TWI816022B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display elements using the same - Google Patents
Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display elements using the same Download PDFInfo
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- TWI816022B TWI816022B TW109104506A TW109104506A TWI816022B TW I816022 B TWI816022 B TW I816022B TW 109104506 A TW109104506 A TW 109104506A TW 109104506 A TW109104506 A TW 109104506A TW I816022 B TWI816022 B TW I816022B
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- Prior art keywords
- group
- liquid crystal
- crystal alignment
- formula
- represented
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 180
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 69
- 229920000642 polymer Polymers 0.000 claims abstract description 74
- 125000000962 organic group Chemical group 0.000 claims abstract description 66
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 49
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 38
- 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 33
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 26
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 37
- -1 9-fluorenylmethoxycarbonyl Chemical group 0.000 claims description 24
- 150000002148 esters Chemical class 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 230000005684 electric field Effects 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 150000002466 imines Chemical group 0.000 claims description 5
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 claims description 4
- JYTUSYBCFIZPBE-AMTLMPIISA-N lactobionic acid Chemical group OC(=O)[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O JYTUSYBCFIZPBE-AMTLMPIISA-N 0.000 claims description 4
- 125000003566 oxetanyl group Chemical group 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 150000005676 cyclic carbonates Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000000466 oxiranyl group Chemical group 0.000 claims description 3
- 125000002009 alkene group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000004426 substituted alkynyl group Chemical group 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 206010047571 Visual impairment Diseases 0.000 abstract description 29
- 238000002834 transmittance Methods 0.000 abstract description 15
- 239000010408 film Substances 0.000 description 60
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 56
- 239000000758 substrate Substances 0.000 description 48
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 37
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- 239000004952 Polyamide Substances 0.000 description 29
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- 230000015572 biosynthetic process Effects 0.000 description 27
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- 238000003786 synthesis reaction Methods 0.000 description 25
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- 239000000243 solution Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
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- 239000011248 coating agent Substances 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
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- 229920005575 poly(amic acid) Polymers 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
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- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 8
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- 238000001035 drying Methods 0.000 description 8
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- 239000000463 material Substances 0.000 description 8
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 6
- 229910052581 Si3N4 Inorganic materials 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 4
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 3
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
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- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 125000000168 pyrrolyl group Chemical group 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- HXJZEGBVQCRLOD-UHFFFAOYSA-N 1-triethoxysilylpropan-2-amine Chemical compound CCO[Si](CC(C)N)(OCC)OCC HXJZEGBVQCRLOD-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 2
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- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- LVYXPOCADCXMLP-UHFFFAOYSA-N 3-butoxy-n,n-dimethylpropanamide Chemical compound CCCCOCCC(=O)N(C)C LVYXPOCADCXMLP-UHFFFAOYSA-N 0.000 description 2
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
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- 238000001354 calcination Methods 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 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 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
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- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
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- KGKAGLNUEHXEQW-UHFFFAOYSA-N (4-aminophenyl) 1-(4-aminophenyl)piperidine-4-carboxylate Chemical compound NC1=CC=C(OC(=O)C2CCN(CC2)C2=CC=C(C=C2)N)C=C1 KGKAGLNUEHXEQW-UHFFFAOYSA-N 0.000 description 1
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- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
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- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 1
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- CYPTUSHYKRVMKI-UHFFFAOYSA-N 2-[2-(3-trimethoxysilylpropylamino)ethylamino]ethyl acetate Chemical compound CO[Si](OC)(OC)CCCNCCNCCOC(C)=O CYPTUSHYKRVMKI-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
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- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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- 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
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- 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
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Abstract
本發明為提供一種可形成以下液晶配向膜的液晶配向劑,該液晶配向膜為來自殘留DC的殘像或AC殘像之產生為少,重工為容易,且透過率高者。 該液晶配向劑為含有具有下述式(1)所示重複單位的聚合物(A),與具有下述式(2)所示重複單位、下述式(3)所示重複單位、下述式(4)所示重複及下述(5)所示重複單位的聚合物(B)。 (式(l)中,X1 為4價有機基,Y1 為2價有機基;式(2)~(5)中,X2 為來自脂環式酸二酐或脂肪族酸二酐的4價有機基,Y2 為式(m-1)或(m-2)所示2價有機基;R2-5 為氫原子或碳數1~4的烷基;Z21-51 、Z22-52 各獨立為氫原子等,*表示鍵結手。X3 為來自脂環式酸二酐或脂肪族酸二酐之4價有機基。Y3 為具有式(l)或式(n)所示部分結構的2價有機基。式(l)、(n)中,Q1 、Q2 表示碳數1~3的烷基,Q3 表示氫原子或碳數1~3的烷基;X4 、X5 為來自芳香族酸二酐的4價有機基。Y4 與式(2)的Y2 同義,Y5 與式(3)的Y3 同義)The present invention is to provide a liquid crystal alignment agent that can form a liquid crystal alignment film that produces less afterimages or AC afterimages from residual DC, is easy to rework, and has high transmittance. The liquid crystal alignment agent contains a polymer (A) having a repeating unit represented by the following formula (1), and a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), and a repeating unit represented by the following formula (3). A polymer (B) having a repeating unit represented by formula (4) and a repeating unit represented by (5) below. (In formula (1), X 1 is a tetravalent organic group, Y 1 is a divalent organic group; in formulas (2) to (5), X 2 is derived from alicyclic acid dianhydride or aliphatic acid dianhydride Tetravalent organic group, Y 2 is a divalent organic group represented by formula (m-1) or (m-2); R 2-5 is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms; Z 21-51 , Z 22-52 are each independently a hydrogen atom, etc. , * represents the bonding hand. ). In the formulas (l) and (n), Q 1 and Q 2 represent alkyl groups having 1 to 3 carbon atoms, and Q 3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ; X 4 and _ _
Description
本發明係關於液晶配向劑、液晶配向膜及使用其之液晶顯示元件。The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element using the same.
自過去,液晶裝置作為個人電腦、手機、智慧型手機、電視機接收者等顯示部而廣泛被使用。液晶裝置中例如具備夾在元件基板與彩色過濾器基板之間的液晶層、對液晶層輸入電場的畫素電極及共通電極、控制液晶層之液晶分子的配向性之配向膜、使供給於畫素電極的電氣信號開關之薄膜電晶體(TFT)等。作為液晶分子之驅動方式,已知有TN方式、VA方式等縱電場方式或IPS方式、FFS(邊緣場開關;Fringe field switch)方式等橫向電場方式(例如專利文獻1)。In the past, liquid crystal devices have been widely used as display parts of personal computers, mobile phones, smart phones, television receivers, and the like. A liquid crystal device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that input an electric field to the liquid crystal layer, an alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, and a liquid crystal layer that controls the alignment of liquid crystal molecules. Thin film transistor (TFT), electrical signal switch of element electrode, etc. As a driving method of liquid crystal molecules, longitudinal electric field methods such as TN method and VA method, or transverse electric field methods such as IPS method and FFS (Fringe field switch) method are known (for example, Patent Document 1).
一般而言,僅於基板的單側上形成電極,於與基板為平行方向上輸入電場的橫向電場方式,與對形成於過去的上下基板上之電極輸入電壓而使液晶驅動的縱電場方式做比較,其可作為具有較廣視野角的特性,且可更高品位顯示之液晶顯示元件。作為使液晶配向成一定方向的方法,有於基板上形成聚醯亞胺等高分子膜,將該表面以布擦拭,進行所謂摩擦處理的方法,該方法在工業上亦廣泛地被使用。Generally speaking, the transverse electric field method in which electrodes are formed on only one side of the substrate and the electric field is input in a direction parallel to the substrate is different from the vertical electric field method in which voltage is input to the electrodes formed on the upper and lower substrates in the past to drive the liquid crystal. In comparison, it can be used as a liquid crystal display element with a wider viewing angle and higher quality display. As a method of aligning liquid crystals in a certain direction, a polymer film such as polyimide is formed on a substrate, and the surface is wiped with a cloth and subjected to a so-called rubbing treatment. This method is also widely used in industry.
液晶顯示元件之構成構件的液晶配向膜為欲使液晶均勻地配列的膜,但對液晶的需求不僅在配向均勻性上而有著種種特性之必要性。例如藉由使液晶驅動的電壓,對液晶配向膜累積電荷,此等被累積的電荷會使液晶配向變亂,或者會有殘像或烙印(以下稱為來自殘留DC的殘像)而對顯示產生影響,而有著液晶顯示元件之顯示品質顯著降低的問題,故已有人提出克服此等課題之液晶配向劑(專利文獻2)。The liquid crystal alignment film that is a component of a liquid crystal display element is a film that is intended to uniformly align liquid crystals. However, the demand for liquid crystals requires not only alignment uniformity but also various characteristics. For example, by driving the liquid crystal to a voltage that accumulates charges on the liquid crystal alignment film, these accumulated charges will cause the liquid crystal alignment to be disordered, or there will be an afterimage or burn-in (hereinafter referred to as an afterimage from residual DC) that will cause damage to the display. Therefore, liquid crystal alignment agents that overcome these problems have been proposed (Patent Document 2).
