CN103502312B - Composition, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display device - Google Patents
Composition, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display device Download PDFInfo
- Publication number
- CN103502312B CN103502312B CN201280020127.9A CN201280020127A CN103502312B CN 103502312 B CN103502312 B CN 103502312B CN 201280020127 A CN201280020127 A CN 201280020127A CN 103502312 B CN103502312 B CN 103502312B
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- liquid crystal
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- polyimide
- diamines
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- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 51
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- 239000004642 Polyimide Substances 0.000 claims abstract description 179
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 126
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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 claims abstract description 35
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 34
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- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 9
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- 125000003545 alkoxy group Chemical group 0.000 claims description 19
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- PQKFGIZEMNKNHY-UHFFFAOYSA-N Nc1cccc([SiH3])c1 Chemical compound Nc1cccc([SiH3])c1 PQKFGIZEMNKNHY-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- 101001062854 Rattus norvegicus Fatty acid-binding protein 5 Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- JABXMSSGPHGCII-UHFFFAOYSA-N acetic acid;propane-1,2-diol Chemical compound CC(O)=O.CC(O)CO JABXMSSGPHGCII-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- BALIDSJNGIOVDT-UHFFFAOYSA-N anthracene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=CC3=C(C(O)=O)C(C(=O)O)=CC=C3C=C21 BALIDSJNGIOVDT-UHFFFAOYSA-N 0.000 description 1
- MRSWDOKCESOYBI-UHFFFAOYSA-N anthracene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C=C(C(C(=O)O)=C3)C(O)=O)C3=CC2=C1 MRSWDOKCESOYBI-UHFFFAOYSA-N 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- GSEZYWGNEACOIW-UHFFFAOYSA-N bis(2-aminophenyl)methanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1N GSEZYWGNEACOIW-UHFFFAOYSA-N 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- LCQVWUUQYVVDLN-UHFFFAOYSA-N butan-2-yloxymethylbenzene Chemical compound CCC(C)OCC1=CC=CC=C1 LCQVWUUQYVVDLN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- JDPQWHLMBJZURR-UHFFFAOYSA-N decan-5-one Chemical compound CCCCCC(=O)CCCC JDPQWHLMBJZURR-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- GQOMZGDXKMTCGK-UHFFFAOYSA-N ethane;2-(oxiran-2-ylmethoxymethyl)oxirane Chemical compound CC.C1OC1COCC1CO1 GQOMZGDXKMTCGK-UHFFFAOYSA-N 0.000 description 1
- PPBYBJMAAYETEG-UHFFFAOYSA-N ethene;formaldehyde;urea Chemical compound C=C.O=C.NC(N)=O PPBYBJMAAYETEG-UHFFFAOYSA-N 0.000 description 1
- HJUFTIJOISQSKQ-UHFFFAOYSA-N fenoxycarb Chemical compound C1=CC(OCCNC(=O)OCC)=CC=C1OC1=CC=CC=C1 HJUFTIJOISQSKQ-UHFFFAOYSA-N 0.000 description 1
- 150000002220 fluorenes Chemical group 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 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 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- IPLONMMJNGTUAI-UHFFFAOYSA-M lithium;bromide;hydrate Chemical compound [Li+].O.[Br-] IPLONMMJNGTUAI-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- ZAJNGDIORYACQU-UHFFFAOYSA-N methyl n-octyl ketone Natural products CCCCCCCCC(C)=O ZAJNGDIORYACQU-UHFFFAOYSA-N 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 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
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- AUCNMQYOQYTGPE-UHFFFAOYSA-N n-(hydroxymethyl)-n-methylprop-2-enamide Chemical compound OCN(C)C(=O)C=C AUCNMQYOQYTGPE-UHFFFAOYSA-N 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical class C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- HBJPJUGOYJOSLR-UHFFFAOYSA-N naphthalene-2,7-diamine Chemical compound C1=CC(N)=CC2=CC(N)=CC=C21 HBJPJUGOYJOSLR-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- UEYGDIASMOPQFG-UHFFFAOYSA-N octane-1,3,5,7-tetracarboxylic acid Chemical compound OC(=O)C(C)CC(C(O)=O)CC(C(O)=O)CCC(O)=O UEYGDIASMOPQFG-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- CEXXQKSPCPPORI-UHFFFAOYSA-N propan-2-yl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC(C)C CEXXQKSPCPPORI-UHFFFAOYSA-N 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JREWFSHZWRKNBM-UHFFFAOYSA-N pyridine-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CN=C(C(O)=O)C(C(O)=O)=C1C(O)=O JREWFSHZWRKNBM-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical class NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000009736 wetting Methods 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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides composition, the particularly aligning agent for liquid crystal by homogeneous high-quality polyimide film, the particularly liquid crystal orientation film of lower thermal treatment temp energy Formation and characteristics.The feature of composition of the present invention is, containing polyimide precursor and/or the polyimide carrying out imidization to this polyimide precursor and obtain and the cyclic ketone of dissolving this polyimide precursor and/or polyimide, described polyimide precursor is reacted with tetracarboxylic dianhydride's composition with alicyclic structure by the diamine component of the second diamines making to comprise the first diamines of representing with formula [1] and represent with formula [2] and obtains.
(R
1, R
2be separately the straight-chain of carbon number 1 ~ 12 or the alkyl of branched; X is the aliphatic group of carbon number 8 ~ 22 or the group that represents with formula [2A]; N is the integer of 1 ~ 4.)
Description
Technical field
The present invention relates to composition used in the formation of film, in particular to the liquid crystal orientation film of aligning agent for liquid crystal used in the formation of liquid crystal orientation film, gained and the liquid crystal display device that uses this liquid crystal orientation film and obtain.
Background technology
Formed easness and the insulating property etc. of the film formed by organic materialss such as macromolecular materials receive publicity, in electron device, be widely used as interlayer dielectric and protective membrane etc.As display device in known liquid crystal display device, the organic membrane formed by organic materials is used as liquid crystal orientation film.
Liquid crystal orientation film is formed at the substrate surface of clamping liquid crystal in liquid crystal display device, plays the effect making liquid crystal along certain direction orientation.Further, liquid crystal orientation film makes liquid crystal along except the effect of certain direction orientation except having, and also has the effect of the tilt angle controlling liquid crystal.
In recent years, realize at liquid crystal display device, in the process of multifunction, its use range expanding day, also requiring that liquid crystal orientation film has the performance and the reliability that realize high display quality for suppressing the display of liquid crystal display device bad.
Now, as the main liquid crystal orientation film of industrial use, widely use excellent in te pins of durability, be suitable for the organic membrane of the polyimide of the control of the tilt angle of liquid crystal.The liquid crystal orientation film formed by the organic membrane of this polyimide comprises formed by aligning agent for liquid crystal, namely as the polyamic acid of polyimide precursor and/or the composition of the solution of polyimide that carries out imidization to polyamic acid and obtain.Namely, the liquid crystal orientation film of polyimide is coated on substrate by the aligning agent for liquid crystal formed by the solution of the solution by polyimide or the polyamic acid as polyimide precursor, usually carries out burning till under the high temperature of 200 DEG C ~ about 300 DEG C being formed (such as, patent documentation 1 reference).
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 09-278724 publication
Summary of the invention
Invent technical problem to be solved
About the firing process for the formation of polyimide liquid crystal orientation film, must extra high temperature in the technique manufacturing liquid crystal display device.Therefore, when using thin and light weight but low heat-resisting plastic base replaces common glass substrate, require that the substrate of liquid crystal display device can burn till at lower temperatures.Similarly, in order to suppress the deterioration of the lower degradation of the look characteristic of colored filter, or in order to cut down the energy cost in the manufacture of liquid crystal display device, the low-temperature firing of liquid crystal orientation film is also required.Further, from suppressing reliability decrease (the characteristic during life-time service degradation) aspect of liquid crystal display device to be considered, the low temperature of firing process is also required.
In addition, in the formation of the films such as the interlayer dielectric in other electron devices etc. and protective membrane, the low temperature of its thermal treatment process is also required.Low-temperature firing can prevent the characteristic of electron device from declining, and effectively cuts down energy cost.
So, the object of the present invention is to provide the composition that can form the organic membrane of the polyimide formed by the heating under low temperature, the aligning agent for liquid crystal particularly forming liquid crystal orientation film by the heating under low temperature, by the liquid crystal orientation film of this aligning agent for liquid crystal gained and the liquid crystal display device that uses this liquid crystal orientation film and obtain.
The technical scheme that technical solution problem adopts
The present inventor has carried out conscientiously studying in order to achieve the above object, and result obtains new discovery by following process.
Namely, usually the formation of the film of polyimide, such as liquid crystal orientation film is described above, by using the solution of polyimide or the solution of polyimide precursor that polyimide or polyimide precursor are dissolved in solvent and obtain, and by this solution coat in substrate, usually heat-treat under the high temperature of 200 DEG C ~ about 300 DEG C and carry out.
By this thermal treatment, when the solution of polyimide precursor being used for film and being formed, the removing carrying out solvent while such as, dehydration closed-loop by carrying out polyamic acid reacts (hot-imide) forms film.
When the solution of polyimide being used for film and being formed, heat treated main purpose is except desolventizing.Therefore, although use thermal treatment temp during polyimide solution to be subject to the impact of the boiling point of used solvent, compared with during use polyamic acid, thermal treatment temp is usually lower.Such as, as Japanese Patent Laid-Open 9-194725 publication disclose, form film by the thermal treatment temp of about 200 DEG C.Therefore, when thermal treatment temp is low temperature, use polyimide solution is more preferably.
On the other hand, when preparing polyimide solution, generally for and dissolved by the polyimide being difficult to dissolve, the selection of solvent is important.As the solvent for this object, METHYLPYRROLIDONE (hereinafter also referred to NMP) contour polar solvent can be used.The boiling point of high polar solvent, the boils up till of such as NMP more than 200 DEG C.When forming film by using NMP as the polyimide solution of solvent, the high thermal treatment temp of about 200 DEG C near the boiling point that must reach NMP.When lower temperature, can residual solvents (NMP) in the film of gained.Consequently, when liquid crystal orientation film etc., cause the reduction of characteristic, the characteristic of liquid crystal display device declines.
In addition, if as the NMP of high polar solvent, owing to having higher surface tension characteristics, thus use with NMP be the polyimide solution of solvent to form film time, the wetting extended attribute on substrate is bad.If make the surface tension of used solvent lower, then the coating of substrate is become better.Consequently, the defect not during the printing such as rejecting property and pore coating, can the film of polyimide of the more homogeneous high-quality of Formation and characteristics.
As mentioned above, heat treated low temperature when film is formed and the raising of coating are important in the formation for the film of the polyimide of target such as the insulating film of electron device or protective membrane, particularly liquid crystal orientation film.
The present inventor the low temperature and coating in order to make the thermal treatment temp in the formation of the liquid crystal orientation film of the film of polyimide, particularly polyimide raising and be studied, find to be dissolved in well containing lower boiling with the diamine component of ad hoc structure and the tetracarboxylic dianhydride's composition polyimide precursor that is raw material gained and/or the polyimide that carries out imidization to this polyimide precursor and obtain and to have in the solvent of the cyclic ketone of characteristic of low surface tension, consequently, can fully achieve the above object.
The present invention is the invention completed based on above-mentioned discovery, comprises following technology contents.
