CN104031082A - Novel thermal radical generator, method for producing the same, liquid crystal sealing agent, and liquid crystal display cell - Google Patents
Novel thermal radical generator, method for producing the same, liquid crystal sealing agent, and liquid crystal display cell Download PDFInfo
- Publication number
- CN104031082A CN104031082A CN201410239409.9A CN201410239409A CN104031082A CN 104031082 A CN104031082 A CN 104031082A CN 201410239409 A CN201410239409 A CN 201410239409A CN 104031082 A CN104031082 A CN 104031082A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- hydrogen atom
- sealing agent
- agent
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 245
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 253
- 238000007789 sealing Methods 0.000 title abstract description 189
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 48
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical class C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 39
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 37
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 13
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 9
- -1 methoxyl group Chemical group 0.000 claims description 95
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000009998 heat setting Methods 0.000 claims description 14
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 11
- RUGHUJBHQWALKM-UHFFFAOYSA-N 1,2,2-triphenylethylbenzene Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C(C=1C=CC=CC=1)C1=CC=CC=C1 RUGHUJBHQWALKM-UHFFFAOYSA-N 0.000 claims description 10
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 9
- 239000006260 foam Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 description 104
- 229920000647 polyepoxide Polymers 0.000 description 104
- 238000001723 curing Methods 0.000 description 39
- 150000003254 radicals Chemical class 0.000 description 39
- 150000001875 compounds Chemical class 0.000 description 33
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 29
- 239000000203 mixture Substances 0.000 description 27
- 239000000853 adhesive Substances 0.000 description 26
- 230000001070 adhesive effect Effects 0.000 description 26
- 150000002148 esters Chemical class 0.000 description 25
- 239000000758 substrate Substances 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 23
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 22
- 238000001029 thermal curing Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 19
- 210000002858 crystal cell Anatomy 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 239000007822 coupling agent Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000005187 foaming Methods 0.000 description 15
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 15
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 14
- 239000011256 inorganic filler Substances 0.000 description 14
- 229910003475 inorganic filler Inorganic materials 0.000 description 14
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 description 13
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 13
- 239000012766 organic filler Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- 125000005103 alkyl silyl group Chemical group 0.000 description 9
- 229940106691 bisphenol a Drugs 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000004880 explosion Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229940059574 pentaerithrityl Drugs 0.000 description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 9
- 238000010030 laminating Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 238000002444 silanisation Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- DTRIDVOOPAQEEL-UHFFFAOYSA-N 4-sulfanylbutanoic acid Chemical class OC(=O)CCCS DTRIDVOOPAQEEL-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RQPNXPWEGVCPCX-UHFFFAOYSA-N 3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O RQPNXPWEGVCPCX-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical class C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 3
- FZFFWZJDHRTEMQ-UHFFFAOYSA-N 1,1,2,2-tetraphenyl-2-trimethylsilyloxyethanol Chemical compound OC(C(C1=CC=CC=C1)(C1=CC=CC=C1)O[Si](C)(C)C)(C1=CC=CC=C1)C1=CC=CC=C1 FZFFWZJDHRTEMQ-UHFFFAOYSA-N 0.000 description 3
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- QSBINWBNXWAVAK-PSXMRANNSA-N PE-NMe(16:0/16:0) Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OCCNC)OC(=O)CCCCCCCCCCCCCCC QSBINWBNXWAVAK-PSXMRANNSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000008062 acetophenones Chemical class 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 3
- 150000001343 alkyl silanes Chemical class 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229940117927 ethylene oxide Drugs 0.000 description 3
- 229960005082 etohexadiol Drugs 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003509 tertiary alcohols Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- UXQJPXLJOJIFOK-UHFFFAOYSA-N 1-ethylbenzo[a]anthracene Chemical compound C1=CC=CC2=CC3=C4C(CC)=CC=CC4=CC=C3C=C21 UXQJPXLJOJIFOK-UHFFFAOYSA-N 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 206010018612 Gonorrhoea Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- XCOBLONWWXQEBS-KPKJPENVSA-N N,O-bis(trimethylsilyl)trifluoroacetamide Chemical compound C[Si](C)(C)O\C(C(F)(F)F)=N\[Si](C)(C)C XCOBLONWWXQEBS-KPKJPENVSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- DGXRZJSPDXZJFG-UHFFFAOYSA-N docosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCC(O)=O DGXRZJSPDXZJFG-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 1
- PBPRZRZXNXUAEJ-UHFFFAOYSA-N 1,2-bis(sulfanyl)butane-1,3-diol Chemical compound CC(O)C(S)C(O)S PBPRZRZXNXUAEJ-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- YGKHJWTVMIMEPQ-UHFFFAOYSA-N 1,2-propanedithiol Chemical compound CC(S)CS YGKHJWTVMIMEPQ-UHFFFAOYSA-N 0.000 description 1
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- DJNJZIFFCJTUDS-UHFFFAOYSA-N 1-phenyldodecan-1-one Chemical compound CCCCCCCCCCCC(=O)C1=CC=CC=C1 DJNJZIFFCJTUDS-UHFFFAOYSA-N 0.000 description 1
- NRKYWOKHZRQRJR-UHFFFAOYSA-N 2,2,2-trifluoroacetamide Chemical class NC(=O)C(F)(F)F NRKYWOKHZRQRJR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CNDCQWGRLNGNNO-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanethiol Chemical compound SCCOCCS CNDCQWGRLNGNNO-UHFFFAOYSA-N 0.000 description 1
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 description 1
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- AJHCCBBKTPDSNT-UHFFFAOYSA-N 2-ethyl-2-(sulfanylmethyl)propane-1,3-dithiol Chemical compound CCC(CS)(CS)CS AJHCCBBKTPDSNT-UHFFFAOYSA-N 0.000 description 1
- HEACGLNJHDPMNR-UHFFFAOYSA-N 2-methylprop-2-enoic acid;zirconium Chemical compound [Zr].CC(=C)C(O)=O HEACGLNJHDPMNR-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- XRNVNMBOTWXTPZ-UHFFFAOYSA-N C(CO)(=O)NC(=O)N.NC(C(=O)O)C(C)C Chemical group C(CO)(=O)NC(=O)N.NC(C(=O)O)C(C)C XRNVNMBOTWXTPZ-UHFFFAOYSA-N 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- PQOFXNCKCJDYOS-UHFFFAOYSA-N C[Si+](C)(C)OC(C(c1ccccc1)(c1ccccc1)O)(c1ccccc1)c1ccccc1 Chemical compound C[Si+](C)(C)OC(C(c1ccccc1)(c1ccccc1)O)(c1ccccc1)c1ccccc1 PQOFXNCKCJDYOS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WPYCRFCQABTEKC-UHFFFAOYSA-N Diglycidyl resorcinol ether Chemical group C1OC1COC(C=1)=CC=CC=1OCC1CO1 WPYCRFCQABTEKC-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 208000031481 Pathologic Constriction Diseases 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- MFPROKIABJECGK-UHFFFAOYSA-K aluminum;2-methylprop-2-enoate Chemical compound [Al+3].CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O MFPROKIABJECGK-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000011324 bead Substances 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
- 230000005540 biological transmission Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- MGZLGROFYWKSCQ-UHFFFAOYSA-N butane-1,2,3-trithiol Chemical compound CC(S)C(S)CS MGZLGROFYWKSCQ-UHFFFAOYSA-N 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HXLVDKGPVGFXTH-UHFFFAOYSA-N butyl(dimethyl)silane Chemical group CCCC[SiH](C)C HXLVDKGPVGFXTH-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 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 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000013033 iniferter Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- RJWUMFHQJJBBOD-UHFFFAOYSA-N isooctadecane Natural products CCCCCCCCCCCCCCCC(C)C RJWUMFHQJJBBOD-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 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
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- RYDVBNBVYVMEDT-UHFFFAOYSA-N n-carbamoyl-2-hydroxyacetamide Chemical group NC(=O)NC(=O)CO RYDVBNBVYVMEDT-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- AHBPBADERZDJKT-UHFFFAOYSA-N pentane-2,3-dione zirconium Chemical compound [Zr].C(C)C(=O)C(=O)C AHBPBADERZDJKT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- HMPSOEYFMTWOFC-UHFFFAOYSA-N propane-2,2-dithiol Chemical compound CC(C)(S)S HMPSOEYFMTWOFC-UHFFFAOYSA-N 0.000 description 1
- KCXHUOHMDNFBDO-UHFFFAOYSA-N propane;trithiole Chemical compound CCC.S1SC=CS1 KCXHUOHMDNFBDO-UHFFFAOYSA-N 0.000 description 1
- UADUAXMDVVGCGW-UHFFFAOYSA-N propanoic acid;zirconium Chemical compound [Zr].CCC(O)=O UADUAXMDVVGCGW-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000036262 stenosis Effects 0.000 description 1
- 208000037804 stenosis Diseases 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WGLLSSPDPJPLOR-UHFFFAOYSA-N tetramethylethylene Natural products CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 1
- 230000035924 thermogenesis Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Sealing Material Composition (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Epoxy Resins (AREA)
Abstract
Provided are a tetraphenylethane derivative represented by general formula (1), a method for producing the same, the use of the tetraphenylethane derivative as a radical generator, a liquid crystal sealing agent containing the tetraphenylethane derivative, and a thermosetting liquid crystal sealing agent for the one-drop fill process in particular. The radical generator does not foam and has excellent thermal radical generating performance, and, when used with a liquid crystal sealing agent, the resulting liquid crystal sealing agent does not contaminate liquid crystals, has a long pot life, and performs well in terms of forming a seal and forming a cell gap. (1) Y1 and Y2 in general formula (1) are each independently a hydrogen atom, phenyl, or silicon atom, R1 through R6 are each independently a hydrogen atom or C1-4 linear or branched alkyl group, and X1 through X4 are each independently a hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, phenoxy group, or halogen group. R1 through R3 or R4 through R6 that bond with Y1 or Y2, respectively, are not present when Y1 or Y2 is a hydrogen atom, and Y1 and Y2 are not both hydrogen atoms.
Description
The application is to be the divisional application of November 12, application number in 2010 Chinese patent application that is 201080051849.1 the applying date.
Technical field
The present invention relates to novel silyl benzpinacone, its liquid crystal display that produces purposes, the liquid crystal sealing agent that comprises this novel silyl benzpinacone of agent and use this liquid crystal sealing agent as hot radical.
Background technology
In the past, as by free-radical polymerised compound heating is made to its radical polymerization and curing free-radical generating agent, known and use widely azo-compound, organo-peroxide, bitter almond oil camphor class, benzoin ethers, acetophenones, benzpinacone class etc.
The most easily produce azo-compound or the organo-peroxide of free radical by thermo-cracking, in the goods such as tackiness agent, sealing agent and gap forming agent, formed material, use as free-radical generating agent.But above-mentioned free-radical generating agent is accompanied by the generation of the gas such as nitrogen or carbonic acid gas in the time producing free radical, therefore there is the significantly worry of infringement said products characteristic of these gases.For example, as there being impaired possible characteristic, can enumerate: adhesive strength decline, high-temperature capability decline, molding shape defect etc.As other free-radical generating agent, can enumerate: bitter almond oil camphor class, benzoin ethers, acetophenones, benzpinacone class etc.Although the foaming in when heating is few in them, there is free-radical generating ability, cannot the obtain desired performance problem of (reactivity and solidified nature).
Open in patent documentation 1: using in ultraviolet ray and the hot system that both are cured, in order to make not solidified by the shadow part of illumination, to be used as hot radical to produce the benzpinacone of agent.Open in patent documentation 2 in addition: in the making of the moldings such as contact lens, various lens or dental material, the free-radical generating agent of iniferter agent type is that effectively its example can be enumerated benzpinacone.In patent documentation 3, the hot radical that the sealing agent of using as flat-panel monitor uses produces agent, has enumerated benzpinacone in addition.
In patent documentation 1 and 3, further enumerate the compound that benzpinacone obtains through chemically modified.Record the further desired effect of performance of this compound.But benzpinacone is the impact of the tertiary alcohol and its hydroxyl steric barrier that is subject to phenyl and reactive poor, and is obtaining still not reporting suitable material aspect stable derivative.
In addition, produce one of use field of agent as hot radical, can enumerate: the liquid crystal sealing agent that liquid crystal display is used.
