JP2006056944A - Tetracarboxylic dianhydride, polymer using the same as raw material, varnish, aligning film and liquid crystal display element using the polymer - Google Patents
Tetracarboxylic dianhydride, polymer using the same as raw material, varnish, aligning film and liquid crystal display element using the polymer Download PDFInfo
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- JP2006056944A JP2006056944A JP2004238357A JP2004238357A JP2006056944A JP 2006056944 A JP2006056944 A JP 2006056944A JP 2004238357 A JP2004238357 A JP 2004238357A JP 2004238357 A JP2004238357 A JP 2004238357A JP 2006056944 A JP2006056944 A JP 2006056944A
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- tetracarboxylic dianhydride
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 125000006158 tetracarboxylic acid group Chemical group 0.000 title claims abstract description 42
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 41
- 239000002966 varnish Substances 0.000 title claims abstract description 39
- 229920000642 polymer Polymers 0.000 title claims abstract description 28
- 239000002994 raw material Substances 0.000 title abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- 125000000962 organic group Chemical group 0.000 claims abstract description 25
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 150000004985 diamines Chemical class 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 239000011593 sulfur Chemical group 0.000 claims description 11
- 229910052717 sulfur Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 6
- 150000001875 compounds Chemical class 0.000 abstract description 66
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 abstract description 30
- 229920001721 polyimide Polymers 0.000 abstract description 12
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 11
- 239000004642 Polyimide Substances 0.000 abstract description 9
- 239000004962 Polyamide-imide Substances 0.000 abstract description 8
- 229920002312 polyamide-imide Polymers 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000011282 treatment Methods 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- UAAXGZRJQCAMJK-UHFFFAOYSA-N 1,3-diethyl-1H-indene-2-carboxylic acid Chemical compound C(C)C1C(=C(C2=CC=CC=C12)CC)C(=O)O UAAXGZRJQCAMJK-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000004337 3-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-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
- HSBOCPVKJMBWTF-UHFFFAOYSA-N 4-[1-(4-aminophenyl)ethyl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)C1=CC=C(N)C=C1 HSBOCPVKJMBWTF-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RDTIGISLOACPEZ-UHFFFAOYSA-N O=C(C(C(C1)C2C(O3)=O)C4C1C2C3=O)OC4=O Chemical compound O=C(C(C(C1)C2C(O3)=O)C4C1C2C3=O)OC4=O RDTIGISLOACPEZ-UHFFFAOYSA-N 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- CJYIPJMCGHGFNN-UHFFFAOYSA-N bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid Chemical compound C1C2C(C(O)=O)C(C(=O)O)C1C(C(O)=O)C2C(O)=O CJYIPJMCGHGFNN-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 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
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-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
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 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
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000843 phenylene group Chemical class C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Liquid Crystal (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
本発明は、新規なテトラカルボン酸二無水物、それを原料とする重合体、この重合体および溶媒を含有するワニス（varnish）、該ワニスから形成される配向膜、ならびに該配向膜を有する液晶表示素子に関する。 The present invention relates to a novel tetracarboxylic dianhydride, a polymer using the same, a varnish containing the polymer and a solvent, an alignment film formed from the varnish, and a liquid crystal having the alignment film The present invention relates to a display element.
液晶表示素子は画面の大型化やカラー化の要求、コントラストや発色等表示品位における向上の要求、さらに応答時間短縮の要求に応えるために、ツイステッド・ネマティック（Twisted Nematic：ＴＮ）から、スーパー・ツイステッド・ネマティック（Super Twisted Nematic：ＳＴＮ）へ、さらに画素一つ一つに薄膜トランジスタ（Thin Film Transistor：ＴＦＴ）を取り付けたＴＦＴ型表示素子へと発展を遂げた。近年ではそのＴＦＴ型表示素子の視野角をさらに拡大するため、または動画表示を目的として応答を高速化するため、イン・プレーン・スイッチング（In-Plain Switching：ＩＰＳ）方式、垂直配向（Vertical Alignment：ＶＡ）方式が開発され、さらに動画対応可能な応答速度を有する光学補償ベンド（Optically Compensated Bend：ＯＣＢ）方式が開発されている。 In order to meet demands for larger screens and colors, improved display quality such as contrast and color development, and demands for shortening response time, liquid crystal display elements have been changed from Twisted Nematic (TN) to Super Twisted. -Development has progressed to nematic (Super Twisted Nematic: STN) and further to TFT type display elements with thin film transistors (TFT) attached to each pixel. In recent years, in order to further increase the viewing angle of the TFT display element or to speed up the response for the purpose of displaying moving images, an in-plane switching (IPS) method, vertical alignment (Vertical Alignment): The VA) method has been developed, and an optically compensated bend (OCB) method having a response speed capable of moving images has been developed.
配向膜は、液晶表示素子において液晶分子を一定方向に配向させること、基板平面に対する所望の傾き角（プレチルト角）を液晶分子に付与すること、の２つの役割を果たしている。配向膜には、分子配向の経時的な、化学的な、および熱的な劣化を最小限に抑えるため、ガラス転移点が高く耐薬品性や耐熱性に優れたポリイミド薄膜が主に使用されている。配向膜は、通常ポリアミック酸またはポリイミドの溶液をスピンナー法や印刷法等により電極付ガラス基板に塗布し、その基板を加熱してポリアミック酸を脱水閉環するか、または溶媒を蒸発させることによってポリイミドの薄膜を得て、さらにラビング等の配向処理を行う工程を経て得られる。 The alignment film plays two roles of aligning liquid crystal molecules in a certain direction in the liquid crystal display element and imparting a desired tilt angle (pretilt angle) to the liquid crystal molecules with respect to the substrate plane. For alignment films, polyimide films with high glass transition point and excellent chemical resistance and heat resistance are mainly used to minimize the deterioration of molecular alignment over time, chemical and thermal. Yes. The alignment film is usually formed by applying a solution of polyamic acid or polyimide to a glass substrate with an electrode by a spinner method or a printing method and heating the substrate to dehydrate and ring the polyamic acid or evaporate the solvent. It is obtained through a step of obtaining a thin film and further performing an orientation treatment such as rubbing.
このような配向膜には、液晶表示素子に必要とされる下記のような特性が要求される。
（１）液晶分子に適切なプレチルト角を付与すること。しかも、該プレチルト角が、ラビング時の押込み強度や、加熱時の温度条件による影響を受けにくいこと。
（２）液晶分子の配向の欠陥が発生しないこと。
（３）液晶表示素子に適切な電圧保持率（Voltage Holding Ratio：ＶＨＲ）を与えること。
（４）液晶表示素子に任意の画像を長時間表示させた後、別の画像に変えた時に前の画像が残像として残る「焼き付き」と呼ばれる現象が起きにくいこと。
特にＴＦＴ型、ＩＰＳ型またはＶＡ型の表示素子に用いられる高品質な配向膜には、高い電圧保持率を有し、しかも焼き付き現象を起こしにくいことが要求されている。
Such an alignment film is required to have the following characteristics required for a liquid crystal display element.
(1) Giving an appropriate pretilt angle to liquid crystal molecules. In addition, the pretilt angle is not easily affected by the indentation strength during rubbing or the temperature conditions during heating.
(2) No alignment defect of liquid crystal molecules occurs.
(3) Give an appropriate voltage holding ratio (VHR) to the liquid crystal display element.
(4) A phenomenon called “burn-in” in which an image is displayed as an afterimage when an arbitrary image is displayed on the liquid crystal display element for a long time and then changed to another image, is less likely to occur.
In particular, a high-quality alignment film used for a TFT-type, IPS-type, or VA-type display element is required to have a high voltage holding ratio and hardly cause a seizure phenomenon.
配向膜用ポリイミドの原料は酸無水物とジアミンである。酸無水物として、式（４）で表される化合物（以下、ＰＭＤＡと略称することがある。）が一般的に知られている。また式（５）で表される化合物（以下、ＢＨＴＡＣと略称することがある。）が特許文献１に記載されている。
しかしながら、ＰＭＤＡを原料として得られた、ポリアミック酸、ポリイミド、ポリアミドイミドまたはこれらの混合物を含有するワニスから形成された配向膜を有する液晶表示素子は、電圧保持率が低下しやすく、また焼き付き現象も起こり易い。ＢＨＴＡＣを原料として得られた、ポリアミック酸、ポリイミド、ポリアミドイミドまたはこれらの混合物を含有するワニスから形成された配向膜を有する液晶表示素子は、電圧保持率が低く、焼き付き現象も起こり易い。また、ラビング時の押込み強度や加熱の温度条件によってプレチルト角が変化する。 However, a liquid crystal display element having an alignment film formed from a varnish containing polyamic acid, polyimide, polyamideimide or a mixture thereof obtained using PMDA as a raw material tends to have a low voltage holding ratio and also has a seizure phenomenon. It is easy to happen. A liquid crystal display element having an alignment film formed from a varnish containing polyamic acid, polyimide, polyamideimide, or a mixture thereof obtained using BHTAC as a raw material has a low voltage holding ratio and is likely to cause image sticking. In addition, the pretilt angle varies depending on the indentation strength during rubbing and the temperature conditions of heating.