(1) composition, it is characterized in that, containing polyimide precursor and/or the polyimide carrying out imidization to this polyimide precursor and obtain and the cyclic ketone solvent dissolving this polyimide precursor and/or polyimide, described polyimide is reacted with tetracarboxylic dianhydride's composition with alicyclic structure by the diamine component of the second diamines making to comprise the first diamines of representing with following formula [1] and represent with following formula [2] and obtains
[changing 1]
In formula [1], R
1and R
2be separately the straight-chain of carbon number 1 ~ 12 or the alkyl of branched;
[changing 2]
In formula [2], X represents substituting group, and be the alkyl of carbon number 8 ~ 22 or the group that represents with following formula [2A], n is the integer of 1 ~ 4;
[changing 3]
In formula [2A], Y
1for singly-bound ,-(CH
2)
a-,-O-,-CH
2o-,-COO-or OCO-, wherein a is the integer of 1 ~ 15; Y
2for singly-bound or (CH
2)
b-, wherein b is the integer of 1 ~ 15; Y
3for singly-bound ,-(CH
2)
c-,-O-,-CH
2o-,-COO-or OCO-, wherein c is the integer of 1 ~ 15;
Y
4it is divalent organic group, it is selected from the organic group of the carbon number 12 ~ 25 of cyclic group or the steroid skeleton having and be selected from phenyl ring, cyclohexane ring and heterocycle, and the arbitrary hydrogen atom on wherein said cyclic group can be replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom; Y
5for being selected from the cyclic group of phenyl ring, cyclohexane ring and heterocycle, the arbitrary hydrogen atom on wherein said cyclic group can be replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom; Y
6for the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18 containing fluoroalkyl, the alkoxyl group of carbon number 1 ~ 18 or the fluoroalkoxy of carbon number 1 ~ 18; N is the integer of 0 ~ 4.
(2) composition as described in above-mentioned (1), wherein, the diamines of the structure represented with described formula [1] is the diamines represented with following formula [1A],
[changing 4]
In formula [1A], R
1for the straight-chain of carbon number 1 ~ 12 or the alkyl of branched, R
5for the alkyl of hydrogen atom or carbon number 1 ~ 12; R
3and R
4be hydrogen atom or methyl independently.
(3) composition as described in above-mentioned (2), wherein, the diamines of the structure represented with described formula [1A] is the diamines of the structure represented with following formula [1B],
[changing 5]
(4) composition as described in above-mentioned (1), wherein, the diamines of the structure represented with described formula [1] is the diamines represented with following formula [1C],
[changing 6]
(5) composition according to any one of above-mentioned (1) ~ (4), in described diamine component, the diamines of the structure represented with described formula [1] is 20 ~ 80 % by mole.
(6) composition according to any one of above-mentioned (1) ~ (4), in described diamine component, the diamines of the structure represented with described formula [2] is 10 ~ 80 % by mole.
(7) composition according to any one of above-mentioned (1) ~ (6), wherein, above-mentioned tetracarboxylic dianhydride is the compound represented with following formula [3],
[changing 7]
In formula [3], Z
1for carbon number 4 ~ 13 4 valency organic groups and containing the non-aromatic cyclic hydrocarbon base of carbon number 4 ~ 10.
(8) composition as described in above-mentioned (7), wherein, the Z of described formula [3]
1the structure represented with following formula [3a] ~ [3j],
[changing 8]
In formula [3a], Z
2~ Z
5for hydrogen atom, methyl, chlorine atom or phenyl ring, they each other can be identical or different; In formula [3g], Z
6and Z
7for hydrogen atom or methyl, they each other can be identical or different.
(9) composition according to any one of above-mentioned (1) ~ (8), wherein, described cyclic ketone solvent comprises the cyclic ketone of at least one party in the cyclic ketone of 5 rings and 6 rings.
(10) aligning agent for liquid crystal, its composition according to any one of above-mentioned (1) ~ (9) is formed.
(11) liquid crystal orientation film, it is obtained by the aligning agent for liquid crystal described in above-mentioned (10).
(12) liquid crystal orientation film as described in above-mentioned (11), it is used to by possessing the liquid crystal display device having liquid crystal layer between a pair substrate of electrode and form, manufacture through following operation, this operation is: between described a pair substrate, configuration packet carries out the liquid-crystal composition of the polymerizable compound be polymerized containing at least one party utilized in active energy beam and heat, applies voltage while make described polymerizable compound be polymerized between described electrode.
(13) liquid crystal display device, it has the liquid crystal orientation film described in above-mentioned (11).
(14) liquid crystal display device as described in above-mentioned (13), it by having liquid crystal layer and forming between a pair substrate possessing electrode and described liquid crystal orientation film, and manufacture through following operation, this operation is: between described a pair substrate, configuration packet carries out the liquid-crystal composition of the polymerizable compound be polymerized containing at least one party utilized in active energy beam and heat, applies voltage while make described polymerizable compound be polymerized between described electrode.
The effect of invention
According to the present invention, defect when coating is excellent, the printing such as rejecting property and pore is not coated with can be provided, pass through the composition of the film of the more homogeneous high-quality polyimide of lower thermal treatment temp energy Formation and characteristics.
Particularly according to the present invention, can provide because coating is excellent and can realize easy fired and can form the aligning agent for liquid crystal of the liquid crystal orientation film not having defective electrical characteristic excellence.Use aligning agent for liquid crystal of the present invention and the liquid crystal orientation film that obtains because of electrical characteristic excellent, thus can obtain the liquid crystal display device with high reliability.
Embodiment
For in order to obtain diamine component that the polyimide precursor used in the present invention and/or the polyimide carrying out imidization to this polyimide precursor and obtain (being sometimes also referred to as polyimide of the present invention below) use and tetracarboxylic dianhydride's composition is described.
The first diamines of < >
The first diamines used to obtain polyimide of the present invention represents with following formula [1].The diamines represented with formula [1] is used to improve the solvability of polyimide relative to solvent.
[changing 9]
In formula [1], R
1, R
2it is separately the alkyl of carbon number 1 ~ 12.
The usage quantity of the first diamines is preferably at more than the 10 quality % in order to obtain the diamine component entirety used in the reaction of polyimide.Consider from the relation of the usage quantity with the second diamines represented with formula [2] illustrated below, preferably below 90 quality %.The preferred usage quantity of the first diamines is 30 ~ 80 quality %.
As the preference of the first diamines, can exemplify there is N-allyl benzene amine structure compound, such as following formula [1A] compound.
[changing 10]
In formula [1A], R
1represent the alkyl of carbon number 1 ~ 12.This alkyl is preferably containing carbon-to-carbon double bond, and more preferably this double bond is between the carbon of second from nitrogen-atoms and the 3rd carbon.In addition, R
1carbon number be preferably less than 6 from the viewpoint of the printing of aligning agent for liquid crystal, more preferably less than 3.
R
5it is the alkyl of hydrogen atom or carbon number 1 ~ 12.It is also harmless that this alkyl contains carbon-to-carbon double bond.In addition, R
5carbon number be preferably less than 6, more preferably less than 3.Particularly preferred R
5it is hydrogen atom.
R
3and R
4be hydrogen atom or methyl independently.R
3, R
4all be preferably hydrogen atom.
In formula [1A], two amino optimum positions relative to N-allyl group, are positioned at 2 on phenyl ring, 4,2,5 or 3,5.
As the preference of the diamines represented with formula [1A], the structure of following formula [1B] can be exemplified.
[changing 11]
More specifically, be the compound represented with following formula [1B-1] ~ [1B-8].Wherein, the diamines of particularly preferably formula [1B-1].The diamines of the structure represented with formula [1A] is not limited to these examples.
[changing 12]
In addition, as the example outside the diamines represented with formula [1], such as, the diamines of the structure of following formula [1C] can be exemplified.
[changing 13]
More specifically, be the compound represented with following formula [1C-1] ~ [1C-6].Wherein, the diamines of particularly preferably formula [1C-1].The diamines of the structure represented with formula [1C] is not limited to these examples.
[changing 14]
The diamines represented with formula [1] according to the characteristic such as solvability, the orientation making the liquid crystal after liquid crystal orientation film, voltage retention, accumulated charge in a solvent after making polyimide, can use a kind or two or more is used in combination.
< the second diamines >
The second diamines used to obtain polyimide used in the present invention represents with following formula [2].The second diamines gives its vertical orientated property object in order to the object that makes the polyimide of gained and improve relative to the solvability of solvent and when polyimide film is used as liquid crystal orientation film uses.
[changing 15]
In formula [2], X is the alkyl of carbon number 8 ~ 22 or the group that represents with following formula [2A].And n is the integer of 1 ~ 4.Hydrophobic side-chain structure is formed preferably by substituent X.
The usage quantity of the second diamines, preferably at more than the 10 quality % in order to obtain the diamine component entirety used in the reaction of polyimide, is considered from the relation of the usage quantity with the first diamines, is preferably below 90 quality %.The preferred usage quantity of the second diamines is 25 ~ 80 quality %.
Then, in the second diamines, when substituent X represents with following formula [2A], the structure concrete to it is described.
[changing 16]
In formula [2A], Y
1singly-bound ,-(CH
2)
a-(a is the integer of 1 ~ 15) ,-O-,-CH
2any one in O-,-COO-and OCO-.Wherein, from the viewpoint of the synthesis easily carrying out side-chain structure, preferred singly-bound ,-(CH
2)
a-(a is the integer of 1 ~ 15) ,-O-,-CH
2any one in O-and COO-.In addition, more preferably singly-bound ,-(CH
2)
a-(a is the integer of 1 ~ 10) ,-O-,-CH
2any one in O-and COO-.
In formula [2A], Y
2singly-bound and (CH
2)
bany one in-(b is the integer of 1 ~ 15).Wherein, preferred singly-bound and (CH
2)
bany one in-(b is the integer of 1 ~ 10).
Y
3singly-bound ,-(CH
2)
c-(c is the integer of 1 ~ 15) ,-O-,-CH
2any one in O-,-COO-and OCO-.Wherein, from the viewpoint of the synthesis easily carrying out side-chain structure, preferred singly-bound ,-(CH
2)
c-(c is the integer of 1 ~ 15) ,-O-,-CH
2any one in O-,-COO-and OCO-.In addition, more preferably singly-bound ,-(CH
2)
c-(c is the integer of 1 ~ 10) ,-O-,-CH
2any one in O-,-COO-and OCO-.
In formula [2A], Y
4be divalent organic group, it is selected from the organic group of the carbon number 12 ~ 25 with cyclic group (the arbitrary hydrogen atom on these cyclic groups can be replaced by any one in the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 and fluorine atom) or the steroid skeleton being selected from phenyl ring, cyclohexane ring and heterocycle.Wherein preferably there is the divalent organic group of the carbon number 12 ~ 25 of any one in phenyl ring, cyclohexane ring and steroid skeleton.
In formula [2A], Y
5be the cyclic group being selected from phenyl ring, cyclohexane ring and heterocycle, the arbitrary hydrogen atom on these cyclic groups can be replaced by any one in the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 and fluorine atom.
In formula [2A], n is the integer of 0 ~ 4.The preferably integer of 0 ~ 2.
In formula [2A], Y
6be the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18 containing any one in fluoroalkyl, the alkoxyl group of carbon number 1 ~ 18 and the fluoroalkoxy of carbon number 1 ~ 18.Wherein, the alkyl of preferred carbon number 1 ~ 18, carbon number 1 ~ 10 containing any one in fluoroalkyl, the alkoxyl group of carbon number 1 ~ 18 and the fluoroalkoxy of carbon number 1 ~ 10.Be more preferably any one in the alkyl of carbon number 1 ~ 12 and the alkoxyl group of carbon number 1 ~ 12.Any one further preferably in the alkyl of carbon number 1 ~ 9 and the alkoxyl group of carbon number 1 ~ 9.
For the Y in the formula [2A] of the substituent X of constitutional formula [2]
1, Y
2, Y
3, Y
4, Y
5, Y
6and the preferably combination of n is as shown in the 2-1 ~ 2-629 in following table 1 ~ 42.
