JP4753601B2 - Photosensitive composition - Google Patents
Photosensitive composition Download PDFInfo
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- JP4753601B2 JP4753601B2 JP2005084279A JP2005084279A JP4753601B2 JP 4753601 B2 JP4753601 B2 JP 4753601B2 JP 2005084279 A JP2005084279 A JP 2005084279A JP 2005084279 A JP2005084279 A JP 2005084279A JP 4753601 B2 JP4753601 B2 JP 4753601B2
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- compound
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 64
- 150000001875 compounds Chemical class 0.000 claims description 94
- 125000004432 carbon atom Chemical group C* 0.000 claims description 72
- 230000003287 optical effect Effects 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 27
- 239000003566 sealing material Substances 0.000 claims description 26
- 125000002091 cationic group Chemical group 0.000 claims description 24
- 125000005843 halogen group Chemical group 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 18
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 230000005540 biological transmission Effects 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 125000003566 oxetanyl group Chemical group 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 150000001491 aromatic compounds Chemical class 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
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- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 claims description 2
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- 238000011156 evaluation Methods 0.000 description 7
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- 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 6
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- 125000002723 alicyclic group Chemical group 0.000 description 6
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
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- 125000000962 organic group Chemical group 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229960000834 vinyl ether Drugs 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 5
- 239000000565 sealant Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 4
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- 239000000853 adhesive Substances 0.000 description 4
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- 125000002947 alkylene group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- 0 *(c1ccccc1)c1ccccc1 Chemical compound *(c1ccccc1)c1ccccc1 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- BIDWUUDRRVHZLQ-UHFFFAOYSA-N 3-ethyl-3-(2-ethylhexoxymethyl)oxetane Chemical compound CCCCC(CC)COCC1(CC)COC1 BIDWUUDRRVHZLQ-UHFFFAOYSA-N 0.000 description 2
- UWFHYGTWXNRUDH-UHFFFAOYSA-N 3-ethyl-3-[4-[(3-ethyloxetan-3-yl)methoxy]butoxymethyl]oxetane Chemical compound C1OCC1(CC)COCCCCOCC1(CC)COC1 UWFHYGTWXNRUDH-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- PWHYOGRKVRMWLT-UHFFFAOYSA-H [F-].[F-].[F-].[F-].[F-].[F-].C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1 Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1.C1(=CC=CC=C1)[I+]C1=CC=CC=C1 PWHYOGRKVRMWLT-UHFFFAOYSA-H 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 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 2
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- 239000012954 diazonium Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- XVSBDEPLEQHLTE-UHFFFAOYSA-N 1,1-bis(ethenoxy)cyclohexane Chemical compound C=COC1(OC=C)CCCCC1 XVSBDEPLEQHLTE-UHFFFAOYSA-N 0.000 description 1
- HIYIGPVBMDKPCR-UHFFFAOYSA-N 1,1-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1(COC=C)CCCCC1 HIYIGPVBMDKPCR-UHFFFAOYSA-N 0.000 description 1
- CGXVUIBINWTLNT-UHFFFAOYSA-N 1,2,3-tris(ethenoxy)propane Chemical compound C=COCC(OC=C)COC=C CGXVUIBINWTLNT-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- XDWRKTULOHXYGN-UHFFFAOYSA-N 1,3-bis(ethenoxy)-2,2-bis(ethenoxymethyl)propane Chemical compound C=COCC(COC=C)(COC=C)COC=C XDWRKTULOHXYGN-UHFFFAOYSA-N 0.000 description 1
- MWZJGRDWJVHRDV-UHFFFAOYSA-N 1,4-bis(ethenoxy)butane Chemical compound C=COCCCCOC=C MWZJGRDWJVHRDV-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- OQOANOQNIDTIHS-UHFFFAOYSA-N 1-[(2,7-dihydroxynaphthalen-1-yl)methyl]naphthalene-2,7-diol Chemical compound C1=C(O)C=C2C(CC3=C(O)C=CC4=CC=C(C=C43)O)=C(O)C=CC2=C1 OQOANOQNIDTIHS-UHFFFAOYSA-N 0.000 description 1
- AWOGBOARESKNBA-UHFFFAOYSA-N 1-[(3-ethyloxetan-3-yl)methoxy]propan-2-ol Chemical compound CC(O)COCC1(CC)COC1 AWOGBOARESKNBA-UHFFFAOYSA-N 0.000 description 1
- CZAVRNDQSIORTH-UHFFFAOYSA-N 1-ethenoxy-2,2-bis(ethenoxymethyl)butane Chemical compound C=COCC(CC)(COC=C)COC=C CZAVRNDQSIORTH-UHFFFAOYSA-N 0.000 description 1
- FLFWDKGWSOCXQK-UHFFFAOYSA-N 1-ethenoxycyclohexan-1-ol Chemical compound C=COC1(O)CCCCC1 FLFWDKGWSOCXQK-UHFFFAOYSA-N 0.000 description 1
- HAVHPQLVZUALTL-UHFFFAOYSA-N 1-ethenoxypropan-2-ol Chemical compound CC(O)COC=C HAVHPQLVZUALTL-UHFFFAOYSA-N 0.000 description 1
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- SUFSXWBMZQUYOC-UHFFFAOYSA-N 2,2-bis(ethenoxymethyl)propane-1,3-diol Chemical compound C=COCC(CO)(CO)COC=C SUFSXWBMZQUYOC-UHFFFAOYSA-N 0.000 description 1
- BGBCQQVUFOHFST-UHFFFAOYSA-N 2,3-bis(ethenoxy)propan-1-ol Chemical compound C=COC(CO)COC=C BGBCQQVUFOHFST-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 description 1
- IARGBXSVZJLGOI-UHFFFAOYSA-N 2-(ethenoxymethyl)-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COC=C IARGBXSVZJLGOI-UHFFFAOYSA-N 0.000 description 1
- MJNGDTGKCWWIOP-UHFFFAOYSA-N 2-[(3-ethyloxetan-3-yl)methoxy]ethanol Chemical compound OCCOCC1(CC)COC1 MJNGDTGKCWWIOP-UHFFFAOYSA-N 0.000 description 1
- SNAGVRNJNARVRV-UHFFFAOYSA-N 2-[(3-ethyloxetan-3-yl)methoxymethyl]oxolane Chemical compound C1CCOC1COCC1(CC)COC1 SNAGVRNJNARVRV-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 1
- XRBWKWGATZNBFW-UHFFFAOYSA-N 2-[2-(2-ethenoxyethoxy)ethoxy]ethanol Chemical compound OCCOCCOCCOC=C XRBWKWGATZNBFW-UHFFFAOYSA-N 0.000 description 1
- DVSDTPMZVLDKRT-UHFFFAOYSA-N 2-[2-[(3-ethyloxetan-3-yl)methoxy]butoxy]ethanol Chemical compound OCCOCC(CC)OCC1(CC)COC1 DVSDTPMZVLDKRT-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyethers (AREA)
- Epoxy Resins (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Manufacturing Optical Record Carriers (AREA)
Description
本発明は、エネルギー線の照射により、極めて高速に硬化塗膜を形成することができ、且つそれにより形成された塗膜は、耐透湿性に優れ、樹脂、金属、ガラスといった様々な基材に対し良好な密着性を有し、加工性にも優れ、また硬化時の収縮も少ない感光性組成物及びその硬化物に関する。
本発明の感光性組成物及びその硬化物は、接着剤、塗料、インキ、フィルムコーティング、特には光学部品用、電子部品用における接着剤、コート材、フォトレジスト、シール材、封止材、絶縁材などの用途として有用である。具体的には、本発明は、反射防止膜形成用コーティング材、ハードコーティング材、光ディスクの貼り合わせ用接着剤、液晶や有機ＥＬ等のディスプレイパネルのシール材として有用であり、特には次世代光ディスクであるＢｌｕ−ｒａｙ Ｄｉｓｋの表面保護層形成材、有機ＥＬディスプレイのシール材として有用な感光性組成物及びその硬化物に関する。
In the present invention, a cured coating film can be formed at an extremely high speed by irradiation with energy rays, and the coating film formed thereby has excellent moisture permeability resistance and can be applied to various substrates such as resin, metal, and glass. The present invention relates to a photosensitive composition having good adhesion, excellent workability, and little shrinkage upon curing, and a cured product thereof.
The photosensitive composition of the present invention and the cured product thereof are adhesives, paints, inks, film coatings, particularly adhesives for optical parts and electronic parts, coating materials, photoresists, sealing materials, sealing materials, insulating materials. This is useful as a material. Specifically, the present invention is useful as a coating material for forming an antireflection film, a hard coating material, an adhesive for laminating optical disks, and a sealing material for display panels such as liquid crystal and organic EL. The present invention relates to a photosensitive composition useful as a surface protective layer forming material of Blu-ray Disk, a sealing material of an organic EL display, and a cured product thereof.
画像、音楽、コンピューターデータ等の多様なデータを記録または再生するための光記録媒体として、ＣＤ（Ｃｏｍｐａｃｔ Ｄｉｓｋ）、ＤＶＤ（Ｄｉｇｉｔａｌ Ｖｅｒｓａｔａｉｌｅ Ｄｉｓｋ）などが実用化されている。現在では、記録密度を更に高くして、１枚のディスクに大容量のデータを記録することが望まれており、次世代光ディスクであるＢｌｕ−ｒａｙ Ｄｉｓｋの開発が進められている。
光ディスクの記録密度は、対物レンズの開口数（NA）と光源のレーザー波長という２つのパラメータによってほぼ決まり、光ディスクの高密度化の手法としては光学系の短波長化、高開口数化が一般的に行われている。短波長化、高開口数化を行うと、光透過層の厚さを薄くする必要性が生じてくる。これは、高開口数化に伴い、ディスクとレーザー光の光軸の傾きに許される角度誤差（チルト・マージン）が狭くなってしまい、光透過層が薄いほどこのチルト・マージンを広げることが可能だからである。
CDs (Compact Disks), DVDs (Digital Versatile Disks), and the like have been put into practical use as optical recording media for recording or reproducing various data such as images, music, and computer data. At present, it is desired to further increase the recording density and record a large amount of data on a single disc, and the development of a Blu-ray Disk, which is a next-generation optical disc, is being promoted.
The recording density of an optical disc is almost determined by two parameters: the numerical aperture (NA) of the objective lens and the laser wavelength of the light source. Generally, the optical system has a shorter wavelength and a higher numerical aperture as a method for increasing the optical disc density. Has been done. When the wavelength is shortened and the numerical aperture is increased, it is necessary to reduce the thickness of the light transmission layer. As the numerical aperture increases, the angle error (tilt margin) allowed for the tilt of the optical axis of the disk and laser light becomes narrower, and the thinner the light transmission layer, the wider the tilt margin. That's why.