本発明は、配向膜に要求される前記の特性（１）〜（４）を満足する液晶表示素子用の配向膜を得ることができ、しかも容易に合成できる新規なテトラカルボン酸二無水物を提供することであり、さらには、該酸二無水物を原料の一つとして得られる、重合体を含有するワニス、該ワニスから形成された配向膜、該配向膜を有する液晶表示素子を提供することである。 The present invention provides a novel tetracarboxylic dianhydride capable of obtaining an alignment film for a liquid crystal display device satisfying the above-mentioned characteristics (1) to (4) required for an alignment film and easily synthesized. Furthermore, the present invention provides a polymer-containing varnish obtained using the acid dianhydride as one of raw materials, an alignment film formed from the varnish, and a liquid crystal display device having the alignment film. That is.
本発明者は、鋭意研究開発を進めた結果、本発明のテトラカルボン酸二無水物を原料として得られる重合体を含有するワニスを用いるとき、これから形成された配向膜を有する液晶表示素子が、高い電圧保持率を有し、しかも焼き付き現象の原因となる残留ＤＣ電圧が低いという電気特性を有することを見出した。また本発明者は、この配向膜がプレチルト角の安定性に優れ、バックライトによる長時間照射を受けても素子性能を損なうことなく、優れた光安定性を有すること、さらに本発明のテトラカルボン酸二無水物が特別な反応装置を必要とせず、容易に合成できることを見出し、これらの知見に基づいて本発明を完成した。 As a result of diligent research and development, the present inventor, when using a varnish containing a polymer obtained using the tetracarboxylic dianhydride of the present invention as a raw material, a liquid crystal display element having an alignment film formed therefrom, It has been found that it has an electrical characteristic that it has a high voltage holding ratio and a low residual DC voltage that causes a burn-in phenomenon. The inventor has also shown that the alignment film has excellent pretilt angle stability, has excellent light stability without deteriorating device performance even when irradiated with a backlight for a long period of time, and the tetracarboxylic acid of the present invention. It was found that acid dianhydride can be easily synthesized without requiring a special reaction apparatus, and the present invention was completed based on these findings.
本発明は、下記の構成からなる。
［１］ 式（１０１）または式（１０２）で表されるテトラカルボン酸二無水物。
［２］ 式（１０２）で表されるテトラカルボン酸二無水物が、Ｃｙｃｌｅが芳香族環または脂肪族環であり、芳香族環または脂肪族環上の任意の水素が炭素数１〜５０の１価の有機基、フッ素、塩素、または臭素で置き換えられていてもよい、［１］項に記載のテトラカルボン酸二無水物。
The present invention has the following configuration.
[1] A tetracarboxylic dianhydride represented by the formula (101) or the formula (102).
[2] In the tetracarboxylic dianhydride represented by the formula (102), Cycle is an aromatic ring or an aliphatic ring, and any hydrogen on the aromatic ring or the aliphatic ring has 1 to 50 carbon atoms. The tetracarboxylic dianhydride according to item [1], which may be substituted with a monovalent organic group, fluorine, chlorine, or bromine.
［３］ 式（１）、式（２）または式（３）で表されるテトラカルボン酸二無水物。
［４］ 式（１）、式（２）および式（３）において、Ｒ１〜Ｒ１４がそれぞれ独立して、フェニル、シクロヘキシル、任意のメチレンが酸素もしくは硫黄で置き換えられてもよいアルキル、これらの基を有する炭素数１〜５０の１価の有機基、水素、またはフッ素である［３］項に記載のテトラカルボン酸二無水物。
［５］ 式（１）、式（２）および式（３）において、Ｒ１〜Ｒ１４がそれぞれ独立して、任意のメチレンが酸素もしくは硫黄で置き換えられてもよい炭素数１〜２０のアルキル、水素またはフッ素である［３］項に記載のテトラカルボン酸二無水物。
［６］ 式（１）、式（２）および式（３）において、Ｒ１〜Ｒ１４がそれぞれ独立して、任意のメチレンが酸素もしくは硫黄で置き換えられてもよい炭素数１〜６のアルキル、水素またはフッ素である［３］項に記載のテトラカルボン酸二無水物。
［７］ 式（１）、式（２）および式（３）において、Ｒ１〜Ｒ１４がそれぞれ独立して、炭素数１〜６のアルキル、水素またはフッ素である［３］項に記載のテトラカルボン酸二無水物。
［８］式（１）、式（２）および式（３）において、Ｒ１〜Ｒ１４がそれぞれ独立して、炭素数１〜３のアルキルまたは水素である［３］項に記載のテトラカルボン酸二無水物。
[4] In Formula (1), Formula (2), and Formula (3), R 1 to R 14 are each independently phenyl, cyclohexyl, alkyl in which any methylene may be replaced with oxygen or sulfur, The tetracarboxylic dianhydride as described in the item [3], which is a monovalent organic group having 1 to 50 carbon atoms, hydrogen, or fluorine.
[5] In Formula (1), Formula (2), and Formula (3), R 1 to R 14 are each independently alkyl having 1 to 20 carbon atoms in which any methylene may be replaced with oxygen or sulfur The tetracarboxylic dianhydride according to item [3], which is hydrogen or fluorine.
[6] In Formula (1), Formula (2), and Formula (3), R 1 to R 14 are each independently alkyl having 1 to 6 carbon atoms in which any methylene may be replaced with oxygen or sulfur The tetracarboxylic dianhydride according to item [3], which is hydrogen or fluorine.
[7] In the formula (1), formula (2), and formula (3), R 1 to R 14 are each independently alkyl having 1 to 6 carbon atoms, hydrogen, or fluorine. Tetracarboxylic dianhydride.
[8] In the formula (1), formula (2), and formula (3), R 1 to R 14 are each independently alkyl having 1 to 3 carbon atoms or hydrogen, and the tetracarboxylic acid according to item [3]. Acid dianhydride.
［９］ ［１］〜［８］項のいずれか１項に記載のテトラカルボン酸二無水物をジアミンと反応させて得られる重合体。
［１０］ ［１］〜［８］項のいずれか１項に記載のテトラカルボン酸二無水物およびジカルボン酸もしくはその誘導体をジアミンと反応させて得られる重合体。
[9] A polymer obtained by reacting the tetracarboxylic dianhydride according to any one of items [1] to [8] with a diamine.
[10] A polymer obtained by reacting the tetracarboxylic dianhydride and dicarboxylic acid or derivative thereof according to any one of items [1] to [8] with a diamine.
［１１］ ［９］項に記載の重合体および［１０］項に記載の重合体から選ばれる少なくとも１つの重合体および溶媒を含有するワニス。 [11] A varnish containing at least one polymer selected from the polymer described in the item [9] and the polymer described in the item [10] and a solvent.
［１２］ ［１１］項に記載のワニスから形成される配向膜。 [12] An alignment film formed from the varnish according to the item [11].
［１３］ ［１２］項に記載の配向膜を有する液晶表示素子。 [13] A liquid crystal display device having the alignment film according to the item [12].
本発明のテトラカルボン酸二無水物を原料の一つとして得られる重合体を含有する本発明のワニスから形成された配向膜を有する液晶表示素子は、電圧保持率が高いこと、かつ、焼き付き現象を起こす原因となる残留ＤＣ電圧が低いという電気特性を有している。また、本発明のテトラカルボン酸二無水物を用いて得られる配向膜は熱的、経時的に高い安定性を有し、プレチルト角の安定性に優れ、さらにラビング時に物理的なラビング傷が発生にくい。しかも本発明のテトラカルボン酸二無水物は合成方法が簡単で、複雑な装置が不要であり、且つ廉価に得ることが可能である。 The liquid crystal display element having an alignment film formed from the varnish of the present invention containing a polymer obtained by using the tetracarboxylic dianhydride of the present invention as one of the raw materials has a high voltage holding ratio and a burn-in phenomenon It has an electrical characteristic that the residual DC voltage that causes the occurrence of low is low. The alignment film obtained using the tetracarboxylic dianhydride of the present invention has high thermal and temporal stability, excellent pretilt angle stability, and physical rubbing scratches are generated during rubbing. Hateful. Moreover, the tetracarboxylic dianhydride of the present invention is easy to synthesize, does not require complicated equipment, and can be obtained at low cost.
