WO2018225544A1 - Photocurable composition and electronic component adhesive - Google Patents
Photocurable composition and electronic component adhesive Download PDFInfo
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- WO2018225544A1 WO2018225544A1 PCT/JP2018/020226 JP2018020226W WO2018225544A1 WO 2018225544 A1 WO2018225544 A1 WO 2018225544A1 JP 2018020226 W JP2018020226 W JP 2018020226W WO 2018225544 A1 WO2018225544 A1 WO 2018225544A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photocurable composition
- composition according
- compound
- liquid crystal
- group
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 98
- 239000000853 adhesive Substances 0.000 title claims abstract description 26
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 26
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 68
- 239000000565 sealant Substances 0.000 claims abstract description 39
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000004956 cell adhesive effect Effects 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 95
- -1 acrylic compound Chemical class 0.000 claims description 55
- 239000004593 Epoxy Substances 0.000 claims description 30
- 239000010419 fine particle Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000012766 organic filler Substances 0.000 claims description 15
- 239000011256 inorganic filler Substances 0.000 claims description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 150000007524 organic acids Chemical group 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 36
- 239000000758 substrate Substances 0.000 description 18
- 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 16
- 238000001723 curing Methods 0.000 description 16
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 15
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- 239000003822 epoxy resin Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
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- 239000007983 Tris buffer Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003999 initiator Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 10
- 239000007870 radical polymerization initiator Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 8
- 238000010526 radical polymerization reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
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- 230000001588 bifunctional effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
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- 125000005647 linker group Chemical group 0.000 description 6
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- 125000001424 substituent group Chemical group 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
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- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 description 4
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
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- 230000009257 reactivity Effects 0.000 description 4
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- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229930192627 Naphthoquinone Natural products 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 125000001931 aliphatic group Chemical group 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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 150000002791 naphthoquinones Chemical class 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
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- 125000006850 spacer group Chemical group 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
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- 150000003512 tertiary amines Chemical class 0.000 description 3
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 2
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OVJHMJJVXOJMBB-UHFFFAOYSA-N 2-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)ethyl prop-2-enoate Chemical compound C1CCCC2C(=O)N(CCOC(=O)C=C)C(=O)C21 OVJHMJJVXOJMBB-UHFFFAOYSA-N 0.000 description 2
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- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- OBGBGHKYJAOXRR-UHFFFAOYSA-N 2-methoxy-1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C(OC)=CC(=O)C2=C1 OBGBGHKYJAOXRR-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-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
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 description 2
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- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
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- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 1
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OXAGUPFRAIIDLT-UHFFFAOYSA-N heptanedihydrazide Chemical compound NNC(=O)CCCCCC(=O)NN OXAGUPFRAIIDLT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- IFZUFHWISBKFJP-UHFFFAOYSA-N n'-[4-[dimethoxy(methyl)silyl]oxybutyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)OCCCCNCCN IFZUFHWISBKFJP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- DDOVHJODVHQLCS-UHFFFAOYSA-N pyridine-2,6-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=N1 DDOVHJODVHQLCS-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
Definitions
- the present invention relates to a photocurable composition, an adhesive for electronic parts, an electronic part, an adhesive for liquid crystal display cells, a liquid crystal sealant, and a liquid crystal display cell using the same.
- Photo-curable compositions are widely used in adhesive applications for electronic parts such as display sealants, solar cell sealants, and semiconductor sealants.
- Examples of the display sealant include a liquid crystal display sealant, an organic EL display sealant, and a touch panel adhesive. These sealants for display are required to have excellent curability and low outgassing and do not damage the display element.
- the photocurable composition does not undergo a curing reaction in a portion where light does not reach, there is a limit to the portion that can be used.
- liquid crystal sealant for a liquid crystal dropping method
- liquid crystal sealant when the liquid crystal sealant is exposed to light by the wiring portion of the array substrate of the liquid crystal display element or the black matrix portion of the color filter substrate.
- the problem of poor display in the vicinity of the seal is more serious than before.
- the primary curing by light becomes insufficient due to the presence of the light shielding portion, a large amount of uncured components remain in the liquid crystal sealant.
- the process proceeds to the secondary curing step by heat in this state, the dissolution of the uncured component in the liquid crystal is promoted by the heat, causing a display defect near the seal.
- Patent Documents 1 and 2 disclose a method using a thermal radical polymerization initiator.
- Patent Documents 3 to 5 disclose a method using a polyvalent carboxylic acid as a curing accelerator.
- the molecular weight in order to efficiently generate radicals in the thermal radical polymerization initiator, the molecular weight must be small to some extent, but low molecular compounds are easily dissolved in liquid crystals and have excellent reactivity, but thermal radical polymerization starts. Liquid crystal contamination by the agent itself becomes a problem. Moreover, when polyvalent carboxylic acid is used, there is a possibility that the moisture resistance reliability may be impaired, and it may not be used depending on the application.
- liquid crystal sealants have been developed very vigorously, but liquid crystal sealants that have excellent light-shielding part curability and low liquid crystal contamination have not yet been realized. Not.
- An object of the present invention is to provide a photocurable composition that is cured by irradiation with light such as ultraviolet light and visible light, and has high sensitivity to light and can be sufficiently cured even by low energy light. To do.
- a photocurable composition containing a compound having both an oxime ester structure and a thioxanthone structure in the molecule [2] The photocurable composition according to [1], which contains a curable compound. [3] The photocurable composition according to [2], wherein the curable compound is a (meth) acrylic compound. [4] The photocurable composition according to [2], wherein the curable compound is a mixture of a (meth) acrylic compound and an epoxy compound. [5] The photocurable composition according to any one of [1] to [4], which contains an organic filler.
- the photocurable composition of the present invention has high curability in a portion where light is not sufficiently irradiated, and has sufficient curability even with low-energy light irradiation considering damage to other members. It is useful as a sealing agent for electronic components or an adhesive for electronic components, particularly a sealing agent for displays, which is used in the manufacture of electronic components having the above and electronic components that need to be cured by visible light.
- the photocurable composition according to the present embodiment contains a compound having both an oxime ester structure and a thioxanthone structure in the molecule (hereinafter also referred to as “specific compound”).
- This specific compound functions as a photopolymerization initiator having a very high sensitivity to low energy light.
- a specific compound may be used individually by 1 type, and may use 2 or more types together.
- the oxime ester structure possessed by the specific compound is, for example, a structure represented by the following formula (1).
- R 1 represents a (C1-C8) alkyl group or a (C1-C8) alkoxy group
- R 2 represents a hydrogen atom, a (C1-C8) alkyl group, or a (C2-C8) alkenyl group. Represents an aryl group or a heteroaryl group.
- Examples of the (C1-C8) alkyl group for R 1 in the above formula (1) include a linear, branched, or cyclic unsubstituted group, and a linear one is preferable. Specific examples include linear groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-hentyl group, n-hexyl group, n-heptyl group, n-octyl group; isopropyl group Branched chain groups such as isobutyl group, sec-butyl group and tert-butyl group; cyclic groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group;
- the (C1-C8) alkyl group may be a group in which a chain alkyl group and a cyclic alkyl group are bonded, such as a 3-cyclopentylpropyl group.
- a (C1-C3) alkyl group is preferable from the viewpoint of compatibility with a curable compound or a solvent, and specific examples include a methyl group, an ethyl group, and an n-propyl group, and a methyl group is more preferable. .
- Examples of the (C1-C8) alkoxy group for R 1 in the above formula (1) include a linear or branched unsubstituted group, and a linear one is preferred. Specific examples include linear groups such as methoxy group, ethoxy group, n-propoxy group and n-butoxy group; branched chain groups such as isopropoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group. And the like. Among these, a methoxy group is preferable.
- R 1 is preferably a methyl group.
- the (C1-C8) alkyl group in R 2 in the above formula (1) has the same meaning as the (C1-C8) alkyl group in R 1 , including preferred ones.
- Examples of the (C2-C8) alkenyl group for R 2 in the above formula (1) include linear or branched unsubstituted groups. Specific examples include vinyl group, 1-propenyl group, 2-propenyl group and the like.
- Examples of the aryl group and heteroaryl group in R 2 in the above formula (1) include a phenyl group, a pyridyl group, and a thienyl group.
- the aryl group and heteroaryl group are substituted with at least one substituent such as a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, an alkyl group, and an alkoxy group. Also good.
- substituent such as a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, an alkyl group, and an alkoxy group.
- substituent such as a carboxy group, a sulfo
- R 2 is preferably a hydrogen atom or a methyl group.
- a bonding position which may be a bonding position with a thioxanthone structure represented by the following formula (2), and the bonding group in the case of bonding to the thioxanthone structure through another bonding group. It may be a coupling position.
- the linking group include an alkylene group, an alkylidene group, and an alkylene oxide group.
- the thioxanthone structure possessed by the specific compound is a structure represented by the following formula (2).
- the thioxanthone structure represented by the above formula (2) may have other substituents in addition to the oxime ester structure represented by the above formula (1).
- substituents include carboxy group, sulfo group, hydroxy group, acetylamino group, halogen atom, cyano group, nitro group, sulfamoyl group, (C1-C8) alkyl group, (C1-C8) alkoxy group, and the like. It is done.
- the substituent may be bonded to R 1 in the formula (1) to form a cyclic structure.
- Specific examples of the specific compound include compounds having the following compound numbers 1 to 20. However, it is not limited to these. Of the compounds of compound numbers 1 to 20, compounds of compound numbers 1 to 17 and 20 are preferred, and compounds of compound number 1 are more preferred.
- the specific compound generates radicals by irradiation with light such as ultraviolet light and visible light, has high sensitivity to light, and exhibits sufficient reactivity even with low energy light. It also has good thermal stability, low volatility, good storage stability, and good solubility and is suitable for photopolymerization in the presence of air (oxygen). Therefore, the specific compound is useful as a photopolymerization initiator for polymerizing a curable compound capable of radical polymerization.
- the content of the specific compound is usually 0.001 to 10% by mass, preferably 0.002 to 5.0% by mass, and more preferably 0.1 to 3.% by mass in the total amount of the photocurable composition. 0% by mass.
- the content of the specific compound is 0.001% by mass or more, the photopolymerization of the photocurable composition tends to proceed sufficiently.
- the content of the specific compound is 10% by mass or less, the number of unreacted compounds decreases. As a result, deterioration of light resistance and storage stability of the photocurable composition and adverse effects on display characteristics when the photocurable composition is used as a sealant for display elements tend to be suppressed.
- the photocurable composition concerning this embodiment may contain other photoinitiators other than the above-mentioned specific compound.
- the other photopolymerization initiator is not particularly limited as long as it is a compound that generates a radical, an acid, a base, or the like by irradiation with ultraviolet light or visible light and initiates a chain polymerization reaction.
- photopolymerization initiators include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [ 4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl disulfide and the like.
- Examples of the photopolymerization initiator having an absorbance at the maximum absorption wavelength ( ⁇ max) in the wavelength region of 200 to 300 nm of 500 or more include IRGACURE RTM 651, 184, and 2959. Examples of the photopolymerization initiator having an absorbance at the maximum absorption wavelength ( ⁇ max) in the wavelength region of 200 to 300 nm of 1500 or more include IRGACURE RTM 2959.
- the photopolymerization initiator preferably has a molecular weight of 150 to 1000 from the viewpoint of preventing outgassing.
- those having a (meth) acryl group in the molecule are preferable, for example, 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy
- the reaction product with 2-methyl-1-propan-1-one is preferably used. This compound can be produced by the method described in International Publication No. 2006/027982.
- the content is preferably 0.001 to 10% by mass in the total amount of the photocurable composition, More preferably, the content is 1 to 5.0% by mass.
- the photocurable composition according to the present embodiment may contain a photoinitiation assistant such as a tertiary amine in order to further improve the curability.
- a photoinitiation assistant such as a tertiary amine
- the tertiary amines include, but are not limited to, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and the like.
- a high molecular weight compound in which a plurality of tertiary amines are branched with a polyhydric alcohol or the like in one molecule can also be used as appropriate.
- the content is preferably 0.005 to 20% by mass in the total amount of the photocurable composition, 0.01 More preferably, it is ⁇ 10% by mass.
- the photocurable composition according to this embodiment preferably contains a curable compound.
- a curable compound preferably contains a curable compound.
- (meth) acrylic compounds such as a (meth) acrylic ester compound and an epoxy (meth) acrylate compound, are preferable.
- a (meth) acryl compound may be used individually by 1 type, and may use 2 or more types together.
- (meth) acrylic ester compounds include N-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane-1,4-dimethanol mono (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy (meta ) Acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromo Enyloxyethyl (meth) acrylate, dicyclopentanyl
- the epoxy (meth) acrylate compound can be obtained by a known method by reacting an epoxy compound with (meth) acrylic acid. Although it does not specifically limit as an epoxy compound used as a raw material, The epoxy compound more than bifunctional is preferable.
- the bifunctional or higher functional epoxy compound include resorcin diglycidyl ether, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolak type Epoxy compounds, bisphenol F novolac type epoxy compounds, alicyclic epoxy compounds, aliphatic chain epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, hydantoin type epoxy compounds, isocyanurate type epoxy compounds, triphenolmethane skeleton Phenol novolac-type epoxy compounds having di- and diglycidyl ethers of bifunctional phenols (catechol, resorcinol, etc.)
- the photocurable composition according to the present embodiment when used as a liquid crystal sealant, bisphenol A type epoxy compounds and resorcin diglycidyl ether are preferable from the viewpoint of liquid crystal contamination.
- the ratio of the epoxy group and the (meth) acryloyl group in the epoxy (meth) acrylate compound is not particularly limited, and is appropriately selected from the viewpoint of process compatibility.
- the photocurable composition according to this embodiment preferably contains an epoxy compound (excluding the (meth) acrylic compound) in addition to the (meth) acrylic compound.
- An epoxy compound may be used individually by 1 type, and may use 2 or more types together.
- the epoxy compound is not particularly limited, but a bifunctional or higher functional epoxy compound is preferable.
- the bifunctional or higher functional epoxy compound include resorcin diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type Epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, triphenolmethane skeleton Phenol novolac epoxy resin containing diglycidyl etherified products of bifunctional phenols (catechol, resorcinol, etc.), difunctional alcohols Glycidyl etherified product, and the like thereof halide or hydrogenated product.
- the photocurable composition according to the present embodiment is
- the content thereof is usually 10 to 80% by mass, preferably 20 to 70% by mass, based on the total amount of the photocurable composition. is there.
- the photocurable composition according to this embodiment contains an epoxy compound, the content is usually 5 to 50% by mass, preferably 5 to 30% by mass, based on the total amount of the photocurable composition. It is.
- the photocurable composition according to the present embodiment may contain an organic filler.
- An organic filler may be used individually by 1 type, and may use 2 or more types together.
- Examples of the organic filler include urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles.
- examples of the silicone fine particles include KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.); Trefill RTM E-5500, 9701, EP-2001 (manufactured by Toray Dow Corning Co., Ltd.). preferable.
- As urethane fine particles JB-800T and HB-800BK (manufactured by Negami Industrial Co., Ltd.) are preferable.
- styrene fine particles Lavalon RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, and SJ6300C (manufactured by Mitsubishi Chemical Corporation) are preferable.
- styrene olefin fine particles Septon RTM SEPS 2004 and SEPS 2063 (manufactured by Kuraray Co., Ltd.) are preferable.
- These organic fillers may be core-shell organic fillers using two or more materials.
- acrylic fine particles and silicone fine particles are preferable.
- acrylic fine particles an acrylic rubber having a core-shell structure composed of two kinds of acrylic rubber is preferable, and the core layer is preferably n-butyl acrylate and the shell layer is more preferably methyl methacrylate.
- Acrylic fine particles whose core layer is n-butyl acrylate and whose shell layer is methyl methacrylate are sold by Aika Kogyo Co., Ltd. as Zefiac RTM F-351.
- Silicone fine particles include organopolysiloxane cross-linked powder, linear dimethylpolysiloxane cross-linked powder, and a composite silicone rubber in which a silicone resin (for example, polyorganosilsesquioxane resin) is coated on the surface of the silicone rubber.
- a silicone resin for example, polyorganosilsesquioxane resin
- Etc is a silicone rubber of a linear dimethylpolysiloxane crosslinked product powder, or a composite silicone rubber fine particle of a silicone resin-coated linear dimethylpolysiloxane crosslinked product powder.
- the shape of the rubber powder is preferably a sphere with little increase in viscosity after addition.
- the content is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the photocurable composition. .
- the photocurable composition according to this embodiment may contain an inorganic filler.
- An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
- examples of the inorganic filler include silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, and hydroxide.
- Examples include magnesium, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably fused silica, crystalline silica, silicon nitride, boron nitride, carbonic acid
- the particles include calcium, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, and aluminum silicate, and particles such as silica, alumina, and talc are preferable.
- the average particle size of the inorganic filler is suitably 2000 nm or less, preferably 1000 nm or less, more preferably 300 nm or less.
- the average particle diameter of the inorganic filler is 2000 nm or less, for example, when producing a narrow gap liquid crystal cell using the photocurable composition according to the present embodiment as a liquid crystal sealing agent for a liquid crystal dropping method, the upper and lower There is a tendency that a gap can be formed well when a glass substrate is bonded.
- a preferable minimum is about 10 nm, More preferably, it is about 100 nm.
- the particle diameter can be measured with a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
- the content of the photocurable composition according to the present embodiment contains an inorganic filler
- the content is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the photocurable composition. .
