KR102578300B1 - Sealing agent for liquid crystal display elements, top and bottom conductive materials, and liquid crystal display elements - Google Patents
Sealing agent for liquid crystal display elements, top and bottom conductive materials, and liquid crystal display elements Download PDFInfo
- Publication number
- KR102578300B1 KR102578300B1 KR1020197015735A KR20197015735A KR102578300B1 KR 102578300 B1 KR102578300 B1 KR 102578300B1 KR 1020197015735 A KR1020197015735 A KR 1020197015735A KR 20197015735 A KR20197015735 A KR 20197015735A KR 102578300 B1 KR102578300 B1 KR 102578300B1
- Authority
- KR
- South Korea
- Prior art keywords
- liquid crystal
- meth
- crystal display
- compound
- acrylate
- Prior art date
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 107
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 57
- 238000007789 sealing Methods 0.000 title claims abstract description 54
- 239000004020 conductor Substances 0.000 title claims 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 121
- -1 acrylic compound Chemical class 0.000 claims abstract description 58
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims description 90
- 239000010419 fine particle Substances 0.000 claims description 14
- 230000007547 defect Effects 0.000 abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 93
- 239000000565 sealant Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000000758 substrate Substances 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 11
- 238000001723 curing Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
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- 150000007524 organic acids Chemical class 0.000 description 8
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
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- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
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- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 239000010425 asbestos 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
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 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
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- IADGHSROEWQWLL-UHFFFAOYSA-M butyl(trimethyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](C)(C)C IADGHSROEWQWLL-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 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
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 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
- 230000007774 longterm Effects 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide 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
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
- Polymerisation Methods In General (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
본 발명은, 도포성 및 장파장의 광에 대한 경화성이 우수하고, 또한 액정 표시 소자를 장기 점등했을 때의 표시 불량을 억제할 수 있는 액정 표시 소자용 시일제를 제공하는 것을 목적으로 한다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공하는 것을 목적으로 한다.
본 발명은, 경화성 수지와 광중합 개시제를 함유하고, 상기 경화성 수지는, 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물을 함유하고, 상기 광중합 개시제는, 하기 식 (1) 로 나타내는 구조를 갖는 화합물을 함유하는 액정 표시 소자용 시일제이다.
식 (1) 중, * 는, 결합 위치이다.
The purpose of the present invention is to provide a sealing agent for liquid crystal display elements that is excellent in applicability and curability to long-wavelength light, and can suppress display defects when the liquid crystal display element is illuminated for a long period of time. Moreover, the purpose of this invention is to provide a vertical conduction material and a liquid crystal display element formed using the sealing agent for liquid crystal display elements.
The present invention contains a curable resin and a photopolymerization initiator, wherein the curable resin contains a (meth)acrylic compound having a molecular weight of 700 or more and 2000 or less, and the photopolymerization initiator is a compound having a structure represented by the following formula (1). It is a sealing agent for liquid crystal display elements containing.
In formula (1), * is a binding position.
Description
본 발명은, 도포성 및 장파장의 광에 대한 경화성이 우수하고, 또한 액정 표시 소자를 장기 점등했을 때의 표시 불량을 억제할 수 있는 액정 표시 소자용 시일제에 관한 것이다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자에 관한 것이다.The present invention relates to a sealing agent for liquid crystal display elements that is excellent in applicability and curability to long-wavelength light, and can suppress display defects when the liquid crystal display element is illuminated for a long period of time. Moreover, this invention relates to a vertical conduction material and a liquid crystal display element formed using the sealing agent for liquid crystal display elements.
최근, 액정 표시 셀 등의 액정 표시 소자의 제조 방법으로는, 택트 타임 단축, 사용 액정량의 최적화 등의 관점에서, 특허문헌 1, 특허문헌 2 에 개시되어 있는 광열 (光熱) 병용 경화형의 시일제를 사용한 적하 공법으로 불리는 액정 적하 방식이 사용되고 있다.Recently, as a method of manufacturing liquid crystal display elements such as liquid crystal display cells, from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used, a light-heat combination curing type sealing agent disclosed in Patent Document 1 and Patent Document 2 A liquid crystal dropping method called the dropping method using is being used.
적하 공법에서는, 먼저, 2 장의 전극이 부착된 투명 기판의 일방에, 디스펜스에 의해 프레임상의 시일 패턴을 형성한다. 이어서, 시일제가 미경화의 상태로 액정의 미소적 (微小滴) 을 투명 기판의 프레임 내 전체면에 적하하고, 바로 타방의 투명 기판을 첩합 (貼合) 하고, 시일부에 자외선 등의 광을 조사하여 임시 경화를 실시한다. 그 후, 액정 어닐시에 가열하여 본 경화를 실시하고, 액정 표시 소자를 제작한다. 기판의 첩합을 감압하에서 실시하도록 하면, 매우 높은 효율로 액정 표시 소자를 제조할 수 있고, 현재 이 적하 공법이 액정 표시 소자의 제조 방법의 주류가 되고 있다.In the dropping method, first, a seal pattern on a frame is formed on one side of a transparent substrate to which two electrodes are attached by dispensing. Next, while the sealant is in an uncured state, small droplets of liquid crystal are dropped onto the entire surface of the frame of the transparent substrate, the other transparent substrate is immediately bonded, and light such as ultraviolet rays is exposed to the sealing portion. Irradiate and perform temporary hardening. Thereafter, main curing is performed by heating during liquid crystal annealing, and a liquid crystal display element is produced. By bonding the substrates together under reduced pressure, liquid crystal display elements can be manufactured with very high efficiency, and this dropping method is currently the mainstream method of manufacturing liquid crystal display elements.
그런데, 휴대 전화, 휴대 게임기 등, 각종 액정 패널이 부착된 모바일 기기가 보급되어 있는 현대에 있어서, 장치의 소형화는 가장 요구되고 있는 과제이다. 장치의 소형화의 수법으로는, 액정 표시부의 프레임 협소화를 들 수 있고, 예를 들어 시일부의 위치를 블랙 매트릭스하에 배치하는 것이 실시되고 있다 (이하, 프레임 협소 설계라고도 한다).However, in modern times, where mobile devices with various liquid crystal panels, such as mobile phones and portable game consoles, are widespread, miniaturization of devices is a most demanded task. Methods for miniaturizing the device include narrowing the frame of the liquid crystal display portion, for example, arranging the position of the seal portion under a black matrix (hereinafter also referred to as narrow frame design).
그러나, 프레임 협소 설계에서는 시일제가 블랙 매트릭스의 바로 아래에 배치되므로, 적하 공법을 실시하면, 시일제를 광경화시킬 때에 조사한 광이 차단되고, 시일제의 내부까지 광이 도달하지 않아 경화가 불충분해진다는 문제가 있었다. 이와 같이 시일제의 경화가 불충분해지면, 미경화의 시일제 성분이 액정 중에 용출되고, 용출된 시일제 성분에 의한 경화 반응이 액정 중에 있어서 진행됨으로써 액정 오염이 발생한다는 문제가 있었다.However, in a narrow frame design, the sealant is placed immediately below the black matrix, so if the dropping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealer, resulting in insufficient curing. There was a problem. In this way, when the curing of the sealant becomes insufficient, there is a problem that the uncured sealant component is eluted into the liquid crystal, and the curing reaction due to the eluted sealant component proceeds in the liquid crystal, resulting in liquid crystal contamination.
또, 통상, 시일제를 광경화시키는 방법으로서 자외선의 조사가 실시되고 있지만, 액정 적하 공법에 있어서는, 액정을 적하한 후에 시일제를 경화시키기 위해, 자외선을 조사함으로써 액정이 열화된다는 문제가 있었다. 자외선에 의한 액정의 열화를 방지하기 위해서는, 장파장의 광에 대한 반응성이 우수한 광중합 개시제를 배합하고, 컷 필터 등을 개재한 장파장의 광에 의해 광경화시키는 것을 생각할 수 있다. 그러나, 장파장의 광에 대한 반응성이 우수한 광중합 개시제를 배합한 것만으로는, 장파장의 광에 의해 충분히 시일제를 광경화시킬 수 없었다. 또, 액정 표시 소자 제조 후, 장기 점등한 경우, 경화 전에 액정 중에 약간 용출된 시일제 성분이 반응하고, 표시 불균일 등의 표시 불량을 일으킨다는 문제가 있었다.In addition, irradiation of ultraviolet rays is usually performed as a method of photocuring the sealing agent, but in the liquid crystal dropping method, there is a problem that the liquid crystal is deteriorated by irradiating ultraviolet rays to cure the sealing agent after dropping the liquid crystal. In order to prevent deterioration of the liquid crystal due to ultraviolet rays, it is conceivable to mix a photopolymerization initiator with excellent reactivity to long-wavelength light and photocure it with long-wavelength light through a cut filter or the like. However, the sealing agent could not be sufficiently photocured with long-wavelength light simply by blending a photopolymerization initiator excellent in reactivity to long-wavelength light. Moreover, when the liquid crystal display element is turned on for a long period of time after manufacturing, there is a problem that the sealing agent component slightly eluted in the liquid crystal before curing reacts, causing display defects such as display unevenness.
본 발명은, 도포성 및 장파장의 광에 대한 경화성이 우수하고, 또한 액정 표시 소자를 장기 점등했을 때의 표시 불량을 억제할 수 있는 액정 표시 소자용 시일제를 제공하는 것을 목적으로 한다. 또, 본 발명은, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공하는 것을 목적으로 한다.The purpose of the present invention is to provide a sealing agent for liquid crystal display elements that is excellent in applicability and curability to long-wavelength light, and can suppress display defects when the liquid crystal display element is illuminated for a long period of time. Moreover, the purpose of this invention is to provide a vertical conduction material and a liquid crystal display element formed using the sealing agent for liquid crystal display elements.
본 발명은, 경화성 수지와 광중합 개시제를 함유하고, 상기 경화성 수지는, 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물을 함유하고, 상기 광중합 개시제는, 하기 식 (1) 로 나타내는 구조를 갖는 화합물을 함유하는 액정 표시 소자용 시일제이다.The present invention contains a curable resin and a photopolymerization initiator, wherein the curable resin contains a (meth)acrylic compound having a molecular weight of 700 or more and 2000 or less, and the photopolymerization initiator is a compound having a structure represented by the following formula (1). It is a sealing agent for liquid crystal display elements containing.
[화학식 1][Formula 1]
식 (1) 중, * 는, 결합 위치이다.In formula (1), * is a binding position.
이하에 본 발명을 상세히 서술한다.The present invention is described in detail below.
본 발명자들은, 분자량이 특정한 범위인 (메트)아크릴 화합물과, 특정한 구조를 갖는 광중합 개시제를 조합하여 사용함으로써, 도포성 및 장파장의 광에 대한 경화성이 우수하고, 또한 액정 표시 소자를 장기 점등했을 때의 표시 불량을 억제할 수 있는 액정 표시 소자용 시일제를 얻을 수 있는 것을 알아내어, 본 발명을 완성시키기에 이르렀다.The present inventors have found that by using a combination of a (meth)acrylic compound with a molecular weight in a specific range and a photopolymerization initiator with a specific structure, the applicability and curing properties to long-wavelength light are excellent, and when the liquid crystal display device is turned on for a long period of time, It was discovered that a sealant for liquid crystal display elements capable of suppressing display defects could be obtained, and the present invention was completed.
본 발명의 액정 표시 소자용 시일제는, 경화성 수지를 함유한다.The sealing agent for liquid crystal display elements of this invention contains curable resin.