第一に、本発明のテトラカルボン酸二無水物について説明する。
本発明のテトラカルボン酸二無水物は、式（１０１）または式（１０２）で表されるテトラカルボン酸二無水物である。本発明の好ましい態様のテトラカルボン酸二無水物は、式（１）、式（２）または式（３）で表されるテトラカルボン酸二無水物である。これらの酸二無水物由来の構成単位を有する重合体を含有するワニスから形成される配向膜を用いると、前述の特性（１）〜（４）を満足する液晶表示素子を得ることができる。式（１０１）、式（１０２）、式（１）、式（２）、式（３）で表わされる化合物をそれぞれ化合物（１０１）、化合物（１０２）、化合物（１）、化合物（２）、化合物（３）と表記することがある。
First, the tetracarboxylic dianhydride of the present invention will be described.
The tetracarboxylic dianhydride of the present invention is a tetracarboxylic dianhydride represented by the formula (101) or the formula (102). The tetracarboxylic dianhydride according to a preferred embodiment of the present invention is a tetracarboxylic dianhydride represented by the formula (1), the formula (2) or the formula (3). When an alignment film formed from a varnish containing a polymer having a structural unit derived from these acid dianhydrides is used, a liquid crystal display element satisfying the above-mentioned characteristics (1) to (4) can be obtained. The compounds represented by formula (101), formula (102), formula (1), formula (2), and formula (3) are respectively compound (101), compound (102), compound (1), compound (2), It may be described as a compound (3).
化合物（１０１）のＲ１０１およびＲ１０２は、水素または炭素数１〜５０の１価の有機基である。化合物（１０２）のＣｙｃｌｅは、芳香族環または脂肪族環であり、芳香族環または脂肪族環上の任意の水素は炭素数１〜５０の１価の有機基またはハロゲンで置き換えられていてもよい。Ｒ１０１およびＲ１０２は同一であっても、異なってもよい。Ｃｙｃｌｅは芳香族環または脂肪族環であり、芳香族環または脂肪族環上の任意の水素が炭素数１〜５０の１価の有機基、フッ素、塩素、または臭素で置き換えられていてもよい環であることが好ましい。化合物（１０１）および化合物（１０２）における炭素数１〜５０の１価の有機基は、化合物（１）、化合物（２）および化合物（３）における炭素数１〜５０の１価の有機基と重複するので、前者の有機基の説明は化合物（１）、化合物（２）および化合物（３）の説明において詳細に述べる。 R 101 and R 102 of the compound (101) are hydrogen or a monovalent organic group having 1 to 50 carbon atoms. Cycle of the compound (102) is an aromatic ring or an aliphatic ring, and any hydrogen on the aromatic ring or the aliphatic ring may be replaced with a monovalent organic group having 1 to 50 carbon atoms or a halogen. Good. R 101 and R 102 may be the same or different. Cycle is an aromatic ring or an aliphatic ring, and any hydrogen on the aromatic ring or the aliphatic ring may be replaced with a monovalent organic group having 1 to 50 carbon atoms, fluorine, chlorine, or bromine. A ring is preferred. The monovalent organic group having 1 to 50 carbon atoms in the compound (101) and the compound (102) is the same as the monovalent organic group having 1 to 50 carbon atoms in the compound (1), the compound (2), and the compound (3). Since they overlap, the description of the former organic group will be described in detail in the description of the compound (1), the compound (2) and the compound (3).
化合物（１）、化合物（２）および化合物（３）のＲ１〜Ｒ１４は、炭素数１〜５０の１価の有機基、水素またはフッ素である。Ｒ１〜Ｒ１４は同一であっても、異なってもよい。Ｒ１〜Ｒ１４は、フェニル、シクロヘキシル、任意のメチレンが酸素もしくは硫黄で置き換えられてもよい炭素数１〜５０のアルキル、これらの基を有する炭素数１〜５０の１価の有機基、水素またはフッ素であることが好ましく、フェニル、シクロヘキシル、任意のメチレンが酸素もしくは硫黄で置き換えられてもよい炭素数１〜２０のアルキル、水素またはフッ素であることがより好ましく、任意のメチレンが酸素もしくは硫黄で置き換えられてもよい炭素数１〜６のアルキル、水素またはフッ素であることが更に好ましく、炭素数１〜６のアルキル、水素またはフッ素であることがより一層好ましく、炭素数１〜３のアルキルまたは水素であることが特に好ましい。これらの説明において、水素またはフッ素以外の基が炭素数１〜５０の１価の有機基の説明に相当する。この炭素数１〜５０の１価の有機基の説明は、化合物（１０１）および化合物（１０２）における炭素数１〜５０の１価の有機基にも適用する。 R < 1 > -R < 14 > of a compound (1), a compound (2), and a compound (3) is a C1-C50 monovalent organic group, hydrogen, or fluorine. R 1 to R 14 may be the same or different. R 1 to R 14 are phenyl, cyclohexyl, alkyl having 1 to 50 carbon atoms in which any methylene may be replaced by oxygen or sulfur, a monovalent organic group having 1 to 50 carbon atoms having these groups, hydrogen Or, it is preferably fluorine, more preferably phenyl, cyclohexyl, alkyl having 1 to 20 carbon atoms in which any methylene may be replaced by oxygen or sulfur, hydrogen or fluorine, and any methylene being oxygen or sulfur. Is more preferably an alkyl having 1 to 6 carbon atoms, hydrogen or fluorine, which may be replaced by, more preferably an alkyl having 1 to 6 carbon atoms, hydrogen or fluorine, and an alkyl having 1 to 3 carbon atoms. Or it is especially preferable that it is hydrogen. In these descriptions, groups other than hydrogen or fluorine correspond to descriptions of monovalent organic groups having 1 to 50 carbon atoms. The description of the monovalent organic group having 1 to 50 carbon atoms also applies to the monovalent organic group having 1 to 50 carbon atoms in the compound (101) and the compound (102).
「任意のメチレンが酸素もしくは硫黄で置き換えられてもよいアルキル」の句の意味を一例で示す。Ｃ４Ｈ９−において任意のメチレン（−ＣＨ２−）を酸素（−Ｏ−）もしくは硫黄（−Ｓ−）で置き換えた基の一部は、Ｃ３Ｈ７Ｏ−、ＣＨ３−Ｏ−（ＣＨ２）２−、ＣＨ３−Ｏ−ＣＨ２−Ｏ−、ＣＨ３−Ｏ−ＣＨ２−Ｓ−、ＣＨ３−Ｓ−（ＣＨ２）２−、およびＣＨ３−Ｓ−ＣＨ２−Ｏ−である。このように用語「任意の」は、「区別なく選択された少なくとも１つの」を意味する。化合物の安定性を考慮して、酸素と酸素とが隣接したＣＨ３−Ｏ−Ｏ−ＣＨ２−よりも、酸素と酸素とが隣接しないＣＨ３−Ｏ−ＣＨ２−Ｏ−の方が好ましい。 The meaning of the phrase “alkyl in which any methylene may be replaced by oxygen or sulfur” is shown as an example. A part of the group in which any methylene (—CH 2 —) in C 4 H 9 — is replaced with oxygen (—O—) or sulfur (—S—) is C 3 H 7 O—, CH 3 —O—. (CH 2) 2 -, CH 3 -O-CH 2 -O-, CH 3 -O-CH 2 -S-, CH 3 -S- (CH 2) 2 -, and CH 3 -S-CH 2 - O-. Thus, the term “arbitrary” means “at least one selected without distinction”. Considering the stability of the compound, CH 3 —O—CH 2 —O— in which oxygen and oxygen are not adjacent to each other is preferable to CH 3 —O—O—CH 2 — in which oxygen and oxygen are adjacent to each other. .