[table 1]
[table 2]
C is the integer of carbon number 1 ~ 10
[table 3]
C is the integer of carbon number 1 ~ 10
[table 4]
C is the integer of carbon number 1 ~ 10
[table 5]
[table 6]
[table 7]
[table 8]
[table 9]
[table 10]
A is the integer of carbon number 1 ~ 10
[table 11]
A is the integer of carbon number 1 ~ 10
[table 12]
A is the integer of carbon number 1 ~ 10
[table 13]
A is the integer of carbon number 1 ~ 10
[table 14]
A is the integer of carbon number 1 ~ 10
[table 15]
A, c are separately the integer of carbon number 1 ~ 10
[table 16]
C is the integer of carbon number 1 ~ 10
[table 17]
C is the integer of carbon number 1 ~ 10
[table 18]
C is the integer of carbon number 1 ~ 10
[table 19]
C is the integer of carbon number 1 ~ 10
[table 20]
C is the integer of carbon number 1 ~ 10
[table 21]
[table 22]
C is the integer of carbon number 1 ~ 10
[table 23]
C is the integer of carbon number 1 ~ 10
[table 24]
[table 25]
B is the integer of carbon number 1 ~ 10
[table 26]
B is the integer of carbon number 1 ~ 10
[table 27]
B is the integer of carbon number 1 ~ 10
[table 28]
B is the integer of carbon number 1 ~ 10
[table 29]
B is the integer of carbon number 1 ~ 10
[table 30]
B is the integer of carbon number 1 ~ 10
[table 31]
B is the integer of carbon number 1 ~ 10
[table 32]
B is the integer of carbon number 1 ~ 10
[table 33]
B is the integer of carbon number 1 ~ 10
[table 34]
B is the integer of carbon number 1 ~ 10
[table 35]
B is the integer of carbon number 1 ~ 10
[table 36]
B is the integer of carbon number 1 ~ 10
[table 37]
B is the integer of carbon number 1 ~ 10
[table 38]
B is the integer of carbon number 1 ~ 10
[table 39]
B is the integer of carbon number 1 ~ 10
[table 40]
B is the integer of carbon number 1 ~ 10
[table 41]
B, c are separately the integer of carbon number 1 ~ 10
[table 42]
B, c are separately the integer of carbon number 1 ~ 10
Then, the concrete example of the diamines of the structure represented with formula [2] can be exemplified, but be not limited to these examples.
Namely, outside 2,3,5,6-TMPD, 2,5-dimethyl-Ursol D, 2,4-dimethyl-mphenylenediamine, 2,5-diaminotoluenes, 2,6-diaminotoluenes, the diamines represented with following formula [2-1] ~ [2-31] can also be exemplified.
[changing 17]
(in formula [2-1] ~ [2-3], R
1for-O-,-OCH
2-,-CH
2o-,-COOCH
2-or CH
2oCO-; R
2for the straight-chain of the straight-chain of the straight-chain of carbon number 1 ~ 22 or branched-chain alkyl, carbon number 1 ~ 22 or branched alkoxyl group, carbon number 1 ~ 22 or branched are containing the straight-chain of fluoroalkyl or carbon number 1 ~ 22 or branched fluoroalkoxy.)
[changing 18]
(in formula [2-4] ~ [2-6], R
3for-COO-,-OCO-,-COOCH
2-,-CH
2oCO-,-CH
2o-,-OCH
2-or CH
2-; R
4for the straight-chain of the straight-chain of the straight-chain of carbon number 1 ~ 22 or branched-chain alkyl, carbon number 1 ~ 22 or branched alkoxyl group, carbon number 1 ~ 22 or branched are containing the straight-chain of fluoroalkyl or carbon number 1 ~ 22 or branched fluoroalkoxy.)
[changing 19]
(in formula [2-7] and formula [2-8], R
5for-COO-,-OCO-,-COOCH
2-,-CH
2oCO-,-CH
2o-,-OCH
2-,-CH
2-or O-; R
6for fluorine-based, cyano group, trifluoromethyl, nitro, azo-group, formyl radical, ethanoyl, acetoxyl group or hydroxyl.)
[changing 20]
(in formula [2-9] and formula [2-10], R
7for straight-chain or the branched-chain alkyl of carbon number 3 ~ 12, the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans-isomer(ide).)
[changing 21]
(in formula [2-11] and formula [2-12], R
8for straight-chain or the branched-chain alkyl of carbon number 3 ~ 12, the cis-trans isomerization of Isosorbide-5-Nitrae-cyclohexylidene is respectively trans-isomer(ide).)
[changing 22]
(in formula [2-13], A
4straight-chain or the branched-chain alkyl of the carbon number 3 ~ 20 that can be replaced by fluorine atoms; A
3isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene; A
2that Sauerstoffatom or COO-* (are wherein with key and the A of " * "
3connect); A
1that Sauerstoffatom or COO-* (are wherein with the key of " * " and (CH
2) a
2connect.) in addition, a
1it is the integer of 0 or 1; a
2it is the integer of 2 ~ 10; a
3it is the integer of 0 or 1.)
[changing 23]
[changing 24]
[changing 25]
[changing 26]
[changing 27]
The diamines represented with formula [2] according to the characteristic such as solvability, the orientation making the liquid crystal after liquid crystal orientation film, voltage retention, accumulated charge in a solvent after making polyimide, can use a kind or two or more is used in combination.
Other diamines of < >
The polyimide that the composition of the present invention diamine component contained by making to comprise the first diamines and the second diamines reacts with tetracarboxylic dianhydride's composition with alicyclic structure and obtains.Now, in the scope not damaging effect of the present invention, can be used together other diamines (also referred to as other diamines) other than the above.
Below, the concrete example of other diamines above-mentioned is exemplified.
As other diamines, such as, mphenylenediamine can be exemplified, Ursol D, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamino benzylalcohol, 2,4-diamino benzylalcohol, 4,6-diaminoresorcinol, 2,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxyl-4,4 '-benzidine, 3,3 '-dicarboxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-biphenyl, 3,3 '-trifluoromethyl-4,4 '-benzidine, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 2,2 '-diaminodiphenyl oxide, 2,3 '-diaminodiphenyl oxide, 4,4 '-alkylsulfonyl dianiline, 3,3 '-alkylsulfonyl dianiline, two (4-aminophenyl) silane, two (3-aminophenyl) silane, dimethyl-bis-(4-aminophenyl) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4 '-diaminodiphenyl sulfide, 3,3 '-diaminodiphenyl sulfide, 4,4 '-diamino-diphenylamine, 3,3 '-diamino-diphenylamine, 3,4 '-diamino-diphenylamine, 2,2 '-diamino-diphenylamine, 2,3 '-diamino-diphenylamine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diamino-diphenyl) amine, N-methyl (3,4 '-diamino-diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) amine, N-methyl (2,3 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, Isosorbide-5-Nitrae-diaminonaphthalene, 2,2 '-diaminobenzophenone, 2,3 '-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalenes, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, two (4-aminophenyl) ethane of 1,2-, two (3-aminophenyl) ethane of 1,2-, two (4-aminophenyl) propane of 1,3-, two (3-aminophenyl) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4 aminophenyl) butane, Isosorbide-5-Nitrae-bis-(3-aminophenyl) butane, two (3,5-diethyl-4-aminophenyl) methane, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminophenyl) benzene, two (4-aminophenyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-aminobenzyl) benzene, two (4-amino-benzene oxygen) benzene of 1,3-, 4,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] pentanoic, 4,4 '-[1,3-phenylene two (methylene radical)] pentanoic, 3,4 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] pentanoic, 3,4 '-[1,3-phenylene two (methylene radical)] pentanoic, 3,3 '-[Isosorbide-5-Nitrae-phenylene two (methylene radical)] pentanoic, 3,3 '-[1,3-phenylene two (methylene radical)] pentanoic, Isosorbide-5-Nitrae-phenylene two [(4-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two [(3-aminophenyl) ketone], 1,3-phenylene two [(4-aminophenyl) ketone], 1,3-phenylene two [(3-aminophenyl) ketone], Isosorbide-5-Nitrae-phenylene two (PABA ester), Isosorbide-5-Nitrae-phenylene two (3-Aminobenzoate), 1,3-phenylene two (PABA ester), 1,3-phenylene two (3-Aminobenzoate), two (4-aminophenyl) terephthalate, two (3-aminophenyl) terephthalate, two (4-aminophenyl) isophthalic acid ester, two (3-aminophenyl) isophthalic acid ester, N, N '-(Isosorbide-5-Nitrae-phenylene) two (4-aminobenzamide), N, N '-(1,3-phenylene) two (4-aminobenzamide), N, N '-(Isosorbide-5-Nitrae-phenylene) two (3-AB), N, N '-(1,3-phenylene) two (3-AB), N, N '-bis-(4-aminophenyl) terephthalamide, N, N '-bis-(3-aminophenyl) terephthalamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophtalamide, two (4-aminophenyl) anthracene of 9,10-, 4,4 '-bis-(4-amino-benzene oxygen) sulfobenzide, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-bis-(4-aminophenyl) HFC-236fa, 2,2 '-bis-(3-aminophenyl) HFC-236fa, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) HFC-236fa, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) propane, two (4-amino-benzene oxygen) propane of 1,3-, two (3-amino-benzene oxygen) propane of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) butane, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) butane, two (4-amino-benzene oxygen) pentane of 1,5-, two (3-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) hexane of 1,6-, two (3-amino-benzene oxygen) hexane of 1,6-, two (4-amino-benzene oxygen) heptane of 1,7-, 1,7-(3-amino-benzene oxygen) heptane, two (4-amino-benzene oxygen) octane of 1,8-, two (3-amino-benzene oxygen) octane of 1,8-, two (4-amino-benzene oxygen) nonane of 1,9-, two (3-amino-benzene oxygen) nonane of 1,9-, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-amino-benzene oxygen) undecane, 1,11-(3-amino-benzene oxygen) undecane, 1,12-(4-amino-benzene oxygen) dodecane, the aromatic diamines such as 1,12-(3-amino-benzene oxygen) dodecane, the ester ring type diamines such as two (4-aminocyclohexyl) methane, two (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropanes, 1,4-Diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diaminoheptane, 1,8-diamino-octane, 1,9-diamino nonane, 1, the aliphatie diamines such as 10-diamino decane, 1,11-diamino undecane, 1,12-diamino dodecane, Deng.
In addition, as other diamines, can also exemplify and there is alkyl, diamines containing fluoroalkyl, aromatic nucleus, aliphatics ring or heterocycle on two amine side chains, or there is the diamines etc. of the large ring-type substituent be made up of them.Specifically, the diamines represented with following formula [DA1] ~ [DA15] can be illustrated.
[changing 28]
(in formula [DA1] ~ [DA6], A
2for-COO-,-OCO-,-CONH-,-NHCO-,-CH
2-,-O-,-CO-or NH-; A
3for the straight-chain of carbon number 1 ~ 22 or the straight-chain of branched-chain alkyl or carbon number 1 ~ 22 or branched are containing fluoroalkyl.)
[changing 29]
(in formula [DA7], p is the integer of 1 ~ 10.)
[changing 30]
(in formula [DA11], m is the integer of 0 ~ 3; In formula [DA15], n is the integer of 1 ~ 5.)
Further, only otherwise damage effect of the present invention, the diamines in the molecule that represents with following formula [DA16] ~ [DA20] with carboxyl can also be used.
