JP2007119684A - Photo-curable resin composition and cured products thereof having lightproof property - Google Patents
Photo-curable resin composition and cured products thereof having lightproof property Download PDFInfo
- Publication number
- JP2007119684A JP2007119684A JP2005316651A JP2005316651A JP2007119684A JP 2007119684 A JP2007119684 A JP 2007119684A JP 2005316651 A JP2005316651 A JP 2005316651A JP 2005316651 A JP2005316651 A JP 2005316651A JP 2007119684 A JP2007119684 A JP 2007119684A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- photocurable resin
- resin composition
- refractive index
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 101
- 239000011347 resin Substances 0.000 claims abstract description 101
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 230000003287 optical effect Effects 0.000 claims description 23
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- -1 acrylate compound Chemical class 0.000 description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-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
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- UHUKCWCIQZILRP-UHFFFAOYSA-N (1-hydroxy-3-methylpentyl) prop-2-enoate Chemical compound CCC(C)CC(O)OC(=O)C=C UHUKCWCIQZILRP-UHFFFAOYSA-N 0.000 description 1
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- ATIAIEWDRRJGSL-UHFFFAOYSA-N 1,3-bis(2-hydroxyethyl)-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(CCO)C(=O)N(CCO)C1=O ATIAIEWDRRJGSL-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- UHLWGJNVYHBNBV-UHFFFAOYSA-N 1-(1-hydroxypropan-2-yloxy)-3-methoxypropan-2-ol;prop-2-enoic acid Chemical compound OC(=O)C=C.COCC(O)COC(C)CO UHLWGJNVYHBNBV-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- ONCICIKBSHQJTB-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]propan-1-one Chemical compound CCC(=O)C1=CC=C(N(C)C)C=C1 ONCICIKBSHQJTB-UHFFFAOYSA-N 0.000 description 1
- OBNIRVVPHSLTEP-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(O)COCCO OBNIRVVPHSLTEP-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- 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
- GHTVHGGJFHMYBA-UHFFFAOYSA-N 2-(7-oxabicyclo[4.1.0]heptane-4-carbonyloxy)ethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCCOC(=O)C1CC2OC2CC1 GHTVHGGJFHMYBA-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- TZLVUWBGUNVFES-UHFFFAOYSA-N 2-ethyl-5-methylpyrazol-3-amine Chemical compound CCN1N=C(C)C=C1N TZLVUWBGUNVFES-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- IXPWKHNDQICVPZ-UHFFFAOYSA-N 2-methylhex-1-en-3-yne Chemical compound CCC#CC(C)=C IXPWKHNDQICVPZ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 1
- RRXFVFZYPPCDAW-UHFFFAOYSA-N 4-(7-oxabicyclo[4.1.0]heptan-4-ylmethoxymethyl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1COCC1CC2OC2CC1 RRXFVFZYPPCDAW-UHFFFAOYSA-N 0.000 description 1
- HYYPKCMPDGCDHE-UHFFFAOYSA-N 4-(7-oxabicyclo[4.1.0]heptan-4-ylmethyl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1CC1CC2OC2CC1 HYYPKCMPDGCDHE-UHFFFAOYSA-N 0.000 description 1
- OEIZUSDQPOLYGQ-UHFFFAOYSA-N 4-(7-oxabicyclo[4.1.0]heptan-4-yloxy)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1OC1CCC2OC2C1 OEIZUSDQPOLYGQ-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- ZZFZWPSAJMHJIP-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.OCC(CO)(CO)CO.C(C=C)(=O)OCC(CO)(CO)CO Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.OCC(CO)(CO)CO.C(C=C)(=O)OCC(CO)(CO)CO ZZFZWPSAJMHJIP-UHFFFAOYSA-N 0.000 description 1
- PCMWMVLSUVMRSV-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(O)C(CC)(CO)CO.C(C=C)(=O)OCC(C)(COC(C=C)=O)C Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(O)C(CC)(CO)CO.C(C=C)(=O)OCC(C)(COC(C=C)=O)C PCMWMVLSUVMRSV-UHFFFAOYSA-N 0.000 description 1
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- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
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- 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
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-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
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 1
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- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- DNWBGZGLCKETOT-UHFFFAOYSA-N cyclohexane;1,3-dioxane Chemical compound C1CCCCC1.C1COCOC1 DNWBGZGLCKETOT-UHFFFAOYSA-N 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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Images
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- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、遮光性を有する光硬化性樹脂組成物、より詳しくは、光硬化性樹脂及び該光硬化性樹脂の硬化物の屈折率との屈折率の差が一定以上の大きさの屈折率を有し、該光硬化性樹脂に対して非相溶性で分散性を有する化合物を含む光硬化性樹脂組成物に関する。本発明の樹脂組成物は、隠ぺい力、遮光性、硬化性、接着性に優れ、光学機器、特にCCDカメラや光ピックなどの光学材料部品の固定や、パッケージ等の成形用樹脂として好適に用いられる。 The present invention relates to a photocurable resin composition having a light shielding property, and more specifically, a refractive index having a difference in refractive index between a photocurable resin and a cured product of the photocurable resin of a certain level or more. And a photocurable resin composition containing a compound that is incompatible and dispersible with the photocurable resin. The resin composition of the present invention is excellent in hiding power, light shielding properties, curability, and adhesiveness, and is suitably used as a resin for molding optical materials such as optical cameras, especially CCD cameras and optical picks, and molding. It is done.