炭素数１〜５０のアルキルの例は、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、イコシル、トリアコンチル、テトラコンチル、ペンタコンチル、イソプロピル、イソブチル、ｓｅｃ−ブチル、ｔ−ブチル、イソペンチル、ネオペンチル、ｔ−ペンチル、１−メチルペンチル、２−メチルペンチル、３−メチルペンチル、４−メチルペンチル、イソへキシル、１−エチルペンチル、２−エチルペンチル、３−エチルペンチル、４−エチルペンチル、および２，４−ジメチルヘキシルである。炭素数１〜５０の置換アルキルの例は、メトキシ、エトキシ、プロピルオキシ、ブチルオキシ、ペンチルオキシ、ヘキシルオキシ、メトキシメチル、メトキシエチル、メトキシプロピル、メトキシブチル、メトキシペンチル、メトキシヘキシル、エトキシメチル、エトキシエチル、エトキシプロピル、エトキシブチル、エトキシペンチル、エトキシへキシル、ヘキシルオキシメチル、ヘキシルオキシエチル、ヘキシルオキシプロピル、ヘキシルオキシブチル、およびヘキシルオキシペンチルである。 Examples of alkyl having 1 to 50 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, icosyl, triacontyl, tetracontyl, pentacontyl, isopropyl, isobutyl, sec- Butyl, t-butyl, isopentyl, neopentyl, t-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, isohexyl, 1-ethylpentyl, 2-ethylpentyl, 3- Ethylpentyl, 4-ethylpentyl, and 2,4-dimethylhexyl. Examples of substituted alkyl having 1 to 50 carbon atoms are methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, ethoxymethyl, ethoxyethyl Ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl, and hexyloxypentyl.
配向膜に要求される特性をさらに効果的に発現させるため、薄膜化したときの表面エネルギーの値が異なるワニスを２種類以上混合する方法（ポリマーブレンド）がしばしば行われている。たとえば、特開平８−４３８３１号公報は、２成分以上の重合体混合液すなわちワニスから樹脂塗膜を形成した場合、表面張力の小さい成分が自発的に膜表面に偏析しやすい特性を利用している。良好な液晶配向特性を有する樹脂塗膜の表面張力を、良好な電気的特性を発現する樹脂塗膜の表面張力よりも２ｄｙｎｅ／ｃｍ以上小さくすることにより、配向膜表面には良好な液晶配向性を示す樹脂塗膜を形成させ、良好な電気的特性を発現する樹脂成分を主成分とする構造の配向膜を得る方法が該公報に開示されている。 In order to more effectively express the characteristics required for the alignment film, a method (polymer blend) in which two or more varnishes having different surface energy values when thinned is mixed is often performed. For example, Japanese Patent Application Laid-Open No. 8-43831 utilizes the property that when a resin coating film is formed from a polymer mixture of two or more components, that is, a varnish, a component having a small surface tension is likely to segregate spontaneously on the film surface. Yes. By making the surface tension of the resin coating film having good liquid crystal alignment characteristics 2 dyne / cm or more smaller than the surface tension of the resin coating film exhibiting good electrical characteristics, the surface of the alignment film has good liquid crystal alignment characteristics. A method of forming an alignment film having a resin component as a main component and forming a resin coating film exhibiting good electrical characteristics is disclosed in this publication.
本発明の化合物（１）、化合物（２）または化合物（３）をこの方法に応用する場合、Ｒ１〜Ｒ１４が水素、炭素数１〜２０のアルキル、またはフェニル、ビフェニルであるとき、化合物（１）、化合物（２）または化合物（３）は、表面張力が相対的に小さな成分として特に好適である。Ｒ１〜Ｒ１４が炭素数２１〜５０を有する基であるとき、化合物（１）、化合物（２）または化合物（３）の表面張力が相対的に大きな成分として特に好適である。 When the compound (1), compound (2) or compound (3) of the present invention is applied to this method, when R 1 to R 14 are hydrogen, alkyl having 1 to 20 carbons, or phenyl or biphenyl, the compound (1), Compound (2) or Compound (3) is particularly suitable as a component having a relatively small surface tension. When R 1 to R 14 are groups having 21 to 50 carbon atoms, the compound (1), the compound (2) or the compound (3) is particularly suitable as a component having a relatively large surface tension.
また、化合物（１）、化合物（２）または化合物（３）と長い側鎖を有するジアミンとを反応させて得られる反応生成物を含有するワニスにおいて、長い側鎖を有するジアミンがもたらす効果を発揮させるためには、化合物（１）、化合物（２）または化合物（３）におけるＲ１〜Ｒ１４を水素、フッ素または炭素数１〜６のアルキルとするのが好ましい。合成し易いという点をも考慮した場合、水素、メチル、エチル、またはプロピルとするのが特に好ましい。 Moreover, in the varnish containing the reaction product obtained by reacting the compound (1), the compound (2) or the compound (3) with a diamine having a long side chain, the effect of the diamine having a long side chain is exhibited. In order to achieve this, R 1 to R 14 in the compound (1), compound (2) or compound (3) are preferably hydrogen, fluorine or alkyl having 1 to 6 carbon atoms. In consideration of easy synthesis, hydrogen, methyl, ethyl, or propyl is particularly preferable.
本発明の化合物（１）は、以下のような方法で容易に合成できる。
本発明の化合物（２）は、以下のような方法で容易に合成できる。
本発明の化合物（３）は、以下のような方法で容易に合成できる。
式（１）におけるＲ１〜Ｒ４の組み合わせを表１に示す。
Ｒは炭素数１〜５０の１価の有機基である。
各パターンとも、Ｈの代わりにそれぞれ独立してＦであってもよい。
Table 1 shows combinations of R 1 to R 4 in the formula (1).
R is a monovalent organic group having 1 to 50 carbon atoms.
Each pattern may be independently F instead of H.
式（２）におけるＲ５〜Ｒ１０の組み合わせを表２に示す。
Ｒは炭素数１〜５０の１価の有機基である。
各パターンとも、Ｈの代わりにそれぞれ独立してＦであってもよい。
Table 2 shows combinations of R 5 to R 10 in the formula (2).
R is a monovalent organic group having 1 to 50 carbon atoms.
Each pattern may be independently F instead of H.
式（３）におけるＲ１１〜Ｒ１４の組み合わせを表３に示す。
Ｒは炭素数１〜５０の１価の有機基である。
各パターンとも、Ｈの代わりにそれぞれ独立してＦであってもよい。
Table 3 shows combinations of R 11 to R 14 in the formula (3).
R is a monovalent organic group having 1 to 50 carbon atoms.
Each pattern may be independently F instead of H.
式（１）で表される化合物の好ましい例を列記する。
パターン（１−１）の場合（Ｒ１〜Ｒ４の全てがＲでない）を例示する。
The case of pattern (1-1) is exemplified (all of R 1 to R 4 are not R).
パターン（１−２）の場合（Ｒ１〜Ｒ４のうち、１つがＲである）を例示する。
パターン（１−３）の場合（Ｒ１〜Ｒ４のうち、２つがＲである）を例示する。
パターン（１−４）の場合（Ｒ１〜Ｒ４のうち、３つがＲである）を例示する。
パターン（１−５）の場合（Ｒ１〜Ｒ４の全てがＲである）を例示する。
式（２）で表される化合物の好ましい例を列記する。
パターン（２−１）の場合（Ｒ５〜Ｒ１０の全てがＲでない）を例示する。
The case of pattern (2-1) (all of R 5 to R 10 are not R) is exemplified.
パターン（２−２）の場合（Ｒ５〜Ｒ１０のうち、１つがＲである）を例示する。
パターン（２−３）の場合（Ｒ５〜Ｒ１０のうち、２つがＲである）を例示する。
パターン（２−４）の場合（Ｒ５〜Ｒ１０のうち、３つがＲである）を例示する。
パターン（２−５）の場合（Ｒ５〜Ｒ１０のうち、４つがＲである）を例示する。
パターン（２−６）の場合（Ｒ５〜Ｒ１０のうち、５つがＲである）を例示する。
パターン（２−７）の場合（Ｒ５〜Ｒ１０のすべてがＲである）を例示する。
式（３）で表される化合物の好ましい例を列記する。
パターン（３−１）の場合（Ｒ１１〜Ｒ１４の全てがＲでない）を例示する。
The case of pattern (3-1) (all of R 11 to R 14 are not R) is exemplified.
