wide range of elastic modulus that can be designed and is highly damping while having excellent shear elongation, is such that the ratio of the number of mercaptoalkyl groups in organopolysiloxane (A) to the number of aliphatic unsaturated groups in organopolysiloxane (B) is 0.70 or more and less than 1.00, and the ratio of the number of mercaptoalkyl groups in organopolysiloxane (A1) to the number of aliphatic unsaturated groups in organopolysiloxane (B) is 0.06 or more. If the ratio of the number of mercaptoalkyl groups in organopolysiloxane (A) to the number of aliphatic unsaturated groups in organopolysiloxane (B) is less than 0.70, crosslinking by thiol-ene reaction is insufficient, and the photocurable silicone resin composition does not cure, and if it is 1.00 or more, the elastic modulus of the cured product becomes too high, and good damping properties are not obtained. Therefore, the ratio of the number of mercaptoalkyl groups in organopolysiloxane (A) to the number of aliphatic unsaturated groups in organopolysiloxane (B) is preferably 0.70 or more and less than 1.00, more preferably 0.70 or more and 0.95 or less, and even more preferably 0.70 or more and 0.90 or less. In addition, if the ratio of the number of mercaptoalkyl groups in organopolysiloxane (A1) to the number of aliphatic unsaturated groups in organopolysiloxane (B) is less than 0.06, good shear elongation of the cured product is not obtained. Therefore, the ratio of the number of mercaptoalkyl groups in organopolysiloxane (A1) to the number of aliphatic unsaturated groups in organopolysiloxane (B) is preferably 0.06 or more, more preferably from 0.06 to 0.5, and even more preferably from 0.1 to 0.5.
（光重合開始剤（Ｃ））
本発明の光硬化性シリコーン樹脂組成物を構成する光重合開始剤（Ｃ）は、紫外線照射下におけるオルガノポリシロキサン（Ａ）中のメルカプトアルキル基とオルガノポリシロキサン（Ｂ）中の脂肪族不飽和基との架橋反応を促進させる成分であり、チオール－エン反応に作用する公知のものを使用できる。具体的には、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、２，２－ジメトキシ－２－フェニルアセトフェノン、キサントン、フルオレノン、ベンズアルデヒド、フルオレン、アントラキノン、トリフェニルアミン、カルバゾール、３－メチルアセトフェノン、４－クロロベンゾフェノン、４，４’－ジメトキシベンゾフェノン、４，４’－ジアミノベンゾフェノン、ミヒラーケトン、ベンゾインプロピルエーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、チオキサントン、ジエチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルホリノ－プロパン－１－オン、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シド、ビス－（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキシド；Ｏｍｎｉｒａｄ１８４、３６９、６５１、５００、９０７、１１７３、ＴＰＯ Ｈ（以上、ＢＡＳＦ社製）等が挙げられ、架橋反応の促進性の観点からアセトフェノン系が好ましい。光重合開始剤（Ｃ）は単独または２種以上組み合わせて適用できる。また、光重合開始剤（Ｃ）の配合量は、紫外線によりチオール－エン反応が開始するのに有効な量とすればよく、オルガノポリシロキサン（Ｂ）１００質量部に対し、０．０５～５０質量部が好ましく、より好ましくは０．１～５質量部である。
(Photopolymerization Initiator (C))
The photopolymerization initiator (C) constituting the photocurable silicone resin composition of the present invention is a component that promotes the crosslinking reaction between the mercaptoalkyl group in the organopolysiloxane (A) and the aliphatic unsaturated group in the organopolysiloxane (B) under ultraviolet irradiation, and any known photopolymerization initiator that acts on the thiol-ene reaction can be used. Specifically, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2- Examples of the photopolymerization initiator (C) include methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; Omnirad 184, 369, 651, 500, 907, 1173, and TPO H (all manufactured by BASF Corporation), and acetophenone-based initiators are preferred from the viewpoint of promoting the crosslinking reaction. The photopolymerization initiator (C) can be used alone or in combination of two or more kinds. The amount of the photopolymerization initiator (C) to be blended should be an amount effective for initiating a thiol-ene reaction by ultraviolet light, and is preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the organopolysiloxane (B).
（充填剤（Ｄ））
本発明の光硬化性シリコーン樹脂組成物は、さらに、硬化物の粘弾性特性やさらなる機能性付与のために充填剤（Ｄ）を含んでいてもよい。充填剤（Ｄ）としては、硬化物に対する粘弾性特性の調整作用や機能性を付与でき、チオール－エン反応を阻害しない粉末状のものであれば特に限定されず、例えば日本アエロジル社のＡＥＲＯＳＩＬ（登録商標）やトクヤマ社のＲＥＯＬＯＳＩＬ（登録商標）、旭化成ワッカー社製ＷＡＣＫＥＲ ＨＤＫ（登録商標）に代表されるヒュームドシリカ、トクヤマ社のＴＯＫＵＳＩＬ（登録商標）などのシリカやシリコーンレジン、アルミナ等の金属酸化物、セルロースナノファイバー等の繊維状化合物など、目的に応じて適宜選択して適用できる。
(Filler (D))
The photocurable silicone resin composition of the present invention may further contain a filler (D) for improving the viscoelastic properties of the cured product or imparting further functionality. The filler (D) is not particularly limited as long as it is a powder that can impart functionality and adjust the viscoelastic properties of the cured product and does not inhibit the thiol-ene reaction, and can be appropriately selected and used according to the purpose, such as fumed silica represented by AEROSIL (registered trademark) from Nippon Aerosil Co., Ltd., REOLOSIL (registered trademark) from Tokuyama Corporation, WACKER HDK (registered trademark) from Asahi Kasei Wacker Corporation, silica or silicone resin such as TOKUSIL (registered trademark) from Tokuyama Corporation, metal oxides such as alumina, and fibrous compounds such as cellulose nanofibers.
さらに本発明の光硬化性シリコーン樹脂組成物には、本発明の効果を阻害しない範囲で任意の添加物を添加してもよく、例えば、顔料や導電性付与剤、難燃剤、分散剤、粘着性・接着性付与剤、重合禁止剤、耐候性を向上させる添加剤として酸化防止剤、紫外線吸収剤、光安定剤など公知のものを必要に応じて適用できる。 In addition, any additive may be added to the photocurable silicone resin composition of the present invention as long as it does not impair the effects of the present invention. For example, known additives such as pigments, conductivity imparting agents, flame retardants, dispersants, tackiness/adhesiveness imparting agents, polymerization inhibitors, and additives for improving weather resistance, such as antioxidants, ultraviolet absorbers, and light stabilizers, may be applied as needed.
