JPWO2018225544A1 - Adhesives for electronic components - Google Patents
Adhesives for electronic components Download PDFInfo
- Publication number
- JPWO2018225544A1 JPWO2018225544A1 JP2018548156A JP2018548156A JPWO2018225544A1 JP WO2018225544 A1 JPWO2018225544 A1 JP WO2018225544A1 JP 2018548156 A JP2018548156 A JP 2018548156A JP 2018548156 A JP2018548156 A JP 2018548156A JP WO2018225544 A1 JPWO2018225544 A1 JP WO2018225544A1
- Authority
- JP
- Japan
- Prior art keywords
- photocurable composition
- compound
- liquid crystal
- group
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000853 adhesive Substances 0.000 title claims abstract description 28
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 98
- 239000000203 mixture Substances 0.000 claims abstract description 97
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 238000007789 sealing Methods 0.000 claims abstract description 34
- 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
- -1 acrylic compound Chemical class 0.000 claims description 51
- 239000004593 Epoxy Substances 0.000 claims description 32
- 239000002245 particle 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 36
- 239000000758 substrate Substances 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007983 Tris buffer Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 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 12
- 238000001723 curing Methods 0.000 description 12
- 239000010419 fine particle Substances 0.000 description 12
- 239000000565 sealant Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000007870 radical polymerization initiator Substances 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 8
- 239000003822 epoxy resin Substances 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 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
- 229920003986 novolac Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 125000005647 linker group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XMQULJHUJRTETE-UHFFFAOYSA-N 2-acetylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(=O)C)=CC=C3SC2=C1 XMQULJHUJRTETE-UHFFFAOYSA-N 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- CSFWPUWCSPOLJW-UHFFFAOYSA-N lawsone Chemical compound C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 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 3
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 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
- 230000001588 bifunctional effect Effects 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 150000002791 naphthoquinones Chemical class 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 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
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-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
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229940091173 hydantoin Drugs 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 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 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
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- 125000005395 methacrylic acid 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
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- 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
- 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
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
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- 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
- 238000010186 staining Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 230000008719 thickening Effects 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
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Sealing Material Composition (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Plural Heterocyclic Compounds (AREA)
- Epoxy Resins (AREA)
- Liquid Crystal (AREA)
Abstract
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、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、及び液晶表示セルを提供する。Photocurable composition containing a compound having both an oxime ester structure and a thioxanthone structure in a molecule, an adhesive for electronic parts using the same, an electronic part, an adhesive for liquid crystal display cells, a liquid crystal sealing agent, and a liquid crystal display cell I will provide a.
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 components using the same, an electronic component, an adhesive for liquid crystal display cells, a liquid crystal sealing agent, and a liquid crystal display cell.
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。 Photocurable compositions are widely used in adhesives for electronic parts such as sealants for displays, sealants for solar cells, semiconductor sealants and the like. Examples of the sealing agent for display include a sealing agent for liquid crystal display, a sealing agent for organic EL display, an adhesive for touch panel, and the like. These display sealants are required to have excellent curability, as well as low outgassing and no damage to display elements.
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, the photocurable composition has a limitation in usable portions because the curing reaction does not proceed in the portion where light does not reach.
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 sealing agent for liquid crystal dropping method (hereinafter, also simply referred to as "liquid crystal sealing agent"), when light strikes the liquid crystal sealing agent by the wiring portion of the array substrate of the liquid crystal display element or the black matrix portion of the color filter substrate. There is no light shield and the problem of display defects near 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 will remain in the liquid crystal sealing agent. In this state, if the process proceeds to the secondary curing step by heat, the dissolution of the uncured component in the liquid crystal is accelerated by the heat, which causes a display failure 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 liquid crystal sealants. That is, in the light-shielding portion, a liquid crystal sealing agent which is not sufficiently cured by light is reacted promptly from low temperature to suppress liquid crystal contamination. For example, Patent Documents 1 and 2 disclose methods using a thermal radical polymerization initiator. Moreover, in patent documents 3-5, the method of using polyvalent carboxylic acid as a hardening accelerator is disclosed.
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 initiation Liquid crystal contamination by the agent itself becomes a problem. Moreover, when polyvalent carboxylic acid is used, there is a possibility that moisture resistance reliability may be impaired, and depending on the application, it may not be used.
