WO2017104391A1 - Photocurable resin composition, display element sealing agent, liquid crystal sealing agent, and liquid crystal display panel and method for producing same - Google Patents
Photocurable resin composition, display element sealing agent, liquid crystal sealing agent, and liquid crystal display panel and method for producing same Download PDFInfo
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- WO2017104391A1 WO2017104391A1 PCT/JP2016/085259 JP2016085259W WO2017104391A1 WO 2017104391 A1 WO2017104391 A1 WO 2017104391A1 JP 2016085259 W JP2016085259 W JP 2016085259W WO 2017104391 A1 WO2017104391 A1 WO 2017104391A1
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- WIPO (PCT)
- Prior art keywords
- liquid crystal
- compound
- group
- resin composition
- molecule
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 134
- 239000011342 resin composition Substances 0.000 title claims abstract description 83
- 238000007789 sealing Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000003795 chemical substances by application Substances 0.000 title abstract description 52
- -1 aminobenzoyl skeleton Chemical group 0.000 claims abstract description 64
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 claims abstract description 57
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 33
- 229940126062 Compound A Drugs 0.000 claims abstract description 31
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims description 176
- 239000000758 substrate Substances 0.000 claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- 239000000565 sealant Substances 0.000 claims description 36
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 28
- 125000003700 epoxy group Chemical group 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 9
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical group C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 2
- 238000011109 contamination Methods 0.000 abstract description 13
- 239000004593 Epoxy Substances 0.000 description 45
- 238000001723 curing Methods 0.000 description 41
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 229920001187 thermosetting polymer Polymers 0.000 description 30
- 239000002245 particle Substances 0.000 description 23
- 238000005259 measurement Methods 0.000 description 22
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 17
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- 238000000034 method Methods 0.000 description 16
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000007259 addition reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000010828 elution Methods 0.000 description 12
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- 229920000647 polyepoxide Polymers 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 10
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
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- 238000010992 reflux Methods 0.000 description 8
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- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
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- 238000010438 heat treatment Methods 0.000 description 5
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- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 4
- 239000005695 Ammonium acetate Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 229940043376 ammonium acetate Drugs 0.000 description 4
- 235000019257 ammonium acetate Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000000132 electrospray ionisation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
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- 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 3
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DVVXXHVHGGWWPE-UHFFFAOYSA-N 2-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC=C1C(O)=O DVVXXHVHGGWWPE-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 1
- 125000004864 4-thiomethylphenyl group Chemical group 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BWPYBAJTDILQPY-UHFFFAOYSA-N Methoxyphenone Chemical compound C1=C(C)C(OC)=CC=C1C(=O)C1=CC=CC(C)=C1 BWPYBAJTDILQPY-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical class [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- GRGBENNNGZARRZ-UHFFFAOYSA-N dodecanedihydrazide Chemical compound NNC(=O)CCCCCCCCCCC(=O)NN GRGBENNNGZARRZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- RXFZJKXZSLVQJV-UHFFFAOYSA-N icosa-8,12-dienedihydrazide Chemical compound NNC(=O)CCCCCCC=CCCC=CCCCCCCC(=O)NN RXFZJKXZSLVQJV-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000005699 methyleneoxy group Chemical group [H]C([H])([*:1])O[*:2] 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical class OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
Definitions
- the present invention relates to a photocurable resin composition, a display element sealant, a liquid crystal sealant, a liquid crystal display panel, and a method for producing the same.
- a liquid crystal display panel includes two transparent substrates having electrodes provided on the surface, a frame-shaped sealing member sandwiched between them, and a liquid crystal material sealed in a region surrounded by the sealing member And have.
- the liquid crystal display panel can be manufactured by a liquid crystal dropping method, for example.
- Production of a liquid crystal display panel by a liquid crystal dropping method is as follows: (1) A liquid crystal sealing agent is applied to the inner edge of a transparent substrate to form a frame for filling with liquid crystal; (2) Liquid crystal is dropped into the frame; (3) After superposing two substrates under high vacuum while the liquid crystal sealant is in an uncured state, (4) curing the liquid crystal sealant.
- liquid crystal dropping method photocuring or thermosetting is performed in a state where the uncured liquid crystal sealant and the liquid crystal material are in contact with each other. Therefore, the liquid crystal sealant is required not only to have high curability but also to reduce contamination of the liquid crystal material.
- a photocurable resin composition containing a compound B (visible light sensitizing compound) obtained by reacting hydroxythioxanthone with a compound having two or more epoxy groups in the molecule has been proposed (for example, Patent Document 1).
- a sealing agent for liquid crystal display elements including a curable resin, a thioxanthone polymerization initiator, and an amine sensitizer having an aminobenzoyl skeleton has been proposed (for example, Patent Document 2).
- a sealing agent for liquid crystal display elements including a curable resin and a compound (photopolymerization initiator) obtained by reacting an oxime ester and a polyfunctional isocyanate has been proposed (for example, Patent Document 3).
- composition shown in Patent Document 3 contains a photopolymerization initiator having low light absorption in the visible light region, the curability to light in the visible light region is low. Since the compositions shown in Patent Documents 1 and 2 contain a compound having an aminobenzoyl skeleton as a photopolymerization initiator or sensitizer, the curability to light in the visible light region is good. It was not possible to sufficiently suppress the elution of the contained compound into the liquid crystal material. Thus, it is desired to provide a photocurable resin composition that has high curability with respect to light in the visible light region and can highly suppress liquid crystal contamination.
- the present invention has been made in view of the above problems.
- the photocurability is high in visible light curing and can highly suppress liquid crystal contamination. It aims at providing a resin composition.
- a curable compound A having an ethylenically unsaturated double bond in the molecule, an aminobenzoyl skeleton and an NHCO group in the molecule, and an NHCO group equivalent represented by the formula (I) is 300 g / eq.
- Formula (I): NHCO group equivalent (g / eq) molecular weight / number of NHCO groups contained in one molecule
- the sensitizer B has 3 or more NHCO groups in the molecule.
- the photocurable resin composition as described.
- R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Y represents an organic group derived from a compound having at least m isocyanate groups in the molecule; m represents an integer of 1 to 5)
- the present invention when used as a display element sealant, particularly a liquid crystal sealant, it is an object to provide a photocurable resin composition that has high curability to visible light and can highly suppress liquid crystal contamination.
- Photocurable resin composition The photocurable resin composition of the present invention comprises a curable compound A, a sensitizer B, and a polymerization initiator C, and if necessary, a thermosetting compound D and a thermosetting agent. E and at least one of other components F may further be included.
- Curable compound A The curable compound A contained in the photocurable resin composition of the present invention is a compound having an ethylenically unsaturated double bond in the molecule.
- the compound having an ethylenically unsaturated double bond in the molecule is preferably a compound having a (meth) acryloyl group in the molecule.
- the number of (meth) acryloyl groups per molecule is 1 or 2 or more.
- the compound having a (meth) acryloyl group in the molecule may be a monomer, an oligomer or a polymer.
- (Meth) acryloyl group means acryloyl group or methacryloyl group
- (meth) acrylate means acrylate or methacrylate.
- Examples of compounds having one (meth) acryloyl group in one molecule include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid 2-hydroxyethyl ester. Alkyl esters are included.
- Examples of compounds having two or more (meth) acryloyl groups in one molecule include di (meth) acrylates such as polyethylene glycol, propylene glycol, and polypropylene glycol; di (meth) tris (2-hydroxyethyl) isocyanurate Acrylate; Di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol; Diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A Di (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane; bisphenol A1 Di (meth) acrylate of a diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to the above; tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate; trimethylolprop
- the curable compound A may further have an epoxy group in the molecule.
- the number of epoxy groups per molecule is 1 or 2 or more. If the curable compound A has not only a (meth) acryloyl group but also an epoxy group in the molecule, it can impart photocurability and thermosetting to the photocurable resin composition containing it. Thereby, the sclerosis
- the compound having a (meth) acryloyl group and an epoxy group in the molecule can be, for example, a (meth) acrylic acid glycidyl ester obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst. .
- the epoxy compound to be reacted may be a polyfunctional epoxy compound having two or more epoxy groups in the molecule, and suppresses the decrease in the adhesiveness of the cured product of the photocurable resin composition due to excessive increase in the crosslinking density.
- a bifunctional epoxy compound is preferable.
- bifunctional epoxy compounds include bisphenol type epoxy compounds (bisphenol A type, bisphenol F type, 2,2′-diallyl bisphenol A type, bisphenol AD type, hydrogenated bisphenol type, etc.), biphenyl type epoxy compounds, And naphthalene type epoxy compounds. Of these, bisphenol A type and bisphenol F type bisphenol type epoxy compounds are preferred from the viewpoint of good coating properties.
- the bisphenol type epoxy compound has advantages such as excellent coating properties as compared with the biphenyl ether type epoxy compound.
- the compound having a (meth) acryloyl group and an epoxy group in the molecule may be one kind or a combination of two or more kinds.
- a compound A1 having a (meth) acryloyl group in the molecule and not having an epoxy group may be combined with a compound A2 having a (meth) acryloyl group and an epoxy group in the molecule.
- the photocurable resin composition further contains an epoxy compound as the thermosetting compound D, the epoxy compound, and the compound A1 having a (meth) acryloyl group in the molecule and not having an epoxy group, Can improve the compatibility.
- the photocurable resin composition contains the sensitizer B having appropriate hydrophilicity, the display element of the photocurable resin composition can be used even if the photocurable resin composition contains the compound A1 that is more hydrophobic than the compound A2. In particular, elution into the liquid crystal can be suppressed.
- the content of the compound A2 having a (meth) acryloyl group and an epoxy group in the molecule is not particularly limited, but may be, for example, 30% by mass or more based on the total of the curable compound A.
- the weight average molecular weight of the curable compound A is preferably about 310 to 1,000.
- the weight average molecular weight of the curable compound A can be measured in terms of polystyrene by, for example, gel permeation chromatography (GPC).
- the content of the curable compound A is preferably 40 to 80% by mass, and more preferably 50 to 75% by mass with respect to the photocurable resin composition.
- Sensitizer B contained in the photocurable resin composition of the present invention has an aminobenzoyl skeleton and an NHCO group in the molecule.
- the aminobenzoyl skeleton contained in the sensitizer B is represented by the following formula (1).
- R 1 and R 2 in the formula (1) each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among them, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, and a methyl group is further preferable.
- the number of aminobenzoyl skeletons per molecule is 1 or 2 or more. Even if the content of the sensitizer B is small, the number of aminobenzoyl skeletons per molecule is preferably 2 or more from the viewpoint that sufficient sensitivity to light in the visible light region can be obtained. It is more preferable.
- the elution of the sensitizer B into the liquid crystal material can be preferably suppressed.
- the number of NHCO groups per molecule is 1 or 2 or more. From the viewpoint of highly suppressing the elution of the sensitizer B into the liquid crystal material, the number of NHCO groups per molecule is preferably 2 or more, and more preferably 3 or more.
- Sensitizer B has a burette skeleton (—NHCO (N—) CONH—) or an allophanate skeleton (—NHCO (N—) COO—) from the viewpoint of easily increasing the number of NHCO groups per molecule. Is preferred.
- Sensitizer B may further have an ethylenically unsaturated double bond in the molecule.
- the sensitizer B further having an ethylenically unsaturated double bond in the molecule can undergo a polymerization reaction between the sensitizer B and the curable compound A at the time of curing, for example. Elution is easily suppressed.
- Sensitizer B can be an addition reaction product of “aminobenzoyl compound b1 having a hydroxy group in the molecule” and “compound b2 having an isocyanate group in the molecule”.
- aminobenzoyl compound b1 having a hydroxy group in the molecule is represented by the following formula (2).
- X in formula (2) is independently a single bond, an alkylene group having 1 to 10 carbon atoms (for example, a methylene group or an ethylene group), or an alkyleneoxy group having 1 to 10 carbon atoms (for example, a methyleneoxy group or an ethyleneoxy group).
- Etc. an arylene group having 6 to 10 carbon atoms, an aryleneoxy group having 6 to 10 carbon atoms (for example, a phenyleneoxy group), or an arylenethio group having 6 to 10 carbon atoms (for example, a phenylenethio group).
- an alkylene group having 1 to 10 carbon atoms is preferable because the shift of the absorption wavelength due to the structure of X hardly occurs and the effect of sensitization due to the aminobenzoyl skeleton can be sufficiently obtained.
- a in the formula (2) is an integer of 1 or more, preferably 1.
- the substitution position of the group represented by — (CO—X—OH) is not limited, but is preferably para to the amino group.
- R 1 and R 2 in the formula (2) each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among them, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, and a methyl group is further preferable.
- the compound represented by the formula (2) is preferably represented by the following formula (2 ′).
- the compound b2 having an isocyanate group in the molecule is a compound having one or more isocyanate groups in the molecule.