[changing 31]
(in formula [DA16], m1 is the integer of 1 ~ 4.In formula [DA17], A
4for singly-bound ,-CH
2-,-C
2h
4-,-C (CH
3)
2-,-CF
2-,-C (CF
3)-,-O-,-CO-,-NH-,-N (CH
3)-,-CONH-,-NHCO-,-CH
2o-,-OCH
2-,-COO-,-OCO-,-CON (CH
3)-or N (CH
3) CO-; m
2and m
3be respectively the integer of 0 ~ 4, and m
2+ m
3it is the integer of 1 ~ 4.
In formula [DA18], m
4and m
5be respectively the integer of 1 ~ 5.
In formula [DA19], A
5for straight-chain or the branched-chain alkyl of carbon number 1 ~ 5; m
6it is the integer of 1 ~ 5.
In formula [DA20], A
6for singly-bound ,-CH
2-,-C
2h
4-,-C (CH
3)
2-,-CF
2-,-C (CF
3)-,-O-,-CO-,-NH-,-N (CH
3)-,-CONH-,-NHCO-,-CH
2o-,-OCH
2-,-COO-,-OCO-,-CON (CH
3)-or N (CH
3) CO-; m
7it is the integer of 1 ~ 4.)
In addition, only otherwise damage effect of the present invention, the diamines represented with following formula [DA21] or formula [DA22] can also be used.
[changing 32]
Further, only otherwise damage effect of the present invention, the diamines represented with following formula [DA23] ~ formula [DA27] can also be used.
[changing 33]
(in formula [DA23] ~ formula [DA27], A
1for straight-chain or the branched-chain alkyl of carbon number 1 ~ 22, or the straight-chain of carbon number 1 ~ 22 or branched are containing fluoroalkyl.)
Other above-mentioned diamines can according to solvability in a solvent after making polyimide, make liquid crystal orientation film time the key property of the liquid crystal orientation film such as liquid crystal aligning, voltage retention, accumulated charge, use a kind or two or more is used in combination.
< tetracarboxylic dianhydride >
In order to obtain polyimide of the present invention, as tetracarboxylic dianhydride's composition, the tetracarboxylic dianhydride (also referred to as specific tetracarboxylic dianhydride) with alicyclic structure can be used.As this specific tetracarboxylic dianhydride, preferably there is the tetracarboxylic dianhydride of the alicyclic structure represented with following formula [3].
[changing 34]
In formula [3], Z
1be 4 valency organic groups of carbon number 4 ~ 13 and the non-aromatic cyclic hydrocarbon base containing carbon number 4 ~ 10.
Specifically, be the structure represented with following formula [3a] ~ [3j].
[changing 35]
In formula [3a], Z
2~ Z
5be the group being selected from hydrogen atom, methyl, chlorine atom and phenyl ring, each group each other can be identical or different.
In formula [3g], Z
6and Z
7be hydrogen atom or methyl, each group each other can be identical or different.
In formula [3], consider from the easiness of polymerisation reactivity and synthesis, Z
1particularly preferred structure be the structure represented with formula [3a], formula [3c], formula [3d], formula [3e], formula [3f] or formula [3g].Wherein, preferred formula [3a] or formula [3f], most preferably formula [3a].
During the tetracarboxylic dianhydride that use represents with formula [3], its usage quantity is preferably more than the 40 quality % in the entirety of tetracarboxylic dianhydride's composition, is more preferably more than 50 quality %.Also can be the tetracarboxylic dianhydride that the tetracarboxylic dianhydride's composition used in polyimide synthesis all adopts formula [3].
In the present invention, only otherwise damage effect of the present invention, other tetracarboxylic dianhydrides beyond specific tetracarboxylic dianhydride can be used.
As the concrete example of other tetracarboxylic dianhydrides, such as Pyromellitic Acid can be exemplified, 2, 3, 6, 7-naphthalenetetracarbacidic acidic, 1, 2, 5, 6-naphthalenetetracarbacidic acidic, 1, 4, 5, 8-naphthalenetetracarbacidic acidic, 2, 3, 6, 7-anthracene tetracarboxylic acid, 1, 2, 5, 6-anthracene tetracarboxylic acid, 3, 3 ', 4, 4 '-bibenzene tetracarboxylic, 2, 3, 3 ', 4-bibenzene tetracarboxylic, two (3, 4-dicarboxyphenyi) ether, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic, two (3, 4-dicarboxyphenyi) sulfone, two (3, 4-dicarboxyphenyi) methane, 2, 2-two (3, 4-dicarboxyphenyi) propane, 1, 1, 1, 3, 3, 3-hexafluoro-2, 2-two (3, 4-dicarboxyphenyi) propane, two (3, 4-dicarboxyphenyi) dimethylsilane, two (3, 4-dicarboxyphenyi) diphenyl silane, 2, 3, 4, 5-pyridine tetracarboxylic acid, 2, 6-two (3, 4-dicarboxyphenyi) pyridine, 3, 3 ', 4, 4 '-diphenyl sulfone tetraformic acid, 3, 4, 9, 10-perylene tetracarboxylic acid, 1, 3-phenylbenzene-1, 2, 3, 4-cyclobutanetetracarboxylic etc.
In composition of the present invention, when such as liquid crystal orientation film, consider the characteristics such as liquid crystal aligning, voltage preserving property and accumulated charge, one kind or two or more use can be selected from other tetracarboxylic dianhydrides above-mentioned.
< polyimide precursor and polyimide >
The polyimide precursor used in composition of the present invention and polyimide are better obtain by the following method.Here, polyimide precursor refers to polyimide acid (also referred to as polyamic acid (polyamic acid)).Namely, polyimide precursor reacts to obtain by the diamine component of the second diamines of making to comprise the first diamines of representing with above-mentioned formula [1] and represent with above-mentioned formula [2] and above-mentioned tetracarboxylic dianhydride's composition with alicyclic structure.
In this situation, the usage quantity of the first diamines is preferably more than 20 % by mole of diamine component entirety, more preferably more than 30 % by mole.In addition, consider from the relation of the preferred usage quantity with the second diamines, be preferably less than 80 % by mole.In addition, the usage quantity of the second diamines is preferably more than 10 % by mole of diamine component entirety, more preferably more than 25 % by mole.In addition, consider from the relation of the preferred usage quantity with the first diamines, be preferably less than 80 % by mole.
Manufacture the concrete method of polyimide precursor as the reaction by diamine component and tetracarboxylic dianhydride, known synthetic method can be adopted.Such as can use the method that diamine component and tetracarboxylic dianhydride react in organic solvent.The method, due in organic solvent to carry out reacting compared with high efficiency and the by product produced is few, is therefore preferred from this side considerations.
As the organic solvent used in the reaction of diamine component and tetracarboxylic dianhydride, as long as the solvent of polyamic acid that solubilized generates, be not particularly limited.As its concrete example, such as N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, methyl-sulphoxide, gamma-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, pimelinketone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone etc.These solvents can be used alone, also can be used in combination.
In addition, even the solvent of polyimide precursor can not be dissolved, use after being mixed into above-mentioned solvent in the scope also can not separated out at the polyamic acid generated.In addition, because the moisture in organic solvent hinders polyreaction, and become the reason that the polyimide precursor of generation is hydrolyzed, so preferably use the organic solvent after dehydrating.
Also following method can be used: when making diamine component and tetracarboxylic dianhydride reacts in organic solvent, stir diamine component being dispersed or dissolved in the solution after organic solvent, more directly add tetracarboxylic dianhydride or tetracarboxylic dianhydride be dispersed or dissolved in the method for carrying out in organic solvent adding.In addition, following method can also be exemplified on the contrary: tetracarboxylic dianhydride is being dispersed or dissolved in the method for adding diamine component in the solution obtained in organic solvent or the method etc. of alternately adding tetracarboxylic dianhydride and diamine component.In the present invention, any one in these methods can be used.In addition, when diamine component or tetracarboxylic dianhydride are made up of multiple compounds, it can be made to react under the state be pre-mixed, it also can be made to react successively respectively, can also make to react respectively and the low-molecular weight hybrid reaction obtained to obtain high molecular body.
The temperature of diamine component and tetracarboxylic dianhydride's reaction can be selected arbitrarily in the scope of-20 ~ 150 DEG C, but considers reaction efficiency, is preferably located at the scope of-5 ~ 100 DEG C.In addition, reaction can be carried out under arbitrary concentration.But, if concentration is too low, be then difficult to the polyimide precursor obtaining high molecular.On the other hand, if excessive concentration, then the viscosity of reaction solution becomes too high and is difficult to stir uniformly.Therefore, preferably 1 ~ 50 quality %, more preferably 5 ~ 30 quality %.In addition, also initial reaction stage can carry out in higher concentrations, add organic solvent afterwards.
For obtaining in the polyreaction of polyimide precursor, the total mole number of diamine component is preferably 0.8 ~ 1.2 with the ratio of the total mole number of tetracarboxylic dianhydride.Identical with common polycondensation, this mol ratio is more close to 1.0, and the molecular weight of the polymkeric substance of generation is larger.Therefore, according to circumstances suitably can select, thus determine total mol ratio.
The polyimide used in the present invention is by making above-mentioned polyimide precursor dehydration closed-loop, carrying out imidization to obtain.In this situation, the dehydration closed-loop rate (imide rate) of polyimide precursor does not need one to be decided to be 100%, can adjust according to purposes or object in the scope of such as 35 ~ 95%, more preferably in the scope of 45 ~ 80%.
As the method making polyimide precursor imidization, the hot-imide of the solution of direct heating polyimide precursor can be exemplified, in the solution of polyimide precursor, add the catalysis imidization etc. of catalyzer.
Temperature when making polyimide precursor carry out hot-imide is in the solution 100 ~ 400 DEG C, preferably 120 ~ 250 DEG C.The imidization of polyimide precursor preferably carries out while the water removing will generated by imidization reaction is to reaction system.
The catalysis imidization of polyimide precursor by adding basic catalyst and acid anhydrides in polyimide precursor solution, and-20 ~ 250 DEG C, preferably at 0 ~ 180 DEG C stir and carry out.The amount of basic catalyst is 0.5 ~ 30 mole times of acid amides acidic group, preferably 2 ~ 20 moles times, and the amount of acid anhydrides is 1 ~ 50 mole times of acid amides acidic group, preferably 3 ~ 30 moles times.
As basic catalyst, pyridine, triethylamine, Trimethylamine 99, Tributylamine, trioctylamine etc. can be exemplified, wherein pyridine have for make reaction carry out for appropriateness alkalescence, therefore preferably.As acid anhydrides, diacetyl oxide, trimellitic acid 1,2-anhydride, pyromellitic dianhydride etc. can be exemplified, wherein, use during diacetyl oxide and be easy to carry out reacting the purifying after terminating, therefore preferably.Adopt the imide rate of catalysis imidization can be controlled by adjustment catalytic amount and temperature of reaction, reaction times.
When reclaiming the polyimide of generation from the reaction soln of polyimide, reaction soln is put in poor solvent and make it precipitate.As the poor solvent for precipitating, methyl alcohol, acetone, hexane, ethylene glycol butyl ether, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc. can be exemplified.The polymkeric substance putting in poor solvent precipitation can after filtered and recycled, under normal or reduced pressure, carries out drying under normal temperature or heating.In addition, if the polymkeric substance repeating to make precipitation reclaim is dissolved in solvent and the redeposition operation 2 ~ 10 times of reclaiming again, then the impurity in polymkeric substance can be reduced.As poor solvent now, can exemplify such as alcohols, ketone, hydro carbons etc., if use the poor solvent being selected from more than 3 kinds of these solvents, then purification efficiency improves further, therefore preferably.
About the molecular weight of polyimide precursor and polyimide, when the operability when painting film strength obtain considering to use it, film formation and the homogeneity of film, the weight-average molecular weight utilizing GPC (gel permeation chromatography) method to measure is preferably 5000 ~ 1000000, is more preferably 10000 ~ 150000.