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, despite the fact that the development of the liquid crystal sealant has been carried out extremely vigorously, the liquid crystal sealant having low liquid crystal contamination properties has been realized while having excellent light-shielding portion curability. 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。 The object of the present invention is to provide a photocurable composition which is cured by irradiation with light such as ultraviolet light and visible light, which has high sensitivity to light and which is sufficiently cured by low energy light. 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 its molecule is very excellent as a hydrogen abstraction type photoinitiator and a decomposition type initiator, and cures sufficiently even with low energy light irradiation. It discovered that it had nature and came to complete the present invention as described in the following [1]-[15].
In the present specification, “(meth) acrylic” means “acrylic and / or methacrylic”, “(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 its 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 particles, acrylic particles, styrene particles, styrene olefin particles, and silicone 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 a liquid crystal display cell using the photocurable composition according to any one of [1] to [10].
[14] A liquid crystal sealing agent using the photocurable composition according to any one of [1] to [10].
[15] A liquid crystal display cell bonded using the adhesive for a liquid crystal display cell according to [13] or the liquid crystal sealing agent 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。 Since the photocurable composition of the present invention is also highly curable at a portion where light is not sufficiently applied, and has sufficient curing even when irradiated with low energy light in consideration of damage to other members, It is useful as a sealant for electronic components or an adhesive for electronic components, particularly a sealant for displays, which is used in the production of electronic components having the same or electronic components which 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 an oxime ester structure and a 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 its molecule (hereinafter, also referred to as a “specific compound”). This particular compound acts as a photoinitiator with very high sensitivity to low energy light. As the specific compounds, one type may be used alone, or two or more types may be used in combination.
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 which a specific compound has is a structure represented, for example by 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 (C1-C8) alkoxy group, R 2 represents a hydrogen atom, (C1-C8) alkyl group, (C2-C8) alkenyl group , 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 linear, branched or cyclic unsubstituted ones, and linear ones are preferable. Specific examples thereof include linear ones such as methyl group, ethyl group, n-propyl group, n-butyl group, n-heptyl group, n-hexyl group, n-heptyl group, n-octyl group and the like; isopropyl group And branched ones such as isobutyl group, sec-butyl group and tert-butyl group; cyclic ones such as cyclopropyl group, cyclopentyl group and cyclohexyl group; The (C1-C8) alkyl group may be a chain alkyl group and a cyclic alkyl group, such as a 3-cyclopentylpropyl group. Among these, from the viewpoint of compatibility with the curable compound and the solvent, (C1-C3) alkyl group is preferable, and specific examples include methyl group, ethyl group and n-propyl group, and 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。As a (C1-C8) alkoxy group in R 1 in the above-mentioned formula (1), a linear or branched unsubstituted one may be mentioned, and a linear one is preferable. Specific examples thereof include linear ones such as methoxy, ethoxy, n-propoxy and n-butoxy; and branched ones such as isopropoxy, isobutoxy, sec-butoxy and tert-butoxy. 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), a methyl group is preferable as R 1 .
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 for R 2 in the above formula (1) has the same meaning as the (C 1 -C 8) alkyl group for R 1 above, including the 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-mentioned formula (1) include linear or branched non-substituted ones. As a specific example, a vinyl group, 1-propenyl group, 2-propenyl group etc. are mentioned.
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。A phenyl group, a pyridyl group, a thienyl group etc. are mentioned as an aryl group and heteroaryl group in R 2 in the said Formula (1). The aryl group and the heteroaryl group are substituted by at least one substituent such as carboxy group, sulfo group, hydroxy group, acetylamino group, halogen atom, cyano group, nitro group, sulfamoyl group, alkyl group, alkoxy group, etc. It is also good. As what has such a substituent, 4-nitrophenyl group is mentioned, for example.
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。 The symbol * in the above formula (1) represents a bonding position, and may be a bonding position to a thioxanthone structure represented by the following formula (2), and the bonding group when bonding to a thioxanthone structure via another bonding group It may be a bonding position with As the linking group, an alkylene group, an alkylidene group, an alkylene oxide group and the like can be mentioned.