상기 경화성 수지는, 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물을 함유한다. 상기 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물을 후술하는 상기 식 (1) 로 나타내는 구조를 갖는 화합물과 조합하여 사용함으로써, 얻어지는 액정 표시 소자용 시일제가 도포성 및 장파장의 광에 대한 경화성이 우수하고, 또한 액정 표시 소자를 장기 점등했을 때의 표시 불량을 억제할 수 있는 것이 된다.The curable resin contains a (meth)acrylic compound with a molecular weight of 700 or more and 2000 or less. By using the (meth)acrylic compound having a molecular weight of 700 or more and 2000 or less in combination with a compound having a structure represented by the formula (1) described later, the sealing agent for a liquid crystal display element obtained has excellent coating properties and curing properties against long-wavelength light. In addition, display defects when the liquid crystal display element is turned on for a long period of time can be suppressed.
상기 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물의 분자량의 바람직한 하한은 750, 바람직한 상한은 1500, 보다 바람직한 하한은 800, 보다 바람직한 상한은 1200 이다.The preferable lower limit of the molecular weight of the (meth)acrylic compound having a molecular weight of 700 to 2000 is 750, the preferable upper limit is 1500, the more preferable lower limit is 800, and the more preferable upper limit is 1200.
또한, 본 명세서에 있어서, 상기 「분자량」은, 분자 구조가 특정되는 화합물에 대해서는, 구조식으로부터 구해지는 분자량이지만, 중합도의 분포가 넓은 화합물 및 변성 부위가 불특정한 화합물에 대해서는, 중량 평균 분자량을 사용하여 나타내는 경우가 있다. 본 명세서에 있어서, 상기 「중량 평균 분자량」은, 겔 퍼미에이션 크로마토그래피 (GPC) 로 측정을 실시하고, 폴리스티렌 환산에 의해 구해지는 값이다. GPC 에 의해 폴리스티렌 환산에 의한 중량 평균 분자량을 측정할 때에 사용하는 칼럼으로는, 예를 들어 Shodex LF-804 (쇼와 전공사 제조) 등을 들 수 있다.In addition, in this specification, the “molecular weight” is the molecular weight determined from the structural formula for compounds with a specified molecular structure, but for compounds with a wide distribution of polymerization degrees and compounds with an unspecified modification site, the weight average molecular weight is used. There are cases where it is indicated. In this specification, the “weight average molecular weight” is a value measured by gel permeation chromatography (GPC) and calculated by polystyrene conversion. Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
또한, 본 명세서에 있어서, 상기 「(메트)아크릴」이란, 아크릴 또는 메타크릴을 의미하고, 상기 「(메트)아크릴 화합물」이란, (메트)아크릴로일기를 갖는 화합물을 의미하고, 상기 「(메트)아크릴로일」이란, 아크릴로일 또는 메타크릴로일을 의미한다.In addition, in this specification, the above “(meth)acryl” means acrylic or methacryl, the above “(meth)acrylic compound” means a compound having a (meth)acryloyl group, and the above “( “meth)acryloyl” means acryloyl or methacryloyl.
상기 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물은, 저액정 오염성의 관점에서 분자량을 비교적 높게 해도 점도 상승이 완만하고, 도포성을 악화시키기 어렵기 때문에, 노볼락형의 (메트)아크릴 화합물인 것이 바람직하고, 노볼락형 에폭시(메트)아크릴레이트인 것이 보다 바람직하다.The (meth)acrylic compound having a molecular weight of 700 or more and 2000 or less has a gradual increase in viscosity even if the molecular weight is relatively high from the viewpoint of low liquid crystal contamination, and it is difficult to deteriorate applicability, so it is a novolak-type (meth)acrylic compound. It is preferable, and it is more preferable that it is novolac type epoxy (meth)acrylate.
또한, 본 명세서에 있어서, 상기 「(메트)아크릴레이트」란, 아크릴레이트 또는 메타크릴레이트를 의미한다. 또, 상기 「에폭시(메트)아크릴레이트」는, 에폭시 화합물의 전부의 에폭시기가 (메트)아크릴산과 반응하고, (메트)아크릴로일기가 도입된 것을 의미한다. 즉, 상기 「노볼락형 에폭시(메트)아크릴레이트」는, 노볼락형 에폭시 화합물의 전부의 에폭시기가 (메트)아크릴산과 반응하고, (메트)아크릴로일기가 도입된 것을 의미한다.In addition, in this specification, the above-mentioned “(meth)acrylate” means acrylate or methacrylate. In addition, the above-mentioned “epoxy (meth)acrylate” means that all epoxy groups of an epoxy compound react with (meth)acrylic acid and a (meth)acryloyl group is introduced. That is, the above-mentioned “novolak-type epoxy (meth)acrylate” means that all epoxy groups of a novolak-type epoxy compound react with (meth)acrylic acid and a (meth)acryloyl group is introduced.
상기 노볼락형 에폭시(메트)아크릴레이트로는, 예를 들어 페놀노볼락형 에폭시(메트)아크릴레이트, 오르토크레졸노볼락형 에폭시(메트)아크릴레이트, 디시클로펜타디엔노볼락형 에폭시(메트)아크릴레이트, 비페닐노볼락형 에폭시(메트)아크릴레이트, 나프탈렌페놀노볼락형 에폭시(메트)아크릴레이트 등을 들 수 있다. 그 중에서도, 페놀노볼락형 에폭시(메트)아크릴레이트가 바람직하다.Examples of the novolak-type epoxy (meth)acrylate include phenol novolak-type epoxy (meth)acrylate, orthocresol novolak-type epoxy (meth)acrylate, and dicyclopentadiene novolak-type epoxy (meth)acrylate. Acrylate, biphenyl novolak type epoxy (meth)acrylate, naphthalene phenol novolak type epoxy (meth)acrylate, etc. are mentioned. Among them, phenol novolak-type epoxy (meth)acrylate is preferable.
상기 노볼락형 에폭시(메트)아크릴레이트는, 노볼락형 에폭시 화합물의 전부의 에폭시기를, 통상적인 방법에 따라 염기성 촉매의 존재하에서 (메트)아크릴산과 반응시킴으로써 얻을 수 있다.The novolak-type epoxy (meth)acrylate can be obtained by reacting all the epoxy groups of a novolak-type epoxy compound with (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.
상기 노볼락형 에폭시(메트)아크릴레이트의 원료가 되는 노볼락형 에폭시 화합물로는, 예를 들어 페놀노볼락형 에폭시 화합물, 오르토크레졸노볼락형 에폭시 화합물, 디시클로펜타디엔노볼락형 에폭시 화합물, 비페닐노볼락형 에폭시 화합물, 나프탈렌페놀노볼락형 에폭시 화합물 등을 들 수 있다. 그 중에서도, 페놀노볼락형 에폭시 화합물이 바람직하다.Examples of the novolak-type epoxy compounds that serve as raw materials for the novolak-type epoxy (meth)acrylate include phenol novolak-type epoxy compounds, orthocresol novolak-type epoxy compounds, dicyclopentadiene novolak-type epoxy compounds, A biphenyl novolak type epoxy compound, a naphthalene phenol novolak type epoxy compound, etc. are mentioned. Among them, phenol novolak-type epoxy compounds are preferable.
또, 상기 노볼락형의 (메트)아크릴 화합물로는, 부분 (메트)아크릴 변성 노볼락형 에폭시 화합물도 바람직하게 사용된다.Additionally, as the novolak-type (meth)acrylic compound, a partially (meth)acrylic-modified novolak-type epoxy compound is also preferably used.
또한, 본 명세서에 있어서, 상기 「부분 (메트)아크릴 변성 노볼락형 에폭시 화합물」은, 노볼락형 에폭시 화합물의 일부의 에폭시기가 (메트)아크릴산과 반응하고, (메트)아크릴로일기가 도입된 것을 의미한다.In addition, in this specification, the “partially (meth)acrylic-modified novolak-type epoxy compound” refers to a product in which a part of the epoxy group of the novolak-type epoxy compound reacts with (meth)acrylic acid and a (meth)acryloyl group is introduced. means that
상기 부분 (메트)아크릴 변성 노볼락형 에폭시 화합물로는, 예를 들어 부분 (메트)아크릴 변성 페놀노볼락형 에폭시 화합물, 부분 (메트)아크릴 변성 오르토크레졸노볼락형 에폭시 화합물, 부분 (메트)아크릴 변성 디시클로펜타디엔노볼락형 에폭시 화합물, 부분 (메트)아크릴 변성 비페닐노볼락형 에폭시 화합물, 부분 (메트)아크릴 변성 나프탈렌페놀노볼락형 에폭시 화합물 등을 들 수 있다. 그 중에서도, 부분 (메트)아크릴 변성 페놀노볼락형 에폭시 화합물이 바람직하다.Examples of the partially (meth)acrylic-modified novolak-type epoxy compound include partially (meth)acrylic-modified phenol novolak-type epoxy compounds, partially (meth)acrylic-modified orthocresol novolak-type epoxy compounds, and partially (meth)acrylic-modified epoxy compounds. Modified dicyclopentadiene novolak-type epoxy compounds, partially (meth)acrylic-modified biphenyl novolak-type epoxy compounds, and partially (meth)acrylic-modified naphthalenephenol novolak-type epoxy compounds. Among them, partially (meth)acrylic-modified phenol novolak-type epoxy compounds are preferable.
상기 부분 (메트)아크릴 변성 노볼락형 에폭시 화합물은, 노볼락형 에폭시 화합물의 일부의 에폭시기를 (메트)아크릴산과 반응시킴으로써, 부분 (메트)아크릴 변성 노볼락형 에폭시 화합물과 노볼락형 에폭시 화합물과 노볼락형 에폭시(메트)아크릴레이트의 혼합물 중에 얻어진다. 상기 노볼락형 에폭시 화합물의 일부의 에폭시기를 (메트)아크릴산과 반응시키는 방법으로는, 예를 들어 통상적인 방법에 따라 염기성 촉매의 존재하에서 반응시키는 방법 등을 들 수 있다.The partially (meth)acrylic-modified novolak-type epoxy compound is obtained by reacting a part of the epoxy group of the novolak-type epoxy compound with (meth)acrylic acid, thereby producing a partially (meth)acrylic-modified novolak-type epoxy compound and a novolak-type epoxy compound. Obtained in a mixture of novolak-type epoxy (meth)acrylates. Methods for reacting a part of the epoxy group of the novolak-type epoxy compound with (meth)acrylic acid include, for example, reacting in the presence of a basic catalyst according to a conventional method.
상기 부분 (메트)아크릴 변성 노볼락형 에폭시 화합물의 원료가 되는 노볼락형 에폭시 화합물로는, 상기 노볼락형 에폭시(메트)아크릴레이트의 원료가 되는 노볼락형 에폭시 화합물과 동일한 것을 들 수 있다.Examples of the novolak-type epoxy compound that serves as a raw material for the partially (meth)acrylic-modified novolak-type epoxy compound include the same novolak-type epoxy compounds that serve as the raw material for the novolak-type epoxy (meth)acrylate.
상기 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물 중, 그 밖의 것으로는, 예를 들어 에틸렌옥사이드 부가 비스페놀 A 형 에폭시(메트)아크릴레이트, 프로필렌옥사이드 부가 비스페놀 A 형 에폭시(메트)아크릴레이트, 카프롤락톤 변성 비스페놀 A 형 에폭시(메트)아크릴레이트 등을 들 수 있다.Among the (meth)acrylic compounds having a molecular weight of 700 to 2000, others include, for example, ethylene oxide-added bisphenol A-type epoxy (meth)acrylate, propylene oxide-added bisphenol A-type epoxy (meth)acrylate, and caprol. Lactone-modified bisphenol A type epoxy (meth)acrylate, etc. can be mentioned.