Along with the maximization of liquid crystal display, in recent years, as the manufacture method of liquid crystal display, introduce production than the higher liquid crystal drop method of manufacture method of the liquid crystal display of liquid crystal vacuum injection mode in the past, thereby carried out the manufacture (referring to Patent Document 4) of large-scale liquid crystal display.Liquid crystal drop method refers to, on crystal liquid substrate, coating forms the weir dike (primary seal) of liquid crystal sealing agent, be coated with one week sealing agent (false sealing) at most peripheral again, then at the inner side of seal inside dropping liquid crystal, another crystal liquid substrate of then fitting relative in a vacuum, is released into normal atmosphere, makes thus sealing liquid crystal, and irradiate and heating is solidified sealing by UV, make thus the manufacture method of liquid crystal display.The liquid crystal sealing material that in this manufacture method, sealing liquid crystal uses, uses photo-thermal curing the liquid crystal sealing agent by type conventionally, instead of thermohardening type liquid crystal sealing agent in the past.The reason that the thermohardening type liquid crystal sealing agent (also referred to as thermoset liquid crystal sealing agent) in past cannot be used for liquid crystal drop method is, while implementing liquid crystal drop method with the thermohardening type liquid crystal sealing agent in past, under vacuum decompression, to heat, therefore can cause the thermal expansion of the liquid crystal while heating and heat by liquid crystal sealing agent the viscosity degradation causing, sealing explosion, thus cannot make sealing liquid crystal.
Photo-thermal curing is also used in the using method of liquid crystal sealing agent of type, the coating on crystal liquid substrate such as use spreader forms the weir dike of liquid crystal sealing agent, then at the inner side of this weir dike dropping liquid crystal, another substrate of fitting relative in a vacuum, then with rayed sealings such as ultraviolet rays, it is temporarily solidified, then under the condition of approximately 120 DEG C, approximately 1 hour, make liquid crystal sealing agent thermofixation, manufacture thus liquid crystal cells.
But photo-thermal curing with in the situation of type, must be to light such as liquid crystal sealing agent irradiation ultraviolet radiations, along with the narrow architrave of liquid crystal cells in recent years, produce following problem.
That is, sealing liquid crystal portion is connected up or black matrix" shading and produce the not part of light irradiation of liquid crystal sealing agent, thereby produces uncured portion.There is following problem: this uncured portion is subject to liquid crystal and infiltrates or occur liquid crystal pollution being heating and curing in step.Therefore, the restriction of generation is, must be so that sealing agent irradiates the mode of more light as far as possible designs in the time of design liquid crystal cells.In addition, make liquid crystal or the deteriorated problem of alignment films owing to producing uviolizing, therefore for making ultraviolet ray not be irradiated to liquid crystal, need to be in uviolizing step with shadow mask by the shading of liquid crystal portion.In addition, along with the maximization of liquid crystal glass base size, thus the problems such as the operating cost increase of generation UV irradiation equipment maximization UV irradiation equipment.
Due to above-mentioned situation, expect in recent years to realize in liquid crystal drop method, do not need uviolizing, and only just can make the thermohardening type liquid crystal sealing agent (liquid crystal drop method thermohardening type liquid crystal sealing agent) of liquid crystal display by thermofixation.
To so far, the motion of the thermohardening type liquid crystal sealing agent that liquid crystal drop method is used is in the middle of carrying out.For example, the value that in patent documentation 5, proposition obtains divided by molecular weight with respect to the hydrogen bonding functional group number in a molecule is 3.5 × 10
-4above curable resin 100 weight parts, the liquid crystal drop method thermofixation liquid crystal sealing agent that contains 3 to 40 weight part thermal curing agents.Openly to: by using this liquid crystal sealing agent to reach low liquid crystal pollution.But, use in the liquid crystal drop method of this thermohardening type liquid crystal sealing agent, be difficult to fully address the problem: the liquid crystal leakage thereby aforementioned weir dike because of the liquid crystal sealing agent in the solidification process of heating lowering viscousity breaks (problem of sealing explosion); And be difficult to fully solve following significant problem: because of the composition of the liquid crystal sealing agent of heating lowering viscousity, similarly due to more than being heated to NI point (being converted to the temperature of mesomorphic phase by isotropic phase), meeting stripping in more holding runny liquid crystal than usual, pollutes liquid crystal.
In addition, in patent documentation 6, propose, by being added with the liquid crystal sealing agent of gelating agent, in the liquid crystal drop method of only carrying out thermofixation, can realize resistance to sealing explosion, can keep sealing shape.But, and the pollution of liquid crystal sealing agent to liquid crystal when being heating and curing of the unresolved problem points as thermofixation liquid crystal drop method.
In patent documentation 7, propose to carry out after the liquid crystal sealing agent that formed by heat reactive resin of coating pre-baked, then carry out liquid crystal drippage, vacuum abutted manufacture method.But the resin that does not clearly disclose concrete liquid crystal sealing agent forms.
In patent documentation 8 and 9, propose to carry out the thermoset liquid crystal drop method liquid crystal sealing agent that pre-baked step was processed as the B stage (semi-cured state).The method need to be processed 80 DEG C of B stageizations of carrying out 20 minutes, therefore has long shortcoming of step time.In addition, in order to shorten the B treatment time in stage of 20 minutes, for example, while treatment temp being increased to more than 100 DEG C, the liquid crystal sealing agent of recording can be cured reaction, therefore not preferred.
In patent documentation 7, propose a kind of liquid crystal sealing agent, it is characterized in that, contain: thermo-cracking type free-radical generating agent, the heat-curable compounds that contains the compound with unsaturated double-bond and addition polymerization type thermal curing agents.And, wherein record the making of carrying out the liquid crystal display device of local UV irradiation in the normal atmosphere laminating of crystal liquid substrate.But, be not documented in and in the vacuum decompression laminating of crystal liquid substrate, do not carry out UV irradiation and only carry out the making of the liquid crystal display device of thermofixation.
As above cited, in liquid crystal drop method, also do not solve the heat-curing type liquid crystal drippage sealing agent of whole issue by thermosetting encapsulants, and not yet realize the liquid crystal drop method of only carrying out thermofixation.
In addition, strongly need to not increase the physical dimension of substrate in recent years and further increase display area.The design of the liquid crystal cells therefore, growing up is that the narrow narrow framework of sealing liquid crystal peripheral part stenosis or sealing liquid crystal width are attenuated etc.Result is to seek to form thin sealed width and sealing shape evenly and be difficult to liquid crystal sealing agent at random, and, even also strong liquid crystal sealing agent of thin its adhesive strength of sealed width.In addition, seeking the liquid crystal sealing agent that variation is little, the serviceable time (Port ッ ト ラ イ Off) is long of the coating condition of liquid crystal sealing agent within the activity duration.
In addition, universal along with LCD TV etc. in recent years, improves the high speed reactivity of liquid crystal for the broadcasting for film, and the cell gap (being filled with the gap of two plate bases of liquid crystal) of liquid crystal narrows gradually.Seeking in the time of vacuum abutted crystal liquid substrate, can easily reach the liquid crystal sealing agent of narrow cell gap.
In addition, for the requirement of high life of liquid crystal cells, deteriorated the become problem of sealing liquid crystal under super-humid conditions.Seeking the deteriorated little liquid crystal sealing agent of the adhesive strength of sealing liquid crystal after high temperature and humidity test.
As mentioned above, seeking following liquid crystal drop method thermoset liquid crystal sealing agent: can realize thermohardening type liquid crystal drop method, can be because heating produces sealing explosion in substrate vacuum abutted, and there is no a liquid crystal pollution, adhesive strength after adhesive strength and humidity test is strong, sealing coating is good, and the lower serviceable time of room temperature is long, easily reaches narrow cell gap.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 57-53508 communique
Patent documentation 2: Japanese kokai publication hei 11-21304 communique
Patent documentation 3: TOHKEMY 2006-10870 communique
Patent documentation 4: Japanese Patent Publication 8-20627 communique
Patent documentation 5: No. 3955038 communique of Japanese Patent
Patent documentation 6: No. 3976749 communique of Japanese Patent
Patent documentation 7: TOHKEMY 2005-92043 communique
Patent documentation 8: TOHKEMY 2007-199710 communique
Patent documentation 9: TOHKEMY 2007-224117 communique
Summary of the invention
The present invention is in view of aforementioned background art, and the first object of the present invention is, does not foam and active higher Novel hot free-radical generating agent when exploitation heating.
In addition, the second object of the present invention is, a kind of thermoset liquid crystal sealing agent that does not need the liquid crystal drop method of uviolizing to use is provided.The second object of the present invention is further, provides that liquid crystal pollution is low, adhesive strength after adhesive strength and humidity test is strong, canned linear is good, the lower serviceable time of room temperature long, can easily reach the liquid crystal drop method thermohardening type liquid crystal sealing agent (below also referred to as liquid crystal drop method thermoset liquid crystal sealing agent) of narrow cell gap.
The inventor has carried out conscientiously research in order to solve above-mentioned problem, found that, by making can have on phenyl ring at least one silicol of substituent benzpinacone, can obtain heating time, do not foam and active higher Novel hot free-radical generating agent, and, by using this hot radical to produce agent, can obtain the liquid crystal drop method thermoset liquid crystal sealing agent of aforementioned object, and complete the present invention.
, the present invention relates to following (1) to (20).
(1) the tetraphenyl ethane derivative that following general formula (1 ') represents,
In formula, Y
1 'or Y
2 'represent independently of one another hydrogen atom or Siliciumatom, R
1to R
6represent independently of one another the straight or branched alkyl of hydrogen atom or carbonatoms 1 to 4, X
1to X
4represent independently of one another hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group, phenoxy group or halogen group; Wherein, respectively with Y
1 'or Y
2 'in conjunction with R
1to R
3or R
4to R
6, at Y
1 'or Y
2 'during for hydrogen atom, do not exist, and get rid of Y
1 'and Y
2 'for the situation of hydrogen atom, and, Y got rid of
1 'and Y
2 'for Siliciumatom, R
1to R
6be all methyl, X
1to X
4it is all the situation of hydrogen atom.
(2) the tetraphenyl ethane derivative as described in above-mentioned (1), wherein, Y in general formula (1 ')
1 'or Y
2 'in any one be hydrogen atom, another one represents Siliciumatom, in the situation of Siliciumatom, R
1r
2r
3y
1 '-or R
4r
5r
6y
2 '-be two (the straight or branched alkyl of carbonatoms 1 to 4) silyl or three (the straight or branched alkyl of carbonatoms 1 to 4) silyl, X
1to X
4be hydrogen atom.
(3) the tetraphenyl ethane derivative as described in above-mentioned (1) or (2), wherein, Y in general formula (1 ')
1 'or Y
2 'in any one be hydrogen atom, another one represents Siliciumatom, in the situation of Siliciumatom, R
1r
2r
3y
1 '-or R
4r
5r
6y
2 '-be trimethyl silyl, triethylsilyl or t-butyldimethylsilyl, X
1to X
4be hydrogen atom.
(4) the tetraphenyl ethane derivative described in any one in above-mentioned (1) to (3), it is 1-hydroxyl-2-trimethylsiloxy-1 that following formula (2) represents, 1,2,2-tetraphenyl ethane
(5) a liquid crystal drop method thermoset liquid crystal sealing agent, is characterized in that, contains:
(a) the tetraphenyl ethane derivative that following general formula (1) represents;
(b) any one in (methyl) vinylformic acid affixture of epoxy resin or epoxy resin or both;
(c) thermal curing agents; And
(d) inorganic filler,
In formula, Y
1or Y
2represent independently of one another hydrogen atom, phenyl or Siliciumatom, R
1to R
6represent independently of one another the straight or branched alkyl of hydrogen atom or carbonatoms 1 to 4, X
1to X
4represent independently of one another hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group, phenoxy group or halogen atom; Wherein, respectively with Y
1or Y
2in conjunction with R
1to R
3or R
4to R
6, at Y
1or Y
2during for hydrogen atom, do not exist, and get rid of Y
1and Y
2be the situation of hydrogen atom.
(6) liquid crystal sealing agent as described in above-mentioned (5), wherein, (a) the tetraphenyl ethane derivative of general formula (1) is the tetraphenyl ethane derivative described in any one in above-mentioned (1) to (4) or aftermentioned (20).
(7) liquid crystal sealing agent as described in above-mentioned (5) or (6), wherein, (a) the tetraphenyl ethane derivative of general formula (1) is the pressed powder below median size 5 μ m.
(8) liquid crystal sealing agent as described in any one in above-mentioned (5) to (7), wherein, (c) thermal curing agents is that fusing point or softening temperature are 100 DEG C of above latent curing agents.
(9) liquid crystal sealing agent as described in any one in above-mentioned (5) to (8), wherein, (d) inorganic filler is aluminum oxide and/or silicon-dioxide.
(10) liquid crystal sealing agent as described in any one in above-mentioned (5) to (9), wherein, (d) median size of inorganic filler is 10 to 2000nm.
(11) liquid crystal sealing agent as described in any one in above-mentioned (5) to (10), is characterized in that, contains (e) curing catalyst.
(12) liquid crystal sealing agent as described in any one in above-mentioned (5) to (11), is characterized in that, contains (f) coupling agent.