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 which a specific compound has is a structure represented by 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 to the oxime ester structure represented by the above formula (1), and in the case of bonding to an oxime ester structure via another bonding group, It may be a bonding position with a bonding group. As the linking group, an alkylene group, an alkylidene group, an alkylene oxide group and the like can be mentioned.
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 said Formula (2) may have another substituent other than the oxime ester structure represented by the said Formula (1). 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. Be
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。If thioxanthone structure represented by the above formula (2) has another substituent, the substituents may form a cyclic structure bonded to R 1 in formula (1).
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, for example, the compounds of the following compound numbers 1 to 20: However, it is not limited to these. Among the compounds of Compound Nos. 1 to 20, the compounds of Compound Nos. 1 to 17 and 20 are preferable, and the compound of Compound No. 1 is more preferable.
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, the 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 also suitable for photopolymerization in the presence of air (oxygen). Therefore, the specific compound is useful as a photopolymerization initiator for polymerizing a radically polymerizable curable compound.
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., based on the total mass of the photocurable composition. It is 0 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 unreacted compound is reduced. 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 sealing agent for display elements tends 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。[Photoinitiator]
The photocurable composition which concerns on this embodiment may contain other photoinitiators other than said specific compound. It will not specifically limit, if it is a compound which generate | occur | produces a radical, an acid, a base, etc. by irradiation of an ultraviolet ray or visible light as another photoinitiator, and starts 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-ethyl anthraquinone, 2-hydroxy-2-methyl propiophenone, 2-methyl- [ 4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, camphor quinone, 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 (above, manufactured by SEIKO CHEMICAL CO., LTD.); And the like. 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 an absorbance of 400 or more at a maximum absorption wavelength (λmax) in the wavelength range of 200 to 300 nm from the viewpoint of enhancing the curability of the photocurable composition by utilizing light absorption of a wide wavelength A photopolymerization initiator having an absorbance of 500 or more at the maximum absorption wavelength (λmax) in the wavelength range of 200 to 300 nm is more preferable, and an absorbance at the maximum absorption wavelength (λmax) in the wavelength range of 200 to 300 nm is 1,500 or more Certain photoinitiators are more preferred. Examples of the photopolymerization initiator having an absorbance of 500 or more at the maximum absorption wavelength (λmax) in the wavelength range of 200 to 300 nm include IRGACURE RTM 651, 184, and 2959. Further, as a photopolymerization initiator having an absorbance of 1,500 or more at the maximum absorption wavelength (λmax) in the wavelength range of 200 to 300 nm, for example, IRGACURE RTM 2959 can be mentioned.
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。 Further, as the photopolymerization initiator, one having a molecular weight of 150 to 1000 is preferable from the viewpoint of preventing outgassing. Similarly, from the viewpoint of preventing outgassing, those having a (meth) acrylic group in the molecule are preferable, for example, 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxyl. The reaction product with -2-methyl-1-propan-1-one is preferably used. This compound can be produced by the method described in WO 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 which concerns on this embodiment contains another photoinitiator, it is preferable that the content rate is 0.001-10 mass% in the total amount of a photocurable composition, and 0 It is more preferable that it is 0.1-5.0 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。[Photo start agent]
The photocurable composition which concerns on this embodiment may contain photoinitiator adjuvants, such as tertiary amine, in order to improve hardenability further. The tertiary amines are not particularly limited, and include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and the like. In addition, a high molecular weight compound in which plural tertiary amines are branched with a polyhydric alcohol or the like in one molecule can be appropriately used.