又,對於IPS方式或FFS方式,液晶配向之穩定性亦成重要。若配向之穩定性小時,使液晶進行長時間驅動時,液晶無法恢復到初期狀態,成為對比的降低或烙印(以下稱為AC殘像)之原因。作為解決上述課題之手法,在專利文獻3中已揭示含有選自由含有特定四羧酸二酐與特定二胺之聚醯胺酸及其醯亞胺化聚合物所成群的1種聚合物,與特定化合物之液晶配向劑。In addition, for the IPS method or the FFS method, the stability of the liquid crystal alignment is also important. If the alignment stability is small, when the liquid crystal is driven for a long time, the liquid crystal cannot return to its initial state, causing contrast reduction or burn-in (hereinafter referred to as AC afterimage). As a means to solve the above-mentioned problems, Patent Document 3 discloses a polymer selected from the group consisting of polyamide containing a specific tetracarboxylic dianhydride and a specific diamine and its imidized polymer. Liquid crystal alignment agent with specific compounds.
且因在生產步驟之經濟性非常重要,故容易使元件基板再生利用成為必要。即,由液晶配向劑形成液晶配向膜後,進行配向性等檢査而產生缺陷時,自基板除去液晶配向膜,回收基板的重工步驟可簡便地實施之技術被期待著。 [先前技術文獻] [專利文獻]And because the economy in the production process is very important, it is necessary to easily recycle component substrates. That is, after a liquid crystal alignment film is formed from a liquid crystal alignment agent, if a defect occurs due to inspection such as alignment, the liquid crystal alignment film is removed from the substrate and the reprocessing step of recycling the substrate is expected to be simple. [Prior technical literature] [Patent Document]
[專利文獻1]日本特開2013-167782號公報 [專利文獻2]國際公開第WO02/33481號手冊 [專利文獻3]國際公開第WO2016/063834號手冊[Patent Document 1] Japanese Patent Application Publication No. 2013-167782 [Patent Document 2] International Publication No. WO02/33481 Manual [Patent Document 3] International Publication No. WO2016/063834 Manual
[發明所解決的問題][Problem solved by the invention]
過去被提案的液晶配向劑之構成未必可達成上述所有課題。又,使用專利文獻2或3所記載的液晶配向劑時,所得之液晶配向膜的透過率有著過低之問題,而尚有改善之空間。本發明為基於以上事項所成者,該目的為提供一種可形成來自殘留DC的殘像或AC殘像的產生為少,重工為容易,且透過率高的液晶配向膜之液晶配向劑。 [解決課題的手段]The composition of liquid crystal alignment agents proposed in the past may not be able to achieve all the above-mentioned issues. In addition, when the liquid crystal alignment agent described in Patent Document 2 or 3 is used, the transmittance of the resulting liquid crystal alignment film is too low, and there is still room for improvement. The present invention is based on the above matters, and its purpose is to provide a liquid crystal alignment agent that can form a liquid crystal alignment film with less residual DC or AC afterimages, easy rework, and high transmittance. [Means to solve the problem]
本發明者進行詳細研究結果,發現藉由使用含有特定成分之液晶配向劑,可解決上述課題,進而完成本發明。 本發明為將下述作為要旨者。 將含有下述(A)成分與(B)成分作為特徵之液晶配向劑。 (A)成分:具有下述式(1)所示重複單位之聚合物(A)。 (B)成分:具有下述式(2)所示重複單位、下述式(3)所示重複單位、下述式(4)所示重複,及下述式(5)所示重複單位,下述式(2)所示重複單位及下述式(3)所示重複單位之合計含有量為全重複單位之60~99.9莫耳%,且下述式(4)所示重複單位及下述式(5)所示重複單位之合計含有量為全重複單位之0.1~40莫耳%的聚合物(B)。 (式(1)中,X1 為4價有機基,Y1 為2價有機基) (X2 為來自脂環式酸二酐或脂肪族酸二酐之4價有機基。Y2 為下述式(m-1)或(m-2)所示2價有機基。R2 為氫原子,或碳數1~4的烷基。Z21 、Z22 各獨立為氫原子、可具有取代基之碳數1~10的烷基、可具有取代基之碳數2~10的烯基、可具有取代基之碳數2~10的炔基、tert-丁氧基羰基,或9-芴基甲氧基羰基) (*表示鍵結手) (X3 為來自脂環式酸二酐或脂肪族酸二酐之4價有機基。Y3 為下述式(l)所示2價有機基,或具有下述式(n)所示部分結構的2價有機基。R3 為氫原子,或碳數1~4的烷基。Z31 、Z32 各獨立為氫原子、可具有取代基之碳數1~10的烷基、可具有取代基之碳數2~10的烯基、可具有取代基之碳數2~10的炔基、tert-丁氧基羰基,或9-芴基甲氧基羰基)。 (Q1 、Q2 為碳數1~3的烷基,Q3 為氫原子或碳數1~3的烷基。*表示鍵結手)。 (X4 、X5 為來自芳香族酸二酐的4價有機基。Y4 與式(2)的Y2 同義,R4 與前述式(2)的R2 同義。Z41 、Z42 各與前述式(2)的Z21 、Z22 同義。Y5 與前述式(3)的Y3 同義,R5 與前述式(3)的R3 同義,Z51 、Z52 各與前述式(3)的Z31 、Z32 同義。) [發明之效果]As a result of detailed research, the inventor found that the above problems can be solved by using a liquid crystal alignment agent containing specific components, and then completed the present invention. The present invention has the following as its gist. A liquid crystal alignment agent characterized by containing the following (A) component and (B) component. (A) Component: Polymer (A) having a repeating unit represented by the following formula (1). (B) Component: having a repeating unit represented by the following formula (2), a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5), The total content of the repeating unit represented by the following formula (2) and the repeating unit represented by the following formula (3) is 60 to 99.9 mol% of the total repeating units, and the repeating unit represented by the following formula (4) and the following The total content of the repeating units represented by the formula (5) is 0.1 to 40 mol% of the polymer (B) based on the total repeating units. (In formula (1), X 1 is a 4-valent organic group, and Y 1 is a 2-valent organic group) (X 2 is a 4-valent organic group derived from alicyclic acid dianhydride or aliphatic acid dianhydride. Y 2 is a 2-valent organic group represented by the following formula (m-1) or (m-2). R 2 is A hydrogen atom, or an alkyl group having 1 to 4 carbon atoms. Z 21 and Z 22 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an alkene group having 2 to 10 carbon atoms which may have a substituent. group, an optionally substituted alkynyl group having 2 to 10 carbon atoms, tert-butoxycarbonyl group, or 9-fluorenylmethoxycarbonyl group) (*indicates bonding hand) (X 3 is a tetravalent organic group derived from alicyclic acid dianhydride or aliphatic acid dianhydride. Y 3 is a divalent organic group represented by the following formula (l), or has a moiety represented by the following formula (n) divalent organic group of the structure. R 3 is a hydrogen atom, or an alkyl group with 1 to 4 carbon atoms. Z 31 and Z 32 are each independently a hydrogen atom, and an alkyl group with 1 to 10 carbon atoms that may have a substituent. Alkenyl group having 2 to 10 carbon atoms as a substituent, alkynyl group having 2 to 10 carbon atoms as a substituent, tert-butoxycarbonyl group, or 9-fluorenylmethoxycarbonyl group). (Q 1 and Q 2 are alkyl groups having 1 to 3 carbon atoms, and Q 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. * indicates a bonding hand). ( X 4 and _ _ _ _ Synonymous with Z 21 and Z 22 in the aforementioned formula (2). Y 5 is synonymous with Y 3 in the aforementioned formula (3), R 5 is synonymous with R 3 in the aforementioned formula (3), and Z 51 and Z 52 are each synonymous with the aforementioned formula ( 3) Synonymous with Z 31 and Z 32. ) [Effects of the invention]
依據本發明之液晶配向劑,可得到重工容易且可得到透過率高之液晶配向膜。又,藉由使用所得之液晶配向膜,可得到來自殘留DC的殘像或AC殘像不易產生,透過率高且對比優良的液晶顯示元件。According to the liquid crystal alignment agent of the present invention, a liquid crystal alignment film that is easy to rework and has high transmittance can be obtained. Furthermore, by using the obtained liquid crystal alignment film, it is possible to obtain a liquid crystal display element that is less likely to produce residual DC or AC residual images, has high transmittance, and has excellent contrast.