このような光ディスクでは、記録層の上に例えばラジカル重合反応により硬化される（メタ）アクリレート系材料を使用した紫外線硬化型樹脂を塗工し、これを光硬化させて光透過層を形成するといった方法等をとっている。しかしながらラジカル硬化系には、硬化収縮が大きいという欠点があり、この収縮により光記録媒体全体が反ってしまうという不都合が発生する。また硬化後においても、高温高湿の条件等で光記録媒体全体が反るという問題も生じる。
この問題を解決する方法として、ラジカル硬化系ではなく、カチオン硬化系材料を使うことが挙げられる。エポキシやビニルエーテル、オキセタン等の材料を使用したカチオン硬化系材料は、（ａ）酸素による硬化阻害を受け難いため、表面および薄膜硬化性に優れる（ｂ）硬化収縮が小さい（ｃ）幅広い基材に対し良好な接着性を有する等、ラジカル硬化系に比べ優れた特長を有するものである。実際、カチオン硬化系の光硬化型樹脂を用いて光透過層を形成する試みがなされており（特許文献１参照）、硬化収縮を抑制することが可能となっている。
In such an optical disk, for example, an ultraviolet curable resin using a (meth) acrylate-based material that is cured by a radical polymerization reaction is applied on the recording layer, and this is photocured to form a light transmission layer. The method is taken. However, the radical curing system has a disadvantage that the curing shrinkage is large, and this shrinkage causes the disadvantage that the entire optical recording medium is warped. In addition, even after curing, there arises a problem that the entire optical recording medium is warped due to high temperature and high humidity conditions.
As a method for solving this problem, it is possible to use a cationic curing material instead of a radical curing system. Cationic curable materials using materials such as epoxy, vinyl ether, oxetane, etc. (a) are less susceptible to curing inhibition by oxygen, and therefore have excellent surface and thin film curability (b) low cure shrinkage (c) wide base materials It has excellent characteristics compared to radical curing systems, such as having good adhesiveness. In fact, attempts have been made to form a light-transmitting layer using a cationically curable photocurable resin (see Patent Document 1), and curing shrinkage can be suppressed.
ただし、カチオン硬化系においても欠点があり、光によってのみ硬化させようとした場合、硬化性が不十分であり重合性モノマーやオリゴマーの転化率が向上しないという問題があり、また金属や記録膜を腐食させ易いという欠点もある。こうした課題をも解決したカチオン硬化系材料は開発されていないのが現状であり、事実、特許文献１においても、光硬化後更に加熱等を行い硬化を促進させたり、カチオン硬化系材料の強い腐食性のために光透過層をラジカル系硬化膜とカチオン系硬化膜の２層構造にするなどの方法を模索している。
他に、光カチオン重合での光硬化性を向上させるため、オキセタニル基とエポキシ基を同一分子内に有する化合物を用いたり（特許文献２参照）、アルミニウムの腐食防止のために保護層を設けたり（特許文献３参照）、腐食を抑制するために防食剤成分を添加する試みがなされているが（特許文献４参照）、優れた光硬化性と低腐食性を兼ね備えたような、光ディスクの光透過層に最適な材料は未だ開発されていない。
However, there is a drawback in the cationic curing system, and when it is attempted to cure only by light, there is a problem that the curability is insufficient and the conversion rate of the polymerizable monomer or oligomer is not improved, and the metal or recording film is not suitable. There is also a drawback of being easily corroded. The present situation is that a cationic curable material that has solved these problems has not been developed. In fact, in Patent Document 1, heating is further promoted after photocuring to accelerate the curing, or strong corrosion of the cationic curable material. For this reason, a method of making the light transmission layer into a two-layer structure of a radical cured film and a cationic cured film is being sought.
In addition, a compound having an oxetanyl group and an epoxy group in the same molecule is used in order to improve photocurability in photocationic polymerization (see Patent Document 2), or a protective layer is provided to prevent corrosion of aluminum. An attempt has been made to add an anticorrosive component to suppress corrosion (see Patent Document 3) (see Patent Document 4), but the light of an optical disk that has both excellent photocurability and low corrosivity. The optimal material for the transmission layer has not yet been developed.
また近年、電子、電気業界において種々の表示素子を利用したフラットパネルディスプレイ（ＦＰＤ）の開発、製造が行われている。これらのディスプレイの多くは、ガラスやプラスチックなどのフラットパネルから成るセルに表示素子を封止したものであり、その代表として、液晶ディスプレイ（ＬＣＤ）、ＥＬＤ、電子ペーパー等が挙げられる。
これらのうちＥＬＤ、とりわけ有機ＥＬＤは自発光ならではの高視野角、高コントラスト性に加え、高輝度、高効率、高速応答性、多色化の点で優れており、薄型フルカラーディスプレイ用途として期待されている。また、電極および発光層が非常に薄膜であるため、プラスチック基材上に形成させることでフレキシブルなディスプレイや、大型平面照明用途としての可能性も検討されている。有機ＥＬ素子は、電子注入電極から直接または電子輸送層を介して発光層に注入された電子と、正孔注入電極から直接または正孔輸送層を介して発光層に注入された正孔との再結合により発光が生じる。
In recent years, flat panel displays (FPDs) using various display elements have been developed and manufactured in the electronic and electrical industries. Many of these displays have a display element sealed in a cell made of a flat panel such as glass or plastic, and representative examples thereof include a liquid crystal display (LCD), ELD, and electronic paper.
Of these, ELDs, especially organic ELDs, are excellent in terms of high brightness, high efficiency, high-speed response, and multiple colors, in addition to the high viewing angle and high contrast that are unique to self-luminous emission, and are expected to be used for thin full-color displays. ing. In addition, since the electrodes and the light emitting layer are very thin films, the possibility of use as a flexible display or a large-sized flat illumination by being formed on a plastic substrate has been studied. The organic EL element includes an electron injected from the electron injection electrode directly or through the electron transport layer into the light emitting layer and a hole injected directly from the hole injection electrode or through the hole transport layer into the light emitting layer. Luminescence occurs due to recombination.
このような発光機構に基づく有機ＥＬ素子の電極には、非常に活性で化学的に不安定な合金が用いられ、外部からの水分や酸素による腐食、酸化が起こりダークスポットと呼ばれる未発光部の形成とその著しい増加および経時での輝度の劣化が見られる。また、有機ＥＬ素子の発光層や電荷輸送層には有機材料が用いられているため、水分や酸素により劣化を受け易く、同様にダークスポットの形成や輝度低下を招くという問題がある。
そのため、実用的な有機ＥＬ素子とするには、有機材料や電極材料に水分や酸素が入らないように素子を効果的に封止（シール）する必要がある。ＦＰＤの封止方法としては、従来ＬＣＤの封止に用いられてきた熱硬化型エポキシ樹脂を用いる方法があるが、この場合１５０℃〜１８０℃という高温で２時間程度加熱硬化する必要があり、生産性が上がらないだけでなく、有機ＥＬのような熱に弱い材料を用いた素子の場合、好ましい方法ではない。
An electrode of an organic EL element based on such a light emission mechanism is made of a highly active and chemically unstable alloy, and corrosion or oxidation due to moisture or oxygen from the outside occurs, and an unlight emitting portion called a dark spot is generated. There is a marked increase in formation and brightness over time. In addition, since an organic material is used for the light-emitting layer and the charge transport layer of the organic EL element, there is a problem that the organic EL element is easily deteriorated by moisture and oxygen, and similarly dark spots are formed and luminance is reduced.
Therefore, in order to make a practical organic EL element, it is necessary to effectively seal (seal) the element so that moisture and oxygen do not enter the organic material and the electrode material. As a sealing method of FPD, there is a method using a thermosetting epoxy resin that has been used for sealing conventional LCDs. In this case, it is necessary to heat and cure at a high temperature of 150 ° C. to 180 ° C. for about 2 hours. Not only does productivity not increase, but an element using a heat-sensitive material such as organic EL is not a preferred method.
これに対し、低温速硬化が可能な方法として光硬化型シール剤の開発が試みられており、通常、光ラジカル硬化型シール剤と光カチオン型シール剤がある。光ラジカル硬化型シール剤の場合、アクリル系樹脂が主に用いられ、多様なアクリレート系モノマーやオリゴマーが利用できるという利点はあるが、一般に耐透湿性が不十分であり、また硬化収縮が大きく基材との接着性が不十分であるといった問題もあり、未だ満足できる性能の材料はない。
一方、光カチオン硬化型シール剤の場合、主にエポキシ系樹脂が用いられており、接着性に優れ、耐透湿性も比較的良好ではあるが、いまだ不十分であるのが実状である。また実質加熱プロセスを用いることなく光によってのみ硬化させようとした場合、硬化性が不十分であり重合性モノマーやオリゴマーの転化率が向上しないという問題があった。このため、光カチオン重合の重合性化合物の光硬化性を向上させるため、水酸基を有する化合物を併用する試みもなされているが（特許文献５参照）十分な光硬化性および耐透湿性は得られていない。
On the other hand, development of a photo-curing sealant has been attempted as a method capable of rapid curing at low temperature, and there are usually a photo-radical curing sealant and a photocationic sealant. In the case of the photo radical curable sealant, acrylic resin is mainly used, and there are advantages that various acrylate monomers and oligomers can be used. However, in general, moisture resistance is insufficient and curing shrinkage is large. There is also a problem that the adhesiveness with the material is insufficient, and there is still no material with satisfactory performance.
On the other hand, in the case of a photocationic curable sealant, an epoxy resin is mainly used, which is excellent in adhesiveness and relatively good in moisture permeability, but is still insufficient. Moreover, when it was made to harden only by light, without using a substantial heating process, there existed a problem that sclerosis | hardenability was inadequate and the conversion rate of a polymerizable monomer or oligomer did not improve. For this reason, attempts have been made to use a compound having a hydroxyl group in order to improve the photocurability of the polymerizable compound of photocationic polymerization (see Patent Document 5), but sufficient photocurability and moisture permeability are obtained. Not.
他に、光カチオン重合系において水酸基を有する化合物を併用する試みとしては、ラジカル型・カチオン型のハイブリッド系において、ビスフェノールＡのエチレンオキサイド付加体やプロピレンオキサイド付加体等を併用する試みもなされているが（特許文献６参照）、光硬化性と耐透湿性はいまだ不十分であり、またラジカル型とのハイブリッド系であるために接着性も十分でない。
本発明は、従来のカチオン系の持つ接着性が良好で硬化収縮も小さいといった性能を保持しながら、これまでにない優れた光硬化性かつ耐透湿性、耐腐食性という性能を有するカチオン系感光性組成物及びその硬化物を提供し、そしてこの感光性組成物及びその硬化物を用いて光ディスクの光透過層を形成し、またこの感光性組成物及びその硬化物をシール材とするＬＣＤ、有機ＥＬＤ、電位ペーパー等のＦＰＤ、及びその製造方法を提供することを目的とする。 The present invention is a cationic photopolymer having excellent photocurability, moisture permeability resistance, and corrosion resistance, which has never been achieved, while maintaining the performance that conventional cationic systems have good adhesion and small cure shrinkage. A photosensitive composition and a cured product thereof, and a light-transmitting layer of an optical disk using the photosensitive composition and the cured product, and an LCD having the photosensitive composition and the cured product as a sealing material, It aims at providing FPD, such as organic ELD and electric potential paper, and its manufacturing method.