粘着性・接着性付与剤としては、例えば、ＭＱ樹脂、ＭＤＱ樹脂、ＭＴ樹脂、ＭＤＴ樹脂、ＭＤＴＱ樹脂、ＤＱ樹脂、ＤＴＱ樹脂及びＴＱ樹脂からなる群から選ばれる１種以上のシリコーン樹脂系接着向上剤（ただし、脂肪族不飽和基及びメルカプト基を含有しない）が好ましく、流動性や光硬化性シリコーン樹脂組成物中への分散性の観点からＭＱ樹脂、ＭＤＱ樹脂、ＭＤＴ樹脂及びＭＤＴＱ樹脂からなる群から選ばれる１種以上のシリコーン樹脂系接着向上剤がより好ましく、粘着性の付与効果と構造制御が容易な観点からＭＱ樹脂が更に好ましい。また、被接着物との密着性を向上させるためシランカップリング剤を添加してもよい。シランカップリング剤としては、例えば、トリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、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トリエトキシシラン、１，３－ビス（３－メタクリロキシプロピル）テトラメチルジシロキサン、トリメトキシシリルプロピルジアリルイソシアヌレート、ビス（トリメトキシシリルプロピル）アリ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、トリエトキシシリルプロピルジアリルイソシアヌレート、ビス（トリエトキシシリルプロピル）アリルイソシアヌレート、トリス（トリエトキシシリルプロピル）イソシアヌレート等が挙げられる。また、シランカップリング剤の他の例として、１，３－ビス（３－メタクリロキシプロピル）テトラメチルジシロキサン等の（メタ）アクリロキシ基、アルコキシ基（例えば、メトキシ、エトキシ、プロポキシ）、アミノ基等の官能基を有するジシロキサン化合物も適用できる。このうち、密着性・接着性向上の点から、脂肪族不飽和基を含有することが好ましく、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、１，３－ビス（３－メタクリロキシプロピル）テトラメチルジシロキサンであることがより好ましい。粘着性・接着性付与剤は１種であっても、２種以上であってもよい。As the tackiness/adhesion imparting agent, for example, one or more silicone resin-based adhesion improvers (not containing aliphatic unsaturated groups and mercapto groups) selected from the group consisting of MQ resin, MDQ resin, MT resin, MDT resin, MDTQ resin, DQ resin, DTQ resin and TQ resin are preferred, and from the viewpoint of flowability and dispersibility in the photocurable silicone resin composition, one or more silicone resin-based adhesion improvers selected from the group consisting of MQ resin, MDQ resin, MDT resin and MDTQ resin are more preferred, and from the viewpoint of the adhesiveness imparting effect and easy structure control, MQ resin is even more preferred. In addition, a silane coupling agent may be added to improve adhesion to the adherend. Examples of the silane coupling agent include triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane, trimethoxysilylpropyl diallyl isocyanurate, bis(trimethoxysilylpropyl)allyl isocyanurate, tris(trimethoxysilylpropyl)isocyanurate, triethoxysilylpropyl diallyl isocyanurate, bis(triethoxysilylpropyl)allyl isocyanurate, tris(triethoxysilylpropyl)isocyanurate, etc. As other examples of the silane coupling agent, disiloxane compounds having functional groups such as (meth)acryloxy groups, alkoxy groups (e.g., methoxy, ethoxy, propoxy), and amino groups, such as 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane, can also be used. Among these, from the viewpoint of improving adhesion and bonding properties, it is preferable that the tackifier contains an aliphatic unsaturated group, and 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane are more preferable. The tackifier and adhesion promoter may be one type or two or more types.
酸化防止剤としては、本発明に係る組成物の硬化物の酸化を防止して、耐候性を改善する機能を付加できるものを使用することができ、例えば、ヒンダードアミン系酸化防止剤やヒンダードフェノール系酸化防止剤等が挙げられる。ヒンダードアミン系酸化防止剤としては、公知のものを適宜選択でき、例えば、Ｎ，Ｎ′，Ｎ″，Ｎ″′－テトラキス－（４，６－ビス（ブチル－（Ｎ－メチル－２，２，６，６－テトラメチルピペリジン－４－イル）アミノ）－トリアジン－２－イル）－４，７－ジアザデカン－１，１０－ジアミン、ジブチルアミン・１，３，５－トリアジン・Ｎ，Ｎ′－ビス－（２，２，６，６－テトラメチル－４－ピペリジル－１，６－ヘキサメチレンジアミン・Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）ブチルアミンの重縮合物、ポリ［｛６－（１，１，３，３－テトラメチルブチル）アミノ－１，３，５－トリアジン－２，４－ジイル｝｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝］、コハク酸ジメチルと４－ヒドロキシ－２，２，６，６－テトラメチル－１－ピペリジンエタノールの重合体、［デカン二酸ビス（２，２，６，６－テトラメチル－１（オクチルオキシ）－４－ピペリジル）エステル、１，１－ジメチルエチルヒドロペルオキシドとオクタンの反応生成物（７０％）］－ポリプロピレン（３０％）、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）［［３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル］ブチルマロネート、メチル１，２，２，６，６－ペンタメチル－４－ピペリジルセバケート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケ－ト、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケ－ト、１－［２－〔３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシ〕エチル］－４－〔３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシ〕－２，２，６，６－テトラメチルピペリジン、４－ベンゾイルオキシ－２，２，６，６－テトラメチルピペリジン、８－アセチル－３－ドデシル－７，７，９，９－テトラメチル－１，３，８－トリアザスピロ［４．５］デカン－２，４－ジオン等が挙げられる。As the antioxidant, one that can prevent oxidation of the cured product of the composition according to the present invention and improve weather resistance can be used, and examples of such antioxidants include hindered amine antioxidants and hindered phenol antioxidants. As the hindered amine antioxidant, a known one can be appropriately selected, and examples thereof include N,N',N",N"'-tetrakis-(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine.1,3,5-triazine.N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine.N-(2,2,6,6-tetramethyl-4 poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidine decanedioate] lysyl) ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane (70%)]-polypropylene (30%), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-pi peridyl) sebacate, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, and the like.
他方、ヒンダードフェノール系酸化防止剤としては、公知のものを適宜選択でき、例えば、ペンタエリストール－テトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、チオジエチレン－ビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート）、Ｎ，Ｎ′－ヘキサン－１，６－ジイルビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピオアミド）、ベンゼンプロパン酸３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシＣ７－Ｃ９側鎖アルキルエステル、２，４－ジメチル－６－（１－メチルペンタデシル）フェノール、ジエチル［［３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル］ホスホネート、３，３′，３″，５，５′，５″－ヘキサン－ｔｅｒｔ－ブチル－４－ａ，ａ′，ａ″－（メシチレン－２，４，６－トリル）トリ－ｐ－クレゾール、カルシウムジエチルビス［［［３，５－ビス－（１，１－ジメチルエチル）－４－ヒドロキシフェニル］メチル］ホスホネート］、４，６－ビス（オクチルチオメチル）－ｏ－クレゾール、エチレンビス（オキシエチレン）ビス［３－（５－ｔｅｒｔ－ブチル－４－ヒドロキシ－ｍ－トリル）プロピオネート］、ヘキサメチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオン、Ｎ－フェニルベンゼンアミンと２，４，４－トリメチルペンテンとの反応生成物、２，６－ジ－ｔｅｒｔ－ブチル－４－（４，６－ビス（オクチルチオ）－１，３，５－トリアジン－２－イルアミノ）フェノール等が挙げられるが、これらに限定されるものではない。上記酸化防止剤は、１種であっても、２種以上であってもよい。On the other hand, as the hindered phenol-based antioxidant, a known one can be appropriately selected, for example, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), N,N'-hexane-1,6-diylbis[3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide), benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3",5,5',5"-hexane-tert-butyl-4-a,a',a"-(mesitylene-2 ,4,6-tolyl)tri-p-cresol, calcium diethyl bis[[[3,5-bis-(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate], 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5- Examples of the antioxidant include, but are not limited to, tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, a reaction product of N-phenylbenzenamine and 2,4,4-trimethylpentene, and 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol. The antioxidant may be one type or two or more types.