The composition > that < film is formed
Composition, such as aligning agent for liquid crystal that film of the present invention is formed are the compositions containing the imide polymer of the present invention obtained described above and the solvent making this polyimide polymer dissolve.The content of polyimide polymer of the present invention contained in composition is preferably 1 ~ 20 quality %, more preferably 3 ~ 15 quality %, particularly preferably 3 ~ 10 quality %.
In the present invention, the whole of component of polymer contained in composition can be polyimide of the present invention, but also can except polyimide of the present invention, polyimide beyond the polyimide be also synthesized into containing the diamine component comprising the first above-mentioned diamines and the second diamines and the tetracarboxylic dianhydride with alicyclic structure, other structures.Now, the content of the polyimide of other structures in component of polymer can adopt 0.5 ~ 15 quality %, preferably 1 ~ 10 quality %.
In composition of the present invention, the component of polymer containing polyimide of the present invention contains with the state of dissolving.As solvent, use cyclic ketone.Cyclic ketone be dissolve polyimide of the present invention, boiling point is low and have the solvent of characteristic of low surface tension compared with NMP.As cyclic ketone, be better the ketone with preferably 4 ~ 10 rings, the particularly preferably alicyclic structure of 5 ~ 7 rings, as preferred concrete example, cyclopentanone, pimelinketone, suberone, cyclooctanone, cyclononanone or ring decanone can be exemplified.Wherein, the mixture of any one or they particularly preferably in pimelinketone and cyclopentanone.
If composition of the present invention, such as use the aligning agent for liquid crystal of said composition, then form uniform film from the viewpoint of by coating, content preferably 70 ~ 99 quality % of solvent.Its content can carry out appropriate change according to the thickness of target film.As solvent, can only use cyclic ketone solvent, but also can in the scope of raising such as not hindering low-temperature firing required in situations such as obtaining liquid crystal orientation film and coating, suitably mixing is containing other organic solvents.
As other organic solvents, specifically N can be exemplified, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, methyl-sulphoxide, gamma-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, pimelinketone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone etc.These solvents can be used alone, also can be used in combination.
Even if when containing these other organic solvents, the content of cyclic ketone solvent is also preferably more than 50 quality %, more preferably more than 60 quality %, particularly preferably more than 70 quality % in whole solvent.
Composition of the present invention, such as aligning agent for liquid crystal can in the scopes not damaging effect of the present invention, in order to the object of the homogeneity and surface smoothness that improve thickness further, containing other organic solvents (hereinafter also referred to poor solvent) for improving coating.
As concrete example, following solvents can be exemplified.Such as, Virahol, methoxymethyl amylalcohol, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monobutyl ether, ethyl carbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol t-butyl ether, DPGME, Diethylene Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol monoacetate list ethyl ether, dipropylene glycol list propyl ether, dipropylene glycol monoacetate list propyl ether, 3-methyl-3-methoxybutyl acetic ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, tetrahydrotoluene, propyl ether, two hexyl ethers, normal hexane, Skellysolve A, octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate list ethyl ether, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, 3-methoxy methyl propionate, 3-ethoxy-propionic acid methylethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, 1-butoxy-2-propyl alcohol, 1-phenoxy group-2-propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol-1-monomethyl ether-2-acetic ester, propylene glycol-1-single ethyl ether-2-acetic ester, dipropylene glycol, 2-(2-oxyethyl group propoxy-) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the solvent etc. of low surface tension.These poor solvents can use a kind or by multiple used in combination.
Even if when containing above-mentioned poor solvent, the content of above-mentioned cyclic ketone solvent is preferably more than 50 quality %, more preferably more than 60 quality %, particularly preferably more than 70 quality %.
Further, composition of the present invention can thickness evenness containing film when making coating in the scope not damaging effect of the present invention and the surface smoothness compound, the compound that the adaptation of formed film and substrate is improved that improve.
As the above-mentioned compound making film uniformity and surface smoothness improve, fluorine class tensio-active agent, siloxane type surfactants, nonionic surfactant etc. can be exemplified.Such as, specifically can exemplify エ Off ト ッ プ EF301, EF303, EF352 (Tuo Kaimu product Co., Ltd. (ト ー ケ system プ ロ ダ クツ society) system), メ ガ Off ァ ッ Network F171, F173, R-30 (Dainippon Ink and Chemicals, Inc (large Japanese イ Application キ society) system), Off ロ ラ ー De FC430, FC431 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ ー エ system society) system), ア サ ヒ ガ ー De AG710, サ ー Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd (Asahi Glass society) system) etc.The usage rate of these tensio-active agents, relative to resinous principle 100 mass parts contained in composition, is preferably 0.01 ~ 2 mass parts, more preferably 0.01 ~ 1 mass parts.
As the concrete example of compound of adaptation that can improve film and the substrate formed, the compound containing functional silanes shown below and the compound containing epoxy group(ing) can be exemplified.Such as, 3-TSL 8330 can be exemplified, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (the oxyethylene group)-3-TSL 8330 of N-, two (the oxyethylene group)-APTES of N-, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N ' ,-four glycidyl group-m-xylene diamine, two (N, the N-diglycidyl amino methyl) hexanaphthene of 1,3-, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane etc.
When use can improve the compound of adaptation of film and the substrate formed, the addition of this compound, relative to component of polymer 100 mass parts contained in composition, is preferably 0.1 ~ 30 mass parts, more preferably 1 ~ 20 mass parts.If less than 0.1 mass parts, then cannot expect the effect that adaptation improves, if more than 30 mass parts, then the orientation of liquid crystal is deteriorated sometimes.
In composition of the present invention, in the scope not damaging effect of the present invention, can also containing the cross-linked compound with epoxy group(ing), isocyanate group, oxetanyl, cyclocarbonate radical, there is at least a kind of substituent cross-linked compound being selected from hydroxyl, hydroxyalkyl and low-grade alkoxy alkyl, or there is the cross-linked compound of polymerizability unsaturated link(age).
As the above-mentioned cross-linked compound with epoxy group(ing) or isocyanate group, such as, can exemplify bisphenol acetone glycidyl ether, novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, the amino diphenylene of four glycidyl group, four glycidyl group m-xylene diamine, two (amino-ethyl) hexanaphthene of four glycidyl group-1,3-, tetraphenyl glycidyl ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro ethanoyl diglycidylether, two (1-(2,3-glycidoxy)-1-trifluoromethyl-2,2, the 2-trifluoromethyl) benzene of 1,3-, two (2, the 3-glycidoxy) octafluorobiphenyl of 4,4-, triglycidyl group p-aminophenol, four glycidyl group m-xylene diamine, 2-(4-(2,3-glycidoxy) phenyl)-2-(4-(two (4-(2, the 3-glycidoxy) phenyl) ethyl of 1,1-) phenyl) propane, 1, two (4-(1-(the 4-(2 of 3-, 3-epoxy group(ing) propoxy-) phenyl)-1-(4-(1-(4-(2,3-glycidoxy phenyl)-1-methylethyl) phenyl) ethyl) phenoxy group)-2-propyl alcohol etc.
As the cross-linked compound with oxetanyl, it is the cross-linked compound with the oxetanyl that at least 2 represent with following formula [4].
[changing 36]
Specifically, be the cross-linked compound represented with following formula [4-1] ~ formula [4-11].
[changing 37]
[changing 38]
[changing 39]
As the cross-linked compound with cyclocarbonate radical, it is the cross-linked compound with the cyclocarbonate radical that at least 2 represent with following formula [5].
[changing 40]
Specifically, be the cross-linked compound represented with following formula [5-1] ~ formula [5-37].
[changing 41]
[changing 42]
[changing 43]
[changing 44]
[changing 45]
[changing 46]
[changing 47]
[changing 48]
(in formula [5-24], n is the integer of 1 ~ 5; In formula [5-25], n is the integer of 1 ~ 5; In formula [5-36], n is the integer of 1 ~ 100; In formula [5-37], n is the integer of 1 ~ 10.)
Also can exemplify the polysiloxane with at least a kind of structure shown in following formula [5-38] ~ [5-40].
[changing 49]
(in formula [5-38] ~ [5-40], R
1, R
2, R
3, R
4and R
5structure, hydrogen atom, hydroxyl, the alkyl of carbon number 1 ~ 10, alkoxyl group, aliphatics ring or aromatic ring separately for representing with formula [5], at least 1 is the structure represented with formula [5]).
More specifically, the compound of following formula [5-41] and formula [5-42] can be exemplified.
[changing 50]
(in formula [5-41], R
6be the structure, hydrogen atom, hydroxyl, the alkyl of carbon number 1 ~ 10, alkoxyl group, aliphatics ring or the aromatic ring that represent with formula [5], at least 1 is the structure represented with formula [5]; In formula [5-42], n is the integer of 1 ~ 10.)
As having at least a kind of substituent cross-linked compound being selected from hydroxyl and alkoxyl group, such as can exemplify the aminoresin with hydroxyl or alkoxyl group, such as melamine resin, urea-formaldehyde resin, guanamine resin, glycolurilformaldehyde resins, succinic diamide-formaldehyde resin, ethylene urea-formaldehyde resin etc.Specifically, melamine derivative, benzoguanamine derivative or the glycoluril that amino hydrogen atom can be used to be instead of by methylol and/or alkoxy methyl.This melamine derivative or benzoguanamine derivative also can exist with dimer or trimerical form.They are better on average have methylol or the alkoxy methyl of more than 3 less than 6 relative to every 1 triazine ring.
As the example of melamine derivative or benzoguanamine derivative, every 1 triazine ring as commercially available product can be exemplified on average by MX-750 that 3.7 methoxymethyies instead of, MW-30 that every 1 triazine ring on average be instead of by 5.8 methoxymethyies (being Sanwa Chemical Co., Ltd (three and ケ ミ カ Le society) system above), サ イ メ Le 300, 301, 303, 350, 370, 771, 325, 327, 703, the methoxymethylated trimeric cyanamides such as 712, サ イ メ Le 235, 236, 238, 212, 253, the methoxymethylated butoxymethyl trimeric cyanamides such as 254, サ イ メ Le 506, the butoxymethyl trimeric cyanamides such as 508, the carboxylic methoxymethylated isobutoxymethyl trimeric cyanamide of サ イ メ Le 1141 and so on, the methoxymethylated ethoxyl methyl benzoguanamine of サ イ メ Le 1123 and so on, the methoxymethylated butoxymethyl benzoguanamine of サ イ メ Le 1123-10 and so on, the butoxymethyl benzoguanamine of サ イ メ Le 1128 and so on, the carboxylic methoxymethylated ethoxyl methyl benzoguanamine (being Mitsui cyanamide Co., Ltd. (Mitsui サ イ ア Na ミ De society) system above) etc. of サ イ メ Le 1125-80 and so on.
As the example of glycoluril, the methoxyl group methylolation glycoluril etc. of the methylolation glycoluril of the butoxymethyl glycoluril of サ イ メ Le 1170 and so on, サ イ メ Le 1172 and so on, パ ウ ダ ー リ Application Network 1174 and so on can be exemplified.
As benzene or the benzene phenoloid with hydroxyl or alkoxyl group, such as 1 can be exemplified, 3,5-tri-(methoxymethyl) benzene, 1,2,4-tri-(i-propoxymethyl) benzene, 1,4-two (sec-butoxymethyl) benzene, 2,6-dihydroxymethyl p-tert-butylphenols etc.
Specifically, be the cross-linked compound represented with following formula [6-1] ~ formula [6-48].