パターン（３−２）の場合（Ｒ１１〜Ｒ１４のうち、１つがＲである）を例示する。
パターン（３−３）の場合（Ｒ１１〜Ｒ１４のうち、２つがＲである）を例示する。
パターン（３−４）の場合（Ｒ１１〜Ｒ１４のうち、３つがＲである）を例示する。
パターン（３−５）の場合（Ｒ１１〜Ｒ１４の全てがＲである）を例示する。
上記のうち、特性に優れ、また合成の容易さの点から１−１−１、１−１−２、１−１−３、１−１−４、１−１−５、１−１−６、１−２−１、１−２−３、１−２−４、１−２−６、１−２−８、１−３−１、１−３−２、１−３−４、１−３−５、１−３−６、１−３−８、１−４−１、１−４−２、１−４−４、１−４−５、１−４−６、１−４−８、１−４−９、１−５−１、１−５−２、１−５−５、１−５−６、１−５−８、１−５−９、２−１−１、２−１−２、２−１−３、２−１−４、２−１−５、２−１−６、２−２−１、２−２−２、２−２−３、２−２−６、２−２−７、２−２−８、２−２−９、２−２−１０、２−２−１１、２−２−１２、２−３−１、２−３−２、２−３−４、２−３−５、２−３−６、２−３−８、２−３−９、２−３−１１、２−３−１２、２−４−１、２−４−２、２−４−３、２−４−４、２−４−５、２−４−６、２−４−８、２−４−９、２−４−１０、２−４−１１、２−４−１２、２−５−１、２−５−２、２−５−３、２−５−５、２−５−６、２−５−８、２−５−９、２−５−１０、２−５−１２、２−６−１、２−６−２、２−６−３、２−６−６、２−６−７、２−６−８、２−６−９、２−６−１０、２−６−１１、２−６−１２、２−７−１、２−７−２、２−７−３、２−７−５、２−７−８、２−７−９、２−７−１０、２−７−１１、３−１−１、３−１−２、３−１−３、３−１−４、３−１−５、３−１−６、３−２−１、３−２−３、３−２−４、３−２−６、３−２−８、３−３−１、３−３−２、３−３−４、３−３−５、３−３−６、３−３−８、３−４−１、３−４−２、３−４−４、３−４−５、３−４−６、３−４−８、３−４−９、３−５−１、３−５−２、３−５−５、３−５−６、３−５−８、および３−５−９がより好ましく、１−１−１、１−１−２、１−１−３、１−１−４、１−１−５、１−１−６、１−２−１、１−２−４、１−２−６、１−２−８、１−３−１、１−３−２、１−３−６、１−３−８、１−４−１、１−４−２、１−４−８、１−４−９、１−５−１、１−５−２、１−５−８、１−５−９、２−１−１、２−１−２、２−１−３、２−１−４、２−１−５、２−１−６、２−２−１、２−２−６、２−２−１０、２−２−１２、２−３−１、２−３−４、２−３−１２、２−４−１、２−４−２、２−４−３、２−４−４、２−４−９、２−４−１０、２−４−１２、２−５−１、２−５−２、２−５−３、２−５−５、２−５−６、２−５−８、２−５−９、２−５−１０、２−５−１２、２−６−１、２−６−２、２−６−６、２−６−７、２−６−９、２−６−１２、２−７−１、２−７−２、２−７−８、２−７−９、２−７−１１、３−１−１、３−１−２、３−１−３、３−１−４、３−１−５、３−１−６、３−２−１、３−２−４、３−２−６、３−２−８、３−３−１、３−３−２、３−３−６、３−３−８、３−４−１、３−４−２、３−４−８、３−４−９、３−５−１、３−５−２、３−５−８、および３−５−９が更に好ましく、１−１−１、１−１−２、１−１−３、１−１−４、１−１−５、１−１−６、１−２−１、１−２−４、１−３−１、１−３−２、１−３−６、１−４−１、１−４−２、１−５−１、１−５−２、２−１−１、２−１−２、２−１−３、２−１−４、２−１−５、２−１−６、２−２−１、２−２−６、２−３−１、２−３−４、２−３−１２、２−４−１、２−４−２、２−４−３、２−４−４、２−４−９、２−４−１０、２−５−１、２−５−２、２−５−３、２−５−５、２−５−６、２−５−１０、２−５−１２、２−６−１、２−６−２、２−６−６、２−６−１２、２−７−１、２−７−２、２−７−８、２−７−１１、３−１−１、３−１−２、３−１−３、３−１−４、３−１−５、３−１−６、３−２−１、３−２−４、３−３−１、３−３−２、３−３−６、３−４−１、３−４−２、３−５−１、および３−５−２がより一層好ましく、１−１−１、１−２−１、１−３−１、１−３−２、１−３−６、１−４−１、１−５−１、２−１−１、２−２−１、２−３−１、２−４−１、２−４−３、２−４−９、２−４−１０、２−５−１、２−５−２、２−５−３、２−５−５、２−５−１０、２−６−１、２−６−２、２−７−１、２−７−２、３−１−１、３−２−１、３−３−１、３−３−２、３−３−６、３−４−１、および３−５−１が特に好ましい。 Among the above, 1-1-1, 1-1-2, 1-1-3, 1-1-4, 1-1-5, 1-1- 1 are excellent in characteristics and easy to synthesize. 6, 1-2-1, 1-2-3, 1-2-4, 1-2-6, 1-2-8, 1-3-1, 1-3-2, 1-3-4, 1-3-5, 1-3-6, 1-3-8, 1-4-1, 1-4-2, 1-4-4, 1-4-5, 1-4-4-, 1- 4-8, 1-4-9, 1-5-1, 1-5-2, 1-5-5, 1-5-6, 1-5-8, 1-5-9, 2-1 1, 2-1-2, 2-1-3, 2-1-4, 2-1-5, 2-1-6, 2-2-1, 2-2-2, 2-2-3, 2-2-6, 2-2-7, 2-2-8, 2-2-9, 2-2-10, 2-2-11, 2-2-12, 2-3-1, 2- 3-2, 2-3-4, 2-3-5, 2-3-6, -3-8, 2-3-9, 2-3-11, 2-3-13, 2-4-1, 2-4-2, 2-4-3, 2-4-4, 2-4 -5, 2-4-6, 2-4-8, 2-4-9, 2-4-10, 2-4-11, 2-4-12, 2-5-1, 2-5-2 2-5-3, 2-5-5, 2-5-6, 2-5-8, 2-5-9, 2-5-10, 2-5-12, 2-6-1, 2 -6-2, 2-6-3, 2-6-6, 2-6-7, 2-6-8, 2-6-9, 2-6-10, 2-6-11, 2-6 -12, 2-7-1, 2-7-2, 2-7-3, 2-7-5, 2-7-8, 2-7-9, 2-7-10, 2-7-11 3-1-1, 3-1-2, 3-1-3, 3-1-4, 3-1-5, 3-1-6, 3-2-1, 3-2-3, 3 -2-4, 3-2-6, 3-2-8, 3-3 1, 3-3-3, 3-3-4, 3-3-5, 3-3-6, 3-3-8, 3-4-1, 3-4-2, 3-4-4, 3-4-5, 3-4-6, 3-4-8, 3-4-9, 3-5-1, 3-5-2, 3-5-5, 3-5-6, 3- 5-8 and 3-5-9 are more preferable, 1-1-1, 1-1-2, 1-1-3, 1-1-4, 1-1-5, 1-1-6, 1-2-1, 1-2-4, 1-2-6, 1-2-8, 1-3-1, 1-3-2, 1-3-6, 1-3-8, 1- 4-1, 1-4-2, 1-4-8, 1-4-9, 1-5-1, 1-5-2, 1-5-8, 1-5-9, 2-1 1, 2-1-2, 2-1-3, 2-1-4, 2-1-5, 2-1-6, 2-2-1, 2-2-6, 2-2-10, 2-2-12, 2-3-1, 1-2-3-4, 2-3-12, 2-4-1, 2-4-2, 2-4-3, 2-4-4, 2-4-9, 2-4-10, 2-4-12, 2-5-1, 2- 5-2, 2-5-3, 2-5-5, 2-5-6, 2-5-8, 2-5-9, 2-5-10, 2-5-12, 2-6 1, 2-6-2, 2-6-6, 2-6-7, 2-6-9, 2-6-12, 2-7-1, 2-7-2, 2-7-8, 2-7-9, 2-7-11, 3-1-1, 3-1-2, 3-1-3, 3-1-4, 3-1-5, 3-1-6, 3- 2-1, 3-2-4, 3-2-6, 3-2-8, 3-3-1, 3-3-2, 3-3-6, 3-3-8, 3-4- 1, 3-4-2, 3-4-8, 3-4-9, 3-5-1, 3-5-2, 3-5-8, and 3-5-9 are more preferable. 1-1, 1-1-2, 1-1-3, 1-1-4 1-1-5, 1-1-6, 1-2-1, 1-2-4, 1-3-1, 1-3-2, 1-3-6, 1-4-1, 1- 4-2, 1-5-1, 1-5-2, 2-1-1, 2-1-2, 2-1-3, 2-1-4, 2-1-5, 2-1 6, 2-2-1, 2-2-2-6, 2-3-1, 1-2-3-4, 2-3-12, 2-4-1, 2-4-2, 2-4-3, 2-4-4, 2-4-9, 2-4-10, 2-5-1, 2-5-2, 2-5-3, 2-5-5, 2-5-6, 2- 5-10, 2-5-12, 2-6-1, 2-6-2, 2-6-6, 2-6-12, 2-7-1, 2-7-2, 2-7- 8, 2-7-11, 3-1-1, 3-1-2, 3-1-3, 3-1-4, 3-1-5, 3-1-6, 3-2-1, 3-2-4, 3-3-1, 3-3-2, 3-3-6, 3- -1, 3-4-2, 3-5-1, and 3-5-2 are more preferable, 1-1-1, 1-2-1, 1-3-1, 1-3-2, 1-3-6, 1-4-1, 1-5-1, 2-2-1, 2-2-1, 2-3-1, 2-4-1, 2-4-2, 2- 4-9, 2-4-10, 2-5-1, 2-5-2, 2-5-3, 2-5-5, 2-5-10, 2-6-1, 2-6-6 2, 2-7-1, 2-7-2, 3-1-1, 3-2-1, 3-3-1, 3-3-2, 3-3-6, 3-4-1, And 3-5-1 are particularly preferred.