光安定剤としては、本発明に係る組成物又はその硬化物の光酸化劣化を防止する機能を付加できるものを使用することができ、例えば、ベンゾトリアゾール系、ヒンダードアミン系、ベンゾエート系化合物等が挙げられる。このうち、光安定剤としては、ヒンダードアミン系光安定剤が好ましい。中でも、第３級アミン含有ヒンダードアミン系光安定剤を用いることが、組成物の保存安定性改良のために好ましい。第３級アミン含有ヒンダードアミン系光安定剤としては、チヌビン６２２ＬＤ、チヌビン１４４、ＣＨＩＭＡＳＳＯＲＣ１１９ＦＬ（以上いずれもＢＡＳＦ社製）；ＭＡＲＫ ＬＡ－５７、ＬＡ－６２、ＬＡ－６７、ＬＡ－６３（以上いずれも旭電化工業株式会社製）；サノールＬＳ－７６５、ＬＳ－２９２、ＬＳ－２６２６、ＬＳ－１１１４、ＬＳ－７４４（以上いずれも三共株式会社製）等の光安定剤が挙げられる。また、耐光性安定剤として機能する紫外線吸収剤としては、例えば、ベンゾトリアゾール系、トリアジン系、ベンゾフェノン系又はベンゾエート系化合物等の紫外線吸収剤等が挙げられる。紫外線吸収剤としては公知のものを適宜選択でき、例えば、２，４－ジ－ｔｅｒｔ－ブチル－６－（５－クロロベンゾトリアゾール－２－イル）フェノール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔｅｒｔ－ペンチルフェノール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール、メチル３－（３－（２Ｈ－ベンゾトリアゾール－２－イル）－５－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート／ポリエチレングリコール３００の反応生成物、２－（２Ｈ－ベンゾトリアゾール－２－イル）－６－（直鎖及び側鎖ドデシル）－４－メチルフェノール等のベンゾトリアゾール系紫外線吸収剤、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－［（ヘキシル）オキシ］－フェノール等のトリアジン系紫外線吸収剤、オクタベンゾン等のベンゾフェノン系紫外線吸収剤、２，４－ジ－ｔｅｒｔ－ブチルフェニル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンゾエート等のベンゾエート系紫外線吸収剤等が挙げられる。上記光安定剤及び紫外線吸収剤は１種であっても、２種以上であってもよい。As the light stabilizer, one that can add a function to prevent photo-oxidative deterioration of the composition according to the present invention or its cured product can be used, and examples thereof include benzotriazole-based, hindered amine-based, and benzoate-based compounds. Of these, hindered amine-based light stabilizers are preferred as light stabilizers. In particular, it is preferred to use a tertiary amine-containing hindered amine-based light stabilizer in order to improve the storage stability of the composition. Examples of tertiary amine-containing hindered amine-based light stabilizers include light stabilizers such as Tinuvin 622LD, Tinuvin 144, and CHIMASSORC119FL (all manufactured by BASF); MARK LA-57, LA-62, LA-67, and LA-63 (all manufactured by Asahi Denka Kogyo Co., Ltd.); and Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all manufactured by Sankyo Co., Ltd.). Examples of ultraviolet absorbers that function as light resistance stabilizers include ultraviolet absorbers such as benzotriazole-based, triazine-based, benzophenone-based, and benzoate-based compounds. Known ultraviolet absorbers can be appropriately selected, and examples thereof include 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 3 ... 00 reaction product, benzotriazole-based ultraviolet absorbers such as 2-(2H-benzotriazol-2-yl)-6-(straight-chain and side-chain dodecyl)-4-methylphenol, triazine-based ultraviolet absorbers such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, benzophenone-based ultraviolet absorbers such as octabenzone, benzoate-based ultraviolet absorbers such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. The above light stabilizers and ultraviolet absorbers may be used alone or in combination of two or more kinds.
（光硬化性シリコーン樹脂組成物の物性）
本発明の光硬化性シリコーン樹脂組成物の物性のうち、組成物の粘度は、用途に応じて適宜設定できるが、塗工性やディスペンサー等による吐出性の観点から、２３℃における粘度が、５０～１００００ｃＰであることが好ましく、７０～９０００ｃＰであることがより好ましく、１００～７０００ｃＰであることが更に好ましい。
(Physical Properties of Photocurable Silicone Resin Composition)
Of the physical properties of the photocurable silicone resin composition of the present invention, the viscosity of the composition can be set appropriately depending on the application. From the standpoint of coatability and dischargeability using a dispenser or the like, the viscosity at 23°C is preferably 50 to 10,000 cP, more preferably 70 to 9,000 cP, and even more preferably 100 to 7,000 cP.
（光硬化性シリコーン樹脂組成物の硬化物の物性）
本発明の光硬化性シリコーン樹脂組成物は、上述の構成とすることによって、オルガノポリシロキサン（Ｂ）にオルガノポリシロキサン（Ａ１）が連結されてオルガノポリシロキサン（Ｂ）が鎖長延長された状態で、オルガノポリシロキサン（Ａ２）と架橋することによって、架橋点間のシロキサン鎖が長くなり、硬化物のせん断伸びの向上等に寄与する。そして、オルガノポリシロキサン（Ｂ）の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ１）中のメルカプトアルキル基の個数の比を、０．０６以上とし、かつ、オルガノポリシロキサン（Ｂ）の脂肪族不飽和基の個数に対する、オルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数の比を、０．７０以上１．００未満とすることにより、成分（Ａ１）と成分（Ｂ）との連結反応、及び鎖長延長された成分（Ｂ）と成分（Ａ２）との架橋反応が、所望の硬化物特性を実現するように行われる。これにより、複素弾性率の設計可能な範囲が広く、高減衰性でありながら、せん断伸びに優れた硬化物特性を有するシリコーンゲルを得ることができる。具体的には、硬化物の減衰性としては、粘弾性特性のｔａｎδ（１０Ｈｚ）が０．５以上であることが好ましく、精密機器用のダンピング材として用いる場合には０．５～２．０の範囲がより好ましい。また、硬化物のせん断伸びは、成分（Ａ１）を含まない、オルガノポリシロキサン（Ａ２）とオルガノポリシロキサン（Ｂ）とからなる組成物であって、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対するオルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数の比が等しい組成物からなる硬化物のせん断伸びに対して、１１０％以上であることが好ましく、２００％以上がより好ましく、３００％以上がさらに好ましい。特に、精密機器用のダンピング材として用いる場合には、ｔａｎδとせん断伸びが上記範囲であることが好ましい。
(Physical Properties of the Cured Product of the Photocurable Silicone Resin Composition)
By having the above-mentioned configuration, the photocurable silicone resin composition of the present invention has organopolysiloxane (B) linked to organopolysiloxane (A1) to extend the chain length of organopolysiloxane (B), and then crosslinked with organopolysiloxane (A2), thereby lengthening the siloxane chain between crosslinking points, which contributes to improving the shear elongation of the cured product. And, by making the ratio of the number of mercaptoalkyl groups in the organopolysiloxane (A1) to the number of aliphatic unsaturated groups in the organopolysiloxane (B) 0.06 or more, and making the ratio of the number of mercaptoalkyl groups in the organopolysiloxane (A) to the number of aliphatic unsaturated groups in the organopolysiloxane (B) 0.70 or more and less than 1.00, the linking reaction between the component (A1) and the component (B) and the crosslinking reaction between the chain-extended component (B) and the component (A2) are carried out so as to realize the desired cured product characteristics. This makes it possible to obtain a silicone gel having a wide designable range of complex elastic modulus, high damping properties, and excellent cured product characteristics in shear elongation. Specifically, as the damping properties of the cured product, the viscoelastic property tan δ (10 Hz) is preferably 0.5 or more, and when used as a damping material for precision instruments, the range of 0.5 to 2.0 is more preferable. The shear elongation of the cured product is preferably 110% or more, more preferably 200% or more, and even more preferably 300% or more, relative to the shear elongation of a cured product of a composition not containing component (A1), which is made of organopolysiloxane (A2) and organopolysiloxane (B), and in which the ratio of the number of mercaptoalkyl groups in organopolysiloxane (A) to the number of aliphatic unsaturated groups in organopolysiloxane (B) is equal. In particular, when used as a damping material for precision instruments, it is preferable that tan δ and shear elongation are within the above ranges.