- the adhesive strength to the glass substrate is improved and the moisture resistance reliability is also improved, so that a decrease in the adhesive strength after moisture absorption tends to be suppressed.
- the content of the inorganic filler is 50% by mass or less, for example, when the liquid crystal cell is produced using the photocurable composition according to the present embodiment as a liquid crystal sealing agent for a liquid crystal dropping method, the inorganic filler is crushed. It tends to be easier and better.
- the photocurable composition according to this embodiment may contain a silane coupling agent in order to improve adhesive strength and moisture resistance.
- a silane coupling agent may be used individually by 1 type, and may use 2 or more types together.
- silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl).
- Ethyltrimethoxysilane N-phenyl- ⁇ -aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxy Silane 3-chloropropyl methyl dimethoxy silane, 3-chloropropyl trimethoxy silane, and the like. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. as KBM series, KBE series, etc., they are easily available from
- the content is preferably 0.05 to 3% by mass in the total amount of the photocurable composition.
- thermosetting agent The photocurable composition according to this embodiment may contain a thermosetting agent.
- a thermosetting agent may be used individually by 1 type, and may use 2 or more types together.
- thermosetting agent reacts nucleophilically with an unshared electron pair or an anion in the molecule, and examples thereof include polyvalent amines, polyhydric phenols, and organic acid hydrazide compounds. Among these, organic acid hydrazide compounds are preferably used.
- examples of the aromatic hydrazide compound include terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzenetrihydrazide, 1, Examples include 4,5,8-naphthoic acid tetrahydrazide and pyromellitic acid tetrahydrazide.
- Examples of the aliphatic hydrazide compound among the organic acid hydrazide compounds include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and pimelic acid dihydrazide.
- organic acid hydrazide compounds isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) are selected from the balance between curing reactivity and potential. ) Isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, and tris (3-hydrazinocarbonylpropyl) isocyanurate are preferred, and tris (2-hydrazinocarbonylethyl) isocyanurate is more preferred.
- the content is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the photocurable composition. %.
- the photocurable composition according to this embodiment may contain a thermal radical polymerization initiator in order to improve the curing rate and curability.
- a thermal radical polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
- the thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction, such as organic peroxide, azo compound, benzoin compound, benzoin ether compound, acetophenone compound, benzopinacol, etc. And benzopinacol is preferably used.
- organic peroxides include Kayamek RTM A, M, R, L, LH, SP-30C, Parkadox CH-50L, BC-FF, Cadox B-40ES, Parkadox 14, Trigonox RTM 22-70E. 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl RTM B, Parkardox 16, Kayacaron RTM BIC-75, AIC-75 (above, manufactured by Kayaku Akzo Co., Ltd.); Permec RTM N, H, S, F, D, G, Perhexa RTM H, HC, TMH, C, V, 22, MC, Pakyua RTM AH, AL, HB, Perbutyl RTM H, C, ND, L , Pakumi RTM H, D, PEROYL RTM IB
- examples of commercially available azo compounds include VA-044, 086, V-070, VPE-0201, VSP-1001 (above, manufactured by Wako Pure Chemical Industries, Ltd.) and the like.
- the content thereof is usually 0.0001 to 10% by mass in the total amount of the photocurable composition, preferably 0.00. It is 0005 to 5% by mass, and more preferably 0.001 to 3% by mass.
- the photocurable composition concerning this embodiment may contain additives, such as a hardening accelerator, a radical polymerization inhibitor, a pigment, a leveling agent, an antifoamer, and a solvent, as needed.
- additives such as a hardening accelerator, a radical polymerization inhibitor, a pigment, a leveling agent, an antifoamer, and a solvent, as needed.
- Examples of the curing accelerator include organic acids and imidazoles.
- Examples of the organic acid include organic carboxylic acid and organic phosphoric acid, and organic carboxylic acid is preferable. Specifically, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, tris (2-Carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (2-carboxypropyl) isocyanurate, bis (2-carboxyethyl) isocyanurate and the like.
- imidazole compounds examples include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl-2.
- the content thereof is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the photocurable composition. %.
- the radical polymerization inhibitor is not particularly limited as long as it is a compound that prevents polymerization by reacting with radicals generated from a photo radical polymerization initiator or a thermal radical polymerization initiator, and is not limited to quinone, piperidine, hinders. Examples include radical polymerization inhibitors such as dophenol and nitroso.
- naphthoquinone 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethyl-4 -Hydroxypiperidine-1-oxyl, 2,2,6,6, -tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxyl, hydroquinone 2-methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearyl ⁇ - (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis 4-ethyl-6-tert-but
- Adeka Adeka and the like.
- naphthoquinone, hydroquinone, nitroso, and piperidine radical polymerization inhibitors are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, polystop 7300P ( Hakuto Co., Ltd.) is more preferable, and Polystop 7300P (Hakuto Co., Ltd.) is more preferable.
- the content thereof is usually 0.0001 to 1% by mass, preferably 0.001 in the total amount of the photocurable composition. It is -0.5 mass%, More preferably, it is 0.01-0.2 mass%.
- the viscosity at 25 ° C. of the photocurable composition according to this embodiment is preferably 150 to 500 Pa ⁇ s, more preferably 200 to 500 Pa ⁇ s.
- the viscosity of the photocurable composition at 25 ° C. is preferably 250 to 400 Pa ⁇ s, and more preferably 280 to 320 Pa ⁇ s.
- Examples of the method for preparing the photocurable composition according to this embodiment include the following methods. First, the specific compound is heated and dissolved in the curable compound. Subsequently, after cooling to room temperature, an organic filler, an inorganic filler, a silane coupling agent, a thermosetting agent, a thermal radical polymerization initiator, an antifoaming agent, a leveling agent, a solvent, etc. are added as needed. And the photocurable composition which concerns on this embodiment can be prepared by mixing uniformly with well-known mixing apparatuses, such as a 3 roll, a sand mill, and a ball mill, and filtering with a metal mesh.
- well-known mixing apparatuses such as a 3 roll, a sand mill, and a ball mill, and filtering with a metal mesh.
- the photocurable composition according to the present embodiment is very useful as an electronic component sealant or an electronic component adhesive.
- the electronic component sealant or the electronic component adhesive include, but are not limited to, flexible printed wiring board adhesives, TAB adhesives, semiconductor adhesives, various display adhesives, and the like. is not.
- the photocurable composition according to this embodiment is very useful as an adhesive for liquid crystal display cells, particularly as a liquid crystal sealant.
- An example is shown below about the liquid crystal display cell at the time of using the photocurable composition which concerns on this embodiment as a liquid-crystal sealing compound.
- a liquid crystal display cell manufactured using an adhesive for a liquid crystal display cell has a pair of substrates each having a predetermined electrode formed on the substrate opposed to each other at a predetermined interval, and the periphery is sealed with a liquid crystal sealant, and a liquid crystal is interposed in the gap. Is enclosed.
- the kind of liquid crystal to be sealed is not particularly limited.
- the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicone, etc. and having light transmission properties.
- the manufacturing method of a liquid crystal display cell is as follows, for example.
- a spacer (gap control material) is added to the liquid crystal sealant.
- the spacer include glass fiber, silica beads, and polymer beads.
- the diameter of the spacer varies depending on the purpose, but is usually 2 to 8 ⁇ m, preferably 4 to 7 ⁇ m.
- the amount of use is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, more preferably about 0.9 to 1.5 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. It is.
- the liquid crystal sealant is irradiated with ultraviolet rays by an ultraviolet irradiator and photocured.
- the amount of ultraviolet irradiation is preferably 500 to 6000 mJ / cm 2 , more preferably 1000 to 4000 mJ / cm 2 . Thereafter, if necessary, it is cured at 90 to 130 ° C. for 1 to 2 hours to obtain a liquid crystal display cell.
- the liquid crystal display cell thus obtained does not have a display defect due to liquid crystal contamination, and has excellent adhesion and moisture resistance reliability.
- the photocurable composition according to the present embodiment is very suitable for use in an electronic component designed to have a light-shielding portion and an adhesive application that needs to be cured with low energy light such as visible light.
- it is suitable as a liquid crystal display sealing agent, an organic EL sealing agent, and a touch panel adhesive used under a wiring light shielding portion.
- thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min.
- 2-Acetylthioxanthone (0.50 g), hydroxylamine hydrochloride (0.20 g), and N, N-dimethylformamide (60 mL) were added to the reaction vessel and reacted at 80 ° C. for 4 hours.
- the reaction was stopped by adding 50 mL of water, extracted with methyl isobutyl ketone (200 mL), and washed with 50 mL of water three times.
- the solvent was removed using an evaporator to obtain an oxime product of 2-acetylthioxanthone (TX-OX / yellow solid).
- TX-OX / yellow solid The yellow solid (crude crystals) obtained here was used for the oxime esterification reaction as it was.
- thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min.
- a total amount of TX-OX, acetic anhydride (0.24 g), and butyl acetate (30 mL) were added to the reaction vessel, and the reaction was carried out at 90 ° C. for 5 hours.
- the reaction was stopped by adding 50 mL of water, extracted with methyl isobutyl ketone (200 mL), and washed with 50 mL of water three times. The solvent was removed using an evaporator to obtain a yellow solid.
- thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min.
- TX-OX 0.5 g
- benzoyl chloride 0.52 g
- triethylamine 0.47 g
- tetrahydrofuran 30 mL
- Examples 1 and 2 The curable compounds (B-1, B-2, B-3) shown in Table 1 below are mixed, the specific compound (A-1) shown in Table 1 below is heated and dissolved at 90 ° C., and then cooled to room temperature. did. Next, the remaining components in Table 1 below were added and stirred, and then dispersed in a three-roll mill. Then, the photocurable composition of Example 1 and 2 was prepared by filtering with a metal mesh (635 mesh). In addition, the numerical value of each component in Table 1 represents a mass part.
- Comparative Examples 1 and 2 Photocuring of Comparative Examples 1 and 2 in the same manner as in Examples 1 and 2, except that other components (O-2, O-3) shown in Table 1 below were used in place of the specific compound (A-1). A sex composition was prepared.
- the photocurable compositions of Examples 1 and 2 using TX-OXE as the specific compound were compared with the comparative photocurable composition using a compound having a similar structure.
- the curability in the deep part (low energy irradiated part) was good in both ultraviolet and visible light. That is, it was confirmed that the photocurable compositions of Examples 1 and 2 have excellent curability at low energy.
Abstract
Provided are: a photocurable composition, the molecules of which comprises both an oxium ester structure and a thioxanthone structure; an electronic component adhesive using the same; an electronic component; an LCD cell adhesive; a liquid crystal sealant; and an LCD cell.
Description
本発明は、光硬化性組成物、並びにそれを用いた電子部品用接着剤、電子部品、液晶表示セル用接着剤、液晶シール剤、及び液晶表示セルに関する。
The present invention relates to a photocurable composition, an adhesive for electronic parts, an electronic part, an adhesive for liquid crystal display cells, a liquid crystal sealant, and a liquid crystal display cell using the same.
光硬化性組成物は、ディスプレイ用封止剤、太陽電池用封止剤、半導体封止剤等の電子部品用接着剤用途で広く用いられている。ディスプレイ用封止剤としては、例えば、液晶ディスプレイ用シール剤、有機ＥＬディスプレイ用封止剤、タッチパネル用接着剤等を挙げることができる。これらのディスプレイ用封止剤には、優れた硬化性を有しながら、アウトガスが少なく、表示素子にダメージを与えないという特性が要求される。
Photo-curable compositions are widely used in adhesive applications for electronic parts such as display sealants, solar cell sealants, and semiconductor sealants. Examples of the display sealant include a liquid crystal display sealant, an organic EL display sealant, and a touch panel adhesive. These sealants for display are required to have excellent curability and low outgassing and do not damage the display element.
しかし、光硬化性組成物は、光の届かない部分で硬化反応が進行しないため、使用できる部分に制限がある。
However, since the photocurable composition does not undergo a curing reaction in a portion where light does not reach, there is a limit to the portion that can be used.
特に、液晶滴下工法用液晶シール剤（以下、単に「液晶シール剤」ともいう。）においては、液晶表示素子のアレイ基板の配線部分やカラーフィルター基板のブラックマトリクス部分により液晶シール剤に光が当たらない遮光部が生じ、シール近傍の表示不良の問題が以前よりも深刻なものとなっている。遮光部の存在によって光による一次硬化が不十分になると、液晶シール剤中に未硬化成分が多量に残存してしまう。この状態で熱による二次硬化工程に進んだ場合、当該未硬化成分の液晶への溶解が熱によって促進され、シール近傍の表示不良を引き起こすことになる。
In particular, in a liquid crystal sealant for a liquid crystal dropping method (hereinafter also simply referred to as “liquid crystal sealant”), when the liquid crystal sealant is exposed to light by the wiring portion of the array substrate of the liquid crystal display element or the black matrix portion of the color filter substrate. As a result, the problem of poor display in the vicinity of the seal is more serious than before. If the primary curing by light becomes insufficient due to the presence of the light shielding portion, a large amount of uncured components remain in the liquid crystal sealant. When the process proceeds to the secondary curing step by heat in this state, the dissolution of the uncured component in the liquid crystal is promoted by the heat, causing a display defect near the seal.
この課題を解決するため、液晶シール剤の熱反応性を改良する様々な検討がなされている。すなわち、遮光部において、光によって十分に硬化していない液晶シール剤を、低温から速やかに反応させ、液晶汚染を抑えようという試みである。例えば、特許文献１及び２では、熱ラジカル重合開始剤を用いる方法が開示されている。また、特許文献３～５では、硬化促進剤として多価カルボン酸を用いる方法が開示されている。
In order to solve this problem, various studies have been made to improve the thermal reactivity of the liquid crystal sealant. That is, it is an attempt to suppress liquid crystal contamination by causing a liquid crystal sealant that is not sufficiently cured by light to react quickly from a low temperature in the light shielding portion. For example, Patent Documents 1 and 2 disclose a method using a thermal radical polymerization initiator. Patent Documents 3 to 5 disclose a method using a polyvalent carboxylic acid as a curing accelerator.
しかし、熱ラジカル重合開始剤に効率よくラジカルを発生させるためには、ある程度分子量の小さいものでなければならないが、低分子化合物は液晶に溶解し易く、反応性には優れるものの、熱ラジカル重合開始剤自身による液晶汚染性が問題となる。また、多価カルボン酸を用いた場合、耐湿信頼性を損なう可能性があり、用途によっては使用できない場合もある。
However, in order to efficiently generate radicals in the thermal radical polymerization initiator, the molecular weight must be small to some extent, but low molecular compounds are easily dissolved in liquid crystals and have excellent reactivity, but thermal radical polymerization starts. Liquid crystal contamination by the agent itself becomes a problem. Moreover, when polyvalent carboxylic acid is used, there is a possibility that the moisture resistance reliability may be impaired, and it may not be used depending on the application.
以上述べたように、液晶シール剤の開発は非常に精力的に行われているにも関わらず、優れた遮光部硬化性を有しながら、低液晶汚染性である液晶シール剤は未だ実現していない。
As described above, liquid crystal sealants have been developed very vigorously, but liquid crystal sealants that have excellent light-shielding part curability and low liquid crystal contamination have not yet been realized. Not.
本発明は、紫外光線や可視光線といった光照射によって硬化する光硬化性組成物であって、光に対する感度が高く、低エネルギー光によっても十分硬化する光硬化性組成物を提供することを目的とする。
An object of the present invention is to provide a photocurable composition that is cured by irradiation with light such as ultraviolet light and visible light, and has high sensitivity to light and can be sufficiently cured even by low energy light. To do.
本発明者らは、鋭意検討の結果、分子内にオキシムエステル構造及びチオキサントン構造を併せ持つ化合物が、水素引抜型光開始剤かつ分解型開始剤として非常に優れ、低エネルギーの光照射でも十分な硬化性を有することを見出し、以下の［１］～［１５］に記載の本発明を完成するに至った。
なお、本明細書中、「（メタ）アクリル」とは「アクリル及び／又はメタクリル」を意味し、「（メタ）アクリレート」とは「アクリレート及び／又はメタクリレート」を意味し、「（メタ）アクリロイル」とは「アクリロイル及び／又はメタクリロイル」を意味する。 As a result of intensive studies, the present inventors have found that a compound having both an oxime ester structure and a thioxanthone structure in the molecule is extremely excellent as a hydrogen abstraction type photoinitiator and a decomposition type initiator, and is sufficiently cured even with low energy light irradiation. As a result, the present invention described in the following [1] to [15] has been completed.
In the present specification, “(meth) acryl” means “acryl and / or methacryl”, “(meth) acrylate” means “acrylate and / or methacrylate”, and “(meth) acryloyl”. "Means" acryloyl and / or methacryloyl ".
なお、本明細書中、「（メタ）アクリル」とは「アクリル及び／又はメタクリル」を意味し、「（メタ）アクリレート」とは「アクリレート及び／又はメタクリレート」を意味し、「（メタ）アクリロイル」とは「アクリロイル及び／又はメタクリロイル」を意味する。 As a result of intensive studies, the present inventors have found that a compound having both an oxime ester structure and a thioxanthone structure in the molecule is extremely excellent as a hydrogen abstraction type photoinitiator and a decomposition type initiator, and is sufficiently cured even with low energy light irradiation. As a result, the present invention described in the following [1] to [15] has been completed.
In the present specification, “(meth) acryl” means “acryl and / or methacryl”, “(meth) acrylate” means “acrylate and / or methacrylate”, and “(meth) acryloyl”. "Means" acryloyl and / or methacryloyl ".