本発明者等は、前記課題を解決するため鋭意検討を行った結果、特段の加熱プロセスを用いなくとも優れた光硬化性を有し、そして耐透湿性、耐腐食性に優れるカチオン重合性感光性組成物を見出し、本発明をなすに至った。
すなわち、本発明は、以下の通りである。
１．（ａ）カチオン重合性化合物 １０〜９５質量％、（ｂ）少なくとも２個の脂肪族水酸基を有する芳香族系化合物 ０．１〜９０質量％、（ｃ）エネルギー線感受性カチオン重合開始剤 ０．１〜２０質量％を含有し、（ａ）がエポキシ基を有する化合物及び／又はオキセタン環を有する化合物であることを特徴とする感光性組成物。
２．成分（ａ）として、エポキシ基を有する化合物及びオキセタン環を有する化合物を少なくとも含有することを特徴とする上記１に記載の感光性組成物。
３．成分（ｂ）が、下記一般式（１）で示される化合物であることを特徴とする上記１又は２に記載の感光性組成物。
As a result of intensive studies to solve the above problems, the present inventors have found that they have excellent photocurability without using a special heating process, and are cationically polymerizable photosensitive materials that are excellent in moisture resistance and corrosion resistance. The present inventors have found an ionic composition and have made the present invention.
That is, the present invention is as follows.
1. (A) Cationic polymerizable compound 10 to 95% by mass, (b) Aromatic compound having at least two aliphatic hydroxyl groups 0.1 to 90% by mass, (c) Energy ray sensitive cationic polymerization initiator 0.1 A photosensitive composition comprising ˜20% by mass , wherein (a) is a compound having an epoxy group and / or a compound having an oxetane ring .
2. 2. The photosensitive composition as described in 1 above, comprising at least a compound having an epoxy group and a compound having an oxetane ring as component (a).
3. 3. The photosensitive composition as described in 1 or 2 above, wherein the component (b) is a compound represented by the following general formula (1).
４．成分（ｂ）が、式（１）におけるＸとして、芳香環を少なくとも２個含んでいる化合物であることを特徴とする上記３に記載の感光性組成物。
５．成分（ｂ）が、式（１）におけるＸとして、下記一般式（２）で示される基を有する化合物であることを特徴とする上記４に記載の感光性組成物。
4). 4. The photosensitive composition as described in 3 above, wherein the component (b) is a compound containing at least two aromatic rings as X in the formula (1).
5 . 5. The photosensitive composition as described in 4 above, wherein the component (b) is a compound having a group represented by the following general formula (2) as X in the formula (1).
６．成分（ｂ）が、式（２）におけるＹとして、単結合或いは下記一般式（３）で示される基を有する化合物であることを特徴とする上記５に記載の感光性組成物。
6 . 6. The photosensitive composition as described in 5 above, wherein the component (b) is a compound having a single bond or a group represented by the following general formula (3) as Y in the formula (2).
７．成分（ｂ）が、式（１）におけるＸとして、下記一般式（４）で示される基を有する化合物であることを特徴とする上記４に記載の感光性組成物。
7). 5. The photosensitive composition as described in 4 above, wherein the component (b) is a compound having a group represented by the following general formula (4) as X in the formula (1).
８．成分（ｂ）が、式（４）におけるＺとして、単結合或いは下記一般式（５）で示される基を有する化合物であることを特徴とする上記７に記載の感光性組成物。
8). 8. The photosensitive composition as described in 7 above, wherein the component (b) is a compound having a single bond or a group represented by the following general formula (5) as Z in the formula (4).
９．成分（ｂ）として、下記一般式（６）、下記一般式（７）又は下記一般式（８）で示される化合物を少なくとも含有することを特徴とする上記１に記載の感光性組成物。
9. 2. The photosensitive composition as described in 1 above, which contains at least a compound represented by the following general formula (6), the following general formula (7) or the following general formula (8) as the component (b).
１０．上記１〜９のいずれかに記載の感光性組成物に、エネルギー線照射することにより得られることを特徴とする硬化物。
１１．光透過層を通して光により記録又は再生を行う光ディスクにおいて、上記１０に記載の硬化物からなる光ディスクの光透過層。
１２．上記１０に記載の硬化物からなるフラットパネルディスプレイ用シール材。
10. A cured product obtained by irradiating the photosensitive composition according to any one of 1 to 9 with energy rays.
11. 11. A light transmission layer of an optical disk comprising the cured product as described in 10 above, wherein recording or reproduction is performed by light through a light transmission layer.
12 11. A flat panel display sealing material comprising the cured product as described in 10 above.
本発明のカチオン重合性感光性組成物及びその硬化物を用いて光ディスクの光透過層を形成することにより、生産性が大幅に向上するだけでなく、反りが発生せず腐食も抑制された良質な光透過層を持った光ディスクを提供することが可能となる。また本発明のカチオン重合性感光性組成物及びその硬化物から成るシール材を用いＦＰＤを製造する場合、該シール材の優れた光硬化性から、生産性が大幅に向上するだけでなく、硬化物の接着性や耐透湿性が優れるため、得られるＦＰＤの寿命を延ばすことができ、信頼性を向上させる等の効果を有する。 By forming a light-transmitting layer of an optical disk using the cationically polymerizable photosensitive composition of the present invention and its cured product, not only productivity is greatly improved, but also high quality with no warpage and suppression of corrosion. It becomes possible to provide an optical disc having a transparent layer. Moreover, when manufacturing FPD using the sealing material which consists of the cationically polymerizable photosensitive composition of this invention and its hardened | cured material, not only productivity improves significantly from the outstanding photocurability of this sealing material, but also hardening. Since the adhesiveness and moisture permeation resistance of the object are excellent, the life of the obtained FPD can be extended, and the reliability can be improved.
本発明について、以下具体的に説明する。
本発明における成分（ａ）のカチオン重合性化合物としては、エポキシ基を有する化合物、オキセタン環を有する化合物、ビニルエーテル化合物、前記以外の環状エーテル化合物、環状ラクトン化合物、環状アセタール化合物、環状チオエーテル化合物、スピロオルソエステル化合物等を挙げることができる。これらの中では、光硬化性や透明性等の硬化膜特性の点で、エポキシ基を有する化合物及び／又はオキセタン環を有する化合物を用いることが好ましい。
エポキシ基を有する化合物としては、グリシジルエーテル型エポキシ化合物、脂環式エポキシ化合物等が挙げられ、その中でも１分子中に少なくとも２個以上のエポキシ基を有する化合物が好ましい。
The present invention will be specifically described below.
As the cationically polymerizable compound of component (a) in the present invention, compounds having an epoxy group, compounds having an oxetane ring, vinyl ether compounds, cyclic ether compounds other than those described above, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro Examples include orthoester compounds. Among these, it is preferable to use a compound having an epoxy group and / or a compound having an oxetane ring from the viewpoint of cured film properties such as photocuring property and transparency.
Examples of the compound having an epoxy group include a glycidyl ether type epoxy compound and an alicyclic epoxy compound. Among them, a compound having at least two epoxy groups in one molecule is preferable.
グリシジルエーテル型エポキシ化合物の具体例としては、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ｐ−ｔｅｒｔ−ブチルフェノールノボラック型エポキシ化合物といったアルキルフェノールノボラック型エポキシ化合物、水添ビスフェノールＡ型エポキシ化合物、ビスフェノールＡのアルキレンオキサイド付加体のジグリシジルエーテル、ビスフェノールＦのアルキレンオキサイド付加体のジグリシジルエーテル、水添ビスフェノールＡのアルキレンオキサイド付加体のジグリシジルエーテル、テトラブロモビスフェノールＡ型エポキシ化合物、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ブタンジオールジグリシジルエーテル、ヘキサンジオールジグリシジルエーテル、シクロヘキサンジメタノールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、トリメチロールプロパンジ及び／又はトリグリシジルエーテル、ペンタエリスリトールトリ及び／又はテトラグリシジルエーテル、ソルビトールヘプタ及び／又はヘキサグリシジルエーテル、レゾルシンジグリシジルエーテル、ジシクロペンタジエン・フェノール付加型グリシジルエーテル、メチレンビス（２，７−ジヒドロキシナフタレン）テトラグリシジルエーテル、１，６−ジヒドロキシナフタレンジグリシジルエーテル、１，５−ジヒドロキシナフタレンジグリシジルエーテル等を挙げることができる。 Specific examples of glycidyl ether type epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolac type epoxy compounds, cresol novolak type epoxy compounds, and alkylphenol novolak type epoxy compounds such as p-tert-butylphenol novolac type epoxy compounds. Hydrogenated bisphenol A type epoxy compound, diglycidyl ether of bisphenol A alkylene oxide adduct, diglycidyl ether of alkylene oxide adduct of bisphenol F, diglycidyl ether of hydrogenated bisphenol A alkylene oxide adduct, tetrabromobisphenol Type A epoxy compound, ethylene glycol diglycidyl ether, propylene glycol diglycid Ether, neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane di and / or triglycidyl ether Pentaerythritol tri and / or tetraglycidyl ether, sorbitol hepta and / or hexaglycidyl ether, resorcin diglycidyl ether, dicyclopentadiene / phenol addition type glycidyl ether, methylenebis (2,7-dihydroxynaphthalene) tetraglycidyl ether, 1, 6-dihydroxynaphthalenediglycidyl ether, 1,5-di It can be given mud carboxymethyl-naphthalene diglycidyl ether.
脂環式エポキシ化合物の具体例としては、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、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−メタ−ジオキサン、ビス（３，４−エポキシシクロヘキシルメチル）アジペート、ビニルシクロヘキセンジオキサイド、４−ビニルエポキシシクロヘキサン、ビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）アジペート、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、メチレンビス（３，４−エポキシシクロヘキサン）、ジシクロペンタジエンジエポキサイド、エチレングリコールジ（３，４−エポキシシクロヘキシルメチル）エーテル、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）、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ−２−エチルヘキシル、１，２，８，９−ジエポキシリモネン等が挙げられる。その他のエポキシ化合物の具体例としては、エポキシ化ポリブタジエン等が挙げられる。 Specific examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy). Cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy -6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ) Ether, ethylenebis (3,4-epoxycyclohexane carboxylate), epoxy hexahydrophthalic acid dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl, 1,2,8,9- diepoxylimonene, and the like. Specific examples of other epoxy compounds include epoxidized polybutadiene.