第二に、本発明の重合体について説明する。本発明の重合体の好ましい例は、ポリアミック酸、ポリイミドおよびポリアミドイミドである。
ポリアミック酸は、本発明のテトラカルボン酸二無水物として化合物（１）、化合物（２）または化合物（３）を溶媒中でジアミンと反応させることによって得られる。ポリイミドは、このポリアミック酸の脱水反応等によって得られる。ポリアミドイミドは、本発明のテトラカルボン酸二無水物として化合物（１）、化合物（２）または化合物（３）、ジアミン、およびトリカルボン酸またはジカルボン酸またはこれらの酸の誘導体とを反応させて得られる。なお、トリカルボン酸またはジカルボン酸の誘導体とは、トリカルボン酸のトリメチルエステル、ジメチルエステル、トリエチルエステル、ジエチルエステル、ジカルボン酸のジメチルエステル、ジエチルエステルなどをいう。反応は通常の公知の反応条件で行えばよい。このとき、本発明のテトラカルボン酸二無水物を単独で使用してもよく、本発明のテトラカルボン酸二無水物を２つ以上組み合わせて使用してもよく、更に本発明のテトラカルボン酸二無水物と公知のテトラカルボン酸二無水物とを組み合わせて使用してもよい。
Secondly, the polymer of the present invention will be described. Preferred examples of the polymer of the present invention are polyamic acid, polyimide and polyamideimide.
A polyamic acid is obtained by making a compound (1), a compound (2), or a compound (3) react with diamine in a solvent as the tetracarboxylic dianhydride of this invention. Polyimide is obtained by dehydration reaction of this polyamic acid. Polyamideimide is obtained by reacting compound (1), compound (2) or compound (3), diamine, and tricarboxylic acid or dicarboxylic acid or derivatives of these acids as the tetracarboxylic dianhydride of the present invention. . The tricarboxylic acid or dicarboxylic acid derivative means tricarboxylic acid trimethyl ester, dimethyl ester, triethyl ester, diethyl ester, dicarboxylic acid dimethyl ester, diethyl ester or the like. The reaction may be performed under ordinary known reaction conditions. At this time, the tetracarboxylic dianhydride of the present invention may be used alone, or two or more of the tetracarboxylic dianhydrides of the present invention may be used in combination. An anhydride and a known tetracarboxylic dianhydride may be used in combination.
本発明のテトラカルボン酸二無水物と反応させることのできるジアミンは、脂肪族ジアミン、脂環式ジアミンおよび芳香族ジアミンである。これらのジアミンの内、好適なジアミンの例を表４〜表６に示す。 Diamines that can be reacted with the tetracarboxylic dianhydrides of the present invention are aliphatic diamines, alicyclic diamines and aromatic diamines. Examples of suitable diamines among these diamines are shown in Tables 4 to 6.
上記以外のジアミンの例は、式（５）で表されるシロキサン系のジアミンである。
これらのジアミンは単独で使用してもよく、２つ以上を組み合わせて使用してもよい。特に好ましいジアミンは、Ｎｏ．４−８、４−９、４−１２、４−１３、４−１４、４−１５、４−１６、４−１８、４−１９、４−２１、４−２７、４−３２、４−３３、４−３４、４−３５、４−３７、４−４２、４−４４、４−４５、および４−４６のジアミンである。さらに、本発明に使用するジアミンは上記化合物以外でもよい。 These diamines may be used alone or in combination of two or more. Particularly preferred diamines are No. 4-8, 4-9, 4-12, 4-13, 4-14, 4-15, 4-16, 4-18, 4-19, 4-21, 4-27, 4-32, 4- 33, 4-34, 4-35, 4-37, 4-42, 4-44, 4-45, and 4-46 diamines. Furthermore, the diamine used in the present invention may be other than the above compounds.
本発明のテトラカルボン酸二無水物と併用することのできる他のテトラカルボン酸二無水物の例を表７に示す。 Table 7 shows examples of other tetracarboxylic dianhydrides that can be used in combination with the tetracarboxylic dianhydride of the present invention.
これらのテトラカルボン酸二無水物と併用する時、電圧保持率が上昇し、また焼き付きの指標である残留ＤＣ電圧が単独使用の時よりも減少する。これらの化合物の中には異性体を含むものがあるが、これらの異性体混合物であってもかまわない。また、これらの化合物を２つ以上併用してもよい。また、本発明のテトラカルボン酸二無水物と併用するテトラカルボン酸二無水物は、上記化合物以外でもよい。これらの化合物において、特に好ましいテトラカルボン酸二無水物は、Ｎｏ．５−１、５−２、５−７、５−１１、および５−１２のテトラカルボン酸二無水物である。 When used in combination with these tetracarboxylic dianhydrides, the voltage holding ratio is increased, and the residual DC voltage, which is an index of burn-in, is reduced as compared with the single use. Some of these compounds include isomers, but a mixture of these isomers may be used. Two or more of these compounds may be used in combination. Moreover, the tetracarboxylic dianhydride used together with the tetracarboxylic dianhydride of the present invention may be other than the above compounds. Among these compounds, particularly preferred tetracarboxylic dianhydrides are No. 5-1, 5-2, 5-7, 5-11, and 5-12 tetracarboxylic dianhydrides.
第三に、本発明のワニスについて説明する。
本発明のワニスは、化合物（１）、化合物（２）または化合物（３）を原料の一部として反応させて得られる重合体を含有する。本発明のワニスは該反応に用いられた反応混合物そのものであってもよいが反応混合物から溶媒を留去して得られた固形物（以下、反応生成物と略称することがある。）を、該反応に用いたのと異なる溶媒に溶解させた溶液であってもよい。
本発明の反応生成物を有機溶媒に溶解してなるワニスを調製するために使用される溶媒の例は、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡｃ）、ジメチルスルホキシド（ＤＭＳＯ）、エチレングリコールモノブチルエーテル（ＢＣ）、エチレングリコールモノエチルエーテル、およびγ−ブチロラクトンである。これらの２種以上を混合して用いてもよい。また、上記溶媒以外であっても反応生成物が可溶であればこれら以外の溶媒を用いてもよい。
Third, the varnish of the present invention will be described.
The varnish of the present invention contains a polymer obtained by reacting compound (1), compound (2) or compound (3) as part of the raw material. The varnish of the present invention may be the reaction mixture itself used in the reaction, but a solid obtained by distilling off the solvent from the reaction mixture (hereinafter sometimes abbreviated as reaction product). It may be a solution dissolved in a solvent different from that used in the reaction.
Examples of the solvent used for preparing a varnish obtained by dissolving the reaction product of the present invention in an organic solvent are N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc). , Dimethyl sulfoxide (DMSO), ethylene glycol monobutyl ether (BC), ethylene glycol monoethyl ether, and γ-butyrolactone. Two or more of these may be mixed and used. In addition to the above solvents, other solvents may be used as long as the reaction product is soluble.
配向膜の特性をさらに改善するために、本発明の重合体としてポリアミック酸、ポリイミドまたはポリアミドイミドを組み合わせて使用してもよい。
上記ポリアミドイミドを添加して用いる場合のポリアミドイミドのワニスへの添加量は、ワニスに含有される反応生成物固形分に対して、０．０１〜３０重量％、好ましくは０．０１〜１０重量％、より好ましくは０．１〜５重量％である。
In order to further improve the properties of the alignment film, polyamic acid, polyimide or polyamideimide may be used in combination as the polymer of the present invention.