[實施發明的型態][Types of carrying out the invention]
以下對於含於本發明之液晶配向劑的各成分,及視必要經任意調配的其他成分進行說明。 <聚合物(A)> 本發明之液晶配向劑含有具有上述式(1)所示重複單位的聚合物(A)。藉此,可得到AC殘像產生為少,透過率高之液晶配向膜,又可得到對比降低受到抑制的液晶顯示元件。對於上述式(1),X1 、Y1 如上述定義。作為式(1)的X1 ,可舉出來自四羧酸二酐的4價有機基,例如可舉出來自芳香族四羧酸二酐、脂肪族四羧酸二酐、脂環式四羧酸二酐的4價有機基。式(1)的Y1 以來自二胺化合物的2價有機基為佳。Each component contained in the liquid crystal alignment agent of the present invention and other components optionally blended as necessary will be described below. <Polymer (A)> The liquid crystal alignment agent of the present invention contains a polymer (A) having a repeating unit represented by the above formula (1). Thereby, a liquid crystal alignment film with less AC afterimage generation and high transmittance can be obtained, and a liquid crystal display element with suppressed contrast reduction can be obtained. Regarding the above formula (1), X 1 and Y 1 are as defined above. Examples of X 1 in formula (1) include tetravalent organic groups derived from tetracarboxylic dianhydride, and examples include aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and alicyclic tetracarboxylic dianhydride. The 4-valent organic group of acid dianhydride. Y 1 in formula (1) is preferably a divalent organic group derived from a diamine compound.
其中,所謂芳香族四羧酸二酐為,含鍵結於芳香環的至少1個羧基之4個羧基藉由分子內脫水而得之酸二酐。所謂脂肪族四羧酸二酐為,鍵結於鏈狀烴結構的4個羧基藉由分子內脫水而得之酸二酐。但,無須僅以鏈狀烴結構而構成,於該一部分可具有脂環式結構或芳香環結構。所謂脂環式四羧酸二酐為,含鍵結於脂環式結構的至少1個羧基的4個羧基藉由分子內脫水而得之酸二酐。但,這些4個羧基皆未鍵結於芳香環。又,無須僅以脂環式結構所構成,於該一部分可具有鏈狀烴結構或芳香環結構。Among them, the so-called aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of at least one carboxyl group and four carboxyl groups bonded to an aromatic ring. Aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not need to be composed only of a chain hydrocarbon structure, and the part may have an alicyclic structure or an aromatic ring structure. Alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. However, these four carboxyl groups are not bonded to the aromatic ring. In addition, it does not need to be composed of only an alicyclic structure, and the part may have a chain hydrocarbon structure or an aromatic ring structure.
對於提高聚合物(A)之溶解性的觀點,X1 以選自由下述式(4a)~(4n)、下述式(5a)及下述式(6a)所成群的4價有機基者為佳。 (x及y各獨立為單鍵、醚(-O-)、羰基(-CO-)、酯( -COO-)、碳數1~5的烷烴二基、1,4-伸苯基、磺醯基或醯胺基。Z1 ~Z6 各獨立表示氫原子、甲基、乙基、丙基、氯原子或苯環。j各獨立為0或1的整數。m為1~5的整數。*表示鍵結手。)From the viewpoint of improving the solubility of the polymer (A), X 1 is a tetravalent organic group selected from the group consisting of the following formulas (4a) to (4n), the following formula (5a), and the following formula (6a). Whichever is better. (x and y are each independently a single bond, ether (-O-), carbonyl group (-CO-), ester (-COO-), alkanediyl with 1 to 5 carbon atoms, 1,4-phenylene group, sulfonate acyl group or amide group. Z 1 to Z 6 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring. j each independently represents an integer of 0 or 1. m is an integer of 1 to 5 .* indicates bonding hand.)
對於較少AC殘像之觀點,作為前述式(4a)的較佳具體例子,可舉出下述式(4a-1)~(4a-4)所示結構。 From the viewpoint of reducing AC afterimages, preferred specific examples of the aforementioned formula (4a) include structures represented by the following formulas (4a-1) to (4a-4).
作為前述式(5a)、(6a)中之碳數1~5的烷烴二基,可舉出亞甲基、伸乙基、1,3-丙烷二基、1,4-丁烷二基、1,5-戊烷二基等。 對於AC殘像較少,保證溶解性之觀點來看,前述式(1)的X1 以選自前述式(4a)~(4h)、(4j)、(4l)、(4m)~(4n)的4價有機基者為佳。Examples of the alkanediyl group having 1 to 5 carbon atoms in the formulas (5a) and (6a) include methylene, ethylidene, 1,3-propanediyl, 1,4-butanediyl, 1,5-Pentanediyl, etc. From the viewpoint of less AC afterimage and ensuring solubility, X 1 in the aforementioned formula (1) is selected from the aforementioned formulas (4a) to (4h), (4j), (4l), (4m) to (4n). ) of 4-valent organic base is preferred.
作為可使用於聚合物(A)的二胺,並無特別限定。作為具體例子,作為脂肪族二胺,例如可舉出間苯二甲胺、乙二胺、1,3-丙烷二胺、四亞甲基二胺、六亞甲基二胺等。作為脂環式二胺,例如可舉出p-環己烷二胺、4,4’-亞甲基雙(環己基胺)等。The diamine that can be used for the polymer (A) is not particularly limited. Specific examples of aliphatic diamines include m-xylylenediamine, ethylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine, and the like. Examples of the alicyclic diamine include p-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), and the like.
作為芳香族二胺,可舉出p-伸苯基二胺、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、4,4’-二胺基偶氮苯、3,5-二胺基安息香酸、雙(4-胺基苯基)胺、N,N-雙(4-胺基苯基)甲基胺、1,4-雙(4-胺基苯基)-哌嗪、N,N’-雙(4-胺基苯基)-聯苯胺、2,2’-二甲基-4,4’-二胺基聯苯基、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]醚、4,4’-雙(4-胺基苯氧基)聯苯基、4-(4-胺基苯氧基羰基)-1-(4-胺基苯基)哌啶、4,4’-[4,4’-丙烷-1,3-二基雙(哌啶-1,4-二基)]二苯胺、1,3-雙(3-胺基丙基)-四甲基二矽氧烷、於具有下述式(H)所示部分結構的2價有機基有2個胺基鍵結的二胺等。 (Q11 為-NQCO-、-COO-、-OCO-、-NQCONQ-、-CONQ-或-(CH2 )n -(n為1~20的整數)但,n為2~20時,任意的-CH2 -在各未鄰接的條件下,可取代為-O-、-COO-、-OCO-、-ND-、-NQCO-、-CONQ-、-NQCONQ-、-NQCOO-或-OCOO-。D表示熱脫離性基,Q表示氫原子或1價有機基。Q12 為單鍵或苯環,於苯環上的任意氫原子可取代為1價有機基。*1、*2表示鍵結手,Q12 為單鍵時,*2鍵結於胺基中之氮原子。Q12 為苯環時,Q11 可為單鍵。)Examples of aromatic diamines include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, and 4,4'-diamine. Azobenzene, 3,5-diaminobenzoic acid, bis(4-aminophenyl)amine, N,N-bis(4-aminophenyl)methylamine, 1,4-bis(4 -Aminophenyl)-piperazine, N,N'-bis(4-aminophenyl)-benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 1 ,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]ether, 4 ,4'-bis(4-aminophenoxy)biphenyl, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 4,4'-[ 4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane , a diamine having two amine groups bonded to a divalent organic group having a partial structure represented by the following formula (H), etc. (Q 11 is -NQCO-, -COO-, -OCO-, -NQCONQ-, -CONQ- or -(CH 2 ) n - (n is an integer from 1 to 20) However, when n is 2 to 20, any -CH 2 - may be substituted by -O-, -COO-, -OCO-, -ND-, -NQCO-, -CONQ-, -NQCONQ-, -NQCOO-, or -OCOO -. D represents a thermally detachable group, Q represents a hydrogen atom or a monovalent organic group. Q 12 is a single bond or a benzene ring, and any hydrogen atom on the benzene ring can be substituted with a monovalent organic group. *1, *2 represent Bonding hand, when Q 12 is a single bond, *2 is bonded to the nitrogen atom in the amine group. When Q 12 is a benzene ring, Q 11 can be a single bond.)
由AC殘像較少的觀點來看,前述式(1)的Y1 以具有前述式(H)所示部分結構之2價有機基者為佳。對於該情況,前述式(H)的R4 為單鍵時,*2鍵結於醯亞胺環中之氮原子。其中前述式(1)的Y1 亦以具有下述式(H-1)~(H-14)中任一所示部分結構的2價有機基者為佳。 (*1、*2表示鍵結手,*2表示鍵結於醯亞胺環中之氮原子。)From the viewpoint of less AC afterimages, Y 1 in the above formula (1) is preferably a divalent organic group having a partial structure represented by the above formula (H). In this case, when R 4 in the aforementioned formula (H) is a single bond, *2 is bonded to the nitrogen atom in the imine ring. Among them, Y 1 in the aforementioned formula (1) is also preferably a divalent organic group having a partial structure represented by any one of the following formulas (H-1) to (H-14). (*1 and *2 indicate the bonding hand, and *2 indicates the nitrogen atom bonded to the imine ring.)