상기 경화성 수지는, 본 발명의 목적을 저해하지 않는 범위에서, 상기 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물에 더하여 그 밖의 경화성 수지를 함유해도 된다.The curable resin may contain other curable resins in addition to the (meth)acrylic compound having a molecular weight of 700 or more and 2000 or less, as long as it does not impair the purpose of the present invention.
상기 경화성 수지가 상기 그 밖의 경화성 수지를 함유하는 경우, 상기 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물의 함유량은, 상기 경화성 수지 100 중량부 중에 있어서, 바람직한 하한이 2 중량부, 바람직한 상한이 30 중량부이다. 상기 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물의 함유량이 2 중량부 이상인 것에 의해, 얻어지는 액정 표시 소자용 시일제가 액정 표시 소자를 장기 점등했을 때의 표시 불량을 억제하는 효과가 보다 우수한 것이 된다. 상기 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물의 함유량이 30 중량부 이하인 것에 의해, 얻어지는 액정 표시 소자용 시일제가 도포성이 보다 우수한 것이 된다. 상기 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물의 함유량의 보다 바람직한 하한은 3 중량부, 보다 바람직한 상한은 25 중량부이다.When the curable resin contains the other curable resins, the content of the (meth)acrylic compound having a molecular weight of 700 or more and 2000 or less has a preferable lower limit of 2 parts by weight and a preferable upper limit of 30 parts by weight in 100 parts by weight of the curable resin. It is a weight part. When the content of the (meth)acrylic compound having a molecular weight of 700 or more and 2000 or less is 2 parts by weight or more, the obtained sealing agent for liquid crystal display elements has a more excellent effect of suppressing display defects when the liquid crystal display element is illuminated for a long period of time. When the content of the (meth)acrylic compound having a molecular weight of 700 or more and 2000 or less is 30 parts by weight or less, the obtained sealing agent for liquid crystal display elements becomes more excellent in applicability. A more preferable lower limit of the content of the (meth)acrylic compound having a molecular weight of 700 or more and 2000 or less is 3 parts by weight, and a more preferable upper limit is 25 parts by weight.
상기 그 밖의 경화성 수지로는, 분자량이 700 미만인 경화성 수지가 바람직하다. 상기 분자량이 700 미만인 경화성 수지로는, 예를 들어 분자량이 700 미만인 (메트)아크릴 화합물, 분자량이 700 미만인 에폭시 화합물 등을 들 수 있다.As for the other curable resins mentioned above, curable resins with a molecular weight of less than 700 are preferable. Examples of the curable resin having a molecular weight of less than 700 include (meth)acrylic compounds with a molecular weight of less than 700, and epoxy compounds with a molecular weight of less than 700.
상기 분자량이 700 미만인 (메트)아크릴 화합물로는, 예를 들어 분자량이 700 미만인 (메트)아크릴산에스테르 화합물, 분자량이 700 미만인 에폭시(메트)아크릴레이트, 분자량이 700 미만인 우레탄(메트)아크릴레이트 등을 들 수 있다. 그 중에서도, 분자량이 700 미만인 에폭시(메트)아크릴레이트가 바람직하다. 또, 상기 분자량이 700 미만인 (메트)아크릴 화합물은, 높은 반응성 면에서 1 분자 중에 (메트)아크릴로일기를 2 개 이상 갖는 것이 바람직하다.Examples of the (meth)acrylic compound with a molecular weight of less than 700 include (meth)acrylic acid ester compounds with a molecular weight of less than 700, epoxy (meth)acrylate with a molecular weight of less than 700, and urethane (meth)acrylate with a molecular weight of less than 700. I can hear it. Among them, epoxy (meth)acrylate with a molecular weight of less than 700 is preferable. In addition, the (meth)acrylic compound having a molecular weight of less than 700 preferably has two or more (meth)acryloyl groups in one molecule from the viewpoint of high reactivity.
상기 분자량이 700 미만인 (메트)아크릴산에스테르 화합물 중 단관능의 것으로는, 예를 들어 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, 이소부틸(메트)아크릴레이트, t-부틸(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, n-옥틸(메트)아크릴레이트, 이소옥틸(메트)아크릴레이트, 이소노닐(메트)아크릴레이트, 이소데실(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 이소미리스틸(메트)아크릴레이트, 스테아릴(메트)아크릴레이트, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 이소보르닐(메트)아크릴레이트, 비시클로펜테닐(메트)아크릴레이트, 벤질(메트)아크릴레이트, 2-메톡시에틸(메트)아크릴레이트, 2-에톡시에틸(메트)아크릴레이트, 2-부톡시에틸(메트)아크릴레이트, 2-페녹시에틸(메트)아크릴레이트, 메톡시에틸렌글리콜(메트)아크릴레이트, 페녹시디에틸렌글리콜(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, 에틸카르비톨(메트)아크릴레이트, 2,2,2-트리플루오로에틸(메트)아크릴레이트, 2,2,3,3-테트라플루오로프로필(메트)아크릴레이트, 1H,1H,5H-옥타플루오로펜틸(메트)아크릴레이트, 이미드(메트)아크릴레이트, 디메틸아미노에틸(메트)아크릴레이트, 디에틸아미노에틸(메트)아크릴레이트, 2-(메트)아크릴로일옥시에틸숙신산, 2-(메트)아크릴로일옥시에틸헥사하이드로프탈산, 2-(메트)아크릴로일옥시에틸2-하이드록시프로필프탈레이트, 2-(메트)아크릴로일옥시에틸포스페이트, 글리시딜(메트)아크릴레이트 등을 들 수 있다.Among the (meth)acrylic acid ester compounds having a molecular weight of less than 700, monofunctional ones include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. , isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth) Acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hyde Roxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, bicyclophene Tenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenok Cyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethylcarbitol (meth)acrylate, 2,2 ,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, imide ( Meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl (meth)acrylate, etc.
또, 상기 분자량이 700 미만인 (메트)아크릴산에스테르 화합물 중 2 관능의 것으로는, 예를 들어 1,3-부탄디올디(메트)아크릴레이트, 1,4-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 1,9-노난디올디(메트)아크릴레이트, 1,10-데칸디올디(메트)아크릴레이트, 에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 테트라에틸렌글리콜디(메트)아크릴레이트, 2-n-부틸-2-에틸-1,3-프로판디올디(메트)아크릴레이트, 디프로필렌글리콜디(메트)아크릴레이트, 트리프로필렌글리콜디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 디메틸올디시클로펜타디에닐디(메트)아크릴레이트, 에틸렌옥사이드 변성 이소시아누르산디(메트)아크릴레이트, 2-하이드록시-3-(메트)아크릴로일옥시프로필(메트)아크릴레이트, 카보네이트디올디(메트)아크릴레이트 등을 들 수 있다.In addition, among the above-mentioned (meth)acrylic acid ester compounds having a molecular weight of less than 700, bifunctional ones include, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6. -Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di( Meth)acrylate, tetraethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene Glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, 2-hydroxy-3- (meth)acryloyloxypropyl (meth)acrylate, carbonate diol di(meth)acrylate, etc. are mentioned.
또, 상기 분자량이 700 미만인 (메트)아크릴산에스테르 화합물 중 3 관능 이상의 것으로는, 예를 들어 트리메틸올프로판트리(메트)아크릴레이트, 글리세린트리(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 트리스(메트)아크릴로일옥시에틸포스페이트, 펜타에리트리톨테트라(메트)아크릴레이트, 디트리메틸올프로판테트라(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트 등을 들 수 있다.In addition, among the above-mentioned (meth)acrylic acid ester compounds having a molecular weight of less than 700, those having three or more functions include, for example, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. , Tris(meth)acryloyloxyethyl phosphate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( Meth)acrylate, etc. can be mentioned.
상기 분자량이 700 미만인 에폭시(메트)아크릴레이트로는, 예를 들어 에폭시 화합물과 (메트)아크릴산을, 통상적인 방법에 따라 염기성 촉매의 존재하에서 반응시킴으로써 얻어지는 것 등을 들 수 있다.Examples of the epoxy (meth)acrylate having a molecular weight of less than 700 include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.
상기 분자량이 700 미만인 에폭시(메트)아크릴레이트를 합성하기 위한 원료가 되는 에폭시 화합물로는, 예를 들어 비스페놀 A 디글리시딜에테르, 비스페놀 F 디글리시딜에테르, 비스페놀 E 디글리시딜에테르, 수소 첨가 비스페놀 A 디글리시딜에테르, 수소 첨가 비스페놀 F 디글리시딜에테르, 수소 첨가 비스페놀 E 디글리시딜에테르, 레조르시놀디글리시딜에테르, 비페닐-4,4'-디일비스(글리시딜에테르), 1,6-나프탈렌디일비스(글리시딜에테르), 에틸렌글리콜디글리시딜에테르, 1,3-프로판디올디글리시딜에테르, 1,4-부탄디올디글리시딜에테르 등을 들 수 있다.Epoxy compounds that serve as raw materials for synthesizing the epoxy (meth)acrylate having a molecular weight of less than 700 include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, resorcinol diglycidyl ether, biphenyl-4,4'-diylbis(glycidyl ether) cidyl ether), 1,6-naphthalenediylbis(glycidyl ether), ethylene glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, etc. can be mentioned.
상기 분자량이 700 미만인 우레탄(메트)아크릴레이트로는, 예를 들어 이소시아네이트 화합물에 대해 수산기를 갖는 (메트)아크릴산 유도체를, 촉매량의 주석계 화합물 존재하에서 반응시킴으로써 얻을 수 있다.The urethane (meth)acrylate having a molecular weight of less than 700 can be obtained, for example, by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin-based compound.
상기 이소시아네이트 화합물로는, 예를 들어 이소포론디이소시아네이트, 2,4-톨릴렌디이소시아네이트, 2,6-톨릴렌디이소시아네이트, 헥사메틸렌디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트, 디페닐메탄-4,4'-디이소시아네이트 (MDI), 수소 첨가 MDI, 1,5-나프탈렌디이소시아네이트, 노르보르난디이소시아네이트, 톨리딘디이소시아네이트, 자일릴렌디이소시아네이트 (XDI), 수소 첨가 XDI, 리신디이소시아네이트, 테트라메틸자일릴렌디이소시아네이트 등을 들 수 있다.Examples of the isocyanate compounds include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4'- Diisocyanate (MDI), hydrogenated MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, tetramethylxylylene diisocyanate, etc. can be mentioned.
상기 수산기를 갖는 (메트)아크릴산 유도체로는, 예를 들어 하이드록시알킬(메트)아크릴레이트, 2 가의 알코올의 모노(메트)아크릴레이트 등을 들 수 있다.Examples of the (meth)acrylic acid derivative having the hydroxyl group include hydroxyalkyl (meth)acrylate, mono(meth)acrylate of dihydric alcohol, etc.
상기 하이드록시알킬(메트)아크릴레이트로는, 예를 들어 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트 등을 들 수 있다.Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4- Hydroxybutyl (meth)acrylate, etc. can be mentioned.
상기 2 가의 알코올로는, 예를 들어 에틸렌글리콜, 프로필렌글리콜, 1,3-프로판디올, 1,3-부탄디올, 1,4-부탄디올 등을 들 수 있다.Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, and 1,4-butanediol.