When the polyamideimide is added and used, the amount of polyamideimide added to the varnish is 0.01 to 30% by weight, preferably 0.01 to 10% by weight based on the solid content of the reaction product contained in the varnish. %, More preferably 0.1 to 5% by weight.
さらに配向膜のガラス基板への密着性の改善や硬さの調節等を行うために、有機シリコン化合物等をこれらに添加してもよい。 Furthermore, in order to improve the adhesion of the alignment film to the glass substrate, adjust the hardness, etc., an organic silicon compound or the like may be added thereto.
本発明のワニスへ添加される有機シリコン化合物の例は、アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン、ビニルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、ビニルトリエトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランなどのシランカップリング剤、ジメチルポリシロキサン、ポリジメチルシロキサン、ポリジフェニルシロキサンなどのシリコーンオイルである。該有機シリコン化合物のワニスへの添加量は、ワニスに含有される反応生成物に対して、０．０１〜５重量％、好ましくは０．１〜３重量％である。 Examples of organosilicon compounds added to the varnish of the present invention include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Silane coupling agents such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and silicone oils such as dimethylpolysiloxane, polydimethylsiloxane, and polydiphenylsiloxane. The amount of the organosilicon compound added to the varnish is 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the reaction product contained in the varnish.
第四に、本発明のワニスから製造される配向膜について説明する。
本発明の配向膜の製造方法は特に限定されるものではないが、具体的にはワニスの総重量の０．１〜３０重量％、好ましくは１〜１０重量％の濃度となるように、本発明の反応生成物である重合体およびその他の成分を溶媒に溶解し、この溶液（ワニス）を刷毛塗り法、浸漬法、スピンナー法、スプレー法、印刷法等により基板上に塗布する。その後５０〜１５０℃、好ましくは８０〜１２０℃で溶媒を蒸発させた後、１５０〜４００℃、好ましくは１８０〜２８０℃で加熱焼成し、成膜する。塗布前に基板表面上をシランカップリング剤で処理し、その上に成膜すれば膜と基板との接着性を改善できる。その後この膜表面を布などで一方向にラビングすると、配向膜が得られる。
本発明のテトラカルボン酸二無水物は、液晶配向膜用重合体の原料以外にも、各種ポリイミドコーティング剤、ポリイミド樹脂の成形品、フィルムまたは繊維等に利用することができる。
Fourth, an alignment film produced from the varnish of the present invention will be described.
The method for producing the alignment film of the present invention is not particularly limited. Specifically, the present invention is performed so that the concentration is 0.1 to 30% by weight, preferably 1 to 10% by weight of the total weight of the varnish. The polymer, which is the reaction product of the invention, and other components are dissolved in a solvent, and this solution (varnish) is applied onto the substrate by a brush coating method, a dipping method, a spinner method, a spray method, a printing method, or the like. Thereafter, the solvent is evaporated at 50 to 150 ° C., preferably 80 to 120 ° C., and then heated and fired at 150 to 400 ° C., preferably 180 to 280 ° C., to form a film. The adhesion between the film and the substrate can be improved by treating the surface of the substrate with a silane coupling agent before coating and forming a film thereon. Thereafter, the film surface is rubbed in one direction with a cloth or the like to obtain an alignment film.
The tetracarboxylic dianhydride of the present invention can be used for various polyimide coating agents, polyimide resin molded products, films, fibers, and the like, in addition to the raw material for the liquid crystal alignment film polymer.
第五に、本発明の配向膜を用いた液晶表示素子について説明する。
本発明の配向膜を使用すれば、公知の全ての液晶表示素子に関し、その特性を改善できるが、特に高い電圧保持率が要求されるＴＦＴ用液晶表示素子の焼き付き改善に本発明の配向膜は効果が大きい。このようなＴＦＴ用液晶表示素子に使用される液晶組成物の例として、特許第３０８６２２８号、特許２６３５４３５号、特表平５−５０１７３５、および特平開９−２５５９５６等に記載された液晶組成物が挙げられる。したがって本発明の配向膜はこれらに記載された液晶組成物と組み合わせて用いることが特に好ましい。
Fifth, a liquid crystal display element using the alignment film of the present invention will be described.
If the alignment film of the present invention is used, the characteristics of all known liquid crystal display elements can be improved. However, the alignment film of the present invention is particularly useful for improving the burn-in of a liquid crystal display element for TFTs that requires a high voltage holding ratio. Great effect. Examples of the liquid crystal composition used in such a liquid crystal display element for TFT include liquid crystal compositions described in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 9-255556, and the like. Is mentioned. Therefore, the alignment film of the present invention is particularly preferably used in combination with the liquid crystal composition described therein.
以下、実施例により、本発明のテトラカルボン酸二無水物およびこの化合物を用いることによって得られる液晶配向膜を詳細に説明する。重合体の分子量の測定はゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用い、ポリスチレンを標準溶液とし、溶出液はＤＭＦを用いた。なお本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the liquid crystal aligning film obtained by using the tetracarboxylic dianhydride of this invention and this compound is demonstrated in detail by an Example. The molecular weight of the polymer was measured using gel permeation chromatography (GPC), polystyrene as a standard solution, and DMF as the eluent. The present invention is not limited to these examples.
液晶表示素子の評価法
１．プレチルト角
クリスタルローテーション法により測定した。
２．焼き付き（残留ＤＣ電圧）
三宅他、信学技報、ＥＩＤ９１−１１１，ｐ１９に記載の方法により、残留ＤＣ電圧を測定した。この残留ＤＣ電圧を焼き付きの指標にした。残留ＤＣ電圧が高いほど焼き付きやすいと判定した。測定時液晶セルに印加した電圧は、５０ｍＶ、１ｋＨｚの交流と、周波数０．００３６Ｈｚの三角波を重畳させた交流電圧である。
３．電圧保持率
「水嶋他、第１４回液晶討論会予稿集 ｐ７８」に記載の方法により、ゲート幅６９μｓ、周波数６０Ｈｚ、波高±４．５Ｖの矩形波をセルに印加して残留ＤＣ電圧を測定した。
実施例中に記載された諸物性の測定値は、特に断りのない限り２５℃で測定した値である。
Evaluation method of liquid crystal display element Pretilt angle Measured by the crystal rotation method.
2. Burn-in (residual DC voltage)
Residual DC voltage was measured by the method described in Miyake et al., Shingaku Giho, EID91-111, p19. This residual DC voltage was used as an index for burn-in. It was determined that the higher the residual DC voltage, the easier it was to burn. The voltage applied to the liquid crystal cell at the time of measurement is an AC voltage obtained by superimposing 50 mV, 1 kHz AC and a triangular wave having a frequency of 0.0036 Hz.
3. Voltage holding ratio By the method described in “Mizushima et al., 14th Liquid Crystal Symposium Proceedings p78”, a rectangular wave having a gate width of 69 μs, a frequency of 60 Hz, and a wave height of ± 4.5 V was applied to the cell, and the residual DC voltage was measured .
The measured values of various physical properties described in the examples are values measured at 25 ° C. unless otherwise specified.