更に具体的には、単官能脂環式エポキシ化合物としては、ＥＴＨＢ、セロキサイド２０００（ダイセル化学工業社製）、２官能脂環式エポキシ化合物としてはセロキサイド２０２１、２０８０、３０００（ダイセル化学工業社製）、サイラキュアＵＶＲ−６１０５、ＵＶＲ−６１２８（ダウ・ケミカル日本社製）、多官能脂環式エポキシ化合物としては、エポリードＧＴ３００、ＧＴ４００、ＥＨＰＥ３１５０（ダイセル化学工業社製）、その他としてはエポリードＰＢ３６００、エポブレンドＡＴ５０１、ＣＴ３１０（ダイセル化学工業社製）等を用いることができる。このうち、脂環式エポキシ化合物がカチオン重合反応性に優れるため好ましい。これらのエポキシ基を有する化合物は、１種単独あるいは２種以上を組み合わせて使用しても良い。 More specifically, as monofunctional alicyclic epoxy compounds, ETHB, Celoxide 2000 (manufactured by Daicel Chemical Industries), and bifunctional alicyclic epoxy compounds as Celoxide 2021, 2080, 3000 (manufactured by Daicel Chemical Industries). , Cyracure UVR-6105, UVR-6128 (manufactured by Dow Chemical Japan Co., Ltd.), polyfunctional alicyclic epoxy compounds such as Epolide GT300, GT400, EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), and others as Epolide PB3600, Epoblend AT501, CT310 (manufactured by Daicel Chemical Industries) or the like can be used. Of these, alicyclic epoxy compounds are preferred because of their excellent cationic polymerization reactivity. These compounds having an epoxy group may be used singly or in combination of two or more.
オキセタン環を有する化合物は、分子中にオキセタン環を少なくとも１個有する化合物であれば特に限定されるものではない。オキセタン環を１個有する化合物の具体例としては、３−エチル−３−ヒドロキシメチルオキセタン、３−（メタ）アリルオキシメチル−３−エチルオキセタン、３−エチル−３−（シクロヘキシロキシ）メチルオキセタン、（３−エチル−３−オキセタニルメトキシ）メチルベンゼン、４−フルオロ−〔１−（３−エチル−３−オキセタニルメトキシ）メチル〕ベンゼン、４−メトキシ−〔１−（３−エチル−３−オキセタニルメトキシ）メチル〕ベンゼン、〔１−（３−エチル−３−オキセタニルメトキシ）エチル〕フェニルエーテル、イソブトキシメチル（３−エチル−３−オキセタニルメチル）エーテル、イソボルニルオキシエチル（３−エチル−３−オキセタニルメチル）エーテル、イソボルニル（３−エチル−３−オキセタニルメチル）エーテル、２−エチルヘキシル（３−エチル−３−オキセタニルメチル）エーテル、エチルジエチレングリコール（３−エチル−３−オキセタニルメチル）エーテル、ジシクロペンタジエン（３−エチル−３−オキセタニルメチル）エーテル、ジシクロペンテニルオキシエチル（３−エチル−３−オキセタニルメチル）エーテル、ジシクロペンテニル（３−エチル−３−オキセタニルメチル）エーテル、テトラヒドロフルフリル（３−エチル−３−オキセタニルメチル）エーテル、テトラブロモフェニル（３−エチル−３−オキセタニルメチル）エーテル、２−テトラブロモフェノキシエチル（３−エチル−３−オキセタニルメチル）エーテル、トリブロモフェニル（３−エチル−３−オキセタニルメチル）エーテル、２−トリブロモフェノキシエチル（３−エチル−３−オキセタニルメチル）エーテル、２−ヒドロキシエチル（３−エチル−３−オキセタニルメチル）エーテル、２−ヒドロキシプロピル（３−エチル−３−オキセタニルメチル）エーテル、ブトキシエチル（３−エチル−３−オキセタニルメチル）エーテル、ペンタクロロフェニル（３−エチル−３−オキセタニルメチル）エーテル、ペンタブロモフェニル（３−エチル−３−オキセタニルメチル）エーテル、ボルニル（３−エチル−３−オキセタニルメチル）エーテル等が挙げられる。 The compound having an oxetane ring is not particularly limited as long as it is a compound having at least one oxetane ring in the molecule. Specific examples of the compound having one oxetane ring include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, 3-ethyl-3- (cyclohexyloxy) methyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) ) Methyl] benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3- Oxetanyl methyl) ether, isobornyl (3-ethyl-3-oxetanyl) Til) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclo Pentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3 -Ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribro Phenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3 -Ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) Examples include ether.
オキセタン環を２個以上有する化合物の具体例としては、３，７−ビス（３−オキセタニル）−５−オキサ−ノナン、３，３’−（１，３−（２−メチレニル）プロパンジイルビス（オキシメチレン））ビス−（３−エチルオキセタン）、ビス〔１−エチル（３−オキセタニル）〕メチルエーテル、１，４−ビス〔（３−エチル−３−オキセタニルメトキシ）メチル〕ベンゼン、１，３−ビス〔（３−エチルオキセタン−３−イル）メトキシ〕ベンゼン、１，２−ビス〔（３−エチル−３−オキセタニルメトキシ）メチル〕エタン、１，３−ビス〔（３−エチル−３−オキセタニルメトキシ）メチル〕プロパン、エチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、ジシクロペンテニルビス（３−エチル−３−オキセタニルメチル）エーテル、トリエチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、テトラエチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、トリシクロデカンジイルジメチレン（３−エチル−３−オキセタニルメチル）エーテル、トリメチロールプロパントリス（３−エチル−３−オキセタニルメチル）エーテル、１，４−ビス（３−エチル−３−オキセタニルメトキシ）ブタン、１，６−ビス（３−エチル−３−オキセタニルメトキシ）ヘキサン、ペンタエリスリトールトリス（３−エチル−３−オキセタニルメチル）エーテル、ペンタエリスリトールテトラキス（３−エチル−３−オキセタニルメチル）エーテル、ポリエチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、ジペンタエリスリトールヘキサキス（３−エチル−３−オキセタニルメチル）エーテル、ジペンタエリスリトールペンタキス（３−エチル−３−オキセタニルメチル）エーテル、ジペンタエリスリトールテトラキス（３−エチル−３−オキセタニルメチル）エーテル、カプロラクトン変性ジペンタエリスリトールヘキサキス（３−エチル−３−オキセタニルメチル）エーテル、カプロラクトン変性ジペンタエリスリトールペンタキス（３−エチル−３−オキセタニルメチル）エーテル、ジトリメチロールプロパンテトラキス（３−エチル−３−オキセタニルメチル）エーテル、ＥＯ変性ビスフェノールＡビス（３−エチル−３−オキセタニルメチル）エーテル、ＰＯ変性ビスフェノールＡビス（３−エチル−３−オキセタニルメチル）エーテル、ＥＯ変性水添ビスフェノールＡビス（３−エチル−３−オキセタニルメチル）エーテル、ＰＯ変性水添ビスフェノールＡビス（３−エチル−３−オキセタニルメチル）エーテル、ＥＯ変性ビスフェノールＦビス（３−エチル−３−オキセタニルメチル）エーテル、オキセタニルシルセスキオキサン、オキセタニルシリケート、フェノールノボラックオキセタン等が挙げられる。 Specific examples of the compound having two or more oxetane rings include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis ( Oxymethylene)) bis- (3-ethyloxetane), bis [1-ethyl (3-oxetanyl)] methyl ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,3 -Bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3- Oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxe) Nylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanyl) Methyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanyl) Methoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) Ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) Ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3) -Oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ) Ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F bis (3- Ethyl-3-oxetanylmethyl) ether, oxetanylsilsesquioxane, oxetanyl silicate, phenol novolac oxetane and the like.
これらのオキセタン環を有する化合物は、１種単独あるいは２種以上を組み合わせて使用しても良い。オキセタン環を有する化合物として例えば、アロンオキセタンＯＸＴ−１０１、ＯＸＴ−２２１、ＯＸＴ−１２１、ＯＸＴ−２１２、ＯＸＴ−２１１（東亞合成社製）等を用いることができる。これらの中でもＯＸＴ−１０１、ＯＸＴ−２２１、ＯＸＴ−１２１が硬化性、硬化膜性能の観点で好ましく、硬化性という観点ではＯＸＴ−１０１がより好ましく、耐透湿性という観点ではＯＸＴ−１２１がより好ましい。
本発明における成分（ａ）のカチオン重合性化合物としては、エポキシ基を有する化合物とオキセタン環を有する化合物を各々単独で用いても良く、或いは併用しても良い。光硬化性を向上させる、特にキセノンランプ等の長波長領域ランプでの硬化性を向上させるためには、エポキシ基を有する化合物とオキセタン環を有する化合物を併用するのが好ましい。
These compounds having an oxetane ring may be used singly or in combination of two or more. As the compound having an oxetane ring, for example, Aron oxetane OXT-101, OXT-221, OXT-121, OXT-212, OXT-211 (manufactured by Toagosei Co., Ltd.) or the like can be used. Among these, OXT-101, OXT-221 and OXT-121 are preferable from the viewpoints of curability and cured film performance, OXT-101 is more preferable from the viewpoint of curability, and OXT-121 is more preferable from the viewpoint of moisture permeability resistance. .
As the cationically polymerizable compound of component (a) in the present invention, a compound having an epoxy group and a compound having an oxetane ring may be used alone or in combination. In order to improve photocurability, particularly in a long wavelength region lamp such as a xenon lamp, it is preferable to use a compound having an epoxy group and a compound having an oxetane ring in combination.
本発明で用いられる成分（ｂ）芳香族系化合物は、少なくとも２個の脂肪族水酸基を有しており、好ましくは下記一般式（１）で示される化合物である。 The component (b) aromatic compound used in the present invention has at least two aliphatic hydroxyl groups, and is preferably a compound represented by the following general formula (1).
多価アルコールの併用技術は、カチオン重合反応速度の向上、柔軟性の付与等を目的として広く知られている。本発明の感光性組成物に用いられる成分（ｂ）として、分子中に少なくとも２個の脂肪族水酸基を有する化合物を用いることにより、硬化性、エポキシ基の反応性、硬化膜物性に優れた系を実現できる。成分（ｂ）の骨格としては、芳香環を少なくとも１個含むことが重要であり、これにより優れた耐透湿性、耐吸湿性、熱膨張係数の低減を実現することができる。
The combined use technique of polyhydric alcohol is widely known for the purpose of improving the cationic polymerization reaction rate and imparting flexibility. As the component (b) used in the photosensitive composition of the present invention, a system having excellent curability, epoxy group reactivity, and cured film physical properties by using a compound having at least two aliphatic hydroxyl groups in the molecule. Can be realized. As the skeleton of the component (b), it is important to contain at least one aromatic ring, and thereby excellent moisture permeability resistance, moisture absorption resistance, and thermal expansion coefficient can be reduced.