（光硬化性シリコーン樹脂組成物の用途）
本発明の光硬化性シリコーン樹脂組成物は、光硬化した硬化物が上記の高減衰性とせん断伸び性を有することから、せん断伸びが１００％を超える場合であっても破損せずに、高減衰性を発揮するシール材、コーティング材、ポッティング材、防振材、制振材、光学接着剤（ＯＣＲ、ＯＣＡ）として用いることができる。また、光ピックアップモジュールなどの光学装置における１０Ｈｚ以上の高周波域の振動に対しても高減衰を保ちながら破断し難く、優れた制振性を備えたダンピング部材として好適である。
(Uses of the photocurable silicone resin composition)
Since the photocurable silicone resin composition of the present invention has the above-mentioned high damping property and shear elongation when photocured, it can be used as a sealing material, coating material, potting material, vibration-proofing material, vibration-damping material, and optical adhesive (OCR, OCA) that exhibits high damping property without breaking even when the shear elongation exceeds 100%. In addition, it is suitable as a damping member with excellent vibration-damping property that is difficult to break while maintaining high damping even against vibrations in the high frequency range of 10 Hz or more in optical devices such as optical pickup modules.
本発明の光硬化性シリコーン樹脂組成物は、上記の（Ａ）～（Ｃ）成分または（Ａ）～（Ｄ）成分、及び必要に応じて添加される充填材やその他の種々成分等を、所定の配合割合で混合することで得られる。上記の（Ａ）～（Ｃ）成分等または（Ａ）～（Ｄ）成分等を、混合する順番は特に限定しない。また、（Ａ）成分として、光重合開始剤（Ｃ）の存在下で（Ａ１）成分と（Ａ２）成分の一部または全部を予め反応させて鎖長延長を図ったのちに（Ｂ）成分や（Ｄ）成分を混合してもよい。混合手段としては、特に限定されず、ハンドミキサーやケミカルミキサーなどの公知の方法を適用できる。本発明の光硬化性シリコーン樹脂組成物は活性エネルギー線を照射することにより、硬化物を形成する。活性エネルギー線としては、紫外線、電子線、Ｘ線又は放射線等が挙げられるが、取り扱いのし易さの観点から、紫外線が好ましく用いられる。照射される紫外線の光源や紫外線の波長範囲は特に限定されず、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ、ナトリウムランプ、ハロゲンランプ、キセノンランプ、ＬＥＤ、蛍光灯、太陽光、電子線照射装置等、あらゆる公知のものを用いることができる。The photocurable silicone resin composition of the present invention is obtained by mixing the above-mentioned (A) to (C) components or (A) to (D) components, and the filler and other various components added as necessary, in a predetermined mixing ratio. The order in which the above-mentioned (A) to (C) components or (A) to (D) components are mixed is not particularly limited. In addition, as the (A) component, a part or all of the (A1) component and the (A2) component may be reacted in advance in the presence of the photopolymerization initiator (C) to extend the chain length, and then the (B) component and the (D) component may be mixed. There is no particular limitation on the mixing means, and known methods such as a hand mixer or a chemical mixer can be applied. The photocurable silicone resin composition of the present invention forms a cured product by irradiating it with active energy rays. Examples of active energy rays include ultraviolet rays, electron beams, X-rays, and radiation, but ultraviolet rays are preferably used from the viewpoint of ease of handling. The light source of the irradiated ultraviolet light and the wavelength range of the ultraviolet light are not particularly limited, and any known light source can be used, such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a black light lamp, a microwave excited mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED, a fluorescent lamp, sunlight, and an electron beam irradiation device.
以下、実施例及び比較例によって、本発明を更に詳細に説明する。なお本発明は、これらの実施例によって限定されるものではない。The present invention will be described in more detail below with reference to examples and comparative examples. Note that the present invention is not limited to these examples.
［測定・評価方法］
実施例および比較例の各組成物について、透明ＰＰフィルム上に硬化物の厚みが２ｍｍとなるように光硬化性シリコーン樹脂組成物をシート状に成形し、天面及び底面の各方向から波長が３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２ずつ照射して硬化させて、測定サンプルとした。上記シートをφ２５ｍｍに抜き成型し、レオメーター（ＡＲＥＳ－Ｇ２、ティー・エイ・インスツルメント社製）を用いて下記（１）～（３）の測定を行った。
[Measurement and evaluation method]
For each composition of the Examples and Comparative Examples, the photocurable silicone resin composition was molded into a sheet on a transparent PP film so that the thickness of the cured product was 2 mm, and the composition was cured by irradiating the top and bottom surfaces with 365 nm ultraviolet light at 3000 mJ/cm2 each to prepare a measurement sample. The sheet was punched into a φ25 mm shape, and the following measurements (1) to (3) were carried out using a rheometer (ARES-G2, manufactured by TA Instruments).
（１）せん断伸び
２５℃、１．０Ｈｚ、ひずみ１００～１５００％で、各測定サンプルのＳｔｒａｉｎ Ｓｗｅｅｐテストを行い、ｔａｎδが最小値となった歪みの値をせん断伸びとした。伸び向上率（％）として、成分（Ａ１）のみを含まない、オルガノポリシロキサン（Ａ２）とオルガノポリシロキサン（Ｂ）とからなる組成物であって、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数（Ｖｉ）に対するオルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数（ＳＨ）の比（以下、ＳＨ／Ｖｉ比と称する）が等しい組成物を各比較例に係る組成物として調製し、この各比較例の測定サンプルのせん断伸びの値に対する各実施例の測定サンプルのせん断伸びの値の比率を求めた。伸び向上率が１１０％以上を合格（○）、１１０％未満を不合格（×）と判定した。なお、伸び向上率を求めるにおいて、後述する各実施例に対応した上記オルガノポリシロキサン（Ａ１）のみを含まず、ＳＨ／Ｖｉ比が等しい構成の比較例は以下の通りである。実施例１、４と比較例７の場合には比較例１、実施例２の場合には比較例２、実施例３の場合には比較例３、実施例５の場合には比較例４、実施例６、９と比較例１４の場合には比較例８、実施例７の場合には比較例９、実施例８の場合には比較例１０、実施例１０の場合には比較例１１である。
(1) Shear elongation A strain sweep test was performed on each measurement sample at 25°C, 1.0 Hz, and strain of 100 to 1500%, and the strain value at which tan δ was the minimum was taken as the shear elongation. As the elongation improvement rate (%), a composition consisting of organopolysiloxane (A2) and organopolysiloxane (B) that does not contain only component (A1), in which the ratio of the number of mercaptoalkyl groups (SH) in organopolysiloxane (A) to the number of aliphatic unsaturated groups (Vi) in organopolysiloxane (B) (hereinafter referred to as SH/Vi ratio) is equal was prepared as a composition according to each comparative example, and the ratio of the shear elongation value of the measurement sample of each comparative example to the shear elongation value of the measurement sample of each comparative example was determined. An elongation improvement rate of 110% or more was judged as pass (○), and an improvement rate of less than 110% was judged as fail (×). In determining the elongation improvement rate, the comparative examples corresponding to each of the examples described later, which do not contain only the organopolysiloxane (A1) and have the same SH/Vi ratio, are as follows: Comparative Example 1 in the case of Examples 1 and 4 and Comparative Example 7, Comparative Example 2 in the case of Example 2, Comparative Example 3 in the case of Example 3, Comparative Example 4 in the case of Example 5, Comparative Example 8 in the case of Examples 6, 9 and Comparative Example 14, Comparative Example 9 in the case of Example 7, Comparative Example 10 in the case of Example 8, and Comparative Example 11 in the case of Example 10.