- a compound having two or more isocyanate groups in the molecule is preferable in that the NHCO group equivalent of the obtained sensitizer B can be easily adjusted to a certain value or less.
- the number of isocyanate groups per molecule is not particularly limited, but is preferably 2 to 4 and more preferably 2 to 3 from the viewpoint that the NHCO group equivalent of sensitizer B can be easily kept below a certain level.
- the compound having two or more isocyanate groups in the molecule preferably further has an NHCO group in the molecule, and includes a burette skeleton (—NHCO (N—) CONH—), an allophanate skeleton (—NHCO (N—) COO— ) Or a urethane skeleton, more preferably a burette skeleton or an allophanate skeleton. That is, a compound having two or more isocyanate groups in the molecule can be represented by, for example, the following formula (3a) or (3b).
- R 3 in formula (3a) and R 4 in formula (3b) are each a linear, branched or cyclic saturated aliphatic hydrocarbon group or aromatic hydrocarbon group which may have an NHCO group. .
- the number of NHCO groups contained in R 3 and R 4 is 0 or 1 or more, and preferably 2 or more.
- R 3 and R 4 preferably include a structure represented by the following formula ( ⁇ ), ( ⁇ ) or ( ⁇ ); and may have a structure represented by the following formula ( ⁇ ) or formula ( ⁇ ). More preferred.
- (R 5 in the formula ( ⁇ ) represents a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group derived from a polyol described later, and n is an integer of 1 or more)
- the compound having two or more isocyanate groups in the molecule may be, for example, a diisocyanate burette or allophanate, or a urethane prepolymer obtained by reacting a polyisocyanate and a polyol and having an isocyanate group at the molecular end. .
- diisocyanates used as raw materials for burettes or allophanates include aliphatic diisocyanates having 1 to 10 carbon atoms such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; cyclohexylene diisocyanate, hydrogenated C6-C15 alicyclic diisocyanates such as xylylene diisocyanate and isophorone diisocyanate; and C6-C15 such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate Aromatic diisocyanates are included.
- the polyisocyanate used as a raw material for the urethane prepolymer is a polyfunctional aliphatic, alicyclic or aromatic isocyanate, and examples thereof include the aforementioned diisocyanate.
- the polyol used as a raw material for the urethane prepolymer include aliphatic polyols such as ethylene glycol, 1,3-propanediol, polyethylene glycol, dipropylene glycol, and pentaerythritol; 1,4-cyclohexanedimethanol, 1,4- Examples include alicyclic polyols such as cyclohexanediol, hydrogenated bisphenol A, and hydrogenated bisphenol F; aromatic polyols such as phenol A and bisphenol F, and the like.
- “Hydroxy group-containing compound b3” is a compound having a hydroxy group in the molecule.
- the hydroxy group of the hydroxy group-containing compound b3 can react with the isocyanate group of the “compound having two or more isocyanate groups in the molecule” to further form —O—CONH—.
- Examples of the hydroxy group-containing compound b3 include monoalcohols having 1 to 20 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, and 1-octadecanol.
- the hydroxy group-containing compound b3 may further have an ethylenically unsaturated double bond. Thereby, an ethylenically unsaturated double bond can be further introduced into the sensitizer B.
- Examples of the hydroxy group-containing compound b3 having an ethylenically unsaturated double bond in the molecule include (meth) acrylate substituted with a hydroxy group such as 4-hydroxybutyl acrylate.
- Sensitizer B is preferably an addition reaction product of “compound represented by formula (2 ′)” and “compound having two or more isocyanate groups in the molecule”; More preferably, it is an addition reaction product between the “compound represented” and the “compound represented by formula (3a) or (3b)”.
- the sensitizer B is preferably a compound represented by the following formula (4).
- X of formula (4), R 1 and R 2 are the same meanings X in formula (2), and R 1 and R 2.
- Y in formula (4) represents a group derived from a compound having at least m isocyanate groups in the molecule.
- the group derived from a compound having at least m isocyanate groups in the molecule is a group derived from a compound having two or more isocyanate groups in the molecule, and from the compound represented by the formula (3a) It is preferably a divalent group derived or a trivalent group derived from a compound represented by the formula (3b).
- M in the formula (4) represents an integer of 1 to 5, preferably 2 or 3.
- sensitizer B examples include addition reaction product of 3-hydroxypropyl-4- (dimethylamino) benzoate and hexamethylene diisocyanate biuret, 3-hydroxypropyl-4- (dimethylamino) benzoate and hexamethylene diisocyanate.
- Examples include addition reaction products with allophanate modified compounds, and compounds obtained by further reacting these compounds with octadecanol or 4-hydroxybutyl acrylate.
- the sensitizer B In order to suppress the contamination of the liquid crystal material by the sensitizer B, it is conceivable to increase the molecular weight of the sensitizer B. However, merely increasing the molecular weight of the sensitizer B may cause a relatively small content ratio per molecule of the aminobenzoyl skeleton that contributes to light absorption. As a result, it is necessary to increase the content of the sensitizer B in order to obtain a light absorptivity above a certain level, which may cause contamination of the liquid crystal material. Therefore, in the present invention, it is important to make the ratio of NHCO groups contained in one molecule equal to or greater than a certain value (ie, make the NHCO group equivalent equal to or less than a certain value).
- the NHCO group equivalent of the sensitizer B is preferably 300 g / eq or less.
- the NHCO group equivalent of the sensitizer B is 300 g / eq or less, since the number of NHCO groups contained in the sensitizer B is relatively large, the hydrophilicity is appropriately increased, and the photocurable resin composition is liquid crystal.
- the elution of the sensitizer B into the liquid crystal material can be suppressed.
- the NHCO group equivalent of the sensitizer B is more preferably 200 g / eq or more, further preferably 200 to 290 g / eq, and further preferably 200 to 250 g / eq.
- the NHCO group equivalent of the sensitizer B is defined by the following formula (I).
- Formula (I): NHCO group equivalent (g / eq) molecular weight / number of NHCO groups contained in one molecule
- the NHCO group equivalent of sensitizer B can be obtained by combining high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC / MS) with NMR measurement or IR measurement. Can be confirmed. Specifically, it can be measured by the following procedure.
- HPLC high performance liquid chromatography
- a solution in which a photocurable resin composition is dissolved in tetrahydrofuran (THF) is centrifuged with a centrifuge to precipitate particle components such as silica particles and thermoplastic resin particles. .
- the obtained solution is filtered through a filter to remove the particle component, thereby obtaining a sample solution.
- a high performance liquid chromatography (HPLC) measurement is performed on the following measurement conditions.
- the sensitizer B includes a “compound represented by the formula (2 ′)” and a “compound having two or more isocyanate groups in the molecule”. It is preferable that it is an addition reaction product of “a compound represented by the formula (2 ′)” and “a compound represented by the formula (3a) or (3b)”.
- Sensitizer B preferably has a molecular weight of, for example, 500 or more and 5000 or less.
- the molecular weight of the sensitizer B is 500 or more, since it is difficult to elute into the liquid crystal, the liquid crystal contamination is easily reduced.
- the molecular weight of the sensitizer B is 5000 or less, the compatibility with the curable compound A is hardly impaired.
- the molecular weight of the sensitizer B is more preferably 500 or more and 3000 or less, and further preferably 700 or more and 1500 or less.
- the molecular weight of the sensitizer B can be measured by the methods 1) and 2) in the above-mentioned measurement of NHCO group equivalent.
- Sensitizer B may be a single type or a combination of two or more types.
- the content of sensitizer B is preferably 0.01 to 10% by mass with respect to the total of curable compound A.
- the content of the sensitizer B is 0.01% by mass or more, the polymerization initiator C can be sufficiently activated, so that sufficient curability is easily obtained. If the content of the sensitizer B is 10% by mass or less, elution into the liquid crystal material is difficult to occur without impairing curability.
- the content of the sensitizer B is more preferably 0.1 to 5% by mass, further preferably 0.1 to 3% by mass, and more preferably 0.1% by mass with respect to the total of the curable compound A. % Or more and less than 2% by mass is particularly preferable.
- Polymerization initiator C is a photopolymerization initiator for causing the curable compound A to undergo a curing reaction.
- the polymerization initiator C shall not contain the above-mentioned aminobenzoyl skeleton.
- the photopolymerization initiator is not particularly limited, but may be a self-cleaving photopolymerization initiator or a hydrogen abstraction photopolymerization initiator.
- Examples of self-cleaving photopolymerization initiators include alkylphenone compounds (for example, benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651); 2-methyl-2 ⁇ -aminoalkylphenones such as morpholino (4-thiomethylphenyl) propan-1-one (IIRGACURE 907); ⁇ -hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184)), acyl Phosphine oxide compounds (for example, 2,4,6-trimethylbenzoindiphenylphosphine oxide), titanocene compounds (for example, bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3) -(1H-pyrrol-1-yl) -phenyl) titanium, etc.), acetophenone compounds (for example, diethoxyacet
- hydrogen abstraction type photopolymerization initiator examples include benzophenone compounds (for example, benzophenone, methyl-4-phenylbenzophenone, o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-).
- benzophenone compounds for example, benzophenone, methyl-4-phenylbenzophenone, o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-).
- Methyl-diphenyl sulfide acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, etc.
- thioxanthone compounds eg 2- Isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-carboxymethoxythioxanthone)-(polytetramethylene glycol 250) diester
- Torakinon compounds such as 2-ethylanthraquinone, etc.
- benzyl-based compounds eg 2- Isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxan
- the polymerization initiator C is preferably a thioxanthone compound (a compound having a thioxanthone skeleton). This is due to the following reason. A polymerization initiator that absorbs too much visible light may be slightly eluted into a liquid crystal or the like to cause display defects. On the other hand, the thioxanthone compound has an appropriate sensitivity to visible light, and therefore can hardly cause a display defect. On the other hand, the thioxanthone compound alone may have a slightly weak visible light absorption, and therefore it is easy to adjust to a more appropriate sensitivity by combining the sensitizer B from the viewpoint of obtaining sufficient curability.
- the thioxanthone compound may further have a hydrophilic functional group (NHCO group or OH group), preferably an NHCO group, from the viewpoint of easily reducing elution into the liquid crystal material.
- a hydrophilic functional group NHCO group or OH group
- the thioxanthone compound having an NHCO group is preferably an addition reaction product of “thioxanthone compound c1 having a hydroxy group in the molecule” and “compound c2 having an isocyanate group in the molecule”.
- the “thioxanthone compound c1 having a hydroxy group in the molecule” is preferably represented by the following formula (5), and more preferably represented by the following formula (5 ′).
- L in the formulas (5) and (5 ′) is independently a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an alkylenethio group having 1 to 10 carbon atoms, It may be an arylene group having 6 to 10 carbon atoms, an aryleneoxy group having 6 to 10 carbon atoms, or an arylenethio group having 6 to 10 carbon atoms. Among these, an alkylenethio group having 1 to 10 carbon atoms or an arylenethio group having 6 to 10 carbon atoms is preferable because it easily absorbs light on a long wavelength side.
- P in the formula (5) is an integer of 1 or more, preferably 1.
- — (L—OH) may be bonded to any one of the 1st to 8th carbon atoms of the thioxanthone skeleton, but is preferably bonded to the 2nd or 7th carbon atom.
- the compound c2 having an isocyanate group in the molecule is a compound having one or more isocyanate groups in the molecule, and has the same meaning as the “compound having an isocyanate group in the molecule (b2)”.
- hydroxy group-containing compound c3 In addition to the addition reaction of “thioxanthone compound c1 having a hydroxy group in the molecule” and “compound c2 having an isocyanate group in the molecule”, “hydroxy group-containing compound c3” may be further reacted.
- the “hydroxy group-containing compound c3” has the same meaning as the “hydroxy group-containing compound b3” described above.
- the thioxanthone compound having an NHCO group is preferably an addition reaction product of “a compound represented by the formula (5 ′)” and “a compound having two or more isocyanate groups in the molecule”.
- the thioxanthone compound having an NHCO group is preferably a compound represented by the following formula (6).
- L in formula (6) is synonymous with L in formula (5).
- Z in the formula (6) represents a group derived from a compound having at least n isocyanate groups in the molecule.
- the group derived from a compound having at least n isocyanate groups in the molecule is a group derived from a compound having two or more isocyanate groups in the molecule, and is represented by the above formula (3a).
- a divalent group derived from a compound or a trivalent group derived from a compound represented by the formula (3b) is preferable.
- N in the formula (6) represents an integer of 2 or more, preferably 2 or 3.
- thioxanthone compound having an NHCO group examples include an addition reaction product of 2-hydroxythioxanthone and a modified hexamethylene diisocyanate biuret, an addition reaction product of 2-hydroxythioxanthone and a modified hexamethylene diisocyanate allophanate, and these Examples include compounds obtained by further reacting compounds with octadecanol or 4-hydroxybutyl acrylate.