(13) liquid crystal sealing agent as described in any one in above-mentioned (5) to (12), wherein, with respect to the total amount of liquid crystal sealing agent, the tetraphenyl ethane derivative that contains (a) general formula (1) with the scope of 0.1 to 10 quality %; With respect to the total amount of liquid crystal sealing agent, (methyl) vinylformic acid affixture that contains (b) epoxy resin and/or epoxy resin with the scope of 30 to 75 quality %; With respect to (b) composition 100 mass parts, contain (c) thermal curing agents with the scope of 5 to 60 mass parts; And with respect to the total amount of liquid crystal sealing agent, contain (d) inorganic filler with the scope of 1 to 30 quality %.
(14) liquid crystal sealing agent as described in any one in above-mentioned (5) to (13), is characterized in that, contains:
(a) tetraphenyl ethane derivative, in general formula (1), Y
1or Y
2in any one be hydrogen atom, another one represents Siliciumatom, in the situation of Siliciumatom, R
1r
2r
3y
1-or R
4r
5r
6y
2-be two (the straight or branched alkyl of carbonatoms 1 to 4) silyl or three (the straight or branched alkyl of carbonatoms 1 to 4) silyl, X
1to X
4be hydrogen atom;
(b) any one in (methyl) vinylformic acid affixture of epoxy resin or epoxy resin or both;
(c) latent curing agent, its for thermal curing agents and fusing point or softening temperature be more than 100 DEG C;
(d) inorganic filler; And
(e) curing catalyst or (f) any one in coupling agent or both.
(15) liquid crystal display, is sealed and is obtained by the cured article of the liquid crystal sealing agent described in any one in above-mentioned (5) to (14).
(16) free-radical generating agent, its tetraphenyl ethane derivative that comprises above-mentioned (5) described general formula (1) is as effective constituent.
(17) the tetraphenyl ethane derivative of the general formula (1) described in above-mentioned (5) is as the purposes of the free-radical generating agent above-mentioned (16) Suo Shu, and it is for the manufacture of thermoset liquid crystal sealing agent.
(18) cured article, by obtaining the radically curing resin combination thermofixation of the tetraphenyl ethane derivative that comprises general formula (1) above-mentioned (5) Suo Shu.
(19) manufacture method for the tetraphenyl ethane derivative that following formula (1 ') represents, its benzpinacone that following general formula (3) is represented reacts with silylating agent,
In formula (1 '), Y
1 'or Y
2 'represent independently of one another hydrogen atom or Siliciumatom, R
1to R
6represent independently of one another the straight or branched alkyl of hydrogen atom or carbonatoms 1 to 4, X
1to X
4represent independently of one another hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group, phenoxy group or halogen group; Wherein, respectively with Y
1 'or Y
2 'in conjunction with R
1to R
3or R
4to R
6, at Y
1 'or Y
2 'during for hydrogen atom, do not exist, and get rid of Y
1 'and Y
2 'be the situation of hydrogen atom,
In formula (3), X
1to X
4represent independently of one another hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group, phenoxy group or halogen group.
(20) the tetraphenyl ethane derivative as described in above-mentioned (1), wherein, Y in general formula (1 ')
1 'or Y
2 'in any one be hydrogen atom, another one is Siliciumatom, in the situation of Siliciumatom, R
1to R
3or R
4to R
6be the straight or branched alkyl of carbonatoms 1 to 4 independently of one another.
Invention effect
The tetraphenyl ethane derivative (also referred to as benzpinacone derivative) that general formula used in the present invention (1) represents, useful as hot radical generation agent, it does not foam in the time of heating, and can improve speed of response.Therefore, hot radical as the deteriorated worry of the physical property not caused by foaming produces agent, can be widely used in various uses, the such as manufacture of tackiness agent, sealing agent and gap forming agent, shaped material etc., can obtain the good goods of physical property (solidifying physical property, adhesive strength, shape stability etc.).Especially, it is good that the hot radical that the thermoset liquid crystal sealing agent using as liquid crystal drop method is used produces agent.
The above-mentioned tetraphenyl ethane derivative that general formula used in the present invention (1) is represented produces as hot radical the thermoset liquid crystal sealing agent that agent is used, most suitable as the thermoset liquid crystal sealing agent that does not need the liquid crystal drop method of sealing liquid crystal portion irradiation ultraviolet radiation to use (below also referred to as liquid crystal sealing agent of the present invention).The advantageous properties such as this liquid crystal sealing agent has that liquid crystal pollution is low, adhesive strength after adhesive strength and humidity test is strong, canned linear is good, at room temperature the serviceable time is long, therefore can easily manufacture the liquid crystal cells of narrow cell gap.As a result, liquid crystal display that can fabrication yield is high, reliability is high, quality is high.In addition, by the liquid crystal display of the present invention of the cured article sealing of liquid crystal sealing agent of the present invention, the demonstration causing without liquid crystal pollution is bad, and tackiness, moisture-proof reliability are good.
In addition, the tetraphenyl ethane derivative that aforementioned formula (1 ') represents is the novel cpd being synthesized by the inventor.
Brief description of the drawings
Fig. 1 is 1-hydroxyl-2-of the present invention trimethylsiloxy-1, NMR (proton) spectrogram (solvent: DMSO-d of 1,2,2-tetraphenyl ethane
6).
Embodiment
Below explain the present invention.
Below in explanation, for asking easy, describe with general formula (1), but except not being contained in the explanation of the situation in the scope of general formula (1 '), in arbitrary explanation, all general formula (1) can be replaced to (1 '), can similarly be applied to general formula (1 ').In addition, for Y
1and Y
2explanation, also can replace to respectively Y
1 'and Y
2 ', except not being contained in Y
1 'and Y
2 'the situation of scope, can similarly be applied to Y
1 'and Y
2 '.
In general formula of the present invention (1), Y
1and Y
2represent independently respectively hydrogen atom, phenyl or Siliciumatom, and at least any one is the group beyond hydrogen atom.Preferably wherein one is hydrogen atom, the situation that another one is Siliciumatom.
In general formula (1) in the present invention, as R
1to R
6the straight or branched alkyl (below also referred to as C1 to C4 alkyl) of middle carbonatoms 1 to 4, for example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, the tertiary butyl etc.In addition, as X
1to X
4in halogen, can enumerate: fluorine atom, chlorine atom, bromine atoms etc.
The Y of general formula (1)
1or Y
2during for group beyond hydrogen atom, R
1r
2r
3y
1-or R
4r
5r
6y
2-preferably phenyl or phenyl or two C1 to C4 alkyl silyls or three C1 to C4 alkyl silyls by 1 to three C1 to C4 alkyl replacement, more preferably two C1 to C4 alkyl silyls or three C1 to 4 alkyl silyls, further preferred three C1 to C4 alkyl silyls.
The R of general formula (1)
1r
2r
3y
1-, R
4r
5r
6y
2-in two or the straight or branched alkyl silyl of thricarbon atom number 1 to 4 in, the alkyl of two or three carbonatomss 1 to 4 can be identical also can be different, as this silyl, can enumerate: two C1 to the C4 alkyl silyls such as dimetylsilyl, diethylsilane base, methylethyl silyl; Or three C1 to the C4 alkyl silyls such as trimethyl silyl, triethylsilyl, dimethylethylsilyl, t-butyldimethylsilyl.In these groups, preferably three C1 to C4 alkyl silyls, more preferably trimethyl silyl.
X
1to X
4represent independently of one another hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group, phenoxy group or halogen group, preferably X
1to X
4it is all the situation of hydrogen atom.
Preferred compound in the tetraphenyl ethane derivative representing as general formula (1), can enumerate: 1-hydroxyl-2-bis-or three (C1 to C4 alkyl) siloxy--1,1,2, two { two or three (C1 to the C4 alkyl) siloxyies }-1,1 of 2-tetraphenyl ethane or 1,2-, 2,2-tetraphenyl ethane, preferably 1-hydroxyl-2-bis-or three (C1 to C4 alkyl) siloxy--1,1,2,2-tetraphenyl ethane, more preferably 1-hydroxyl-2-tri-(C1 to C4 alkyl) siloxy--1,1,2,2-tetraphenyl ethane.
In addition, in two or three (C1 to C4 alkyl) siloxy-of above-mentioned tetraphenyl ethane, two or three alkyl on silyl can be identical also can be different.For example, as three (C1 to C4 alkyl) siloxy-, comprise trimethylsiloxy, silicoheptane alcoxyl base or t-butyldimethylsilyloxy base etc.
As the preferred compound of this tetraphenyl ethane derivative, particularly, for example can enumerate: 1, two (trimethylsiloxy)-1 of 2-, 1, 2, 2-tetraphenyl ethane, 1, two (the silicoheptane alcoxyl bases)-1 of 2-, 1, 2, 2-tetraphenyl ethane, 1, two (the t-butyldimethylsilyloxy bases)-1 of 2-, 1, 2, 2-tetraphenyl ethane, 1-hydroxyl-2-trimethylsiloxy-1, 1, 2, 2-tetraphenyl ethane, 1-hydroxyl-2-triethyl-silicane Oxy-1, 1, 2, 2-tetraphenyl ethane, 1-hydroxyl-2-t-butyldimethylsilyloxy base-1, 1, 2, 2-tetraphenyl ethane.Preferably can enumerate: 1-hydroxyl-2-trimethylsiloxy-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-triethyl-silicane Oxy-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-t-butyldimethylsilyloxy base-1,1,2,2-tetraphenyl ethane.
In these materials, more preferably 1-hydroxyl-2-trimethylsiloxy-1 in the present invention, 1,2,2-tetraphenyl ethane, 1-hydroxyl-2-triethyl-silicane Oxy-1,1,2,2-tetraphenyl ethane or 1-hydroxyl-2-t-butyldimethylsilyloxy base-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-trimethylsiloxy-1 that further preferred formula (2) represents, 1,2,2-tetraphenyl ethane.
The tetraphenyl ethane derivative that general formula of the present invention (1) represents, is characterized in that, has the structure that uses various silylating agents that the benzpinacone silanization of general formula (3) expression is obtained.
The tetraphenyl ethane derivative that general formula of the present invention (1) represents, can be synthesized into by the following method: benzpinacone and various silylating agent that general formula (3) is represented heat under the basic catalysts such as pyridine.
As silylating agent, as long as reaching the silylating agent of two C1 to C4 alkyl silanes or three C1 to C4 alkyl silanes, phenyl two C1 to C4 alkyl silanes, can be any one, preferably three (C1 to C4 alkyl) silylating agent.As preferred silylating agent, can enumerate: as trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), the N of general known trimethyl silyl agent, two (trimethyl silyl) trifluoroacetamides (BSTFA) of O-; Or as the chlorotriethyl silane (TECS) of triethylsilyl agent; As tertiary butyl dimethylsilane (TBMS) of t-butyldimethylsilyl agent etc.
These reagent can easily be obtained on the market from silicon derivative manufacturers etc.Hydroxyl 1 equivalent of the benzpinacone representing with respect to formula (3), preferably 1.0 to 5.0 times of equivalents of the reacting weight (silanization equivalent) of silylating agent.More preferably 1.5 to 3.0 times of equivalents.Reaction efficiency variation when very few, reaction times are elongated and promote thermolysis.In addition, too much time, in reclaiming, be not easy to separate, be difficult to purifying and become.
As basic catalyst, can enumerate: pyridine, triethylamine etc.Basic catalyst has following effect: the hydrogenchloride producing when catching reaction and reaction system is remained to alkalescence or remove the hydrogen atom of hydroxyl and further promote reaction.As usage quantity, with respect to hydroxyl 1 equivalent of objectification compound, count 0.5 times of equivalent above with the equivalent of basic group, also can be used as solvent and use.Conventionally,, with respect to hydroxyl 1 equivalent of objectification compound, count 1 to 5 times of equivalent with the equivalent of the basic group of basic catalyst.
As solvent, the non-polar organic solvents such as hexane, ether, toluene do not participate in reaction, therefore preferred.In addition, also preferably pyridine, dimethylformaldehyde (DMF), methyl-sulphoxide (DMSO), tetrahydrofuran (THF) (THF) and acetonitrile isopolarity solvent.As usage quantity, the weight concentration that preferably makes solute is approximately 5 to approximately 40 quality %.More preferably 10 to 30 quality %.When very few, react slack-off, promote the decomposition that caused by heat and yield is reduced.In addition, too much time, secondary resultant becomes many, and yield is reduced.