（２）減衰性（ｔａｎδ）
ＪＩＳ Ｋ７２４４－１０に準拠して、各測定サンプルの動的粘弾性測定を行い、２５℃、１０Ｈｚにおけるｔａｎδを得た。ｔａｎδが０．５以上を合格（○）、０．５未満を不合格（×）と判定した。
(2) Damping (tan δ)
Dynamic viscoelasticity of each measurement sample was measured in accordance with JIS K7244-10 to obtain tan δ at 25° C. and 10 Hz. Tan δ of 0.5 or more was judged as pass (◯), and tan δ of less than 0.5 was judged as fail (×).
（３）弾性率（複素弾性率Ｇ＊）
ＪＩＳ Ｋ７２４４－１０に準拠して、各測定サンプルの動的粘弾性測定を行い、２５℃、１０Ｈｚにおける複素弾性率Ｇ＊を得た。
(3) Elastic modulus (complex elastic modulus G * )
In accordance with JIS K7244-10, dynamic viscoelasticity measurement was carried out on each measurement sample to obtain the complex modulus G * at 25° C. and 10 Hz.
［実施例１］
オルガノポリシロキサン（Ａ１）として、信越化学工業社製品・型番：Ｘ－２２－１６７Ｃ（メルカプト基当量：０．４３４８ｍｍｏｌ／ｇ）が０．６０ｇと、オルガノポリシロキサン（Ａ２）として、信越化学工業社製品・型番：ＫＦ－２００１（メルカプト基当量：０．５２６３ｍｍｏｌ／ｇ、以下表において成分Ａ２－１と称する）が０．９３ｇと、オルガノポリシロキサン（Ｂ）として、Ｇｅｌｅｓｔ社製品・型番：ＤＭＳ－Ｖ３３（ビニル基当量：０．０４６５ｍｍｏｌ／ｇ、以下表において成分Ｂ－１と称する）が１８．０７ｇと、光重合開始剤（Ｃ）として、ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．社製品・型番：Ｏｍｎｉｒａｄ１１７３が０．４０ｇと、を蓋つきプラスチック容器に投入した。構成成分における、ＳＨ／Ｖｉ比は０．８９、オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数（Ｖｉ）に対する、オルガノポリシロキサン（Ａ１）中のメルカプトアルキル基の個数（ＳＨ（Ａ１））の比（以下、ＳＨ（Ａ１）／Ｖｉ比と称する）は０．３１となるように配合した。この配合物を自転・公転ミキサー（製品名：あわとり練太郎（登録商標）ＡＲＥ－３５０、株式会社シンキー社製品）を用いて、２０００ｒｐｍにて３分間混練後、２２００ｒｐｍにて１分間遠心脱泡して、実施例１の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Example 1]
As the organopolysiloxane (A1), 0.60 g of Shin-Etsu Chemical Co., Ltd.'s product, model number: X-22-167C (mercapto group equivalent: 0.4348 mmol/g) was used; as the organopolysiloxane (A2), 0.93 g of Shin-Etsu Chemical Co., Ltd.'s product, model number: KF-2001 (mercapto group equivalent: 0.5263 mmol/g; hereinafter referred to as component A2-1 in the table) was used; as the organopolysiloxane (B), 18.07 g of Gelest's product, model number: DMS-V33 (vinyl group equivalent: 0.0465 mmol/g; hereinafter referred to as component B-1 in the table) was used; and as the photopolymerization initiator (C), 1.07 g of IGM Resins B.V. The components were mixed so that the SH/Vi ratio in the components was 0.89, and the ratio of the number of mercaptoalkyl groups in the organopolysiloxane (A1) (SH(A1)) to the number of aliphatic unsaturated groups in the organopolysiloxane (B) (Vi) (hereinafter referred to as the SH(A1)/Vi ratio) was 0.31. This mixture was kneaded for 3 minutes at 2000 rpm using a rotation/revolution mixer (product name: Awatori Rentaro (registered trademark) ARE-350, product of Thinky Corporation), and then centrifugal degassed for 1 minute at 2200 rpm to obtain a photocurable silicone resin composition of Example 1. This photocurable silicone resin composition was subjected to measurement and evaluation of (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［実施例２］
実施例１において、成分（Ａ１）、成分（Ａ２）、成分（Ｂ）、成分（Ｃ）（以下、各構成成分とも称す。）を表１に示す配合に替えて、ＳＨ／Ｖｉ比が０．７０、ＳＨ（Ａ１）／Ｖｉ比が０．３１とした以外は実施例１と同様にして、実施例２の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Example 2]
A photocurable silicone resin composition of Example 2 was obtained in the same manner as in Example 1, except that in Example 1, components (A1), (A2), (B), and (C) (hereinafter also referred to as each component) were replaced with the formulations shown in Table 1, and the SH/Vi ratio was 0.70 and the SH(A1)/Vi ratio was 0.31. For this photocurable silicone resin composition, (1) shear elongation, (2) damping property, and (3) elastic modulus were measured and evaluated according to the measurement and evaluation methods described above.