このような化合物としては、フェノール系化合物にエチレンオキシド、プロピレンオキシド、ブチレンオキシド等のアルキレンオキシドを反応させた化合物が好ましい。アルキレンオキシドの付加モル数により発現性能をコントロールすることが可能であり、またエーテル鎖の存在により基材との接着性が向上するからである。
一般式（１）で示される化合物のうち、式中ｎは２〜２０の整数であり、ｎが２以上の整数であると光硬化性、硬化膜特性の点で優れる。耐透湿性の点からｎ＝２〜１０が好ましく、より好ましくはｎ＝２〜５、更に好ましくはｎ＝２又は３、最も好ましくはｎ＝２である。また式中ｍは１〜２０の整数を表し、光硬化性、可とう性、硬度、接着性等の観点からｍ＝１〜１０が好ましい。
このような一般式（１）で示される化合物のうち、式中のＸとしては、アルキレンオキサイドと反応可能なフェノール系化合物であれば特に限定されるものではない。フェノール系化合物としては、非特許文献（「新エポキシ樹脂」、垣内弘編、昭晃堂発行、１９８５年）（「総説エポキシ樹脂」、エポキシ樹脂技術協会編、エポキシ樹脂技術協会発行、２００３年）に記載のフェノール系化合物、または同文献に記載のエポキシ樹脂の原料フェノール化合物を挙げることができる。
As such a compound, a compound obtained by reacting a phenolic compound with an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide is preferable. This is because the expression performance can be controlled by the number of added moles of alkylene oxide, and the adhesion to the substrate is improved by the presence of the ether chain.
Among the compounds represented by the general formula (1), n is an integer of 2 to 20, and when n is an integer of 2 or more, it is excellent in terms of photocurability and cured film characteristics. From the viewpoint of moisture permeation resistance, n = 2 to 10 is preferable, n = 2 to 5, more preferably n = 2 or 3 , and most preferably n = 2. In the formula, m represents an integer of 1 to 20, and m = 1 to 10 is preferable from the viewpoint of photocurability, flexibility, hardness, adhesiveness, and the like.
Among the compounds represented by the general formula (1), X in the formula is not particularly limited as long as it is a phenolic compound capable of reacting with alkylene oxide. Non-patent literature (“New Epoxy Resin”, edited by Hiroshi Kakiuchi, published by Shoshodo, 1985) (“Review Epoxy Resin”, edited by Epoxy Resin Technology Association, published by Epoxy Resin Technology Association, 2003) Or the raw material phenol compound of the epoxy resin described in the document.
式中のＸとしては例えば、式中ｎ＝２となる化合物として下記一般式（２）や As X in the formula, for example, as a compound in which n = 2 in the formula,
下記一般式（４）
The following general formula (4)
式中ｎ＝２となるその他の化合物として下記一般式（９）
As other compounds in which n = 2 in the formula, the following general formula ( 9 )
これらのうち、本発明に用いられる成分（ｂ）としては、式（１）におけるＸとして芳香環を少なくとも２個含んでいる化合物であると、耐透湿性の点で好ましい。また一般式（１）で示される化合物のうち、（ａ）カチオン重合性化合物との相溶性及び反応性の点から、式中のＸが一般式（２）又は一般式（４）で示される化合物が好ましい。更に式（２）におけるＹとして単結合或いは一般式（３）で示される化合物、式（４）におけるＺとして単結合或いは一般式（５）で示される化合物であると、光硬化性や耐透湿性等の硬化膜特性の点で好ましい。
Among these, the component (b) used in the present invention is preferably a compound containing at least two aromatic rings as X in the formula (1) in terms of moisture resistance. Of the compounds represented by the general formula (1), X in the formula is represented by the general formula (2) or the general formula (4) from the viewpoint of compatibility and reactivity with the (a) cationic polymerizable compound. Compounds are preferred. Furthermore, when Y in formula (2) is a single bond or a compound represented by general formula (3), and Z in formula (4) is a single bond or a compound represented by general formula (5), photocurability and permeation resistance It is preferable in terms of cured film characteristics such as wetness.
これらの中で、耐透湿性という点で、より好ましくは、下記一般式（６）
Among these, in terms of moisture resistance, more preferably, the following general formula ( 6 )
下記一般式（７）
The following general formula ( 7 )
下記一般式（８）で表される化合物である。
It is a compound represented by the following general formula ( 8 ).
上記一般式（７）で表される化合物としては、式中Ｒｐがハロゲン原子であると耐透湿性の点で好ましく、例えば下記一般式（１１）で表される化合物が挙げられる。
本発明で用いられる成分（ｂ）少なくとも２個の脂肪族水酸基を有する芳香族系化合物は、１種単独あるいは２種以上を組み合わせて使用しても良い。
また、成分（ｂ）として、下記一般式（１２）で示される化合物を含有すると好ましい。
As the compound represented by the general formula (7), Rp is preferably a halogen atom in terms of moisture resistance, and examples thereof include compounds represented by the following general formula (11).
The component (b) aromatic compound having at least two aliphatic hydroxyl groups used in the present invention may be used singly or in combination of two or more.
Moreover, it is preferable to contain the compound shown by the following general formula ( 12 ) as a component (b).
この一般式（１２）で示される化合物は、成分（ａ）との相溶性に優れるという利点があり、また、一般式（１２）で示される化合物以外の成分（ｂ）と成分（ａ）との相溶性を向上させる効果がある。式中ｑは１〜２０の整数であるが、相溶性や光硬化性、硬度の点で、複数のＲｈのうち少なくとも１個が水素以外の場合は、ｑが１〜１０の整数であることが好ましく、複数のＲｈが全て水素である場合には、ｑは１０以下の整数であり２個のｑのうちの少なくとも１個は２以上の整数であることが好ましい。
本発明の（ｃ）エネルギー線感受性カチオン重合開始剤とは、エネルギー線照射によりカチオン重合を開始させる物質を放出することが可能な化合物であり、特に好ましいものとしては照射によりルイス酸を放出するオニウム塩である。このようなものとしては、ルイス酸のジアゾニウム塩、ルイス酸のヨードニウム塩、ルイス酸のスルホニウム塩等が挙げられ、これらはカチオン部分がそれぞれ芳香属ジアゾニウム、芳香属ヨードニウム、芳香属スルホニウムであり、アニオン部分がＢＦ４−、ＰＦ６−、ＳｂＦ６−、［ＢＸ４］−（ただし、Ｘは少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基）等により構成されたオニウム塩である。
Compound represented by the general formula (12) has the advantage of excellent compatibility with the component (a), also components other than the compound represented by the general formula (12) and (b) to component (a) There is an effect of improving the compatibility. In the formula, q is an integer of 1 to 20, but in terms of compatibility, photocurability, and hardness, q is an integer of 1 to 10 when at least one of the plurality of Rhs is other than hydrogen. In the case where a plurality of Rh are all hydrogen, q is an integer of 10 or less, and at least one of the two qs is preferably an integer of 2 or more.
The (c) energy ray-sensitive cationic polymerization initiator of the present invention is a compound capable of releasing a substance that initiates cationic polymerization upon irradiation with energy rays, and particularly preferred is an onium that releases a Lewis acid upon irradiation. Salt. Examples of such compounds include Lewis acid diazonium salts, Lewis acid iodonium salts, Lewis acid sulfonium salts, etc., and these have cationic moieties aromatic diazonium, aromatic iodonium, aromatic sulfonium, respectively, and anions The moiety is an onium salt composed of BF4-, PF6-, SbF6-, [BX4]-(wherein X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups) or the like.
具体的には、四フッ化ホウ素のフェニルジアゾニウム塩、六フッ化リンのジフェニルヨードニウム塩、六フッ化アンチモンのジフェニルヨードニウム塩、六フッ化ヒ素のトリ−４−メチルフェニルスルホニウム塩、四フッ化アンチモンのトリ−４−メチルフェニルスルホニウム塩、テトラキス（ペンタフルオロフェニル）ホウ素のジフェニルヨードニウム塩、アセチルアセトンアルミニウム塩とオルトニトロベンジルシリルエーテル混合体、フェニルチオピリジウム塩、六フッ化リンアレン−鉄錯体等を挙げることができる。更に具体的には、ＣＤ−１０１２（商品名：ＳＡＲＴＯＭＥＲ社製）、ＰＣＩ−０１９、ＰＣＩ−０２１（商品名：日本化薬社製）、オプトマーＳＰ−１５０、オプトマーＳＰ−１７０（商品名：旭電化社製）、ＵＶＩ−６９９０（商品名：ダウケミカル社製）、ＣＰＩ−１００Ｐ、ＣＰＩ−１００Ａ（商品名：サンアプロ社製）、ＴＥＰＢＩ−Ｓ（商品名：日本触媒社製）等を用いることができ、これらは単独でも２種以上を組み合わせて使用することもできる。
本発明のエネルギー線感受性カチオン重合開始剤には、ベンゾフェノン、ベンゾインイソプロピルエーテル、チオキサントン、アントラセン等の光増感剤を併用することもでき、具体的には４，４’−ビス（ジエチルアミノ）ベンゾフェノン、２，４’−ジエチルチオキサントン、イソプロピルチオキサントン、９，１０−ジエトキシアントラセン、９，１０−ジブトキシアントラセン等が挙げられる。
Specifically, boron difluoride phenyldiazonium salt, phosphorus hexafluoride diphenyliodonium salt, antimony hexafluoride diphenyliodonium salt, arsenic hexafluoride tri-4-methylphenylsulfonium salt, antimony tetrafluoride Tri-4-methylphenylsulfonium salt, tetrakis (pentafluorophenyl) boron diphenyliodonium salt, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridium salt, phosphorus hexafluoride allene-iron complex, etc. be able to. More specifically, CD-1012 (trade name: manufactured by SARTOMER), PCI-019, PCI-021 (trade name: manufactured by Nippon Kayaku Co., Ltd.), Optmer SP-150, Optomer SP-170 (trade name: Asahi) Denki Co., Ltd.), UVI-6990 (trade name: manufactured by Dow Chemical Co., Ltd.), CPI-100P, CPI-100A (trade name: manufactured by San Apro), TEPBI-S (trade name: manufactured by Nippon Shokubai Co., Ltd.), etc. These can be used alone or in combination of two or more.
A photosensitizer such as benzophenone, benzoin isopropyl ether, thioxanthone, and anthracene can be used in combination with the energy ray-sensitive cationic polymerization initiator of the present invention. Specifically, 4,4′-bis (diethylamino) benzophenone, 2,4′-diethylthioxanthone, isopropylthioxanthone, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and the like can be mentioned.