近年、種々のディスプレイや光学レンズ、光ピック、センサーなどの電子光学機器の高性能化に伴い、高感度を実現・維持するために、部材や固定樹脂層からの透過光や隙間からの漏光による損失を低下させることが必要不可欠となっている(図1参照)。特に、固定部などのように強度・耐久性・耐湿性など種々の特性を求められる部分では、同一の樹脂でこれらの特性と光損失の低下防止を両立することが必要である。 In recent years, with the improvement in performance of electro-optical devices such as various displays, optical lenses, optical picks, and sensors, in order to realize and maintain high sensitivity, light transmitted from members and fixed resin layers and leaked from gaps It is indispensable to reduce the loss (see FIG. 1). In particular, in a portion where various characteristics such as strength, durability, and moisture resistance are required, such as a fixed part, it is necessary to satisfy both of these characteristics and prevention of reduction in light loss with the same resin.
上記課題に対して、熱可塑性樹脂や熱硬化性樹脂にカーボンブラック又はチタンブラックといった無機顔料や種々の有機顔料(染料)のどちらか一方もしくは両方を添加し、これら添加物による透過光の表面反射や吸収を高めるといった方法が提案され、その高い効果から、光学機器の部材ではこの方法が一般的に利用されている。 In response to the above problems, either or both of inorganic pigments such as carbon black and titanium black and various organic pigments (dyes) are added to thermoplastic resins and thermosetting resins, and the surface reflection of transmitted light by these additives And a method of increasing absorption, and due to its high effect, this method is generally used for members of optical instruments.
一方、近年、生産性の向上と操作の簡便さから固定用接着剤や封止用樹脂として光硬化性樹脂が一般的に使用されるようになり、光硬化性樹脂にも、強度・耐久性・耐湿性など種々の特性に加えて、遮光性が求められている。 On the other hand, in recent years, photo-curing resins are generally used as fixing adhesives and sealing resins due to the improvement of productivity and ease of operation. -In addition to various properties such as moisture resistance, light shielding properties are required.
この要求に伴い、無機又は有機顔料を用いる上記の従来法をそのまま光硬化性に応用した報告もいくつかあり、一応の遮光性を得ている(特許文献1及び2)。しかしながら、従来法を光硬化性樹脂に応用した場合には、顔料を完全遮光に近い添加量で使用すると、硬化に必要な光も遮光してしまうため硬化不良になりやすく、樹脂厚さを厚くすることができず、厚さの範囲が限られてしまうといった問題点がある。また、光損失を低下させるためには、樹脂に対して顔料を多量に添加する必要があるため、ベース樹脂の特性を著しく変化させてしまうという問題点とともに顔料の分散が困難であるという問題点を抱えている。このため、現在では、遮光と固定の際の強度・耐久性・耐湿性など種々の特性とを両立するための手段として、固定用樹脂で部材を固定した後、遮光樹脂で固定用樹脂の外装を被覆するか(図2参照)、あるいは、遮光用樹脂から遮光スペーサを作製し、これを固定用樹脂とセンサー等の間に設置することで樹脂部からの光損失を低下させて高感度を実現・維持している(特許文献3;図3参照)。しかし、この方法では、生産性が低下するなどの問題が発生している。
本発明者らは、上記の課題を解決するために鋭意検討した結果、ベース樹脂の光硬化性樹脂の硬化物とそれに添加する化合物との間の屈折率差を利用することにより、光によって効果的に硬化し、そのため厚い膜厚の樹脂でも硬化が可能で、得られる硬化樹脂の光透過率が低い、光硬化性樹脂組成物を提供できることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have obtained an effect by light by utilizing the difference in refractive index between the cured product of the photocurable resin of the base resin and the compound added thereto. The present invention has been completed by finding that a photocurable resin composition can be provided which can be cured even with a thick film of resin, and can be cured, and the resulting cured resin has low light transmittance.
すなわち、本発明は、
(1)光硬化性樹脂及び該光硬化性樹脂の硬化物の屈折率との屈折率の差が0.01以上となる屈折率を有し、該光硬化性樹脂に対して非相溶性で分散性を有する化合物を含む光硬化性樹脂組成物;
(2)屈折率の差が0.1以上である、上記(1)記載の光硬化性樹脂組成物;
(3)光硬化性樹脂がアクリル変性樹脂又はエポキシ樹脂である、上記(1)又は(2)記載の光硬化性樹脂組成物;
(4)さらに、光重合開始剤を含む、上記(1)〜(3)のいずれか1項記載の光硬化性樹脂組成物;
(5)上記(1)〜(4)のいずれか1項記載の光重合性樹脂組成物の硬化物;
(6)上記(5)記載の硬化物を含む光学機器部材;
(7)上記(6)記載の光学機器部材を含む光学機器
である。
That is, the present invention
(1) A refractive index difference between the refractive index of the photocurable resin and the cured product of the photocurable resin is 0.01 or more, and is incompatible with the photocurable resin. A photocurable resin composition comprising a compound having dispersibility;
(2) The photocurable resin composition according to (1), wherein the difference in refractive index is 0.1 or more;
(3) The photocurable resin composition according to the above (1) or (2), wherein the photocurable resin is an acrylic-modified resin or an epoxy resin;
(4) The photocurable resin composition according to any one of (1) to (3), further comprising a photopolymerization initiator;
(5) A cured product of the photopolymerizable resin composition according to any one of (1) to (4) above;
(6) An optical device member containing the cured product according to (5) above;
(7) An optical apparatus including the optical apparatus member according to (6).
本発明の光学機器部材の概念を図4に示す。 The concept of the optical device member of the present invention is shown in FIG.