In the time silyl being incorporated into a hydroxyl of benzpinacone of general formula (3), temperature of reaction is preferably below 80 DEG C, and the reaction times is in 2.5 hours, preferably in 2 hours.Because the benzpinacone of for example general formula of benzpinacone derivative (3) or the target compound generating can cause thermolysis due to heating, therefore preferably react at low temperatures, but reactive owing to lacking for the tertiary alcohol, therefore by reacting at short notice below at 80 DEG C, can obtain the target compound of high yield.Also while considering reaction efficiency etc., preferably approximately 50 to approximately 80 DEG C.Reaction times is approximately 30 minutes to approximately 2.5 hours, preferably approximately 30 minutes to approximately 2 hours.
While silyl being incorporated into two hydroxyls of benzpinacone of general formula (3), the preferably for example temperature of approximately 75 to approximately 100 DEG C of higher temperature, but think that yield can decline.
The tetraphenyl ethane derivative that general formula of the present invention (1) represents, can be used as free-radical generating agent and uses.Particularly, can be used as hot radical and produce agent or optical free radical generation agent and use in various fields, in the present invention, particularly preferably produce agent as hot radical and use.
Hot radical of the present invention produces agent and also can in the purposes that other optical free radical generation agent is difficult to reach, use.For example, can for illumination less than part solidify or can problematic part while irradiating strong energy curing.Particularly, the hot radical that can be used as that hot radical in the sealing agent of precision machinery produces agent, the curing hot radical that can be used as the region of the lower-molecular substance that coexists of the worry for there being decomposition produces agent and can be used as organic synthesis for being caused by thermal response etc. produces agent and uses.In addition, hot radical of the present invention produces agent and in the time producing free radical, does not follow foaming, even and also do not damage on a small quantity curing speed, therefore can expect to keep the form of cured article or improve physical property.In the present invention, the usage quantity as free-radical generating agent of the tetraphenyl ethane derivative of above-mentioned general formula (1), can be according to as solidifying the kind of polymerization single polymerization monomer etc. of object or use field and different, and addition can suitably be selected.
Hot radical of the present invention produces one of preferred use field of agent, uses for the hot radical as in radically curing resin combination produces agent.In this situation, with respect to the total amount of said composition, hot radical of the present invention produces the content of agent (the tetraphenyl ethane derivative of general formula (1)), is not particularly limited, and is generally approximately 0.1 to approximately 10 quality %.All the other are free-radical polymerised resin and the additive that contains as required.By by this resin combination thermofixation, can obtain the cured article of this resin combination, this cured article is owing to producing the muddiness being caused by foaming, and therefore the transparency is good, and tackiness, moisture-proof tackiness etc. are good.In addition, as radically curing resin, can enumerate: epoxy resin or (methyl) acrylic resin etc.Particularly, as one of useful radically curing resin combination, can enumerate thermosetting encapsulants, wherein be suitably for most liquid crystal drop method thermoset liquid crystal sealing agent.
Liquid crystal drop method thermoset liquid crystal sealing agent of the present invention, contains following (a) to (d) as essential component: (methyl) vinylformic acid affixture of tetraphenyl ethane derivative, (b) epoxy resin and/or epoxy resin that (a) aforementioned formula (1) represents, (c) thermal curing agents and (d) inorganic filler.
Liquid crystal drop method of the present invention is with in thermoset liquid crystal sealing agent, and the tetraphenyl ethane derivative that contains (a) general formula (1) expression in order to improve solidified nature produces agent as hot radical.For easy, below tetraphenyl ethane derivative that general formula (1) is represented be also recited as (a) composition or hot radical and produce agent (a).
Conventionally, hot radical produces agent, refers to by heating to dissociate and produces the compound of free radical, for example can enumerate: azo-compound, organo-peroxide, bitter almond oil camphor class, benzoin ethers, acetophenones, benzpinacone class etc.But azo-compound or organo-peroxide, produce nitrogen or carbonic acid gas etc. in adding thermogenesis free radical, can foam.Therefore in cured article, contain bubble, this can cause curing physical property, adhesive strength to decline.In addition, although can not foam when the heating such as benzoin derivatives, benzpinacone, but there is following problem: during for the manufacture of liquid crystal panel, insufficient thermo-cracking at the temperature of approximately 90 to approximately 130 DEG C of the heat curing temperatures of sealing agent, cannot obtain desired degree of cure.
Therefore, the inventor etc., through various research, found that, by benzpinacone is carried out to chemically modified, can obtain active hot radical high and that liquid crystal pollution is few and produce agent.And find, consider from the easness of synthetic method, more preferably at least one hydroxyl of tetramethyl ethylene ketone forms the benzpinacone derivative of ehter bond.As ehter bond, for example can enumerate: methyl ether base, ether base, propyl ether base, isopropyl ether, butyl ether base, phenyl ether, silyl ether etc.In these groups, consider preferably phenyl ether or silyl ether, the tetraphenyl ethane derivative that more preferably aforementioned formula (1) represents from the viewpoint of activity etc.
The tetraphenyl ethane derivative (a) representing as the preferred general formula (1) using in the present invention, can enumerate: 1-hydroxyl-2-bis-or three (C1 to C4 alkyl) siloxy--1,1,2, two { two or three (C1 to the C4 alkyl) siloxyies }-1,1 of 2-tetraphenyl ethane or 1,2-, 2,2-tetraphenyl ethane, more preferably 1-hydroxyl-2-bis-or three (C1 to C4 alkyl) siloxy--1,1,2,2-tetraphenyl ethane, further preferred 1-hydroxyl-2-tri-(C1 to C4 alkyl) siloxy--1,1,2,2-tetraphenyl ethane.Concrete compound as previously mentioned.
This hot radical produces agent (a) (the tetraphenyl ethane derivative (a) that general formula (1) represents), and preferable particle size is trickle and dispersed.When its median size is excessive, in the time manufacturing the liquid crystal cells in narrow gap, can become upper lower glass substrate laminating time, gap such as cannot successfully form at the bad main cause, therefore preferably below 5 μ m, more preferably below 3 μ m.In addition, (a) particle diameter of composition can be infinitely fine, but its lower limit is counted approximately 0.1 μ m with median size conventionally.
In liquid crystal sealing agent of the present invention, with respect to the total amount of this liquid crystal sealing agent, (a) content of hot radical generation agent is generally 0.1 to 10 quality %, preferably 0.3 to 7 quality %, more preferably 0.5 to 5 quality %.When content is very few, solidified nature variation and produce sealing explosion, when content is too much, has the tendency of liquid crystal pollution grow.
In the present invention, as long as can reach effect of the present invention, also can be used together above-mentioned (a) composition free-radical generating agent in addition, but preferred above-mentioned (a) composition of use is separately as free-radical generating agent conventionally.
(methyl) vinylformic acid affixture (b) of the epoxy resin containing in thermoset liquid crystal sealing agent and/or epoxy resin for liquid crystal drop method of the present invention, uses as curable resin.At this, " (methyl) vinylformic acid " refers to " vinylformic acid " and/or " methacrylic acid ".In (methyl) vinylformic acid affixture (b) of epoxy resin and/or epoxy resin, all preferred, solvability is low, resin viscosity is low materials low to the contaminative of liquid crystal.
As this epoxy resin, preferably for example can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, the bisphenol-s epoxy resin of ethyleneoxide addition, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, bisphenol F phenolic varnish type epoxy resin, resorcinol diglycidyl ether, alicyclic epoxy resin, aliphatics chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glycolylurea type epoxy resin, isocyanuric acid ester type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, there is the phenol novolak type epoxy resin of triphenol methane skeleton, the 2-glycidyl etherate of other two senses phenols, the 2-glycidyl etherate of other two senses alcohols etc.These epoxy resin can use separately also can mix two or more uses.In these materials, consider from the viewpoint of liquid crystal pollution and viscosity, more preferably the bisphenol-s epoxy resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin, ethyleneoxide addition, resorcinol diglycidyl ether, wherein resorcinol diglycidyl ether particularly preferably.
(methyl) vinylformic acid affixture (following for asking easy also referred to as " epoxy resin of (methyl) acrylated ") of this epoxy resin, refer to by the acrylic acid compound obtaining that reacts of epoxy resin and (methyl), can be any one in following: addition (methyl) vinylformic acid in whole epoxy group(ing) of epoxy resin and the compound that obtains, or the epoxy group(ing) of epoxy resin react with (methyl) vinylformic acid of not enough equivalent and deliberately stay epoxy group(ing) compound (below also referred to as part (methyl) acrylated epoxy resin).
As the epoxy resin of (methyl) acrylated, preferably there is the compound of (methyl) acryls more than two senses.In addition, partly in the epoxy resin of (methyl) acrylated, epoxy group(ing) does not limit with the ratio of (methyl) acryl, can consider suitably to select from the viewpoint of step suitability and liquid crystal pollution.
In the present invention, conventionally preferably with respect to the whole epoxy group(ing) that contain in epoxy resin, with 50 to 100%, preferably 70 to 100%, more preferably 80 to 100% ratio addition (methyl) vinylformic acid obtains the epoxy resin of (methyl) acrylated.Conventionally, in (methyl) vinylformic acid, consider from the viewpoint of inexpensive grade, often use vinylformic acid.Therefore, preferably use the epoxy group(ing) addition vinylformic acid of epoxy resin and the compound that obtains.
As the epoxy resin of the raw material of the epoxy resin of this (methyl) acrylated, be not particularly limited, preferably epoxy resin more than two senses.
For example can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, the bisphenol-s epoxy resin of ethyleneoxide addition, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, bisphenol F phenolic varnish type epoxy resin, resorcinol diglycidyl ether, alicyclic epoxy resin, aliphatics chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glycolylurea type epoxy resin, isocyanuric acid ester type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, there is the phenol novolak type epoxy resin of triphenol methane skeleton, the 2-glycidyl etherate of other two trifunctional phenols class, the 2-glycidyl etherate of other two senses alcohols etc.
Preferably bisphenol A type epoxy resin, bisphenol f type epoxy resin or resorcinol diglycidyl ether, wherein more preferably resorcinol diglycidyl ether.
Therefore, as the epoxy resin of (methyl) acrylated, preferably, by selecting at least one in the group that free bisphenol A type epoxy resin, bisphenol f type epoxy resin and resorcinol diglycidyl ether form to react the epoxy resin of (methyl) acrylated obtaining with (methyl) vinylformic acid, more preferably react the epoxy resin of (methyl) acrylated obtaining with (methyl) vinylformic acid by resorcinol diglycidyl ether.
As the epoxy resin of (methyl) acrylated, consider from the viewpoint of solidified nature, preferably by epoxy resin and acrylic acid epoxy resin that reacts the acrylated obtaining.More preferably select at least one in the group that vinylformic acid affixture, the vinylformic acid affixture of bisphenol f type epoxy resin and the vinylformic acid affixture of resorcinol diglycidyl ether of free bisphenol A type epoxy resin form.
The epoxy resin of above-mentioned (methyl) acrylated can use separately also can mix two or more uses.
In preferred mode, the epoxy resin of above-mentioned preferred (methyl) acrylated accounts for whole amount of the epoxy resin of (methyl) acrylated in foregoing liquid crystal sealing agent.
In liquid crystal sealing agent of the present invention, with respect to the total amount of liquid crystal sealing agent, the content of the epoxy resin (b) (below also only referred to as curable resin (b)) of epoxy resin and/or (methyl) acrylated is generally 30 to 75 quality %, preferably 40 to 65 quality %.When content is very few, reaction when thermofixation is slack-off, drips legal system while making liquid crystal cells by liquid crystal, and the weir dike of sealing agent is because the thermal expansion of liquid crystal and the heating lowering viscousity of sealing agent produce sealing explosion.When content is too much, cannot obtain sufficient adhesive strength.
One of as curable resin (b), and the optimal way that is sealing agent of the present invention by epoxy resin and the mode of the epoxy resin of (methyl) acrylated.
In addition, particularly in epoxy resin and the epoxy resin of (methyl) acrylated the situation of use, with respect to the total amount of curable resin (b), epoxy resin content in curable resin (b) is generally 3 to 40 quality %, preferably 3 to 30 quality %, more preferably from about 5 to approximately 30 quality %, further preferred 8 to 30 quality %.In addition, according to circumstances, also preferably 5 to 20 quality %, more preferably 8 to 15 quality % sometimes.All the other are the epoxy resin of (methyl) acrylated.Concrete is recited as, and with respect to the total amount of curable resin (b), the content of the epoxy resin of (methyl) acrylated is 60 to 97 quality %, preferably 70 to 95 quality %, more preferably 70 to 92 quality %.When epoxy resin content is very few, adhesive strength dies down, when epoxy resin content is too much, curing slack-off, likely easily produces sealing explosion.