- the NHCO group equivalent of the thioxanthone compound having an NHCO group is preferably 350 g / eq or less, more preferably 200 to 350 g / eq, more preferably 230 to 330 g / eq, from the viewpoint of suppressing contamination of the liquid crystal material. More preferably.
- the NHCO group equivalent of the thioxanthone compound is defined by the aforementioned formula (I).
- the molecular weight of the polymerization initiator C is preferably 500 or more and 5000 or less, for example.
- the molecular weight of the polymerization initiator C is preferably 500 or more and 5000 or less, for example.
- the molecular weight of the polymerization initiator C is more preferably 500 or more and 3000 or less, and further preferably 700 or more and 1500 or less.
- the molecular weight of the polymerization initiator C is defined in the same manner as the molecular weight of the sensitizer B described above.
- the molecular weight of the polymerization initiator C can be measured in the same manner as the molecular weight of the sensitizer B.
- the content of the polymerization initiator C is preferably 0.01 to 10% by mass with respect to the total of the curable compound A.
- the content of the polymerization initiator C is 0.01% by mass or more, sufficient photocurability is easily obtained.
- the content of the polymerization initiator C is 10% by mass or less, elution into the liquid crystal material hardly occurs, and sufficient photocurability is easily obtained.
- the content of the polymerization initiator C is more preferably 0.1 to 5% by mass, further preferably 0.1 to 3% by mass, and more preferably 0.1% by mass with respect to the total of the curable compound A. % Or more and less than 2% by mass is particularly preferable.
- thermosetting compound D is preferably an epoxy compound having an epoxy group in the molecule. However, the thermosetting compound D is different from the curable compound A.
- the thermosetting compound D is more preferably an epoxy compound having no (meth) acryloyl group in the molecule.
- the epoxy compound may be any of a monomer, an oligomer or a polymer. Epoxy compounds, for example, have low solubility and diffusibility in liquid crystal when using a photocurable resin composition as a liquid crystal sealant, and not only improve the display characteristics of the resulting liquid crystal panel, but also the moisture resistance of the cured product. Can increase sex.
- the epoxy compound may be an aromatic epoxy compound having a weight average molecular weight of 500 to 10,000, preferably 1,000 to 5,000.
- the weight average molecular weight of the epoxy compound can be measured in terms of polystyrene by gel permeation chromatography (GPC).
- aromatic epoxy compounds include the reaction of aromatic diols typified by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, etc., and diols modified with ethylene glycol, propylene glycol, alkylene glycol, and epichlorohydrin.
- Polyvalent glycidyl ether compounds; xylylene phenol resin glycidyl ether compounds and the like are included.
- cresol novolac type epoxy compound cresol novolac type epoxy compound, phenol novolac type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, triphenolmethane type epoxy compound, triphenolethane type epoxy compound, trisphenol type epoxy compound, dicyclopentadiene type Epoxy compounds, diphenyl ether type epoxy compounds and biphenyl type epoxy compounds are preferred.
- the epoxy compound may be one type or a combination of two or more types.
- the epoxy compound may be liquid or solid.
- a solid epoxy compound is preferable from the viewpoint of easily improving the moisture resistance of the cured product.
- the softening point of the solid epoxy compound is preferably 40 ° C. or higher and 150 ° C. or lower.
- the content of the thermosetting compound D is preferably 3 to 20% by mass with respect to the photocurable resin composition.
- the content of the thermosetting compound D is preferably 3 to 20% by mass with respect to the photocurable resin composition.
- the content of the thermosetting compound D is more preferably 3 to 15% by mass, and further preferably 5 to 15% by mass with respect to the photocurable resin composition.
- thermosetting agent E does not cure the thermosetting compound D or the curable compound A (when the curable compound A further has an epoxy group in the molecule) under normal storage conditions (room temperature, under visible light, etc.). Is a compound that cures the compound when heated.
- the photocurable resin composition containing the thermosetting agent E is excellent in storage stability and thermosetting.
- the thermosetting agent E is preferably an epoxy curing agent.
- Epoxy curing agent is an epoxy curing agent having a melting point of 50 ° C. or more and 250 ° C. or less, although it depends on the heat curing temperature from the viewpoint of enhancing the viscosity stability of the photo-curable resin composition and not impairing the moisture resistance of the cured product
- An epoxy curing agent having a melting point of 100 ° C. or higher and 200 ° C. or lower is more preferable, and an epoxy curing agent having a melting point of 150 ° C. or higher and 200 ° C. or lower is further preferable.
- epoxy curing agent examples include organic acid dihydrazide thermal latent curing agent, imidazole thermal latent curing agent, amine adduct thermal latent curing agent, and polyamine thermal latent curing agent.
- organic acid dihydrazide thermal latent curing agents include adipic acid dihydrazide (melting point 181 ° C.), 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (melting point 120 ° C.), 7,11-octa Decadiene-1,18-dicarbohydrazide (melting point 160 ° C.), dodecanedioic acid dihydrazide (melting point 190 ° C.), sebacic acid dihydrazide (melting point 189 ° C.) and the like.
- imidazole-based thermal latent curing agents examples include 2,4-diamino-6- [2′-ethylimidazolyl- (1 ′)]-ethyltriazine (melting point 215 to 225 ° C.) and 2-phenylimidazole (melting point) 137-147 ° C.) and the like.
- the amine adduct thermal latent curing agent is a thermal latent curing agent comprising an addition compound obtained by reacting an amine compound having catalytic activity with an arbitrary compound, and examples thereof include Ajinomoto Fine Techno Co., Ltd. ) Amicure PN-40 (melting point 110 ° C.), Ajinomoto Fine Techno Co., Ltd.
- the polyamine thermal latent curing agent is a thermal latent curing agent having a polymer structure obtained by reacting an amine and an epoxy.
- ADEKA HARDNER EH4339S softening point 120 to 130, manufactured by ADEKA Corporation.
- Adeka Hardener EH4357S softening point 73 to 83 ° C.
- dihydrazide thermal latent curing agents, imidazole thermal latent curing agents, amine adduct thermal latent curing agents, and polyamine thermal latent curing agents are preferred.
- the epoxy curing agent may be only one type or a combination of two or more types.
- the content of the thermosetting agent E is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and more preferably 5 to 20% by mass with respect to the photocurable resin composition. Further preferred.
- the photocurable resin composition containing the thermosetting agent E can be a one-component curable resin composition.
- the one-component curable resin composition is excellent in workability because it is not necessary to mix the main agent and the curing agent in use.
- the total content of the thermosetting compound D and the thermosetting agent E is preferably 6 to 50% by mass, more preferably 6 to 35% by mass, with respect to the photocurable resin composition. More preferably, it is 30 mass%.
- the photocurable resin composition of the present invention may further contain thermoplastic resin particles as necessary.
- the thermoplastic resin particles include a thermoplastic resin having a softening point temperature measured by the ring and ball method of 50 to 120 ° C., preferably 70 to 100 ° C., and a number average particle diameter of 0.05 to 5 ⁇ m, preferably 0.8. It can be 1 to 3 ⁇ m.
- the photocurable resin composition containing such thermoplastic resin particles can relieve the shrinkage stress generated in the cured product.
- the number average particle diameter is set to the upper limit value or less, it is possible to prevent the coating stability from being lowered by the thermoplastic resin particles when forming a seal member having a thin line width.
- the number average particle diameter can be measured with a dry particle size distribution meter.
- thermoplastic resin particles include fine particles obtained by suspension polymerization of a resin containing an epoxy group and a double bond group with a monomer capable of radical polymerization.
- the resin containing an epoxy group and a double bond group include a resin obtained by reacting a bisphenol F type epoxy resin and methacrylic acid in the presence of a tertiary amine.
- radically polymerizable monomers include butyl acrylate, glycidyl methacrylate, and divinylbenzene.
- the content of the thermoplastic resin particles is preferably 5 to 40% by mass, more preferably 7 to 30% by mass with respect to the photocurable resin composition.
- the thermoplastic resin particles can preferably relieve the shrinkage stress during the heat curing of the photocurable resin composition, and it is easy to form a seal member with a target line width. .
- the photocurable resin composition of the present invention may further contain a filler as necessary.
- a photocurable resin composition containing a filler may have good viscosity, strength of a cured product, linear expansion, and the like.
- fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, titanium nitride, aluminum oxide (alumina), zinc oxide, silicon dioxide, potassium titanate, Inorganic fillers such as kaolin, talc, glass beads, sericite, activated clay, bentonite, aluminum nitride, silicon nitride are included. Of these, silicon dioxide and talc are preferable.
- the shape of the filler may be a regular shape such as a spherical shape, a plate shape, or a needle shape, or may be an irregular shape.
- the average primary particle diameter of the filler is preferably 1.5 ⁇ m or less, and the specific surface area is preferably 0.5 to 20 m 2 / g.
- the average primary particle diameter of the filler can be measured by a laser diffraction method described in JIS Z8825-1.
- the specific surface area of the filler can be measured by the BET method described in JIS Z8830.
- the content of the filler is preferably 1 to 50% by mass with respect to the photocurable resin composition.
- the coating stability of a photocurable resin composition is hard to be impaired as content of a filler is 50 mass% or less.
- the content of the filler is more preferably 10 to 30% by mass with respect to the photocurable resin composition.
- the photo-curable resin composition of the present invention is optionally combined with a thermal radical polymerization initiator, a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a plasticizer, and a quenching agent.
- a coupling agent such as a silane coupling agent, an ion trapping agent, an ion exchange agent, a leveling agent, a pigment, a dye, a plasticizer, and a quenching agent.
- An additive such as a foaming agent may be further included.
- silane coupling agent examples include vinyltrimethoxysilane, ⁇ - (meth) acryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and the like.
- the content of the silane coupling agent may be 0.01 to 5% by mass with respect to the photocurable resin composition. When the content of the silane coupling agent is 0.01% by mass or more, the cured product of the photocurable resin composition tends to have sufficient adhesiveness.
- the photocurable resin composition of the present invention may further contain a spacer for adjusting the gap of the liquid crystal display panel.
- the viscosity of the photocurable resin composition of the present invention at 25 ° C. and 2.5 rpm of the E-type viscometer is preferably 200 to 450 Pa ⁇ s, and preferably 300 to 400 Pa ⁇ s. It is more preferable that When the viscosity is in the above range, the applicability of the photocurable resin composition by the dispenser is good.
- the photocurable resin composition of the present invention can be used as, for example, a sealing agent.
- the sealing agent is preferably a display element sealing agent used for sealing display elements such as liquid crystal display elements, organic EL elements, and LED elements.
- the display element sealant is particularly preferably a liquid crystal sealant, and more preferably a liquid crystal sealant for a liquid crystal dropping method.
- the sensitizer B contained in the photocurable resin composition of the present invention is easy to activate the polymerization initiator C, good curability is easily obtained. This makes it possible to cure in a short time while reducing damage to the display element such as the liquid crystal layer due to light. Further, since the sensitizer B includes a certain amount of hydrophilic NHCO groups in the molecule, elution into the liquid crystal having hydrophobicity can be highly suppressed.
- the display element panel includes a pair of substrates, a display element disposed between the pair of substrates, and a seal member for sealing the display element.
- the seal member can be a cured product of the display element sealant of the present invention.
- the display element sealing agent of the present invention is composed of the photocurable resin composition of the present invention.
- Examples of display elements include liquid crystal display elements, organic EL elements, LED elements, and the like.
- a liquid crystal display element is preferable because the photocurable resin composition of the present invention can satisfactorily suppress liquid crystal contamination.
- the liquid crystal display panel of the present invention includes a space surrounded by a pair of substrates, a frame-shaped seal member disposed between the pair of substrates, and a frame-shaped seal member between the pair of substrates.
- a filled liquid crystal layer liquid crystal display element.
- the seal member can be a cured product of the liquid crystal sealant of the present invention.
- the liquid crystal sealing agent of the present invention comprises the photocurable resin composition of the present invention.
- the pair of substrates are both transparent substrates.
- the material of the transparent substrate can be glass or plastic such as polycarbonate, polyethylene terephthalate, polyethersulfone and PMMA.
- a matrix-like TFT, a color filter, a black matrix, or the like can be disposed on the surface of one of the pair of substrates.
- An alignment film may be further disposed on the surface of the one substrate.
- the alignment film contains a known organic alignment agent or inorganic alignment agent.
- the liquid crystal display panel is manufactured using the liquid crystal sealant of the present invention.
- a liquid crystal dropping method and a liquid crystal injecting method as a method for manufacturing a liquid crystal display panel, but the liquid crystal display panel of the present invention is preferably manufactured by a liquid crystal dropping method.
- the manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is 1) forming a seal pattern of the liquid crystal sealant of the present invention on one substrate; 2) dropping the liquid crystal in a region surrounded by the seal pattern of the substrate or a region of the other substrate facing the region surrounded by the seal pattern in a state where the seal pattern is uncured; 3) a step of superimposing one substrate and the other substrate through a seal pattern; 4) curing the seal pattern.