本発明の光硬化性樹脂組成物は、光で効率よく硬化するので厚膜硬化が可能であり、得られる硬化物は、内外からの光透過性が低く、かつ、強度・耐久性・耐湿性など種々の特性に優れている。また、固定(封止)用樹脂と遮光用樹脂を同一の樹脂で行うことができるので生産性を大きく向上できる。 The photo-curable resin composition of the present invention can be cured with a thick film because it is efficiently cured with light, and the resulting cured product has low light transmittance from inside and outside, and has strength, durability, and moisture resistance. It is excellent in various characteristics. Further, since the fixing (sealing) resin and the light shielding resin can be made of the same resin, productivity can be greatly improved.
これらのため、本発明の光硬化性樹脂組成物は、種々の光学機器部材や成形樹脂等の製造用樹脂として適している。 For these reasons, the photocurable resin composition of the present invention is suitable as a resin for production of various optical device members and molding resins.
本発明は、ベース樹脂である光硬化性樹脂及び該光硬化性樹脂の硬化物の屈折率との屈折率の差が0.01以上となる屈折率を有し、該光硬化性樹脂に対して非相溶性で分散性を有する化合物を含む光硬化性樹脂組成物である。 The present invention has a refractive index such that the difference in refractive index between the photocurable resin as a base resin and the refractive index of a cured product of the photocurable resin is 0.01 or more, and the photocurable resin And a photocurable resin composition containing a compound that is incompatible and dispersible.
本発明におけるベース樹脂とは、本発明の光硬化性樹脂組成物の連続相を形成する樹脂を意味し、したがって、光硬化性樹脂組成物を硬化した硬化物においても連続相を形成し得る。 The base resin in the present invention means a resin that forms a continuous phase of the photocurable resin composition of the present invention. Therefore, a continuous phase can also be formed in a cured product obtained by curing the photocurable resin composition.
本発明における光硬化性樹脂は、可視光、紫外線等の光によって硬化する樹脂であれば特に限定されず、例えば、(メタ)アクリル樹脂、ウレタンアクリレート樹脂、ポリエステルアクリレート樹脂、エポキシ樹脂、オキセタン樹脂が挙げられる。光硬化性樹脂としては、好ましくは、アクリル変性樹脂及びエポキシ樹脂が挙げられる。 The photocurable resin in the present invention is not particularly limited as long as it is a resin that is cured by light such as visible light and ultraviolet light. For example, (meth) acrylic resin, urethane acrylate resin, polyester acrylate resin, epoxy resin, oxetane resin are used. Can be mentioned. As a photocurable resin, Preferably, an acrylic modified resin and an epoxy resin are mentioned.
アクリル変性樹脂は、アクリロイル基もしくはメタクリロイル基を有する単官能性および多官能性の(メタ)アクリレート化合物と定義され、例えば、メチルアクリレート、エチルアクリレート、n−プロピルアクリレート、n−ブチルアクリレート、t−ブチルアクリレート、イソブチルアクリレート、エチルヘキシルアクリレート、イソデシルアクリレート、n−ヘキシルアクリレート、ステアリルアクリレート、ラウリルアクリレート、トリデシルアクリレート、エトキシエチルアクリレート、メトキシエチルアクリレート、グリシジルアクリレート、ブトキシエチルアクリレート、2−ヒドロキシエチルアクリレート、2−ヒドロキシプロピルアクリレート、2−メトキシエチルアクリレート、2−エトキシエトキシエチルアクリレート、メトキシジエチレングリコールアクリレート、エトキシジエチレングリコールアクリレート、メトキシジプロピレングリコールアクリレート、オクタフルオロペンチルアクリレート、N,N−ジメチルアミノエチルアクリレート、N,N−ジエチルアミノエチルアクリレート、アリルアクリレート、1,3−ブタンジオールアクリレート、1,4−ブタンジオールアクリレート、アクリロイルモルフォリン、1,6−ヘキサンジオールアクリレート、ポリエチレングリコールジアクリレート、ジエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリエチレングリコールジアクリレート、トリプロピレングリコールジアクリレート、ヒドロキシピバリン酸エステル、ネオペンチルグリコールジアクリレート、トリメチロールプロパンジアクリレート、1,3−ビス(ヒドロキシエチル)−5、5−ジメチルヒダントイン、3−メチルペンタンジオールアクリレート、α,ω−ジアクリルビスジエチレングリコールフタレート、トリメチロールプロパントリアクリレート、ペンタエリトリットアクリレート、ペンタエリトリットヘキサアクリレート、ジペンタエリトリットモノヒドロキシペンタアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、トリヒドロキシエチルイソシアヌレートのトリ(メタ)アクリレート、ジペンタエリスリトールヘキサアクリレート、及びこれらのEO及び/又はPO付加物、α,ω−テトラアリルビストリメチロールプロパンテトラヒドロフタレート、2−ヒドロキシエチルアクリロイルフォスフェート、トリメチロールプロパントリメタクリレート、エチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジメタクリレート、ジアクリロキシエチルフォスフェート、N−ビニルピロリドン及びこれらの光反応性官能基を有するオリゴマーが例示できる。 The acrylic-modified resin is defined as a monofunctional and polyfunctional (meth) acrylate compound having an acryloyl group or a methacryloyl group. For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl Acrylate, isobutyl acrylate, ethyl hexyl acrylate, isodecyl acrylate, n-hexyl acrylate, stearyl acrylate, lauryl acrylate, tridecyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, butoxyethyl acrylate, 2-hydroxyethyl acrylate, 2- Hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate Methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, octafluoropentyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, allyl acrylate, 1,3-butanediol acrylate, 1 , 4-butanediol acrylate, acryloyl morpholine, 1,6-hexanediol acrylate, polyethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalate ester Neopentyl glycol diacrylate Trimethylolpropane diacrylate, 1,3-bis (hydroxyethyl) -5,5-dimethylhydantoin, 3-methylpentanediol acrylate, α, ω-diacrylbisdiethylene glycol phthalate, trimethylolpropane triacrylate, pentaerythritol acrylate Pentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tri (meth) acrylate of trihydroxyethyl isocyanurate, dipentaerythritol hexaacrylate, and their EO and / or Or PO adduct, α, ω-tetraallylbistrimethylolpropane tetrahydrophthalate, 2-hydroxy ester Ruacryloyl phosphate, trimethylolpropane trimethacrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, Examples thereof include 6-hexanediol di (meth) acrylate, neopentylglycol dimethacrylate, diacryloxyethyl phosphate, N-vinylpyrrolidone and oligomers having these photoreactive functional groups.