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 the present embodiment contains a photoinitiation aid, the content is preferably 0.005 to 20% by mass in the total amount of the photocurable composition, and 0.01 It is more preferable that it is 10 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]
It is preferable that the photocurable composition which concerns on this embodiment contains a curable compound. The curable compound is not particularly limited as long as it is a compound which is cured by light, heat or the like, but (meth) acrylic compounds such as (meth) acrylic ester compounds and epoxy (meth) acrylate compounds are preferable. A (meth) acrylic 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。 As the (meth) acrylic ester compound, for example, N-acryloyloxyethyl hexahydrophthalimide, acryloyl morpholine, 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 (meth) ) Acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobonyl (meth) acrylate, tribromophenyl Nyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1, 9 nonane diol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris ((meth) acryloxy ethyl) isocyanurate, pen Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) Acrylate, trimethylolpropane polyethoxytri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ester diacrylate of neopentyl glycol and hydroxypivalic acid, ε-caprolactone addition of ester of neopentyl glycol and hydroxypivalic acid Diacrylates and the like. 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 is obtained by the reaction of an epoxy compound and (meth) acrylic acid by a known method. Although it does not specifically limit as an epoxy compound used as a raw material, The epoxy compound of bifunctional or more is preferable. Examples of the bifunctional or higher epoxy compound include resorcinol diglycidyl ether, bisphenol A epoxy compound, bisphenol F epoxy compound, bisphenol S epoxy compound, phenol novolac epoxy compound, cresol novolac epoxy compound, bisphenol A novolac epoxy 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 Novolak type epoxy compounds having a diglycidyl ether of difunctional phenols (catechol, resorcinol, etc.) Things, difunctional alcohols diglycidyl ethers of, and the like thereof halide or hydrogenated product. Among these, in the case of using the photocurable composition according to this embodiment as a liquid crystal sealing agent, bisphenol A epoxy compounds and resorcin diglycidyl ether are preferable from the viewpoint of liquid crystal staining. The ratio of the epoxy group to 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。 It is preferable that the photocurable composition which concerns on this embodiment contains an epoxy compound (however, except a (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 difunctional or more epoxy compound is preferable. Examples of the bifunctional or higher epoxy compound include resorcin diglycidyl ether, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy Epoxy resin, bisphenol F novolac epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, hydantoin epoxy resin, isocyanurate epoxy resin, triphenolmethane skeleton Novolak type epoxy resin having a hydroxyl group, diglycidyl ether of difunctional phenols (catechol, resorcinol, etc.), difunctional difunctional alcohols Glycidyl etherified product, and the like thereof halide or hydrogenated product. Among these, in the case of using the photocurable composition according to the present embodiment as a liquid crystal sealing agent, bisphenol A 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 the present embodiment contains a curable compound, its content 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 the present 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.
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. As silicone particles, KMP-594, KMP-597, KMP-598 (above, Shin-Etsu Chemical Co., Ltd. make); Trefil RTM E-5500, 9701, EP-2001 (above, Toray Dow Corning Co., Ltd.) preferable. As urethane microparticles, JB-800T and HB-800BK (above, manufactured by Negami Industrial Co., Ltd.) are preferable. As the styrene fine particles, Lavalon RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (all manufactured by Mitsubishi Chemical Corporation) are preferable. As the styrene olefin fine particles, Septon RTM SEPS 2004, SEPS 2063 (manufactured by Kuraray Co., Ltd.) are preferable. These organic fillers may be organic fillers having a core-shell structure 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 particles and silicone particles are preferred.
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, acrylic rubber having a core-shell structure composed of two types of acrylic rubber is preferable, and one in which the core layer is n-butyl acrylate and the shell layer is methyl methacrylate is more preferable. Acrylic fine particles in which the core layer is n-butyl acrylate and the shell layer is methyl methacrylate are sold by Aika Industry 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。 Also, as silicone fine particles, complex silicone rubber in which organopolysiloxane crosslinked powder powder, linear dimethylpolysiloxane crosslinked powder powder, silicone rubber surface is coated with silicone resin (for example, polyorganosilsesquioxane resin) Etc. Among these silicone fine particles, preferred are silicone rubber of linear dimethylpolysiloxane crosslinked powder or composite silicone rubber fine particles of silicone resin-coated linear dimethylpolysiloxane crosslinked powder. The shape of the rubber powder is preferably spherical with less thickening of 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 the present 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。 As the inorganic filler, for example, 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, hydroxide Magnesium, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos etc. are mentioned, preferably fused silica, crystalline silica, silicon nitride, boron nitride, carbonate Particles of calcium, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate and the like can be mentioned, and particles of silica, alumina, talc and the like 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 manufacturing the narrow gap liquid crystal cell by using the photocurable composition according to the present embodiment as a liquid crystal sealing agent for liquid crystal dropping method, It tends to be able to form a gap well at the time of bonding of a glass substrate. The lower limit is preferably about 10 nm, and more preferably about 100 nm. The particle diameter can be measured by a laser diffraction / scattering type particle size distribution measuring device (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 the decrease in adhesive strength after moisture absorption tends to be suppressed. When the content of the inorganic filler is 50% by mass or less, the inorganic filler is crushed, for example, when a liquid crystal cell is manufactured using the photocurable composition according to the present embodiment as a liquid crystal sealing agent for liquid crystal dropping method. 