또, 상기 분자량이 700 미만인 (메트)아크릴 화합물로는, 분자량이 700 미만인 부분 (메트)아크릴 변성 에폭시 화합물을 사용해도 된다.Additionally, as the (meth)acrylic compound with a molecular weight of less than 700, a partially (meth)acrylic modified epoxy compound with a molecular weight of less than 700 may be used.
또한, 본 명세서에 있어서 상기 「부분 (메트)아크릴 변성 에폭시 화합물」이란, 에폭시 화합물의 일부의 에폭시기가 (메트)아크릴산과 반응하고, (메트)아크릴로일기가 도입된 것을 의미한다.In addition, in this specification, the above-mentioned “partially (meth)acrylic-modified epoxy compound” means that a part of the epoxy group of the epoxy compound reacts with (meth)acrylic acid and a (meth)acryloyl group is introduced.
상기 분자량이 700 미만인 부분 (메트)아크릴 변성 에폭시 화합물을 합성하기 위한 원료가 되는 에폭시 화합물로는, 예를 들어 상기 분자량이 700 미만인 에폭시(메트)아크릴레이트를 합성하기 위한 원료가 되는 에폭시 화합물 등을 들 수 있다.Examples of the epoxy compound that serves as a raw material for synthesizing the partially (meth)acrylic modified epoxy compound with a molecular weight of less than 700 include, for example, an epoxy compound that serves as a raw material for synthesizing the epoxy (meth)acrylate with a molecular weight of less than 700. I can hear it.
상기 분자량이 700 미만인 에폭시 화합물로는, 예를 들어 상기 분자량이 700 미만인 에폭시(메트)아크릴레이트를 합성하기 위한 원료가 되는 에폭시 화합물 등을 들 수 있다.Examples of the epoxy compound having a molecular weight of less than 700 include epoxy compounds that serve as raw materials for synthesizing epoxy (meth)acrylate having a molecular weight of less than 700.
본 발명의 액정 표시 소자용 시일제는, 광중합 개시제를 함유한다.The sealing agent for liquid crystal display elements of this invention contains a photoinitiator.
상기 광중합 개시제는, 상기 식 (1) 로 나타내는 구조를 갖는 화합물을 함유한다. 상기 식 (1) 로 나타내는 구조를 갖는 화합물은, 장파장의 광에 대한 반응성이 우수하고, 또한 상기 서술한 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물과 조합하여 사용함으로써, 액정 표시 소자를 장기 점등했을 때의 표시 불량을 억제할 수 있다.The photopolymerization initiator contains a compound having a structure represented by the formula (1). The compound having the structure represented by the above formula (1) is excellent in reactivity to long-wavelength light, and by using it in combination with the above-mentioned (meth)acrylic compound having a molecular weight of 700 to 2000, the liquid crystal display element can be illuminated for a long period of time. Display defects can be suppressed.
상기 식 (1) 로 나타내는 구조를 갖는 화합물은, 1 분자 중에 1 개의 상기 식 (1) 로 나타내는 구조를 갖는 화합물이어도 된다. 상기 1 분자 중에 1 개의 상기 식 (1) 로 나타내는 구조를 갖는 화합물로는, 하기 식 (2-1) 로 나타내는 화합물 및/또는 하기 식 (2-2) 로 나타내는 화합물이 바람직하다.The compound having the structure represented by the formula (1) may be one compound having the structure represented by the formula (1) in one molecule. The compound having one structure represented by the formula (1) in one molecule is preferably a compound represented by the formula (2-1) below and/or a compound represented by the formula (2-2) below.
[화학식 2][Formula 2]
식 (2-1), (2-2) 중, R 은, 단관능 에폭시 화합물에서 유래되는 구조이다.In formulas (2-1) and (2-2), R is a structure derived from a monofunctional epoxy compound.
상기 식 (2-1) 로 나타내는 화합물을 제조하는 방법으로는, 예를 들어 염기성 촉매의 존재하에서, 2-(카르복시메톡시)-9H-티오크산텐-9-온과 단관능 에폭시 화합물을 80 ℃ 이상 130 ℃ 이하의 조건에서 6 ∼ 72 시간 교반하면서 반응시키는 방법 등을 들 수 있다.As a method for producing the compound represented by the above formula (2-1), for example, in the presence of a basic catalyst, 2-(carboxymethoxy)-9H-thioxanthene-9-one and a monofunctional epoxy compound are reacted at 80 °C. A method of reacting while stirring for 6 to 72 hours under conditions of 130°C or higher is included.
또, 상기 식 (2-2) 로 나타내는 화합물을 제조하는 방법으로는, 예를 들어 염기성 촉매의 존재하에서, 2-하이드록시-9H-티오크산텐-9-온과 단관능 에폭시 화합물을 80 ℃ 이상 130 ℃ 이하의 조건에서 6 ∼ 72 시간 교반하면서 반응시키는 방법 등을 들 수 있다.Additionally, as a method for producing the compound represented by the above formula (2-2), for example, 2-hydroxy-9H-thioxanthene-9-one and a monofunctional epoxy compound are heated at 80°C in the presence of a basic catalyst. A method of reacting while stirring for 6 to 72 hours under conditions of 130°C or lower may be included.
이하, 2-(카르복시메톡시)-9H-티오크산텐-9-온과 2-하이드록시-9H-티오크산텐-9-온에 대해서는, 「원료 티오크산톤 유도체」라고도 한다.Hereinafter, 2-(carboxymethoxy)-9H-thioxanthen-9-one and 2-hydroxy-9H-thioxanthen-9-one are also referred to as “raw material thioxanthone derivatives.”
상기 단관능 에폭시 화합물은, 탄소수 1 이상의 치환기를 적어도 1 개 이상 갖는 방향족 고리 또는 탄소수 1 이상의 치환기를 적어도 1 개 이상 갖는 지방족 고리를 갖는 것이 바람직하다.The monofunctional epoxy compound preferably has an aromatic ring having at least one substituent having 1 or more carbon atoms or an aliphatic ring having at least one substituent having 1 or more carbon atoms.
상기 방향족 고리 또는 상기 지방족 고리로는, 예를 들어 벤젠 고리, 나프탈렌 고리, 안트라센 고리, 시클로부탄 고리, 시클로펜탄 고리, 시클로헥산 고리, 시클로옥탄 고리, 노르보르넨 고리, 트리시클로데칸 고리 등의 방향족 고리 또는 지방족 고리에 있어서의 적어도 1 개 이상의 수소 원자가 탄소수 1 이상의 치환기로 치환된 것을 들 수 있다.Examples of the aromatic ring or aliphatic ring include aromatic rings such as benzene ring, naphthalene ring, anthracene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclooctane ring, norbornene ring, and tricyclodecane ring. Examples include those in which at least one hydrogen atom in the ring or aliphatic ring is substituted with a substituent having 1 or more carbon atoms.
상기 탄소수 1 이상의 치환기는, 직사슬형이어도 되고, 분기 사슬형이어도 된다. 상기 탄소수 1 이상의 치환기가 직사슬형인 경우는, 탄소수 6 이상인 것이 바람직하고, 탄소수 10 이상인 것이 보다 바람직하다. 상기 탄소수 1 이상의 치환기가 분기 사슬형인 경우는, 탄소수 4 이상인 것이 바람직하다. 또, 상기 방향족 고리 또는 상기 지방족 고리가 갖는 탄소수 1 이상의 치환기의 탄소수는, 상기 단관능 에폭시 화합물의 분자량이 후술하는 300 이하가 되는 수인 것이 바람직하다.The substituent having 1 or more carbon atoms may be linear or branched. When the substituent having 1 or more carbon atoms is linear, it is preferably 6 or more carbon atoms, and more preferably 10 or more carbon atoms. When the substituent having 1 or more carbon atoms is branched, it is preferably 4 or more carbon atoms. In addition, the number of carbon atoms of the substituent having 1 or more carbon atoms on the aromatic ring or the aliphatic ring is preferably such that the molecular weight of the monofunctional epoxy compound is 300 or less as described later.
상기 방향족 고리 또는 상기 지방족 고리가 갖는 탄소수 1 이상의 치환기로는, 알킬기가 바람직하다.As the substituent of the aromatic ring or the aliphatic ring having 1 or more carbon atoms, an alkyl group is preferable.
상기 단관능 에폭시 화합물로는, 예를 들어 알킬페닐글리시딜에테르, 글리시딜기를 갖는 톨루엔술포네이트, 2-에폭시-4-비닐시클로헥산, 3,4-에폭시시클로헥실메틸메타아크릴레이트 등을 들 수 있다.Examples of the monofunctional epoxy compound include alkylphenyl glycidyl ether, toluene sulfonate having a glycidyl group, 2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, etc. I can hear it.
상기 알킬페닐글리시딜에테르로는, 예를 들어 o-메틸페닐글리시딜에테르, m-메틸페닐글리시딜에테르, p-메틸페닐글리시딜에테르, p-tert-부틸페닐글리시딜에테르 등을 들 수 있다.Examples of the alkylphenyl glycidyl ether include o-methylphenyl glycidyl ether, m-methylphenyl glycidyl ether, p-methylphenyl glycidyl ether, and p-tert-butylphenyl glycidyl ether. You can.
상기 단관능 에폭시 화합물 중 시판되고 있는 것으로는, 예를 들어 나가세켐텍스사 제조의 단관능 에폭시 화합물, ADEKA 사 제조의 단관능 에폭시 화합물, 미츠비시 케미컬사 제조의 단관능 에폭시 화합물, 도쿄 화성 공업사 제조의 단관능 에폭시 화합물, 다이셀사 제조의 단관능 에폭시 화합물 등을 들 수 있다.Among the above-mentioned monofunctional epoxy compounds, commercially available ones include, for example, monofunctional epoxy compounds manufactured by Nagase Chemtex, monofunctional epoxy compounds manufactured by ADEKA, monofunctional epoxy compounds manufactured by Mitsubishi Chemical, and Tokyo Chemical Industry Co., Ltd. A monofunctional epoxy compound, a monofunctional epoxy compound manufactured by Daicel, etc. may be mentioned.
상기 나가세켐텍스사 제조의 단관능 에폭시 화합물로는, 예를 들어 데나콜 EX-146 등을 들 수 있다.Examples of the monofunctional epoxy compound manufactured by Nagase Chemtex Corporation include Denacol EX-146.
상기 ADEKA 사 제조의 단관능 에폭시 화합물로는, 예를 들어 ED-509S, ED-509E, ED-529 등을 들 수 있다.Examples of the monofunctional epoxy compounds manufactured by ADEKA include ED-509S, ED-509E, and ED-529.
상기 미츠비시 케미컬사 제조의 단관능 에폭시 화합물로는, 예를 들어 YED-122 등을 들 수 있다.Examples of the monofunctional epoxy compound manufactured by Mitsubishi Chemical Corporation include YED-122.
상기 도쿄 화성 공업사 제조의 단관능 에폭시 화합물로는, 예를 들어 글리시딜2-메톡시페닐에테르, 1-메틸-1,2-에폭시시클로헥산 등을 들 수 있다.Examples of the monofunctional epoxy compound manufactured by Tokyo Chemical Industry Co., Ltd. include glycidyl 2-methoxyphenyl ether, 1-methyl-1,2-epoxycyclohexane, and the like.
상기 다이셀사 제조의 단관능 에폭시 화합물로는, 예를 들어 셀록사이드 2000, 사이크로머 M100 등을 들 수 있다.Examples of the monofunctional epoxy compound manufactured by Daicel include Celoxide 2000 and Cychromer M100.