［１］ 分子内にオキシムエステル構造及びチオキサントン構造を併せ持つ化合物を含有する光硬化性組成物。
［２］ 硬化性化合物を含有する［１］に記載の光硬化性組成物。
［３］ 前記硬化性化合物が（メタ）アクリル化合物である［２］に記載の光硬化性組成物。
［４］ 前記硬化性化合物が、（メタ）アクリル化合物とエポキシ化合物との混合物である［２］に記載の光硬化性組成物。
［５］ 有機フィラーを含有する［１］～［４］のいずれか一項に記載の光硬化性組成物。
［６］ 前記有機フィラーが、ウレタン微粒子、アクリル微粒子、スチレン微粒子、スチレンオレフィン微粒子、及びシリコーン微粒子からなる群より選択される少なくとも１種の有機フィラーである［５］に記載の光硬化性組成物。
［７］ 無機フィラーを含有する［１］～［６］のいずれか一項に記載の光硬化性組成物。
［８］ シランカップリング剤を含有する［１］～［７］のいずれか一項に記載の光硬化性組成物。
［９］ 熱硬化剤を含有する［１］～［８］のいずれか一項に記載の光硬化性組成物。
［１０］ 前記熱硬化剤が有機酸ヒドラジド化合物である［９］に記載の光硬化性組成物。
［１１］ ［１］～［１０］のいずれか一項に記載の光硬化性組成物を用いた電子部品用接着剤。
［１２］ ［１１］に記載の電子部品用接着剤を硬化して得られる硬化物で接着された電子部品。
［１３］ ［１］～［１０］のいずれか一項に記載の光硬化性組成物を用いた液晶表示セル用接着剤。
［１４］ ［１］～［１０］のいずれか一項に記載の光硬化性組成物を用いた液晶シール剤。
［１５］ ［１３］に記載の液晶表示セル用接着剤又は［１４］に記載の液晶シール剤を用いて接着された液晶表示セル。 [1] A photocurable composition containing a compound having both an oxime ester structure and a thioxanthone structure in the molecule.
[2] The photocurable composition according to [1], which contains a curable compound.
[3] The photocurable composition according to [2], wherein the curable compound is a (meth) acrylic compound.
[4] The photocurable composition according to [2], wherein the curable compound is a mixture of a (meth) acrylic compound and an epoxy compound.
[5] The photocurable composition according to any one of [1] to [4], which contains an organic filler.
[6] The photocurable composition according to [5], wherein the organic filler is at least one organic filler selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. .
[7] The photocurable composition according to any one of [1] to [6], which contains an inorganic filler.
[8] The photocurable composition according to any one of [1] to [7], which contains a silane coupling agent.
[9] The photocurable composition according to any one of [1] to [8], which contains a thermosetting agent.
[10] The photocurable composition according to [9], wherein the thermosetting agent is an organic acid hydrazide compound.
[11] An adhesive for electronic parts using the photocurable composition according to any one of [1] to [10].
[12] An electronic component bonded with a cured product obtained by curing the adhesive for electronic components according to [11].
[13] An adhesive for liquid crystal display cells using the photocurable composition according to any one of [1] to [10].
[14] A liquid crystal sealant using the photocurable composition according to any one of [1] to [10].
[15] A liquid crystal display cell bonded using the liquid crystal display cell adhesive according to [13] or the liquid crystal sealant according to [14].
［２］ 硬化性化合物を含有する［１］に記載の光硬化性組成物。
［３］ 前記硬化性化合物が（メタ）アクリル化合物である［２］に記載の光硬化性組成物。
［４］ 前記硬化性化合物が、（メタ）アクリル化合物とエポキシ化合物との混合物である［２］に記載の光硬化性組成物。
［５］ 有機フィラーを含有する［１］～［４］のいずれか一項に記載の光硬化性組成物。
［６］ 前記有機フィラーが、ウレタン微粒子、アクリル微粒子、スチレン微粒子、スチレンオレフィン微粒子、及びシリコーン微粒子からなる群より選択される少なくとも１種の有機フィラーである［５］に記載の光硬化性組成物。
［７］ 無機フィラーを含有する［１］～［６］のいずれか一項に記載の光硬化性組成物。
［８］ シランカップリング剤を含有する［１］～［７］のいずれか一項に記載の光硬化性組成物。
［９］ 熱硬化剤を含有する［１］～［８］のいずれか一項に記載の光硬化性組成物。
［１０］ 前記熱硬化剤が有機酸ヒドラジド化合物である［９］に記載の光硬化性組成物。
［１１］ ［１］～［１０］のいずれか一項に記載の光硬化性組成物を用いた電子部品用接着剤。
［１２］ ［１１］に記載の電子部品用接着剤を硬化して得られる硬化物で接着された電子部品。
［１３］ ［１］～［１０］のいずれか一項に記載の光硬化性組成物を用いた液晶表示セル用接着剤。
［１４］ ［１］～［１０］のいずれか一項に記載の光硬化性組成物を用いた液晶シール剤。
［１５］ ［１３］に記載の液晶表示セル用接着剤又は［１４］に記載の液晶シール剤を用いて接着された液晶表示セル。 [1] A photocurable composition containing a compound having both an oxime ester structure and a thioxanthone structure in the molecule.
[2] The photocurable composition according to [1], which contains a curable compound.
[3] The photocurable composition according to [2], wherein the curable compound is a (meth) acrylic compound.
[4] The photocurable composition according to [2], wherein the curable compound is a mixture of a (meth) acrylic compound and an epoxy compound.
[5] The photocurable composition according to any one of [1] to [4], which contains an organic filler.
[6] The photocurable composition according to [5], wherein the organic filler is at least one organic filler selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. .
[7] The photocurable composition according to any one of [1] to [6], which contains an inorganic filler.
[8] The photocurable composition according to any one of [1] to [7], which contains a silane coupling agent.
[9] The photocurable composition according to any one of [1] to [8], which contains a thermosetting agent.
[10] The photocurable composition according to [9], wherein the thermosetting agent is an organic acid hydrazide compound.
[11] An adhesive for electronic parts using the photocurable composition according to any one of [1] to [10].
[12] An electronic component bonded with a cured product obtained by curing the adhesive for electronic components according to [11].
[13] An adhesive for liquid crystal display cells using the photocurable composition according to any one of [1] to [10].
[14] A liquid crystal sealant using the photocurable composition according to any one of [1] to [10].
[15] A liquid crystal display cell bonded using the liquid crystal display cell adhesive according to [13] or the liquid crystal sealant according to [14].
本発明の光硬化性組成物は、光が十分に当たらない部分における硬化性も高く、また他の部材へのダメージを考慮した低エネルギーの光照射でも十分な硬化性を有するため、遮光部分を有する電子部品や可視光によって硬化させる必要のある電子部品の製造に用いられる電子部品用封止剤又は電子部品用接着剤、特にディスプレイ用封止剤として有用である。
The photocurable composition of the present invention has high curability in a portion where light is not sufficiently irradiated, and has sufficient curability even with low-energy light irradiation considering damage to other members. It is useful as a sealing agent for electronic components or an adhesive for electronic components, particularly a sealing agent for displays, which is used in the manufacture of electronic components having the above and electronic components that need to be cured by visible light.
＜光硬化性組成物＞
［分子内にオキシムエステル構造及びチオキサントン構造を併せ持つ化合物］
本実施形態に係る光硬化性組成物は、分子内にオキシムエステル構造及びチオキサントン構造を併せ持つ化合物（以下、「特定化合物」ともいう。）を含有する。この特定化合物は、低エネルギー光に対する感度が非常に高い光重合開始剤として機能する。特定化合物は、１種を単独で使用してもよく、２種以上を併用してもよい。 <Photocurable composition>
[Compound having both oxime ester structure and thioxanthone structure in the molecule]
The photocurable composition according to the present embodiment contains a compound having both an oxime ester structure and a thioxanthone structure in the molecule (hereinafter also referred to as “specific compound”). This specific compound functions as a photopolymerization initiator having a very high sensitivity to low energy light. A specific compound may be used individually by 1 type, and may use 2 or more types together.
［分子内にオキシムエステル構造及びチオキサントン構造を併せ持つ化合物］
本実施形態に係る光硬化性組成物は、分子内にオキシムエステル構造及びチオキサントン構造を併せ持つ化合物（以下、「特定化合物」ともいう。）を含有する。この特定化合物は、低エネルギー光に対する感度が非常に高い光重合開始剤として機能する。特定化合物は、１種を単独で使用してもよく、２種以上を併用してもよい。 <Photocurable composition>
[Compound having both oxime ester structure and thioxanthone structure in the molecule]
The photocurable composition according to the present embodiment contains a compound having both an oxime ester structure and a thioxanthone structure in the molecule (hereinafter also referred to as “specific compound”). This specific compound functions as a photopolymerization initiator having a very high sensitivity to low energy light. A specific compound may be used individually by 1 type, and may use 2 or more types together.
特定化合物が有するオキシムエステル構造は、例えば、下記式（１）で表される構造である。
The oxime ester structure possessed by the specific compound is, for example, a structure represented by the following formula (1).
上記式（１）中、Ｒ１は（Ｃ１－Ｃ８）アルキル基、又は（Ｃ１－Ｃ８）アルコキシ基を表し、Ｒ２は水素原子、（Ｃ１－Ｃ８）アルキル基、（Ｃ２－Ｃ８）アルケニル基、アリール基、又はヘテロアリール基を表す。
In the above formula (1), R 1 represents a (C1-C8) alkyl group or a (C1-C8) alkoxy group, and R 2 represents a hydrogen atom, a (C1-C8) alkyl group, or a (C2-C8) alkenyl group. Represents an aryl group or a heteroaryl group.
上記式（１）中のＲ１における（Ｃ１－Ｃ８）アルキル基としては、直鎖状、分岐鎖状、又は環状の非置換のものが挙げられ、直鎖状のものが好ましい。具体例としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ヘンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基等の直鎖状のもの；イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等の分岐鎖状のもの；シクロプロピル基、シクロペンチル基、シクロヘキシル基等の環状のもの；などが挙げられる。（Ｃ１－Ｃ８）アルキル基は、３－シクロペンチルプロピル基等のように、鎖状のアルキル基と環状のアルキル基とが結合したものであってもよい。これらの中でも、硬化性化合物や溶剤との相溶性の観点から（Ｃ１－Ｃ３）アルキル基が好ましく、具体例としては、メチル基、エチル基、ｎ－プロピル基が挙げられ、メチル基がより好ましい。
Examples of the (C1-C8) alkyl group for R 1 in the above formula (1) include a linear, branched, or cyclic unsubstituted group, and a linear one is preferable. Specific examples include linear groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-hentyl group, n-hexyl group, n-heptyl group, n-octyl group; isopropyl group Branched chain groups such as isobutyl group, sec-butyl group and tert-butyl group; cyclic groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group; The (C1-C8) alkyl group may be a group in which a chain alkyl group and a cyclic alkyl group are bonded, such as a 3-cyclopentylpropyl group. Among these, a (C1-C3) alkyl group is preferable from the viewpoint of compatibility with a curable compound or a solvent, and specific examples include a methyl group, an ethyl group, and an n-propyl group, and a methyl group is more preferable. .
上記式（１）中のＲ１における（Ｃ１－Ｃ８）アルコキシ基としては、直鎖状又は分岐鎖状の非置換のものが挙げられ、直鎖状のものが好ましい。具体例としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｎ－ブトキシ基等の直鎖状のもの；イソプロポキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基等の分岐鎖状のもの；などが挙げられる。これらの中でも、メトキシ基が好ましい。
Examples of the (C1-C8) alkoxy group for R 1 in the above formula (1) include a linear or branched unsubstituted group, and a linear one is preferred. Specific examples include linear groups such as methoxy group, ethoxy group, n-propoxy group and n-butoxy group; branched chain groups such as isopropoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group. And the like. Among these, a methoxy group is preferable.
上記式（１）において、Ｒ１としてはメチル基が好ましい。
In the above formula (1), R 1 is preferably a methyl group.
上記式（１）中のＲ２における（Ｃ１－Ｃ８）アルキル基は、好ましいものを含め、上記Ｒ１における（Ｃ１－Ｃ８）アルキル基と同じ意味を表す。
The (C1-C8) alkyl group in R 2 in the above formula (1) has the same meaning as the (C1-C8) alkyl group in R 1 , including preferred ones.
上記式（１）中のＲ２における（Ｃ２－Ｃ８）アルケニル基としては、直鎖状又は分岐鎖状の非置換のものが挙げられる。具体例としては、ビニル基、１－プロペニル基、２－プロペニル基等が挙げられる。
Examples of the (C2-C8) alkenyl group for R 2 in the above formula (1) include linear or branched unsubstituted groups. Specific examples include vinyl group, 1-propenyl group, 2-propenyl group and the like.
上記式（１）中のＲ２におけるアリール基及びヘテロアリール基としては、フェニル基、ピリジル基、チエニル基等が挙げられる。アリール基及びヘテロアリール基は、カルボキシ基、スルホ基、ヒドロキシ基、アセチルアミノ基、ハロゲン原子、シアノ基、ニトロ基、スルファモイル基、アルキル基、アルコキシ基等の少なくとも１つの置換基で置換されていてもよい。このような置換基を有するものとしては、例えば、４－ニトロフェニル基が挙げられる。
Examples of the aryl group and heteroaryl group in R 2 in the above formula (1) include a phenyl group, a pyridyl group, and a thienyl group. The aryl group and heteroaryl group are substituted with at least one substituent such as a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, an alkyl group, and an alkoxy group. Also good. Examples of those having such a substituent include a 4-nitrophenyl group.
上記式（１）において、Ｒ２としては水素原子又はメチル基が好ましい。
In the above formula (1), R 2 is preferably a hydrogen atom or a methyl group.
上記式（１）中の＊は結合位置を表し、下記式（２）で表されるチオキサントン構造との結合位置でもよく、他の結合基を介してチオキサントン構造と結合する場合の、当該結合基との結合位置でもよい。結合基としては、アルキレン基、アルキリデン基、アルキレンオキシド基等が挙げられる。
* In the above formula (1) represents a bonding position, which may be a bonding position with a thioxanthone structure represented by the following formula (2), and the bonding group in the case of bonding to the thioxanthone structure through another bonding group. It may be a coupling position. Examples of the linking group include an alkylene group, an alkylidene group, and an alkylene oxide group.
特定化合物が有するチオキサントン構造は、下記式（２）で表される構造である。
The thioxanthone structure possessed by the specific compound is a structure represented by the following formula (2).
上記式（２）中の＊は結合位置を表し、上記式（１）で表されるオキシムエステル構造との結合位置でもよく、他の結合基を介してオキシムエステル構造と結合する場合の、当該結合基との結合位置でもよい。結合基としては、アルキレン基、アルキリデン基、アルキレンオキシド基等が挙げられる。
* In the above formula (2) represents a bonding position, which may be a bonding position with the oxime ester structure represented by the above formula (1), and in the case of bonding to the oxime ester structure through another bonding group, It may be a bonding position with a bonding group. Examples of the linking group include an alkylene group, an alkylidene group, and an alkylene oxide group.
上記式（２）で表されるチオキサントン構造は、上記式（１）で表されるオキシムエステル構造以外に、他の置換基を有していてもよい。他の置換基としては、カルボキシ基、スルホ基、ヒドロキシ基、アセチルアミノ基、ハロゲン原子、シアノ基、ニトロ基、スルファモイル基、（Ｃ１－Ｃ８）アルキル基、（Ｃ１－Ｃ８）アルコキシ基等が挙げられる。
The thioxanthone structure represented by the above formula (2) may have other substituents in addition to the oxime ester structure represented by the above formula (1). Examples of other substituents include carboxy group, sulfo group, hydroxy group, acetylamino group, halogen atom, cyano group, nitro group, sulfamoyl group, (C1-C8) alkyl group, (C1-C8) alkoxy group, and the like. It is done.
上記式（２）で表されるチオキサントン構造が他の置換基を有する場合、当該置換基は、上記式（１）中のＲ１と結合して環状構造を形成していてもよい。
When the thioxanthone structure represented by the formula (2) has another substituent, the substituent may be bonded to R 1 in the formula (1) to form a cyclic structure.
特定化合物の具体的としては、例えば、以下の化合物番号１～２０の化合物が挙げられる。ただし、これらに限定されるものではない。化合物番号１～２０の化合物の中では、化合物番号１～１７、２０の化合物が好ましく、化合物番号１の化合物がより好ましい。
Specific examples of the specific compound include compounds having the following compound numbers 1 to 20. However, it is not limited to these. Of the compounds of compound numbers 1 to 20, compounds of compound numbers 1 to 17 and 20 are preferred, and compounds of compound number 1 are more preferred.
特定化合物のうち、例えば化合物番号１及び化合物番号２０の化合物は、後述する合成例１に記載の方法で合成することができる。
Among the specific compounds, for example, compounds of Compound No. 1 and Compound No. 20 can be synthesized by the method described in Synthesis Example 1 described later.
特定化合物は、紫外光線や可視光線といった光照射によってラジカルを発生させるものであり、光に対する感度が高く、低エネルギー光によっても十分な反応性を示す。また、良好な熱安定性、低い揮発性、良好な貯蔵安定性、及び良好な溶解性を有し、空気（酸素）の存在下での光重合にも適している。したがって、特定化合物は、ラジカル重合可能な硬化性化合物を重合させる光重合開始剤として有用である。
The specific compound generates radicals by irradiation with light such as ultraviolet light and visible light, has high sensitivity to light, and exhibits sufficient reactivity even with low energy light. It also has good thermal stability, low volatility, good storage stability, and good solubility and is suitable for photopolymerization in the presence of air (oxygen). Therefore, the specific compound is useful as a photopolymerization initiator for polymerizing a curable compound capable of radical polymerization.