[changing 51]
[changing 52]
[changing 53]
[changing 54]
[changing 55]
As the cross-linked compound with polymerizability unsaturated link(age), such as, can exemplify the cross-linked compound in trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, three (methyl) acryloyloxyethoxy TriMethylolPropane(TMP), poly-(methyl) acrylate equimolecular of glycerine polyglycidyl ether with 3 polymerizability unsaturated groups, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, oxyethane bisphenol A-type two (methyl) acrylate, propylene oxide bisphenol type two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, glycerine two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol diglycidyl glyceryl ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, there is in hydroxy new pentane acid neopentyl glycol two (methyl) acrylate equimolecular the cross-linked compound of 2 polymerizability unsaturated groups, and (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxybutyl, (methyl) vinylformic acid-2-phenoxy group-2-hydroxy propyl ester, phthalic acid-2-(methyl) acryloxy-2-hydroxy propyl ester, (methyl) vinylformic acid-3-chlorine-2-hydroxyl propyl ester, glycerine list (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl phosphoric acid ester, there is in N-methylol (methyl) acrylamide equimolecular the cross-linked compound of 1 polymerizability unsaturated group, Deng.
The compound represented with following formula [7] can also be used.
[changing 56]
In formula [7], E
1the group being selected from cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, fluorenes ring, anthracene nucleus and phenanthrene ring, E
2be the group being selected from following formula [7a] and formula [7b], n is the integer of 1 ~ 4.
[changing 57]
Above-claimed cpd is an example of cross-linked compound, is not limited thereto.In addition, cross-linked compound contained in composition of the present invention both can be a kind of, also can be two or more combinations.
The content of the cross-linked compound in composition of the present invention is preferably 0.1 ~ 150 mass parts relative to component of polymer 100 mass parts.Show target effect to make crosslinking reaction and the orientation of liquid crystal is not declined, being more preferably 0.1 ~ 100 mass parts relative to component of polymer 100 mass parts, especially most preferably 1 ~ 50 mass parts.
In composition of the present invention in addition to those specified above, as long as in the scope not damaging effect of the present invention, can add and change the resistance of film, the dielectric medium of object of the electrical characteristic such as specific inductivity, electroconductibility of liquid crystal orientation film and conducting material for reaching.
Also have, when composition of the present invention is aligning agent for liquid crystal, as the Charger transfer in the liquid crystal orientation film promoting to be formed, the compound promoting the electric charge release of the liquid crystal cell using this liquid crystal orientation film, the nitrogen-containing hetero cyclammonium represented with following formula [M1] ~ [M156] can also be added.Even if these amine directly add in the solution of composition also harmless, but preferably to make concentration with suitable solvent be add after the solution of 0.1 ~ 10 quality %, preferably 1 ~ 7 quality % again.As this solvent, except above-mentioned cyclic ketone solvent, as long as the organic solvent of polyimide can be dissolved, be not particularly limited.
[changing 58]
[changing 59]
[changing 60]
[changing 61]
[changing 62]
[changing 63]
< liquid crystal orientation film and liquid crystal display device >
For the aligning agent for liquid crystal as one of composition of the present invention, the situation forming liquid crystal orientation film from aligning agent for liquid crystal is described.Aligning agent for liquid crystal to be coated on substrate and after being burnt till by thermal treatment, by the orientation process such as friction treatment or rayed, thus to form liquid crystal orientation film.In addition, in the situations such as vertical orientated purposes, even if do not carry out orientation process can form liquid crystal orientation film yet.
As substrate, as long as the substrate that the transparency is high, be not particularly limited, except glass substrate, also can use the plastic bases etc. such as vinylformic acid substrate, polycarbonate substrate.From the viewpoint of work simplification, preferably use the substrate of the ITO electrode etc. be formed with for liquid crystal drive.In addition, in reflection type liquid crystal display element, also can use the opaque substrates such as silicon wafer, but be only limitted to one-sided substrate, electrode now also can use the material of the reflected light such as aluminium.
Be not particularly limited the coating process of aligning agent for liquid crystal, the method be coated with is carried out in industrial usual employing by silk screen printing, offset printing, flexographic printing, ink jet method etc.As other coating processes, also have dip coating, rolling method, slot coated method, spin-coating method, spraying method etc., these methods can be used according to object.Even if aligning agent for liquid crystal of the present invention is using in above coating method situation, coating is also good.
Aligning agent for liquid crystal is coated after on substrate, can pass through the heating units such as hot-plate, heat-circulation type stove, IR (infrared rays) type stove 50 ~ 180 DEG C, preferably at 80 ~ 150 DEG C, solvent is evaporated, thus formed film.If the film after burning till is blocked up, then unfavorable in the power consumption of liquid crystal display device, if excessively thin, then the reliability of liquid crystal display device reduces sometimes, therefore preferably 5 ~ 300nm, more preferably 10 ~ 100nm.When making liquid crystal horizontal alignment or tilted alignment, by friction or polarisation uviolizing etc., the film after burning till is processed.
Liquid crystal display device, after being with the substrate of liquid crystal orientation film by aforesaid method by aligning agent for liquid crystal acquisition of the present invention, is manufactured the liquid crystal display device of liquid crystal cell by known method.
As the manufacture method of liquid crystal cell, following method can be illustrated: a pair substrate preparing to be formed with liquid crystal orientation film, the liquid crystal orientation film of one piece of substrate scatters spacer, is in the mode of inner side by another block baseplate-laminating with liquid crystal aligning face, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with spacer after, baseplate-laminating is carried out the method etc. sealed.
Liquid crystal orientation film is applicable to by possessing the liquid crystal display device having liquid crystal layer between a pair substrate of electrode and form, manufacture through following operation, this operation is: between a pair substrate, configuration packet carries out the liquid-crystal composition of the polymerizable compound be polymerized containing at least one party utilized in active energy beam and heat, applies voltage while by the irradiation of active energy beam and add at least one party hankered and make polymerizable compound be polymerized between electrode.Here, the preferred ultraviolet of active energy beam.
Above-mentioned liquid crystal display device controls the tilt angle of liquid crystal molecule by PSA (Polymer Sustained Alignment: polymer stabilizing orientation) mode.In PSA mode, a small amount of photopolymerizable compound, such as photopolymerization monomer is mixed in advance in liquid crystal material, after assembling liquid crystal cell, to photopolymerizable compound irradiation ultraviolet radiation etc. under the state of voltage liquid crystal layer being applied to regulation, the polymkeric substance generated is utilized to control the tilt angle of liquid crystal molecule.The state of orientation of liquid crystal molecule when polymkeric substance generates also can be remembered after removal of the voltage, so by controlling the electric field etc. formed in liquid crystal layer, can adjust the tilt angle of liquid crystal molecule.In addition, when adopting PSA mode, friction treatment is not needed, so be applicable to the formation being difficult to the liquid crystal layer being controlled the vertical orientating type of tilt angle by friction treatment.
Namely, liquid crystal display device can be made into liquid crystal display device as described below: by aforesaid method by aligning agent for liquid crystal of the present invention obtain be with liquid crystal orientation film substrate after, manufacture liquid crystal cell, by ultraviolet irradiation and add at least one party hankered and make polymerizable compound be polymerized, thus control the liquid crystal display device of the orientation of liquid crystal molecule.
If exemplify an example of the liquid crystal cell manufacturing PSA mode, following method can be exemplified: a pair substrate preparing to be formed with liquid crystal orientation film, the liquid crystal orientation film of one piece of substrate scatters spacer, be in the mode of inner side by another block baseplate-laminating with liquid crystal aligning face, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with spacer after, baseplate-laminating is carried out the method etc. sealed.
Can mix in liquid crystal and carry out by heating or irradiation ultraviolet radiation the polymerizable compound that is polymerized.As polymerizable compound, the compound of the polymerizability unsaturated group such as acrylate-based or methacrylate based with more than 1 can be exemplified in molecule.Now, polymerizable compound is preferably 0.01 ~ 10 mass parts relative to liquid crystal composition 100 mass parts, more preferably 0.1 ~ 5 mass parts.If polymerizable compound is less than 0.01 mass parts, then polymerizable compound is not polymerized, and cannot carry out the tropism control of liquid crystal, if more than 10 mass parts, then unreacted polymerizable compound increases, and the burning screen characteristics (Japanese: baked I pays I characteristic) of liquid crystal display device declines.
After making liquid crystal cell, liquid crystal cell is applied to the voltage of interchange or direct current, while heating or irradiation ultraviolet radiation, polymerizable compound is polymerized.Control the orientation of liquid crystal molecule by this.
Also have, aligning agent for liquid crystal of the present invention can perform well in liquid crystal display device, this liquid crystal display device by possess between a pair substrate of electrode, there is liquid crystal layer and form and through following operation obtain, this operation is: between a pair substrate, configuration packet carries out the liquid crystal orientation film of the polymerizable group be polymerized containing at least one party utilized in active energy beam and heat, between electrode, apply voltage.Here, the preferred ultraviolet of active energy beam.Ultraviolet wavelength is 300 ~ 400nm, preferably 310 ~ 360nm.If utilize the polymerization of heating, then Heating temperature is 40 ~ 120 DEG C, preferably 60 ~ 80 DEG C.
At least one party in active energy beam and heat is utilized and the liquid crystal orientation film of the polymerizable group be polymerized in order to obtain to comprise, the method of adding the compound containing this polymerizable group in aligning agent for liquid crystal can be exemplified, and use the method for the component of polymer containing polymerizable group.Aligning agent for liquid crystal of the present invention contains to have and utilizes heat or ultraviolet irradiation and the specific compound at the double bond position of reacting, so by ultraviolet irradiation and can add the orientation that at least one party hankered controls liquid crystal molecule.
An example of liquid crystal cell is manufactured if exemplify, following method can be exemplified: a pair substrate preparing to be formed with liquid crystal orientation film, the liquid crystal orientation film of one piece of substrate scatters spacer, is in the mode of inner side by another block baseplate-laminating with liquid crystal aligning face, decompression injects liquid crystal and the method for sealing; Or drip liquid crystal on the liquid crystal aligning face being scattered with spacer after, baseplate-laminating is carried out the method etc. sealed.
Liquid crystal display device can be obtained through above-mentioned operation.These liquid crystal display device, owing to using liquid crystal orientation film of the present invention as liquid crystal orientation film, so the temperature of manufacturing process is lower, excellent in reliability, are applicable to the LCD TV etc. of large picture and high-resolution.
Embodiment
Below, exemplify embodiment and be described, but the present invention should not be interpreted as limiting by these embodiments.Abbreviation used in embodiment and comparative example is as follows.
The first diamines > of the structure that < represents with formula [1]
D1:N, N-diallyl-2,4-diamino aniline
[changing 64]
The second diamines > of the structure that < represents with formula [2]
D2:1,3-diamino-4-[4-(trans-4-n-heptyl cyclohexyl) phenoxy group] benzene
[changing 65]
Other diamines of < >
D3: Ursol D
[changing 66]
< tetracarboxylic dianhydride >
M1:1,2,3,4-tetramethylene tetracarboxylic dianhydride
M2: two rings [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
M3: pyromellitic acid anhydride
[changing 67]
< cyclic ketone solvent >
CHN: pimelinketone
CPN: cyclopentanone
Other organic solvents of < >
NMP:N-N-methyl-2-2-pyrrolidone N-
BCS: ethylene glycol monobutyl ether
PGME: propylene glycol monomethyl ether
In addition, the physical property such as molecular weight and imide rate of polyimide is evaluated as follows.
(molecular weight determination of polyimide)
The molecular weight of the polyimide in synthesis example uses normal temperature gel permeation chromatography (GPC) device (GPC-101) (Showa Denko K. K (Showa Electricity work society) system) and post (KD-803, KD-805) (Xiao Deshi Co., Ltd. (Shodex society) system) to measure in accordance with the following methods.
Column temperature: 50 DEG C.