［実施例３］
実施例１において、各構成成分を表１に示す配合に替えて、ＳＨ／Ｖｉ比が０．９９、ＳＨ（Ａ１）／Ｖｉ比が０．３１とした以外は実施例１と同様にして、実施例３の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Example 3]
A photocurable silicone resin composition of Example 3 was obtained in the same manner as in Example 1, except that in Example 1, the components were replaced with the formulation shown in Table 1, the SH/Vi ratio was 0.99, and the SH(A1)/Vi ratio was 0.31. This photocurable silicone resin composition was subjected to measurement and evaluation of (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［実施例４］
実施例１において、各構成成分を表１に示す配合に替えて、ＳＨ／Ｖｉ比が０．８９、ＳＨ（Ａ１）／Ｖｉ比が０．０６とした以外は実施例１と同様にして、実施例４の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Example 4]
A photocurable silicone resin composition of Example 4 was obtained in the same manner as in Example 1, except that in Example 1, the components were replaced with the formulation shown in Table 1, the SH/Vi ratio was 0.89, and the SH(A1)/Vi ratio was 0.06. This photocurable silicone resin composition was subjected to measurement and evaluation of (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［実施例５］
実施例１において、さらに充填剤（Ｄ）としてフュームドシリカ（ＡＥＲＯＳＩＬ社製品・型番：Ｒ９７２）０．４０ｇ（成分（Ａ１）、成分（Ａ２）、成分（Ｂ）、成分（Ｃ）の合計重量に対し２．００ｗｔ％に相当）を配合した以外は実施例１と同様にして、実施例５の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Example 5]
The photocurable silicone resin composition of Example 5 was obtained in the same manner as in Example 1, except that 0.40 g (corresponding to 2.00 wt % based on the total weight of components (A1), (A2), (B), and (C)) of fumed silica (product of AEROSIL, model number: R972) was further blended as filler (D). For this photocurable silicone resin composition, (1) shear elongation, (2) damping property, and (3) elastic modulus were measured and evaluated according to the measurement and evaluation methods described above.
［実施例６］
実施例１において、オルガノポリシロキサン（Ａ２）をＧｅｌｅｓｔ社製品・型番：ＳＭＳ－０２２（メルカプト基当量：０．３２８６ｍｍｏｌ／ｇ、以下表において成分Ａ２－２と称する）に、オルガノポリシロキサン（Ｂ）をＧｅｌｅｓｔ社製品・型番：ＤＭＳ－Ｖ２２（ビニル基当量：０．２２２２ｍｍｏｌ／ｇ、以下表において成分Ｂ－２と称する）に、それぞれ変更し、表２に示す配合とした。構成成分における、ＳＨ／Ｖｉ比は０．８９、ＳＨ（Ａ１）／Ｖｉ比は０．１０となるように配合した。実施例１と同様にして、実施例６の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Example 6]
In Example 1, the organopolysiloxane (A2) was changed to Gelest's product, model number: SMS-022 (mercapto group equivalent: 0.3286 mmol/g, hereinafter referred to as component A2-2 in the table), and the organopolysiloxane (B) was changed to Gelest's product, model number: DMS-V22 (vinyl group equivalent: 0.2222 mmol/g, hereinafter referred to as component B-2 in the table), respectively, to obtain the formulation shown in Table 2. The components were blended so that the SH/Vi ratio was 0.89 and the SH(A1)/Vi ratio was 0.10. The photocurable silicone resin composition of Example 6 was obtained in the same manner as in Example 1. For this photocurable silicone resin composition, (1) shear elongation, (2) damping property, and (3) elastic modulus were measured and evaluated according to the above-mentioned measurement and evaluation methods.
［実施例７］
実施例６において、各構成成分を表２に示す配合に替えて、ＳＨ／Ｖｉ比が０．８０、ＳＨ（Ａ１）／Ｖｉ比が０．０９とした以外は実施例６と同様にして、実施例７の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Example 7]
A photocurable silicone resin composition of Example 7 was obtained in the same manner as in Example 6, except that the components in Example 6 were replaced with the formulation shown in Table 2, the SH/Vi ratio was 0.80, and the SH(A1)/Vi ratio was 0.09. This photocurable silicone resin composition was measured and evaluated for (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［実施例８］
実施例６において、各構成成分を表２に示す配合に替えて、ＳＨ／Ｖｉ比が０．９９、ＳＨ（Ａ１）／Ｖｉ比が０．１０とした以外は実施例６と同様にして、実施例８の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Example 8]
The photocurable silicone resin composition of Example 8 was obtained in the same manner as in Example 6, except that the components in Example 6 were replaced with the formulation shown in Table 2, the SH/Vi ratio was 0.99, and the SH(A1)/Vi ratio was 0.10. This photocurable silicone resin composition was measured and evaluated for (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［実施例９］
実施例６において、各構成成分を表２に示す配合に替えて、ＳＨ／Ｖｉ比が０．８９、ＳＨ（Ａ１）／Ｖｉ比が０．０６とした以外は実施例６と同様にして、実施例９の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Example 9]
A photocurable silicone resin composition of Example 9 was obtained in the same manner as in Example 6, except that the components in Example 6 were replaced with the formulation shown in Table 2, the SH/Vi ratio was 0.89, and the SH(A1)/Vi ratio was 0.06. This photocurable silicone resin composition was subjected to measurement and evaluation of (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［実施例１０］
実施例６において、さらに充填剤（Ｄ）としてフュームドシリカ（ＡＥＲＯＳＩＬ社製品・型番：Ｒ９７２）０．４０ｇ（成分（Ａ１）、成分（Ａ２）、成分（Ｂ）、成分（Ｃ）の合計重量に対し２．０４ｗｔ％に相当）を配合した以外は実施例６と同様にして、実施例１０の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Example 10]
The photocurable silicone resin composition of Example 10 was obtained in the same manner as in Example 6, except that 0.40 g (corresponding to 2.04 wt % based on the total weight of components (A1), (A2), (B), and (C)) of fumed silica (product of AEROSIL, model number: R972) was further blended as filler (D). For this photocurable silicone resin composition, (1) shear elongation, (2) damping property, and (3) elastic modulus were measured and evaluated according to the measurement and evaluation methods described above.
［比較例１］
実施例１において、各構成成分を表３に示す配合に替えて、成分（Ａ１）を含まず、ＳＨ／Ｖｉ比が０．８９、ＳＨ（Ａ１）／Ｖｉ比が０．００とした以外は実施例１と同様にして、比較例１の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 1]
A photocurable silicone resin composition of Comparative Example 1 was obtained in the same manner as in Example 1, except that in Example 1, the components were replaced with those shown in Table 3, component (A1) was not included, the SH/Vi ratio was 0.89, and the SH(A1)/Vi ratio was 0.00. This photocurable silicone resin composition was subjected to measurement and evaluation of (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例２］
比較例１において、各構成成分を表３に示す配合に替えて、ＳＨ／Ｖｉ比を０．７０とした以外は比較例１と同様にして、比較例２の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 2]
A photocurable silicone resin composition of Comparative Example 2 was obtained in the same manner as in Comparative Example 1, except that the components were replaced with the formulation shown in Table 3 and the SH/Vi ratio was changed to 0.70. This photocurable silicone resin composition was subjected to measurement and evaluation of (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例３］
比較例１において、各構成成分を表３に示す配合に替えて、ＳＨ／Ｖｉ比を０．９９とした以外は比較例１と同様にして、比較例３の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 3]
A photocurable silicone resin composition of Comparative Example 3 was obtained in the same manner as in Comparative Example 1, except that the components were replaced with the formulation shown in Table 3 and the SH/Vi ratio was changed to 0.99. This photocurable silicone resin composition was subjected to measurement and evaluation of (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例４］
比較例１において、さらに充填剤（Ｄ）としてフュームドシリカ（ＡＥＲＯＳＩＬ社製品・型番：Ｒ９７２）を配合し、各構成成分を表３に示す配合に替えて、ＳＨ／Ｖｉ比を０．８９とした以外は比較例１と同様にして、比較例４の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 4]
A photocurable silicone resin composition of Comparative Example 4 was obtained in the same manner as in Comparative Example 1, except that in Comparative Example 1, fumed silica (product of AEROSIL, model number: R972) was further blended as filler (D), the components were replaced with the blend shown in Table 3, and the SH/Vi ratio was set to 0.89. For this photocurable silicone resin composition, (1) shear elongation, (2) damping property, and (3) elastic modulus were measured and evaluated according to the measurement and evaluation methods described above.