特定化合物の含有率は、光硬化性組成物の総量中、通常０．００１～１０質量％であり、好ましくは０．００２～５．０質量％であり、より好ましくは０．１～３．０質量％である。特定化合物の含有率が０．００１質量％以上であると、光硬化性組成物の光重合が十分に進行する傾向にある。一方、特定化合物の含有率が１０質量％以下であると、未反応の化合物が少なくなる。その結果、光硬化性組成物の耐光性及び保存安定性の悪化や、光硬化性組成物を表示素子用封止剤として用いた場合における表示特性への悪影響が抑えられる傾向にある。
The content of the specific compound is usually 0.001 to 10% by mass, preferably 0.002 to 5.0% by mass, and more preferably 0.1 to 3.% by mass in the total amount of the photocurable composition. 0% by mass. When the content of the specific compound is 0.001% by mass or more, the photopolymerization of the photocurable composition tends to proceed sufficiently. On the other hand, when the content of the specific compound is 10% by mass or less, the number of unreacted compounds decreases. As a result, deterioration of light resistance and storage stability of the photocurable composition and adverse effects on display characteristics when the photocurable composition is used as a sealant for display elements tend to be suppressed.
［光重合開始剤］
本実施形態に係る光硬化性組成物は、上記の特定化合物以外に、他の光重合開始剤を含有していてもよい。他の光重合開始剤としては、紫外光線や可視光線の照射によってラジカル、酸、塩基等を発生し、連鎖重合反応を開始させる化合物であれば特に限定されない。 [Photopolymerization initiator]
The photocurable composition concerning this embodiment may contain other photoinitiators other than the above-mentioned specific compound. The other photopolymerization initiator is not particularly limited as long as it is a compound that generates a radical, an acid, a base, or the like by irradiation with ultraviolet light or visible light and initiates a chain polymerization reaction.
本実施形態に係る光硬化性組成物は、上記の特定化合物以外に、他の光重合開始剤を含有していてもよい。他の光重合開始剤としては、紫外光線や可視光線の照射によってラジカル、酸、塩基等を発生し、連鎖重合反応を開始させる化合物であれば特に限定されない。 [Photopolymerization initiator]
The photocurable composition concerning this embodiment may contain other photoinitiators other than the above-mentioned specific compound. The other photopolymerization initiator is not particularly limited as long as it is a compound that generates a radical, an acid, a base, or the like by irradiation with ultraviolet light or visible light and initiates a chain polymerization reaction.
他の光重合開始剤の具体例としては、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、ジエチルチオキサントン、ベンゾフェノン、２－エチルアンスラキノン、２－ヒドロキシ－２－メチルプロピオフェノン、２－メチル－〔４－（メチルチオ）フェニル〕－２－モルフォリノ－１－プロパン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、カンファーキノン、９－フルオレノン、ジフェニルジスルフィド等が挙げられる。市販品としては、ＩＲＧＡＣＵＲＥＲＴＭ ６５１、１８４、２９５９、１２７、９０７、３９６、３７９ＥＧ、８１９、７８４、７５４、５００、ＯＸＥ０１、ＯＸＥ０２、ＤＡＲＯＣＵＲＥＲＴＭ １１７３、ＬＵＣＩＲＩＮＲＴＭ ＴＰＯ（以上、ＢＡＳＦ社製）；セイクオールＲＴＭＺ、ＢＺ、ＢＥＥ、ＢＩＰ、ＢＢＩ（以上、精工化学株式会社製）；等が挙げられる。なお、本明細書において上付きの「ＲＴＭ」は登録商標を意味する。
Specific examples of other photopolymerization initiators include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [ 4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyl disulfide and the like. Examples of commercially available products, IRGACURE RTM 651,184,2959,127,907,396,379EG, 819,784,754,500, OXE01 , OXE02, DAROCURE RTM 1173, LUCIRIN RTM TPO ( manufactured by BASF); Seikuoru RTM Z, BZ, BEE, BIP, BBI (manufactured by Seiko Chemical Co., Ltd.); In the present specification, the superscript “RTM” means a registered trademark.
これらの中でも、幅広い波長の光吸収を利用し、光硬化性組成物の硬化性を高める観点から、２００～３００ｎｍの波長領域における極大吸収波長（λｍａｘ）の吸光度が４００以上である光重合開始剤が好ましく、２００～３００ｎｍの波長領域における極大吸収波長（λｍａｘ）の吸光度が５００以上である光重合開始剤がより好ましく、２００～３００ｎｍの波長領域における極大吸収波長（λｍａｘ）の吸光度が１５００以上である光重合開始剤がさらに好ましい。２００～３００ｎｍの波長領域における極大吸収波長（λｍａｘ）の吸光度が５００以上である光重合開始剤としては、例えば、ＩＲＧＡＣＵＲＥＲＴＭ ６５１、１８４、２９５９が挙げられる。また、２００～３００ｎｍの波長領域における極大吸収波長（λｍａｘ）の吸光度が１５００以上である光重合開始剤としては、例えば、ＩＲＧＡＣＵＲＥＲＴＭ ２９５９が挙げられる。
Among these, a photopolymerization initiator having a maximum absorption wavelength (λmax) absorbance of 400 or more in a wavelength region of 200 to 300 nm from the viewpoint of enhancing light curability of a photocurable composition by utilizing light absorption in a wide range of wavelengths. More preferable is a photopolymerization initiator having an absorbance at a maximum absorption wavelength (λmax) in the wavelength region of 200 to 300 nm of 500 or more, and an absorbance at a maximum absorption wavelength (λmax) in the wavelength region of 200 to 300 nm is more than 1500. Some photoinitiators are more preferred. Examples of the photopolymerization initiator having an absorbance at the maximum absorption wavelength (λmax) in the wavelength region of 200 to 300 nm of 500 or more include IRGACURE RTM 651, 184, and 2959. Examples of the photopolymerization initiator having an absorbance at the maximum absorption wavelength (λmax) in the wavelength region of 200 to 300 nm of 1500 or more include IRGACURE RTM 2959.
また、光重合開始剤としては、アウトガス防止の観点から、分子量１５０～１０００のものが好ましい。同様に、アウトガス防止の観点から、分子内に（メタ）アクリル基を有するものが好ましく、例えば、２－メタクリロイルオキシエチルイソシアネートと１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２メチル－１－プロパン－１－オンとの反応生成物が好適に用いられる。この化合物は、国際公開第２００６／０２７９８２号記載の方法にて製造することができる。
The photopolymerization initiator preferably has a molecular weight of 150 to 1000 from the viewpoint of preventing outgassing. Similarly, from the viewpoint of preventing outgassing, those having a (meth) acryl group in the molecule are preferable, for example, 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy The reaction product with 2-methyl-1-propan-1-one is preferably used. This compound can be produced by the method described in International Publication No. 2006/027982.
本実施形態に係る光硬化性組成物が他の光重合開始剤を含有する場合、その含有率は、光硬化性組成物の総量中、０．００１～１０質量％であることが好ましく、０．１～５．０質量％であることがより好ましい。
When the photocurable composition according to this embodiment contains other photopolymerization initiator, the content is preferably 0.001 to 10% by mass in the total amount of the photocurable composition, More preferably, the content is 1 to 5.0% by mass.
［光開始助剤］
本実施形態に係る光硬化性組成物は、硬化性をさらに高めるため、三級アミン類等の光開始助剤を含有していてもよい。三級アミン類としては、特に限定されないが、ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジメチルアミノ安息香酸イソアミル、Ｎ，Ｎ－ジメチルベンジルアミン等が挙げられる。また、一分子内に複数の三級アミン類を多価アルコール等で分岐させた高分子量化合物も適宜使用することができる。 [Photoinitiator]
The photocurable composition according to the present embodiment may contain a photoinitiation assistant such as a tertiary amine in order to further improve the curability. The tertiary amines include, but are not limited to, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and the like. Moreover, a high molecular weight compound in which a plurality of tertiary amines are branched with a polyhydric alcohol or the like in one molecule can also be used as appropriate.
本実施形態に係る光硬化性組成物は、硬化性をさらに高めるため、三級アミン類等の光開始助剤を含有していてもよい。三級アミン類としては、特に限定されないが、ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジメチルアミノ安息香酸イソアミル、Ｎ，Ｎ－ジメチルベンジルアミン等が挙げられる。また、一分子内に複数の三級アミン類を多価アルコール等で分岐させた高分子量化合物も適宜使用することができる。 [Photoinitiator]
The photocurable composition according to the present embodiment may contain a photoinitiation assistant such as a tertiary amine in order to further improve the curability. The tertiary amines include, but are not limited to, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and the like. Moreover, a high molecular weight compound in which a plurality of tertiary amines are branched with a polyhydric alcohol or the like in one molecule can also be used as appropriate.
本実施形態に係る光硬化性組成物が光開始助剤を含有する場合、その含有率は、光硬化性組成物の総量中、０．００５～２０質量％であることが好ましく、０．０１～１０質量％であることがより好ましい。
When the photocurable composition according to this embodiment contains a photoinitiator auxiliary, the content is preferably 0.005 to 20% by mass in the total amount of the photocurable composition, 0.01 More preferably, it is ˜10% by mass.
［硬化性化合物］
本実施形態に係る光硬化性組成物は、硬化性化合物を含有することが好ましい。硬化性化合物としては、光、熱等によって硬化する化合物であれば特に限定されないが、（メタ）アクリルエステル化合物、エポキシ（メタ）アクリレート化合物等の（メタ）アクリル化合物が好ましい。（メタ）アクリル化合物は、１種を単独で使用してもよく、２種以上を併用してもよい。 [Curable compound]
The photocurable composition according to this embodiment preferably contains a curable compound. Although it will not specifically limit as a sclerosing | hardenable compound if it is a compound hardened | cured by light, heat | fever, etc., (meth) acrylic compounds, such as a (meth) acrylic ester compound and an epoxy (meth) acrylate compound, are preferable. A (meth) acryl compound may be used individually by 1 type, and may use 2 or more types together.
本実施形態に係る光硬化性組成物は、硬化性化合物を含有することが好ましい。硬化性化合物としては、光、熱等によって硬化する化合物であれば特に限定されないが、（メタ）アクリルエステル化合物、エポキシ（メタ）アクリレート化合物等の（メタ）アクリル化合物が好ましい。（メタ）アクリル化合物は、１種を単独で使用してもよく、２種以上を併用してもよい。 [Curable compound]
The photocurable composition according to this embodiment preferably contains a curable compound. Although it will not specifically limit as a sclerosing | hardenable compound if it is a compound hardened | cured by light, heat | fever, etc., (meth) acrylic compounds, such as a (meth) acrylic ester compound and an epoxy (meth) acrylate compound, are preferable. A (meth) acryl compound may be used individually by 1 type, and may use 2 or more types together.
（メタ）アクリルエステル化合物としては、例えば、Ｎ－アクリロイルオキシエチルヘキサヒドロフタルイミド、アクリロイルモルホリン、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、シクロヘキサン－１，４－ジメタノールモノ（メタ）アクリレート、テトラヒドロフロフリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェニルポリエトキシ（メタ）アクリレート、２－ヒドロキシ－３－フェニルオキシプロピル（メタ）アクリレート、ｏ－フェニルフェノールモノエトキシ（メタ）アクリレート、ｏ－フェニルフェノールポリエトキシ（メタ）アクリレート、ｐ－クミルフェノキシエチル（メタ）アクリレート、イソボニル（メタ）アクリレート、トリブロモフェニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（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、１，９－ノナンジオールジ（メタ）アクリレート、トリシクロデカンジメタノール（メタ）アクリレート、ビスフェノールＡポリエトキシジ（メタ）アクリレート、ビスフェノールＡポリプロポキシジ（メタ）アクリレート、ビスフェノールＦポリエトキシジ（メタ）アクリレート、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、トリス（（メタ）アクリロキシエチル）イソシアヌレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ネオペンチルグリコールとヒドロキシピバリン酸とのエステルジアクリレート、ネオペンチルグリコールとヒドロキシピバリン酸とのエステルのε－カプロラクトン付加物のジアクリレート等が挙げられる。これらの中でも、Ｎ－アクリロイルオキシエチルヘキサヒドロフタルイミド、フェノキシエチル（メタ）アクリレート、及びジシクロペンテニルオキシエチル（メタ）アクリレートが好ましい。
Examples of (meth) acrylic ester compounds include N-acryloyloxyethylhexahydrophthalimide, acryloylmorpholine, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane-1,4-dimethanol mono (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy (meta ) Acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromo Enyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, pe Taerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylolpropane tri (meta) ) Acrylate, trimethylolpropane polyethoxytri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ester diacrylate of neopentyl glycol and hydroxypivalic acid, ε-caprolactone of ester of neopentyl glycol and hydroxypivalic acid Examples thereof include diacrylates of adducts. Among these, N-acryloyloxyethyl hexahydrophthalimide, phenoxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate are preferable.
エポキシ（メタ）アクリレート化合物は、エポキシ化合物と（メタ）アクリル酸との反応により公知の方法で得られる。原料となるエポキシ化合物としては、特に限定されるものではないが、２官能以上のエポキシ化合物が好ましい。２官能以上のエポキシ化合物としては、例えば、レゾルシンジグリシジルエーテル、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、ビスフェノールＳ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、ビスフェノールＡノボラック型エポキシ化合物、ビスフェノールＦノボラック型エポキシ化合物、脂環式エポキシ化合物、脂肪族鎖状エポキシ化合物、グリシジルエステル型エポキシ化合物、グリシジルアミン型エポキシ化合物、ヒダントイン型エポキシ化合物、イソシアヌレート型エポキシ化合物、トリフェノールメタン骨格を有するフェノールノボラック型エポキシ化合物、二官能フェノール類（カテコール、レゾルシノール等）のジグリシジルエーテル化物、二官能アルコール類のジグリシジルエーテル化物、及びそれらのハロゲン化物又は水素添加物などが挙げられる。これらの中でも、本実施形態に係る光硬化性組成物を液晶シール剤として用いる場合には、液晶汚染性の観点から、ビスフェノールＡ型エポキシ化合物及びレゾルシンジグリシジルエーテルが好ましい。エポキシ（メタ）アクリレート化合物におけるエポキシ基と（メタ）アクリロイル基との比率は特に限定されず、工程適合性の観点から適切に選択される。
The epoxy (meth) acrylate compound can be obtained by a known method by reacting an epoxy compound with (meth) acrylic acid. Although it does not specifically limit as an epoxy compound used as a raw material, The epoxy compound more than bifunctional is preferable. Examples of the bifunctional or higher functional epoxy compound include resorcin diglycidyl ether, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, phenol novolac type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolak type Epoxy compounds, bisphenol F novolac type epoxy compounds, alicyclic epoxy compounds, aliphatic chain epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, hydantoin type epoxy compounds, isocyanurate type epoxy compounds, triphenolmethane skeleton Phenol novolac-type epoxy compounds having di- and diglycidyl ethers of bifunctional phenols (catechol, resorcinol, etc.) Things, difunctional alcohols diglycidyl ethers of, and the like thereof halide or hydrogenated product. Among these, when the photocurable composition according to the present embodiment is used as a liquid crystal sealant, bisphenol A type epoxy compounds and resorcin diglycidyl ether are preferable from the viewpoint of liquid crystal contamination. The ratio of the epoxy group and the (meth) acryloyl group in the epoxy (meth) acrylate compound is not particularly limited, and is appropriately selected from the viewpoint of process compatibility.
本実施形態に係る光硬化性組成物は、（メタ）アクリル化合物に加えて、エポキシ化合物（ただし、（メタ）アクリル化合物を除く）を含有することが好ましい。エポキシ化合物は、１種を単独で使用してもよく、２種以上を併用してもよい。
The photocurable composition according to this embodiment preferably contains an epoxy compound (excluding the (meth) acrylic compound) in addition to the (meth) acrylic compound. An epoxy compound may be used individually by 1 type, and may use 2 or more types together.
エポキシ化合物としては、特に限定されるものではないが、２官能以上のエポキシ化合物が好ましい。２官能以上のエポキシ化合物としては、例えば、レゾルシンジグリシジルエーテル、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂、トリフェノールメタン骨格を有するフェノールノボラック型エポキシ樹脂、二官能フェノール類（カテコール、レゾルシノール等）のジグリシジルエーテル化物、二官能アルコール類のジグリシジルエーテル化物、及びそれらのハロゲン化物又は水素添加物などが挙げられる。これらの中でも、本実施形態に係る光硬化性組成物を液晶シール剤として用いる場合には、液晶汚染性の観点から、ビスフェノールＡ型エポキシ樹脂やレゾルシンジグリシジルエーテルが好ましい。
The epoxy compound is not particularly limited, but a bifunctional or higher functional epoxy compound is preferable. Examples of the bifunctional or higher functional epoxy compound include resorcin diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type Epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, triphenolmethane skeleton Phenol novolac epoxy resin containing diglycidyl etherified products of bifunctional phenols (catechol, resorcinol, etc.), difunctional alcohols Glycidyl etherified product, and the like thereof halide or hydrogenated product. Among these, when the photocurable composition according to the present embodiment is used as a liquid crystal sealant, bisphenol A type epoxy resin and resorcin diglycidyl ether are preferable from the viewpoint of liquid crystal contamination.