エポキシ樹脂は、エポキシ基を1個以上有する分子構造を有する化合物と定義され、例えば、ビフェノール、ビスフェノールA、水添ビスフェノールA、ビスフェノールF、ビスフェノールAD、ビスフェノールS、テトラメチルビスフェノールA、テトラメチルビスフェノールF、テトラクロロビスフェノールA、テトラブロモビスフェノールA等のビスフェノール類のジグリシジルエーテル類、フェノールノボラック、クレゾールノボラック、ブロム化フェノールノボラック、オルトクレゾールノボラック等のノボラック樹脂のポリグリシジルエーテル類、エチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ブタンジオール、1,6−ヘキサンジオール、ネオペンチルグリコール、トリメチロールプロパン、1,4−シクロヘキサンジメタノール、ビスフェノールAのエチレンオサイド付加物、ビスフェノールAのプロピレンオキサイド付加物等のアルキレングリコール類のジグリシジルエーテル類、ヘキサヒドロフタル酸のグリシジルエステルやダイマー酸のジグリシジルエステル等のグリシジルエステル類、3,4−エポキシシクロヘキシルメチル−3’,4’−エポキシシクロヘキサンカルボキシレート、3,4−エポキシシクロヘキシルエチル−3’,4’−エポキシシクロヘキサンカルボキシレート、3,4−エポキシ−6−メチルシクロヘキシル−3’,4’−エポキシ−6’−メチルシクロヘキサンカルボキシレート、ビニルシクロヘキセンジオキサイド、3,4−エポキシ−4−メチルシクロヘキシル−2−プロピレンオキサイド、2−(3,4−エポキシシクロヘキシル−5,5−スピロ−3,4−エポキシ)シクロヘキサン−m−ジオキサン、ビス(3,4−エポキシシクロヘキシル)アジペート、ビス(3,4−エポキシシクロヘキシルメチル)アジペート、ラクトン変性3,4−エポキシシクロヘキシルメチル−3’,4’−エポキシシクロヘキサンカルボキシレート、メチレンビス(3,4−エポキシシクロヘキサン)、エチレンビス(3,4−エポキシシクロヘキサンカルボキシレート)、ジシクロペンタジエンジエポキシド、ビス(3,4−エポキシシクロヘキシル)エーテル、ビス(3,4−エポキシシクロヘキシルメチル)エーテル、テトラ(3,4−エポキシシクロヘキシルメチル)ブタンテトラカルボキシレート、ビス(3,4−エポキシシクロヘキシルメチル)−4,5−エポキシテトラヒドロフタレート、ビス(3,4−エポキシシクロヘキシル)ジエチルシロキサン等の脂環式エポキシ化合物及びこれらの光反応性官能基を有するオリゴマーが例示できる。 The epoxy resin is defined as a compound having a molecular structure having one or more epoxy groups, for example, biphenol, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F. Diglycidyl ethers of bisphenols such as tetrachlorobisphenol A and tetrabromobisphenol A, polyglycidyl ethers of novolac resins such as phenol novolak, cresol novolak, brominated phenol novolak, orthocresol novolak, ethylene glycol, polyethylene glycol, Polypropylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, 1 Diglycidyl ethers of alkylene glycols such as 4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycidyl such as glycidyl ester of hexahydrophthalic acid and diglycidyl ester of dimer acid Esters, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methyl Cyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, vinylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, -(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, Lactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), ethylene bis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, Bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, tetra (3,4-epoxycyclohexylmethyl) butanetetracarboxylate, bis (3,4-epoxycyclohexyl) Examples thereof include alicyclic epoxy compounds such as (silmethyl) -4,5-epoxytetrahydrophthalate and bis (3,4-epoxycyclohexyl) diethylsiloxane, and oligomers having these photoreactive functional groups.
本発明における光硬化性樹脂は、硬化後の屈折率により特に限定されるものではなく、任意の屈折率を有する硬化物を与える光硬化性樹脂が使用可能である。 The photocurable resin in the present invention is not particularly limited by the refractive index after curing, and a photocurable resin that gives a cured product having an arbitrary refractive index can be used.
光硬化性樹脂の硬化物の屈折率は、アッベ屈折計(アタゴ株式会社製)を使用しD線により測定する。 The refractive index of the cured product of the photocurable resin is measured by D-line using an Abbe refractometer (manufactured by Atago Co., Ltd.).