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 the present embodiment may contain a silane coupling agent in order to improve adhesion 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。 As a silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 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, - chloropropyl methyl dimethoxy silane, 3-chloropropyl trimethoxy silane, and the like. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. etc. 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 which concerns on this embodiment contains a silane coupling agent, 0.05-3 mass% is suitable for the content rate in the total amount of a 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 the present 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 is reacted nucleophilically by a noncovalent electron pair or an anion in the molecule, and examples thereof include polyhydric amines, polyhydric phenols, organic acid hydrazide compounds and the like. 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, as an aromatic hydrazide compound, for example, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridine dihydrazide, 1,2,4-benzenetrihydrazide, 1, 4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide and the like can be mentioned. Among the organic acid hydrazide compounds, as the aliphatic hydrazide compound, for example, form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide Sebacic acid dihydrazide, 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylene bissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexane tricarboxylic acid trihydrazide, 1 Hydantoin skeleton such as 2,3-bis (hydrazino carbonoethyl) -5-isopropyl hydantoin, preferably valine hydantoin skeleton ( Dihydrazide compound having a skeleton in which carbon atom of dantoin ring is substituted with isopropyl group, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (1-hydrazinocarbonyl) Ethyl) isocyanurate, tris (3-hydrazino carbonyl propyl) isocyanurate, bis (2-hydrazino carbonyl ethyl) isocyanurate etc. are mentioned.
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 the organic acid hydrazide compounds, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl), from the balance of curing reactivity and latency. 2.) 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 thereof is usually 0.1 to 10% by mass, preferably 1 to 5% by mass in 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 the present embodiment may contain a thermal radical polymerization initiator in order to improve the curing speed and the 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 to initiate chain polymerization reaction, and organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, 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。Commercial products of organic peroxides include Kayamec RTM A, M, R, L, LH, SP-30C, Percadox CH-50 L, BC-FF, Cadox B-40 ES, Percadox 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-50 E, AN, Kayabutyl RTM B, Perka Dox 16, Kayacarvone RTM BIC-75, AIC-75 (all, 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。 Moreover, as a commercial item of an azo compound, VA-044, 086, V-070, VPE-0201, VSP-1001 (above, Wako Pure Chemical Industries Ltd. make) etc. are mentioned.
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, preferably 0. 1 to 10% by mass in the total amount of the photocurable composition. It is 5 to 5% by mass, 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 which concerns on 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。(Hardening accelerator)
As a curing accelerator, an organic acid, an imidazole, etc. are mentioned.
As an organic acid, organic carboxylic acid, organic phosphoric acid, etc. are mentioned, 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 Examples include (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, 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: 3 adduct of 2-methylimidazole isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole And 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 the present embodiment contains a curing accelerator, the content thereof is usually 0.1 to 10% by mass, preferably 1 to 5% by mass in 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 which reacts with a radical generated from a photo radical polymerization initiator, a thermal radical polymerization initiator or the like to prevent polymerization, and quinones, piperidines, hindered Examples thereof include radical polymerization inhibitors such as dophenol type and nitroso type. 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-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis 4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9 -Bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxaspiro [5,5 5] Undecane, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl propionate)] 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 hydroxy amine, trade name ADK STAB LA-81, include the trade name ADK STAB LA-82 (all manufactured by Ltd. Adeka) and the like. Among these, naphthoquinone type, hydroquinone type, nitroso type and piperidine type radical polymerization inhibitors are preferable, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol, polystop 7300P ( Satoto Co., Ltd.) is more preferable, and Polystop 7300P (Teato 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 the present embodiment contains a radical polymerization inhibitor, the content is usually 0.0001 to 1% by mass, preferably 0.001% of 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]
150-500 Pa.s is preferable and, as for the viscosity at 25 degrees C of the photocurable composition which concerns on this embodiment, 200-500 Pa.s is more preferable. When using the photocurable composition which concerns on this embodiment as a liquid-crystal sealing agent especially, 250-400 Pa.s is preferable and, as for the viscosity at 25 degrees C of a photocurable composition, 280-320 Pa.s is more preferable. By setting the viscosity to 250 Pa · s or more, the occurrence of insertion of the liquid crystal is suppressed, and cell formation tends to be facilitated. By setting the viscosity to 400 Pa · s or less, application of the liquid crystal sealant tends to be facilitated.