상기 단관능 에폭시 화합물의 분자량은, 상기 식 (1) 로 나타내는 구조를 갖는 화합물의 경화성 수지와의 상용성의 관점에서, 300 이하인 것이 바람직하다.The molecular weight of the monofunctional epoxy compound is preferably 300 or less from the viewpoint of compatibility with the curable resin of the compound having the structure represented by the formula (1).
상기 원료 티오크산톤 유도체와 상기 단관능 에폭시 화합물을 반응시킬 때의 사용 비율로는, 몰비로, 원료 티오크산톤 유도체 : 단관능 에폭시 화합물 = 1 : 1 ∼ 10 : 1 인 것이 바람직하다. 상기 원료 티오크산톤 유도체와 상기 단관능 에폭시 화합물의 사용 비율이 이 범위인 것에 의해, 상기 식 (2-1) 로 나타내는 화합물 또는 상기 식 (2-2) 로 나타내는 화합물을 고수율로 제조할 수 있다.The use ratio when reacting the raw material thioxanthone derivative and the monofunctional epoxy compound is preferably, in molar ratio, raw material thioxanthone derivative:monofunctional epoxy compound = 1:1 to 10:1. By using the raw material thioxanthone derivative and the monofunctional epoxy compound in this range, the compound represented by the formula (2-1) or the compound represented by the formula (2-2) can be produced in high yield. there is.
상기 원료 티오크산톤 유도체와 상기 단관능 에폭시 화합물과 반응시킬 때에 사용하는 염기성 촉매로는, 3 가의 유기 인산 화합물 및/또는 아민 화합물이 바람직하다.As a basic catalyst used when reacting the raw material thioxanthone derivative with the monofunctional epoxy compound, a trivalent organic phosphoric acid compound and/or an amine compound are preferable.
상기 염기성 촉매로는, 구체적으로는 예를 들어 트리페닐포스핀, 트리에틸아민, 트리프로필아민, 테트라메틸에틸렌디아민, 디메틸라우릴아민, 트리에틸벤질암모늄클로라이드, 트리메틸세틸암모늄브로마이드, 테트라부틸암모늄브로마이드, 트리메틸부틸포스포늄브로마이드, 테트라부틸포스포늄브로마이드 등을 들 수 있다. 그 중에서도, 트리페닐포스핀이 바람직하다.Specific examples of the basic catalyst include triphenylphosphine, triethylamine, tripropylamine, tetramethylethylenediamine, dimethyllaurylamine, triethylbenzylammonium chloride, trimethylcetylammonium bromide, and tetrabutylammonium bromide. , trimethylbutylphosphonium bromide, and tetrabutylphosphonium bromide. Among them, triphenylphosphine is preferable.
또, 상기 염기성 촉매는, 폴리머에 담지시켜, 폴리머 담지 염기성 촉매로서 사용할 수도 있다.Additionally, the basic catalyst can also be supported on a polymer and used as a polymer-supported basic catalyst.
상기 식 (1) 로 나타내는 구조를 갖는 화합물은, 1 분자 중에 2 개 이상의 상기 식 (1) 로 나타내는 구조를 갖는 화합물이어도 된다. 상기 1 분자 중에 2 개 이상의 상기 식 (1) 로 나타내는 구조를 갖는 화합물로는, 하기 식 (3) 으로 나타내는 화합물이 바람직하다.The compound having the structure represented by the formula (1) may be a compound having two or more structures represented by the formula (1) in one molecule. As the compound having two or more structures represented by the formula (1) in one molecule, a compound represented by the formula (3) below is preferable.
[화학식 3][Formula 3]
식 (3) 중, n 은, 1 ∼ 10 (평균값) 이다.In formula (3), n is 1 to 10 (average value).
상기 식 (3) 으로 나타내는 화합물 중 시판되고 있는 것으로는, 예를 들어 Omnipol TX (IGM Resins 사 제조) 등을 들 수 있다.Among the compounds represented by the formula (3), commercially available compounds include, for example, Omnipol TX (manufactured by IGM Resins).
상기 식 (1) 로 나타내는 구조를 갖는 화합물의 함유량은, 상기 경화성 수지 100 중량부에 대해, 바람직한 하한이 0.5 중량부, 바람직한 상한이 20 중량부이다. 상기 식 (1) 로 나타내는 구조를 갖는 화합물의 함유량이 0.5 중량부 이상인 것에 의해, 얻어지는 액정 표시 소자용 시일제가 장파장의 광에 대한 경화성이 보다 우수한 것이 된다. 상기 식 (1) 로 나타내는 구조를 갖는 화합물의 함유량이 20 중량부 이하인 것에 의해, 얻어지는 액정 표시 소자용 시일제가 액정 표시 소자의 표시 불량을 억제하는 효과가 보다 우수한 것이 된다. 상기 식 (1) 로 나타내는 구조를 갖는 화합물의 함유량의 보다 바람직한 하한은 2 중량부, 보다 바람직한 상한은 10 중량부이다.The content of the compound having the structure represented by the formula (1) has a preferable lower limit of 0.5 parts by weight and a preferable upper limit of 20 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the compound having the structure represented by the formula (1) is 0.5 parts by weight or more, the obtained sealing agent for liquid crystal display elements becomes more excellent in curing properties to long-wavelength light. When the content of the compound having the structure represented by the above formula (1) is 20 parts by weight or less, the obtained sealing agent for liquid crystal display elements becomes more excellent in the effect of suppressing display defects of the liquid crystal display element. The more preferable lower limit of the content of the compound having the structure represented by the above formula (1) is 2 parts by weight, and the more preferable upper limit is 10 parts by weight.
상기 광중합 개시제는, 본 발명의 목적을 저해하지 않는 범위에서, 상기 식 (1) 로 나타내는 구조를 갖는 화합물 이외의 다른 광중합 개시제를 함유해도 된다.The photopolymerization initiator may contain other photopolymerization initiators other than the compound having the structure represented by the formula (1), as long as it does not impair the purpose of the present invention.
상기 다른 광중합 개시제로는, 예를 들어 비스(2,4,6-트리메틸벤조일)페닐포스핀옥사이드, 1-(4-(페닐티오)페닐)-1,2-옥탄디온2-(O-벤조일옥심), O-아세틸-1-(6-(2-메틸벤조일)-9-에틸-9H-카르바졸-3-일)에탄온옥심 등을 들 수 있다.Other photopolymerization initiators include, for example, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime), O-acetyl-1-(6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl)ethanone oxime, etc.
본 발명의 액정 표시 소자용 시일제는, 본 발명의 목적을 저해하지 않는 범위에서, 열중합 개시제를 함유해도 된다.The sealing agent for liquid crystal display elements of this invention may contain a thermal polymerization initiator in the range which does not impair the objective of this invention.
상기 열중합 개시제로는, 예를 들어 아조 화합물, 유기 과산화물 등으로 이루어지는 것을 들 수 있다. 그 중에서도, 고분자 아조 화합물로 이루어지는 고분자 아조 개시제가 바람직하다.Examples of the thermal polymerization initiator include those made of azo compounds, organic peroxides, etc. Among them, a polymer azo initiator composed of a polymer azo compound is preferable.
상기 열중합 개시제는, 단독으로 사용되어도 되고, 2 종 이상이 조합되어 사용되어도 된다.The thermal polymerization initiator may be used individually, or two or more types may be used in combination.
또한, 본 명세서에 있어서 상기 「고분자 아조 화합물」이란, 아조기를 갖고, 열에 의해 (메트)아크릴로일옥시기를 경화시킬 수 있는 라디칼을 생성하는, 수평균 분자량이 300 이상인 화합물을 의미한다.In addition, in this specification, the “polymeric azo compound” refers to a compound having an azo group, generating a radical capable of curing a (meth)acryloyloxy group by heat, and having a number average molecular weight of 300 or more.
상기 고분자 아조 화합물의 수평균 분자량의 바람직한 하한은 1000, 바람직한 상한은 30 만이다. 상기 고분자 아조 화합물의 수평균 분자량이 이 범위인 것에 의해, 액정 오염을 억제하면서, 경화성 수지와 용이하게 혼합할 수 있다. 상기 고분자 아조 화합물의 수평균 분자량의 보다 바람직한 하한은 5000, 보다 바람직한 상한은 10 만이고, 더욱 바람직한 하한은 1 만, 더욱 바람직한 상한은 9 만이다.The preferred lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferred upper limit is 300,000. When the number average molecular weight of the polymer azo compound is within this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the polymer azo compound is 5,000, the more preferable upper limit is 100,000, the more preferable lower limit is 10,000, and the more preferable upper limit is 90,000.
또한, 본 명세서에 있어서, 상기 수평균 분자량은, 겔 퍼미에이션 크로마토그래피 (GPC) 로 용매로서 테트라하이드로푸란을 사용하여 측정을 실시하고, 폴리스티렌 환산에 의해 구해지는 값이다. GPC 에 의해 폴리스티렌 환산에 의한 수평균 분자량을 측정할 때의 칼럼으로는, 예를 들어 Shodex LF-804 (쇼와 전공사 제조) 등을 들 수 있다.In this specification, the number average molecular weight is a value determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converted to polystyrene. Examples of the column used to measure the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
상기 고분자 아조 화합물로는, 예를 들어 아조기를 개재하여 폴리알킬렌옥사이드나 폴리디메틸실록산 등의 유닛이 복수 결합한 구조를 갖는 것을 들 수 있다.Examples of the polymer azo compound include those having a structure in which multiple units such as polyalkylene oxide and polydimethylsiloxane are bonded through an azo group.
상기 아조기를 개재하여 폴리알킬렌옥사이드 등의 유닛이 복수 결합한 구조를 갖는 고분자 아조 화합물로는, 폴리에틸렌옥사이드 구조를 갖는 것이 바람직하다.As a polymer azo compound having a structure in which multiple units such as polyalkylene oxide are bonded through the azo group, one preferably has a polyethylene oxide structure.
상기 고분자 아조 화합물로는, 구체적으로는 예를 들어, 4,4'-아조비스(4-시아노펜탄산) 과 폴리알킬렌글리콜의 중축합물이나, 4,4'-아조비스(4-시아노펜탄산) 과 말단 아미노기를 갖는 폴리디메틸실록산의 중축합물 등을 들 수 있다.Specifically, the polymer azo compound includes, for example, a polycondensate of 4,4'-azobis(4-cyanopentanoic acid) and polyalkylene glycol, or 4,4'-azobis(4-cyanophen). carbonic acid) and a polycondensate of polydimethylsiloxane having a terminal amino group.