Elutriant: N, N'-dimethyl formamide (as additive, lithiumbromide hydrate (LiBrH
2o) be 30 mM/ls, phosphoric anhydride crystallization (o-phosphoric acid) is 30 mM/ls, tetrahydrofuran (THF) (THF) is 10ml/L (liter)).
Flow velocity: 1.0ml/ minute.
Calibration curve making standard test specimen: TSK standard polyethylene oxide (molecular weight is about 900000,150000,100000 and 30000) ((East ソ ー society of TOSOH Co., Ltd) is made), and polyoxyethylene glycol (molecular weight is about 12000,4000 and 1000) (Polymer Laboratory company (Port リ マ ー ラ ボ ラ ト リ ー society) system).
(mensuration of imide rate)
The imide rate of the polyimide in synthesis example measures as follows.
Polyimide powder (20mg) is joined NMR stopple coupon (the specification φ 5 of NMR stopple coupon, wasteland's science Co., Ltd. (wasteland's science society) makes), add deuterated dimethyl sulfoxide (DMSO-d6,0.05 quality %TMS(tetramethylsilane) mixture) (0.53ml), apply ultrasonic wave and make it dissolve completely.For this solution, determine the proton N MR of 500MHz with NMR (nucleus magnetic resonance) determinator (JNW-ECA500) (NEC Dan Ding Co., Ltd. (Japanese Electricity デ ー タ system society) system).Imide rate is as described below tries to achieve: utilize the proton coming from the structure do not changed before and after imidization as standard proton, utilize the accumulated value of this proton peak and come from the accumulated value of proton peak of NH base of amido acid of neighbouring appearance of 9.5 ~ 10.0ppm, tried to achieve by following formula.
Imide rate (%)=(1-α x/y) × 100
In above-mentioned formula, x is the accumulated value of the proton peak of the NH base coming from amido acid, and y is the accumulated value at standard proton peak, and α is the number ratio relative to the standard proton of 1 NH matrix of amido acid time polyamic acid (imide rate is 0%).
The synthesis > of < polyimide
< synthesis example 1>
By M2 (2.75g, 11.0 mmoles), D1 (2.68g, 13.2 mmoles) and D2 (3.35g, 8.8 mmoles) mixing in NMP (26.4g), it is made after 5 hours, to add M1 (2.14g, 10.9 mmoles) and NMP (17.3g) in 80 DEG C of reactions, make it in 40 DEG C of reactions 6 hours, obtain polyamic acid solution.
Add NMP in this polyamic acid solution (20.0g) with after being diluted to 6 quality %, add diacetyl oxide (4.11g) and pyridine (1.59g) as imidization catalyst, make it in 100 DEG C of reactions 3 hours.This reaction soln is put in methyl alcohol (253ml), the throw out of filtering separation gained.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (A).The imide rate of this polyimide is 80%, and number-average molecular weight is 21500, and weight-average molecular weight is 68700.
< synthesis example 2>
By M1 (3.61g, 18.4 mmoles), D1 (2.81g, 13.8 mmoles) and D2 (3.50g, 9.2 mmoles) mixing in NMP (29.7g), it is made after 15 hours, to add M3 (0.95g, 4.4 mmoles) and NMP (13.7g) in 25 DEG C of reactions, make it in 25 DEG C of reactions 4 hours, obtain polyamic acid solution.
Add NMP in this polyamic acid solution (20.0g) with after being diluted to 6 quality %, add diacetyl oxide (2.58g) and pyridine (1.07g) as imidization catalyst, make it in 40 DEG C of reactions 1 hour 30 minutes.This reaction soln is put in methyl alcohol (246ml), the throw out that filtering separation obtains.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (B).The imide rate of this polyimide is 51%, and number-average molecular weight is 18700, and weight-average molecular weight is 57800.
< synthesis example 3>
By M1 (4.29g, 21.9 mmoles), D1 (3.13g, 15.4 mmoles) and D2 (2.51g, 6.6 mmoles) mixing in NMP (39.7g), make it in 25 DEG C of reactions 24 hours, obtain polyamic acid solution.
Add NMP in this polyamic acid solution (10.0g) with after being diluted to 6 quality %, add diacetyl oxide (1.35g) and pyridine (0.56g) as imidization catalyst, make it in 40 DEG C of reactions 2 hours.This reaction soln is put in methyl alcohol (123ml), the throw out that filtering separation obtains.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (C).The imide rate of this polyimide is 53%, and number-average molecular weight is 19800, and weight-average molecular weight is 55900.
< synthesis example 4>
By M1 (4.61g, 23.5 mmoles), D1 (1.95g, 9.6 mmoles), D2 (2.74g, 7.2 mmoles) and D3 (0.78g, 7.2 mmoles) mixing in NMP (40.3g), make it in 25 DEG C of reactions 24 hours, obtain polyamic acid solution.
Add NMP in this polyamic acid solution (10.0g) with after being diluted to 6 quality %, add diacetyl oxide (1.44g) and pyridine (0.60g) as imidization catalyst, make it in 40 DEG C of reactions 2 hours.This reaction soln is put in methyl alcohol (124ml), the throw out that filtering separation obtains.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (D).The imide rate of this polyimide is 48%, and number-average molecular weight is 17200, and weight-average molecular weight is 48100.
< synthesis example 5>
By M2 (5.63g, 22.5 mmoles) and D3 (3.24g, 30.0 mmoles) mixing in NMP (26.6g), after making it react 5 hours in 40 DEG C, add M1 (1.24g, 6.3 mmoles) and NMP (13.8g), make it in 25 DEG C of reactions 6 hours, obtain polyamic acid solution.
Add NMP in this polyamic acid solution (20.0g) with after being diluted to 5 quality %, add diacetyl oxide (2.96g) and pyridine (2.29g) as imidization catalyst, make it in 90 DEG C of reactions 2.5 hours.This reaction soln is put in methyl alcohol (298ml), the throw out that filtering separation obtains.By this throw out washed with methanol, drying under reduced pressure at 100 DEG C and obtain polyimide powder (E).The imide rate of this polyimide is 51%, and number-average molecular weight is 15300, and weight-average molecular weight is 68800.In addition, this polyimide does not use the first diamines and the second diamines in diamine component.
By the polyimide by synthesis example 1 ~ 5 gained form and imide rate gathers and is shown in table 43.
[table 43]
The dissolubility test > of < polyimide
< embodiment 1 ~ 4 and comparative example 1>
Use the polyimide powder obtained by synthesis example 1 ~ 5, carry out as the deliquescent test in the pimelinketone (CHN) of cyclic ketone solvent and cyclopentanone (CPN).
In each polyimide powder (1.0g) of polyimide powder (A) ~ (E), add CHN (15.7g), stir 24 hours in 25 DEG C, by visual confirmation with or without muddy or precipitation etc.
Then, in each polyimide powder (1.0g) of polyimide powder (A) ~ (E), add CPN (15.7g), stir 24 hours in 25 DEG C, by visual confirmation with or without muddy or precipitation etc.
The result of dissolubility test is shown in table 44.
[table 44]
According to above result, confirm that the polyimide powder of embodiment 1 ~ 4 is dissolved in cyclic ketone solvent equably.On the other hand, the polyimide powder (E) of comparative example 1 is insoluble to cyclic ketone solvent.
< contains the composition of polyimide and solvent and the preparation > of aligning agent for liquid crystal
< embodiment 5 ~ 8>
In polyimide powder (A) ~ (D) (each 1.0g) of synthesis example 1 ~ 4, respectively add CHN (27.57g), stir 24 hours in 50 DEG C, each polyimide is dissolved.Confirming that any polyimide solution does not all find that muddiness or precipitation etc. are abnormal, is uniform solution.
Then, carry out pressure filtration to the film filter of each polyimide solution fine pore 1 μm of gained, the content obtaining polyimide component is aligning agent for liquid crystal (1) ~ (4) of 3.5 quality %.
< embodiment 9 ~ 12>
In polyimide powder (A) ~ (D) (each 1.0g) of synthesis example 1 ~ 4, respectively add CPN (27.6g), stir 24 hours in 50 DEG C, each polyimide is dissolved.Confirming that any polyimide solution does not all find that muddiness or precipitation etc. are abnormal, is uniform solution.
Then, carry out pressure filtration to the film filter of each polyimide solution fine pore 1 μm of gained, the content obtaining polyimide component is aligning agent for liquid crystal (5) ~ (8) of 3.5 quality %.
< embodiment 13 ~ 15>
In polyimide powder (A) ~ (C) (each 1.0g) of synthesis example 1 ~ 3, respectively add CHN (13.3g), stir 24 hours in 50 DEG C, each polyimide is dissolved.Then, in each solution of gained, add NMP (14.3g) again, stir, obtain each polyimide solution containing CHN and NMP.Confirming that any polyimide solution does not all find that muddiness or precipitation etc. are abnormal, is uniform solution.
Then, carry out pressure filtration to the film filter of each polyimide solution fine pore 1 μm containing CHN and NMP, the content obtaining polyimide component is aligning agent for liquid crystal (9) ~ (11) of 3.5 quality %.
< embodiment 16 ~ 18>
In polyimide powder (A) ~ (C) (each 1.0g) of synthesis example 1 ~ 3, respectively add CPN (13.3g), stir 24 hours in 50 DEG C, each polyimide is dissolved.Then, in each solution of gained, add NMP (14.3g) again, stir, obtain each polyimide solution containing CPN and NMP.Confirming that any polyimide solution does not all find that muddiness or precipitation etc. are abnormal, is uniform solution.
Then, carry out pressure filtration to the film filter of each polyimide solution fine pore 1 μm containing CPN and NMP, the content obtaining polyimide component is aligning agent for liquid crystal (12) ~ (14) of 3.5 quality %.
< embodiment 19 ~ 21>
In polyimide powder (A) ~ (C) (each 1.0g) of synthesis example 1 ~ 3, respectively add CHN (13.3g), stir 24 hours in 50 DEG C, each polyimide is dissolved.Then, in each solution of gained, add NMP (5.72g) and BCS (8.57g) again, stir, obtain each polyimide solution containing CHN, NMP and BCS.Confirming that any polyimide solution does not all find that muddiness or precipitation etc. are abnormal, is uniform solution.
Then, carry out pressure filtration to the film filter of each polyimide solution fine pore 1 μm containing CHN, NMP and BCS, the content obtaining polyimide component is aligning agent for liquid crystal (15) ~ (17) of 3.5 quality %.
< embodiment 22 ~ 24>
In polyimide powder (A) ~ (C) (each 1.0g) of synthesis example 1 ~ 3, respectively add CPN (13.3g), stir 24 hours in 50 DEG C, each polyimide is dissolved.Then, in each solution of gained, add NMP (5.72g) and BCS (8.57g) again, stir, obtain each polyimide solution containing CPN, NMP and BCS.Confirming that any polyimide solution does not all find that muddiness or precipitation etc. are abnormal, is uniform solution.
Then, carry out pressure filtration to the film filter of each polyimide solution fine pore 1 μm containing CPN, NMP and BCS, the content obtaining polyimide component is aligning agent for liquid crystal (18) ~ (20) of 3.5 quality %.
< embodiment 25 ~ 27>
In polyimide powder (A) ~ (C) (each 1.0g) of synthesis example 1 ~ 3, respectively add CHN (19.0g), stir 24 hours in 50 DEG C, each polyimide is dissolved.Then, in each solution of gained, add PGME (8.57g) again, stir, obtain each polyimide solution containing CHN and PGME.Confirming that any polyimide solution does not all find that muddiness or precipitation etc. are abnormal, is uniform solution.
Then, carry out pressure filtration to the film filter of each polyimide solution fine pore 1 μm containing CHN and PGME, the content obtaining polyimide component is aligning agent for liquid crystal (21) ~ (23) of 3.5 quality %.