對於合成的容易度之觀點來看,前述式(1)的Y1 以前述式(H-1)~(H-14)中任一所示2價有機基或下述式(MH-1)~(MH-2)所示2價有機基者為佳。 (*1與醯亞胺環中之氮原子鍵結。Boc表示tert-丁氧基羰基。)From the viewpoint of ease of synthesis, Y 1 in the above formula (1) is a divalent organic group represented by any one of the above formulas (H-1) to (H-14) or the following formula (MH-1) The divalent organic group represented by ~(MH-2) is preferred. (*1 is bonded to the nitrogen atom in the imine ring. Boc represents tert-butoxycarbonyl.)
聚合物(A)除上述式(1)所示重複單位以外,亦可具有下述式(PA-1)所示重複單位。 The polymer (A) may have a repeating unit represented by the following formula (PA-1) in addition to the repeating unit represented by the above-mentioned formula (1).
式(PA-1)中,X1 及Y1 各與含較佳態樣的式(1)之X1 及Y1 同義。R1 為氫原子,或碳數1~5的烷基。Z11 、Z12 各獨立為氫原子、可具有取代基之碳數1~10的烷基、可具有取代基之碳數2~10的烯基、可具有取代基之碳數2~10的炔基、tert-丁氧基羰基或9-芴基甲氧基羰基。In formula (PA-1), X 1 and Y 1 are each synonymous with X 1 and Y 1 of formula (1) in a preferred aspect. R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z 11 and Z 12 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, or an alkyl group having 2 to 10 carbon atoms which may have a substituent. Alkynyl, tert-butoxycarbonyl or 9-fluorenylmethoxycarbonyl.
作為上述R1 的碳數1~5的烷基之具體例子,可舉出甲基、乙基、丙基、i-丙基、n-丁基、i-丁基、s-丁基、t-丁基、n-戊基等。由藉由加熱可使醯亞胺化容易之觀點來看,R1 以氫原子或甲基者為佳。Specific examples of the alkyl group having 1 to 5 carbon atoms in R 1 include methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, s-butyl, t -Butyl, n-pentyl, etc. From the viewpoint that acyl imidization can be facilitated by heating, R 1 is preferably a hydrogen atom or a methyl group.
作為上述Z11 、Z12 的碳數1~10的烷基之具體例子,除可舉出在上述R1 所例示的碳數1~5的烷基之具體例子,亦可舉出己基、庚基、辛基、壬基、癸基等。作為Z11 、Z12 的碳數2~10之烯基的具體例子,例如可舉出乙烯基、丙烯基、丁炔基等,此等可為直鏈狀亦可為支鏈狀。作為Z11 、Z12 的碳數2~10的炔基之具體例子,例如可舉出乙炔基、1-丙炔基、2-丙炔基等。Specific examples of the alkyl group having 1 to 10 carbon atoms in Z 11 and Z 12 include, in addition to the specific examples of the alkyl group having 1 to 5 carbon atoms exemplified for R 1 , hexyl group, heptyl group, etc. Base, octyl, nonyl, decyl, etc. Specific examples of the alkenyl group having 2 to 10 carbon atoms in Z 11 and Z 12 include vinyl, propenyl, butynyl, etc., and these may be linear or branched. Specific examples of the alkynyl group having 2 to 10 carbon atoms in Z 11 and Z 12 include an ethynyl group, a 1-propynyl group, a 2-propynyl group, and the like.
Z11 、Z12 可具有取代基,作為該取代基,例如可舉出鹵素原子(氟原子、氯原子、溴原子、碘原子)、羥基、氰基、烷氧基等。 由AC殘像較少的觀點來看,Z11 、Z12 各獨立以氫原子或甲基者為佳。 由AC殘像較少的觀點來看,聚合物(A)中之前述式(1)所示重複單位的含有比率以聚合物(A)所具有全重複單位之10~95莫耳%者為佳,以15~95莫耳%者為較佳。又,此時聚合物(A)中上述式(PA-1)所示重複單位的含有比率以5~90莫耳%為佳,以5~85莫耳%為較佳。Z 11 and Z 12 may have a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a cyano group, an alkoxy group, and the like. From the viewpoint of less AC afterimage, it is preferable that Z 11 and Z 12 each independently contain a hydrogen atom or a methyl group. From the viewpoint of reducing AC afterimages, the content ratio of the repeating units represented by the aforementioned formula (1) in the polymer (A) is 10 to 95 mol% of the total repeating units of the polymer (A). The best is 15-95 mol%. In addition, at this time, the content ratio of the repeating unit represented by the above formula (PA-1) in the polymer (A) is preferably 5 to 90 mol%, and more preferably 5 to 85 mol%.
<聚合物(B)> 本發明之液晶配向劑含有:具有上述式(2)所示重複單位、上述式(3)所示重複單位、上述式(4)所示重複單位及上述式(5)所示重複單位,上述式(2)所示重複單位及上述式(3)所示重複單位之合計量為全重複單位的60~99.9莫耳%之聚合物(B)。藉由如此構成,可得到重工性優良,且來自殘留DC的殘像減低之液晶配向膜。 對於上述式(2)、(3),X2 、X3 、Y2 、Y3 、R2 、R3 、Z21 、Z22 、Z31 、Z32 與上述定義相通。<Polymer (B)> The liquid crystal alignment agent of the present invention contains: a repeating unit represented by the above formula (2), a repeating unit represented by the above formula (3), a repeating unit represented by the above formula (4) and the above formula (5) ), the total amount of the repeating unit represented by the above formula (2) and the repeating unit represented by the above formula (3) is 60 to 99.9 mol% of the polymer (B) based on the total repeating units. With this structure, a liquid crystal alignment film can be obtained that has excellent reworkability and reduces residual images due to residual DC. Regarding the above formulas (2) and (3), X 2 , X 3 , Y 2 , Y 3 , R 2 , R 3 , Z 21 , Z 22 , Z 31 , and Z 32 are consistent with the above definitions.
作為上述R2 、R3 的碳數1~5的烷基之具體例子,可舉出上述式(PA-1)的R1 中所例示的結構。由藉由加熱可容易進行醯亞胺化的觀點來看,R2 及R3 各獨立以氫原子或甲基者為佳。 作為上述Z21 、Z22 、Z31 、Z32 的碳數1~10的烷基、碳數2~10的烯基、碳數2~10的炔基之具體例子,可舉出上述式(PA-1)之Z11 、 Z12 所例示的結構等。 Z21 、Z22 、Z31 、Z32 可具有取代基,作為該取代基,例如可舉出上述式(PA-1)的Z11 、 Z12 所例示之結構等。 由AC殘像較少的觀點來看,Z21 、Z22 、Z31 、Z32 各獨立以氫原子或甲基者為佳。Specific examples of the alkyl group having 1 to 5 carbon atoms in R 2 and R 3 include the structure illustrated for R 1 in the above formula (PA-1). From the viewpoint of easy imidization by heating, it is preferred that R 2 and R 3 each independently be a hydrogen atom or a methyl group. Specific examples of the alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, and the alkynyl group having 2 to 10 carbon atoms in Z 21 , Z 22 , Z 31 , and Z 32 include the above formula ( The structures exemplified by Z 11 and Z 12 of PA-1), etc. Z 21 , Z 22 , Z 31 , and Z 32 may have a substituent. Examples of the substituent include the structures exemplified by Z 11 and Z 12 of the above formula (PA-1). From the viewpoint of less AC afterimage, it is preferable that Z 21 , Z 22 , Z 31 , and Z 32 each independently consist of a hydrogen atom or a methyl group.
作為來自上述X2 、X3 的脂環式四羧酸二酐或脂肪族四羧酸二酐的4價有機基,可舉出來自上述X1 所例示的脂環式四羧酸二酐或脂肪族四羧酸二酐之4價有機基。由抑制AC殘像的觀點來看,X2 、X3 以選自由上述式(4a)~(4n)所成群的4價有機基者為佳。Examples of the tetravalent organic group derived from the alicyclic tetracarboxylic dianhydride or aliphatic tetracarboxylic dianhydride of X 2 and X 3 include the alicyclic tetracarboxylic dianhydride or aliphatic tetracarboxylic dianhydride exemplified by The 4-valent organic group of aliphatic tetracarboxylic dianhydride. From the viewpoint of suppressing AC afterimages, X 2 and X 3 are preferably selected from a tetravalent organic group consisting of the above formulas (4a) to (4n).
作為對於上述式(l)或(n)中之Q1 、Q2 、Q3 的碳數1~3的烷基,可舉出甲基、乙基、丙基等。由提高液晶配向膜之透過率,且由抑制AC殘像與來自殘留DC的殘像之觀點來看,Q1 、Q2 、Q3 以甲基者為佳。且,式(n)中之苯環的任意氫原子可由一價有機基所取代。作為該一價有機基,可舉出具有碳數1~3之烷基、烯基、烷氧基、氟烷基、氟烯基或者氟烷氧基等。Examples of the alkyl group having 1 to 3 carbon atoms for Q 1 , Q 2 , and Q 3 in the above formula (l) or (n) include methyl, ethyl, propyl, and the like. From the viewpoint of improving the transmittance of the liquid crystal alignment film and suppressing AC afterimages and residual DC afterimages, Q 1 , Q 2 , and Q 3 are preferably methyl groups. Furthermore, any hydrogen atom of the benzene ring in formula (n) may be substituted by a monovalent organic group. Examples of the monovalent organic group include an alkyl group, alkenyl group, alkoxy group, fluoroalkyl group, fluoroalkenyl group or fluoroalkoxy group having 1 to 3 carbon atoms.