Liquid crystal drop method of the present invention contains thermal curing agents (c) with thermoset liquid crystal sealing agent.As thermal curing agents (c), can use in the past any one in the thermal curing agents using, but in the present invention, preferably there is the thermal curing agents (below also referred to as latent thermal curing agents) of latent.Latent curing agent refers to, normal temperature is that fusing point or the softening temperature of solid is 100 DEG C of above compounds, and do not react with resinous principle under room temperature, do not show the effect as solidifying agent, by being heated to more than 100 DEG C, be generally approximately 100 to approximately 150 DEG C, thus preferably approximately 110 to approximately 130 DEG C and slowly melting or melting react with resinous principle, show the material as the effect of solidifying agent.
In addition, in the present invention, fusing point or softening temperature use the logical Analysis of overheat of poor formula scanning calorimeter (DSC) and measure.Particularly, use poor formula scanning calorimeter (EXSTAR6000, セ イ コ ー イ ンスツル Co., Ltd. system) heat up with 5 DEG C/min and measure.
As above-mentioned latent curing agent, can enumerate: many hydrazide compounds, polyamine compounds, imdazole derivatives, urea derivative etc.Preferred many hydrazide derivatives, and for thering is the compound of more than two hydrazide group in molecule.Preferably two to four hydrazide compounds, more preferably two or three hydrazide compounds.
As many hydrazide compounds, for example can enumerate: careless acid dihydrazide, propanedioic acid two hydrazides, succinic acid hydrazide ii, adipic dihydrazide, pimelic acid two hydrazides, suberic acid two hydrazides, nonane diacid two hydrazides, sebacic dihydrazide, dodecanedioic acid two hydrazides, Thapsic acid two hydrazides, Malaysia acid dihydrazide, fumaric acid two hydrazides, glycol ether acid dihydrazide, winestone acid dihydrazide, apple acid dihydrazide, isophthalic dihydrazide, terephthaldehyde's acid dihydrazide, 2, 6-naphthoic acid two hydrazides, 4, two benzene two hydrazides of 4-, 1, 4-naphthoic acid two hydrazides, 2, 6-pyridine two hydrazides, 1, 2, 4-benzene three hydrazides, pyromellitic acid four hydrazides, 1, 4, 5, 8-naphthoic acid four hydrazides, there is the hydrazide compound of two (diazanyl carbonyl the ethyl)-glycolylurea skeletons such as 5-sec.-propyl glycolylurea of 1,3-, preferred α-amino-isovaleric acid glycolylurea skeleton (skeleton that the carbon atom of glycolylurea ring is replaced by sec.-propyl), two or three (diazanyl carbonyl C1 to C3 alkyl) isocyanuric acid ester, as three (1-diazanyl carbonyl methyl) isocyanuric acid ester, three (2-diazanyl carbonyl ethyl) isocyanuric acid ester, three (3-diazanyl carbonyl propyl group) isocyanuric acid ester, two (2-diazanyl carbonyl ethyl) isocyanuric acid ester etc., they can use separately also can mix two or more uses.Two or three (diazanyl carbonyl C1 to C3 alkyl) isocyanuric acid ester is one of preferred material as two or three hydrazide compounds.
Preferred two or tricarboxylic two or three hydrazides in these many hydrazide compounds, more specifically, can enumerate: except the carbon of carboxylic acid, two hydrazides of C4 to C8 aliphatics or aromatic dicarboxylic acid or two or three (diazanyl carbonyl C1 to C3 alkyl) isocyanuric acid ester etc.More preferably select at least one in two hydrazides, the group that phthalic acid two hydrazides, three (diazanyl carbonyl C1 to C3 alkyl) isocyanuric acid ester forms of free C4 to C8 docosandioic acid.
As preferred many hydrazides, particularly can enumerate: adipic dihydrazide, sebacic dihydrazide, isophthalic dihydrazide, 1, two (diazanyl carbonyl ethyl)-5-sec.-propyl glycolylurea, three (1-diazanyl carbonyl methyl) isocyanuric acid ester, three (2-diazanyl carbonyl ethyl) isocyanuric acid ester, three (the 3-diazanyl carbonyl propyl group) isocyanuric acid esters of 3-, two (2-diazanyl carbonyl ethyl) isocyanuric acid ester.
More preferably can enumerate: adipic dihydrazide, sebacic dihydrazide, isophthalic dihydrazide, three (2-diazanyl carbonyl ethyl) isocyanuric acid ester.
In order to become quick-setting latent curing agent, this thermal curing agents (c) preferable particle size is fine and dispersed.When its median size is excessive, in the time manufacturing the liquid crystal cells in narrow gap, can become upper lower glass substrate laminating time, gap such as cannot successfully form at the bad main cause.Therefore this particle diameter is preferably below 4 μ m, more preferably below 3 μ m.Its particle diameter is measured by laser diffraction/diffuse transmission type particle size distribution device (dry type) (the セ イ シ of Co., Ltd. Application system: LMS-30).And, in the time that median size is too small, easily cause aggegation, therefore preferably for example, be prepared in the mode that does not reach extremely little (0.1 μ m is following).
In liquid crystal sealing agent of the present invention, with respect to 100 mass parts as epoxy resin and or the curable resin (b) of the epoxy resin of (methyl) acrylated, the content of thermal curing agents (c) is generally approximately 5 mass parts to approximately 60 mass parts, preferably 10 mass parts to 40 mass parts.When thermal curing agents (c) is less than 5 mass parts, thermofixation reaction becomes insufficient, adhesive power, second-order transition temperature step-down.On the other hand, when thermal curing agents (c) exceedes 60 mass parts, thereby the residual adhesive power of solidifying agent declines, and the serviceable time also worsens.
Liquid crystal drop method of the present invention contains inorganic filler (d) with thermoset liquid crystal sealing agent.As this inorganic filler (d), can enumerate: aluminum oxide, silicon-dioxide (spherical silicon dioxide or aerosil etc.), talcum, clay, wilkinite, organobentonite; Metal oxide, as barium titanate, titanium oxide, cobalt oxide, magnesium oxide, nickel oxide, zirconium white etc.; Carbonate, as calcium carbonate, magnesiumcarbonate etc.; Vitriol, as barium sulfate, calcium sulfate etc.; Metal hydroxides, as aluminium hydroxide, magnesium hydroxide etc.; Silicate, as Calucium Silicate powder, pure aluminium silicate, zirconium silicate; Deng.They can use separately also can mix two or more uses.In these inorganic fillers, particularly preferably aluminum oxide and/or silicon-dioxide.
The median size of this inorganic filler (d) is preferably below 3 μ m.When median size is excessive, gap when upper lower glass substrate laminating while manufacturing liquid crystal cells forms and produces obstacle.The lower limit of the median size of inorganic filler (d) is generally approximately 0.01 μ m.
The content of inorganic filler in liquid crystal sealing agent of the present invention (d) is generally 1 to 30 quality %, preferably 2 to 20 quality %, more preferably 3 to 15 quality %.When content is very few, the adhesive strength of glass substrate is declined.In addition, when weighting agent content is too much, thereby the too high coating of viscosity worsens.
In liquid crystal sealing agent of the present invention, contain curing catalyst (e) in order to promote the solidified nature of thermofixation reaction.
As curing catalyst (e), the curing catalyst of the serviceable time deterioration that thermofixation reaction promotion property is high, low to the contaminative of liquid crystal, normal temperature can not make liquid crystal sealing agent while preservation during as long as heating, is not particularly limited.
For example can enumerate: there is the polycarboxylic acid of isocyanuric acid ring skeleton or epoxy resin amine additives, imdazole derivatives, urea derivative etc.They can use separately also can be used together two or more.As preferred curing catalyst, can enumerate: urea compounds curing catalyst or the polycarboxylic acid curing catalyst that contains isocyanuric acid ring skeleton.Particularly, can enumerate: aliphatics dimethyl urea (trade(brand)name: UCAT3503N, サ Application ア プ ロ Co., Ltd. system) (on cyclohexane ring, continuous position replaces and the compound that obtains through methyl and two dimethyl urea groups), aromatic series dimethyl urea (trade(brand)name: UCAT3502T, サ Application ア プ ロ Co., Ltd. system) (2 and 3 of toluene are upper to be replaced and the compounds that obtain through two dimethyl urea groups), three (carboxyl C1 to C3 alkyl) isocyanuric acid ester.As three (carboxyl C1 to C3 alkyl) isocyanuric acid ester, for example can enumerate: three (1-carboxyl methyl) isocyanuric acid ester, three (2-carboxy ethyl) isocyanuric acid ester, three (3-carboxyl propyl group) isocyanuric acid esters, two (2-carboxy ethyl) isocyanuric acid ester.Wherein preferred three (3-carboxyl propyl group) isocyanuric acid ester.
This curing catalyst (e) is in order to become quick-setting On The Latent Accelerator, and preferable particle size is fine and dispersed.When its median size is excessive, in the time manufacturing the liquid crystal cells in narrow gap, can become upper lower glass substrate laminating time, gap such as cannot successfully form at the bad main cause.Therefore median size is preferably below 4 μ m, more preferably below 3 μ m.The lower limit of median size is generally approximately 0.1 μ m.
In liquid crystal sealing agent of the present invention, with respect to the total amount of this liquid crystal sealing agent, the content of curing catalyst (e) is 0.5 to 15 quality % preferably, more preferably 1 to 8 quality %.When content is very few, solidified nature worsens and produces sealing explosion, when content is too much, and the linear deterioration of room temperature preservation stability and sealing.
In liquid crystal sealing agent of the present invention, also can add coupling agent (f) in order to improve adhesive strength.This coupling agent (f) is not particularly limited.
As this coupling agent (f), for example can enumerate: silane coupling agent, as 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-sulfydryl propyl trimethoxy silicane, vinyltrimethoxy silane, N-(2-(vinyl benzene methylamino) ethyl)-3-TSL 8330 hydrochloride, 3-methacryloxypropyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane etc., titanium base coupling agent, as sec.-propyl (N-ethylamino ethylamino) titanic acid ester, sec.-propyl three isooctadecane acyl titanates, titanium two (dioctylphyrophosphoric acid ester) glycolic acid esters, tetra isopropyl two (dioctyl phosphorous acid ester) titanic acid ester, new alkoxyl group three (p-is (beta-aminoethyl) aminophenyl just) titanic acid ester etc., zirconium base coupling agent, as methyl ethyl diketone zirconium, methacrylic acid zirconium, propionic acid zirconium, new alkoxy zirconium ester, the new new caprinoyl zirconate of alkoxyl group three, new alkoxyl group three (dodecanoyl) benzene sulfonyl zirconate, new alkoxyl group three (ethylene amino-ethyl) zirconate, new alkoxyl group three (m-aminophenyl base) zirconate, zirconium carbonate ammonium etc., aluminium base coupling agent, as aluminium acetylacetonate, aluminium methacrylate, propionic acid aluminium etc., they can use separately also can mix two or more uses.
In these coupling agents, preferred silane coupling agent, more preferably amino silicane coupling agent or epoxy silane coupling.
By using this coupling agent, can obtain that moisture-proof reliability is good, the few liquid crystal sealing agent of decline of adhesive strength after moisture absorption.While containing this coupling agent in liquid crystal sealing agent of the present invention, its content is approximately 0.05 to approximately 3 quality %.