< embodiment 28 ~ 30>
In polyimide powder (A) ~ (C) (each 1.0g) of synthesis example 1 ~ 3, respectively add CPN (19.0g), stir 24 hours in 50 DEG C, each polyimide is dissolved.Then, in each solution of gained, add PGME (8.57g) again, stir, obtain each polyimide solution containing CPN and PGME.Confirming that any polyimide solution does not all find that muddiness or precipitation etc. are abnormal, is uniform solution.
Then, carry out pressure filtration to the film filter of each polyimide solution fine pore 1 μm containing CPN and PGME, the content obtaining polyimide component is aligning agent for liquid crystal (24) ~ (26) of 3.5 quality %.
< comparative example 2 ~ 4>
In polyimide powder (A) ~ (C) (each 2.0g) of embodiment 1 ~ 3, respectively add NMP (31.3g), stir 24 hours in 50 DEG C, each polyimide is dissolved.Confirming that any polyimide solution does not all find that muddiness or precipitation etc. are abnormal, is uniform solution.
Then, carry out pressure filtration to the film filter of each polyimide solution fine pore 1 μm of gained, the content obtaining polyimide component is aligning agent for liquid crystal (27) ~ (29) of 6 quality %.
The kind of the polyimide of the aligning agent for liquid crystal by embodiment 5 ~ 30 and comparative example 2 ~ 4 gained and solvent, solvability are shown in table 45 ~ 47.
[table 45]
[table 46]
[table 47]
The manufacture > of < liquid crystal orientation film and liquid crystal display device
Use and manufacture liquid crystal orientation film by the aligning agent for liquid crystal of embodiment 5 ~ 30 gained, and manufacture the liquid crystal display device employing this liquid crystal orientation film.As liquid crystal display device, manufacture the vertical orientated liquid crystal cell corresponding with the characteristic of liquid crystal orientation film.
As the manufacture method of liquid crystal cell, aligning agent for liquid crystal is spun on the glass substrate (long 40mm × wide 30mm, thick 0.7mm) of band ITO electrode, on the hot-plate of 80 DEG C heat treated 5 minutes, in thermal cycling type cleaning stove in 220 DEG C of heat treated after 30 minutes, form the liquid crystal orientation film as film of thickness 100nm, obtain the substrate of band liquid crystal orientation film.The homogeneity of the thickness of the liquid crystal orientation film that substrate is formed is all excellent, and known aligning agent for liquid crystal shows excellent coating.
Prepare the substrate of two pieces of above-mentioned band liquid crystal orientation films, after the liquid crystal aligning face of a side scatters the spacer of 6 μm, printing and sealing agent thereon (XN-1500T, Mitsui Chemicals, Inc (Mitsui Chemicals society) makes).Then, after fitting to make the liquid crystal orientation film mode relative with the substrate of the opposing party, negative crystal born of the same parents are manufactured by within 90 minutes, being cured in 150 DEG C of heat treated in thermal cycling type cleaning stove by sealing agent.Adopt decompression injection method, in this negative crystal born of the same parents, inject nematic liquid crystal (MLC-6608, Merck & Co., Inc. (メ ルク society) makes), inlet is sealed, obtains vertical orientated liquid crystal cell (liquid crystal display device).
The liquid crystal cell of gained is observed to the state of orientation of liquid crystal with polarizing microscope (ECLIPSE E600WPOL, Nikon Corp. (ニ コ Application society) makes), results verification defines does not have the vertical orientated of defective, uniform liquid crystal.
The result of the state of orientation of the liquid crystal of liquid crystal display device is shown in table 48 and table 49.
[table 48]
[table 49]
Then, the aligning agent for liquid crystal of embodiment 5 ~ 11 and comparative example 2 ~ 4 is used to manufacture liquid crystal display device.Above-mentioned method used for liquid crystal display element manufactures.At the temperature of 80 DEG C, apply the voltage 60 μm of 1V to these liquid crystal display device, measure the voltage after 50ms, compared with just applying after voltage, voltage can keep how many, this is illustrated as voltage retention.In addition, measure and use VHR-1 voltage retention determinator (Toyo Corp. (East Yang テ Network ニ カ society) system), voltage be ± 1V, pulse width is 60 μ s, the frame period be the imposing a condition of 50ms under carry out.
The result of the voltage retention of liquid crystal display device is shown in table 50.
[table 50]
According to above result, knownly can provide aligning agent for liquid crystal of the present invention, and the coating of this aligning agent for liquid crystal is excellent.In addition, the known liquid crystal orientation film employing aligning agent for liquid crystal of the present invention can be manufactured by easy fired.
The possibility that industry utilizes
Composition of the present invention can be widely used in the formation of the film such as interlayer dielectric and protective membrane in electron device etc.; particularly as aligning agent for liquid crystal, there is coating excellence and the characteristic of energy easy fired, so can be used for the formation of the liquid crystal orientation film used in the high liquid crystal display device of reliability.
Quote the announcement of full content as specification sheets of the present invention of the specification sheets of No. 2011-049430, the Japanese patent application that on March 7th, 2011 files an application, claims and specification digest here.
Claims (14)
1. composition, it is characterized in that, containing polyimide precursor and/or the polyimide carrying out imidization to this polyimide precursor and obtain and the cyclic ketone solvent dissolving this polyimide precursor and/or polyimide, described polyimide precursor is reacted with tetracarboxylic dianhydride's composition with alicyclic structure by the diamine component of the second diamines making to comprise the first diamines of representing with following formula [1] and represent with following formula [2] and obtains
[changing 1]
In formula [1], R
1and R
2be separately the straight-chain of carbon number 1 ~ 12 or the alkyl of branched;
[changing 2]
In formula [2], X represents substituting group, and be the alkyl of carbon number 8 ~ 22 or the group that represents with following formula [2A], n is the integer of 1 ~ 4;
[changing 3]
In formula [2A], Y
1for singly-bound ,-(CH
2)
a-,-O-,-CH
2o-,-COO-or OCO-, wherein a is the integer of 1 ~ 15; Y
2for singly-bound or (CH
2)
b-, wherein b is the integer of 1 ~ 15; Y
3for singly-bound ,-(CH
2)
c-,-O-,-CH
2o-,-COO-or OCO-, wherein c is the integer of 1 ~ 15;
Y
4it is divalent organic group, it is selected from the organic group of the carbon number 12 ~ 25 of cyclic group or the steroid skeleton having and be selected from phenyl ring, cyclohexane ring and heterocycle, and the arbitrary hydrogen atom on wherein said cyclic group can be replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom; Y
5for being selected from the cyclic group of phenyl ring, cyclohexane ring and heterocycle, the arbitrary hydrogen atom on wherein said cyclic group can be replaced by the fluoroalkoxy containing fluoroalkyl, carbon number 1 ~ 3 of the alkoxyl group of the alkyl of carbon number 1 ~ 3, carbon number 1 ~ 3, carbon number 1 ~ 3 or fluorine atom; Y
6for the alkyl of carbon number 1 ~ 18, carbon number 1 ~ 18 containing fluoroalkyl, the alkoxyl group of carbon number 1 ~ 18 or the fluoroalkoxy of carbon number 1 ~ 18; N is the integer of 0 ~ 4.
2. composition as claimed in claim 1, it is characterized in that, the diamines represented with described formula [1] is the diamines represented with following formula [1A],
[changing 4]
In formula [1A], R
1for the straight-chain of carbon number 1 ~ 12 or the alkyl of branched, R
5for the alkyl of hydrogen atom or carbon number 1 ~ 12; R
3and R
4be hydrogen atom or methyl independently.
3. composition as claimed in claim 2, it is characterized in that, the diamines of the structure represented with described formula [1A] is the diamines represented with following formula [1B],
[changing 5]
4. composition as claimed in claim 1, it is characterized in that, the diamines of the structure represented with described formula [1] is the diamines represented with following formula [1C],
[changing 6]
5. the composition according to any one of Claims 1 to 4, is characterized in that, in described diamine component, the diamines of the structure represented with described formula [1] is 20 ~ 80 % by mole.
6. the composition according to any one of Claims 1 to 4, is characterized in that, in described diamine component, the diamines of the structure represented with described formula [2] is 10 ~ 80 % by mole.
7. the composition according to any one of Claims 1 to 4, is characterized in that, described tetracarboxylic dianhydride is the compound represented with following formula [3],
[changing 7]
In formula [3], Z
1for carbon number 4 ~ 13 4 valency organic groups and containing the non-aromatic cyclic hydrocarbon base of carbon number 4 ~ 10.
8. composition as claimed in claim 7, is characterized in that, the Z of described formula [3]
1the structure represented with following formula [3a] ~ [3j],
[changing 8]
In formula [3a], Z
2~ Z
5for hydrogen atom, methyl, chlorine atom or phenyl ring, they each other can be identical or different; In formula [3g], Z
6and Z
7for hydrogen atom or methyl, they each other can be identical or different.
9. the composition according to any one of Claims 1 to 4, is characterized in that, described cyclic ketone solvent comprises the cyclic ketone of at least one party in the cyclic ketone of 5 rings and 6 rings.
10. aligning agent for liquid crystal, is characterized in that, the composition according to any one of claim 1 ~ 9 is formed.
11. liquid crystal orientation films, is characterized in that, are obtained by aligning agent for liquid crystal according to claim 10.
12. liquid crystal orientation films as claimed in claim 11, it is characterized in that, be used to by possessing the liquid crystal display device that there is between a pair substrate of electrode liquid crystal layer and form, manufacture through following operation, this operation is: between described a pair substrate, configuration packet carries out the liquid-crystal composition of the polymerizable compound be polymerized containing at least one party utilized in active energy beam and heat, applies voltage while make described polymerizable compound be polymerized between described electrode.
13. 1 kinds of liquid crystal display device, is characterized in that, have liquid crystal orientation film according to claim 11.
14. liquid crystal display device as claimed in claim 13, it is characterized in that, form by there is liquid crystal layer between a pair substrate possessing electrode and described liquid crystal orientation film, and manufacture through following operation, this operation is: between described a pair substrate, configuration packet carries out the liquid-crystal composition of the polymerizable compound be polymerized containing at least one party utilized in active energy beam and heat, applies voltage while make described polymerizable compound be polymerized between described electrode.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011-049430 | 2011-03-07 | ||
| JP2011049430 | 2011-03-07 | ||
| PCT/JP2012/055709 WO2012121257A1 (en) | 2011-03-07 | 2012-03-06 | Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
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| CN103502312B true CN103502312B (en) | 2015-07-29 |
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|---|---|
| JP (1) | JP6003882B2 (en) |
| KR (1) | KR101842740B1 (en) |
| CN (1) | CN103502312B (en) |
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| CN105940342B (en) * | 2013-11-28 | 2019-06-21 | 日产化学工业株式会社 | Aligning agent for liquid crystal and the liquid crystal expression element for having used it |
| KR102710871B1 (en) * | 2015-10-14 | 2024-09-26 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| CN115490852A (en) * | 2022-06-21 | 2022-12-20 | 广东鸿翔瑞材料科技有限公司 | Modified polyimide, preparation method thereof and polyimide film |
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| Publication number | Publication date |
|---|---|
| TWI525129B (en) | 2016-03-11 |
| JP6003882B2 (en) | 2016-10-05 |
| KR20140015441A (en) | 2014-02-06 |
| TW201249897A (en) | 2012-12-16 |
| CN103502312A (en) | 2014-01-08 |
| JPWO2012121257A1 (en) | 2014-07-17 |
| WO2012121257A1 (en) | 2012-09-13 |
| KR101842740B1 (en) | 2018-05-14 |
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