- the uncured state of the seal pattern means a state in which the curing reaction of the liquid crystal sealant has not progressed to the gel point. For this reason, in the step 2), in order to suppress dissolution of the liquid crystal sealant in the liquid crystal, the seal pattern may be semi-cured by light irradiation or heating.
- step 4 only curing by light irradiation may be performed, but after curing by light irradiation, curing by heating may be performed. That is, step 4) includes a step of irradiating the seal pattern with light to cure the seal pattern; when the liquid crystal sealant further includes the above-described thermosetting agent E , the seal pattern irradiated with light is heated. And curing it. Since the liquid crystal sealant can be cured in a short time by curing by light irradiation, dissolution in the liquid crystal can be suppressed. By combining curing by light irradiation and curing by heating, damage to the liquid crystal layer due to light can be reduced compared to the case of only curing by light irradiation.
- the light to be irradiated is preferably light having a wavelength of 370 to 450 nm. This is because the light having the above wavelength causes relatively little damage to the liquid crystal material and the drive electrode.
- a known light source that emits ultraviolet light or visible light can be used.
- a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, or the like can be used.
- the light irradiation energy may be energy that can cure the curable compound A.
- the photocuring time is, for example, about 10 minutes although it depends on the composition of the liquid crystal sealant.
- thermosetting temperature is 120 ° C., for example, although it depends on the composition of the liquid crystal sealant, and the thermosetting time is about 2 hours.
- the liquid crystal sealant of the present invention has reduced dissolution in liquid crystals. Therefore, a liquid crystal display panel having a cured product of the liquid crystal sealant of the present invention is less contaminated with liquid crystals and can have high quality display performance.
- Compound R-5 3-hydroxypropyl-4- (dimethylamino) benzoate
- Compound R-6 4- (dimethylamino) benzyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., the following compound)
- Compound R-7 Omnipol-ASA (manufactured by IGM Resins, the following compound)
- the relative molecular mass corresponding to the peak apex of the detected main peak was measured by liquid chromatography mass spectrometry (LC / MS).
- NI point of liquid crystal 0.1 g of the prepared compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture Got. Next, this liquid crystal mixture was taken out, 10 mg was put in an aluminum open pan (manufactured by Epolide Service), and the NI point was measured with a DTA-TG apparatus (manufactured by Seiko Instruments Inc.). The case where the amount of change with respect to the NI point of the liquid crystal was less than 3 ° C. was evaluated as ⁇ : the case where it was 3 ° C. or higher and lower than 5 ° C.
- Curing compound A-1 methacrylic acid-modified bisphenol F type epoxy resin (95% partially methacrylic product) obtained in Synthesis Example 8 below (Synthesis Example 8) 160 g of liquid bisphenol F type epoxy resin (YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, 0.2 g of triethanolamine as a catalyst, and 81.7 g of methacrylic acid was charged into the flask, dried air was fed into the flask, and the mixture was reacted at 90 ° C.
- liquid bisphenol F type epoxy resin YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq
- 0.1 g of p-methoxyphenol as a polymerization inhibitor 0.1 g of p-methoxyphenol as a polymerization inhibitor
- Kyoeisha Chemical Light Acrylate 14EG-A Polyethylene glycol diacrylate represented by the following formula (molecular weight 600) Curing Compound A-2: Acrylic acid-modified bisphenol F type epoxy resin (50% partially acrylate) obtained in Synthesis Example 9 below (Synthesis Example 9) First, in a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 175 g of bisphenol F type epoxy resin (YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq), 37 g Acrylic acid, 0.2 g of triethanolamine as a catalyst, and 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed, and the reaction was conducted by heating and stirring at 110 ° C.
- bisphenol F type epoxy resin YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
- a modified bisphenol F type epoxy resin was obtained.
- the obtained resin was repeatedly washed with ultrapure water 12 times and analyzed by HPLC and NMR. As a result, it was confirmed that 50% of the epoxy groups were acryloyl-modified bisphenol F type epoxy resin. Further, as a result of GPC analysis of the obtained resin, the weight average molecular weight was 692.
- thermosetting compound D Epoxy resin: Mitsubishi Chemical Corporation, jER1004, softening point 97 ° C
- thermosetting agent E Adipic acid dihydrazide: Nippon Kasei Co., Ltd., ADH, melting point 177-184 ° C
- Silica particles Nippon Shokubai Co., Ltd., S-100 Thermoplastic resin particles (manufactured by Aika Industries, F351, softening point 120 ° C., average particle size 0.3 ⁇ m) ⁇ -glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
- Example 1 420 parts by mass of the curable compound A-1 obtained in Synthesis Example 8 as the curable compound A, 200 parts by mass of polyethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate 14EG-A), and the sensitizer B 10 parts by mass of Compound B-1 obtained in Synthesis Example 1, 10 parts by mass of Omnipol-TX (manufactured by IGM Resins) as a polymerization initiator C, and an epoxy resin (manufactured by Mitsubishi Chemical Corporation) as a thermosetting compound D , JER1004), 50 parts by mass, 90 parts by mass of adipic acid dihydrazide (manufactured by Nippon Kasei Co., Ltd., ADH) as thermosetting agent E, and 130 parts by mass of silica particles (manufactured by Nippon Shokubai Co., Ltd., S-100) as component F Parts, 70 parts by mass of F351 manufactured by Aika Kogyo Co
- thermoplastic resin particles as thermoplastic resin particles, and ⁇ -glycidoxypropyltrimeth as a silane coupling agent Shishiran (Shin-Etsu Chemical Co., Ltd., KBM-403) and 20 parts by weight, were mixed in sufficient a uniform liquid using a three-roll to obtain a photocurable resin composition.
- ⁇ -glycidoxypropyltrimeth as a silane coupling agent Shishiran (Shin-Etsu Chemical Co., Ltd., KBM-403) and 20 parts by weight, were mixed in sufficient a uniform liquid using a three-roll to obtain a photocurable resin composition.
- Examples 2 to 9, Comparative Examples 1 to 7 A photocurable resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 4 or 5 was changed.
- the display characteristics of the obtained photocurable resin composition were evaluated by the following methods.
- a 40 mm ⁇ 45 mm glass substrate (RT-DM88-PIN, manufactured by EHC) on which a transparent electrode and an alignment film were formed in advance using a dispenser (shot master: manufactured by Musashi Engineering)
- a 35 mm ⁇ 40 mm square seal pattern cross-sectional area 3500 ⁇ m 2 ) (main seal) and a similar seal pattern (38 mm ⁇ 43 mm square seal pattern) were formed on the outer periphery.
- a liquid crystal material (MLC-7021-000, manufactured by Merck & Co., Inc.) corresponding to the volume of the panel after bonding was precisely dropped into the main seal frame using a dispenser.
- a pair of glass substrates was bonded together under reduced pressure, and then bonded to the atmosphere. Then, the two glass substrates bonded together are held in a light shielding box for 3 minutes, and then light with a wavelength of 370 to 450 nm is 3000 mJ in a state where the main seal is masked with a substrate coated with a square black matrix of 36 mm ⁇ 41 mm. / Cm 2 , and after heating at 120 ° C.
- liquid crystal display panel (LCD panel display characteristics test when energized) A liquid crystal display panel was produced in the same manner as the liquid crystal display panel display characteristic test described above. When this liquid crystal display panel is driven with an applied voltage of 5 V using a DC power source, the liquid crystal display function in the vicinity of the main seal can be exhibited. The case where it occurred was indicated by ⁇ , and the case where white unevenness occurred over a range of 1 mm or more from the vicinity of the main seal and it was not driven normally was indicated by ⁇ .
- the present invention is such that the evaluation result of the display characteristic test at the time of non-energization is ⁇ and the evaluation result of the display characteristic test at the time of energization is ⁇ or more.
- the evaluation results of Examples 1 to 9 are shown in Table 4, and the evaluation results of Comparative Examples 1 to 7 are shown in Table 5.
- the photocurable resin compositions of Examples 1 to 9 containing the sensitizer B having an aminobenzoyl skeleton and having an NHCO group equivalent of 300 g / eq or less were used when the current was applied. It can be seen that good display characteristics are exhibited at any time during energization.
- the photocurable resin compositions of Comparative Examples 1 and 2 including a comparative compound having an NHCO group equivalent of more than 300 g / eq, and a comparative compound having no NHCO group are included. It can be seen that the photocurable resin compositions of Comparative Examples 5 and 6 are inferior in display characteristics. This is presumably because liquid crystal contamination could not be sufficiently suppressed because the comparative compound had little or no hydrophilic NHCO group.
- Examples 1 to 3 including compounds B-1 to B-3 having an aminobenzoyl skeleton the light of Comparative Examples 3 and 4 including comparative compounds R-3 and R-4 having no aminobenzoyl skeleton It can be seen that the curable resin composition has poor display characteristics. This is probably because the sensitizing ability of the comparative compound was low, so that the sealing material was not sufficiently cured, and the liquid crystal elution of the sealing material component could not be sufficiently suppressed.
- the present invention can provide a photo-curable resin composition that is highly curable with respect to visible light when used as, for example, a liquid crystal sealant and can highly suppress liquid crystal contamination.
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Abstract
Description
式(I):NHCO基当量(g/eq)=分子量/1分子に含まれるNHCO基の数
[2] 前記増感剤Bが、分子内に3以上のNHCO基を有する、[1]に記載の光硬化性樹脂組成物。
[3] 前記増感剤Bが、分子内にビューレット骨格又はアロファネート骨格を有する、[1]又は[2]に記載の光硬化性樹脂組成物。
[4] 前記増感剤Bは、下記式(4)で表される化合物である、[1]~[3]のいずれかに記載の光硬化性樹脂組成物。
Xは、単結合、炭素数1~10のアルキレン基、炭素数1~10のアルキレンオキシ基、炭素数6~10のアリーレン基、炭素数6~10のアリーレンオキシ基又は炭素数6~10のアリーレンチオ基を表し、
R1及びR2は、それぞれ独立して水素原子又は炭素数1~10のアルキル基を表し、
Yは、分子内に少なくともm個のイソシアネート基を有する化合物から誘導される有機基を表し、
mは、1~5の整数を表す)
[5] 前記増感剤Bの含有量が、前記硬化性化合物Aに対して0.01~10質量%である、[1]~[4]のいずれかに記載の光硬化性樹脂組成物。
[6] 前記重合開始剤Cが、チオキサントン骨格を有する、[1]~[5]のいずれかに記載の光硬化性樹脂組成物。
[7] 前記硬化性化合物Aが、分子内にエポキシ基をさらに有する、[1]~[6]のいずれかに記載の光硬化性樹脂組成物。
[8] [1]~[7]のいずれかに記載の光硬化性樹脂組成物からなる、表示素子シール剤。
[9] [1]~[7]のいずれかに記載の光硬化性樹脂組成物からなる、液晶シール剤。
[10] [9]に記載の液晶シール剤を用いて、一方の基板にシールパターンを形成する工程と、前記シールパターンが未硬化の状態において、前記シールパターンの領域内、又は前記一方の基板と対になる他方の基板に液晶を滴下する工程と、前記一方の基板と前記他方の基板とを、前記シールパターンを介して重ね合わせる工程と、前記シールパターンを硬化させる工程とを含む、液晶表示パネルの製造方法。
[11] 前記シールパターンを硬化させる工程は、前記シールパターンに光を照射して前記シールパターンを硬化させる工程を含む、[10]に記載の液晶表示パネルの製造方法。
[12] 前記シールパターンに照射する光は、可視光領域の光を含む、[11]に記載の液晶表示パネルの製造方法。
[13] 一対の基板と、前記一対の基板の間に配置された枠状のシール部材と、前記一対の基板の間の前記シール部材で囲まれた空間に充填された液晶層とを含み、前記シール部材が、[9]に記載の液晶シール剤の硬化物である、液晶表示パネル。 [1] A curable compound A having an ethylenically unsaturated double bond in the molecule, an aminobenzoyl skeleton and an NHCO group in the molecule, and an NHCO group equivalent represented by the formula (I) is 300 g / eq. The photocurable resin composition containing the following sensitizer B and the polymerization initiator C.
Formula (I): NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule [2] The sensitizer B has 3 or more NHCO groups in the molecule. The photocurable resin composition as described.
[3] The photocurable resin composition according to [1] or [2], wherein the sensitizer B has a burette skeleton or an allophanate skeleton in a molecule.
[4] The photocurable resin composition according to any one of [1] to [3], wherein the sensitizer B is a compound represented by the following formula (4).
X is a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an aryleneoxy group having 6 to 10 carbon atoms, or an alkyl group having 6 to 10 carbon atoms. Represents an arylenethio group,
R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
Y represents an organic group derived from a compound having at least m isocyanate groups in the molecule;
m represents an integer of 1 to 5)
[5] The photocurable resin composition according to any one of [1] to [4], wherein the content of the sensitizer B is 0.01 to 10% by mass with respect to the curable compound A. .