本実施形態に係る光硬化性組成物が硬化性化合物を含有する場合、その含有率は、光硬化性組成物の総量中、通常１０～８０質量％であり、好ましくは２０～７０質量％である。
また、本実施形態に係る光硬化性組成物がエポキシ化合物を含有する場合、その含有率は、光硬化性組成物の総量中、通常５～５０質量％であり、好ましくは５～３０質量％である。 When the photocurable composition according to this embodiment contains a curable compound, the content thereof is usually 10 to 80% by mass, preferably 20 to 70% by mass, based on the total amount of the photocurable composition. is there.
When the photocurable composition according to this embodiment contains an epoxy compound, the content is usually 5 to 50% by mass, preferably 5 to 30% by mass, based on the total amount of the photocurable composition. It is.
また、本実施形態に係る光硬化性組成物がエポキシ化合物を含有する場合、その含有率は、光硬化性組成物の総量中、通常５～５０質量％であり、好ましくは５～３０質量％である。 When the photocurable composition according to this embodiment contains a curable compound, the content thereof is usually 10 to 80% by mass, preferably 20 to 70% by mass, based on the total amount of the photocurable composition. is there.
When the photocurable composition according to this embodiment contains an epoxy compound, the content is usually 5 to 50% by mass, preferably 5 to 30% by mass, based on the total amount of the photocurable composition. It is.
［有機フィラー］
本実施形態に係る光硬化性組成物は、有機フィラーを含有していてもよい。有機フィラーは、１種を単独で使用してもよく、２種以上を併用してもよい。 [Organic filler]
The photocurable composition according to the present embodiment may contain an organic filler. An organic filler may be used individually by 1 type, and may use 2 or more types together.
本実施形態に係る光硬化性組成物は、有機フィラーを含有していてもよい。有機フィラーは、１種を単独で使用してもよく、２種以上を併用してもよい。 [Organic filler]
The photocurable composition according to the present embodiment may contain an organic filler. An organic filler may be used individually by 1 type, and may use 2 or more types together.
有機フィラーとしては、例えば、ウレタン微粒子、アクリル微粒子、スチレン微粒子、スチレンオレフィン微粒子、及びシリコーン微粒子が挙げられる。シリコーン微粒子としては、ＫＭＰ－５９４、ＫＭＰ－５９７、ＫＭＰ－５９８（以上、信越化学工業株式会社製）；トレフィルＲＴＭＥ－５５００、９７０１、ＥＰ－２００１（以上、東レ・ダウコーニング株式会社製）が好ましい。ウレタン微粒子としては、ＪＢ－８００Ｔ、ＨＢ－８００ＢＫ（以上、根上工業株式会社製）が好ましい。スチレン微粒子としては、ラバロンＲＴＭＴ３２０Ｃ、Ｔ３３１Ｃ、ＳＪ４４００、ＳＪ５４００、ＳＪ６４００、ＳＪ４３００Ｃ、ＳＪ５３００Ｃ、ＳＪ６３００Ｃ（以上、三菱化学株式会社製）が好ましい。スチレンオレフィン微粒子としては、セプトンＲＴＭＳＥＰＳ２００４、ＳＥＰＳ２０６３（以上、株式会社クラレ製）が好ましい。これらの有機フィラーは、２種以上の材料を用いたコアシェル構造の有機フィラーであってもよい。
Examples of the organic filler include urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. Examples of the silicone fine particles include KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.); Trefill RTM E-5500, 9701, EP-2001 (manufactured by Toray Dow Corning Co., Ltd.). preferable. As urethane fine particles, JB-800T and HB-800BK (manufactured by Negami Industrial Co., Ltd.) are preferable. As the styrene fine particles, Lavalon RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, and SJ6300C (manufactured by Mitsubishi Chemical Corporation) are preferable. As the styrene olefin fine particles, Septon RTM SEPS 2004 and SEPS 2063 (manufactured by Kuraray Co., Ltd.) are preferable. These organic fillers may be core-shell organic fillers using two or more materials.
これらの有機フィラーの中でも、アクリル微粒子及びシリコーン微粒子が好ましい。
Among these organic fillers, acrylic fine particles and silicone fine particles are preferable.
アクリル微粒子としては、２種類のアクリルゴムからなるコアシェル構造のアクリルゴムが好ましく、コア層がｎ－ブチルアクリレートであり、シェル層がメチルメタクリレートであるものがより好ましい。コア層がｎ－ブチルアクリレートであり、シェル層がメチルメタクリレートであるアクリル微粒子は、ゼフィアックＲＴＭＦ－３５１としてアイカ工業株式会社から販売されている。
As the acrylic fine particles, an acrylic rubber having a core-shell structure composed of two kinds of acrylic rubber is preferable, and the core layer is preferably n-butyl acrylate and the shell layer is more preferably methyl methacrylate. Acrylic fine particles whose core layer is n-butyl acrylate and whose shell layer is methyl methacrylate are sold by Aika Kogyo Co., Ltd. as Zefiac RTM F-351.
また、シリコーン微粒子としては、オルガノポリシロキサン架橋物粉体、直鎖のジメチルポリシロキサン架橋物粉体、シリコーンゴムの表面にシリコーン樹脂（例えば、ポリオルガノシルセスキオキサン樹脂）を被覆した複合シリコーンゴム等が挙げられる。これらのシリコーン微粒子のうち、好ましいものとしては、直鎖のジメチルポリシロキサン架橋物粉末のシリコーンゴム、又はシリコーン樹脂被覆直鎖ジメチルポリシロキサン架橋物粉末の複合シリコーンゴム微粒子である。ゴム粉末の形状は、添加後の粘度の増粘が少ない球状がよい。
Silicone fine particles include organopolysiloxane cross-linked powder, linear dimethylpolysiloxane cross-linked powder, and a composite silicone rubber in which a silicone resin (for example, polyorganosilsesquioxane resin) is coated on the surface of the silicone rubber. Etc. Among these silicone fine particles, preferred is a silicone rubber of a linear dimethylpolysiloxane crosslinked product powder, or a composite silicone rubber fine particle of a silicone resin-coated linear dimethylpolysiloxane crosslinked product powder. The shape of the rubber powder is preferably a sphere with little increase in viscosity after addition.
本実施形態に係る光硬化性組成物が有機フィラーを含有する場合、その含有率は、光硬化性組成物の総量中、通常５～５０質量％であり、好ましくは５～４０質量％である。
When the photocurable composition according to the present embodiment contains an organic filler, the content is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the photocurable composition. .
［無機フィラー］
本実施形態に係る光硬化性組成物は、無機フィラーを含有していてもよい。無機フィラーは、１種を単独で使用してもよく、２種以上を併用してもよい。 [Inorganic filler]
The photocurable composition according to this embodiment may contain an inorganic filler. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
本実施形態に係る光硬化性組成物は、無機フィラーを含有していてもよい。無機フィラーは、１種を単独で使用してもよく、２種以上を併用してもよい。 [Inorganic filler]
The photocurable composition according to this embodiment may contain an inorganic filler. An inorganic filler may be used individually by 1 type, and may use 2 or more types together.
無機フィラーとしては、例えば、シリカ、シリコンカーバイド、窒化珪素、窒化ホウ素、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、硫酸カルシウム、マイカ、タルク、クレー、アルミナ、酸化マグネシウム、酸化ジルコニウム、水酸化アルミニウム、水酸化マグネシウム、珪酸カルシウム、珪酸アルミニウム、珪酸リチウムアルミニウム、珪酸ジルコニウム、チタン酸バリウム、硝子繊維、炭素繊維、二硫化モリブデン、アスベスト等が挙げられ、好ましくは溶融シリカ、結晶シリカ、窒化珪素、窒化ホウ素、炭酸カルシウム、硫酸バリウム、硫酸カルシウム、マイカ、タルク、クレー、アルミナ、水酸化アルミニウム、珪酸カルシウム、珪酸アルミニウム等の粒子が挙げられ、シリカ、アルミナ、タルク等の粒子が好ましい。
Examples of the inorganic filler include silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, and hydroxide. Examples include magnesium, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably fused silica, crystalline silica, silicon nitride, boron nitride, carbonic acid Examples of the particles include calcium, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, and aluminum silicate, and particles such as silica, alumina, and talc are preferable.
無機フィラーの平均粒子径は、２０００ｎｍ以下が適当であり、好ましくは１０００ｎｍ以下、より好ましくは３００ｎｍ以下である。無機フィラーの平均粒子径を２０００ｎｍ以下とすることで、例えば、本実施形態に係る光硬化性組成物を液晶滴下工法用液晶シール剤として用いて狭ギャップの液晶セルを製造する際に、上下のガラス基板の貼り合わせ時のギャップ形成がうまくできる傾向にある。また、好ましい下限は１０ｎｍ程度であり、より好ましくは１００ｎｍ程度である。粒子径は、レーザー回折・散乱式粒度分布測定器（乾式）（株式会社セイシン企業製；ＬＭＳ－３０）により測定することができる。
The average particle size of the inorganic filler is suitably 2000 nm or less, preferably 1000 nm or less, more preferably 300 nm or less. When the average particle diameter of the inorganic filler is 2000 nm or less, for example, when producing a narrow gap liquid crystal cell using the photocurable composition according to the present embodiment as a liquid crystal sealing agent for a liquid crystal dropping method, the upper and lower There is a tendency that a gap can be formed well when a glass substrate is bonded. Moreover, a preferable minimum is about 10 nm, More preferably, it is about 100 nm. The particle diameter can be measured with a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
本実施形態に係る光硬化性組成物が無機フィラーを含有する場合、その含有率は、光硬化性組成物の総量中、通常５～５０質量％であり、好ましくは５～４０質量％である。無機フィラーの含有量を５質量％以上とすることで、ガラス基板に対する接着強度が向上し、また耐湿信頼性も向上するために、吸湿後の接着強度の低下が抑えられる傾向にある。無機フィラーの含有量を５０質量％以下とすることで、例えば、本実施形態に係る光硬化性組成物を液晶滴下工法用液晶シール剤として用いて液晶セルを製造する際に、無機フィラーが潰れやすくなり、うまくできる傾向にある。
When the photocurable composition according to the present embodiment contains an inorganic filler, the content is usually 5 to 50% by mass, preferably 5 to 40% by mass, based on the total amount of the photocurable composition. . By setting the content of the inorganic filler to 5% by mass or more, the adhesive strength to the glass substrate is improved and the moisture resistance reliability is also improved, so that a decrease in the adhesive strength after moisture absorption tends to be suppressed. When the content of the inorganic filler is 50% by mass or less, for example, when the liquid crystal cell is produced using the photocurable composition according to the present embodiment as a liquid crystal sealing agent for a liquid crystal dropping method, the inorganic filler is crushed. It tends to be easier and better.
［シランカップリング剤］
本実施形態に係る光硬化性組成物は、接着強度や耐湿性の向上を図るため、シランカップリング剤を含有していてもよい。シランカップリング剤は、１種を単独で使用してもよく、２種以上を併用してもよい。 [Silane coupling agent]
The photocurable composition according to this embodiment may contain a silane coupling agent in order to improve adhesive strength and moisture resistance. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.
本実施形態に係る光硬化性組成物は、接着強度や耐湿性の向上を図るため、シランカップリング剤を含有していてもよい。シランカップリング剤は、１種を単独で使用してもよく、２種以上を併用してもよい。 [Silane coupling agent]
The photocurable composition according to this embodiment may contain a silane coupling agent in order to improve adhesive strength and moisture resistance. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.
シランカップリング剤としては、例えば、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）３－アミノプロピルメチルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、ビニルトリメトキシシラン、Ｎ－（２－（ビニルベンジルアミノ）エチル）３－アミノプロピルトリメトキシシラン塩酸塩、３－メタクリロキシプロピルトリメトキシシラン、３－クロロプロピルメチルジメトキシシラン、３－クロロプロピルトリメトキシシラン等が挙げられる。これらのシランカップリング剤は、ＫＢＭシリーズ、ＫＢＥシリーズ等として信越化学工業株式会社等によって販売されているため、市場から容易に入手可能である。
Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl). Ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxy Silane 3-chloropropyl methyl dimethoxy silane, 3-chloropropyl trimethoxy silane, and the like. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. as KBM series, KBE series, etc., they are easily available from the market.
本実施形態に係る光硬化性組成物がシランカップリング剤を含有する場合、その含有率は、光硬化性組成物の総量中、０．０５～３質量％が好適である。
When the photocurable composition according to this embodiment contains a silane coupling agent, the content is preferably 0.05 to 3% by mass in the total amount of the photocurable composition.
［熱硬化剤］
本実施形態に係る光硬化性組成物は、熱硬化剤を含有していてもよい。熱硬化剤は、１種を単独で使用してもよく、２種以上を併用してもよい。 [Thermosetting agent]
The photocurable composition according to this embodiment may contain a thermosetting agent. A thermosetting agent may be used individually by 1 type, and may use 2 or more types together.
本実施形態に係る光硬化性組成物は、熱硬化剤を含有していてもよい。熱硬化剤は、１種を単独で使用してもよく、２種以上を併用してもよい。 [Thermosetting agent]
The photocurable composition according to this embodiment may contain a thermosetting agent. A thermosetting agent may be used individually by 1 type, and may use 2 or more types together.
熱硬化剤は、非共有電子対や分子内のアニオンによって、求核的に反応するものであり、例えば、多価アミン類、多価フェノール類、有機酸ヒドラジド化合物等を挙げることができる。これらの中でも、有機酸ヒドラジド化合物が好適に用いられる。
The thermosetting agent reacts nucleophilically with an unshared electron pair or an anion in the molecule, and examples thereof include polyvalent amines, polyhydric phenols, and organic acid hydrazide compounds. Among these, organic acid hydrazide compounds are preferably used.
有機酸ヒドラジド化合物のうち芳香族ヒドラジド化合物としては、例えば、テレフタル酸ジヒドラジド、イソフタル酸ジヒドラジド、２，６－ナフトエ酸ジヒドラジド、２，６－ピリジンジヒドラジド、１，２，４－ベンゼントリヒドラジド、１，４，５，８－ナフトエ酸テトラヒドラジド、ピロメリット酸テトラヒドラジド等が挙げられる。また、有機酸ヒドラジド化合物のうち脂肪族ヒドラジド化合物としては、例えば、ホルムヒドラジド、アセトヒドラジド、プロピオン酸ヒドラジド、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジド、ピメリン酸ジヒドラジド、セバシン酸ジヒドラジド、１，４－シクロヘキサンジヒドラジド、酒石酸ジヒドラジド、リンゴ酸ジヒドラジド、イミノジ酢酸ジヒドラジド、Ｎ，Ｎ’－ヘキサメチレンビスセミカルバジド、クエン酸トリヒドラジド、ニトリロ酢酸トリヒドラジド、シクロヘキサントリカルボン酸トリヒドラジド、１，３－ビス（ヒドラジノカルボノエチル）－５－イソプロピルヒダントイン等のヒダントイン骨格、好ましくはバリンヒダントイン骨格（ヒダントイン環の炭素原子がイソプロピル基で置換された骨格）を有するジヒドラジド化合物、トリス（１－ヒドラジノカルボニルメチル）イソシアヌレート、トリス（２－ヒドラジノカルボニルエチル）イソシアヌレート、トリス（１－ヒドラジノカルボニルエチル）イソシアヌレート、トリス（３－ヒドラジノカルボニルプロピル）イソシアヌレート、ビス（２－ヒドラジノカルボニルエチル）イソシアヌレート等が挙げられる。
Among the organic acid hydrazide compounds, examples of the aromatic hydrazide compound include terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzenetrihydrazide, 1, Examples include 4,5,8-naphthoic acid tetrahydrazide and pyromellitic acid tetrahydrazide. Examples of the aliphatic hydrazide compound among the organic acid hydrazide compounds include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and pimelic acid dihydrazide. , Sebacic acid dihydrazide, 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N′-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1 , 3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin and the like, preferably a valine hydantoin skeleton ( Dihydrazide compounds having a skeleton in which the carbon atom of the danttoin ring is substituted with an isopropyl group), tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (1-hydrazinocarbonyl) And ethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, and bis (2-hydrazinocarbonylethyl) isocyanurate.
有機酸ヒドラジド化合物の中でも、硬化反応性と潜在性とのバランスから、イソフタル酸ジヒドラジド、マロン酸ジヒドラジド、アジピン酸ジヒドラジド、トリス（１－ヒドラジノカルボニルメチル）イソシアヌレート、トリス（１－ヒドラジノカルボニルエチル）イソシアヌレート、トリス（２－ヒドラジノカルボニルエチル）イソシアヌレート、及びトリス（３－ヒドラジノカルボニルプロピル）イソシアヌレートが好ましく、トリス（２－ヒドラジノカルボニルエチル）イソシアヌレートがより好ましい。
Among organic acid hydrazide compounds, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) are selected from the balance between curing reactivity and potential. ) Isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, and tris (3-hydrazinocarbonylpropyl) isocyanurate are preferred, and tris (2-hydrazinocarbonylethyl) isocyanurate is more preferred.
本実施形態に係る光硬化性組成物が熱硬化剤を含有する場合、その含有率は、光硬化性組成物の総量中、通常０．１～１０質量％であり、好ましくは１～５質量％である。
When the photocurable composition according to the present embodiment contains a thermosetting agent, the content is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the photocurable composition. %.