本発明において、光硬化性樹脂は、上記の樹脂から、使用する部位において求められる性能を考慮して1種又は2種以上の混合物として選択される。 In the present invention, the photocurable resin is selected from the above resins as one or a mixture of two or more in consideration of the performance required at the site to be used.
本発明における、光硬化性樹脂の硬化物の屈折率との屈折率の差が0.01以上となる屈折率を有し、該光硬化性樹脂に対して非相溶性で分散性を有する化合物は、該光硬化性樹脂の硬化物の屈折率、及び該光硬化性樹脂に対する非相溶性、分散性によって選択され、光硬化性樹脂の硬化物の屈折率よりも0.01以上大きい屈折率を有する化合物(高屈折率化合物)及び光硬化性樹脂の硬化物の屈折率よりも0.01以上小さい屈折率を有する化合物(低屈折率化合物)に大別される。屈折率が異なる化合物は、有機化合物又は無機化合物である。 Compound having a refractive index in which the difference in refractive index from the refractive index of the cured product of the photocurable resin in the present invention is 0.01 or more, incompatible with the photocurable resin, and having dispersibility Is selected by the refractive index of the cured product of the photocurable resin, the incompatibility with the photocurable resin, and the dispersibility, and a refractive index that is 0.01 or more larger than the refractive index of the cured product of the photocurable resin. And a compound (low refractive index compound) having a refractive index smaller by 0.01 or more than the refractive index of the cured product of the photocurable resin (high refractive index compound). Compounds having different refractive indexes are organic compounds or inorganic compounds.
光硬化性樹脂に対して「非相溶性」であるとは、光硬化性樹脂と均一に混和しないことを意味し、光硬化性樹脂に対して「分散性」であるとは、撹拌直後に二層に分離しないこと意味する。 “Incompatible” with the photocurable resin means that it is not uniformly mixed with the photocurable resin, and “dispersible” with respect to the photocurable resin means immediately after stirring. It means not to separate into two layers.
本発明で使用できるベース樹脂と屈折率が0.01以上異なる無機化合物には、例えばZnO、TiO2、CeO2、Sb2 O5、SnO2 、ITO、Y2 O3、La2 O3、ZrO2、Al2 O3、シリカ、オパール、ガラス、ホワイトカーボンが包含され、好ましくは、屈折率が1.60以上のアルミナ、チタン化合物、ジルコニア化合物が挙げられる。無機化合物は、その表面を種々の無機・有機化合物によって被覆されていてもよい。また、無機化合物の形状は、球状、針状、板状などの任意の形状であってよく、その粒子径も限定されないが、粒子径が小さいほうがより好ましい。粒子径は、好ましくは0.1〜100μm、より好ましくは0.1〜10μm、特に0.1〜1μmである。 Examples of the inorganic compound having a refractive index of 0.01 or more different from the base resin that can be used in the present invention include ZnO, TiO 2 , CeO 2 , Sb 2 O 5 , SnO 2 , ITO, Y 2 O 3 , La 2 O 3 , ZrO 2 , Al 2 O 3 , silica, opal, glass and white carbon are included, and preferred examples include alumina, a titanium compound and a zirconia compound having a refractive index of 1.60 or more. The surface of the inorganic compound may be coated with various inorganic / organic compounds. Further, the shape of the inorganic compound may be any shape such as a spherical shape, a needle shape, or a plate shape, and the particle diameter is not limited, but a smaller particle diameter is more preferable. The particle diameter is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm, and particularly 0.1 to 1 μm.
本発明で使用できるベース樹脂と屈折率が0.01以上異なる有機化合物は、液状又は固体のモノマー、オリゴマー又はポリマー化合物のいずれであってもよく、また、熱可塑性樹脂、熱硬化性樹脂、光硬化性樹脂のいずれであっても問題はないが、ベース樹脂である光硬化性樹脂に対して、非相溶性でありかつ分散性が良好なものでなければならない。例えば、(メタ)アクリル樹脂、ウレタンアクリレート樹脂、ポリエステルアクリレート樹脂、エポキシ樹脂、オキセタン樹脂、ポリスチレン等のスチロール系樹脂、ポリエチレンテレフタレート、ポリビニルカルバゾール、ビスフェノールAのポリカーボネート、ポリ塩化ビニル、ポリテトラブロモビスフェノールAグリシジルエーテル、ポリビスフェノールSグリシジルエーテル、ポリビニルピリジン、チオウレタン樹脂、チオエポキシ樹脂、フッ素含有(メタ)アクリレート類、フッ化アルキレンエーテル・オリゴマー類(平均分子量:4000以下)の一官能および二官能以上の多官能(メタ)アクリレート類、シリコン含有(メタ)アクリレート類、ポリエチレンやポリテトラフルオロエチレンといった結晶性高分子が包含される。また、有機化合物が固形である場合、その形状は、球状、針状、板状などの任意の形状であってよく、その粒子径も限定されないが、粒子径が小さいほうが好ましい。その粒子径は、好ましくは0.1〜100μm、より好ましくは0.1〜10μm、特に0.1〜1μmである。有機化合物が液状である場合、該化合物は、光硬化性樹脂に分散させる。分散粒子の粒子径は、好ましくは0.1〜100μm、より好ましくは0.1〜10μm、特に0.1〜1μmである。 The organic compound having a refractive index different by 0.01 or more from the base resin that can be used in the present invention may be any of a liquid or solid monomer, oligomer, or polymer compound, and may be a thermoplastic resin, a thermosetting resin, light. There is no problem with any of the curable resins, but it must be incompatible with the photocurable resin as the base resin and have good dispersibility. For example, (meth) acrylic resin, urethane acrylate resin, polyester acrylate resin, epoxy resin, oxetane resin, polystyrene resin such as polystyrene, polyethylene terephthalate, polyvinyl carbazole, polycarbonate of bisphenol A, polyvinyl chloride, polytetrabromobisphenol A glycidyl Ether, polybisphenol S glycidyl ether, polyvinyl pyridine, thiourethane resin, thioepoxy resin, fluorine-containing (meth) acrylates, fluorinated alkylene ether oligomers (average molecular weight: 4000 or less) monofunctional and bifunctional or more polyfunctional Crystalline polymers such as (meth) acrylates, silicon-containing (meth) acrylates, polyethylene and polytetrafluoroethylene are included.When the organic compound is solid, the shape thereof may be any shape such as a spherical shape, a needle shape, or a plate shape, and the particle size is not limited, but a smaller particle size is preferable. The particle diameter is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm, and particularly 0.1 to 1 μm. When the organic compound is in a liquid state, the compound is dispersed in a photocurable resin. The particle diameter of the dispersed particles is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm, particularly 0.1 to 1 μm.