［比較例５］
実施例１において、各構成成分を表３に示す配合に替えて、ＳＨ／Ｖｉ比が０．６７、ＳＨ（Ａ１）／Ｖｉ比が０．３０とした以外は実施例１と同様にして、比較例５の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 5]
A photocurable silicone resin composition of Comparative Example 5 was obtained in the same manner as in Example 1, except that in Example 1, the components were replaced with the formulation shown in Table 3, the SH/Vi ratio was 0.67, and the SH(A1)/Vi ratio was 0.30. This photocurable silicone resin composition was measured and evaluated for (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例６］
実施例１において、各構成成分を表３に示す配合に替えて、ＳＨ／Ｖｉ比が１．０５、ＳＨ（Ａ１）／Ｖｉ比が０．３１とした以外は実施例１と同様にして、比較例６の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 6]
A photocurable silicone resin composition of Comparative Example 6 was obtained in the same manner as in Example 1, except that in Example 1, the components were replaced with the formulation shown in Table 3, the SH/Vi ratio was 1.05, and the SH(A1)/Vi ratio was 0.31. This photocurable silicone resin composition was measured and evaluated for (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例７］
実施例１において、各構成成分を表３に示す配合に替えて、ＳＨ／Ｖｉ比が０．８９、ＳＨ（Ａ１）／Ｖｉ比が０．０５とした以外は実施例１と同様にして、比較例７の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 7]
A photocurable silicone resin composition of Comparative Example 7 was obtained in the same manner as in Example 1, except that in Example 1, the components were replaced with the formulation shown in Table 3, the SH/Vi ratio was 0.89, and the SH(A1)/Vi ratio was 0.05. This photocurable silicone resin composition was measured and evaluated for (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例８］
実施例６において、各構成成分を表４に示す配合に替えて、成分（Ａ１）を含まず、ＳＨ／Ｖｉ比が０．８９、ＳＨ（Ａ１）／Ｖｉ比が０．００とした以外は実施例６と同様にして、比較例８の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 8]
A photocurable silicone resin composition of Comparative Example 8 was obtained in the same manner as in Example 6, except that in Example 6, the components were replaced with those shown in Table 4, component (A1) was not included, the SH/Vi ratio was 0.89, and the SH(A1)/Vi ratio was 0.00. This photocurable silicone resin composition was subjected to measurement and evaluation of (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例９］
比較例８において、各構成成分を表４に示す配合に替えて、ＳＨ／Ｖｉ比を０．８０とした以外は比較例８と同様にして、比較例９の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 9]
A photocurable silicone resin composition of Comparative Example 9 was obtained in the same manner as in Comparative Example 8, except that the components were replaced with the formulation shown in Table 4 and the SH/Vi ratio was changed to 0.80. This photocurable silicone resin composition was subjected to measurement and evaluation of (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例１０］
比較例８において、各構成成分を表４に示す配合に替えて、ＳＨ／Ｖｉ比を０．９９とした以外は比較例８と同様にして、比較例１０の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 10]
A photocurable silicone resin composition of Comparative Example 10 was obtained in the same manner as in Comparative Example 8, except that the components were replaced with the formulation shown in Table 4 and the SH/Vi ratio was changed to 0.99. This photocurable silicone resin composition was measured and evaluated for (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例１１］
比較例８において、さらに充填剤（Ｄ）としてフュームドシリカ（ＡＥＲＯＳＩＬ社製品・型番：Ｒ９７２）を配合し、各構成成分を表４に示す配合に替えて、ＳＨ／Ｖｉ比を０．８９とした以外は比較例８と同様にして、比較例１１の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 11]
A photocurable silicone resin composition of Comparative Example 11 was obtained in the same manner as in Comparative Example 8, except that in Comparative Example 8, fumed silica (product of AEROSIL, model number: R972) was further blended as filler (D), the components were replaced with the blend shown in Table 4, and the SH/Vi ratio was set to 0.89. For this photocurable silicone resin composition, (1) shear elongation, (2) damping property, and (3) elastic modulus were measured and evaluated according to the measurement and evaluation methods described above.
［比較例１２］
実施例６において、各構成成分を表４に示す配合に替えて、ＳＨ／Ｖｉ比が０．６９、ＳＨ（Ａ１）／Ｖｉ比が０．０９とした以外は実施例６と同様にして、比較例１２の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った
[Comparative Example 12]
A photocurable silicone resin composition of Comparative Example 12 was obtained in the same manner as in Example 6, except that in Example 6, the components were replaced with the formulation shown in Table 4, the SH/Vi ratio was 0.69, and the SH(A1)/Vi ratio was 0.09. This photocurable silicone resin composition was measured and evaluated for (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例１３］
実施例６において、各構成成分を表４に示す配合に替えて、ＳＨ／Ｖｉ比が１．０５、ＳＨ（Ａ１）／Ｖｉ比が０．１０とした以外は実施例６と同様にして、比較例１３の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 13]
A photocurable silicone resin composition of Comparative Example 13 was obtained in the same manner as in Example 6, except that the components in Example 6 were replaced with the formulation shown in Table 4, the SH/Vi ratio was 1.05, and the SH(A1)/Vi ratio was 0.10. This photocurable silicone resin composition was measured and evaluated for (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
［比較例１４］
実施例６において、各構成成分を表４に示す配合に替えて、ＳＨ／Ｖｉ比が０．８９、ＳＨ（Ａ１）／Ｖｉ比が０．０５とした以外は実施例６と同様にして、比較例１４の光硬化性シリコーン樹脂組成物を得た。この光硬化性シリコーン樹脂組成物について、上述した測定・評価方法に従い、（１）せん断伸び、（２）減衰性及び（３）弾性率の測定・評価を行った。
[Comparative Example 14]
A photocurable silicone resin composition of Comparative Example 14 was obtained in the same manner as in Example 6, except that in Example 6, the components were replaced with the formulation shown in Table 4, the SH/Vi ratio was 0.89, and the SH(A1)/Vi ratio was 0.05. This photocurable silicone resin composition was measured and evaluated for (1) shear elongation, (2) damping property, and (3) elastic modulus according to the measurement and evaluation methods described above.
実施例１～５の評価結果を表１に、実施例６～１０の評価結果を表２にそれぞれ示した。また、比較例１～７の評価結果を表３に、比較例８～１４の評価結果を表４に、それぞれ示した。The evaluation results of Examples 1 to 5 are shown in Table 1, and the evaluation results of Examples 6 to 10 are shown in Table 2. The evaluation results of Comparative Examples 1 to 7 are shown in Table 3, and the evaluation results of Comparative Examples 8 to 14 are shown in Table 4.