상기 고분자 아조 화합물 중 시판되고 있는 것으로는, 예를 들어 VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (모두 후지 필름 와코 순약사 제조) 등을 들 수 있다.Examples of commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
또, 고분자가 아닌 아조 화합물로는, 예를 들어 V-65, V-501 (모두 후지 필름 와코 순약사 제조) 등을 들 수 있다.In addition, examples of non-polymer azo compounds include V-65 and V-501 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
상기 유기 과산화물로는, 예를 들어 케톤퍼옥사이드, 퍼옥시케탈, 하이드로퍼옥사이드, 디알킬퍼옥사이드, 퍼옥시에스테르, 디아실퍼옥사이드, 퍼옥시디카보네이트 등을 들 수 있다.Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
상기 열중합 개시제의 함유량은, 상기 경화성 수지 100 중량부에 대해, 바람직한 하한이 0.05 중량부, 바람직한 상한이 10 중량부이다. 상기 열중합 개시제의 함유량이 0.05 중량부 이상인 것에 의해, 본 발명의 액정 표시 소자용 시일제가 열경화성이 보다 우수한 것이 된다. 상기 열중합 개시제의 함유량이 10 중량부 이하인 것에 의해, 본 발명의 액정 표시 소자용 시일제가 저액정 오염성이나 보존 안정성이 보다 우수한 것이 된다. 상기 열중합 개시제의 함유량의 보다 바람직한 하한은 0.1 중량부, 보다 바람직한 상한은 5 중량부이다.The content of the thermal polymerization initiator has a preferable lower limit of 0.05 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermal polymerization initiator is 0.05 parts by weight or more, the sealing agent for liquid crystal display elements of the present invention has more excellent thermosetting properties. When the content of the thermal polymerization initiator is 10 parts by weight or less, the sealing agent for liquid crystal display elements of the present invention has low liquid crystal contamination and is more excellent in storage stability. The more preferable lower limit of the content of the thermal polymerization initiator is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 열경화제를 함유해도 된다.The sealing agent for liquid crystal display elements of this invention may contain a thermosetting agent.
상기 열경화제로는, 예를 들어 유기산 하이드라지드, 이미다졸 유도체, 아민 화합물, 다가 페놀계 화합물, 산 무수물 등을 들 수 있다. 그 중에서도, 유기산 하이드라지드가 바람직하게 사용된다.Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, and acid anhydrides. Among them, organic acid hydrazide is preferably used.
상기 열경화제는, 단독으로 사용되어도 되고, 2 종 이상이 조합되어 사용되어도 된다.The said thermosetting agent may be used individually, and 2 or more types may be used in combination.
상기 유기산 하이드라지드로는, 예를 들어 세바크산디하이드라지드, 이소프탈산디하이드라지드, 아디프산디하이드라지드, 말론산디하이드라지드 등을 들 수 있다.Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide.
상기 유기산 하이드라지드 중 시판되고 있는 것으로는, 예를 들어 오오츠카 화학사 제조의 유기산 하이드라지드, 아지노모토 파인테크노사 제조의 유기산 하이드라지드 등을 들 수 있다.Examples of commercially available organic acid hydrazide include Otsuka Chemical Co., Ltd.'s organic acid hydrazide and Ajinomoto Fine Techno Co., Ltd.'s organic acid hydrazide.
상기 오오츠카 화학사 제조의 유기산 하이드라지드로는, 예를 들어 SDH, ADH 등을 들 수 있다.Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH, ADH, and the like.
상기 아지노모토 파인테크노사 제조의 유기산 하이드라지드로는, 예를 들어 아미큐어 VDH, 아미큐어 VDH-J, 아미큐어 UDH, 아미큐어 UDH-J 등을 들 수 있다.Examples of the organic acid hydrazide manufactured by Ajinomoto Fine Techno include Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J.
상기 열경화제의 함유량은, 상기 경화성 수지 100 중량부에 대해, 바람직한 하한이 1 중량부, 바람직한 상한이 50 중량부이다. 상기 열경화제의 함유량이 이 범위인 것에 의해, 얻어지는 액정 표시 소자용 시일제의 도포성 등을 악화시키지 않고, 보다 열경화성이 우수한 것으로 할 수 있다. 상기 열경화제의 함유량의 보다 바람직한 상한은 30 중량부이다.The content of the thermosetting agent has a preferable lower limit of 1 part by weight and a preferable upper limit of 50 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermosetting agent is within this range, the resulting sealant for liquid crystal display elements can be more excellent in thermosetting properties without deteriorating the applicability, etc. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 점도의 향상, 응력 분산 효과에 의한 접착성의 개선, 선팽창률의 개선 등을 목적으로 하여 충전제를 함유하는 것이 바람직하다.It is preferable that the sealing agent for liquid crystal display elements of this invention contains a filler for the purposes of improving viscosity, improving adhesiveness by a stress dispersion effect, improving linear expansion coefficient, etc.
상기 충전제로는, 무기 충전제나 유기 충전제를 사용할 수 있다.As the filler, an inorganic filler or an organic filler can be used.
상기 무기 충전제로는, 예를 들어 실리카, 탤크, 유리 비즈, 석면, 석고, 규조토, 스멕타이트, 벤토나이트, 몬모릴로나이트, 세리사이트, 활성 백토, 알루미나, 산화 아연, 산화 철, 산화 마그네슘, 산화 주석, 산화 티탄, 탄산칼슘, 탄산마그네슘, 수산화 마그네슘, 수산화 알루미늄, 질화 알루미늄, 질화 규소, 황산바륨, 규산칼슘 등을 들 수 있다.Examples of the inorganic fillers include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide. , calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc.
상기 유기 충전제로는, 예를 들어 폴리에스테르 미립자, 폴리우레탄 미립자, 비닐 중합체 미립자, 아크릴 중합체 미립자 등을 들 수 있다.Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
상기 충전제는, 단독으로 사용되어도 되고, 2 종 이상이 조합되어 사용되어도 된다.The above fillers may be used individually, or two or more types may be used in combination.
본 발명의 액정 표시 소자용 시일제 100 중량부 중에 있어서의 상기 충전제의 함유량의 바람직한 하한은 10 중량부, 바람직한 상한은 70 중량부이다. 상기 충전제의 함유량이 이 범위인 것에 의해, 도포성 등을 악화시키지 않고, 접착성의 개선 등의 효과가 보다 우수한 것이 된다. 상기 충전제의 함유량의 보다 바람직한 하한은 20 중량부, 보다 바람직한 상한은 60 중량부이다.The preferable lower limit of content of the said filler in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 10 weight part, and a preferable upper limit is 70 weight part. When the content of the filler is within this range, applicability, etc. do not deteriorate, and effects such as improvement in adhesion are more excellent. A more preferable lower limit of the content of the filler is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 실란 커플링제를 함유하는 것이 바람직하다. 상기 실란 커플링제는, 주로 시일제와 기판 등을 양호하게 접착하기 위한 접착 보조제로서의 역할을 갖는다.It is preferable that the sealing agent for liquid crystal display elements of this invention contains a silane coupling agent. The silane coupling agent mainly serves as an adhesion aid for good adhesion between the sealant and the substrate.
상기 실란 커플링제로는, 예를 들어 3-아미노프로필트리메톡시실란, 3-메르캅토프로필트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-이소시아네이트프로필트리메톡시실란 등이 바람직하게 사용된다. 이들은, 기판 등과의 접착성을 향상시키는 효과가 우수하고, 경화성 수지와 화학 결합함으로써 액정 중에 대한 경화성 수지의 유출을 억제할 수 있다.Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatepropyltrimethoxysilane. It is preferably used. These are excellent in the effect of improving adhesion to a substrate, etc., and can suppress outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin.
본 발명의 액정 표시 소자용 시일제 100 중량부 중에 있어서의 상기 실란 커플링제의 함유량의 바람직한 하한은 0.1 중량부, 바람직한 상한은 10 중량부이다. 상기 실란 커플링제의 함유량이 이 범위인 것에 의해, 액정 오염의 발생을 억제하면서, 접착성을 향상시키는 효과가 보다 우수한 것이 된다. 상기 실란 커플링제의 함유량의 보다 바람직한 하한은 0.3 중량부, 보다 바람직한 상한은 5 중량부이다.The preferable lower limit of content of the said silane coupling agent in 100 weight part of sealing agents for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part. When the content of the silane coupling agent is within this range, the effect of improving adhesion while suppressing the occurrence of liquid crystal contamination becomes more excellent. The more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.
본 발명의 액정 표시 소자용 시일제는, 추가로, 필요에 따라, 반응성 희석제, 요변제, 스페이서, 경화 촉진제, 소포제, 레벨링제, 중합 금지제 등의 첨가제를 함유해도 된다.The sealing agent for liquid crystal display elements of the present invention may further contain additives, such as a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoamer, a leveling agent, and a polymerization inhibitor, as needed.
본 발명의 액정 표시 소자용 시일제를 제조하는 방법으로는, 예를 들어 호모 디스퍼, 호모 믹서, 만능 믹서, 플래너터리 믹서, 니더, 3 본롤 등의 혼합기를 사용하여, 경화성 수지와, 광중합 개시제와, 필요에 따라 첨가하는 실란 커플링제 등을 혼합하는 방법 등을 들 수 있다.As a method of manufacturing the sealant for liquid crystal display elements of the present invention, for example, a curable resin and a photopolymerization initiator are used using a mixer such as a homodisper, homomixer, universal mixer, planetary mixer, kneader, or three-bone roll. and a method of mixing a silane coupling agent, etc., added as needed.
본 발명의 액정 표시 소자용 시일제에, 도전성 미립자를 배합함으로써, 상하 도통 재료를 제조할 수 있다. 이와 같은 본 발명의 액정 표시 소자용 시일제와 도전성 미립자를 함유하는 상하 도통 재료도 또한, 본 발명의 하나이다.A vertical conduction material can be manufactured by mixing conductive fine particles with the sealing agent for liquid crystal display elements of the present invention. The vertical conduction material containing such a sealing agent for a liquid crystal display element of the present invention and conductive fine particles is also one of the present invention.
상기 도전성 미립자로는, 금속 볼, 수지 미립자의 표면에 도전 금속층을 형성한 것 등을 사용할 수 있다. 그 중에서도, 수지 미립자의 표면에 도전 금속층을 형성한 것은, 수지 미립자의 우수한 탄성에 의해, 투명 기판 등을 손상시키지 않고 도전 접속이 가능하므로 바람직하다.As the conductive fine particles, metal balls, resin fine particles with a conductive metal layer formed on the surface, etc. can be used. Among these, a conductive metal layer formed on the surface of the resin fine particles is preferable because the excellent elasticity of the resin fine particles allows conductive connection without damaging the transparent substrate, etc.
본 발명의 액정 표시 소자용 시일제 또는 본 발명의 상하 도통 재료를 사용하여 이루어지는 액정 표시 소자도 또한, 본 발명의 하나이다.A liquid crystal display element formed using the sealing agent for a liquid crystal display element of the present invention or the vertical conduction material of the present invention is also one of the present invention.
본 발명의 액정 표시 소자를 제조하는 방법으로는, 액정 적하 공법이 바람직하게 사용되고, 구체적으로는 예를 들어 이하의 각 공정을 갖는 방법 등을 들 수 있다.As a method for manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method is preferably used, and specific examples include a method having the following steps.
먼저, ITO 박막 등의 전극이 부착된 유리 기판이나 폴리에틸렌테레프탈레이트 기판 등의 2 장의 기판의 일방에, 본 발명의 액정 표시 소자용 시일제를, 스크린 인쇄, 디스펜서 도포 등에 의해 도포하여 프레임상의 시일 패턴을 형성하는 공정을 실시한다. 이어서, 본 발명의 액정 표시 소자용 시일제가 미경화의 상태로 액정의 미소적을 기판의 시일 패턴의 프레임 내에 적하 도포하고, 진공하에서 다른 기판을 중첩하는 공정을 실시한다. 그 후, 본 발명의 액정 표시 소자용 시일제의 시일 패턴 부분에 400 ㎚ 컷 필터 등을 개재하여 광을 조사함으로써, 장파장의 광에 의해 시일제를 광경화시키는 공정을 실시하는 방법에 의해, 액정 표시 소자를 얻을 수 있다. 또, 상기 시일제를 광경화시키는 공정에 더하여, 시일제를 가열하여 열경화시키는 공정을 실시해도 된다.First, the sealing agent for liquid crystal display elements of the present invention is applied to one of two substrates, such as a glass substrate or a polyethylene terephthalate substrate, to which electrodes such as an ITO thin film are attached, by screen printing, dispenser coating, etc., to form a seal pattern on a frame. The process of forming is carried out. Next, in the uncured state of the sealing agent for liquid crystal display elements of the present invention, microdroplets of liquid crystal are applied dropwise into the frame of the seal pattern of the substrate, and a process of overlapping another substrate under vacuum is performed. Thereafter, by irradiating light through a 400 nm cut filter or the like to the seal pattern portion of the sealant for liquid crystal display elements of the present invention, a process of photocuring the sealant with long-wavelength light is performed, thereby forming a liquid crystal display. elements can be obtained. Moreover, in addition to the process of photocuring the said sealing agent, you may perform the process of heating the sealing agent and thermosetting it.