由AC殘像較少之觀點來看,上述式(l)以下述式(l-1)所示結構者為佳。 From the viewpoint of less AC afterimage, the above formula (l) is preferably one having a structure represented by the following formula (l-1).
對於上述式(n),由-NQ3 -Ph(Ph表示伸苯基)之鍵結位置較少立體障礙之觀點來看,以鍵結於咔唑骨架之第3位者為佳。 由來自殘留DC的殘像較少的觀點來看,具有前述式(n)所示部分結構之2價有機基以選自由下述式(n-1)~(n-3)所成群的2價有機基者為佳。 Regarding the above formula (n), from the viewpoint that the bonding position of -NQ 3 -Ph (Ph represents phenylene group) has less steric hindrance, it is preferable to bond to the third position of the carbazole skeleton. From the viewpoint of less afterimages from residual DC, the divalent organic group having the partial structure represented by the aforementioned formula (n) is selected from the group consisting of the following formulas (n-1) to (n-3). Bivalent organic base is preferred.
式(n-1)~(n-3)中,Q2 、Q3 各與含前述式(n)的Q2 、Q3 之較佳具體例子同義。Q4 表示單鍵或以下式(Ar)的結構,n表示1~3的整數。*表示鍵結手。進一步苯環之任意氫原子與上述式(n)之情況同樣地,可由一價有機基所取代。 (Q5 表示選自單鍵、-O-、-COO-、-OCO-、-(CH2 )l -、 -O(CH2 )m O-、-CONQ-及-NQCO-的2價有機基,k表示1~5的整數。且Q表示氫或者一價有機基,l、m表示1~5的整數。*1、*2表示鍵結手,*1 表示與式(n-1)~式(n-3)中之苯環鍵結。) 作為前述式(Ar)之Q中之一價有機基,可舉出碳數1~3的烷基。In the formulas (n-1) to (n-3), Q 2 and Q 3 are each synonymous with preferred specific examples of Q 2 and Q 3 including the aforementioned formula (n). Q 4 represents a single bond or the structure of the following formula (Ar), and n represents an integer of 1 to 3. *Indicates key knot hand. Furthermore, any hydrogen atom of the benzene ring may be substituted with a monovalent organic group in the same manner as in the case of the above formula (n). (Q 5 represents a divalent organic compound selected from single bonds, -O-, -COO-, -OCO-, -(CH 2 ) l -, -O(CH 2 ) m O-, -CONQ- and -NQCO- Base, k represents an integer from 1 to 5. And Q represents hydrogen or a monovalent organic group, l and m represent integers from 1 to 5. *1 and *2 represent bonding hands, and * 1 represents the same as formula (n-1) ~The benzene ring in the formula (n-3) is bonded.) Examples of the monovalent organic group in Q in the formula (Ar) include an alkyl group having 1 to 3 carbon atoms.
由容易合成的觀點來看,具有前述式(n)所示部分結構之2價有機基以下述式(cbz-1)~(cbz-7)中任一所示2價有機基者為佳。*表示鍵結手。 From the viewpoint of easy synthesis, the divalent organic group having a partial structure represented by the aforementioned formula (n) is preferably a divalent organic group represented by any one of the following formulas (cbz-1) to (cbz-7). *Indicates key knot hand.
前述聚合物(B)由AC殘像與來自殘留DC的殘像較少的觀點來看,作為前述式(3)所示重複單位,以具有Y3 為前述式(l)所示2價有機基的重複單位,與Y3 為具有前述式(n)所示部分結構的2價有機基之重複單位者為佳。From the viewpoint that the polymer (B) has less afterimages from AC and residual DC, having Y 3 as the repeating unit represented by the aforementioned formula (3) is a divalent organic compound represented by the aforementioned formula (l). The repeating unit of the group is preferably a repeating unit of a divalent organic group having a partial structure represented by the aforementioned formula ( n ).
前述聚合物(B)由來自殘留DC的殘像較少的觀點來看,具有下述式(4)所示重複單位及下述式(5)所示重複單位。 The polymer (B) has a repeating unit represented by the following formula (4) and a repeating unit represented by the following formula (5) from the viewpoint of less afterimages due to residual DC.
式(4)、(5)中,X4 、X5 為來自芳香族四羧酸二酐的4價有機基,可舉出在前述式(1)的X1 所例示的來自芳香族四羧酸二酐的4價有機基。由AC殘像與來自殘留DC的殘像較少的觀點來看,X4 、X5 以選自上述X1 的較佳例所記載的式(5a)、(6a)之4價有機基者為佳。In the formulas (4) and ( 5 ), X 4 and The 4-valent organic group of acid dianhydride. From the viewpoint of fewer afterimages from AC and residual DC, X 4 and Better.
Y4 與前述式(2)之Y2 及含較佳態樣者同義。R4 與前述式(2)的R2 及含較佳態樣者同義。Z41 、Z42 各與前述式(2)的Z21 、Z22 及含較佳態樣者同義。Y5 與前述式(3)的Y3 及含較佳態樣者同義。R5 與前述式(3)的R3 及含較佳態樣者同義。Z51 、Z52 各與前述式(3)的Z31 、Z32 及含較佳態樣者同義。Y 4 is synonymous with Y 2 in the aforementioned formula (2) and the one containing better aspects. R 4 is synonymous with R 2 in the aforementioned formula (2) and those containing better aspects. Z 41 and Z 42 are each synonymous with Z 21 and Z 22 of the aforementioned formula (2) and those containing better aspects. Y 5 is synonymous with Y 3 in the aforementioned formula (3) and those containing better aspects. R 5 is synonymous with R 3 in the aforementioned formula (3) and those containing better aspects. Z 51 and Z 52 are each synonymous with Z 31 and Z 32 of the aforementioned formula (3) and those with better aspects.
對於聚合物(B),選自由上述式(2)所示重複單位及上述式(3)所示重複單位所成群的至少1種重複單位之合計含有量,由得到高透過率之觀點來看,以全重複單位的60~99.9莫耳%者為佳,以65~90莫耳%者為較佳。 上述式(2)所示重複單位與上述式(3)所示重複單位之含有量比例,前者/後者之莫耳%比以10/90~50/50者為佳,以15/85~50/50者為較佳。 聚合物(B)中,選自由上述式(4)所示重複單位及上述式(5)所示重複單位所成群的至少1種重複單位的合計含有量,由可得到高透過率之觀點來看,以全重複單位的0.1~40莫耳%者為佳,以10~35莫耳%為較佳。 上述式(4)所示重複單位與上述式(5)所示重複單位之含有量的比例以前者/後者之莫耳%比表示時,以10/90~50/50者為佳,以15/85~50/50為較佳。Regarding the polymer (B), the total content of at least one repeating unit selected from the group of repeating units represented by the above formula (2) and the repeating unit represented by the above formula (3) is determined from the viewpoint of obtaining high transmittance. Look, the one with 60-99.9 mol% of the whole repeating unit is better, and the one with 65-90 mol% is better. The content ratio of the repeating unit represented by the above formula (2) and the repeating unit represented by the above formula (3), the molar % ratio of the former/the latter is preferably 10/90 to 50/50, and 15/85 to 50 /50 is better. In the polymer (B), the total content of at least one repeating unit selected from the group of repeating units represented by the above formula (4) and the repeating unit represented by the above formula (5) is from the viewpoint of obtaining high transmittance. From a certain point of view, 0.1 to 40 mol% of the total repeating unit is preferred, and 10 to 35 mol% is preferred. When the content ratio of the repeating unit represented by the above formula (4) and the repeating unit represented by the above formula (5) is expressed by the molar % ratio of the former/the latter, it is preferably 10/90 to 50/50, and 15 /85~50/50 is better.
聚合物(B)除上述式(2)所示重複單位、上述式(3)所示重複單位、上述式(4)所示重複單位、上述式(5)所示重複單位以外,亦可具有下述式(PA-2)所示重複單位。 In addition to the repeating unit represented by the above formula (2), the repeating unit represented by the above formula (3), the repeating unit represented by the above formula (4), and the repeating unit represented by the above formula (5), the polymer (B) may also have The repeating unit is represented by the following formula (PA-2).