[6] The photocurable resin composition according to any one of [1] to [5], wherein the polymerization initiator C has a thioxanthone skeleton.
[7] The photocurable resin composition according to any one of [1] to [6], wherein the curable compound A further has an epoxy group in the molecule.
[8] A display element sealing agent comprising the photocurable resin composition according to any one of [1] to [7].
[9] A liquid crystal sealant comprising the photocurable resin composition according to any one of [1] to [7].
[10] A step of forming a seal pattern on one substrate using the liquid crystal sealant according to [9], and in the state of the seal pattern in the uncured state of the seal pattern, or the one substrate A step of dropping a liquid crystal on the other substrate paired with the other substrate, a step of superposing the one substrate and the other substrate through the seal pattern, and a step of curing the seal pattern. Manufacturing method of display panel.
[11] The method of manufacturing a liquid crystal display panel according to [10], wherein the step of curing the seal pattern includes a step of curing the seal pattern by irradiating the seal pattern with light.
[12] The method for manufacturing a liquid crystal display panel according to [11], wherein the light applied to the seal pattern includes light in a visible light region.
[13] including a pair of substrates, a frame-shaped sealing member disposed between the pair of substrates, and a liquid crystal layer filled in a space surrounded by the sealing member between the pair of substrates, A liquid crystal display panel, wherein the seal member is a cured product of the liquid crystal sealant according to [9].
本発明の光硬化性樹脂組成物は、硬化性化合物Aと、増感剤Bと、重合開始剤Cとを含み、必要に応じて熱硬化性化合物D、熱硬化剤E、及びその他の成分Fの少なくとも一つをさらに含み得る。 1. Photocurable resin composition The photocurable resin composition of the present invention comprises a curable compound A, a sensitizer B, and a polymerization initiator C, and if necessary, a thermosetting compound D and a thermosetting agent. E and at least one of other components F may further be included.
本発明の光硬化性樹脂組成物に含まれる硬化性化合物Aは、分子内にエチレン性不飽和二重結合を有する化合物である。分子内にエチレン性不飽和二重結合を有する化合物は、分子内に(メタ)アクリロイル基を有する化合物であることが好ましい。1分子あたりの(メタ)アクリロイル基の数は、1又は2以上である。分子内に(メタ)アクリロイル基を有する化合物は、モノマー、オリゴマー又はポリマーのいずれであってもよい。(メタ)アクリロイル基は、アクリロイル基又はメタクリロイル基を意味し、(メタ)アクリレートは、アクリレート又はメタクリレートを意味する。 1-1. Curable compound A
The curable compound A contained in the photocurable resin composition of the present invention is a compound having an ethylenically unsaturated double bond in the molecule. The compound having an ethylenically unsaturated double bond in the molecule is preferably a compound having a (meth) acryloyl group in the molecule. The number of (meth) acryloyl groups per molecule is 1 or 2 or more. The compound having a (meth) acryloyl group in the molecule may be a monomer, an oligomer or a polymer. (Meth) acryloyl group means acryloyl group or methacryloyl group, and (meth) acrylate means acrylate or methacrylate.
本発明の光硬化性樹脂組成物に含まれる増感剤Bは、分子内にアミノベンゾイル骨格と、NHCO基とを有する。 1-2. Sensitizer B
Sensitizer B contained in the photocurable resin composition of the present invention has an aminobenzoyl skeleton and an NHCO group in the molecule.
式(I):NHCO基当量(g/eq)=分子量/1分子に含まれるNHCO基の数 That is, the NHCO group equivalent of the sensitizer B is preferably 300 g / eq or less. When the NHCO group equivalent of the sensitizer B is 300 g / eq or less, since the number of NHCO groups contained in the sensitizer B is relatively large, the hydrophilicity is appropriately increased, and the photocurable resin composition is liquid crystal. When used as a sealant, the elution of the sensitizer B into the liquid crystal material can be suppressed. The NHCO group equivalent of the sensitizer B is more preferably 200 g / eq or more, further preferably 200 to 290 g / eq, and further preferably 200 to 250 g / eq. When the NHCO group equivalent of the sensitizer B is 200 g / eq or more, the moisture resistance of the cured product of the photocurable resin composition is hardly impaired. The NHCO group equivalent of the sensitizer B is defined by the following formula (I).
Formula (I): NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule
1)高速液体クロマトグラフィー(HPLC)測定
光硬化性樹脂組成物をテトラヒドロフラン(THF)に溶解させた溶液を、遠心分離機により遠心分離し、シリカ粒子や熱可塑性樹脂粒子等の粒子成分を沈降させる。得られた溶液をフィルターで濾過して粒子成分を除去し、試料液を得る。得られた試料液について、下記測定条件で高速液体クロマトグラフィー(HPLC)測定を行う。
(HPLC測定条件)
装置:waters製 Acquity TM UPLC H-Class system
カラム:Acquity UPLC BEH C18、2.1mmID×100mm 粒子径:1.7μm
移動相:A:アセトニトリル
B:5mM酢酸アンモニウム水溶液
A/B = 60/40(0~4分)
95/5(4~9分)
95/5(9~10分)
流速:0.4mL/分
PDA検出器:測定波長:190~500nm、抽出波長:305nm The NHCO group equivalent of sensitizer B can be obtained by combining high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC / MS) with NMR measurement or IR measurement. Can be confirmed. Specifically, it can be measured by the following procedure.
1) High-performance liquid chromatography (HPLC) measurement A solution in which a photocurable resin composition is dissolved in tetrahydrofuran (THF) is centrifuged with a centrifuge to precipitate particle components such as silica particles and thermoplastic resin particles. . The obtained solution is filtered through a filter to remove the particle component, thereby obtaining a sample solution. About the obtained sample liquid, a high performance liquid chromatography (HPLC) measurement is performed on the following measurement conditions.
(HPLC measurement conditions)
Equipment: Acquity TM UPLC H-Class system made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile B: 5 mM ammonium acetate aqueous solution A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4 mL / min PDA detector: Measurement wavelength: 190-500 nm, Extraction wavelength: 305 nm
前述の1)の測定において、アミノベンゾイル骨格に特徴的な波長305nmの検出器で検出されたメインピークの、ピーク頂点に対応する相対分子質量と組成式を、液体クロマトグラフィー質量分析(LC/MS)により測定する。「メインピーク」とは、検出波長305nmで検出された全ピークのうち、最も強度が大きいピーク(ピークの高さが最も高いピーク)をいう。
(LC/MS測定条件)
装置:waters製 Acquity TM H-Class system / SQ Detector
カラム:Acquity UPLC BEH C18、2.1mmID×100mm 粒子径:1.7μm
移動相:A:アセトニトリル
B:5mM酢酸アンモニウム水溶液
A/B = 60/40(0~4分)
95/5(4~9分)
95/5(9~10分)
流速:0.4mL/分
イオン化:ESI(エレクトロスプレーイオン化)、正・負イオン測定
PDA検出器:測定波長:190~500nm、抽出波長:305nm
3)NMR測定又はIR測定
また、上記試料液を用いて、NMR測定又はIR測定を行う。それにより、NHCO基やアミノベンゾイル骨格に特徴的なスペクトルの有無を確認し、化学構造を特定する。
4)前記1)及び2)で得られた分子量と、前記3)で得られたNHCO基の数とを、前述の式(I)に当てはめてNHCO基当量(g/eq)を求める。 2) Liquid Chromatography Mass Spectrometry (LC / MS) Measurement In the measurement of the above 1), the relative molecular mass corresponding to the peak apex of the main peak detected by the detector having a wavelength of 305 nm characteristic of the aminobenzoyl skeleton The composition formula is measured by liquid chromatography mass spectrometry (LC / MS). The “main peak” refers to a peak having the highest intensity (a peak having the highest peak height) among all peaks detected at a detection wavelength of 305 nm.
(LC / MS measurement conditions)
Equipment: Acquity TM H-Class system / SQ Detector made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile B: 5 mM ammonium acetate aqueous solution A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4 mL / min Ionization: ESI (electrospray ionization), positive / negative ion measurement PDA detector: Measurement wavelength: 190-500 nm, Extraction wavelength: 305 nm
3) NMR measurement or IR measurement Further, NMR measurement or IR measurement is performed using the sample solution. Thereby, the presence or absence of a spectrum characteristic of the NHCO group or aminobenzoyl skeleton is confirmed, and the chemical structure is specified.
4) The molecular weight obtained in 1) and 2) above and the number of NHCO groups obtained in 3) above are applied to the above formula (I) to obtain the NHCO group equivalent (g / eq).
重合開始剤Cは、硬化性化合物Aを硬化反応させるための光重合開始剤である。但し、重合開始剤Cは、前述のアミノベンゾイル骨格を含まないものとする。 1-3. Polymerization initiator C
The polymerization initiator C is a photopolymerization initiator for causing the curable compound A to undergo a curing reaction. However, the polymerization initiator C shall not contain the above-mentioned aminobenzoyl skeleton.
熱硬化性化合物Dは、分子内にエポキシ基を有するエポキシ化合物であることが好ましい。但し、熱硬化性化合物Dは、硬化性化合物Aとは異なるものとする。熱硬化性化合物Dは、分子内に(メタ)アクリロイル基を有さないエポキシ化合物であることがより好ましい。エポキシ化合物は、モノマー、オリゴマー又はポリマーのいずれであってもよい。エポキシ化合物は、例えば光硬化性樹脂組成物を液晶シール剤として用いた際に、液晶に対する溶解性や拡散性が低く、得られる液晶パネルの表示特性を良好とするだけでなく、硬化物の耐湿性を高め得る。 1-4. Thermosetting compound D
The thermosetting compound D is preferably an epoxy compound having an epoxy group in the molecule. However, the thermosetting compound D is different from the curable compound A. The thermosetting compound D is more preferably an epoxy compound having no (meth) acryloyl group in the molecule. The epoxy compound may be any of a monomer, an oligomer or a polymer. Epoxy compounds, for example, have low solubility and diffusibility in liquid crystal when using a photocurable resin composition as a liquid crystal sealant, and not only improve the display characteristics of the resulting liquid crystal panel, but also the moisture resistance of the cured product. Can increase sex.
熱硬化剤Eは、通常の保存条件下(室温、可視光線下等)では熱硬化性化合物Dや(硬化性化合物Aが分子内にエポキシ基をさらに有する場合は)硬化性化合物Aを硬化させないが、熱を与えられると当該化合物を硬化させる化合物である。熱硬化剤Eを含有する光硬化性樹脂組成物は、保存安定性に優れ、且つ熱硬化性に優れる。熱硬化剤Eは、エポキシ硬化剤であることが好ましい。 1-5. Thermosetting agent E
The thermosetting agent E does not cure the thermosetting compound D or the curable compound A (when the curable compound A further has an epoxy group in the molecule) under normal storage conditions (room temperature, under visible light, etc.). Is a compound that cures the compound when heated. The photocurable resin composition containing the thermosetting agent E is excellent in storage stability and thermosetting. The thermosetting agent E is preferably an epoxy curing agent.
1-6-1.熱可塑性樹脂粒子
本発明の光硬化性樹脂組成物は、必要に応じて熱可塑性樹脂粒子をさらに含んでいてもよい。熱可塑性樹脂粒子は、環球法により測定される軟化点温度が50~120℃、好ましくは70~100℃の熱可塑性樹脂を含み、且つ数平均粒子径が0.05~5μm、好ましくは0.1~3μmでありうる。そのような熱可塑性樹脂粒子を含む光硬化性樹脂組成物は、硬化物に発生する収縮応力を緩和できる。また、数平均粒子径を上限値以下とすることにより、線幅の細いシール部材を形成する際に、熱可塑性樹脂粒子によって、塗工安定性が低下することを防ぐことができる。数平均粒子径は、乾式粒度分布計で測定されうる。 1-6. Other ingredients F
1-6-1. Thermoplastic resin particles
The photocurable resin composition of the present invention may further contain thermoplastic resin particles as necessary. The thermoplastic resin particles include a thermoplastic resin having a softening point temperature measured by the ring and ball method of 50 to 120 ° C., preferably 70 to 100 ° C., and a number average particle diameter of 0.05 to 5 μm, preferably 0.8. It can be 1 to 3 μm. The photocurable resin composition containing such thermoplastic resin particles can relieve the shrinkage stress generated in the cured product. Moreover, when the number average particle diameter is set to the upper limit value or less, it is possible to prevent the coating stability from being lowered by the thermoplastic resin particles when forming a seal member having a thin line width. The number average particle diameter can be measured with a dry particle size distribution meter.
本発明の光硬化性樹脂組成物は、必要に応じて充填剤をさらに含んでいてもよい。充填剤を含む光硬化性樹脂組成物は、粘度や硬化物の強度、及び線膨張性等が良好でありうる。 1-6-2. Filler The photocurable resin composition of the present invention may further contain a filler as necessary. A photocurable resin composition containing a filler may have good viscosity, strength of a cured product, linear expansion, and the like.