In liquid crystal sealing agent of the present invention, also can contain multi-thioalcohol compound (g) in order to further raising solidified nature.As this multi-thioalcohol compound, preferably in molecule, there is the compound of more than two sulfydryl.For example can enumerate: first two mercaptan, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 2,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-tri-thiol propane, Isosorbide-5-Nitrae-dimercapto butane, 1,6-dimercapto hexane, two (2-mercaptoethyl) thioether, two (the 2-sulfydryl ethylmercapto group) ethane of 1,2-, 1,5-dimercapto-3-oxa-pentane, 1,8-dimercapto-3,6-dioxa octane, 2,2-dimethylpropane-1,3-bis-mercaptan, 3,4-dimethoxy-butane-1,2-bis-mercaptan, 2-mercapto methyl-1,3-dimercaptopropane, 2-mercapto methyl-Isosorbide-5-Nitrae-dimercapto butane, 2-(2-sulfydryl ethylmercapto group)-1,3-dimercaptopropane, two (2-sulfydryl the ethylmercapto group)-3-sulfydryl propane of 1,2-, 1,1,1-tri-(mercapto methyl) propane, four (mercapto methyl) methane, ethylene glycol bis (2-Thiovanic acid) ester, ethylene glycol bis (3-thiohydracrylic acid) ester, two (2-Thiovanic acid) esters of BDO, two (3-thiohydracrylic acid) esters of BDO, three (methylol) propane three (2-Thiovanic acid) ester, trimethylolpropane tris (3-thiohydracrylic acid) ester, tetramethylolmethane four (2-Thiovanic acid) ester, tetramethylolmethane four (3-thiohydracrylic acid) ester, 1,1-dimercapto hexanaphthene, Isosorbide-5-Nitrae-dimercapto hexanaphthene, 1,3-dimercapto hexanaphthene, 1,2-dimercapto hexanaphthene, Dipentaerythritol six (3-thiohydracrylic acid) ester, Dipentaerythritol six (2-Thiovanic acid) ester, 1,2-thioresorcin, 1,3-dimercapto-2-propyl alcohol, 2,3-dimercapto-1-propyl alcohol, 1,2-dimercapto-1,3 butylene glycol, hydroxymethyl-tri-(sulfydryl ethylmercapto group methyl) methane, hydroxyl ethylmercapto group methyl-tri-(sulfydryl ethylmercapto group) methane, ethylene glycol bis (3-thiohydracrylic acid) ester, two (3-thiohydracrylic acid) esters of propylene glycol, two (3-thiohydracrylic acid) esters of butyleneglycol, two (3-thiohydracrylic acid) esters of ethohexadiol, two (3-thiohydracrylic acid) esters of TEG, ethylene glycol bis (4-sulfydryl butyric acid) ester, two (the 4-sulfydryl butyric acid) esters of propylene glycol, two (the 4-sulfydryl butyric acid) esters of butyleneglycol, two (the 4-sulfydryl butyric acid) esters of ethohexadiol, three (methylol) propane three (4-sulfydryl butyric acid) ester, tetramethylolmethane four (4-sulfydryl butyric acid) ester, ethylene glycol bis (6-mercaptopentanoic acid) ester, two (6-mercaptopentanoic acid) esters of propylene glycol, two (6-mercaptopentanoic acid) esters of butyleneglycol, two (6-mercaptopentanoic acid) esters of ethohexadiol, three (methylol) propane three (6-mercaptopentanoic acid) ester, tetramethylolmethane four (6-mercaptopentanoic acid) ester, 1,6-ethanthiol, 1,9-mercaptan in the ninth of the ten Heavenly Stems two, 1,10-mercaptan in the last of the ten Heavenly stems two, 4,4 '-bis-(mercapto methyl) diphenyl sulfide, 2,4 '-bis-(mercapto methyl) diphenyl sulfide, 2,4,4 '-tri-(mercapto methyl) diphenyl sulfide, 2,2 ', 4,4 '-tetra-(mercapto methyl) diphenyl sulfide, 1,3,5-tri-[2-(3-sulfydryl propionyloxy) ethyl]-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones, 1,3,5-tri-(3-sulfydryl butyl oxygen base ethyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones, tetramethylolmethane four (3-sulfydryl butyric acid) ester, Isosorbide-5-Nitrae-bis-(3-sulfydryl butyryl acyloxy) butane etc., they can use separately also can mix two or more uses.
In these multi-thioalcohol compounds, preferably three (methylol) propane three (3-thiohydracrylic acid) ester, tetramethylolmethane four (3-thiohydracrylic acid) ester, Dipentaerythritol six (3-thiohydracrylic acid) ester, 1, 3, 5-tri-[2-(3-sulfydryl propionyloxy) ethyl]-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, 1, 3, 5-tri-(3-sulfydryl butyl oxygen base ethyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, tetramethylolmethane four (3-sulfydryl butyric acid) ester, further preferably, consider from the viewpoint of liquid crystal pollution and room temperature preservation stability, particularly preferably there is 1 of secondary mercaptan structure, 3, 5-tri-(3-sulfydryl butyl oxygen base ethyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, tetramethylolmethane four (3-sulfydryl butyric acid) ester.
Liquid crystal drop method of the present invention is when containing this multi-thioalcohol compound (g) in thermoset liquid crystal sealing agent, its content is generally 0.1 to 10 quality %, preferably 0.3 to 5 quality %.When content is very few, solidified nature worsens, and becomes easy generation sealing explosion, and when content is too much, room temperature preservation stability easily worsens.
Liquid crystal drop method of the present invention, with in thermoset liquid crystal sealing agent, in the scope of characteristic that does not affect liquid crystal sealing agent, also can be added organic filler (h).As this organic filler (h), for example can enumerate: polysiloxane rubber particulate, acrylic rubber particulate, hud typed acrylic resin particulate etc.These organic fillers can use separately also can mix two or more uses.
The median size of the organic filler that can add is generally below 5 μ m, preferably below 2 μ m.When median size is excessive, be difficult to forming unit gap.But when organic filler is polysiloxane rubber powder, even if median size greatly also can forming unit gap, therefore the preferred median size of polysiloxane rubber powder is below 15 μ m.
In addition, while containing this organic filler in liquid crystal sealing agent of the present invention, with respect to the total amount of this liquid crystal sealing agent, its content is preferably below 40 quality %, more preferably below 30 quality %.Lower limit can be 0 quality %.Conventionally, more than preferably containing 1 quality %, more than more preferably containing 5 quality %.Too much time, thereby viscosity uprises and is difficult to forming unit gap.One of the mode that contains this organic filler in liquid crystal sealing agent of the present invention is optimal way.
In addition, as organic filler, and with polysiloxane rubber particulate and other organic filler, for example (methyl) acrylic resin particulate, preferably the mode of hud typed (methyl) acrylic resin particulate is also one of optimal way of the present invention.Now, with respect to other organic filler 1 mass parts, polysiloxane rubber particulate preferably uses the ratio of 1 to 10 mass parts, the more preferably ratio of 3 to 7 mass parts conventionally.
In liquid crystal sealing agent of the present invention, can coordinate as required additive, as optical free radical polymerization starter, organic solvent, pigment, levelling (leveling) agent, defoamer etc.
Below for recording some optimal ways about sealing agent of the present invention.
1., in the invention that in (5) to (14) recorded in aforementioned " summary of the invention ", any one is recorded, curable resin (b) is also used epoxy resin and the mode of the epoxy resin of (methyl) acrylated.
2. as above-mentioned 1 mode of being recorded, wherein, with respect to the total amount of curable resin (b), the content of epoxy resin is 3 to 40 quality %, and the content of the epoxy resin of (methyl) acrylated is 60 to 97 quality %.
3. in the situation of the mode (invention that (11) in above-mentioned 1 in (5) to (14) are recorded to (14)) that contains curing catalyst (e) in above-mentioned 1 or 2, with respect to the total amount of sealing agent of the present invention, the content of curing catalyst is 0.5 to 15 quality %, the preferably mode of 1 to 8 quality %.
4. as above-mentioned 3 modes of being recorded, wherein, curing catalyst (e) is the polycarboxylic acid curing catalyst that contains isocyanuric acid ring skeleton.
5. as above-mentioned 4 modes of being recorded, wherein, curing catalyst (e) is three (carboxyl C1 to C3 alkyl) isocyanuric acid ester.
6. the mode of being recorded as any one in above-mentioned 1 to 5, in the situation of the mode (invention that (12) in above-mentioned 1 in (5) to (14) are recorded to (14)) that contains the coupling agent that in above-mentioned 1 to 5, any one is recorded (f), with respect to the total amount of sealing agent of the present invention, the content of coupling agent (f) is 0.05 to 3 quality %.
7. as above-mentioned 6 modes of being recorded, wherein, coupling agent (f) is silane coupling agent.
8. the mode of being recorded as any one in above-mentioned 1 to 7, wherein, with respect to the total amount of sealing agent of the present invention, further contains the multi-thioalcohol compound (g) of 0.1 to 10 quality %.
9. the mode of being recorded as any one in above-mentioned 1 to 8, wherein, with respect to the total amount of sealing agent of the present invention, further contains organic filler (h) in the scope of 1 to 40 quality %.
In order to obtain liquid crystal sealing agent of the present invention, the epoxy resin (b) of aforesaid epoxy resin and/or (methyl) acrylated, coupling agent, additive etc. are as required dissolved and mixed, suitably add therein aforementioned hot solidifying agent (c), aforementioned hot free-radical generating agent (a), aforementioned inorganic filler (d), aforementioned curing catalyst (e) and other any composition, use common mixing device, such as three-roll mill (3 ロ ー Le), sand mill, ball mill etc. evenly mix.Mix and finish rear preferred enforcement for removing the filtration treatment of foreign matter.
Liquid crystal display of the present invention, for a pair of substrate that is formed with predetermined electrode is configured relatively with predetermined space, seals with liquid crystal sealing agent of the present invention in surrounding, and encloses liquid crystal in gap betwixt and the liquid crystal display that obtains.The kind of the liquid crystal of enclosing is not particularly limited.
At this, substrate is made up of glass, quartz, plastics, silicon etc.Use in the manufacture method of liquid crystal display of thermohardening type liquid crystal drop method, first, in liquid crystal sealing agent of the present invention, add the spacers such as glass fibre (spacer) (gap control material), and mix.For example can enumerate as spacer: glass fibre, silicon-dioxide microballon, polymer bead etc.Its diameter is according to object and difference is generally 2 to 8 μ m, preferably 3 to 6 μ m, and with respect to liquid crystal sealing agent 100 mass parts, its usage quantity is generally 0.1 to 4 mass parts, preferably 0.5 to 2 mass parts, more preferably from about 0.9 to approximately 1.5 mass parts.
The side that the liquid crystal sealing agent that is combined with spacer is coated to substrate by spreader etc. forms weir dike (primary seal), then for sealing liquid crystal substrate is remained to vacuum, then is coated with one week sealing agent (false sealing) at most peripheral.Then, at the inner side dropping liquid crystal of the weir of seal inside dike, another glass substrate of fitting in a vacuum, is then released into normal atmosphere, carries out thus gap formation.For sealing liquid crystal substrate being remained to the dummy sealant of vacuum, do not contact with liquid crystal, and cut after liquid crystal cells forms, therefore the sealing agent identical with liquid crystal sealing agent be can use, other UV curing sealing agent, visible-light curing type sealing agent or thermohardening type sealing agent also can be used.After vacuum gap forms, while being used as the UV curing sealing agent of light-cured type sealing agent or visible-light curing type sealing agent to seal as vacation, to false sealing irradiation ultraviolet radiation or visible ray, false sealing is solidified by ultraviolet irradiation machine or radiation of visible light device.While not using light-cured type sealing agent to seal as vacation, can omit rayed step.Gapped substrate will be formed, 90 to 130 DEG C of heating 1 to 2 hour, then, by false sealing excision, liquid crystal display of the present invention can be obtained thus.
There is this liquid crystal display of the present invention obtaining, bad without the caused demonstration of liquid crystal pollution, and tackiness, moisture-proof reliability are good.
Embodiment
The present invention is described by the following examples in further detail.
In addition, the present invention is not limited to following examples.
In addition, if nothing is clearly recorded in embodiment, part refers to that mass parts, % refer to quality %.
Embodiment A
1-hydroxyl-2-trimethylsiloxy-1, synthetic (benzpinacone of silanization) of 1,2,2-tetraphenyl ethane
Benzpinacone (Tokyo changes into system) commercially available to 100 parts (0.28 mole) is dissolved in 350 parts of dimethylformaldehyde.Add therein as the pyridine of basic catalyst 32 parts (0.4 mole), as 150 parts of the BSTFA (SHIN-ETSU HANTOTAI's chemical industry system) (0.58 mole) of silylating agent, be warming up to 70 DEG C, stir 2 hours.By cooling obtained reaction solution, when stirring, add 200 parts, water, resultant is precipitated and make unreacted silylating agent inactivation.By fully washing after the resultant filtering separation of precipitation.Then, obtained resultant is dissolved in to acetone, adds water to make its recrystallize, purifying.Obtain 105.6 parts of target 1-hydroxyl-2-trimethylsiloxy-1,1,2,2-tetraphenyl ethane (yield 88.3%).
Analyze by HPLC (high performance liquid chromatography), result, purity is 99.0% (area percentage).
In HPLC-MASS (High Performance Liquid Chromatography/Mass Spectrometry analysis), obtain 438 molion peak.In addition, from NMR spectrogram (solvent DMSO-d
6) obtain hydroxyl proton 5.8ppm (1H), siloxy-methyl proton 0.0ppm (9H), phenyl protons 7.1ppm (16H), 7.4ppm (4H) as chemical displacement value, confirm as target compound.This NMR spectrogram as shown in Figure 1.
In addition, after in two tertiary alcohols of benzpinacone derivative one reacts, further reduce because large steric barrier makes the reactivity of another hydroxyl, therefore think in above-mentioned reaction and optionally introduced silyl a side.
Experimental example 1
In order to see that hot radical of the present invention produces the effect of agent, implement gelation time (time that on the hot plate of 120 DEG C is cured) and the frothing test of sample at 120 DEG C.