본 발명에 의하면, 도포성 및 장파장의 광에 대한 경화성이 우수하고, 또한 액정 표시 소자를 장기 점등했을 때의 표시 불량을 억제할 수 있는 액정 표시 소자용 시일제를 제공할 수 있다. 또, 본 발명에 의하면, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공할 수 있다.According to the present invention, it is possible to provide a sealing agent for a liquid crystal display element that is excellent in applicability and curability with respect to long-wavelength light, and can suppress display defects when the liquid crystal display element is illuminated for a long period of time. Moreover, according to this invention, a vertical conduction material and a liquid crystal display element formed using the sealing agent for liquid crystal display elements can be provided.
이하에 실시예를 들어 본 발명을 더욱 상세하게 설명하는데, 본 발명은 이들 실시예에만 한정되지 않는다.The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
(노볼락형 에폭시아크릴레이트 B 의 제조)(Manufacture of novolak-type epoxy acrylate B)
페놀노볼락형 에폭시 화합물 (DIC 사 제조, 「EPICLON N-740」) 557 중량부를, 톨루엔 1800 ㎖ 에 용해시킨 후, 트리페닐포스핀 0.5 중량부를 첨가하고, 균일한 용액으로 하였다. 얻어진 용액에 아크릴산 244 중량부를 환류 교반하에서 2 시간 적하한 후, 추가로 환류 교반을 6 시간 실시하였다. 이어서, 톨루엔을 감압 제거함으로써, 노볼락형 에폭시아크릴레이트 B 를 얻었다.After dissolving 557 parts by weight of a phenol novolak-type epoxy compound (“EPICLON N-740” manufactured by DIC) in 1800 ml of toluene, 0.5 parts by weight of triphenylphosphine was added to obtain a uniform solution. 244 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux and stirring for 2 hours, and then reflux and stirring were further performed for 6 hours. Next, toluene was removed under reduced pressure to obtain novolak-type epoxy acrylate B.
또한, 얻어진 노볼락형 에폭시아크릴레이트 B 의 구조는, 1H-NMR, 13C-NMR, 및 FT-IR 에 의해 확인하였다.In addition, the structure of the obtained novolak-type epoxy acrylate B was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
또, 얻어진 노볼락형 에폭시아크릴레이트 B 의 중량 평균 분자량은 1400 이었다.Moreover, the weight average molecular weight of the obtained novolak-type epoxy acrylate B was 1400.
(노볼락형 에폭시아크릴레이트 C 의 제조)(Manufacture of novolak-type epoxy acrylate C)
페놀노볼락형 에폭시 화합물 (DIC 사 제조, 「EPICLON N-770」) 965 중량부를, 톨루엔 2500 ㎖ 에 용해시킨 후, 트리페닐포스핀 0.5 중량부를 첨가하고, 균일한 용액으로 하였다. 얻어진 용액에 아크릴산 432 중량부를 환류 교반하에서 2 시간 적하한 후, 추가로 환류 교반을 6 시간 실시하였다. 이어서, 톨루엔을 감압 제거함으로써, 노볼락형 에폭시아크릴레이트 C 를 얻었다.After dissolving 965 parts by weight of a phenol novolak-type epoxy compound (“EPICLON N-770” manufactured by DIC) in 2500 ml of toluene, 0.5 parts by weight of triphenylphosphine was added to obtain a uniform solution. 432 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux and stirring for 2 hours, and then reflux and stirring were further performed for 6 hours. Next, toluene was removed under reduced pressure to obtain novolak-type epoxy acrylate C.
또한, 얻어진 노볼락형 에폭시아크릴레이트 C 의 구조는, 1H-NMR, 13C-NMR, 및 FT-IR 에 의해 확인하였다.In addition, the structure of the obtained novolak-type epoxy acrylate C was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
또, 얻어진 노볼락형 에폭시아크릴레이트 C 의 중량 평균 분자량은 2700 이었다.Additionally, the weight average molecular weight of the obtained novolak-type epoxy acrylate C was 2700.
(식 (2-1) 로 나타내는 화합물의 제조)(Preparation of compound represented by formula (2-1))
2-(카르복시메톡시)-9H-티오크산텐-9-온 87 중량부와, 단관능 에폭시 화합물로서 p-tert-부틸페닐글리시딜에테르 (ADEKA 사 제조, 「ED-509S」) 62 중량부를, 염기성 촉매의 존재하에서, 110 ℃ 에서 48 시간 교반하면서 반응시킴으로써, 상기 식 (2-1) 로 나타내는 화합물을 얻었다. 염기성 촉매로는, PS-PPh3 (바이오타지·재팬사 제조, 폴리스티렌 (PS) 에 트리페닐포스핀을 담지한 염기성 촉매) 5.2 중량부를 사용하였다.87 parts by weight of 2-(carboxymethoxy)-9H-thioxanthen-9-one, and 62 parts by weight of p-tert-butylphenylglycidyl ether (manufactured by ADEKA, “ED-509S”) as a monofunctional epoxy compound. The compound represented by the above formula (2-1) was obtained by reacting the reaction mixture in the presence of a basic catalyst at 110°C with stirring for 48 hours. As a basic catalyst, 5.2 parts by weight of PS-PPh 3 (manufactured by Biotage Japan, a basic catalyst carrying triphenylphosphine on polystyrene (PS)) was used.
또한, 얻어진 상기 식 (2-1) 로 나타내는 화합물의 구조는, 1H-NMR, 13C-NMR, 및 FT-IR 에 의해 확인하였다.In addition, the structure of the obtained compound represented by the formula (2-1) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
또, 2-(카르복시메톡시)-9H-티오크산텐-9-온과 p-tert-부틸페닐글리시딜에테르의 배합 비율은, 몰비로, 2-(카르복시메톡시)-9H-티오크산텐-9-온 : p-tert-부틸페닐글리시딜에테르 = 1 : 1 이다.In addition, the mixing ratio of 2-(carboxymethoxy)-9H-thioxanthen-9-one and p-tert-butylphenylglycidyl ether is 2-(carboxymethoxy)-9H-thioc in molar ratio. Santhen-9-one: p-tert-butylphenylglycidyl ether = 1:1.
(식 (2-2) 로 나타내는 화합물의 제조)(Preparation of compound represented by formula (2-2))
2-하이드록시-9H-티오크산텐-9-온 69 중량부와, 단관능 에폭시 화합물로서 p-tert-부틸페닐글리시딜에테르 (ADEKA 사 제조, 「ED-509S」) 62 중량부를, 염기성 촉매의 존재하에서, 110 ℃ 에서 48 시간 교반하면서 반응시킴으로써, 상기 식 (2-2) 로 나타내는 화합물을 얻었다. 염기성 촉매로는, PS-PPh3 (바이오타지·재팬사 제조, 폴리스티렌 (PS) 에 트리페닐포스핀을 담지한 염기성 촉매) 5.2 중량부를 사용하였다.69 parts by weight of 2-hydroxy-9H-thioxanthen-9-one and 62 parts by weight of p-tert-butylphenylglycidyl ether (manufactured by ADEKA, “ED-509S”) as a monofunctional epoxy compound were added as a basic The compound represented by the above formula (2-2) was obtained by reacting in the presence of a catalyst while stirring at 110°C for 48 hours. As a basic catalyst, 5.2 parts by weight of PS-PPh 3 (manufactured by Biotage Japan, a basic catalyst carrying triphenylphosphine on polystyrene (PS)) was used.
또한, 얻어진 상기 식 (2-2) 로 나타내는 화합물의 구조는, 1H-NMR, 13C-NMR, 및 FT-IR 에 의해 확인하였다.In addition, the structure of the obtained compound represented by the formula (2-2) was confirmed by 1 H-NMR, 13 C-NMR, and FT-IR.
또, 2-하이드록시-9H-티오크산텐-9-온과 p-tert-부틸페닐글리시딜에테르의 배합 비율은, 몰비로, 2-하이드록시-9H-티오크산텐-9-온 : p-tert-부틸페닐글리시딜에테르 = 1 : 1 이다.In addition, the mixing ratio of 2-hydroxy-9H-thioxanthen-9-one and p-tert-butylphenylglycidyl ether is, in molar ratio, 2-hydroxy-9H-thioxanthen-9-one: p-tert-butylphenylglycidyl ether = 1:1.
(실시예 1 ∼ 9 및 비교예 1 ∼ 4)(Examples 1 to 9 and Comparative Examples 1 to 4)
표 1, 2 에 기재된 배합비에 따라, 각 재료를 유성식 교반기 (싱키사 제조, 「아와토리 렌타로」) 를 사용하여 혼합한 후, 추가로 3 본롤을 사용하여 혼합함으로써 실시예 1 ∼ 9 및 비교예 1 ∼ 4 의 액정 표시 소자용 시일제를 조제하였다.According to the mixing ratios shown in Tables 1 and 2, each material was mixed using a planetary stirrer (manufactured by Shinki, “Awatori Rentaro”), and then mixed using 3 bone rolls to obtain Examples 1 to 9 and The sealing compound for liquid crystal display elements of Comparative Examples 1 to 4 was prepared.
<평가><Evaluation>
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제에 대해 이하의 평가를 실시하였다. 결과를 표 1, 2 에 나타냈다.The following evaluation was performed on each sealing agent for liquid crystal display elements obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.
(도포성)(Applicability)
디스펜서 (무사시 엔지니어링사 제조, 「SHOTMASTER300」) 를 사용하고, 디스펜스 노즐을 400 ㎛, 노즐 갭을 30 ㎛, 토출압을 300 ㎪ 로 고정시키고, 유리 기판 상에 실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제를 도포하였다. 긁힘이나 흐름이 없이 도포할 수 있었던 것을 「○」, 약간 긁힘이나 흐름이 발생한 것을 「△」, 큰 도포 갈라짐이나 도포 불균일이 발생하거나, 전혀 도포할 수 없거나 한 것을 「×」로 하여 도포성을 평가하였다.Using a dispenser (“SHOTMASTER300” manufactured by Musashi Engineering Co., Ltd.), the dispensing nozzle was fixed to 400 μm, the nozzle gap was fixed to 30 μm, and the discharge pressure was fixed to 300 kPa, and each liquid crystal display obtained in the examples and comparative examples was displayed on a glass substrate. A sealant for the device was applied. The applicability rating is given as “○” when the product was able to be applied without scratches or bleeding, “△” when there were slight scratches or leaks, and “×” when there were major cracks in the application, uneven application, or the product could not be applied at all. evaluated.