本発明の光硬化性樹脂組成物の、E型粘度計の25℃、2.5rpmにおける粘度は、200~450Pa・sであることが好ましく、300~400Pa・sであることがより好ましい。粘度が上記範囲にあると、光硬化性樹脂組成物のディスペンサーによる塗布性が良好となる。 1-7. Physical Properties of Photocurable Resin Composition The viscosity of the photocurable resin composition of the present invention at 25 ° C. and 2.5 rpm of the E-type viscometer is preferably 200 to 450 Pa · s, and preferably 300 to 400 Pa · s. It is more preferable that When the viscosity is in the above range, the applicability of the photocurable resin composition by the dispenser is good.
表示素子パネルは、一対の基板と、該一対の基板の間に配置される表示素子と、該表示素子を封止するシール部材とを含む。シール部材を、本発明の表示素子シール剤の硬化物としうる。本発明の表示素子シール剤は、本発明の光硬化性樹脂組成物からなる。 2. Display element panel and manufacturing method thereof The display element panel includes a pair of substrates, a display element disposed between the pair of substrates, and a seal member for sealing the display element. The seal member can be a cured product of the display element sealant of the present invention. The display element sealing agent of the present invention is composed of the photocurable resin composition of the present invention.
1)一方の基板に、本発明の液晶シール剤のシールパターンを形成する工程と、
2)シールパターンが未硬化の状態において、基板のシールパターンで囲まれた領域内、又はシールパターンで囲まれた領域に対向する他方の基板の領域に、液晶を滴下する工程と、
3)一方の基板と他方の基板とをシールパターンを介して重ね合わせる工程と、
4)シールパターンを硬化させる工程とを含む。 The manufacturing method of the liquid crystal display panel by the liquid crystal dropping method is
1) forming a seal pattern of the liquid crystal sealant of the present invention on one substrate;
2) dropping the liquid crystal in a region surrounded by the seal pattern of the substrate or a region of the other substrate facing the region surrounded by the seal pattern in a state where the seal pattern is uncured;
3) a step of superimposing one substrate and the other substrate through a seal pattern;
4) curing the seal pattern.
(合成例1)
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、3-ヒドロキシプロピル-4-(ジメチルアミノ)ベンゾエート 4.00g(1.79×10-2モル)と、トルエン30gとを投入し、80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートビウレット変性体(三井化学社製、タケネートD-165N、イソシアネート当量179.5g/eq)3.86gをトルエン10gに溶解させた溶液を15分かけて滴下した後、そのまま窒素雰囲気下80℃で4時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷して沈降した液状成分を分離した。回収した液状成分を、オーブンで十分に乾燥させて、化合物B-1を得た。 1. Synthesis and Evaluation of Sensitizer B and Comparative Compound (Synthesis Example 1)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 4.00 g (1.79 × 10 −2 mol) of 3-hydroxypropyl-4- (dimethylamino) benzoate, After adding 30 g of toluene and stirring at 80 ° C., 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) 3.86 g dissolved in 10 g of toluene was added dropwise over 15 minutes, and then a nitrogen atmosphere as it was The mixture was stirred at 80 ° C. for 4 hours. After completion of the reaction, the four-necked flask was allowed to cool at room temperature to separate the precipitated liquid component. The recovered liquid component was sufficiently dried in an oven to obtain Compound B-1.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、3-ヒドロキシプロピル-4-(ジメチルアミノ)ベンゾエート 4.00g(1.79×10-2モル)とトルエン30gとを投入し、80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートアロファネート変性体(三井化学社製、タケネートD-178NL、イソシアネート当量216.1g/eq)4.64gをトルエン10gに溶解させた溶液を20分かけて滴下した後、そのまま窒素雰囲気下80℃で3時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷することで沈降した液状成分を分離した。回収した液状成分をオーブンで十分に乾燥し、化合物B-2を得た。 (Synthesis Example 2)
In a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 4.00 g (1.79 × 10 −2 mol) of 3-hydroxypropyl-4- (dimethylamino) benzoate and toluene 30 g was added and stirred at 80 ° C., and then 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate allophanate modified product (manufactured by Mitsui Chemicals, Takenate D-178NL, isocyanate equivalent 216.1 g / eq) of 4.64 g dissolved in 10 g of toluene was added dropwise over 20 minutes, and then nitrogen atmosphere as it was The mixture was stirred at 80 ° C. for 3 hours. After completion of the reaction, the precipitated liquid component was separated by allowing the four-necked flask to cool at room temperature. The recovered liquid component was sufficiently dried in an oven to obtain Compound B-2.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、3-ヒドロキシプロピル-4-(ジメチルアミノ)ベンゾエート 4.00g(1.79×10-2モル)とトルエン30gとを投入して、80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートビウレット変性体(三井化学社製、タケネートD-165N、イソシアネート当量179.5g/eq)2.14gをトルエン10gに溶解させた溶液を15分かけて滴下した。
薄層クロマトグラフィー(TLC)にて3-ヒドロキシプロピル-4-(ジメチルアミノ)ベンゾエートの消失を確認した後、1-オクタデカノール(東京化成社製)1.94g(7.16×10-3モル)をトルエン10gに溶解させた溶液をさらに滴下して加え、窒素雰囲気下80℃で2時間撹拌した。反応終了後、4つ口フラスコを氷浴で冷却して沈降した液状成分を分離した。回収した液状成分をオーブンで十分に乾燥させて、化合物B-3を得た。 (Synthesis Example 3)
In a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 4.00 g (1.79 × 10 −2 mol) of 3-hydroxypropyl-4- (dimethylamino) benzoate and toluene 30 g was added and stirred at 80 ° C., and 1 drop of dibutyltin was added as a catalyst. Subsequently, a solution prepared by dissolving 2.14 g of a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) in 10 g of toluene was added dropwise over 15 minutes.
After confirming the disappearance of 3-hydroxypropyl-4- (dimethylamino) benzoate by thin layer chromatography (TLC), 1.94 g (7.16 × 10 −3 ) of 1-octadecanol (manufactured by Tokyo Chemical Industry Co., Ltd.) Mol) was further added dropwise and stirred at 80 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, the 4-necked flask was cooled in an ice bath to separate the precipitated liquid component. The recovered liquid component was sufficiently dried in an oven to obtain Compound B-3.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中に、3-ヒドロキシプロピル-4-(ジメチルアミノ)ベンゾエート 2.00g(8.95×10-3モル)と酢酸エチル30gを加えて70℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネート(東京化成工業社製)1.81gを酢酸エチル10gに溶解させた溶液を10分かけて滴下した後、そのまま窒素雰囲気下70℃で3時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷して沈降した液状成分を分離した。回収した液状成分をオーブンで十分に乾燥させて、化合物R-1を得た。 (Synthesis Example 4)
In a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 2.00 g (8.95 × 10 −3 mol) of 3-hydroxypropyl-4- (dimethylamino) benzoate and acetic acid After adding 30 g of ethyl and stirring at 70 ° C., 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 1.81 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 g of ethyl acetate was added dropwise over 10 minutes, and then stirred at 70 ° C. for 3 hours in a nitrogen atmosphere. After completion of the reaction, the four-necked flask was allowed to cool at room temperature to separate the precipitated liquid component. The recovered liquid component was sufficiently dried in an oven to obtain Compound R-1.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、3-ヒドロキシプロピル-4-(ジメチルアミノ)ベンゾエート 2.00g(8.95×10-3モル)とメチルイソブチルケトン30gを加えて80℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ジシクロヘキシルメタン-4,4'-ジイソシアナート(東京化成工業社製)2.35gをメチルイソブチルケトン10gに溶解させた溶液を10分かけて滴下した後、そのまま窒素雰囲気下80℃で3時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷して沈降した液状成分を分離した。回収した液状成分をオーブンで十分に乾燥させて、化合物R-2を得た。 (Synthesis Example 5)
Into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer, 2.00 g (8.95 × 10 −3 mol) of 3-hydroxypropyl-4- (dimethylamino) benzoate and methyl After adding 30 g of isobutyl ketone and stirring at 80 ° C., 1 drop of dibutyltin was added as a catalyst. Next, a solution prepared by dissolving 2.35 g of dicyclohexylmethane-4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 g of methyl isobutyl ketone was added dropwise over 10 minutes, and the solution was directly added at 80 ° C. in a nitrogen atmosphere at 80 ° C. Stir for hours. After completion of the reaction, the four-necked flask was allowed to cool at room temperature to separate the precipitated liquid component. The collected liquid component was sufficiently dried in an oven to obtain Compound R-2.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、4-(ジメチルアミノ)ベンジルアルコール(東京化成工業社製) 2.00g(1.32×10-2モル)とトルエン50gを加えて90℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートビウレット変性体(三井化学社製、タケネートD-165N、イソシアネート当量179.5g/eq)2.84gをトルエン15gに溶解させた溶液を10分かけて滴下した後、そのまま窒素雰囲気下90℃で3時間撹拌した。反応終了後4つ口フラスコを室温にて放冷した後、ろ過を実施した。回収したろ液を、エバポレーターを用いて溶媒留去することで、液状の化合物R-3を得た。 (Synthesis Example 6)
2.00 g (1.32 × 10 −2 mol) of 4- (dimethylamino) benzyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer And 50 g of toluene were added and stirred at 90 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate biuret modified product (manufactured by Mitsui Chemicals, Takenate D-165N, isocyanate equivalent 179.5 g / eq) 2.84 g dissolved in 15 g of toluene was added dropwise over 10 minutes, followed by a nitrogen atmosphere. The mixture was stirred at 90 ° C. for 3 hours. After completion of the reaction, the four-necked flask was allowed to cool at room temperature and then filtered. The collected filtrate was subjected to solvent distillation using an evaporator to obtain a liquid compound R-3.
攪拌機、窒素ガス導入管、還流冷却管、温度計を備えた4つ口フラスコ中へ、4-(ジメチルアミノ)ベンジルアルコール(東京化成工業社製) 2.00g(1.32×10-2モル)とトルエン30gを加えて90℃で撹拌した後、ジブチル錫を触媒として1滴添加した。次いで、ヘキサメチレンジイソシアネートアロファネート変性体(三井化学社製、タケネートD-178NL、イソシアネート当量216.1g/eq)3.42gをトルエン15gに溶解させた溶液を10分かけて滴下した後、そのまま窒素雰囲気下90℃で3時間撹拌した。反応終了後、4つ口フラスコを室温にて放冷した後、ろ過を実施した。回収したろ液を、エバポレーターを用いて溶媒留去することで、液状の化合物R-4を得た。 (Synthesis Example 7)
2.00 g (1.32 × 10 −2 mol) of 4- (dimethylamino) benzyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) into a four-necked flask equipped with a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a thermometer And 30 g of toluene were added and stirred at 90 ° C., and 1 drop of dibutyltin was added as a catalyst. Next, a hexamethylene diisocyanate allophanate modified product (manufactured by Mitsui Chemicals, Takenate D-178NL, isocyanate equivalent 216.1 g / eq) of 3.42 g dissolved in 15 g of toluene was added dropwise over 10 minutes, and then a nitrogen atmosphere as it was The mixture was stirred at 90 ° C. for 3 hours. After completion of the reaction, the four-necked flask was allowed to cool at room temperature and then filtered. The collected filtrate was evaporated using an evaporator to obtain a liquid compound R-4.
準備した化合物B-1~B-3及び比較化合物R-1~R-7の1)分子量、2)液晶の電圧保持率、及び3)液晶のN-I点降下を、以下の方法で評価した。 (Experimental Examples 1 to 3, Comparative Experimental Examples 1 to 7)
The prepared compounds B-1 to B-3 and comparative compounds R-1 to R-7 were evaluated for 1) molecular weight, 2) liquid crystal voltage holding ratio, and 3) liquid crystal NI point drop by the following methods. did.
準備した化合物を、テトラヒドロフラン(THF)に溶解した試料液を調製し、下記測定条件で高速液体クロマトグラフフィー(HPLC)測定を行った。そして、検出波長305nmで検出された全ピークのうち、最も強度が大きいピーク(高さが最も高いピーク)をメインピークとした。
(HPLC測定条件)
装置:waters製 Acquity TM UPLC H-Class system
カラム:Acquity UPLC BEH C18、2.1mmID×100mm 粒子径:1.7μm
移動相:A:アセトニトリル
B:5mM酢酸アンモニウム水溶液
A/B = 60/40(0~4分)
95/5(4~9分)
95/5(9~10分)
流速:0.4mL/分
PDA検出器:測定波長:190~500nm、抽出波長:305nm 1) Molecular weight A sample solution in which the prepared compound was dissolved in tetrahydrofuran (THF) was prepared, and high performance liquid chromatography (HPLC) measurement was performed under the following measurement conditions. Of all peaks detected at a detection wavelength of 305 nm, the peak with the highest intensity (the peak with the highest height) was taken as the main peak.