式(PA-2)中,X6 表示4價有機基,Y6 表示2價有機基。但,Y6 為選自上述式(m-1)~(m-2)的基,未含有上述式(l)所示2價有機基及具有上述式(n)所示部分結構的2價有機基。R6 與前述式(2)的R2 及含較佳態樣者同義。Z61 、Z62 與前述式(2)的Z61 、Z62 及含較佳態樣者同義。In the formula (PA-2), X 6 represents a tetravalent organic group, and Y 6 represents a divalent organic group. However, Y 6 is a group selected from the above formulas (m-1) to (m-2), and does not contain a divalent organic group represented by the above formula (l) and a divalent organic group having a partial structure represented by the above formula (n). Organic based. R 6 is synonymous with R 2 in the aforementioned formula (2) and those containing better aspects. Z 61 and Z 62 are synonymous with Z 61 and Z 62 of the aforementioned formula (2) and those containing better aspects.
作為X6 的具體例子,可舉出在上述式(1)之X1 所例示的來自芳香族四羧酸二酐、脂肪族四羧酸二酐、脂環式四羧酸二酐的4價有機基。作為Y6 的具體例子,除在上述式(1)的Y1 所例示的來自二胺的結構以外,亦可舉出在國際公開公報(以下亦稱為WO)2017/126627號所記載的來自具有吡咯結構之二胺的結構,較佳為來自具有下式(pr)所示結構的二胺之結構、 (式(pr)中,R1 表示氫原子、氫、氟原子、氰基、羥基、甲基,R2 各獨立表示單鍵或基「*1-R3 -Ph-*2」,R3 表示選自單鍵、-O-、-COO-、-OCO-、-(CH2 )l -、-O(CH2 )m O-、-CONH-及-NHCO-的2價有機基(l、m表示1~5的整數)、*1表示與式(pr)中之苯環鍵結的位置,*2表示與式(pr)中之胺基鍵結的位置。Ph表示伸苯基。n表示1~3)、在WO2018/062197號所記載的來自具有吡咯結構的二胺之結構、較佳為來自具有下式(pn)所示結構的二胺之結構、 (式(pn)中,R1 及R2 表示氫原子或甲基,R3 各獨立表示單鍵或基「*1-R4 -Ph-*2」,R4 表示選自單鍵、-O-、 -COO-、-OCO-、-(CH2 )l -、-O(CH2 )m O-、-CONH-及 -NHCO-的2價有機基(l、m表示1~5的整數)、*1表示與式(pn)中之苯環鍵結的位置,*2表示與式(pn)中之胺基鍵結的位置。Ph表示伸苯基。n表示1~3)、在WO2018/092759號所記載的來自具有噻吩或呋喃結構的二胺之結構,較佳為來自具有下式(sf)所示結構的二胺之結構、 (式(sf)中,Y1 表示硫原子或氧原子,R2 各獨立表示單鍵或基「*1-R5 -Ph-*2」,R5 表示選自單鍵、-O-、-COO-、 -OCO-、-(CH2 )l -、-O(CH2 )m O-、-CONH-及-NHCO-的2價有機基(l、m表示1~5的整數),*1表示與式(pn)中之苯環鍵結的位置,*2表示與式(pn)中之胺基鍵結的位置。Ph表示伸苯基。n表示1~3。)、在WO2018-181566號之段落[0013]~[0030]所記載的2價有機基等。Specific examples of X 6 include the tetravalent dianhydrides exemplified as Organic based. Specific examples of Y 6 include, in addition to the structures derived from diamines exemplified for Y 1 in the above formula (1), structures derived from diamines described in International Publication (hereinafter also referred to as WO) No. 2017/126627 The structure of the diamine having a pyrrole structure is preferably a structure derived from a diamine having a structure represented by the following formula (pr), (In formula (pr), R 1 represents a hydrogen atom, hydrogen, fluorine atom, cyano group, hydroxyl group, methyl group, R 2 each independently represents a single bond or group "*1-R 3 -Ph-*2", R 3 Represents a divalent organic group (l selected from a single bond, -O-, -COO-, -OCO-, -(CH 2 ) l -, -O(CH 2 ) m O-, -CONH-, and -NHCO- , m represents an integer of 1 to 5), *1 represents the position bonded to the benzene ring in formula (pr), *2 represents the position bonded to the amine group in formula (pr). Ph represents phenylene group. n represents 1 to 3), the structure derived from the diamine having a pyrrole structure described in WO2018/062197, preferably the structure derived from the diamine having the structure represented by the following formula (pn), (In the formula (pn), R 1 and R 2 represent a hydrogen atom or a methyl group, R 3 each independently represents a single bond or a group "*1-R 4 -Ph-*2", and R 4 represents a single bond, - O-, -COO-, -OCO-, -(CH 2 ) l -, -O(CH 2 ) m O-, -CONH- and -NHCO- divalent organic groups (l and m represent 1 to 5 Integer), *1 represents the position bonded to the benzene ring in formula (pn), *2 represents the position bonded to the amine group in formula (pn). Ph represents phenylene group. n represents 1 to 3), The structure derived from a diamine having a thiophene or furan structure described in WO2018/092759 is preferably a structure derived from a diamine having a structure represented by the following formula (sf): (In the formula (sf), Y 1 represents a sulfur atom or an oxygen atom, R 2 each independently represents a single bond or a group "*1-R 5 -Ph-*2", and R 5 represents a single bond, -O-, -COO-, -OCO-, -(CH 2 ) l -, -O(CH 2 ) m O-, -CONH- and -NHCO- divalent organic groups (l and m represent integers from 1 to 5), *1 represents the position bonded to the benzene ring in formula (pn), *2 represents the position bonded to the amine group in formula (pn). Ph represents phenylene group. n represents 1 to 3.), in WO2018 - Divalent organic groups described in paragraphs [0013] to [0030] of No. 181566, etc.
由AC殘像與來自殘留DC的殘像較少的觀點來看,前述聚合物(A)與前述聚合物(B)的含有比例,在聚合物(A)/聚合物(B)之重量比下以5/95~95/5者為佳。由可得到再現性高之液晶配向膜的觀點來看,上述聚合物(A)/聚合物(B)以10/90~90/10為較佳,以20/80~80/20為更佳。From the viewpoint of fewer afterimages from AC and residual DC, the content ratio of the aforementioned polymer (A) to the aforementioned polymer (B) is based on the weight ratio of polymer (A)/polymer (B). Below, 5/95~95/5 is better. From the viewpoint of obtaining a liquid crystal alignment film with high reproducibility, the polymer (A)/polymer (B) is preferably 10/90 to 90/10, and more preferably 20/80 to 80/20. .
<聚醯胺酸之製造方法> 使用於本發明的聚醯亞胺前驅物之聚醯胺酸可藉由以下所示方法進行合成。 具體而言,將四羧酸二酐與二胺在有機溶劑的存在下,可在-20℃~150℃,較佳為0℃~50℃下,進行30分鐘~24小時,較佳為進行1~12小時之反應而合成。 使用於上述反應的有機溶劑,由單體及聚合物之溶解性來看,以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮或γ-丁內酯為佳,這些可使用1種或混合2種以上使用。聚合物之濃度,由不容易引起聚合物之析出,且容易得到高分子聚體之觀點來看,以1~30重量%為佳,以5~20重量%為較佳。<Production method of polyamide> The polyamide acid used as the polyimide precursor of the present invention can be synthesized by the method shown below. Specifically, tetracarboxylic dianhydride and diamine can be processed in the presence of an organic solvent at -20°C to 150°C, preferably at 0°C to 50°C, for 30 minutes to 24 hours, preferably at It is synthesized in a reaction of 1 to 12 hours. The organic solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone based on the solubility of the monomer and polymer. , these can be used alone or in a mixture of two or more types. The concentration of the polymer is preferably 1 to 30% by weight, and more preferably 5 to 20% by weight, from the viewpoint of not easily causing precipitation of the polymer and easily obtaining a polymer.
如上述所得之聚醯胺酸,因可一邊充分地攪拌反應溶液下一邊注入於貧溶劑中,故可析出聚合物而回收。又,進行數次析出,並以貧溶劑進行洗淨後,藉由常溫或者加熱乾燥使其純化而可得到聚醯胺酸之粉末。貧溶劑雖無特別限定,但可舉出水、甲醇、乙醇、己烷、丁基溶纖劑、丙酮、甲苯等。The polyamide obtained as described above can be injected into a poor solvent while stirring the reaction solution sufficiently, so that the polymer can be precipitated and recovered. In addition, after precipitating several times and washing with a poor solvent, the powder of polyamic acid can be obtained by purifying it by drying at room temperature or heating. Although the lean solvent is not particularly limited, examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene, and the like.
<聚醯胺酸酯之製造方法> 使用於本發明的聚醯亞胺前驅物之聚醯胺酸酯,例如可藉由以下所示(1)、(2)或(3)的方法進行合成。 (1)由聚醯胺酸進行合成之情況 聚醯胺酸酯可藉由將四羧酸二酐與由二胺所得的聚醯胺酸進行酯化而合成。 具體而言,使聚醯胺酸與酯化劑在有機溶劑的存在下,可藉由在-20℃~150℃,較佳為在0℃~50℃,進行30分鐘~24小時,較佳為進行1~4小時的反應而合成。<Production method of polyamide ester> The polyamide ester used as the polyimide precursor of the present invention can be synthesized, for example, by the method (1), (2) or (3) shown below. (1) Synthesis from polyamide acid Polyamic acid ester can be synthesized by esterifying tetracarboxylic dianhydride and polyamic acid obtained from diamine. Specifically, the polyamide and the esterification agent can be processed in the presence of an organic solvent at -20°C to 150°C, preferably at 0°C to 50°C, for 30 minutes to 24 hours, preferably It is synthesized to allow a reaction of 1 to 4 hours.