本発明の感光性組成物には、硬化性や硬化時の膜物性に悪影響を及ぼさない程度にカチオン重合性を示す他の化合物を添加することができる。これらの化合物としては、例えば水酸基を有するビニルエーテル化合物が挙げられる。ここで用いられる水酸基を有するビニルエーテル化合物としては、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、シクロヘキサンジオールモノビニルエーテル、９−ヒドロキシノニルビニルエーテル、プロピレングリコールモノビニルエーテル、ネオペンチルグリコールモノビニルエーテル、グリセロールジビニルエーテル、グリセロールモノビニルエーテル、トリメチロールプロパンジビニルエーテル、トリメチロールプロパンモノビニルエーテル、ペンタエリスリトールモノビニルエーテル、ペンタエリスリトールジビニルエーテル、ペンタエリスリトールトリビニルエーテル、ジエチレングリコールモノビニルエーテル、トリエチレングリコールモノビニルエーテル、テトラエチレングリコールモノビニルエーテル、トリシクロデカンジオールモノビニルエーテル、トリシクロデカンジメタノールモノビニルエーテル等を挙げることができる。 To the photosensitive composition of the present invention, other compounds exhibiting cationic polymerizability can be added to such an extent that the curability and the film physical properties upon curing are not adversely affected. Examples of these compounds include vinyl ether compounds having a hydroxyl group. Examples of the vinyl ether compound having a hydroxyl group used herein include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, cyclohexane dimethanol monovinyl ether, cyclohexanediol monovinyl ether, 9-hydroxynonyl vinyl ether, propylene glycol monovinyl ether, neopentyl glycol monovinyl ether, glycerol divinyl ether. Vinyl ether, glycerol monovinyl ether, trimethylolpropane divinyl ether, trimethylolpropane monovinyl ether, pentaerythritol monovinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether Ether, tetraethylene glycol monomethyl ether, tricyclodecane diol monovinyl ether and tricyclodecanedimethanol monovinyl ether and the like.
また、水酸基を含有しない多官能ビニルエーテルを併用することも可能である。これらのものとしては、例えばエチレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、シクロヘキサンジオールジビニルエーテル、トリメチロールプロパントリビニルエーテル、ペンタエリスリトールテトラビニルエーテル、グリセロールトリビニルエーテル、トリエチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル等を挙げることができる。
また、カチオン重合性を示す他の化合物としては、例えば前記以外の低分子量のエポキシ化合物は希釈剤として用いることでき、また前記以外の環状エーテル化合物や環状ラクトン化合物、環状アセタール化合物、環状チオエーテル化合物、スピロオルソエステル化合物等が挙げられる。また従来用いられる、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等の多価アルコールを、硬化性を損なわない範囲で用いることもできる。
It is also possible to use a polyfunctional vinyl ether containing no hydroxyl group. These include, for example, ethylene glycol divinyl ether, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, glycerol trivinyl ether, triethylene glycol divinyl ether, diethylene glycol. A divinyl ether etc. can be mentioned.
In addition, as other compounds exhibiting cationic polymerization, for example, low molecular weight epoxy compounds other than those described above can be used as diluents, and other cyclic ether compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, Examples include spiro orthoester compounds. Also, conventionally used polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane and pentaerythritol can be used as long as the curability is not impaired.
本発明の感光性組成物には、さらに必要に応じて（メタ）アクリレートモノマー類やオリゴマー類、および光ラジカル開始剤、消泡剤、レベリング剤、重合禁止剤、ワックス類、酸化防止剤、非反応性ポリマー、微粒子無機フィラー、シランカップリング剤、光安定剤、紫外線吸収剤、帯電防止剤、スリップ剤、腐食防止剤等を添加することもできる。腐食防止剤としては、例えば、イオン交換体、多価カルボン酸、ヒドロキシカルボン酸、有機錫化合物、スルフィド化合物等が挙げられる。
次に、本発明において用いられる感光性組成物中の各成分の組成割合について説明する。
The photosensitive composition of the present invention further includes (meth) acrylate monomers and oligomers, and photo radical initiators, antifoaming agents, leveling agents, polymerization inhibitors, waxes, antioxidants, A reactive polymer, fine particle inorganic filler, silane coupling agent, light stabilizer, ultraviolet absorber, antistatic agent, slip agent, corrosion inhibitor and the like can also be added. Examples of the corrosion inhibitor include ion exchangers, polyvalent carboxylic acids, hydroxycarboxylic acids, organic tin compounds, and sulfide compounds.
Next, the composition ratio of each component in the photosensitive composition used in the present invention will be described.
感光性組成物において、（ｂ）少なくとも２個の脂肪族水酸基を有する芳香族系化合物中の水酸基の官能基濃度（芳香族系化合物のモル数×１分子中の水酸基数と定義する）は、（ａ）カチオン重合性化合物中のカチオン重合性基の官能基濃度（カチオン重合性化合物のモル数×１分子中のカチオン重合性基数と定義する）以下であることが好ましい。これは、組成物中のカチオン重合性基に比べ水酸基が過剰に存在すると、光硬化性が不十分となったり、耐透湿性等の硬化膜特性が不十分となるためである。
実際の配合割合としては、成分（ａ）としてカチオン重合性化合物 １０〜９５質量％、成分（ｂ）として少なくとも２個の脂肪族水酸基を有する芳香族系化合物 ０．１〜９０質量％、成分（ｃ）としてエネルギー線感受性カチオン重合開始剤 ０．１〜２０質量％である。
In the photosensitive composition, (b) the functional group concentration of the hydroxyl group in the aromatic compound having at least two aliphatic hydroxyl groups (defined as the number of moles of the aromatic compound × the number of hydroxyl groups in one molecule) is: (A) The functional group concentration of the cationic polymerizable group in the cationic polymerizable compound (defined as the number of moles of the cationic polymerizable compound × the number of cationic polymerizable groups in one molecule) is preferable. This is because when the hydroxyl group is present in excess as compared with the cationically polymerizable group in the composition, the photocurability becomes insufficient and the cured film properties such as moisture permeability resistance become insufficient.
As an actual blending ratio, 10 to 95% by mass of the cationic polymerizable compound as the component (a), 0.1 to 90% by mass of the aromatic compound having at least two aliphatic hydroxyl groups as the component (b), and the component ( c) Energy ray-sensitive cationic polymerization initiator is 0.1 to 20% by mass.
成分（ａ）としては、前述のように光硬化性を特に向上させるためには、エポキシ基を有する化合物とオキセタン環を有する化合物を併用するのが好ましい。その配合割合は、エポキシ基を有する化合物１０重量部に対して、オキセタン環を有する化合物を０．１〜１０００重量部含むのが好ましく、より好ましくは１〜５００重量部、最も好ましくは１〜２００重量部である。ただし、光硬化性よりも耐透湿性を重視する場合にはこの限りではない。
成分（ｂ）の含有量は、０．１〜９０質量％、好ましくは１〜８０質量％、より好ましくは１〜７０質量％であると、前述のような理由により優れた光硬化性及び硬化膜特性が得られる。
As the component (a), in order to particularly improve the photocurability as described above, it is preferable to use a compound having an epoxy group and a compound having an oxetane ring in combination. The blending ratio preferably includes 0.1 to 1000 parts by weight of the compound having an oxetane ring with respect to 10 parts by weight of the compound having an epoxy group, more preferably 1 to 500 parts by weight, and most preferably 1 to 200 parts by weight. Parts by weight. However, this is not the case when moisture permeation resistance is more important than photocurability.
The content of the component (b) is 0.1 to 90% by mass, preferably 1 to 80% by mass, and more preferably 1 to 70% by mass. Film characteristics can be obtained.
成分（ｃ）の含有量は、０．１〜２０質量％であり、好ましくは０．２〜１５質量％である。生産性の観点から、開始剤を過剰に使用しない方が望ましく、開始剤を過剰に使用すると、光線透過率が低下し、膜底部の硬化が不足したり、腐食性が強くなる場合がある。また少な過ぎる場合、エネルギー線照射により発生する活性カチオン物質の量が不足し、十分な硬化性や硬化物が得られなくなる場合がある。
本発明のカチオン重合性感光性組成物及びその硬化物は、その優れた硬化性から重合転化率が高く、生産性に優れ、しかも接着性および耐透湿性に優れ腐食性も低いことから、光ディスクの光透過層の用途として好適である。
Content of a component (c) is 0.1-20 mass%, Preferably it is 0.2-15 mass%. From the viewpoint of productivity, it is desirable not to use an initiator excessively. If an initiator is used excessively, the light transmittance may be lowered, the film bottom may be insufficiently cured, and the corrosivity may be increased. Moreover, when there are too few, the quantity of the active cationic substance generated by energy ray irradiation may be insufficient, and sufficient curability and hardened | cured material may no longer be obtained.
Cationic polymerizable photosensitive composition and the cured product thereof of the present invention has high its excellent polymerization conversion rate of a curable, excellent productivity, moreover since also low excellent corrosion resistance to adhesion and moisture impermeability, the optical disk It is suitable as a use of the light transmission layer .
光ディスクの製造方法としては、例えば以下のような方法を挙げることができる。本発明の感光性組成物を、スピンコート法やスクリーン印刷法等の方法により記録層上に塗工した後、エネルギー線照射により塗工層を硬化させて光透過層を形成し、光ディスクを得る方法。また、２枚の基材を用意して、本発明の感光性組成物を一方の基材上に滴下、或いは塗工し、もう１枚の基材を重ね合わせ、必要に応じてスピンコート法等により組成物を均一に延ばした後、エネルギー線照射により硬化させて光ディスクを得る方法。或いは、２枚の基材を用意して、本発明の感光性組成物を一方の基材上に滴下或いは塗工した後、エネルギー線を照射し、もう１枚の基材を貼り合わせてから必要に応じてスピンコート法等により組成物を均一に延ばして、光ディスクを得る方法等がある。
As an optical disk manufacturing method, for example, the following method can be cited. After coating the photosensitive composition of the present invention on the recording layer by a method such as spin coating or screen printing, the coating layer is cured by irradiation with energy rays to form a light transmission layer to obtain an optical disc. Method. In addition, two base materials are prepared, the photosensitive composition of the present invention is dropped or coated on one base material, the other base material is overlapped, and a spin coating method is performed if necessary. A method of obtaining an optical disc by uniformly stretching the composition by, for example, and then curing it by irradiation with energy rays. Alternatively, after preparing two substrates and dropping or coating the photosensitive composition of the present invention on one substrate, irradiating with energy rays and bonding another substrate together. There is a method of obtaining an optical disc by uniformly extending the composition by a spin coating method or the like as necessary.