実施例１
１，２，３，４−テトラヒドロ−１，４−メタノナフタレン−１，２−３，４−テトラカルボン酸二無水物（１−１）の合成
Example 1
Synthesis of 1,2,3,4-tetrahydro-1,4-methanonaphthalene-1,2,3,4-tetracarboxylic dianhydride (1-1)
（１）１，３−ジエチルカルボキシインデンの合成
（２）１，２，３，４−テトラヒドロ−１，４−メタノナフタレン−１，４−ジエチルカルボキシ−２，３−ジカルボン酸二無水物の合成
（３）１，２，３，４−テトラヒドロ−１，４−メタノナフタレン−１，２−３，４−テトラカルボン酸の合成
（４）１，２，３，４−テトラヒドロ−１，４−メタノナフタレン−１，２−３，４−テトラカルボン酸二無水物の合成
１Ｈ−ＮＭＲ（ｐｐｍ）：２．９１（ＣＨ２，ｄ，Ｊ＝７Ｈｚ），３．８０（ＣＨ，ｓ），６．９１−７．３０（ａｒｏｍａｔｉｃ Ｈ，ｂｒ）．
(4) Synthesis of 1,2,3,4-tetrahydro-1,4-methanonaphthalene-1,3-3,4-tetracarboxylic dianhydride
1 H-NMR (ppm): 2.91 (CH 2 , d, J = 7 Hz), 3.80 (CH, s), 6.91-7.30 (aromatic H, br).
実施例２
ポリアミック酸の合成
攪拌機、窒素導入口、温度計、および原料導入口を供えた１００ｍｌの４つ口フラスコに、４,４'−ジアミノジフェニルメタン（以下、ＤＤＭと略称する。）７９２ｍｇ（４ｍｍｏｌ）を入れ、Ｎ−メチル−２−ピロリドン（ＮＭＰ）１０ｇに溶解した。ここに実施例１で合成した１，２，３，４−テトラヒドロ−１，４−メタノナフタレン−１，２−３，４−テトラカルボン酸二無水物２８４ｍｇ（１ｍｍｏｌ）を加え、６時間攪拌した。その後、この反応混合物をＮＭＰ３０ｇで希釈することにより、ポリアミック酸約５重量％の透明溶液が得られた。この溶液中の重合体の重量平均分子量をポリスチレン標準のゲルパーミエーションクロマトグラフィー（カラム：Ｓｈｏｄｅｘ ＧＦ−７ＭＨＱ、溶媒：ＤＭＦ、流量：０．５ｍｌ／ｍｉｎ、測定温度：５０℃）で測定したところ、５．７万であった。また、この溶液の２５℃での粘度は３５ｍＰａ・ｓであった。以下、この溶液をワニスＡとする。
Example 2
Synthesis of polyamic acid 792 mg (4 mmol) of 4,4′-diaminodiphenylmethane (hereinafter abbreviated as DDM) was placed in a 100 ml four-necked flask equipped with a stirrer, a nitrogen inlet, a thermometer, and a raw material inlet. , N-methyl-2-pyrrolidone (NMP) 10 g. To this, 284 mg (1 mmol) of 1,2,3,4-tetrahydro-1,4-methanonaphthalene-1,3-3,4-tetracarboxylic dianhydride synthesized in Example 1 was added and stirred for 6 hours. . Thereafter, the reaction mixture was diluted with 30 g of NMP to obtain a clear solution of about 5% by weight of polyamic acid. When the weight average molecular weight of the polymer in this solution was measured by polystyrene standard gel permeation chromatography (column: Shodex GF-7MHQ, solvent: DMF, flow rate: 0.5 ml / min, measurement temperature: 50 ° C.), It was 57,000. The viscosity of this solution at 25 ° C. was 35 mPa · s. Hereinafter, this solution is referred to as varnish A.
実施例３〜５、比較例１〜３
実施例２に準じた方法によって、表８に示した原料モル比の酸二無水物およびジアミンを用いて実施例３〜５のワニスを調製した（表８には実施例２も再掲する）。また、本発明の化合物以外の酸二無水物を用いて得られた比較例１〜３のワニスについても、表８に示した。これらのワニス中の重合体の重量平均分子量およびワニスの粘度を表９に示した。
Examples 3-5, Comparative Examples 1-3
By the method according to Example 2, the varnishes of Examples 3 to 5 were prepared using the acid dianhydride and diamine in the raw material molar ratio shown in Table 8 (Example 2 is also shown in Table 8). Table 8 also shows the varnishes of Comparative Examples 1 to 3 obtained using an acid dianhydride other than the compound of the present invention. Table 9 shows the weight average molecular weights of the polymers in these varnishes and the varnish viscosity.
ＢＨＴＡＣ：ビシクロ［２，２，１］ヘプタン−２，３，５，６−テトラカルボン酸二無水物： （表７、Ｎｏ．５−１３）
ＤＤＭ：４，４’−ジアミノジフェニルメタン： （表４、Ｎｏ．４−１３）
ＤＤＥｔ：４，４’−ジアミノジフェニルエタン： （表４、Ｎｏ．４−１８）
BHTAC: Bicyclo [2,2,1] heptane-2,3,5,6-tetracarboxylic dianhydride: (Table 7, No. 5-13)
DDM: 4,4′-diaminodiphenylmethane: (Table 4, No. 4-13)
DDEt: 4,4′-diaminodiphenylethane: (Table 4, No. 4-18)
実施例２の配向膜の特性評価として、スクリューバイアルに実施例２で得られたワニスＡを１８．２ｍｌ量り取り、ブチルセロソルブ（ＢＣ）１２ｍｌを加え、室温で１時間攪拌して、約３重量％の樹脂組成物を得た。片面にＩＴＯ電極を設けた透明ガラス基板上に、この組成物を滴下し、スピンナー法により塗布した（２５００ｒｐｍ、１５秒）。塗布後８０℃で５分間加熱し、溶媒を蒸発させた後、オーブン中で２５０℃、３０分間加熱焼成処理を行い、膜厚約６０ｎｍのポリイミド樹脂薄膜を得た。該樹脂薄膜が形成されたガラス基板をラビング処理し、ラビング方向が逆平行になるようにこれらの２枚を貼り合わせ、セル厚２０μｍの液晶セルを組み立てた。このセルに下記の液晶組成物Ａを注入し、１１０℃で３０分間アイソトロピック処理を行い、室温まで冷却し液晶表示素子を得た。この液晶表示素子の残留ＤＣ電圧は２５℃で０．０４Ｖであり、２０℃、６０℃、９０℃における電圧保持率はそれぞれ９８．５％、９８．０％、９７．６％であった（この値を初期値とする）。またこの表示素子を用いてプレチルト角を測定した結果、１．３度であった。このセルを１１０℃で２０時間静置、室温まで冷却した後、これらの値を再測定した（この値を高温後値とする）。その結果、残留ＤＣ電圧は０．０６Ｖ（２５℃）、電圧保持率は９７．３％（２０℃）、９６．９％（６０℃）、９６．６％（９０℃）、プレチルト角は１．７度であった。実施例３〜５および比較例１〜３として、上記ワニスＡをワニスＢ〜Ｇに代え、それ以外は実施例２に準拠して液晶表示素子を製作した。これらの特性の測定結果を表１０に示した。 As an evaluation of the properties of the alignment film of Example 2, 18.2 ml of varnish A obtained in Example 2 was weighed into a screw vial, 12 ml of butyl cellosolve (BC) was added, and the mixture was stirred at room temperature for 1 hour. A resin composition was obtained. This composition was dropped onto a transparent glass substrate provided with an ITO electrode on one side and applied by a spinner method (2500 rpm, 15 seconds). After coating, the film was heated at 80 ° C. for 5 minutes to evaporate the solvent, and then subjected to a baking process at 250 ° C. for 30 minutes in an oven to obtain a polyimide resin thin film having a thickness of about 60 nm. The glass substrate on which the resin thin film was formed was rubbed, and these two sheets were bonded so that the rubbing directions were antiparallel to assemble a liquid crystal cell having a cell thickness of 20 μm. The following liquid crystal composition A was poured into this cell, subjected to isotropic treatment at 110 ° C. for 30 minutes, and cooled to room temperature to obtain a liquid crystal display element. The residual DC voltage of this liquid crystal display element was 0.04 V at 25 ° C., and the voltage holding ratios at 20 ° C., 60 ° C., and 90 ° C. were 98.5%, 98.0%, and 97.6%, respectively ( This value is the initial value). Further, the pretilt angle was measured using this display element and found to be 1.3 degrees. The cell was allowed to stand at 110 ° C. for 20 hours and cooled to room temperature, and then these values were re-measured (this value is regarded as a post-high temperature value). As a result, the residual DC voltage was 0.06 V (25 ° C.), the voltage holding ratio was 97.3% (20 ° C.), 96.9% (60 ° C.), 96.6% (90 ° C.), and the pretilt angle was 1. It was 7 degrees. As Examples 3 to 5 and Comparative Examples 1 to 3, the varnish A was replaced with varnishes B to G, and liquid crystal display elements were produced according to Example 2 except that. The measurement results of these characteristics are shown in Table 10.
Claims (13)
A liquid crystal display device having the alignment film according to claim 12.
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| JP2008127311A (en) * | 2006-11-20 | 2008-06-05 | Mitsui Chemicals Inc | Diels-alder reaction composition of indene derivative |
| CN110452251A (en) * | 2019-09-02 | 2019-11-15 | 北京八亿时空液晶科技股份有限公司 | A kind of anhydride compounds and the preparation method and application thereof |
| CN110511229A (en) * | 2019-09-02 | 2019-11-29 | 北京八亿时空液晶科技股份有限公司 | A kind of anhydride compounds and the preparation method and application thereof |
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