(test method)
With respect to the vinylformic acid affixture (Nippon Kayaku K. K's system: R93100) of 10 parts of bisphenol A type epoxy resins, in test example 1 (the present invention), mix 0.1 part of 1-hydroxyl-2-of the present invention trimethylsiloxy-1 that produces agent as hot radical, 1,2,2-tetraphenyl ethane; In test example 2 (relatively using), mix 0.1 part of benzpinacone that produces agent as hot radical; In test example 3 (relatively using), mix 0.1 part of peroxidation (2 ethyl hexanoic acid) tert-butyl ester (chemical drug ア Network ゾ Co., Ltd. system: カ ヤ エ ス テ Le O) that produces agent as hot radical, use three-roll mill is mixed, preparation sample separately.
Observe obtained sample is placed on to muddy the having or not that time (gelation times at 120 DEG C) of being cured on the hot plate of 120 DEG C and visual observation cured article are caused by foaming.Its result is as shown in Table A.In addition, about set time, with glass stick contact sample, be measured to the time of sample till without wire drawing.
The muddy metewand having or not being caused by foaming is in addition as described below.
The muddy evaluation having or not being caused by foaming
Zero: the muddiness not caused by foaming in cured article, transparent.
△: cured article has gonorrhoea sense slightly because of foaming, transparency also declines slightly.
×: in whole cured article, obviously observe the gonorrhoea being caused by foaming, transparency also obviously reduces.
Table A
As shown in Table A, hot radical of the present invention produces agent (test example 1), and curing speed is fast, nothing foams, do not produce muddiness, is therefore also applicable to need transparent various uses.
On the other hand, as a comparison in the test example 2 of object, although transparency aspect is no problem, but thereby grow the problem that has workability set time, although test example 3, good aspect set time, produces the muddiness being caused by foaming, therefore transparent deteriorated, therefore be unsuitable for needing transparent purposes, and, the worry that has the physical property of the cured article being caused by foaming to decline.
Embodiment 1,2, comparative example 1,2
Epoxy resin, epoxy resin, the silane coupling agent of the acrylated of recording in aftermentioned table 1 are obtained by mixing to resin liquid.
In obtained resin liquid, coordinate respectively benzpinacone, multi-thioalcohol compound, polysiloxane rubber powder (organic filler) and the nucleocapsid acrylic resin particulate (organic filler) of inorganic filler, thermal curing agents, curing catalyst, silanization according to the use level of recording in table 1, use three-roll mill is mixed, and obtains the liquid crystal sealing agent of embodiment 1 and 2.
In the composition of above-described embodiment 1, use the benzpinacone of the amount that table 1 records to replace the benzpinacone of silanization, operate same with embodiment, obtains the liquid crystal sealing agent of comparative example 1 in addition.
In addition, use the organo-peroxide of the amount that table 1 records to replace the benzpinacone of silanization in the composition of embodiment 1, operation similarly to Example 1 in addition, obtains the liquid crystal sealing agent of comparative example 2.
With reference to synthesis example 1 (synthesizing of the full vinylformic acid compound of resorcinol diglycidyl ether)
By 140 parts of resorcinol diglycidyl ether resin dissolves in 160 parts of toluene.Add therein as 0.48 part of the butylated hydroxytoluene of polymerization retarder, be warming up to 60 DEG C.Then, add 100 parts of vinylformic acid (100% equivalent of the epoxy group(ing) of resorcinol diglycidyl ether resin), be further warming up to 80 DEG C, add therein as 0.96 part of the trimethyl ammonium chloride of catalysts, 98 DEG C of stir abouts 50 hours.By the washing of obtained reaction solution, toluene is removed in distillation, obtains thus 241 parts of the epoxy acrylate of Resorcinol.
Table 1
Numerical value in table 1 is weight part.
﹡ 1: the full vinylformic acid compound (with reference to the compound obtaining in synthesis example 1) of resorcinol diglycidyl ether
﹡ 2: resorcinol diglycidyl ether (Nippon Kayaku K. K's system, trade(brand)name: RGE-HH)
﹡ 3: spherical silicon dioxide (Shin-Etsu Chemial Co., Ltd's system, trade(brand)name: X-24-9163A; A median size 110nm)
﹡ 4: polysiloxane rubber powder (Shin-Etsu Chemial Co., Ltd's system, trade(brand)name: KMP-598; Median size 13 μ m)
﹡ 5:3-glycidoxypropyltrime,hoxysilane (チ ッ ソ Co., Ltd. system, trade(brand)name: サ イ ラ エ ー ス
rTMs-510)
﹡ 6:N-2 (amino-ethyl) APTES (Shin-Etsu Chemial Co., Ltd's system, trade(brand)name: KBM603)
7: three (2-diazanyl carbonyl ethyl) isocyanuric acid ester Crushing of Ultrafine product of ﹡ (using jet mill by Japan of Co., Ltd. Off ァ イ Application ケ system system, trade(brand)name: HCIC Crushing of Ultrafine is the Crushing of Ultrafine product that median size 1.5 μ m obtain)
﹡ 8:1-hydroxyl-2-trimethylsiloxy-1,1,2,2-tetraphenyl ethane (using jet mill is the Crushing of Ultrafine product that median size 1.9 μ m obtain by compound (benzpinacone of the silanization) Crushing of Ultrafine similarly obtaining with embodiment A)
﹡ 9: benzpinacone Crushing of Ultrafine product (the Crushing of Ultrafine product that use jet mill that the benzpinacone Crushing of Ultrafine of Tokyo HuaCheng Industry Co., Ltd's system is obtained for median size 1.9 μ m)
﹡ 10: the peroxidation 2 ethyl hexanoic acid tert-butyl ester (chemical drug ア Network ゾ Co., Ltd. system, trade(brand)name: カ ヤ エ ス テ Le
rTMo)
﹡ 11: tetramethylolmethane four (3-sulfydryl butyric acid) ester (Showa Denko K. K's system, trade(brand)name: カ レ Application ズ
rTMmT PE1)
12: three (3-carboxyl propyl group) isocyanuric acid ester pulverized products (using jet mill is the Crushing of Ultrafine product that median size 1.5 μ m obtain by Shikoku Chem's system, trade(brand)name: C3-CIC acid Crushing of Ultrafine) of ﹡
﹡ 13: (ガ Application Star changes into Co., Ltd.'s system, trade(brand)name: F351S to nucleocapsid acrylic resin particulate; Median size 0.3 μ m)
Evaluate the making with liquid crystal cells
In the embodiment 1,2 of each 100g or the liquid crystal sealing agent of comparative example 1,2, add the 5 μ m glass fibre 1g as spacer, carry out mix and blend, deaeration, and be filled into injection tube.On the glass substrate with ito transparent electrode, be coated with alignment films liquid (trade(brand)name: PIA-5540-05A, チ ッ ソ Co., Ltd. system), calcining, implements to grind (ラ PVC Application グ) and processes.Use spreader (SHOTMASTER300: Musashi エ Application ジ ニ ア リ Application グ Co., Ltd. system) to be pre-charged with the embodiment of injection tube and each liquid crystal sealing agent of comparative example carries out the coating of seal pattern and false seal pattern, then, micro-drop of liquid crystal (trade(brand)name: JC-5015LA, チ ッ ソ Co., Ltd. system) is dropped onto in the frame of seal pattern.Then, carry out (the trade(brand)name: Na ト コ ス ペ ー サ KSEB-525F, Na ト コ Co., Ltd. system of pattern inside clearance on the glass substrate after milled processed at another sheet, gap width 5 μ after laminating m), carry out thermal fixation, use vacuum forming apparatus in a vacuum with the baseplate-laminating that completes in advance liquid crystal drippage.Then, be released in atmosphere and form behind gap, drops in 120 DEG C of baking boxs it is heating and curing 1 hour, make evaluation liquid crystal test cell.
The sealing shape of liquid crystal cells and the situation at random of liquid crystal aligning for the evaluation of making by polarized light microscope observing, the results are shown in table 2.In addition, for the gap of made liquid crystal cells, use liquid crystal characteristic evaluating apparatus (trade(brand)name: OMS-NK3, Central Motor Wheel Co., Ltd.'s system) to measure, the results are shown in table 2.The situation at random of sealing shape, liquid crystal aligning and gap of liquid crystal cell be evaluated as following level Four.
The evaluation of sealing shape
Zero: the linearity of sealing does not have at random.
△: observe the distortion of sealing, but liquid crystal be sealed into no problem degree.
×: liquid crystal infiltrates sealing, liquid crystal be sealed into the degree that can have problems.
× ×: sealing is burst and cannot forming unit.
The evaluation of gap of liquid crystal cell
Zero: in unit, adequate relief becomes the cell gap of 5 μ m.
△: element memory is about the situation of the cell gap of 5.5 μ m in formation.
×: element memory is being formed as the situation of cell gaps more than 6 μ m.
× ×: sealing is burst and cannot forming unit.
The evaluation of liquid crystal aligning
Zero: near sealing, the orientation of liquid crystal is without at random.
△: near little region sealing, orientation has at random.
×: from random to the orientation of region existence widely near sealing.
× ×: sealing is burst and cannot forming unit.
Table 2
The test of liquid crystal sealing agent adhesive strength
In the embodiment 1,2 of each 100g or the liquid crystal sealing agent of comparative example 1,2, add the 5 μ m glass fibre 1g as spacer, carry out mix and blend.This liquid crystal sealing agent is coated on the glass substrate of 50mm × 50mm, the sheet glass of the 1.5mm × 1.5mm that fits on this liquid crystal sealing agent, drops in 120 DEG C of baking boxs it is solidified 1 hour.Use bond strength tester (ボ Application De テ ス タ ー) (trade(brand)name: SS-30WD, Xi Jin business Co., Ltd. system) to measure the shearing adhesive strength of this sheet glass.The results are shown in following table 3.
The test of liquid crystal sealing agent moisture-proof adhesive strength
Make with foregoing liquid crystal sealing agent adhesive strength and test same mensuration sample.By the pressure cooker testing machine (trade(brand)name: TPC-411 under the condition of 121 DEG C, two normal atmosphere of this mensuration sample input, humidity 100%, タ バ イ エ ス ペ ッ Network Co., Ltd. system) 20 minutes, use bond strength tester (trade(brand)name: SS-30WD, Xi Jin business Co., Ltd. system) to measure gains.The results are shown in following table 3.
Serviceable time
Use R type viscometer (Toki Sangyo Co., Ltd.'s system), measure the viscosity of the liquid crystal sealing agent obtaining at 25 DEG C and change.Viscosity increment rate (%) with respect to initial stage viscosity is shown in following table 3.
Table 3
As Table 2,3, use the benzpinacone of silanization as the liquid crystal sealing agent of the embodiment of the present invention of free-radical generating agent, compared with using with comparative example 1 liquid crystal sealing agent that benzpinacone obtains as free-radical generating agent, any one aspect aspect liquid crystal aligning, after adhesive strength and moisture-proof in adhesive strength, all outstanding significantly.
Industrial applicability
From above, tetraphenyl ethane derivative of the present invention, high and without foaming by hot free-radical generating performance, therefore short as the gelation time in radically curing resin combination, to produce agent without the hot radical of foaming useful.In addition, the transparent reduction also not caused by foaming or the physical property of other cured article reduce, and therefore can obtain the resin cured matter that transparency is high, physical property is good.In addition, while using this tetraphenyl ethane derivative to produce agent as the hot radical in liquid crystal sealing agent, sealing agent has following feature: liquid crystal pollution is low, serviceable time is long, the formative in formative, the gap of sealing is also good, therefore workability is also good, and after adhesive strength and moisture-proof, adhesive strength is all good.Therefore, be particularly suitable as liquid crystal drop method thermoset liquid crystal sealing agent.
Claims (8)
1. the tetraphenyl ethane derivative that following general formula (1 ') represents,
In formula, Y
1 'or Y
2 'represent independently of one another hydrogen atom or Siliciumatom, R
1to R
6represent independently of one another the straight or branched alkyl of hydrogen atom or carbonatoms 1 to 4, X
1to X
4represent independently of one another hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group, phenoxy group or halogen group; Wherein, Y
1 'or Y
2 'in any one be hydrogen atom, another one represents Siliciumatom, Y
1 'or Y
2 'in situation for hydrogen atom, R
1to R
3or R
4to R
6do not exist.
2. tetraphenyl ethane derivative as claimed in claim 1, wherein, Y in general formula (1 ')
1 'or Y
2 'in any one be hydrogen atom, another one represents Siliciumatom, Y
1 'or Y
2 'in situation for Siliciumatom, R
1r
2r
3y
1 '-or R
4r
5r
6y
2 '-be two (the straight or branched alkyl of carbonatoms 1 to 4) silyl or three (the straight or branched alkyl of carbonatoms 1 to 4) silyl, X
1to X
4be hydrogen atom.