本発明の感光性組成物を硬化させるのに使用できる光源としては、所定の作業時間内で硬化させることができるものであれば特に制限はなく、通常、紫外線、可視光線の波長の光を照射できるものであり、例えば低圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライド灯、無電極放電ランプ等が挙げられる。
なお、硬化を促進するために、上記方法で得られたディスクを恒温槽、赤外線ヒーター等で加温しても良い。
光透過層の層厚は、所望とする光ディスクの特性や用途によって設定され、硬化処理前の塗工層の層厚は、所望とする光透過層の層厚に応じて設定すればよい。光透過層の層厚としては、例えば３〜２００μｍとすることができる。
The light source that can be used to cure the photosensitive composition of the present invention is not particularly limited as long as it can be cured within a predetermined working time, and is usually irradiated with light having a wavelength of ultraviolet or visible light. Examples thereof include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, xenon lamps, metal halide lamps, and electrodeless discharge lamps.
In order to accelerate curing, the disk obtained by the above method may be heated with a thermostatic bath, an infrared heater or the like.
The layer thickness of the light transmission layer is set according to the desired characteristics and use of the optical disc, and the layer thickness of the coating layer before the curing process may be set according to the desired layer thickness of the light transmission layer. The layer thickness of the light transmission layer can be, for example, 3 to 200 μm.
本発明に係わるシール材は、前記カチオン重合性感光性組成物及びその硬化物から成っており、その優れた硬化性から重合転化率が高く、生産性に優れ、しかも接着性および耐透湿性に優れることからＬＣＤ、ＥＬＤ、電子ペーパー等のＦＰＤ用シール材として好適である。とりわけ有機ＥＬＤ用シール材には、高い耐透湿性が求められることから、本発明に係わるシール材にとって最も好ましい適用例である。
フラットパネルディスプレイである有機ＥＬＤの製造方法としては、例えば以下のような方法を挙げることができる。一般的な有機ＥＬＤは、基板の上に正孔注入電極が形成され、その上部に正孔輸送層と発光層が形成され、さらにその上に電子注入電極が形成される。そして、これらの積層体の周囲には外部から素子を守るための封止材が形成され、この封止材は正孔注入電極と接着剤により張り合わされている。基板としては、透明または半透明なガラス、またはポリカーボネート、ポリエチレンテレフタレート、環状オレフィン系ポリマー等の樹脂等が用いられるが、これらの材料を薄膜化したフレキシブルな基板を用いることもできる。封止材としては、通常ステンレスやガラス等の水蒸気バリア性に優れた材料が用いられ、これを本発明の特徴であるカチオン重合性感光性組成物及びその硬化物から成るシール材を用いて、対向の正孔注入電極が形成された基板と張り合わされる。その他の封止構造としては固体膜による全面封止があり、封止材としてフレキシブルな材質のものを用いる場合、特に有効な方法である。
The sealing material according to the present invention is composed of the cationic polymerizable photosensitive composition and a cured product thereof, and from its excellent curability, the polymerization conversion rate is high, the productivity is excellent, and the adhesiveness and moisture permeability resistance are also high. Since it is excellent, it is suitable as a sealing material for FPD such as LCD, ELD, and electronic paper. In particular, since the organic ELD sealing material is required to have high moisture permeability, it is the most preferable application example for the sealing material according to the present invention.
As a manufacturing method of organic ELD which is a flat panel display, the following methods can be mentioned, for example. In a general organic ELD, a hole injection electrode is formed on a substrate, a hole transport layer and a light emitting layer are formed thereon, and an electron injection electrode is further formed thereon. A sealing material for protecting the element from the outside is formed around these laminates, and the sealing material is bonded to the hole injection electrode with an adhesive. As the substrate, transparent or translucent glass, or a resin such as polycarbonate, polyethylene terephthalate, or cyclic olefin polymer is used, but a flexible substrate obtained by thinning these materials can also be used. As the sealing material, a material excellent in water vapor barrier properties such as stainless steel and glass is usually used, and this is used by using a cationically polymerizable photosensitive composition which is a feature of the present invention and a sealing material comprising a cured product thereof. It is bonded to the substrate on which the opposite hole injection electrode is formed. Other sealing structures include full-surface sealing with a solid film, which is a particularly effective method when a flexible material is used as the sealing material.
基板上に、上記正孔注入電極、正孔輸送層、発光層、電子注入電極を形成する方法としては、公知の方法である抵抗加熱蒸着法やイオンビームスパッタ法等を用いて行うことができる。また、本発明に係わるシール材を基板上に塗布する方法としては、シール剤が均一に塗布できる方法であれば特に制約はないが、例えばスクリーン印刷、フレキソ印刷等の印刷法によるものやディスペンサーを用いて塗布する方法等が挙げられる。
このように塗布されたシール材は、対向する基板と張り合わされた後、封止材側または基板面側から光を照射することにより硬化が行われる。ここで使用できる光源としては、所定の作業時間内で硬化させることができるものであれば特に制限はなく、通常、紫外線、可視光線の波長の光を照射できるものであり、例えば低圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライド灯、無電極放電ランプ等が挙げられる。
As a method for forming the hole injection electrode, the hole transport layer, the light emitting layer, and the electron injection electrode on the substrate, a known method such as resistance heating vapor deposition or ion beam sputtering can be used. . Further, the method for applying the sealing material according to the present invention on the substrate is not particularly limited as long as the sealing agent can be applied uniformly. For example, a printing method such as screen printing or flexographic printing or a dispenser can be used. And a method of coating using the same.
The sealing material applied in this way is bonded to the opposing substrate, and then cured by irradiating light from the sealing material side or the substrate surface side. The light source that can be used here is not particularly limited as long as it can be cured within a predetermined working time, and is usually a light that can be irradiated with light having a wavelength of ultraviolet light or visible light. Examples include mercury lamps, ultra-high pressure mercury lamps, xenon lamps, metal halide lamps, and electrodeless discharge lamps.
本発明は、光硬化性に優れ、且つ接着性および耐透湿性や耐腐食性にも優れたカチオン重合性感光性組成物及びその硬化物を提供し、該硬化物から成るＦＰＤ用シール材、特には有機ＥＬＤ用シール材を提供するものであり、また本発明に係わるカチオン重合性感光性組成物の硬化物からなる光ディスクの光透過層を提供するものである。
The present invention is excellent in light-curable, and adhesion and penetration resistance provides moisture and cationic polymerizable photosensitive composition also excellent in corrosion resistance and a cured product thereof, FPD sealing material made of the cured product, especially is intended to provide an organic ELD sealing material, also provides an optical transmission layer of an optical disc comprising the cured product of the cationic polymerizable photosensitive composition according to the present invention.
本発明を実施例に基づいて説明する。なお、感光性組成物及びその硬化物を用いて光ディスクの光透過層や有機ＥＬＤのシール材を形成する工程は、実施例においては、本発明のカチオン重合性感光性組成物の光硬化特性および硬化後の接着性、透湿性、腐食性を評価することで、製造される光ディスク及び有機ＥＬＤの評価に代えるものとする。
＜硬化膜の特性評価＞
（１）光硬化性：ベルトコンベア式露光装置を用いて露光してから被膜を指触観察し、硬化完了までに必要な露光回数を求めた。
（２）接着性：ガラス基板上に形成された硬化膜（厚さ約１０μｍ）に対し碁盤目テープ
剥離試験を行い、残存率の測定を行った。硬くて脆い膜はこの試験で容易に剥離するため、可とう性についても同時に評価している。
（３）透湿性：ＪＩＳ Ｋ７１２９Ａに準じて、光硬化させたシール材により得たフィルム（厚み１００μｍ）の４０℃×９０％ＲＨ条件での透湿度を、水蒸気透過度テスター：Ｌ８０−５０００型（ＬＹＳＳＹ社製）を用い測定した。
（４）腐食性：アルミニウム薄膜付きシリコンウェハー上で硬化した被膜（厚さ約１０μｍ）を、温度９０℃、湿度８０％条件下にて１００時間放置した後、アルミニウムの表面状態を目視にて観察した。
The present invention will be described based on examples. In addition, the process of forming the light transmission layer of an optical disk and the sealing material of organic ELD using a photosensitive composition and its hardened | cured material in the Example WHEREIN: The photocurable characteristic of the cationically polymerizable photosensitive composition of this invention and By evaluating the adhesiveness, moisture permeability, and corrosivity after curing, the evaluation should be made in place of the manufactured optical disk and organic ELD.
<Characteristic evaluation of cured film>
(1) Photocurability: The film was exposed using a belt conveyor type exposure apparatus, and the coating film was touched to determine the number of exposures required until the curing was completed.
(2) Adhesiveness: cross-cut tape for a cured film (thickness of about 10 μm) formed on a glass substrate
A peel test was performed and the residual ratio was measured. Since a hard and brittle film peels easily in this test, the flexibility is also evaluated at the same time.
(3) Moisture permeability: According to JIS K7129A, the water vapor permeability tester: L80-5000 type was measured using a film obtained by a photocured sealing material (thickness: 100 μm) under the condition of 40 ° C. × 90% RH. (Manufactured by LYSSY).
(4) Corrosiveness: A film (thickness of about 10 μm) cured on a silicon wafer with an aluminum thin film is allowed to stand for 100 hours at a temperature of 90 ° C. and a humidity of 80%, and then the surface condition of the aluminum is visually observed. did.
なお、原材料として用いているＺＥ−２（製品名：明成化学工業社製）は、下記一般式（１３）で表される化合物である。
ZE-2 (product name: manufactured by Meisei Chemical Industry Co., Ltd.) used as a raw material is a compound represented by the following general formula (1 3 ).