［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 of Preparing Photocurable Composition]
The following method is mentioned as an example of the preparation method of the photocurable composition which concerns on this embodiment. First, the specific compound is heated and dissolved in a curable compound. Next, after cooling to room temperature, an organic filler, an inorganic filler, a silane coupling agent, a heat curing agent, a thermal radical polymerization initiator, an antifoaming agent, a leveling agent, a solvent and the like are added as necessary. And the photocurable composition which concerns on this embodiment can be prepared by uniformly mixing with well-known mixing apparatuses, such as 3 rolls, a sand mill, a ball mill, and filtering with 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。<Applications of Photocurable Composition>
The photocurable composition according to the present embodiment is very useful as a sealant for electronic components or an adhesive for electronic components. Examples of sealants for electronic components or adhesives for electronic components include adhesives for flexible printed wiring boards, adhesives for TAB, adhesives for semiconductors, adhesives for various displays, etc., but are limited thereto. 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。 In addition, the photocurable composition according to the present embodiment is very useful as an adhesive for liquid crystal display cells, particularly as a liquid crystal sealing agent. An example is shown below about a 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。 In a liquid crystal display cell manufactured using an adhesive for liquid crystal display cell, a pair of substrates having a predetermined electrode formed on the substrate is disposed opposite to each other at a predetermined interval, the periphery is sealed with a liquid crystal sealing agent, Is enclosed. The type of liquid crystal to be enclosed is not particularly limited. The substrate is composed of a combination of light transmitting materials in at least one of glass, quartz, plastic, silicone and the like.
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 method of manufacturing the liquid crystal display cell is, for example, as follows.
First, a spacer (space control material) is added to the liquid crystal sealing agent. As a spacer, glass fiber, a silica bead, a polymer bead etc. are mentioned. The diameter of the spacer varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount thereof used 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 sealing agent. 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。Subsequently, after apply | coating a liquid-crystal sealing compound to a one of a pair of board | substrates using a dispenser, a screen printing apparatus, etc., temporary hardening is performed at 80-120 degreeC as needed. Thereafter, liquid crystal is dropped on the inner side of the liquid crystal sealing agent, the other glass substrate is superposed in vacuum, and the gap is taken out. The liquid crystal display cell can be obtained by curing at 90 to 130 ° C. for 1 to 2 hours after forming the gap. Moreover, when using it as a light-and-heat combined use type | mold, it is made to photocure by making a liquid-crystal sealing agent irradiate an ultraviolet-ray by an ultraviolet irradiation machine. UV irradiation dose is preferably 500~6000mJ / cm 2, more preferably 1000~4000mJ / cm 2. Then, a liquid crystal display cell can be obtained by hardening at 90-130 degreeC for 1 to 2 hours as needed. The liquid crystal display cell thus obtained is free from display defects due to liquid crystal contamination, and is excellent in adhesion and moisture resistance.
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 part designed to have a light shielding part or an adhesive application that needs to be cured by low energy light such as visible light. For example, it is suitable as a sealing agent for liquid crystal displays, a sealing agent for organic EL, and an adhesive agent for touch panels used under the wiring light shielding part.
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 by way of examples, but the present invention is not limited to the examples. In addition, unless there is special description, it is mass standard to have "%" in the text.
＜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 art (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 condenser were installed in a 200 mL four-necked reaction vessel, and 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 a reaction vessel, and the reaction was carried out at 80 ° C. for 4 hours. The reaction was quenched by the addition of 50 mL water, extracted with methyl isobutyl ketone (200 mL) and washed three times with 50 mL water. The solvent was removed using an evaporator to obtain an oximated form of 2-acetylthioxanthone (TX-OX / yellow solid). The yellow solid (crude crystals) obtained here was used as it was for the oxime esterification reaction.