［熱ラジカル重合開始剤］
本実施形態に係る光硬化性組成物は、硬化速度及び硬化性を向上するため、熱ラジカル重合開始剤を含有していてもよい。熱ラジカル重合開始剤は、１種を単独で使用してもよく、２種以上を併用してもよい。 [Thermal radical polymerization initiator]
The photocurable composition according to this embodiment may contain a thermal radical polymerization initiator in order to improve the curing rate and curability. A thermal radical polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
本実施形態に係る光硬化性組成物は、硬化速度及び硬化性を向上するため、熱ラジカル重合開始剤を含有していてもよい。熱ラジカル重合開始剤は、１種を単独で使用してもよく、２種以上を併用してもよい。 [Thermal radical polymerization initiator]
The photocurable composition according to this embodiment may contain a thermal radical polymerization initiator in order to improve the curing rate and curability. A thermal radical polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
熱ラジカル重合開始剤としては、加熱によりラジカルを生じ、連鎖重合反応を開始させる化合物であれば特に限定されず、有機過酸化物、アゾ化合物、ベンゾイン化合物、ベンゾインエーテル化合物、アセトフェノン化合物、ベンゾピナコール等が挙げられ、ベンゾピナコールが好適に用いられる。
The thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction, such as organic peroxide, azo compound, benzoin compound, benzoin ether compound, acetophenone compound, benzopinacol, etc. And benzopinacol is preferably used.
有機過酸化物の市販品としては、カヤメックＲＴＭＡ、Ｍ、Ｒ、Ｌ、ＬＨ、ＳＰ－３０Ｃ、パーカドックスＣＨ－５０Ｌ、ＢＣ－ＦＦ、カドックスＢ－４０ＥＳ、パーカドックス１４、トリゴノックスＲＴＭ２２－７０Ｅ、２３－Ｃ７０、１２１、１２１－５０Ｅ、１２１－ＬＳ５０Ｅ、２１－ＬＳ５０Ｅ、４２、４２ＬＳ、カヤエステルＲＴＭＰ－７０、ＴＭＰＯ－７０、ＣＮＤ－Ｃ７０、ＯＯ－５０Ｅ、ＡＮ、カヤブチルＲＴＭＢ、パーカドックス１６、カヤカルボンＲＴＭＢＩＣ－７５、ＡＩＣ－７５（以上、化薬アクゾ株式会社製）；パーメックＲＴＭＮ、Ｈ、Ｓ、Ｆ、Ｄ、Ｇ、パーヘキサＲＴＭＨ、ＨＣ、ＴＭＨ、Ｃ、Ｖ、２２、ＭＣ、パーキュアーＲＴＭＡＨ、ＡＬ、ＨＢ、パーブチルＲＴＭＨ、Ｃ、ＮＤ、Ｌ、パークミルＲＴＭＨ、Ｄ、パーロイルＲＴＭＩＢ、ＩＰＰ、パーオクタＲＴＭＮＤ（以上、日油株式会社製）；等が挙げられる。
Commercially available organic peroxides include Kayamek RTM A, M, R, L, LH, SP-30C, Parkadox CH-50L, BC-FF, Cadox B-40ES, Parkadox 14, Trigonox RTM 22-70E. 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl RTM B, Parkardox 16, Kayacaron RTM BIC-75, AIC-75 (above, manufactured by Kayaku Akzo Co., Ltd.); Permec RTM N, H, S, F, D, G, Perhexa RTM H, HC, TMH, C, V, 22, MC, Pakyua RTM AH, AL, HB, Perbutyl RTM H, C, ND, L , Pakumi RTM H, D, PEROYL RTM IB, IPP, Perocta RTM ND (manufactured by NOF CORPORATION); and the like.
また、アゾ化合物の市販品としては、ＶＡ－０４４、０８６、Ｖ－０７０、ＶＰＥ－０２０１、ＶＳＰ－１００１（以上、和光純薬工業株式会社製）等が挙げられる。
Further, examples of commercially available azo compounds include VA-044, 086, V-070, VPE-0201, VSP-1001 (above, manufactured by Wako Pure Chemical Industries, Ltd.) and the like.
本実施形態に係る光硬化性組成物が熱ラジカル重合開始剤を含有する場合、その含有率は、光硬化性組成物の総量中、通常０．０００１～１０質量％であり、好ましくは０．０００５～５質量％であり、より好ましくは０．００１～３質量％である。
When the photocurable composition according to the present embodiment contains a thermal radical polymerization initiator, the content thereof is usually 0.0001 to 10% by mass in the total amount of the photocurable composition, preferably 0.00. It is 0005 to 5% by mass, and more preferably 0.001 to 3% by mass.
［その他の成分］
本実施形態に係る光硬化性組成物は、必要に応じて、硬化促進剤、ラジカル重合防止剤、顔料、レベリング剤、消泡剤、溶剤などの添加剤を含有していてもよい。 [Other ingredients]
The photocurable composition concerning this embodiment may contain additives, such as a hardening accelerator, a radical polymerization inhibitor, a pigment, a leveling agent, an antifoamer, and a solvent, as needed.
本実施形態に係る光硬化性組成物は、必要に応じて、硬化促進剤、ラジカル重合防止剤、顔料、レベリング剤、消泡剤、溶剤などの添加剤を含有していてもよい。 [Other ingredients]
The photocurable composition concerning this embodiment may contain additives, such as a hardening accelerator, a radical polymerization inhibitor, a pigment, a leveling agent, an antifoamer, and a solvent, as needed.
（硬化促進剤）
硬化促進剤としては、有機酸、イミダゾール等が挙げられる。
有機酸としては、有機カルボン酸、有機リン酸等が挙げられ、有機カルボン酸が好ましい。具体的には、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、フランジカルボン酸、コハク酸、アジピン酸、ドデカン二酸、セバシン酸、チオジプロピオン酸、シクロヘキサンジカルボン酸、トリス（２－カルボキシメチル）イソシアヌレート、トリス（２－カルボキシエチル）イソシアヌレート、トリス（２－カルボキシプロピル）イソシアヌレート、ビス（２－カルボキシエチル）イソシアヌレート等が挙げられる。
イミダゾール化合物としては、２－メチルイミダゾール、２－フェニルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、２－フェニル－４－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－シアノエチル－２－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール、２，４－ジアミノ－６（２’－メチルイミダゾール（１’））エチル－ｓ－トリアジン、２，４－ジアミノ－６（２’－ウンデシルイミダゾール（１’））エチル－ｓ－トリアジン、２，４－ジアミノ－６（２’－エチル－４－メチルイミダゾール（１’））エチル－ｓ－トリアジン、２，４－ジアミノ－６（２’－メチルイミダゾール（１’））エチル－ｓ－トリアジン・イソシアヌル酸付加物、２－メチルイミダゾールイソシアヌル酸の２：３付加物、２－フェニルイミダゾールイソシアヌル酸付加物、２－フェニル－３，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－ヒドロキシメチル－５－メチルイミダゾール、１－シアノエチル－２－フェニル－３，５－ジシアノエトキシメチルイミダゾール等が挙げられる。 (Curing accelerator)
Examples of the curing accelerator include organic acids and imidazoles.
Examples of the organic acid include organic carboxylic acid and organic phosphoric acid, and organic carboxylic acid is preferable. Specifically, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, tris (2-Carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (2-carboxypropyl) isocyanurate, bis (2-carboxyethyl) isocyanurate and the like.
Examples of imidazole compounds include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl-2. -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl-4-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-methyl) Midazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and the like.
硬化促進剤としては、有機酸、イミダゾール等が挙げられる。
有機酸としては、有機カルボン酸、有機リン酸等が挙げられ、有機カルボン酸が好ましい。具体的には、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、フランジカルボン酸、コハク酸、アジピン酸、ドデカン二酸、セバシン酸、チオジプロピオン酸、シクロヘキサンジカルボン酸、トリス（２－カルボキシメチル）イソシアヌレート、トリス（２－カルボキシエチル）イソシアヌレート、トリス（２－カルボキシプロピル）イソシアヌレート、ビス（２－カルボキシエチル）イソシアヌレート等が挙げられる。
イミダゾール化合物としては、２－メチルイミダゾール、２－フェニルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、２－フェニル－４－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－シアノエチル－２－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール、２，４－ジアミノ－６（２’－メチルイミダゾール（１’））エチル－ｓ－トリアジン、２，４－ジアミノ－６（２’－ウンデシルイミダゾール（１’））エチル－ｓ－トリアジン、２，４－ジアミノ－６（２’－エチル－４－メチルイミダゾール（１’））エチル－ｓ－トリアジン、２，４－ジアミノ－６（２’－メチルイミダゾール（１’））エチル－ｓ－トリアジン・イソシアヌル酸付加物、２－メチルイミダゾールイソシアヌル酸の２：３付加物、２－フェニルイミダゾールイソシアヌル酸付加物、２－フェニル－３，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－ヒドロキシメチル－５－メチルイミダゾール、１－シアノエチル－２－フェニル－３，５－ジシアノエトキシメチルイミダゾール等が挙げられる。 (Curing accelerator)
Examples of the curing accelerator include organic acids and imidazoles.
Examples of the organic acid include organic carboxylic acid and organic phosphoric acid, and organic carboxylic acid is preferable. Specifically, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid, cyclohexanedicarboxylic acid, tris (2-Carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (2-carboxypropyl) isocyanurate, bis (2-carboxyethyl) isocyanurate and the like.
Examples of imidazole compounds include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl-2. -Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl-4-methylimidazole (1 ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-methyl) Midazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and the like.
本実施形態に係る光硬化性組成物が硬化促進剤を含有する場合、その含有率は、光硬化性組成物の総量中、通常０．１～１０質量％であり、好ましくは１～５質量％である。
When the photocurable composition according to this embodiment contains a curing accelerator, the content thereof is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the photocurable composition. %.
（ラジカル重合防止剤）
ラジカル重合防止剤としては、光ラジカル重合開始剤や熱ラジカル重合開始剤等から発生するラジカルと反応して重合を防止する化合物であれば特に限定されるものではなく、キノン系、ピペリジン系、ヒンダードフェノール系、ニトロソ系等のラジカル重合防止剤が挙げられる。具体的には、ナフトキノン、２－ヒドロキシナフトキノン、２－メチルナフトキノン、２－メトキシナフトキノン、２，２，６，６－テトラメチルピペリジン－１－オキシル、２，２，６，６－テトラメチル－４－ヒドロキシピペリジン－１－オキシル、２，２，６，６，－テトラメチル－４－メトキシピペリジン－１－オキシル、２，２，６，６－テトラメチル－４－フェノキシピペリジン－１－オキシル、ハイドロキノン、２－メチルハイドロキノン、２－メトキシハイドロキノン、パラベンゾキノン、ブチル化ヒドロキシアニソール、２，６－ジ－ｔ－ブチル－４－エチルフェノール、２，６－ジ－ｔ－ブチルクレゾール、ステアリルβ－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、２，２’－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、４，４’－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、３，９－ビス［１，１－ジメチル－２－［β―（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ］エチル］、２，４，８，１０－テトラオキサスピロ［５，５］ウンデカン、テトラキス－［メチレン－３－（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシフェニルプロピオネート）］メタン、１，３，５－トリス（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシベンジル）－ｓｅｃ－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）トリオン、パラメトキシフェノール、４－メトキシ－１－ナフトール、チオジフェニルアミン、Ｎ－ニトロソフェニルヒドロキシアミンのアルミニウム塩、商品名アデカスタブＬＡ－８１、商品名アデカスタブＬＡ－８２（いずれも株式会社アデカ製）等が挙げられる。これらの中でも、ナフトキノン系、ハイドロキノン系、ニトロソ系、ピペリジン系のラジカル重合防止剤が好ましく、ナフトキノン、２－ヒドロキシナフトキノン、ハイドロキノン、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ポリストップ７３００Ｐ（伯東株式会社製）がより好ましく、ポリストップ７３００Ｐ（伯東株式会社製）がさらに好ましい。 (Radical polymerization inhibitor)
The radical polymerization inhibitor is not particularly limited as long as it is a compound that prevents polymerization by reacting with radicals generated from a photo radical polymerization initiator or a thermal radical polymerization initiator, and is not limited to quinone, piperidine, hinders. Examples include radical polymerization inhibitors such as dophenol and nitroso. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethyl-4 -Hydroxypiperidine-1-oxyl, 2,2,6,6, -tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxyl, hydroquinone 2-methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearyl β- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis 4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9 -Bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxaspiro [5 5] Undecane, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenylpropionate)] methane, 1,3,5-tris (3 ′, 5′-di -T-butyl-4'-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, paramethoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N- Toro Seo aluminum salts of phenyl hydroxylamine, trade name ADK STAB LA-81, include the trade name ADK STAB LA-82 (all manufactured by Ltd. Adeka) and the like. Of these, naphthoquinone, hydroquinone, nitroso, and piperidine radical polymerization inhibitors are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, polystop 7300P ( Hakuto Co., Ltd.) is more preferable, and Polystop 7300P (Hakuto Co., Ltd.) is more preferable.
ラジカル重合防止剤としては、光ラジカル重合開始剤や熱ラジカル重合開始剤等から発生するラジカルと反応して重合を防止する化合物であれば特に限定されるものではなく、キノン系、ピペリジン系、ヒンダードフェノール系、ニトロソ系等のラジカル重合防止剤が挙げられる。具体的には、ナフトキノン、２－ヒドロキシナフトキノン、２－メチルナフトキノン、２－メトキシナフトキノン、２，２，６，６－テトラメチルピペリジン－１－オキシル、２，２，６，６－テトラメチル－４－ヒドロキシピペリジン－１－オキシル、２，２，６，６，－テトラメチル－４－メトキシピペリジン－１－オキシル、２，２，６，６－テトラメチル－４－フェノキシピペリジン－１－オキシル、ハイドロキノン、２－メチルハイドロキノン、２－メトキシハイドロキノン、パラベンゾキノン、ブチル化ヒドロキシアニソール、２，６－ジ－ｔ－ブチル－４－エチルフェノール、２，６－ジ－ｔ－ブチルクレゾール、ステアリルβ－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、２，２’－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、４，４’－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、３，９－ビス［１，１－ジメチル－２－［β―（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ］エチル］、２，４，８，１０－テトラオキサスピロ［５，５］ウンデカン、テトラキス－［メチレン－３－（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシフェニルプロピオネート）］メタン、１，３，５－トリス（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシベンジル）－ｓｅｃ－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）トリオン、パラメトキシフェノール、４－メトキシ－１－ナフトール、チオジフェニルアミン、Ｎ－ニトロソフェニルヒドロキシアミンのアルミニウム塩、商品名アデカスタブＬＡ－８１、商品名アデカスタブＬＡ－８２（いずれも株式会社アデカ製）等が挙げられる。これらの中でも、ナフトキノン系、ハイドロキノン系、ニトロソ系、ピペリジン系のラジカル重合防止剤が好ましく、ナフトキノン、２－ヒドロキシナフトキノン、ハイドロキノン、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ポリストップ７３００Ｐ（伯東株式会社製）がより好ましく、ポリストップ７３００Ｐ（伯東株式会社製）がさらに好ましい。 (Radical polymerization inhibitor)
The radical polymerization inhibitor is not particularly limited as long as it is a compound that prevents polymerization by reacting with radicals generated from a photo radical polymerization initiator or a thermal radical polymerization initiator, and is not limited to quinone, piperidine, hinders. Examples include radical polymerization inhibitors such as dophenol and nitroso. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethyl-4 -Hydroxypiperidine-1-oxyl, 2,2,6,6, -tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4-phenoxypiperidine-1-oxyl, hydroquinone 2-methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearyl β- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis 4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9 -Bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxaspiro [5 5] Undecane, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenylpropionate)] methane, 1,3,5-tris (3 ′, 5′-di -T-butyl-4'-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, paramethoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N- Toro Seo aluminum salts of phenyl hydroxylamine, trade name ADK STAB LA-81, include the trade name ADK STAB LA-82 (all manufactured by Ltd. Adeka) and the like. Of these, naphthoquinone, hydroquinone, nitroso, and piperidine radical polymerization inhibitors are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, polystop 7300P ( Hakuto Co., Ltd.) is more preferable, and Polystop 7300P (Hakuto Co., Ltd.) is more preferable.
本実施形態に係る光硬化性組成物がラジカル重合防止剤を含有する場合、その含有率は、光硬化性組成物の総量中、通常０．０００１～１質量％であり、好ましくは０．００１～０．５質量％であり、より好ましくは０．０１～０．２質量％である。
When the photocurable composition according to this embodiment contains a radical polymerization inhibitor, the content thereof is usually 0.0001 to 1% by mass, preferably 0.001 in the total amount of the photocurable composition. It is -0.5 mass%, More preferably, it is 0.01-0.2 mass%.
［光硬化性組成物の粘度］
本実施形態に係る光硬化性組成物の２５℃における粘度は、１５０～５００Ｐａ・ｓが好ましく、２００～５００Ｐａ・ｓがより好ましい。特に、本実施形態に係る光硬化性組成物を液晶シール剤として用いる場合、光硬化性組成物の２５℃における粘度は、２５０～４００Ｐａ・ｓが好ましく、２８０～３２０Ｐａ・ｓがより好ましい。粘度を２５０Ｐａ・ｓ以上とすることで、液晶の差し込みの発生が抑えられ、セル化が容易になる傾向にある。粘度を４００Ｐａ・ｓ以下とすることで、液晶シール剤の塗布が容易になる傾向にある。 [Viscosity of photocurable composition]
The viscosity at 25 ° C. of the photocurable composition according to this embodiment is preferably 150 to 500 Pa · s, more preferably 200 to 500 Pa · s. In particular, when the photocurable composition according to this embodiment is used as a liquid crystal sealant, the viscosity of the photocurable composition at 25 ° C. is preferably 250 to 400 Pa · s, and more preferably 280 to 320 Pa · s. By setting the viscosity to 250 Pa · s or more, occurrence of liquid crystal insertion is suppressed, and cell formation tends to be facilitated. When the viscosity is 400 Pa · s or less, application of the liquid crystal sealant tends to be easy.