(광경화성)(Gwanggyeong Hwaseong)
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제 100 중량부에 스페이서 미립자 (세키스이 화학 공업사 제조, 「마이크로펄 SI-H050」) 1 중량부를 분산시켰다. 이어서, 시일제를 디스펜스용의 실린지 (무사시 엔지니어링사 제조, 「PSY-10E」) 에 충전하고, 탈포 처리를 실시하고 나서, 디스펜서 (무사시 엔지니어링사 제조, 「SHOTMASTER300」) 로 유리 기판 상에 도포하였다. 그 기판에 진공 첩합 장치로 5 ㎩ 의 감압하에서 동 사이즈의 유리 기판을 첩합하였다. 첩합한 유리 기판의 시일제 부분에 메탈할라이드 램프를 사용하여 100 ㎽/㎠ 의 광을 10 초 조사하였다. 광 조사는 400 ㎚ 컷 필터 없음의 경우와 400 ㎚ 컷 필터 있음의 경우의 2 패턴을 실시하였다.1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Industries, Ltd.) was dispersed in 100 parts by weight of each liquid crystal display device sealant obtained in the examples and comparative examples. Next, the sealant was filled into a dispensing syringe ("PSY-10E", manufactured by Musashi Engineering), subjected to defoaming treatment, and then applied on a glass substrate using a dispenser ("SHOTMASTER300", manufactured by Musashi Engineering). did. A glass substrate of the same size was bonded to the substrate under reduced pressure of 5 Pa using a vacuum bonding device. The sealing part of the bonded glass substrate was irradiated with 100 mW/cm2 light for 10 seconds using a metal halide lamp. Light irradiation was performed in two patterns: without a 400 nm cut filter and with a 400 nm cut filter.
적외 분광 장치 (BIORAD 사 제조, 「FTS3000」) 를 사용하여 시일제의 FT-IR 측정을 실시하고, (메트)아크릴로일기 유래 피크의 광 조사 전후에서의 변화량을 측정함으로써 경화성의 평가를 실시하였다. 광 조사 후에 (메트)아크릴로일기 유래의 피크가 95 % 이상 감소한 경우를 「◎」, 85 % 이상 95 % 미만 감소한 경우를 「○」, 75 % 이상 85 % 미만 감소한 경우를 「△」, 광 조사 후의 (메트)아크릴로일기 유래의 피크의 감소가 75 % 미만이었던 경우를 「×」로 하여 광경화성을 평가하였다.FT-IR measurement of the sealant was performed using an infrared spectroscopy device (“FTS3000” manufactured by BIORAD), and curability was evaluated by measuring the amount of change in the peak derived from the (meth)acryloyl group before and after light irradiation. . After light irradiation, “◎” indicates a decrease in the peak derived from the (meth)acryloyl group by more than 95%, “○” indicates a decrease of 85% to less than 95%, and “△” indicates a decrease of 75% to less than 85%. Photocurability was evaluated by setting the case where the decrease in the peak derived from the (meth)acryloyl group after irradiation was less than 75% as "×".
(장기 점등시의 액정 표시 소자의 표시 성능)(Display performance of liquid crystal display element during long-term lighting)
실시예 및 비교예에서 얻어진 각 액정 표시 소자용 시일제 100 중량부에 스페이서 미립자 (세키스이 화학 공업사 제조, 「마이크로펄 SI-H050」) 1 중량부를 분산시켰다. 이어서, 시일제를 디스펜스용의 실린지 (무사시 엔지니어링사 제조, 「PSY-10E」) 에 충전하고, 탈포 처리를 실시하고 나서, 디스펜서 (무사시 엔지니어링사 제조, 「SHOTMASTER300」) 로, 2 장의 ITO 박막이 부착된 투명 전극 기판의 일방에 시일제를 프레임상으로 도포하였다. 계속해서, TN 액정 (칫소사 제조, 「JC-5001LA」) 의 미소적을 액정 적하 장치로 시일제의 프레임 내에 적하 도포하고, 진공 첩합 장치로 5 ㎩ 의 감압하에서 타방의 투명 전극 기판을 첩합하였다. 첩합한 투명 전극 기판의 시일제 부분에 메탈할라이드 램프를 사용하여 100 ㎽/㎠ 의 자외선을 400 ㎚ 컷 필터를 개재하여 10 초 조사한 후, 120 ℃ 에서 1 시간 가열하여 시일제를 경화시키고, 액정 표시 소자를 얻었다.1 part by weight of spacer fine particles ("Micropearl SI-H050", manufactured by Sekisui Chemical Industries, Ltd.) was dispersed in 100 parts by weight of each liquid crystal display device sealant obtained in the examples and comparative examples. Next, the sealant was filled into a dispensing syringe ("PSY-10E", manufactured by Musashi Engineering Co., Ltd.), and after performing a defoaming treatment, two ITO thin films were dispensed with a dispenser ("SHOTMASTER300", manufactured by Musashi Engineering Co., Ltd.). A sealant was applied in the form of a frame to one side of the attached transparent electrode substrate. Subsequently, microdroplets of TN liquid crystal (manufactured by Chisso Corporation, "JC-5001LA") were applied dropwise into the frame of the sealant using a liquid crystal dropping device, and the other transparent electrode substrate was bonded together under reduced pressure of 5 Pa using a vacuum bonding device. The sealing agent portion of the bonded transparent electrode substrate is irradiated with ultraviolet rays of 100 mW/cm2 for 10 seconds through a 400 nm cut filter using a metal halide lamp, and then heated at 120°C for 1 hour to cure the sealant, thereby producing a liquid crystal display. I got a small object.
얻어진 액정 표시 소자에 대해, 85 ℃ 85 %RH 의 환경하에서 100 시간 전압 인가 상태로 하면서 백색 LED 램프를 사용하여 광을 계속 점등한 후, 표시 불균일의 정도를 육안에 의해 확인하였다.With respect to the obtained liquid crystal display element, light was continuously turned on using a white LED lamp while voltage was applied for 100 hours in an environment of 85°C and 85%RH, and then the degree of display unevenness was confirmed with the naked eye.
액정 표시 소자에 표시 불균일이 전혀 확인되지 않았던 경우를 「◎」, 주변부에 조금 얇은 표시 불균일이 확인된 경우를 「○」, 주변부에 확실한 진한 표시 불균일이 확인된 경우를 「△」, 확실한 진한 표시 불균일이 주변부뿐만 아니라, 중앙부까지 확장되어 있었던 경우를 「×」로 하여 액정 표시 소자의 표시 성능을 평가하였다.“◎” indicates a case in which no display unevenness is confirmed on the liquid crystal display element, “○” indicates a slightly thin display unevenness in the peripheral area, and “△” indicates a clear dark display unevenness in the peripheral area, and a certain dark display. The display performance of the liquid crystal display element was evaluated by setting the case where the unevenness extended not only to the periphery but also to the center as “×”.
또한, 평가가 「◎」, 「○」인 액정 표시 소자는, 실용에 전혀 문제가 없는 레벨이고, 「△」는 액정 표시 소자의 표시 설계에 의해 문제가 될 가능성이 있는 레벨이며, 「×」는 실용에 견딜 수 없는 레벨이다.In addition, liquid crystal display elements with evaluations of “◎” and “○” are levels that pose no problems in practical use, “△” are levels that may cause problems depending on the display design of the liquid crystal display elements, and “×” is a level that is unbearable for practical use.
본 발명에 의하면, 도포성 및 장파장의 광에 대한 경화성이 우수하고, 또한, 액정 표시 소자를 장기 점등했을 때의 표시 불량을 억제할 수 있는 액정 표시 소자용 시일제를 제공할 수 있다. 또, 본 발명에 의하면, 그 액정 표시 소자용 시일제를 사용하여 이루어지는 상하 도통 재료 및 액정 표시 소자를 제공할 수 있다.According to the present invention, it is possible to provide a sealing agent for a liquid crystal display element that is excellent in applicability and curability to long-wavelength light, and can suppress display defects when the liquid crystal display element is illuminated for a long period of time. Moreover, according to this invention, a vertical conduction material and a liquid crystal display element formed using the sealing agent for liquid crystal display elements can be provided.
Claims (8)
상기 경화성 수지는, 중량 평균 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물을 함유하고,
상기 중량 평균 분자량이 700 이상 2000 이하인 (메트)아크릴 화합물은, 노볼락형의 (메트)아크릴 화합물이고,
상기 광중합 개시제는, 하기 식 (1) 로 나타내는 구조를 갖는 화합물을 함유하는 것을 특징으로 하는 액정 표시 소자용 시일제.
식 (1) 중, * 는, 결합 위치이다.Contains a curable resin and a photopolymerization initiator,
The curable resin contains a (meth)acrylic compound having a weight average molecular weight of 700 or more and 2000 or less,
The (meth)acrylic compound having a weight average molecular weight of 700 or more and 2000 or less is a novolak-type (meth)acrylic compound,
The said photopolymerization initiator contains the compound which has a structure shown by following formula (1), A sealing agent for liquid crystal display elements characterized by the above-mentioned.
In formula (1), * is a binding position.
상기 식 (1) 로 나타내는 구조를 갖는 화합물은, 1 분자 중에 1 개의 상기 식 (1) 로 나타내는 구조를 갖는 화합물인 액정 표시 소자용 시일제.According to claim 1,
The compound having a structure represented by the formula (1) is a sealing agent for liquid crystal display elements that is a compound having one structure represented by the formula (1) in one molecule.
상기 식 (1) 로 나타내는 구조를 갖는 화합물은, 하기 식 (2-1) 로 나타내는 화합물 및/또는 하기 식 (2-2) 로 나타내는 화합물인 액정 표시 소자용 시일제.
식 (2-1), (2-2) 중, R 은, 단관능 에폭시 화합물에서 유래되는 구조이다.According to claim 2,
The compound having a structure represented by the above formula (1) is a sealing agent for liquid crystal display elements that is a compound represented by the following formula (2-1) and/or a compound represented by the following formula (2-2).
In formulas (2-1) and (2-2), R is a structure derived from a monofunctional epoxy compound.
상기 식 (1) 로 나타내는 구조를 갖는 화합물은, 1 분자 중에 2 개 이상의 상기 식 (1) 로 나타내는 구조를 갖는 화합물인 액정 표시 소자용 시일제.According to claim 1,
The compound having a structure represented by the formula (1) is a sealing agent for liquid crystal display elements that is a compound having two or more structures represented by the formula (1) in one molecule.
상기 식 (1) 로 나타내는 구조를 갖는 화합물은, 하기 식 (3) 으로 나타내는 화합물인 액정 표시 소자용 시일제.
식 (3) 중, n 은, 1 ∼ 10 (평균값) 이다.According to claim 4,
The compound having a structure represented by the formula (1) is a sealing agent for liquid crystal display elements that is a compound represented by the following formula (3).
In formula (3), n is 1 to 10 (average value).
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KR102588717B1 (en) * | 2015-06-02 | 2023-10-12 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
JP2017149794A (en) * | 2016-02-22 | 2017-08-31 | 三井化学株式会社 | Photocurable resin composition, display element sealant, liquid crystal sealant and liquid crystal display panel |
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WO2017104391A1 (en) * | 2015-12-17 | 2017-06-22 | 三井化学株式会社 | Photocurable resin composition, display element sealing agent, liquid crystal sealing agent, and liquid crystal display panel and method for producing same |
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CN110168442B (en) | 2022-06-28 |
CN110168442A (en) | 2019-08-23 |
KR20200032026A (en) | 2020-03-25 |
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JPWO2019013065A1 (en) | 2020-05-07 |
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WO2019013065A1 (en) | 2019-01-17 |
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