(HPLC measurement conditions)
Equipment: Acquity TM UPLC H-Class system made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile B: 5 mM ammonium acetate aqueous solution A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4mL / min PDA detector: Measurement wavelength: 190-500nm, Extraction wavelength: 305nm
装置:waters製 Acquity TM H-Class system / SQ Detector
カラム:Acquity UPLC BEH C18、2.1mmID×100mm 粒子径:1.7μm
移動相:A:アセトニトリル
B:5mM酢酸アンモニウム水溶液
A/B = 60/40(0~4分)
95/5(4~9分)
95/5(9~10分)
流速:0.4mL/分
イオン化:ESI(エレクトロスプレーイオン化)、正・負イオン測定
PDA検出器:測定波長:190~500nm、抽出波長:305nm (LC / MS measurement conditions)
Equipment: Acquity TM H-Class system / SQ Detector made by waters
Column: Acquity UPLC BEH C18, 2.1mmID × 100mm Particle size: 1.7μm
Mobile phase: A: Acetonitrile B: 5 mM ammonium acetate aqueous solution A / B = 60/40 (0-4 minutes)
95/5 (4-9 minutes)
95/5 (9-10 minutes)
Flow rate: 0.4 mL / min Ionization: ESI (electrospray ionization), positive / negative ion measurement PDA detector: Measurement wavelength: 190-500 nm, Extraction wavelength: 305 nm
準備した化合物を0.1gと、液晶(MLC-7021-000、メルク社製)を1gとをバイアル瓶に投入し、120℃で1時間加熱して、液晶混合物を得た。次いで、この液晶混合物を取り出して、透明電極が予め形成されたガラスセル(KSSZ-10/B111M1NSS05、EHC社製)に注入し、電圧1Vを印加し、60Hzでの電圧保持率を6254型測定装置(東陽テクニカ製)により測定した。
電圧保持率が95%以上である場合を◎、90%以上95%未満である場合を○、90%未満である場合を×とした。 2) Voltage holding ratio of liquid crystal 0.1 g of the prepared compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture. Obtained. Next, this liquid crystal mixture is taken out, poured into a glass cell (KSSZ-10 / B111M1NSS05, manufactured by EHC) in which a transparent electrode is formed in advance, a voltage of 1 V is applied, and a voltage holding ratio at 60 Hz is measured by a 6254 type measuring device. It was measured by (Toyo Technica).
The case where the voltage holding ratio was 95% or more was marked with ◎, the case where it was 90% or more and less than 95%, and the case where it was less than 90%.
準備した化合物を0.1gと、液晶(MLC-7021-000、メルク社製)を1gとをバイアル瓶に投入し、120℃で1時間加熱して液晶混合物を得た。次いで、この液晶混合物を取り出して、アルミ製オープンパン(エポリードサービス社製)に10mg入れ、DTA-TG装置(セイコーインスツルメンツ社製)によりN-I点を測定した。
液晶のN-I点に対する変化量が3℃未満である場合を◎、3℃以上5℃未満の場合を○、5℃以上の場合を×とした。 3) Depressing NI point of liquid crystal 0.1 g of the prepared compound and 1 g of liquid crystal (MLC-7021-000, manufactured by Merck & Co.) were put into a vial and heated at 120 ° C. for 1 hour to obtain a liquid crystal mixture Got. Next, this liquid crystal mixture was taken out, 10 mg was put in an aluminum open pan (manufactured by Epolide Service), and the NI point was measured with a DTA-TG apparatus (manufactured by Seiko Instruments Inc.).
The case where the amount of change with respect to the NI point of the liquid crystal was less than 3 ° C. was evaluated as ◎: the case where it was 3 ° C. or higher and lower than 5 ° C.
(硬化性化合物A)
硬化性化合物A-1:下記合成例8で得られたメタアクリル酸変性ビスフェノールF型エポキシ樹脂(95%部分メタアクリル化物)
(合成例8)
160gの液状ビスフェノールF型エポキシ樹脂(YDF-8170C、新日鉄住金化学社製、エポキシ当量160g/eq)、重合禁止剤として0.1gのp-メトキシフェノール、触媒として0.2gのトリエタノールアミン、及び81.7gのメタアクリル酸をフラスコ内に仕込み、乾燥空気を送り込んで90℃で還流攪拌しながら5時間反応させた。得られた化合物を、超純水にて20回洗浄し、メタアクリル酸変性ビスフェノールF型エポキシ樹脂を得た。
得られた樹脂をHPLC、NMRで分析した結果、エポキシ基の95%がメタクリロイル変性されたメタアクリル酸変性ビスフェノールF型エポキシ樹脂であることを確認した。また、得られた樹脂をGPC分析した結果、重量平均分子量は792であった。
共栄社化学製ライトアクリレート14EG-A:下記式で表されるポリエチレングリコールジアクリレート(分子量600)
(合成例9)
先ず、攪拌機、気体導入管、温度計、冷却管を備えた500mlの四つ口フラスコに、175gのビスフェノールF型エポキシ樹脂(YDF-8170C、新日鉄住金化学社製、エポキシ当量160g/eq)、37gのアクリル酸、触媒として0.2gのトリエタノールアミン、重合禁止剤として0.2gのヒドロキノンモノメチルエーテルを混合し、乾燥空気を吹き込みながら、110℃、12時間加熱攪拌して反応させて、アクリル酸変性ビスフェノールF型エポキシ樹脂を得た。
得られた樹脂を、超純水にて12回洗浄処理を繰り返した後、HPLC、NMRで分析した結果、エポキシ基の50%がアクリロイル変性されたビスフェノールF型エポキシ樹脂であることを確認した。また、得られた樹脂をGPC分析した結果、重量平均分子量は692であった。 2. Preparation and Evaluation of Photocurable Resin Composition (Curable Compound A)
Curing compound A-1: methacrylic acid-modified bisphenol F type epoxy resin (95% partially methacrylic product) obtained in Synthesis Example 8 below
(Synthesis Example 8)
160 g of liquid bisphenol F type epoxy resin (YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq), 0.1 g of p-methoxyphenol as a polymerization inhibitor, 0.2 g of triethanolamine as a catalyst, and 81.7 g of methacrylic acid was charged into the flask, dried air was fed into the flask, and the mixture was reacted at 90 ° C. with stirring under reflux for 5 hours. The obtained compound was washed 20 times with ultrapure water to obtain a methacrylic acid-modified bisphenol F type epoxy resin.
As a result of analyzing the obtained resin by HPLC and NMR, it was confirmed that 95% of the epoxy groups were methacrylic acid-modified bisphenol F type epoxy resin modified with methacryloyl. Further, as a result of GPC analysis of the obtained resin, the weight average molecular weight was 792.
Kyoeisha Chemical Light Acrylate 14EG-A: Polyethylene glycol diacrylate represented by the following formula (molecular weight 600)
(Synthesis Example 9)
First, in a 500 ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 175 g of bisphenol F type epoxy resin (YDF-8170C, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent 160 g / eq), 37 g Acrylic acid, 0.2 g of triethanolamine as a catalyst, and 0.2 g of hydroquinone monomethyl ether as a polymerization inhibitor were mixed, and the reaction was conducted by heating and stirring at 110 ° C. for 12 hours while blowing dry air. A modified bisphenol F type epoxy resin was obtained.
The obtained resin was repeatedly washed with ultrapure water 12 times and analyzed by HPLC and NMR. As a result, it was confirmed that 50% of the epoxy groups were acryloyl-modified bisphenol F type epoxy resin. Further, as a result of GPC analysis of the obtained resin, the weight average molecular weight was 692.
合成例1~3の化合物B-1~B-3
(比較化合物)
合成例4~7の化合物R-1~R-4、及び化合物R-5~R-7 (Sensitizer B)
Compounds B-1 to B-3 of Synthesis Examples 1 to 3
(Comparative compound)
Compounds R-1 to R-4 and Compounds R-5 to R-7 in Synthesis Examples 4 to 7
Omnipol-TX:IGM Resins社製、2-カルボキシメトキシチオキサントン)-(ポリテトラメチレングリコール250)ジエステル (Polymerization initiator C)
Omnipol-TX: manufactured by IGM Resins, 2-carboxymethoxythioxanthone)-(polytetramethylene glycol 250) diester
エポキシ樹脂:三菱化学社製、jER1004、軟化点97℃ (Thermosetting compound D)
Epoxy resin: Mitsubishi Chemical Corporation, jER1004, softening point 97 ° C
アジピン酸ジヒドラジド:日本化成社製、ADH、融点177~184℃ (Thermosetting agent E)
Adipic acid dihydrazide: Nippon Kasei Co., Ltd., ADH, melting point 177-184 ° C
シリカ粒子:(株)日本触媒社製、S-100
熱可塑性樹脂粒子(アイカ工業社製、F351、軟化点120℃、平均粒子径0.3μm)
γ-グリシドキシプロピルトリメトキシシラン(信越化学工業社製、KBM-403) (Other components F)
Silica particles: Nippon Shokubai Co., Ltd., S-100
Thermoplastic resin particles (manufactured by Aika Industries, F351, softening point 120 ° C., average particle size 0.3 μm)
γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
硬化性化合物Aとして合成例8で得られた硬化性化合物A-1を420質量部と、ポリエチレングリコールジアクリレート(共栄社化学製、ライトアクリレート14EG-A)を200質量部と、増感剤Bとして合成例1で得られた化合物B-1を10質量部と、重合開始剤CとしてOmnipol-TX(IGM Resins社製)を10質量部と、熱硬化性化合物Dとしてエポキシ樹脂(三菱化学社製、jER1004)を50質量部と、熱硬化剤Eとしてアジピン酸ジヒドラジド(日本化成社製、ADH)を90質量部と、その他成分Fとしてシリカ粒子(日本触媒社製、S-100)を130質量部と、熱可塑性樹脂粒子としてアイカ工業社製F351を70質量部と、シランカップリング剤としてγ-グリシドキシプロピルトリメトキシシラン(信越化学工業社製、KBM-403)を20質量部とを、三本ロールを用いて均一な液となるように十分に混合して、光硬化性樹脂組成物を得た。 Example 1
420 parts by mass of the curable compound A-1 obtained in Synthesis Example 8 as the curable compound A, 200 parts by mass of polyethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate 14EG-A), and the sensitizer B 10 parts by mass of Compound B-1 obtained in Synthesis Example 1, 10 parts by mass of Omnipol-TX (manufactured by IGM Resins) as a polymerization initiator C, and an epoxy resin (manufactured by Mitsubishi Chemical Corporation) as a thermosetting compound D , JER1004), 50 parts by mass, 90 parts by mass of adipic acid dihydrazide (manufactured by Nippon Kasei Co., Ltd., ADH) as thermosetting agent E, and 130 parts by mass of silica particles (manufactured by Nippon Shokubai Co., Ltd., S-100) as component F Parts, 70 parts by mass of F351 manufactured by Aika Kogyo Co., Ltd. as thermoplastic resin particles, and γ-glycidoxypropyltrimeth as a silane coupling agent Shishiran (Shin-Etsu Chemical Co., Ltd., KBM-403) and 20 parts by weight, were mixed in sufficient a uniform liquid using a three-roll to obtain a photocurable resin composition.
表4又は5に示される組成に変更した以外は実施例1と同様にして光硬化性樹脂組成物を得た。 (Examples 2 to 9, Comparative Examples 1 to 7)
A photocurable resin composition was obtained in the same manner as in Example 1 except that the composition shown in Table 4 or 5 was changed.
得られた光硬化性樹脂組成物を、ディスペンサー(ショットマスター:武蔵エンジニアリング製)を用いて、透明電極と配向膜が予め形成された40mm×45mmガラス基板(RT-DM88-PIN、EHC社製)上に、35mm×40mmの四角形のシールパターン(断面積3500μm2)(メインシール)と、その外周に同様のシールパターン(38mm×43mmの四角形のシールパターン)とを形成した。 (LCD panel display characteristics test when no power is supplied)
Using the obtained photocurable resin composition, a 40 mm × 45 mm glass substrate (RT-DM88-PIN, manufactured by EHC) on which a transparent electrode and an alignment film were formed in advance using a dispenser (shot master: manufactured by Musashi Engineering) A 35 mm × 40 mm square seal pattern (cross-sectional area 3500 μm 2 ) (main seal) and a similar seal pattern (38 mm × 43 mm square seal pattern) were formed on the outer periphery.