作為酯化劑,以可藉由純化而容易除去者為佳,可舉出N,N-二甲基甲醯胺二甲基縮醛、N,N-二甲基甲醯胺二-t-丁基縮醛、1-甲基-3-p-甲苯基三氮烯、4-(4,6-二甲氧基-1,3,5-三嗪-2-基)-4-甲基嗎啉鎓氯化物等。酯化劑的使用量對於聚醯胺酸之重複單位1莫耳而言以2~6莫耳當量為佳。 使用於上述反應的溶劑,由聚合物之溶解性來看,以N,N-二甲基甲醯胺、N-甲基-2-吡咯啶酮或γ-丁內酯為佳,此等可混合2種以上而使用。合成時之濃度,由不易引起聚合物之析出,且容易得到高分子聚體之觀點來看,以1~30重量%為佳,以5~20重量%為較佳。The esterifying agent is preferably one that can be easily removed by purification, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide di-t- Butyl acetal, 1-methyl-3-p-tolyltriazene, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methyl Morpholinium chloride, etc. The usage amount of the esterifying agent is preferably 2 to 6 molar equivalents based on 1 mole of the repeating unit of polyamide acid. The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone in view of the solubility of the polymer. These can Use by mixing 2 or more types. The concentration during synthesis is preferably 1 to 30% by weight, and more preferably 5 to 20% by weight, from the viewpoint of not easily causing precipitation of the polymer and easily obtaining a polymer.
(2)藉由四羧酸二酯二氯化物與二胺之反應進行合成之情況 聚醯胺酸酯可由四羧酸二酯二氯化物與二胺進行合成。 具體而言,可將四羧酸二酯二氯化物與二胺在鹼與有機溶劑之存在下,在-20℃~150℃,較佳為在0℃~50℃下,進行30分鐘~24小時,較佳為進行1~4小時的反應而合成。 前述鹼中可使用吡啶、三乙基胺等,其中由可使反應穩定地進行來看以吡啶為佳。鹼之使用量由可容易除去的量,且可容易得到高分子聚體之觀點來看,對於四羧酸二酯二氯化物以2~4倍莫耳者為佳。(2) Synthesis by reaction of tetracarboxylic acid diester dichloride and diamine Polyamide can be synthesized from tetracarboxylic acid diester dichloride and diamine. Specifically, the tetracarboxylic acid diester dichloride and the diamine can be processed in the presence of an alkali and an organic solvent at -20°C to 150°C, preferably at 0°C to 50°C, for 30 minutes to 24 hours, preferably 1 to 4 hours for the reaction to be synthesized. Pyridine, triethylamine, etc. can be used as the said base. Among them, pyridine is preferable because it can make reaction proceed stably. The usage amount of the base is preferably 2 to 4 moles of the tetracarboxylic acid diester dichloride from the viewpoint of easily removing the base and easily obtaining a polymer.
使用於上述反應的溶劑,由單體及聚合物之溶解性的觀點來看,以N-甲基-2-吡咯啶酮或γ-丁內酯為佳,此等可混合2種以上後使用。合成時之聚合物濃度,由不易引起聚合物之析出,且容易得到高分子聚體之觀點來看,以1~30重量%為佳,以5~20重量%為較佳。又,欲防止四羧酸二酯二氯化物之水解,故以可將使用於聚醯胺酸酯的合成之溶劑盡可能地脫水者為佳,在氮環境中以防止外氣混入者為佳。The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of the solubility of the monomer and polymer. Two or more of these can be mixed and used. . The polymer concentration during synthesis is preferably 1 to 30% by weight, and more preferably 5 to 20% by weight, from the viewpoint of not easily causing precipitation of the polymer and easily obtaining a polymer. In addition, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, it is preferable to dehydrate the solvent used for the synthesis of the polyamide ester as much as possible, and to prevent the mixing of outside air in a nitrogen environment. .
(3)由四羧酸二酯與二胺合成聚醯胺酸酯之情況 聚醯胺酸酯可藉由將四羧酸二酯與二胺進行聚縮合而合成。 具體而言,可將四羧酸二酯與二胺在縮合劑、鹼及有機溶劑之存在下,於0℃~150℃,較佳為0℃~100℃下,進行30分鐘~24小時,較佳為進行3~15小時反應而合成。(3) Synthesis of polyamide ester from tetracarboxylic acid diester and diamine Polyamic acid ester can be synthesized by polycondensation of tetracarboxylic acid diester and diamine. Specifically, the tetracarboxylic acid diester and the diamine can be combined in the presence of a condensing agent, a base and an organic solvent at 0°C to 150°C, preferably 0°C to 100°C, for 30 minutes to 24 hours. It is preferable to carry out the reaction for 3 to 15 hours for synthesis.
前述縮合劑中,可使用三苯基亞磷酸酯、二環己基碳二亞胺、1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽、N,N’-羰基二咪唑、二甲氧基-1,3,5-三嗪基甲基嗎啉鎓等公知化合物。 前述鹼中可使用吡啶等3級胺。 在上述3個聚醯胺酸酯之製造方法中,欲得到高分子量之聚醯胺酸酯,以上述(1)或上述(2)之製造方法為特佳。Among the aforementioned condensation agents, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium and other well-known compounds. As the aforementioned base, tertiary amines such as pyridine can be used. Among the above three methods for producing polyamic acid esters, in order to obtain a polyamic acid ester with a high molecular weight, the method of producing the above (1) or the above (2) is particularly preferred.
<聚醯亞胺之製造方法> 使用於本發明的聚醯亞胺可藉由使前述聚醯胺酸酯或聚醯胺酸進行醯亞胺化而製造。由聚醯胺酸酯製造聚醯亞胺時,於前述聚醯胺酸酯溶液,或於使聚醯胺酸酯樹脂粉末溶解於有機溶劑而得之聚醯胺酸溶液中,添加鹼性觸媒的化學性醯亞胺化而簡便地進行。化學性醯亞胺化為在比較低溫下進行醯亞胺化反應,在醯亞胺化之過程中不容易引起聚合物之分子量降低者為佳。<Production method of polyimide> The polyimide used in the present invention can be produced by imidizing the above-mentioned polyamide ester or polyamide acid. When producing polyimide from polyamide ester, an alkaline contact agent is added to the polyamide ester solution or a polyamide solution obtained by dissolving polyamide ester resin powder in an organic solvent. The chemical imidization of the media can be easily carried out. Chemical imidization is carried out at a relatively low temperature, and the molecular weight of the polymer is not likely to decrease during the imidization process.
化學性醯亞胺化可為將欲進行醯亞胺化的聚合物在有機溶劑中在鹼性觸媒與酸酐之存在下進行攪拌而進行。作為有機溶劑可使用在前述聚合反應時所使用的溶劑。作為鹼性觸媒,可舉出吡啶、三乙基胺、三甲基胺、三丁基胺、三辛基胺等。其中吡啶因在進行反應時可具有適度鹼性故較佳。又,作為酸酐可舉出乙酸酐、偏苯三酸酐、苯四酸酐等,其中若使用乙酸酐時因可使反應終了後之純化變得容易故較佳。Chemical imidization can be performed by stirring the polymer to be imidized in an organic solvent in the presence of an alkaline catalyst and an acid anhydride. As the organic solvent, the solvent used in the aforementioned polymerization reaction can be used. Examples of the alkaline catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferred because it can be moderately alkaline during the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferred because purification after completion of the reaction can be facilitated.
進行醯亞胺化反應時的溫度為-20℃~140℃,較佳為0℃~100℃,反應時間可為1~100小時。鹼性觸媒之量為醯胺酸基的0.5~30莫耳倍,較佳為2~20莫耳倍,酸酐之量為醯胺酸基的1~50莫耳倍,較佳為3~30莫耳倍。所得之聚合物的醯亞胺化率可藉由調節觸媒量、溫度、反應時間而控制。 於聚醯胺酸酯或聚醯胺酸之醯亞胺化反應後的溶液中,因殘存所添加之觸媒等,故藉由以下所述的手段,可回收所得之醯亞胺化聚合物,以有機溶劑進行再溶解,可成為本發明之液晶配向劑者為佳。The temperature during the imidization reaction is -20°C to 140°C, preferably 0°C to 100°C, and the reaction time can be 1 to 100 hours. The amount of the alkaline catalyst is 0.5 to 30 mol times of the amide acid group, preferably 2 to 20 mol times, and the amount of the acid anhydride is 1 to 50 mol times of the amide acid group, preferably 3 to 30 mol times. The imidization rate of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. In the solution after the imidization reaction of polyamide ester or polyamide acid, the added catalyst, etc. remain, so the obtained imidized polymer can be recovered by the following means. , is preferably redissolved with an organic solvent and can become the liquid crystal alignment agent of the present invention.