本実施形態に係る光硬化性組成物の２５℃における粘度は、１５０～５００Ｐａ・ｓが好ましく、２００～５００Ｐａ・ｓがより好ましい。特に、本実施形態に係る光硬化性組成物を液晶シール剤として用いる場合、光硬化性組成物の２５℃における粘度は、２５０～４００Ｐａ・ｓが好ましく、２８０～３２０Ｐａ・ｓがより好ましい。粘度を２５０Ｐａ・ｓ以上とすることで、液晶の差し込みの発生が抑えられ、セル化が容易になる傾向にある。粘度を４００Ｐａ・ｓ以下とすることで、液晶シール剤の塗布が容易になる傾向にある。 [Viscosity of photocurable composition]
The viscosity at 25 ° C. of the photocurable composition according to this embodiment is preferably 150 to 500 Pa · s, more preferably 200 to 500 Pa · s. In particular, when the photocurable composition according to this embodiment is used as a liquid crystal sealant, the viscosity of the photocurable composition at 25 ° C. is preferably 250 to 400 Pa · s, and more preferably 280 to 320 Pa · s. By setting the viscosity to 250 Pa · s or more, occurrence of liquid crystal insertion is suppressed, and cell formation tends to be facilitated. When the viscosity is 400 Pa · s or less, application of the liquid crystal sealant tends to be easy.
［光硬化性組成物の調製方法］
本実施形態に係る光硬化性組成物の調製方法の一例としては、次に示す方法が挙げられる。まず、硬化性化合物に、上記特定化合物を加熱溶解する。次いで、室温まで冷却した後、必要に応じて、有機フィラー、無機フィラー、シランカップリング剤、熱硬化剤、熱ラジカル重合開始剤、消泡剤、レベリング剤、溶剤等を添加する。そして、３本ロール、サンドミル、ボールミル等の公知の混合装置により均一に混合し、金属メッシュにて濾過することにより、本実施形態に係る光硬化性組成物を調製することができる。 [Method for Preparing Photocurable Composition]
Examples of the method for preparing the photocurable composition according to this embodiment include the following methods. First, the specific compound is heated and dissolved in the curable compound. Subsequently, after cooling to room temperature, an organic filler, an inorganic filler, a silane coupling agent, a thermosetting agent, a thermal radical polymerization initiator, an antifoaming agent, a leveling agent, a solvent, etc. are added as needed. And the photocurable composition which concerns on this embodiment can be prepared by mixing uniformly with well-known mixing apparatuses, such as a 3 roll, a sand mill, and a ball mill, and filtering with a metal mesh.
本実施形態に係る光硬化性組成物の調製方法の一例としては、次に示す方法が挙げられる。まず、硬化性化合物に、上記特定化合物を加熱溶解する。次いで、室温まで冷却した後、必要に応じて、有機フィラー、無機フィラー、シランカップリング剤、熱硬化剤、熱ラジカル重合開始剤、消泡剤、レベリング剤、溶剤等を添加する。そして、３本ロール、サンドミル、ボールミル等の公知の混合装置により均一に混合し、金属メッシュにて濾過することにより、本実施形態に係る光硬化性組成物を調製することができる。 [Method for Preparing Photocurable Composition]
Examples of the method for preparing the photocurable composition according to this embodiment include the following methods. First, the specific compound is heated and dissolved in the curable compound. Subsequently, after cooling to room temperature, an organic filler, an inorganic filler, a silane coupling agent, a thermosetting agent, a thermal radical polymerization initiator, an antifoaming agent, a leveling agent, a solvent, etc. are added as needed. And the photocurable composition which concerns on this embodiment can be prepared by mixing uniformly with well-known mixing apparatuses, such as a 3 roll, a sand mill, and a ball mill, and filtering with a metal mesh.
＜光硬化性組成物の用途等＞
本実施形態に係る光硬化性組成物は、電子部品用封止剤又は電子部品用接着剤として非常に有用である。電子部品用封止剤又は電子部品用接着剤としては、フレキシブルプリント配線板用接着剤、ＴＡＢ用接着剤、半導体用接着剤、各種ディスプレイ用接着剤等が挙げられるが、これらに限定されるものではない。 <Uses of photocurable composition>
The photocurable composition according to the present embodiment is very useful as an electronic component sealant or an electronic component adhesive. Examples of the electronic component sealant or the electronic component adhesive include, but are not limited to, flexible printed wiring board adhesives, TAB adhesives, semiconductor adhesives, various display adhesives, and the like. is not.
本実施形態に係る光硬化性組成物は、電子部品用封止剤又は電子部品用接着剤として非常に有用である。電子部品用封止剤又は電子部品用接着剤としては、フレキシブルプリント配線板用接着剤、ＴＡＢ用接着剤、半導体用接着剤、各種ディスプレイ用接着剤等が挙げられるが、これらに限定されるものではない。 <Uses of photocurable composition>
The photocurable composition according to the present embodiment is very useful as an electronic component sealant or an electronic component adhesive. Examples of the electronic component sealant or the electronic component adhesive include, but are not limited to, flexible printed wiring board adhesives, TAB adhesives, semiconductor adhesives, various display adhesives, and the like. is not.
また、本実施形態に係る光硬化性組成物は、液晶表示セル用接着剤として、特に液晶シール剤として非常に有用である。本実施形態に係る光硬化性組成物を液晶シール剤として用いた場合の液晶表示セルについて、以下に例を示す。
Also, the photocurable composition according to this embodiment is very useful as an adhesive for liquid crystal display cells, particularly as a liquid crystal sealant. An example is shown below about the liquid crystal display cell at the time of using the photocurable composition which concerns on this embodiment as a liquid-crystal sealing compound.
液晶表示セル用接着剤を用いて製造される液晶表示セルは、基板に所定の電極を形成した一対の基板を所定の間隔に対向配置し、周囲を液晶シール剤でシールし、その間隙に液晶が封入されたものである。封入される液晶の種類は特に限定されない。基板は、ガラス、石英、プラスチック、シリコーン等からなる少なくとも一方に光透過性がある組み合わせの基板から構成される。
A liquid crystal display cell manufactured using an adhesive for a liquid crystal display cell has a pair of substrates each having a predetermined electrode formed on the substrate opposed to each other at a predetermined interval, and the periphery is sealed with a liquid crystal sealant, and a liquid crystal is interposed in the gap. Is enclosed. The kind of liquid crystal to be sealed is not particularly limited. The substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicone, etc. and having light transmission properties.
液晶表示セルの製造方法は、例えば以下のとおりである。
まず、液晶シール剤にスペーサ（間隙制御材）を添加する。スペーサとしては、グラスファイバー、シリカビーズ、ポリマービーズ等が挙げられる。スペーサの直径は目的に応じ異なるが、通常２～８μｍ、好ましくは４～７μｍである。その使用量は、液晶シール剤１００質量部に対し、通常０．１～４質量部であり、好ましくは０．５～２質量部であり、より好ましくは０．９～１．５質量部程度である。 The manufacturing method of a liquid crystal display cell is as follows, for example.
First, a spacer (gap control material) is added to the liquid crystal sealant. Examples of the spacer include glass fiber, silica beads, and polymer beads. The diameter of the spacer varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount of use is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, more preferably about 0.9 to 1.5 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. It is.
まず、液晶シール剤にスペーサ（間隙制御材）を添加する。スペーサとしては、グラスファイバー、シリカビーズ、ポリマービーズ等が挙げられる。スペーサの直径は目的に応じ異なるが、通常２～８μｍ、好ましくは４～７μｍである。その使用量は、液晶シール剤１００質量部に対し、通常０．１～４質量部であり、好ましくは０．５～２質量部であり、より好ましくは０．９～１．５質量部程度である。 The manufacturing method of a liquid crystal display cell is as follows, for example.
First, a spacer (gap control material) is added to the liquid crystal sealant. Examples of the spacer include glass fiber, silica beads, and polymer beads. The diameter of the spacer varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount of use is usually 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, more preferably about 0.9 to 1.5 parts by mass with respect to 100 parts by mass of the liquid crystal sealant. It is.
次いで、一対の基板の一方にディスペンサー、スクリーン印刷装置等を用いて液晶シール剤を塗布した後、必要に応じて８０～１２０℃で仮硬化を行う。その後、液晶シール剤の堰の内側に液晶を滴下し、真空中にてもう一方のガラス基板を重ね合わせ、ギャップ出しを行う。ギャップ形成後、９０～１３０℃で１～２時間硬化することにより、液晶表示セルを得ることができる。また、光熱併用型として使用する場合は、紫外線照射機により液晶シール剤に紫外線を照射させて光硬化させる。紫外線照射量は、好ましくは５００～６０００ｍＪ／ｃｍ２、より好ましくは１０００～４０００ｍＪ／ｃｍ２である。その後、必要に応じて９０～１３０℃で１～２時間硬化することにより、液晶表示セルを得ることができる。このようにして得られた液晶表示セルは、液晶汚染による表示不良がなく、接着性及び耐湿信頼性に優れたものである。
Next, after applying a liquid crystal sealant to one of the pair of substrates using a dispenser, a screen printing apparatus, or the like, temporary curing is performed at 80 to 120 ° C. as necessary. Thereafter, the liquid crystal is dropped inside the weir of the liquid crystal sealant, and the other glass substrate is overlaid in a vacuum to create a gap. After forming the gap, the liquid crystal display cell can be obtained by curing at 90 to 130 ° C. for 1 to 2 hours. When used as a photothermal combination type, the liquid crystal sealant is irradiated with ultraviolet rays by an ultraviolet irradiator and photocured. The amount of ultraviolet irradiation is preferably 500 to 6000 mJ / cm 2 , more preferably 1000 to 4000 mJ / cm 2 . Thereafter, if necessary, it is cured at 90 to 130 ° C. for 1 to 2 hours to obtain a liquid crystal display cell. The liquid crystal display cell thus obtained does not have a display defect due to liquid crystal contamination, and has excellent adhesion and moisture resistance reliability.
本実施形態に係る光硬化性組成物は、遮光部を有する設計の電子部品や可視光のような低エネルギー光で硬化する必要のある接着剤用途の使用に非常に適するものである。例えば、配線遮光部下で用いられる液晶表示用シール剤、有機ＥＬ用封止剤、タッチパネル用接着剤として好適である。
The photocurable composition according to the present embodiment is very suitable for use in an electronic component designed to have a light-shielding portion and an adhesive application that needs to be cured with low energy light such as visible light. For example, it is suitable as a liquid crystal display sealing agent, an organic EL sealing agent, and a touch panel adhesive used under a wiring light shielding portion.
以下、実施例により本発明をさらに詳細に説明するが、本発明は実施例に限定されるものではない。なお、特別の記載のない限り、本文中「％」とあるのは質量基準である。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. Unless otherwise specified, “%” in the text is based on mass.
＜合成例１＞
［２－アセチルチオキサントンの合成］ <Synthesis Example 1>
[Synthesis of 2-acetylthioxanthone]
［２－アセチルチオキサントンの合成］ <Synthesis Example 1>
[Synthesis of 2-acetylthioxanthone]
２－アセチルチオキサントンは、先行文献（Ｍａｔｅｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ，Ｖｏｌ．２７，Ｎｏ．６（２００９），ｐｐ．２４２－２５１）記載の合成手順に従い合成した。
2-Acetylthioxanthone was synthesized according to the synthesis procedure described in the prior literature (Material Technology, Vol. 27, No. 6 (2009), pp. 242-251).
［ＴＸ－ＯＸＥ（化合物番号１）の合成］
[Synthesis of TX-OXE (Compound No. 1)]
２００ｍＬの４つ口反応容器に温度計及び冷却管を設置し、流速３０ｍＬ／ｍｉｎで窒素フローを開始した。反応容器に２－アセチルチオキサントン（０．５０ｇ）、ヒドロキシルアミン塩酸塩（０．２０ｇ）、及びＮ，Ｎ－ジメチルホルムアミド（６０ｍＬ）を加え、８０℃で４時間反応を行った。水５０ｍＬを加えて反応を停止させ、メチルイソブチルケトン（２００ｍＬ）で抽出し、水５０ｍＬで３回水洗した。エバポレータを用いて溶剤を除去し、２－アセチルチオキサントンのオキシム化体（ＴＸ－ＯＸ／黄色固体）を得た。ここで得られた黄色固体（粗結晶）をそのままオキシムエステル化反応に用いた。
A thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min. 2-Acetylthioxanthone (0.50 g), hydroxylamine hydrochloride (0.20 g), and N, N-dimethylformamide (60 mL) were added to the reaction vessel and reacted at 80 ° C. for 4 hours. The reaction was stopped by adding 50 mL of water, extracted with methyl isobutyl ketone (200 mL), and washed with 50 mL of water three times. The solvent was removed using an evaporator to obtain an oxime product of 2-acetylthioxanthone (TX-OX / yellow solid). The yellow solid (crude crystals) obtained here was used for the oxime esterification reaction as it was.
２００ｍＬの４つ口反応容器に温度計及び冷却管を設置し、流速３０ｍＬ／ｍｉｎで窒素フローを開始した。反応容器にＴＸ－ＯＸの全量、無水酢酸（０．２４ｇ）、及び酢酸ブチル（３０ｍＬ）を加え、９０℃で５時間反応を行った。水５０ｍＬを加えて反応を停止させ、メチルイソブチルケトン（２００ｍＬ）で抽出し、水５０ｍＬで３回水洗した。エバポレータを用いて溶剤を除去し、黄色固体を得た。ここで得られた黄色固体をアセトン及び水で再結晶し、２－アセチルチオキサントンのオキシムエステル体（ＴＸ－ＯＸＥ／黄色固体）を０．３５ｇ（２段階反応の収率：５７％）得た。
１Ｈ―ＮＭＲ（４００ＭＨｚ，ＤＭＳＯ―ｄ６）；δ（ｐｐｍ）２．３０（ｓ，３Ｈ），２．５１（ｓ，３Ｈ），７．５３（ｄｄｄ，１Ｈ）７．５９－７．６（ｍ，２Ｈ），７．６４－７．６８（ｍ，１Ｈ），８．２５（ｄｄ，１Ｈ），８．６０－８．６６（ｍ，１Ｈ），８．８５（ｄ，１Ｈ） A thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min. A total amount of TX-OX, acetic anhydride (0.24 g), and butyl acetate (30 mL) were added to the reaction vessel, and the reaction was carried out at 90 ° C. for 5 hours. The reaction was stopped by adding 50 mL of water, extracted with methyl isobutyl ketone (200 mL), and washed with 50 mL of water three times. The solvent was removed using an evaporator to obtain a yellow solid. The yellow solid obtained here was recrystallized from acetone and water to obtain 0.35 g of 2-acetylthioxanthone oxime ester (TX-OXE / yellow solid) (yield of two-step reaction: 57%).
1 H-NMR (400 MHz, DMSO-d6); δ (ppm) 2.30 (s, 3H), 2.51 (s, 3H), 7.53 (ddd, 1H) 7.59-7.6 ( m, 2H), 7.64-7.68 (m, 1H), 8.25 (dd, 1H), 8.60-8.66 (m, 1H), 8.85 (d, 1H)
１Ｈ―ＮＭＲ（４００ＭＨｚ，ＤＭＳＯ―ｄ６）；δ（ｐｐｍ）２．３０（ｓ，３Ｈ），２．５１（ｓ，３Ｈ），７．５３（ｄｄｄ，１Ｈ）７．５９－７．６（ｍ，２Ｈ），７．６４－７．６８（ｍ，１Ｈ），８．２５（ｄｄ，１Ｈ），８．６０－８．６６（ｍ，１Ｈ），８．８５（ｄ，１Ｈ） A thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min. A total amount of TX-OX, acetic anhydride (0.24 g), and butyl acetate (30 mL) were added to the reaction vessel, and the reaction was carried out at 90 ° C. for 5 hours. The reaction was stopped by adding 50 mL of water, extracted with methyl isobutyl ketone (200 mL), and washed with 50 mL of water three times. The solvent was removed using an evaporator to obtain a yellow solid. The yellow solid obtained here was recrystallized from acetone and water to obtain 0.35 g of 2-acetylthioxanthone oxime ester (TX-OXE / yellow solid) (yield of two-step reaction: 57%).