実施例１～１０の結果から、本発明の光硬化性シリコーン樹脂組成物は、少なくとも両末端に脂肪族不飽和基を含有する直鎖状のオルガノポリシロキサン（Ｂ）と、オルガノポリシロキサン（Ｂ）の鎖長延長剤として機能する両末端にメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ１）と、オルガノポリシロキサン（Ｂ）を架橋する硬化剤として機能するケイ素原子に結合するメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ２）と、光重合開始剤（Ｃ）とを含み、ＳＨ／Ｖｉ比が０．７０以上１．００未満、かつＳＨ（Ａ１）／Ｖｉ比が０．０６以上となる構成とすることによって、高減衰性でありながら、せん断伸びに優れた光硬化性シリコーン樹脂組成物が得られることが分かった。また、実施例１～５群及び実施例６～１０群における複素弾性率Ｇ＊の結果から、オルガノポリシロキサンポリマーだけの構成であっても硬化物の複素弾性率を幅広く設計できることが分かった。 From the results of Examples 1 to 10, it was found that the photocurable silicone resin composition of the present invention comprises a linear organopolysiloxane (B) containing at least an aliphatic unsaturated group at both ends, an organopolysiloxane (A1) containing mercaptoalkyl groups at both ends functioning as a chain extender for the organopolysiloxane (B), an organopolysiloxane (A2) containing mercaptoalkyl groups bonded to silicon atoms functioning as a curing agent for crosslinking the organopolysiloxane (B), and a photopolymerization initiator (C), and by configuring the SH/Vi ratio to be 0.70 or more and less than 1.00, and the SH(A1)/Vi ratio to be 0.06 or more, a photocurable silicone resin composition having high damping properties and excellent shear elongation can be obtained.In addition, from the results of the complex elastic modulus G * in Examples 1 to 5 and Examples 6 to 10, it was found that the complex elastic modulus of the cured product can be designed widely even if the composition is made of only organopolysiloxane polymer.
また、実施例５及び実施例１０の結果から、充填剤（Ｄ）を含んだ構成としても、せん断伸びに優れ、高い伸び向上率を示すことが分かった。また、実施例１～５群と実施例６～１０群との結果の比較から、オルガノポリシロキサン（Ａ２）とオルガノポリシロキサン（Ｂ）の種類を変更しても本発明の効果が得られることが分かった。 Furthermore, the results of Examples 5 and 10 show that even in a composition containing filler (D), the composition exhibits excellent shear elongation and a high elongation improvement rate. Furthermore, a comparison of the results of Examples 1 to 5 and Examples 6 to 10 shows that the effects of the present invention can be obtained even when the types of organopolysiloxane (A2) and organopolysiloxane (B) are changed.
一方、実施例１～４の結果と比較例１～４の結果との比較、並びに実施例６～９の結果と比較例８～１１の結果との比較から、各構成成分とＳＨ／Ｖｉ比が同じ条件であっても、オルガノポリシロキサン（Ｂ）の鎖長延長剤として機能する両末端にメルカプトアルキル基を有するオルガノポリシロキサン（Ａ１）を含まない場合には、せん断伸びの測定値も減衰性（ｔａｎδ）の測定値も劣っており、せん断伸びと減衰性とを両立することができないことが分かった。また、比較例の結果によれば、弾性率（Ｇ＊）の測定値も大きくなっており、硬化物の複素弾性率の設計可能範囲が限定されてしまうことが示された。また、比較例５、１２の結果からＳＨ／Ｖｉ比が０．７０未満の場合にはチオール－エン反応による架橋が不十分となって硬化せず、比較例６、１３の結果からＳＨ／Ｖｉ比が１．００以上の場合には良好な減衰性が得られなかった。さらに、比較例７及び比較例１４の結果から、ＳＨ（Ａ１）／Ｖｉ比が０．０６未満であると、せん断伸びの向上が得られなかった。これらの結果から、各構成成分の配合は、ＳＨ（Ａ１）／Ｖｉ比が０．０６以上であり、かつＳＨ／Ｖｉ比が０．７０以上１．００未満とすることが重要であることが分かった。 On the other hand, from the comparison of the results of Examples 1 to 4 with the results of Comparative Examples 1 to 4, and from the comparison of the results of Examples 6 to 9 with the results of Comparative Examples 8 to 11, it was found that even under the same conditions of each component and SH/Vi ratio, when the organopolysiloxane (A1) having mercaptoalkyl groups at both ends, which functions as a chain extender for the organopolysiloxane (B), is not included, the measured values of shear elongation and damping property (tan δ) are both inferior, and it is not possible to achieve both shear elongation and damping property. In addition, according to the results of the comparative examples, the measured values of the elastic modulus (G * ) are also large, indicating that the designable range of the complex modulus of elasticity of the cured product is limited. In addition, from the results of Comparative Examples 5 and 12, when the SH/Vi ratio is less than 0.70, crosslinking by the thiol-ene reaction becomes insufficient and the product does not cure, and from the results of Comparative Examples 6 and 13, when the SH/Vi ratio is 1.00 or more, good damping property is not obtained. Furthermore, from the results of Comparative Example 7 and Comparative Example 14, when the SH(A1)/Vi ratio was less than 0.06, no improvement in shear elongation was obtained. From these results, it was found that it is important that the blending of each component is such that the SH(A1)/Vi ratio is 0.06 or more and the SH/Vi ratio is 0.70 or more and less than 1.00.
本発明の光硬化性シリコーン樹脂組成物は、複素弾性率の設計可能な範囲が広く、高減衰性でありながら、せん断伸びに優れている硬化物を形成するので、例えば電気・電子部品のシール材、センサー類などのコーティング材、ポッティング材、ダンピング材、画像表示装置の光学接着剤（ＯＣＲ、ＯＣＡ）として有用であり、特に小型電気・電子製品における狭スペース部分に適用される用途に最適である。The photocurable silicone resin composition of the present invention has a wide range of complex elastic modulus designable, and forms a cured product that has high damping properties and excellent shear elongation. Therefore, it is useful, for example, as a sealing material for electrical and electronic components, a coating material for sensors, a potting material, a damping material, and an optical adhesive (OCR, OCA) for image display devices, and is particularly suitable for use in narrow spaces in small electrical and electronic products.
Claims (4)
前記オルガノポリシロキサン（Ａ）は、両末端にメルカプトアルキル基を含有するオルガノポリシロキサン（Ａ１）と、ケイ素原子に結合するメルカプトアルキル基を１分子当たり２個以上含有するオルガノポリシロキサン（Ａ２）とからなり、
前記オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、前記オルガノポリシロキサン（Ａ）中のメルカプトアルキル基の個数の比が、０．７０以上１．００未満、かつ、
前記オルガノポリシロキサン（Ｂ）中の脂肪族不飽和基の個数に対する、前記オルガノポリシロキサン（Ａ１）中のメルカプトアルキル基の個数の比が、０．０６以上であることを特徴とする光硬化性シリコーン樹脂組成物。 A photocurable silicone resin composition comprising (A) an organopolysiloxane containing a mercaptoalkyl group, (B) a linear organopolysiloxane containing aliphatic unsaturated groups at least at both ends, and (C) a photopolymerization initiator,
The organopolysiloxane (A) comprises an organopolysiloxane (A1) having mercaptoalkyl groups at both ends, and an organopolysiloxane (A2) having two or more mercaptoalkyl groups bonded to silicon atoms per molecule,
the ratio of the number of mercaptoalkyl groups in the organopolysiloxane (A) to the number of aliphatic unsaturated groups in the organopolysiloxane (B) is 0.70 or more and less than 1.00; and
1. A photocurable silicone resin composition, wherein the ratio of the number of mercaptoalkyl groups in said organopolysiloxane (A1) to the number of aliphatic unsaturated groups in said organopolysiloxane (B) is 0.06 or more.
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