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 condenser were installed in a 200 mL four-necked reaction vessel, and nitrogen flow was started at a flow rate of 30 mL / min. The total amount of TX-OX, acetic anhydride (0.24 g), and butyl acetate (30 mL) were added to a reaction vessel, and reaction was carried out at 90 ° C. for 5 hours. The reaction was quenched by the addition of 50 mL water, extracted with methyl isobutyl ketone (200 mL) and washed three times with 50 mL water. The solvent was removed using an evaporator to give a yellow solid. The yellow solid obtained here was recrystallized with acetone and water to obtain 0.35 g (yield of two-step reaction: 57%) of an oxime ester of 2-acetylthioxanthone (TX-OXE / yellow solid).
1 H-NMR (400 MHz, DMSO-d6); δ (ppm) 2.30 (s, 3 H), 2.51 (s, 3 H), 7.53 (ddd, 1 H) 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 condenser were installed in a 200 mL four-necked reaction vessel, and 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 a reaction vessel, and reaction was carried out at 55 ° C. for 8 hours. The reaction was quenched by adding 30 mL of water, and the precipitated solid was separated by filtration. The yellow solid obtained here was recrystallized with dimethyl sulfoxide and water to obtain 0.28 g (yield: 40%) of an oxime ester of 2-acetylthioxanthone (TX-OXE-2 / yellow solid).
1 H-NMR (400 MHz, DMSO-d6); δ (ppm) 2.65 (s, 3 H), 7.58-7.67 (m, 3 H), 7.72-7.85 (m, 2 H) 7.89-8.28 (m, 5 H), 8.51 (d, 1 H), 8. 85 (s, 1 H)
＜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 and B-3) shown in Table 1 below are mixed, and the specific compound (A-1) shown in Table 1 below is dissolved by heating 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 using a three-roll mill. Then, the photocurable composition of Example 1 and 2 was prepared by filtering with 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 the other components (O-2 and O-3) shown in Table 1 below were used instead 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>
[Hardening width of light shielding part (ultraviolet irradiation)]
A liquid crystal sealing agent was prepared by adding 1% by mass of 4 μm glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) to each of the photocurable compositions of Examples 1 and 2 and Comparative Examples 1 and 2. A liquid crystal sealing agent was applied to a glass substrate provided with a line and a space of 100 μm by etching chromium, and a black matrix substrate was bonded as a counter substrate. Next, ultraviolet light with a wavelength of 365 nm was irradiated at an irradiation amount of 3000 mJ / cm 2 (100 mW / cm 2 for 30 seconds) from the side of the substrate provided with the line / space, 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。[Shading width hardening width (visible light irradiation)]
A liquid crystal sealing agent was prepared by adding 1% by mass of 4 μm glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) to each of the photocurable compositions of Examples 1 and 2 and Comparative Examples 1 and 2. A liquid crystal sealing agent was applied to a glass substrate provided with a line and a space of 100 μm by etching chromium, and a black matrix substrate was bonded as a counter substrate. Next, visible light with a wavelength of 405 nm was irradiated from the side of the substrate provided with lines / spaces at an irradiation dose 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.
［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 (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 are compared to the photocurable composition for comparison using a compound having a similar structure. The ultraviolet ray and visible light had good curability at the deep portion (low energy irradiated portion). That is, it was confirmed that the photocurable compositions of Examples 1 and 2 have excellent curability at low energy.
Claims (15)
A liquid crystal display cell bonded using the adhesive for a liquid crystal display cell according to claim 13 or the liquid crystal sealing agent according to claim 14.
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| JP5193565B2 (en) * | 2007-11-07 | 2013-05-08 | 太陽ホールディングス株式会社 | Photocurable resin composition, cured product pattern thereof, and printed wiring board comprising the cured product pattern |
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| JP6061697B2 (en) * | 2013-01-24 | 2017-01-18 | 株式会社日本化学工業所 | Novel photopolymerization initiator and method of using the same |
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