3. tetraphenyl ethane derivative as claimed in claim 1, wherein, Y in general formula (1 ')
1 'or Y
2 'in any one be hydrogen atom, another one represents Siliciumatom, Y
1 'or Y
2 'in situation for Siliciumatom, R
1r
2r
3y
1 '-or R
4r
5r
6y
2 '-be trimethyl silyl, triethylsilyl or t-butyldimethylsilyl, X
1to X
4be hydrogen atom.
4. tetraphenyl ethane derivative as claimed in claim 1, it is 1-hydroxyl-2-trimethylsiloxy-1 that following formula (2) represents, 1,2,2-tetraphenyl ethane
5. a free-radical generating agent, its tetraphenyl ethane derivative that comprises the general formula described in any one (1 ') in claim 1 to 4 is as effective constituent.
6. a cured article, by obtaining the radically curing resin combination thermofixation of the tetraphenyl ethane derivative that comprises general formula (1 ') described in any one in claim 1 to 4.
7. a manufacture method for the tetraphenyl ethane derivative that following formula (1 ') represents, wherein, the benzpinacone that following general formula (3) is represented reacts with silylating agent,
In formula (1 '), Y
1 'or Y
2 'represent independently of one another hydrogen atom or Siliciumatom, R
1to R
6represent independently of one another the straight or branched alkyl of hydrogen atom or carbonatoms 1 to 4, X
1to X
4represent independently of one another hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group, phenoxy group or halogen group; Wherein, Y
1 'or Y
2 'in any one be hydrogen atom, another one represents Siliciumatom, Y
1 'or Y
2 'in situation for hydrogen atom, R
1to R
3or R
4to R
6do not exist,
In formula (3), X
1to X
4represent independently of one another hydrogen atom, methyl, ethyl, methoxyl group, oxyethyl group, phenoxy group or halogen group.
8. tetraphenyl ethane derivative as claimed in claim 1, wherein, Y in general formula (1 ')
1 'or Y
2 'in any one be hydrogen atom, another one is Siliciumatom, Y
1 'or Y
2 'in situation for Siliciumatom, R
1to R
3or R
4to R
6be the straight or branched alkyl of carbonatoms 1 to 4 independently of one another.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009261421 | 2009-11-17 | ||
| JP2009-261421 | 2009-11-17 | ||
| JP2009269727 | 2009-11-27 | ||
| JP2009-269727 | 2009-11-27 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080051849.1A Division CN102612521B (en) | 2009-11-17 | 2010-11-12 | Novel hot free-radical generating agent, its manufacture method, liquid crystal sealing agent and liquid crystal display |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104031082A true CN104031082A (en) | 2014-09-10 |
Family
ID=44059397
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080051849.1A Active CN102612521B (en) | 2009-11-17 | 2010-11-12 | Novel hot free-radical generating agent, its manufacture method, liquid crystal sealing agent and liquid crystal display |
| CN201410239409.9A Pending CN104031082A (en) | 2009-11-17 | 2010-11-12 | Novel thermal radical generator, method for producing the same, liquid crystal sealing agent, and liquid crystal display cell |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080051849.1A Active CN102612521B (en) | 2009-11-17 | 2010-11-12 | Novel hot free-radical generating agent, its manufacture method, liquid crystal sealing agent and liquid crystal display |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5783606B2 (en) |
| KR (1) | KR101806152B1 (en) |
| CN (2) | CN102612521B (en) |
| TW (2) | TWI482777B (en) |
| WO (1) | WO2011061910A1 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011050035A1 (en) * | 2011-05-02 | 2012-11-08 | Byk-Chemie Gmbh | Low-emission, by free-radical polymerization thermally curable fiber-matrix semifinished product |
| TWI543992B (en) * | 2011-07-13 | 2016-08-01 | Nippon Kayaku Kk | A liquid crystal sealant and a liquid crystal display unit using the liquid crystal sealant |
| TW201420736A (en) * | 2012-07-17 | 2014-06-01 | Nippon Kayaku Kk | Liquid-crystal sealant and LCD cell using same |
| TWI576360B (en) * | 2012-08-27 | 2017-04-01 | Nippon Kayaku Kk | A liquid crystal sealant and a liquid crystal display cell using the liquid crystal sealant |
| CN105242459A (en) * | 2013-03-07 | 2016-01-13 | 日本化药株式会社 | Method for manufacturing liquid-crystal display cells and liquid-crystal display cells obtained via said method |
| JP5531166B1 (en) * | 2013-03-07 | 2014-06-25 | 日本化薬株式会社 | Manufacturing method of liquid crystal display cell and liquid crystal display cell obtained by the method |
| JP6144961B2 (en) * | 2013-05-09 | 2017-06-07 | 積水化学工業株式会社 | Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element |
| JP6182999B2 (en) * | 2013-06-25 | 2017-08-23 | 日油株式会社 | Thermosetting resin composition for color filter protective film, and color filter provided with the cured film |
| JP6288756B2 (en) * | 2013-07-16 | 2018-03-07 | 日本化薬株式会社 | Manufacturing method of liquid crystal display cell and liquid crystal display cell obtained by the method |
| JP6235297B2 (en) * | 2013-10-16 | 2017-11-22 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
| JP6238761B2 (en) * | 2014-01-20 | 2017-11-29 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
| JP2015215514A (en) * | 2014-05-12 | 2015-12-03 | 協立化学産業株式会社 | Sealant for liquid crystal display |
| JP6370382B2 (en) * | 2014-07-24 | 2018-08-08 | 三井化学株式会社 | Liquid crystal sealant and liquid crystal display panel manufacturing method |
| JP2016038507A (en) | 2014-08-08 | 2016-03-22 | 日本化薬株式会社 | Liquid crystal sealing agent and liquid crystal display cell having the same |
| JP6465740B2 (en) * | 2015-05-11 | 2019-02-06 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
| JP6465741B2 (en) * | 2015-05-11 | 2019-02-06 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
| JP6482371B2 (en) * | 2015-05-11 | 2019-03-13 | 日本化薬株式会社 | Method for producing resin composition |
| WO2019098028A1 (en) | 2017-11-16 | 2019-05-23 | 三菱ケミカル株式会社 | Thermosetting resin composition, prepreg, and fiber-reinforced composite material and production method therefor |
| WO2019221027A1 (en) * | 2018-05-17 | 2019-11-21 | 積水化学工業株式会社 | Liquid crystal display element sealing agent, vertical conduction material, and liquid crystal display element |
| JP7432492B2 (en) | 2020-12-11 | 2024-02-16 | 日本化薬株式会社 | Liquid crystal sealant for liquid crystal dripping method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3931355A (en) * | 1971-12-24 | 1976-01-06 | Bayer Aktiengesellschaft | Radical-initiated polymerization reactions and mixture |
| US6376615B1 (en) * | 1997-10-23 | 2002-04-23 | Centro De Investigacion En Quimica Aplicada | Method for functionalizing a polymer and preparing copolymers and terpolymers |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2164482C3 (en) * | 1971-12-24 | 1980-07-31 | Bayer Ag, 5090 Leverkusen | Initiators for radical polymerization reactions |
| JPS57142990A (en) * | 1981-02-27 | 1982-09-03 | Yuki Gosei Yakuhin Kogyo Kk | Silylating reagent |
| US4393185A (en) * | 1981-06-02 | 1983-07-12 | Ciba-Geigy Corporation | Thermally polymerizable mixtures and processes for the thermally-initiated polymerization of cationically polymerizable compounds |
| JPH0311083A (en) * | 1989-06-08 | 1991-01-18 | Toray Dow Corning Silicone Co Ltd | Silylating agent |
| JP3874073B2 (en) * | 2001-04-06 | 2007-01-31 | 信越化学工業株式会社 | Method for producing chlorosilane compound having texyl group |
| JP4405325B2 (en) | 2004-06-23 | 2010-01-27 | 積水化学工業株式会社 | Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element |
-
2010
- 2010-11-12 KR KR1020127013344A patent/KR101806152B1/en active IP Right Grant
- 2010-11-12 CN CN201080051849.1A patent/CN102612521B/en active Active
- 2010-11-12 WO PCT/JP2010/006651 patent/WO2011061910A1/en active Application Filing
- 2010-11-12 CN CN201410239409.9A patent/CN104031082A/en active Pending
- 2010-11-12 JP JP2011541804A patent/JP5783606B2/en active Active
- 2010-11-16 TW TW099139293A patent/TWI482777B/en active
- 2010-11-16 TW TW103121871A patent/TWI511974B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3931355A (en) * | 1971-12-24 | 1976-01-06 | Bayer Aktiengesellschaft | Radical-initiated polymerization reactions and mixture |
| US6376615B1 (en) * | 1997-10-23 | 2002-04-23 | Centro De Investigacion En Quimica Aplicada | Method for functionalizing a polymer and preparing copolymers and terpolymers |
Non-Patent Citations (3)
| Title |
|---|
| HANS-DIETER BECKER: "Thermal and Photochemical Addition Reactions of Organosilicon Hydrides", 《THE JOURNAL OF ORGANIC CHEMISTRY》, 31 December 1968 (1968-12-31), pages 2469 - 2472 * |
| HORST HILLGARTNEV等，: "Bis(trimethy1zinln)benzpinakolat, seine reversible radikalische Dissoziation und Reaktionen", 《LIEBIGS ANN. CHEM.》, 31 December 1975 (1975-12-31) * |
| J. V. CRIVELLO等，: "Polydimethylsiloxane-Vinyl Block Polymers. I. The Synthesis of Polydimethylsiloxane Macroinitiators Containing Thermolyzable Bis(Sily1 Pinacolate) Groups in Their Backbones", 《JOURNAL OF POLYMER SCIENCE: PART A POLYMER CHEMISTRY》, 31 December 1986 (1986-12-31), pages 1197 - 1215 * |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI482777B (en) | 2015-05-01 |
| JP5783606B2 (en) | 2015-09-24 |
| CN102612521B (en) | 2015-10-07 |
| JPWO2011061910A1 (en) | 2013-04-04 |
| KR101806152B1 (en) | 2017-12-07 |
| CN102612521A (en) | 2012-07-25 |
| TW201129574A (en) | 2011-09-01 |
| TW201437220A (en) | 2014-10-01 |
| TWI511974B (en) | 2015-12-11 |
| WO2011061910A1 (en) | 2011-05-26 |
| KR20120085855A (en) | 2012-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102612521B (en) | Novel hot free-radical generating agent, its manufacture method, liquid crystal sealing agent and liquid crystal display | |
| CN101861545B (en) | Liquid crystal sealing agent and liquid crystal display cell using the same | |
| TWI453512B (en) | Liquid crystal sealing agent, fabricating method for liquid crystal display panel by using thereof and liquid crystal display panel | |
| TWI473829B (en) | Liquid crystal sealant, liquid crystal display panel and fabricating method thereof using the same | |
| WO2012002028A1 (en) | Curable resin composition | |
| CN102472928A (en) | Liquid crystal sealing agent for liquid crystal dropping method and liquid crystal display cell using same | |
| CN1703458A (en) | Sealant composition for liquid crystal and process for producing liquid-crystal display panel with the same | |
| CN1711300A (en) | Sealing material for liquid crystal and liquid crystal display cell using same | |
| TWI534168B (en) | Liquid crystal sealing agent, fabricating method of liquid crystal display panel using the same and liquid crystal display panel | |
| CN101044184A (en) | Radiation curable resin, liquid crystal sealing material, and liquid crystal display cell using same | |
| CN105700252A (en) | Liquid crystal sealing agent and a liquid crystal display unit using the same | |
| JP5571436B2 (en) | Liquid crystal sealant, liquid crystal display panel manufacturing method using the same, and liquid crystal display panel | |
| JP2010014771A (en) | Thermosetting liquid crystal sealing material for liquid crystal dropping method and liquid crystal display cell using the same | |
| CN103443698B (en) | Sealant for liquid crystal dripping process, upper and lower conductive material and liquid crystal display cells | |
| CN103649825B (en) | Liquid crystal sealing agent and use its liquid crystal display | |
| CN107615151A (en) | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells | |
| CN102827352B (en) | Thermal curing agents and preparation method thereof, sealed plastic box, display panel, display unit | |
| CN103229094B (en) | Sealant for liquid crystal dropping technique, method for producing sealant for liquid crystal dropping technique, vertical conducting material, and liquid crystal display element | |
| CN101313244B (en) | Sealing agent for liquid crystals and process for production of liquid crystal panels with the same | |
| CN103827741A (en) | Liquid crystal sealing agent, and liquid crystal display cell using same | |
| CN105368365A (en) | Liquid crystal sealant and liquid crystal display unit using the same | |
| CN103890649B (en) | Liquid crystal sealing agent and use its liquid crystal display | |
| CN106366999A (en) | Liquid crystal sealing agent and liquid crystal display cell using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140910 |