本発明において使用し得る化合物の幾つかについて、その屈折率を以下に例示する。
ZnO(屈折率1.90)、TiO2 (屈折率2.3〜2.7)、CeO2 (屈折率1.95)、Sb2 O5 (屈折率1.71)、SnO2 、ITO(屈折率1.95)、Y2 O3 (屈折率1.87)、La2 O3 (屈折率1.95)、ZrO2 (屈折率2.05)、Al2 O3 (屈折率1.63)、メラミン樹脂(1.6)、ナイロン(1.53)、ポリスチレン(1.6)、ポリエチレン(1.53)、ポリテトラフルオロエチレン(1.35)、メタクリル酸メチル樹脂(1.49)、塩化ビニル樹脂(1.54)、シリコーン油(1.4)
The refractive index of some of the compounds that can be used in the present invention is exemplified below.
ZnO (refractive index 1.90), TiO 2 (refractive index 2.3 to 2.7), CeO 2 (refractive index 1.95), Sb 2 O 5 (refractive index 1.71), SnO 2 , ITO ( Refractive index 1.95), Y 2 O 3 (refractive index 1.87), La 2 O 3 (refractive index 1.95), ZrO 2 (refractive index 2.05), Al 2 O 3 (refractive index 1. 63), melamine resin (1.6), nylon (1.53), polystyrene (1.6), polyethylene (1.53), polytetrafluoroethylene (1.35), methyl methacrylate resin (1.49) ), Vinyl chloride resin (1.54), silicone oil (1.4)
本発明の光硬化性樹脂組成物は、有機及び無機の高屈折率化合物並びに有機及び無機の低屈折率化合物の1つ又はこれらの2以上の組み合わせを含み得る。 The photocurable resin composition of the present invention may contain one or a combination of two or more of organic and inorganic high refractive index compounds and organic and inorganic low refractive index compounds.
本発明の光硬化性樹脂組成物において、高屈折率化合物及び/又は低屈折率化合物は、光硬化性樹脂100重量部に対して、例えば、0.1〜50重量部、好ましくは0.1〜30重量部、より好ましくは1〜20重量部、特に好ましくは1〜10重量部の量で使用される。 In the photocurable resin composition of the present invention, the high refractive index compound and / or the low refractive index compound is, for example, 0.1 to 50 parts by weight, preferably 0.1 to 100 parts by weight of the photocurable resin. It is used in an amount of -30 parts by weight, more preferably 1-20 parts by weight, particularly preferably 1-10 parts by weight.
本発明において、光硬化性樹脂の硬化物の屈折率との屈折率の差は、好ましくは0.1以上であり、特に好ましくは0.15以上である。 In the present invention, the difference in refractive index from the refractive index of the cured product of the photocurable resin is preferably 0.1 or more, particularly preferably 0.15 or more.
本発明の光硬化性樹脂組成物は、さらに、光重合開始剤を含み得る。光重合開始剤として、一般的に市販されているラジカルもしくはカチオン系開始剤が包含され、例えば、カルボニル基系:ベンゾフェノン、ジアセチル、ベンジル、ベンゾイン、ω−ブロモアセトフェノン、クロロアセトン、アセトフェノン、2,2−ジエトキシアセトフェノン、2,2−ジメトキシ−2−フェニルアセトン、p−ジメチルアミノアセトフェノン、p−ジメチルアミノプロピオフェノン、2−クロロベンゾフェノン、p,p’−ビスジエチルアミノベンゾフェノン、ミヒラーケトン、ベンゾインメチルエーテル、ベンゾインイソブチルエーテル、ベンゾイン−n−ブチルエーテル、ベンジルジメチルケタール、1−ヒドロキシシクロヘキシルフェニルケトン、2−ヒドロキシ−2−メチル−1−オン、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、メチルベンゾイルホルメート、2,2−ジエトキシアセトフェノン、4−N,N’−ジメチルアセトフェノン類;スルフィド系:ジフェニルジスルフィド、ジベンジルジスルフィド;キノン系:ベンゾキノン、アントラキノン;アゾ系:アゾビスイソブチロニトリル、2,2’−アゾビスプロパンを例示できる。光重合開始剤は、一般的に使用される量、例えば、光硬化性樹脂100重量部に対して1〜10重量部の量で使用することができる。照射光は可視光線、紫外線のいずれであってもよい。 The photocurable resin composition of the present invention may further contain a photopolymerization initiator. Examples of the photopolymerization initiator include generally commercially available radical or cationic initiators. For example, carbonyl group systems: benzophenone, diacetyl, benzyl, benzoin, ω-bromoacetophenone, chloroacetone, acetophenone, 2,2 -Diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, Benzoin isobutyl ether, benzoin-n-butyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-one, 1- (4-isopropyl Phenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2,2-diethoxyacetophenone, 4-N, N′-dimethylacetophenones; sulfide systems: diphenyl disulfide, dibenzyl disulfide; Examples include quinone series: benzoquinone, anthraquinone; azo series: azobisisobutyronitrile, 2,2′-azobispropane. A photoinitiator can be used in the quantity generally used, for example, the quantity of 1-10 weight part with respect to 100 weight part of photocurable resins. Irradiation light may be either visible light or ultraviolet light.