その液晶表示パネルのメインシール際まで液晶が配向されて色ムラが全くない場合を○、メインシール際の近傍に1mm未満の範囲にわたり色ムラが発生している場合を△、メインシール際近傍から1mm以上の範囲にわたり色ムラが発生している場合を×として評価した。 Next, a liquid crystal material (MLC-7021-000, manufactured by Merck & Co., Inc.) corresponding to the volume of the panel after bonding was precisely dropped into the main seal frame using a dispenser. Next, a pair of glass substrates was bonded together under reduced pressure, and then bonded to the atmosphere. Then, the two glass substrates bonded together are held in a light shielding box for 3 minutes, and then light with a wavelength of 370 to 450 nm is 3000 mJ in a state where the main seal is masked with a substrate coated with a square black matrix of 36 mm × 41 mm. / Cm 2 , and after heating at 120 ° C. for 1 hour, a polarizing film was pasted on both sides to obtain a liquid crystal display panel.
When the liquid crystal is aligned until the main seal of the liquid crystal display panel and there is no color unevenness, ○, when the color unevenness occurs over a range of less than 1 mm in the vicinity of the main seal, from the vicinity of the main seal The case where color unevenness occurred over a range of 1 mm or more was evaluated as x.
前述の液晶表示パネル表示特性テストと同様にして液晶表示パネルを作製した。この液晶表示パネルを、直流電源を用いて5Vの印加電圧で駆動させた際に、メインシール近傍の液晶表示機能が発揮できている場合を○、メインシール近傍に1mm未満の範囲にわたり白ムラが発生している場合を△、メインシール近傍から1mm以上の範囲にわたり白ムラが発生し正常に駆動しない場合を×とした。 (LCD panel display characteristics test when energized)
A liquid crystal display panel was produced in the same manner as the liquid crystal display panel display characteristic test described above. When this liquid crystal display panel is driven with an applied voltage of 5 V using a DC power source, the liquid crystal display function in the vicinity of the main seal can be exhibited. The case where it occurred was indicated by Δ, and the case where white unevenness occurred over a range of 1 mm or more from the vicinity of the main seal and it was not driven normally was indicated by ×.
Claims (13)
- 分子内にエチレン性不飽和二重結合を有する硬化性化合物Aと、
分子内にアミノベンゾイル骨格とNHCO基とを有し、式(I)で表されるNHCO基当量が300g/eq以下である増感剤Bと、
重合開始剤C(但し、分子内にアミノベンゾイル骨格を有する重合開始剤を除く)とを含む、光硬化性樹脂組成物。
式(I):NHCO基当量(g/eq)=分子量/1分子に含まれるNHCO基の数 A curable compound A having an ethylenically unsaturated double bond in the molecule;
A sensitizer B having an aminobenzoyl skeleton and an NHCO group in the molecule and having an NHCO group equivalent represented by the formula (I) of 300 g / eq or less;
A photocurable resin composition comprising a polymerization initiator C (excluding a polymerization initiator having an aminobenzoyl skeleton in the molecule).
Formula (I): NHCO group equivalent (g / eq) = molecular weight / number of NHCO groups contained in one molecule - 前記増感剤Bが、分子内に3以上のNHCO基を有する、請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the sensitizer B has 3 or more NHCO groups in the molecule.
- 前記増感剤Bが、分子内にビューレット骨格又はアロファネート骨格を有する、請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the sensitizer B has a burette skeleton or an allophanate skeleton in the molecule.
- 前記増感剤Bは、下記式(4)で表される化合物である、請求項1に記載の光硬化性樹脂組成物。
Xは、単結合、炭素数1~10のアルキレン基、炭素数1~10のアルキレンオキシ基、炭素数6~10のアリーレン基、炭素数6~10のアリーレンオキシ基又は炭素数6~10のアリーレンチオ基を表し、
R1及びR2は、それぞれ独立して水素原子又は炭素数1~10のアルキル基を表し、
Yは、分子内に少なくともm個のイソシアネート基を有する化合物から誘導される有機基を表し、
mは、1~5の整数を表す) The said sensitizer B is a photocurable resin composition of Claim 1 which is a compound represented by following formula (4).
X is a single bond, an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an aryleneoxy group having 6 to 10 carbon atoms, or an alkyl group having 6 to 10 carbon atoms. Represents an arylenethio group,
R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
Y represents an organic group derived from a compound having at least m isocyanate groups in the molecule;
m represents an integer of 1 to 5) - 前記増感剤Bの含有量が、前記硬化性化合物Aに対して0.01~10質量%である、請求項1に記載の光硬化性樹脂組成物。 2. The photocurable resin composition according to claim 1, wherein the content of the sensitizer B is 0.01 to 10% by mass with respect to the curable compound A.
- 前記重合開始剤Cが、チオキサントン骨格を有する、請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the polymerization initiator C has a thioxanthone skeleton.
- 前記硬化性化合物Aが、分子内にエポキシ基をさらに有する、請求項1に記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the curable compound A further has an epoxy group in the molecule.
- 請求項1に記載の光硬化性樹脂組成物からなる、表示素子シール剤。 A display element sealant comprising the photocurable resin composition according to claim 1.
- 請求項1に記載の光硬化性樹脂組成物からなる、液晶シール剤。 A liquid crystal sealant comprising the photocurable resin composition according to claim 1.
- 請求項9に記載の液晶シール剤を用いて、一方の基板にシールパターンを形成する工程と、
前記シールパターンが未硬化の状態において、前記シールパターンの領域内、又は前記一方の基板と対になる他方の基板に液晶を滴下する工程と、
前記一方の基板と前記他方の基板とを、前記シールパターンを介して重ね合わせる工程と、
前記シールパターンを硬化させる工程と、を含む、液晶表示パネルの製造方法。 Using the liquid crystal sealant according to claim 9 to form a seal pattern on one substrate;
In the uncured state of the seal pattern, dropping the liquid crystal on the other substrate that is paired with the one substrate in the region of the seal pattern;
Superimposing the one substrate and the other substrate through the seal pattern;
And a step of curing the seal pattern. - 前記シールパターンを硬化させる工程は、前記シールパターンに光を照射して前記シールパターンを硬化させる工程を含む、請求項10に記載の液晶表示パネルの製造方法。 The method of manufacturing a liquid crystal display panel according to claim 10, wherein the step of curing the seal pattern includes a step of irradiating the seal pattern with light to cure the seal pattern.
- 前記シールパターンに照射する光は、可視光領域の光を含む、請求項11に記載の液晶表示パネルの製造方法。 12. The method of manufacturing a liquid crystal display panel according to claim 11, wherein the light applied to the seal pattern includes light in a visible light region.
- 一対の基板と、
前記一対の基板の間に配置された枠状のシール部材と、
前記一対の基板の間の前記シール部材で囲まれた空間に充填された液晶層とを含み、
前記シール部材が、請求項9に記載の液晶シール剤の硬化物である、液晶表示パネル。 A pair of substrates;
A frame-shaped sealing member disposed between the pair of substrates;
A liquid crystal layer filled in a space surrounded by the seal member between the pair of substrates,
A liquid crystal display panel, wherein the seal member is a cured product of the liquid crystal sealant according to claim 9.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110168442A (en) * | 2017-07-14 | 2019-08-23 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
CN110325904A (en) * | 2017-07-14 | 2019-10-11 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
WO2020084988A1 (en) * | 2018-10-26 | 2020-04-30 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
CN111936527A (en) * | 2018-04-03 | 2020-11-13 | 协立化学产业株式会社 | Curable composition, liquid crystal sealant, liquid crystal panel, and method for producing liquid crystal panel |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110226120A (en) * | 2017-07-14 | 2019-09-10 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
CN113661437A (en) * | 2019-05-17 | 2021-11-16 | 三井化学株式会社 | Sealant for liquid crystal dropping process, liquid crystal display panel using same, and method for manufacturing same |
GB201915023D0 (en) * | 2019-10-17 | 2019-12-04 | Lambson Ltd | Amine co-initiator mixture |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005037483A (en) * | 2003-07-16 | 2005-02-10 | Konica Minolta Medical & Graphic Inc | Photosensitive planographic printing plate, processing method for same, and image forming method for photosensitive planographic printing plate |
JP2014227344A (en) * | 2013-05-17 | 2014-12-08 | 協立化学産業株式会社 | Compound suitable for photopolymerization initiator |
WO2015072416A1 (en) * | 2013-11-13 | 2015-05-21 | 積水化学工業株式会社 | Liquid-crystal-display-element sealant, vertical conductive material, and liquid-crystal display element |
WO2015072415A1 (en) * | 2013-11-13 | 2015-05-21 | 積水化学工業株式会社 | Liquid-crystal-display-element sealant, vertical conductive material, and liquid-crystal display element |
WO2017002362A1 (en) * | 2015-06-30 | 2017-01-05 | 三井化学株式会社 | Photocurable resin composition, display element sealing agent, liquid crystal sealing agent, liquid crystal display panel and method for producing liquid crystal display panel |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4119510A (en) * | 1975-11-07 | 1978-10-10 | Phillips Petroleum Company | Photocurable diisocyanate compositions |
ZA815377B (en) | 1980-08-07 | 1982-08-25 | Cedomir M Sliepcevich | Process for preparation or reactivation of metal catalysts |
JP4011811B2 (en) * | 2000-01-14 | 2007-11-21 | Jsr株式会社 | Photocurable resin composition and optical member |
US6503960B1 (en) * | 2000-11-21 | 2003-01-07 | Loctite Corporation | Dispersion stable curable compositions and method for making hollow shells using same |
JP3982377B2 (en) * | 2002-10-08 | 2007-09-26 | Jsr株式会社 | Photocurable resin composition and optical member |
CN1454933A (en) * | 2003-04-01 | 2003-11-12 | 四川大学 | Photocurable resin composition |
EP1789464B1 (en) * | 2004-09-17 | 2008-11-05 | Akzo Nobel Coatings International BV | Coating composition based on thiol-nco curing |
JP5513711B2 (en) * | 2007-10-01 | 2014-06-04 | 太陽ホールディングス株式会社 | Photosensitive resin composition and cured product thereof |
CN101270181A (en) * | 2008-03-27 | 2008-09-24 | 江南大学 | Photo-curing water-base resin composition and method for preparing coating with self-assembly method |
KR101627725B1 (en) * | 2009-02-03 | 2016-06-07 | 삼성전자 주식회사 | Photocurable compound |
EP2218742A1 (en) * | 2009-02-12 | 2010-08-18 | Bayer MaterialScience AG | Photopolymer compounds as compressible formulations |
WO2012077720A1 (en) | 2010-12-09 | 2012-06-14 | 協立化学産業株式会社 | Compound suitable for photopolymerization initiator, photopolymerization initiator, and photocurable resin composition |
CN103930493A (en) * | 2012-05-15 | 2014-07-16 | 株式会社艾迪科 | Photocurable resin composition |
JP5337293B1 (en) | 2012-11-13 | 2013-11-06 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
-
2015
- 2015-12-17 JP JP2015246116A patent/JP6197020B2/en active Active
-
2016
- 2016-11-29 KR KR1020187016372A patent/KR101962082B1/en active IP Right Grant
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- 2016-11-29 WO PCT/JP2016/085259 patent/WO2017104391A1/en active Application Filing
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005037483A (en) * | 2003-07-16 | 2005-02-10 | Konica Minolta Medical & Graphic Inc | Photosensitive planographic printing plate, processing method for same, and image forming method for photosensitive planographic printing plate |
JP2014227344A (en) * | 2013-05-17 | 2014-12-08 | 協立化学産業株式会社 | Compound suitable for photopolymerization initiator |
WO2015072416A1 (en) * | 2013-11-13 | 2015-05-21 | 積水化学工業株式会社 | Liquid-crystal-display-element sealant, vertical conductive material, and liquid-crystal display element |
WO2015072415A1 (en) * | 2013-11-13 | 2015-05-21 | 積水化学工業株式会社 | Liquid-crystal-display-element sealant, vertical conductive material, and liquid-crystal display element |
WO2017002362A1 (en) * | 2015-06-30 | 2017-01-05 | 三井化学株式会社 | Photocurable resin composition, display element sealing agent, liquid crystal sealing agent, liquid crystal display panel and method for producing liquid crystal display panel |
Cited By (8)
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CN110168442A (en) * | 2017-07-14 | 2019-08-23 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
CN110325904A (en) * | 2017-07-14 | 2019-10-11 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
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CN110325904B (en) * | 2017-07-14 | 2022-11-01 | 积水化学工业株式会社 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
KR102578300B1 (en) * | 2017-07-14 | 2023-09-13 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal display elements, top and bottom conductive materials, and liquid crystal display elements |
CN111936527A (en) * | 2018-04-03 | 2020-11-13 | 协立化学产业株式会社 | Curable composition, liquid crystal sealant, liquid crystal panel, and method for producing liquid crystal panel |
WO2020084988A1 (en) * | 2018-10-26 | 2020-04-30 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
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CN108368190B (en) | 2019-12-31 |
TW201731950A (en) | 2017-09-16 |
JP2017110120A (en) | 2017-06-22 |
CN108368190A (en) | 2018-08-03 |
TWI698486B (en) | 2020-07-11 |
JP6197020B2 (en) | 2017-09-13 |
KR101962082B1 (en) | 2019-03-25 |
KR20180082529A (en) | 2018-07-18 |
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