1 H-NMR (400 MHz, DMSO-d6); δ (ppm) 2.30 (s, 3H), 2.51 (s, 3H), 7.53 (ddd, 1H) 7.59-7.6 ( m, 2H), 7.64-7.68 (m, 1H), 8.25 (dd, 1H), 8.60-8.66 (m, 1H), 8.85 (d, 1H)
［ＴＸ－ＯＸＥ－２（化合物番号２０）の合成］
[Synthesis of TX-OXE-2 (Compound No. 20)]
２００ｍＬの４つ口反応容器に温度計及び冷却管を設置し、流速３０ｍＬ／ｍｉｎで窒素フローを開始した。反応容器にＴＸ－ＯＸ（０．５ｇ）、塩化ベンゾイル（０．５２ｇ）、トリエチルアミン（０．４７ｇ）、及びテトラヒドロフラン（３０ｍＬ）を加え、５５℃で８時間反応を行った。水３０ｍＬを加えて反応を停止させ、析出した固体を濾過で分取した。ここで得られた黄色固体をジメチルスルホキシド及び水で再結晶し、２－アセチルチオキサントンのオキシムエステル体（ＴＸ－ＯＸＥ－２／黄色固体）を０．２８ｇ（収率：４０％）得た。
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＤＭＳＯ－ｄ６）；δ（ｐｐｍ）２．６５（ｓ，３Ｈ），７．５８－７．６７（ｍ，３Ｈ），７．７２－７．８５（ｍ，２Ｈ）７．８９－８．２８（ｍ，５Ｈ），８．５１（ｄ，１Ｈ），８．８５（ｓ，１Ｈ） A thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min. TX-OX (0.5 g), benzoyl chloride (0.52 g), triethylamine (0.47 g), and tetrahydrofuran (30 mL) were added to the reaction vessel, and the reaction was carried out at 55 ° C. for 8 hours. The reaction was stopped by adding 30 mL of water, and the precipitated solid was collected by filtration. The yellow solid obtained here was recrystallized with dimethyl sulfoxide and water to obtain 0.28 g (yield: 40%) of 2-acetylthioxanthone oxime ester (TX-OXE-2 / yellow solid).
1 H-NMR (400 MHz, DMSO-d6); δ (ppm) 2.65 (s, 3H), 7.58-7.67 (m, 3H), 7.72-7.85 (m, 2H) 7.89-8.28 (m, 5H), 8.51 (d, 1H), 8.85 (s, 1H)
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＤＭＳＯ－ｄ６）；δ（ｐｐｍ）２．６５（ｓ，３Ｈ），７．５８－７．６７（ｍ，３Ｈ），７．７２－７．８５（ｍ，２Ｈ）７．８９－８．２８（ｍ，５Ｈ），８．５１（ｄ，１Ｈ），８．８５（ｓ，１Ｈ） A thermometer and a cooling pipe were installed in a 200 mL four-necked reaction vessel, and a nitrogen flow was started at a flow rate of 30 mL / min. TX-OX (0.5 g), benzoyl chloride (0.52 g), triethylamine (0.47 g), and tetrahydrofuran (30 mL) were added to the reaction vessel, and the reaction was carried out at 55 ° C. for 8 hours. The reaction was stopped by adding 30 mL of water, and the precipitated solid was collected by filtration. The yellow solid obtained here was recrystallized with dimethyl sulfoxide and water to obtain 0.28 g (yield: 40%) of 2-acetylthioxanthone oxime ester (TX-OXE-2 / yellow solid).
1 H-NMR (400 MHz, DMSO-d6); δ (ppm) 2.65 (s, 3H), 7.58-7.67 (m, 3H), 7.72-7.85 (m, 2H) 7.89-8.28 (m, 5H), 8.51 (d, 1H), 8.85 (s, 1H)
＜実施例１及び２＞
下記表１に示す硬化性化合物（Ｂ－１、Ｂ－２、Ｂ－３）を混合し、下記表１に示す特定化合物（Ａ－１）を９０℃で加熱溶解させた後、室温まで冷却した。次いで、下記表１の残りの成分を添加して撹拌した後、３本ロールミルにて分散させた。その後、金属メッシュ（６３５メッシュ）で濾過することにより、実施例１及び２の光硬化性組成物を調製した。なお、表１中の各成分の数値は質量部を表す。 <Examples 1 and 2>
The curable compounds (B-1, B-2, B-3) shown in Table 1 below are mixed, the specific compound (A-1) shown in Table 1 below is heated and dissolved at 90 ° C., and then cooled to room temperature. did. Next, the remaining components in Table 1 below were added and stirred, and then dispersed in a three-roll mill. Then, the photocurable composition of Example 1 and 2 was prepared by filtering with a metal mesh (635 mesh). In addition, the numerical value of each component in Table 1 represents a mass part.
下記表１に示す硬化性化合物（Ｂ－１、Ｂ－２、Ｂ－３）を混合し、下記表１に示す特定化合物（Ａ－１）を９０℃で加熱溶解させた後、室温まで冷却した。次いで、下記表１の残りの成分を添加して撹拌した後、３本ロールミルにて分散させた。その後、金属メッシュ（６３５メッシュ）で濾過することにより、実施例１及び２の光硬化性組成物を調製した。なお、表１中の各成分の数値は質量部を表す。 <Examples 1 and 2>
The curable compounds (B-1, B-2, B-3) shown in Table 1 below are mixed, the specific compound (A-1) shown in Table 1 below is heated and dissolved at 90 ° C., and then cooled to room temperature. did. Next, the remaining components in Table 1 below were added and stirred, and then dispersed in a three-roll mill. Then, the photocurable composition of Example 1 and 2 was prepared by filtering with a metal mesh (635 mesh). In addition, the numerical value of each component in Table 1 represents a mass part.
＜比較例１及び２＞
特定化合物（Ａ－１）の代わりに下記表１に示すその他の成分（Ｏ－２、Ｏ－３）を用いたほかは実施例１及び２と同様にして、比較例１及び２の光硬化性組成物を調製した。 <Comparative Examples 1 and 2>
Photocuring of Comparative Examples 1 and 2 in the same manner as in Examples 1 and 2, except that other components (O-2, O-3) shown in Table 1 below were used in place of the specific compound (A-1). A sex composition was prepared.
特定化合物（Ａ－１）の代わりに下記表１に示すその他の成分（Ｏ－２、Ｏ－３）を用いたほかは実施例１及び２と同様にして、比較例１及び２の光硬化性組成物を調製した。 <Comparative Examples 1 and 2>
Photocuring of Comparative Examples 1 and 2 in the same manner as in Examples 1 and 2, except that other components (O-2, O-3) shown in Table 1 below were used in place of the specific compound (A-1). A sex composition was prepared.
＜評価＞
［遮光部硬化幅（紫外線照射）］
実施例１及び２、比較例１及び２の各光硬化性組成物に４μｍのグラスファイバー（日本電気硝子株式会社製）を１質量％添加し、液晶シール剤を調製した。クロムをエッチングすることによって１００μｍのライン及びスペースを設けたガラス基板に液晶シール剤を塗布し、対向基板としてブラックマトリクス基板を貼り合わせた。次いで、ライン／スペースを設けた基板側から波長３６５ｎｍの紫外光を３０００ｍＪ／ｃｍ２（１００ｍＷ／ｃｍ２で３０秒）の照射量で照射し、顕微鏡にて硬化幅を測定した。結果を下記表１に示す。 <Evaluation>
[Light-shielding part curing width (UV irradiation)]
1% by mass of 4 μm glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) was added to each of the photocurable compositions of Examples 1 and 2 and Comparative Examples 1 and 2, to prepare a liquid crystal sealant. A liquid crystal sealant was applied to a glass substrate provided with 100 μm lines and spaces by etching chromium, and a black matrix substrate was bonded as a counter substrate. Next, ultraviolet light having a wavelength of 365 nm was irradiated from the substrate side provided with the line / space at an irradiation amount of 3000 mJ / cm 2 (100 mW / cm 2 for 30 seconds), and the curing width was measured with a microscope. The results are shown in Table 1 below.
［遮光部硬化幅（紫外線照射）］
実施例１及び２、比較例１及び２の各光硬化性組成物に４μｍのグラスファイバー（日本電気硝子株式会社製）を１質量％添加し、液晶シール剤を調製した。クロムをエッチングすることによって１００μｍのライン及びスペースを設けたガラス基板に液晶シール剤を塗布し、対向基板としてブラックマトリクス基板を貼り合わせた。次いで、ライン／スペースを設けた基板側から波長３６５ｎｍの紫外光を３０００ｍＪ／ｃｍ２（１００ｍＷ／ｃｍ２で３０秒）の照射量で照射し、顕微鏡にて硬化幅を測定した。結果を下記表１に示す。 <Evaluation>
[Light-shielding part curing width (UV irradiation)]
1% by mass of 4 μm glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) was added to each of the photocurable compositions of Examples 1 and 2 and Comparative Examples 1 and 2, to prepare a liquid crystal sealant. A liquid crystal sealant was applied to a glass substrate provided with 100 μm lines and spaces by etching chromium, and a black matrix substrate was bonded as a counter substrate. Next, ultraviolet light having a wavelength of 365 nm was irradiated from the substrate side provided with the line / space at an irradiation amount of 3000 mJ / cm 2 (100 mW / cm 2 for 30 seconds), and the curing width was measured with a microscope. The results are shown in Table 1 below.
［遮光部硬化幅（可視光照射）］
実施例１及び２、比較例１及び２の各光硬化性組成物に４μｍのグラスファイバー（日本電気硝子株式会社製）を１質量％添加し、液晶シール剤を調製した。クロムをエッチングすることによって１００μｍのライン及びスペースを設けたガラス基板に液晶シール剤を塗布し、対向基板としてブラックマトリクス基板を貼り合わせた。次いで、ライン／スペースを設けた基板側から波長４０５ｎｍの可視光を３０００ｍＪ／ｃｍ２（１００ｍＷ／ｃｍ２で３０秒）の照射量で照射し、顕微鏡にて硬化幅を測定した。結果を下記表１に示す。 [Light-shielding part curing width (visible light irradiation)]
1% by mass of 4 μm glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) was added to each of the photocurable compositions of Examples 1 and 2 and Comparative Examples 1 and 2, to prepare a liquid crystal sealant. A liquid crystal sealant was applied to a glass substrate provided with 100 μm lines and spaces by etching chromium, and a black matrix substrate was bonded as a counter substrate. Next, visible light having a wavelength of 405 nm was irradiated at a dose of 3000 mJ / cm 2 (100 mW / cm 2 for 30 seconds) from the side of the substrate on which the line / space was provided, and the curing width was measured with a microscope. The results are shown in Table 1 below.
実施例１及び２、比較例１及び２の各光硬化性組成物に４μｍのグラスファイバー（日本電気硝子株式会社製）を１質量％添加し、液晶シール剤を調製した。クロムをエッチングすることによって１００μｍのライン及びスペースを設けたガラス基板に液晶シール剤を塗布し、対向基板としてブラックマトリクス基板を貼り合わせた。次いで、ライン／スペースを設けた基板側から波長４０５ｎｍの可視光を３０００ｍＪ／ｃｍ２（１００ｍＷ／ｃｍ２で３０秒）の照射量で照射し、顕微鏡にて硬化幅を測定した。結果を下記表１に示す。 [Light-shielding part curing width (visible light irradiation)]
1% by mass of 4 μm glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) was added to each of the photocurable compositions of Examples 1 and 2 and Comparative Examples 1 and 2, to prepare a liquid crystal sealant. A liquid crystal sealant was applied to a glass substrate provided with 100 μm lines and spaces by etching chromium, and a black matrix substrate was bonded as a counter substrate. Next, visible light having a wavelength of 405 nm was irradiated at a dose of 3000 mJ / cm 2 (100 mW / cm 2 for 30 seconds) from the side of the substrate on which the line / space was provided, and the curing width was measured with a microscope. The results are shown in Table 1 below.
［粘度］
Ｅ型粘度計（Ｒ１１５型粘度計（東機産業株式会社製））により実施例１及び２、比較例１及び２の各光硬化性組成物の２５℃における粘度（Ｐａ・ｓ）を測定した。結果を下記表１に示す。 [viscosity]
The viscosity (Pa · s) at 25 ° C. of each of the photocurable compositions of Examples 1 and 2 and Comparative Examples 1 and 2 was measured with an E type viscometer (R115 type viscometer (manufactured by Toki Sangyo Co., Ltd.)). . The results are shown in Table 1 below.
Ｅ型粘度計（Ｒ１１５型粘度計（東機産業株式会社製））により実施例１及び２、比較例１及び２の各光硬化性組成物の２５℃における粘度（Ｐａ・ｓ）を測定した。結果を下記表１に示す。 [viscosity]
The viscosity (Pa · s) at 25 ° C. of each of the photocurable compositions of Examples 1 and 2 and Comparative Examples 1 and 2 was measured with an E type viscometer (R115 type viscometer (manufactured by Toki Sangyo Co., Ltd.)). . The results are shown in Table 1 below.
表１に示されるように、特定化合物としてＴＸ－ＯＸＥを用いた実施例１及び２の光硬化性組成物は、類似構造を有する化合物を用いた比較用の光硬化性組成物に比べて、紫外線でも可視光でも深部（低エネルギー照射部分）での硬化性が良好であった。すなわち、実施例１及び２の光硬化性組成物は、低エネルギーでの優れた硬化性を有することが確認された。
As shown in Table 1, the photocurable compositions of Examples 1 and 2 using TX-OXE as the specific compound were compared with the comparative photocurable composition using a compound having a similar structure. The curability in the deep part (low energy irradiated part) was good in both ultraviolet and visible light. That is, it was confirmed that the photocurable compositions of Examples 1 and 2 have excellent curability at low energy.
As shown in Table 1, the photocurable compositions of Examples 1 and 2 using TX-OXE as the specific compound were compared with the comparative photocurable composition using a compound having a similar structure. The curability in the deep part (low energy irradiated part) was good in both ultraviolet and visible light. That is, it was confirmed that the photocurable compositions of Examples 1 and 2 have excellent curability at low energy.
Claims (15)
- 分子内にオキシムエステル構造及びチオキサントン構造を併せ持つ化合物を含有する光硬化性組成物。 A photocurable composition containing a compound having both an oxime ester structure and a thioxanthone structure in the molecule.
- 硬化性化合物を含有する請求項１に記載の光硬化性組成物。 The photocurable composition according to claim 1, comprising a curable compound.
- 前記硬化性化合物が（メタ）アクリル化合物である請求項２に記載の光硬化性組成物。 The photocurable composition according to claim 2, wherein the curable compound is a (meth) acrylic compound.
- 前記硬化性化合物が、（メタ）アクリル化合物とエポキシ化合物との混合物である請求項２に記載の光硬化性組成物。 The photocurable composition according to claim 2, wherein the curable compound is a mixture of a (meth) acrylic compound and an epoxy compound.
- 有機フィラーを含有する請求項１～４のいずれか一項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 4, comprising an organic filler.
- 前記有機フィラーが、ウレタン微粒子、アクリル微粒子、スチレン微粒子、スチレンオレフィン微粒子、及びシリコーン微粒子からなる群より選択される少なくとも１種の有機フィラーである請求項５に記載の光硬化性組成物。 6. The photocurable composition according to claim 5, wherein the organic filler is at least one organic filler selected from the group consisting of urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles.
- 無機フィラーを含有する請求項１～６のいずれか一項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 6, comprising an inorganic filler.
- シランカップリング剤を含有する請求項１～７のいずれか一項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 7, which contains a silane coupling agent.
- 熱硬化剤を含有する請求項１～８のいずれか一項に記載の光硬化性組成物。 The photocurable composition according to any one of claims 1 to 8, which contains a thermosetting agent.
- 前記熱硬化剤が有機酸ヒドラジド化合物である請求項９に記載の光硬化性組成物。 The photocurable composition according to claim 9, wherein the thermosetting agent is an organic acid hydrazide compound.
- 請求項１～１０のいずれか一項に記載の光硬化性組成物を用いた電子部品用接着剤。 An adhesive for electronic parts using the photocurable composition according to any one of claims 1 to 10.
- 請求項１１に記載の電子部品用接着剤を硬化して得られる硬化物で接着された電子部品。 An electronic component bonded with a cured product obtained by curing the adhesive for electronic components according to claim 11.
- 請求項１～１０のいずれか一項に記載の光硬化性組成物を用いた液晶表示セル用接着剤。 An adhesive for a liquid crystal display cell using the photocurable composition according to any one of claims 1 to 10.
- 請求項１～１０のいずれか一項に記載の光硬化性組成物を用いた液晶シール剤。 A liquid crystal sealant using the photocurable composition according to any one of claims 1 to 10.
- 請求項１３に記載の液晶表示セル用接着剤又は請求項１４に記載の液晶シール剤を用いて接着された液晶表示セル。
A liquid crystal display cell bonded using the liquid crystal display cell adhesive according to claim 13 or the liquid crystal sealant according to claim 14.
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| CN201880025666.9A CN110536908B (en) | 2017-06-06 | 2018-05-25 | Photocurable composition and adhesive for electronic component |
| JP2018548156A JP6486571B1 (en) | 2017-06-06 | 2018-05-25 | Adhesive for electronic parts |
| KR1020197034155A KR20200015487A (en) | 2017-06-06 | 2018-05-25 | Photocurable Compositions and Adhesives for Electronic Components |
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| PCT/JP2018/020226 WO2018225544A1 (en) | 2017-06-06 | 2018-05-25 | Photocurable composition and electronic component adhesive |
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| JP (1) | JP6486571B1 (en) |
| KR (1) | KR20200015487A (en) |
| CN (1) | CN110536908B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690355A (en) * | 2019-03-15 | 2020-09-22 | 日本化药株式会社 | Sealant for display and liquid crystal display |
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| CN110536908A (en) | 2019-12-03 |
| TWI774777B (en) | 2022-08-21 |
| JPWO2018225544A1 (en) | 2019-06-27 |
| KR20200015487A (en) | 2020-02-12 |
| TW201903098A (en) | 2019-01-16 |
| CN110536908B (en) | 2022-04-19 |
| JP6486571B1 (en) | 2019-03-20 |
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