本発明の光硬化性樹脂組成物は、目的に応じて、さらに、その他の公知の添加剤、例えば、酸化防止剤、紫外線吸収剤、光安定剤、シランカップリング剤、熱重合禁止剤、レベリング剤、界面活性剤、着色剤、保存安定剤、可塑剤、滑剤、溶媒、フィラー、老化防止剤、濡れ性改良剤、離型剤等を添加することができる。また、本発明の光硬化性樹脂組成物は、樹脂の光透過性や反射率を低下させるために、有機・無機着色顔料を、本発明の効果を損なわない範囲で(光硬化性樹脂100重量部に対して例えば数重量部以下、特に1重量%以下)添加することができる。 Depending on the purpose, the photocurable resin composition of the present invention may further include other known additives such as antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, thermal polymerization inhibitors, and leveling. Agents, surfactants, colorants, storage stabilizers, plasticizers, lubricants, solvents, fillers, anti-aging agents, wettability improvers, mold release agents, and the like can be added. In addition, the photocurable resin composition of the present invention has an organic / inorganic color pigment within a range that does not impair the effects of the present invention (photocuring resin 100 weight) in order to reduce the light transmittance and reflectance of the resin. For example, several parts by weight or less, particularly 1% by weight or less).
本発明の光硬化性樹脂組成物は、前記各成分を常法により混合して製造することができる。各成分の添加の順番は特に限定されない。高屈折率又は低屈折率化合物が液状である場合には、該化合物を光硬化性樹脂に細かい粒径で分散させることが好ましい。 The photocurable resin composition of the present invention can be produced by mixing the above components by a conventional method. The order of adding each component is not particularly limited. When the high refractive index or low refractive index compound is liquid, it is preferable to disperse the compound in a photocurable resin with a fine particle size.
本発明の光硬化性樹脂組成物は、可視光、紫外線等の光により効果的に硬化することができ、広い範囲の膜厚、例えば0.5μm以上の範囲の膜厚において硬化が可能である。光硬化の条件は、樹脂組成物の組成や膜厚等によって変化し得るが、例えば、ベース樹脂;ウレタンアクリレート、高屈折率化合物;アルミナ、膜厚;500μmの場合、紫外線照射量は1500〜3000mJ/cm2である。 The photocurable resin composition of the present invention can be effectively cured by light such as visible light and ultraviolet light, and can be cured in a wide range of film thickness, for example, in a range of 0.5 μm or more. . The photocuring conditions may vary depending on the composition and film thickness of the resin composition. For example, in the case of base resin; urethane acrylate, high refractive index compound; alumina, film thickness: 500 μm, the ultraviolet irradiation amount is 1500 to 3000 mJ. / cm 2 .
本発明は、光硬化性樹脂組成物の硬化物を含む。この硬化物は、強度・耐久性・耐湿性など種々の特性と遮光性に優れているので、固定(封止)用樹脂と遮光用樹脂の特性を同時に満足する。本発明の硬化物は、0.5μm〜3mmの範囲の膜厚において、300〜800nmにおける光透過率を1%以下、例えば0.5%以下、好ましくは、0.1%以下、特に0.05%以下、さらには0.01%以下とすることができる。 The present invention includes a cured product of the photocurable resin composition. Since this cured product is excellent in various properties such as strength, durability and moisture resistance and light shielding properties, it satisfies the properties of the fixing (sealing) resin and the light shielding resin at the same time. The cured product of the present invention has a light transmittance at 300 to 800 nm of 1% or less, for example, 0.5% or less, preferably 0.1% or less, and particularly preferably at a film thickness in the range of 0.5 μm to 3 mm. It can be made 05% or less, and further 0.01% or less.
本発明は、上記の硬化物を含む光学機器部材も含む。光学機器部材としては、例えばセンサー、光ピック、光学レンズ、LEDが挙げられる。 The present invention also includes an optical device member containing the above cured product. Examples of the optical device member include a sensor, an optical pick, an optical lens, and an LED.
本発明は、さらに、上記の光学機器部材を含む光学機器にも関係する。光学機器としては、例えば、デジタルカメラ、各種ディスプレイ、各種記録メディアプレイヤーなどが挙げられる。 The present invention further relates to an optical apparatus including the above-described optical apparatus member. Examples of the optical device include a digital camera, various displays, various recording media players, and the like.
以下に、実施例及び比較例により本発明を詳細に説明するが、本発明はこれら実施例に限定されるものではない。以下において、「部」は重量基準である。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, “part” is based on weight.