成分（ａ）のカチオン重合性化合物に該当するものとして、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を２５質量％、及び１，４−ビス｛〔（３−エチルオキセタン−３−イル）メトキシ〕メチル｝ベンゼンを主成分とするアロンオキセタンＯＸＴ−１２１（製品名：東亞合成社製）を３７質量％、成分（ｂ）の少なくとも２個の脂肪族水酸基を有する芳香族系化合物に該当するものとして、ビス（２−ヒドロキシエチル）テトラブロモビスフェノールＡであるＴＢＡ−ＥＯ２０（製品名：明成化学工業社製）を２７質量％、更にポリオキシエチレンビスフェノールＡエーテルとしてユニオールＤＡ−４００（製品名：日本油脂社製）を７質量％、成分（ｃ）のエネルギー線感受性カチオン重合開始剤としてスルホニウムＰＦ６塩型のＣＰＩ−１００Ｐ（製品名：サンアプロ社製）４質量％を十分混合することにより透明な感光性組成物を得た。
このようにして得られた感光性組成物の特性を評価するために、まずバーコーターを用い膜厚５０μｍになるように塗工した後、ベルトコンベア式ＵＶランプシステム（Ｖバルブ、光源距離１２３ｍｍ、ベルトコンベアスピード１６ｍ／ｍｉｎ：フュージョンＵＶシステムズ・ジャパン社製）を用いて光硬化性を評価した。また、バーコーターを用い膜厚１０μｍになるように塗工した後、４００Ｗ高圧水銀灯露光機（セン特殊光源社製）で１０００ｍＪ／ｃｍ ２ 露光し、硬化膜の接着性及び腐食性の評価を行った。なお透湿度測定用フィルム作成は、剥離処理ＰＥＴフィルム上で３０００ｍＪ／ｃｍ ２ 露光を行って感光性組成物を硬化させた後、剥離処理ＰＥＴフィルムを剥がすことにより行った。結果を表１に示す。
As corresponding to the cationically polymerizable compound of component (a), 25% by mass of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 1,4-bis {[(3-ethyloxetane- Aron oxetane OXT-121 (product name: manufactured by Toagosei Co., Ltd.) containing 3-yl) methoxy] methyl} benzene as a main component, 37% by mass, and an aromatic system having at least two aliphatic hydroxyl groups as component (b) As a compound, TBA-EO20 (product name: manufactured by Meisei Chemical Co., Ltd.), which is bis (2-hydroxyethyl) tetrabromobisphenol A, is 27% by mass, and UNIOL DA-400 as polyoxyethylene bisphenol A ether. 7% by mass (product name: manufactured by NOF Corporation), energy ray sensitive cation of component (c) CPI-100P sulfonium PF6 salt as initiator (product name: manufactured by San-Apro Ltd.) to obtain a transparent photosensitive composition by a 4 wt% be sufficiently mixed.
In order to evaluate the characteristics of the photosensitive composition thus obtained, first, coating was performed to a film thickness of 50 μm using a bar coater, and then a belt conveyor type UV lamp system (V bulb, light source distance 123 mm, Photocurability was evaluated using a belt conveyor speed of 16 m / min (manufactured by Fusion UV Systems Japan). In addition, after coating with a bar coater to a film thickness of 10 μm, the film was exposed to 1000 mJ / cm 2 with a 400 W high pressure mercury lamp exposure machine (manufactured by Sen Special Light Source Co., Ltd.) to evaluate the adhesiveness and corrosivity of the cured film. It was. The film for measuring moisture permeability was prepared by peeling the release-treated PET film after exposing the release composition to 3000 mJ / cm 2 to cure the photosensitive composition. The results are shown in Table 1.
［実施例２］
成分（ａ）として、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を８０質量％、成分（ｂ）としてＴＢＡ−ＥＯ２０を１６質量％、成分（ｃ）としてＣＰＩ−１００Ｐ（商品名：サンアプロ社製）４質量％を十分混合することにより透明な感光性組成物を得た。特性評価は実施例１と同様にして行った。結果を表１に示す。
［実施例３］
成分（ｂ）としてＺＥ−２を１６質量％用いる以外は、実施例２と同様にして感光性組成物を得、特性評価を行った。結果を表１に示す。
［実施例４］
成分（ａ）として、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を２１質量％、及びアロンオキセタンＯＸＴ−１２１を４２質量％、成分（ｂ）としてＴＢＡ−ＥＯ２０を１４質量％、ユニオールＤＡ−４００を２１質量％、成分（ｃ）としてＣＰＩ−１００Ｐを２質量％の割合で配合し、十分混合することにより透明な感光性組成物を得た。特性評価は実施例１と同様にして行った。結果を表１に示す。
[Example 2]
As component (a), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is 80% by mass, as component (b) is 16% by mass of TBA-EO20, and as component (c) is CPI-100P (product) A transparent photosensitive composition was obtained by sufficiently mixing 4% by mass (name: San Apro). Characteristic evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
[Example 3]
A photosensitive composition was obtained in the same manner as in Example 2 except that 16% by mass of ZE-2 was used as the component (b), and the characteristics were evaluated. The results are shown in Table 1.
[Example 4]
As component (a), 21% by mass of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 42% by mass of Aron oxetane OXT-121, and 14% by mass of TBA-EO20 as component (b) A transparent photosensitive composition was obtained by blending 21% by mass of Uniol DA-400 and 2% by mass of CPI-100P as component (c) and mixing them sufficiently. Characteristic evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
［比較例１］
成分（ａ）として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を９６質量％、及び成分（ｃ）としてＣＰＩ−１００Ｐを４質量％から成るエポキシ樹脂のみで構成される感光性組成物を得た。この組成物の性能評価結果を表１に示す。
［比較例２］
成分（ａ）として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を４８質量％、及びアロンオキセタンＯＸＴ−１２１を４８質量％、成分（ｃ）としてＣＰＩ−１００Ｐを４質量％の割合で配合し、十分混合することにより透明な感光性組成物を得た。特性評価は実施例１と同様にして行った。結果を表１に示す。
［比較例３］
成分（ａ）として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を８１質量％、成分（ｃ）としてＣＰＩ−１００Ｐを４質量％、一般的な脂肪族アルコールとしてジエチレングリコール１５質量％を十分混合することにより透明な感光性組成物を得た。特性評価は実施例１と同様にして行った。結果を表１に示す。
[Comparative Example 1]
Photosensitivity comprising only an epoxy resin comprising 96% by mass of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as component (a) and 4% by mass of CPI-100P as component (c). A composition was obtained. The performance evaluation results of this composition are shown in Table 1.
[Comparative Example 2]
48% by mass of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as component (a) and 48% by mass of Alonoxetane OXT-121, 4% by mass of CPI-100P as component (c) The transparent photosensitive composition was obtained by mix | blending in a ratio and fully mixing. Characteristic evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
[Comparative Example 3]
81% by mass of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as component (a), 4% by mass of CPI-100P as component (c), 15% by mass of diethylene glycol as a general aliphatic alcohol Was sufficiently mixed to obtain a transparent photosensitive composition. Characteristic evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
以上の結果から、本発明に係わるカチオン重合性感光性組成物は、比較例に示されるエポキシ樹脂単独系、エポキシ樹脂とオキセタン化合物の併用系、エポキシ樹脂と汎用の脂肪族アルコールの併用系等から成る従来のカチオン型感光性組成物に比べ、優れた光硬化性かつ十分な接着性を有しながら、優れた耐透湿性及び耐腐食性を示すことがわかる。このことから、本発明に係わるカチオン重合性感光性組成物及びその硬化物を用いて光透過層を形成される光ディスクや、本発明に係わるカチオン重合性感光性組成物をシール材とするＬＣＤ、有機ＥＬＤ、電位ペーパー等のフラットパネルディスプレイは、本感光性組成物の優れた光硬化性から高い生産性が期待でき、且つ得られる硬化膜の耐透湿性と耐腐食性が従来に比べ優れていることから、製品寿命の大幅な改善が期待でき、これまで以上に信頼性の高い光ディスク及びＦＰＤの提供を可能とするものである。 From the above results, the cationically polymerizable photosensitive composition according to the present invention is based on the epoxy resin alone system, the combined system of epoxy resin and oxetane compound, the combined system of epoxy resin and general-purpose aliphatic alcohol, etc. shown in Comparative Examples. It can be seen that, as compared with the conventional cationic photosensitive composition, it exhibits excellent moisture resistance and corrosion resistance while having excellent photocurability and sufficient adhesion. From this, the cation polymerizable photosensitive composition according to the present invention and an optical disk in which a light transmission layer is formed using the cured product thereof, an LCD using the cation polymerizable photosensitive composition according to the present invention as a sealing material, Flat panel displays such as organic ELDs and potential papers can be expected to have high productivity due to the excellent photocurability of the photosensitive composition, and the cured film obtained has superior moisture resistance and corrosion resistance compared to conventional products. Therefore, it is possible to expect a significant improvement in product life and to provide an optical disk and FPD with higher reliability than ever.
本発明の感光性組成物及びその硬化物は、これまでのエポキシ化合物からなる感光性組成物同様、高い透明性及び硬化収縮も小さく接着性も高いといった性能を保持しながら、優れた光硬化性、耐透湿性及び耐腐食性というこれまでにない性質を持っていることから、光ディスク及びフラットパネルディスプレイの分野で好適に利用できる。 The photosensitive composition of the present invention and its cured product, like the conventional photosensitive compositions composed of epoxy compounds, have excellent photocurability while maintaining high transparency and performance such as low curing shrinkage and high adhesion. Since it has unprecedented properties of moisture permeability and corrosion resistance, it can be suitably used in the fields of optical disks and flat panel displays.
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| CA2911352A1 (en) | 2013-05-10 | 2014-11-13 | British Columbia Cancer Agency Branch | Ester derivatives of androgen receptor modulators and methods for their use |
| US9375496B2 (en) | 2013-09-09 | 2016-06-28 | British Columbia Cancer Agency Branch | Halogenated compounds for cancer imaging and treatment and methods for their use |
| KR101832522B1 (en) * | 2013-11-29 | 2018-04-04 | 주식회사 엘지화학 | Composition for forming adhesive film, adhesive film before light curing for further processing, adhesive film and electronic paper display |
| CA2973036A1 (en) | 2015-01-13 | 2016-07-21 | British Columbia Cancer Agency Branch | Heterocyclic compounds for cancer imaging and treatment and methods for their use |
| US10471023B2 (en) | 2015-03-12 | 2019-11-12 | British Columbia Cancer Agency Branch | Bisphenol ether derivatives and methods for using the same |
| US20170298033A1 (en) | 2016-04-15 | 2017-10-19 | The University Of British Columbia | Bisphenol derivatives and their use as androgen receptor activity modulators |
| WO2019226991A1 (en) | 2018-05-25 | 2019-11-28 | Essa Pharma, Inc. | Androgen receptor modulators and methods for their use |
| CN113195441B (en) | 2018-10-18 | 2024-07-12 | 埃萨制药股份有限公司 | Androgen receptor modulators and methods of use thereof |
| JP7197609B2 (en) * | 2019-01-17 | 2022-12-27 | デンカ株式会社 | Sealing agent, cured body, organic electroluminescence display device, and method for manufacturing device |
| US12109179B2 (en) | 2019-03-28 | 2024-10-08 | Essa Pharma Inc. | Pharmaceutical compositions and combinations comprising inhibitors of the androgen receptor and uses thereof |
| JP2023522040A (en) | 2020-04-17 | 2023-05-26 | エッサ ファーマ，インコーポレイテッド | Solid forms of N-terminal domain androgen receptor inhibitors and uses thereof |
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| DE59701299D1 (en) * | 1996-07-29 | 2000-04-27 | Ciba Sc Holding Ag | Liquid, radiation-curable composition, especially for stereolithography |
| JP4197361B2 (en) * | 1996-12-02 | 2008-12-17 | 株式会社Ａｄｅｋａ | Optical three-dimensional modeling resin composition and optical three-dimensional modeling method |
| JP2000204108A (en) * | 1999-01-13 | 2000-07-25 | Jsr Corp | Photocurable resin composition |
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