(実施例1)
表1に示す割合で、ウレタンアクリレート樹脂(U-4HA、新中村化学社製)と光重合開始剤(I-184、CIBA CHWMICALS社製)を常法に従って混合しアクリル系ベース樹脂Aを、また、エポキシ樹脂(EP-830S、大日本インキ化学社製)と光重合開始剤(SP150、サンアプロ社製)を常法に従って混合しエポキシ系ベース樹脂Bを得た。さらに表2に示す割合で、作製したベース樹脂と各種材料を常法に従って混合し、光硬化性遮光樹脂組成物を得た。具体的には、室温のアクリル系ベース樹脂Aの100重量部を容器に装入した後、20重量部の球状アルミナを添加し500rpmの撹拌条件下、23℃で15分撹拌した。
Example 1
In the proportion shown in Table 1, urethane acrylate resin (U-4HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) and photopolymerization initiator (I-184, manufactured by CIBA CHWMICALS) were mixed according to a conventional method, and acrylic base resin A was added. Epoxy resin (EP-830S, manufactured by Dainippon Ink Chemical Co., Ltd.) and a photopolymerization initiator (SP150, manufactured by Sun Apro) were mixed according to a conventional method to obtain an epoxy base resin B. Furthermore, the produced base resin and various materials were mixed according to a conventional method at a ratio shown in Table 2 to obtain a photocurable light-shielding resin composition. Specifically, 100 parts by weight of the acrylic base resin A at room temperature was charged into a container, 20 parts by weight of spherical alumina was added, and the mixture was stirred at 23 ° C. for 15 minutes under a stirring condition of 500 rpm.
得られた光硬化性樹脂組成物の光硬化性および硬化物の光透過性は、次のような試験で評価し、それらの結果を表3に示す。 The photocurability of the obtained photocurable resin composition and the light transmittance of the cured product were evaluated by the following tests, and the results are shown in Table 3.
〔深部硬化性〕;上部以外を密閉した容器(大きさ;内径=6mm深さ=15mm)に光硬化性樹脂組成物を充填し、上部から6000mJ/cm2の紫外線を照射した後、硬化した樹脂の厚みをマイクロメーターにより測定し、この厚みをもって深部硬化性の評価とした。 [Deep part curability]: The photocurable resin composition was filled in a container (size; inner diameter = 6 mm depth = 15 mm) which was sealed except the upper part, and cured after being irradiated with ultraviolet rays of 6000 mJ / cm 2 from the upper part. The thickness of the resin was measured with a micrometer, and this thickness was used as an evaluation of deep part curability.
〔硬化物の光透過性〕:ガラス基板上に直径が1cmで厚さが50μm、500μm又は1mmにそれぞれ成形した光硬化性遮光樹脂組成物を1500〜12000mJ/cm2の紫外線照射によって光硬化させた後、UV分光器を用いて波長300〜800nmにおける硬化物の光透過性を評価した。その結果を表3に示す。 [Light transmittance of cured product]: A photocurable light-shielding resin composition formed on a glass substrate to have a diameter of 1 cm and a thickness of 50 μm, 500 μm or 1 mm is photocured by irradiation with ultraviolet rays of 1500 to 12000 mJ / cm 2. Then, the light transmittance of the cured product at a wavelength of 300 to 800 nm was evaluated using a UV spectrometer. The results are shown in Table 3.
(実施例2〜12)
表2に示すような割合で、実施例1と同様にして、混合し光硬化性樹脂組成物を得た。ベース樹脂A及びBのみからなる光硬化性樹脂組成物を参考例1及び2とした。
(Examples 2 to 12)
In the same manner as in Example 1 at a ratio as shown in Table 2, mixing was performed to obtain a photocurable resin composition. Reference examples 1 and 2 were photocurable resin compositions consisting only of the base resins A and B.
得られた樹脂組成物の光硬化性および硬化物の光透過性は、実施例1と同様な試験で評価し、それらの結果を表3及び表4に示す。 The photocurability of the obtained resin composition and the light transmittance of the cured product were evaluated by the same test as in Example 1, and the results are shown in Tables 3 and 4.
(比較例1〜3)
高屈折率化合物及び低屈折率化合物の代わりにカーボンブラックを加える以外は、実施例1と全く同様に操作し、表5に示すような割合で光硬化性樹脂組成物を得た。これらを実施例1と同様に評価し、その結果を表6に示す。
(Comparative Examples 1-3)
Except for adding carbon black in place of the high refractive index compound and the low refractive index compound, the same operation as in Example 1 was carried out to obtain a photocurable resin composition at the ratio shown in Table 5. These were evaluated in the same manner as in Example 1, and the results are shown in Table 6.
本発明の光硬化性樹脂組成物は、厚膜硬化が可能であり、光透過性が低く、かつ、強度・耐久性・耐湿性など種々の特性に優れており、固定(封止)用樹脂と遮光用樹脂を同一の樹脂で行うことができるので生産性が大きく向上し、遮光性を必要とする種々の光学機器部材や成形樹脂等の製造用樹脂として適している。 The photocurable resin composition of the present invention is capable of curing a thick film, has low light transmittance, and is excellent in various properties such as strength, durability, and moisture resistance, and is a fixing (sealing) resin. And the light shielding resin can be made of the same resin, the productivity is greatly improved, and it is suitable as a production resin for various optical equipment members and molding resins that require light shielding properties.
A:レンズ、B:固定(封止)樹脂、C:センサー、D:被覆遮光層、
E:遮光スペーサ、F:遮光性固定(封止)樹脂
1:入射光、2:外部透過光、3:内部透過光(損失光)
A: Lens, B: Fixed (sealing) resin, C: Sensor, D: Covered light shielding layer,
E: light blocking spacer, F: light blocking fixing (sealing) resin 1: incident light, 2: external transmitted light, 3: internal transmitted light (loss light)
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