如上述所得之聚醯亞胺的溶液可藉由一邊充分攪拌一邊注入於貧溶劑可析出聚合物。進行數次析出,以貧溶劑洗淨後,經常溫或者加熱進行乾燥而可得到純化的聚醯胺酸酯之粉末。 前述貧溶劑雖無特別限定,可舉出甲醇、丙酮、己烷、丁基溶纖劑、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯等。The polyimide solution obtained as described above can be poured into a poor solvent while being thoroughly stirred to precipitate the polymer. After several precipitations, washing with a poor solvent, and drying at room temperature or heating, the purified polyamic acid ester powder can be obtained. Although the aforementioned poor solvent is not particularly limited, examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and the like.
<液晶配向劑> 本發明之液晶配向劑含有聚合物(A)及聚合物(B)。本發明之液晶配向劑除可含有聚合物(A)及聚合物(B)以外,亦可含有其他聚合物。作為其他聚合物之種類,可舉出聚醯胺酸、聚醯亞胺、聚醯胺酸酯、聚酯、聚醯胺、聚脲、聚有機矽氧烷、纖維素衍生物、聚縮醛、聚苯乙烯或其衍生物、聚(苯乙烯-苯基馬來醯亞胺)衍生物、聚(甲基)丙烯酸酯等。<Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains polymer (A) and polymer (B). In addition to polymer (A) and polymer (B), the liquid crystal alignment agent of the present invention may also contain other polymers. Examples of other polymer types include polyamide acid, polyamide imide, polyamide ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, and polyacetal. , polystyrene or its derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylate, etc.
液晶配向劑為使用於製作液晶配向膜時者,由可形成均勻且薄膜的觀點來決定塗布液之形態。對於本發明之液晶配向劑,亦以含有前述聚合物成分與有機溶劑之塗布液者為佳。此時,液晶配向劑中之聚合物的濃度可藉由所要形成的塗膜厚度之設定而做適宜地變更。由可在均勻且無缺陷下形成塗膜的觀點來看,以1重量%以上為佳,由溶液之保存穩定性的觀點來看,以10重量%以下為佳。特佳為聚合物之濃度為2~8重量%。Liquid crystal alignment agents are used in the production of liquid crystal alignment films. The form of the coating liquid is determined from the perspective of forming a uniform and thin film. The liquid crystal alignment agent of the present invention is also preferably a coating liquid containing the aforementioned polymer component and an organic solvent. At this time, the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a coating film uniformly and without defects, the content is preferably 1% by weight or more, and from the viewpoint of storage stability of the solution, the content is preferably 10% by weight or less. Particularly preferred is a polymer concentration of 2 to 8% by weight.
含於液晶配向劑的有機溶劑若為可使聚合物成分均勻地溶解者即可,並無特別限定。若要舉出該具體例子,可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、二甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、甲基乙基酮、環己酮、環戊酮、3-甲氧基-N,N-二甲基丙烷醯胺、3-丁氧基-N,N-二甲基丙烷醯胺等。其中亦以N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、3-甲氧基-N,N-二甲基丙烷醯胺、3-丁氧基-N,N-二甲基丙烷醯胺或γ-丁內酯。The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as it can dissolve the polymer component uniformly. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, and N-ethyl-2 -pyrrolidinone, dimethyltrisoxide, γ-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N , N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide or γ-butyrolactone.
又,含於液晶配向劑的有機溶劑,以除如上述溶劑以外,以並用可提高塗布液晶配向劑時的塗布性或塗膜之表面平滑性的溶劑的混合溶劑為佳。所要並用的有機溶劑之具體例子可舉出下述者但並未限定於該等例。 例如可舉出二異丙基醚、二異丁基醚、二異丁基甲醇(Carbinol)、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、1,2-丁氧基乙烷、二乙二醇二甲基醚、二乙二醇二乙基醚、4-羥基-4-甲基-2-戊酮、二乙二醇甲基乙基醚、二乙二醇二丁基醚、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、伸丙基碳酸酯、伸乙基碳酸酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁基醚(丁基溶纖劑)、乙二醇單異戊基醚、乙二醇單己基醚、2-(己氧基)乙醇、丙二醇單丁基醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲基醚乙酸酯、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二甲基醚、乙二醇單丁基醚乙酸酯(丁基溶纖劑乙酸酯)、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、丙二醇二乙酸酯、乙酸n-丁基、乙酸丙二醇單乙基醚、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸n-丁基酯、乳酸異戊基酯、二乙二醇單乙基醚、二異丁基酮等。In addition, the organic solvent contained in the liquid crystal alignment agent is preferably a mixed solvent that can improve the coating properties when applying the liquid crystal alignment agent or the surface smoothness of the coating film, in addition to the above-mentioned solvents. Specific examples of the organic solvent to be used in combination include the following, but are not limited to these examples. Examples include diisopropyl ether, diisobutyl ether, diisobutylmethanol (Carbinol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1 ,2-Butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether , diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, Ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethyl carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether (butyl cellosolve agent), ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, propylene glycol monobutyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate (butyl cellosolve acetate), ethylene glycol mono Acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl Acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate , ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isopentyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone, etc.
其中,亦以二異丁基甲醇(Carbinol)、丙二醇單丁基醚、丙二醇二乙酸酯、二乙二醇二乙基醚、二丙二醇單甲基醚、二丙二醇二甲基醚、4-羥基-4-甲基-2-戊酮、乙二醇單丁基醚、乙二醇單丁基醚乙酸酯、二異丁基酮為佳。溶劑之種類及含有量可配合液晶配向劑之塗布裝置、塗布條件、塗布環境等而適宜地選擇。Among them, diisobutyl carbinol (Carbinol), propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4- Hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and diisobutyl ketone are preferred. The type and content of the solvent can be appropriately selected according to the coating device, coating conditions, coating environment, etc. of the liquid crystal alignment agent.
作為良溶劑與貧溶劑之較佳溶劑的組合,可舉出N-甲基-2-吡咯啶酮與乙二醇單丁基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與乙二醇單丁基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚、N-乙基-2-吡咯啶酮與丙二醇單丁基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與4-羥基-4-甲基-2-戊酮與二乙二醇二乙基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚與2,6-二甲基-4-庚酮、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚與二異丙基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與丙二醇單丁基醚與2,6-二甲基-4-庚醇、N-甲基-2-吡咯啶酮與γ-丁內酯與二丙二醇二甲基醚、N-甲基-2-吡咯啶酮與丙二醇單丁基醚與二丙二醇二甲基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與乙二醇單丁基醚與二丙二醇單甲基醚、N-甲基-2-吡咯啶酮與γ-丁內酯與乙二醇單丁基醚單乙酸酯、N-甲基-2-吡咯啶酮與γ-丁內酯與乙二醇單丁基醚單乙酸酯與二丙二醇單甲基醚等。貧溶劑以含於液晶配向劑之溶劑全體的1~80重量%為佳,以10~80重量%為較佳,以20~70重量%為特佳。溶劑之種類及含有量可配合液晶配向劑之塗布裝置、條件、環境等做適宜選擇。Preferable solvent combinations of good solvents and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butylene Esters and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone With γ-butyrolactone and propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and dimethyl Isopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidine Ketone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether monoacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, ethylene glycol monobutyl ether monoacetate, dipropylene glycol monomethyl ether, etc. The lean solvent is preferably 1 to 80% by weight of the total solvent contained in the liquid crystal alignment agent, preferably 10 to 80% by weight, and particularly preferably 20 to 70% by weight. The type and content of the solvent can be appropriately selected according to the coating device, conditions, and environment of the liquid crystal alignment agent.
本發明之液晶配向劑中可追加含有聚合物成分及有機溶劑以外的成分。作為如此追加成分,可舉出使用於提高液晶配向膜與基板的密著性或液晶配向膜與密封材之密著性的密著助劑、使用於提高液晶配向膜之強度的化合物(以下亦稱為交聯性化合物)、使用於調整液晶配向膜的介電率或電阻之介電體或導電物質等。The liquid crystal alignment agent of the present invention may additionally contain components other than polymer components and organic solvents. Examples of such additional components include adhesion aids used to improve the adhesion between the liquid crystal alignment film and the substrate or the adhesion between the liquid crystal alignment film and the sealing material, and compounds used to improve the strength of the liquid crystal alignment film (hereinafter also referred to as (called cross-linking compounds), dielectrics or conductive substances used to adjust the dielectric constant or resistance of the liquid crystal alignment film.
作為前述交聯性化合物,由AC殘像的產生為少,且膜強度之改善效果較高的觀點來看,以選自具有由選自環氧乙烷基、氧雜環丁烷基、保護異氰酸酯基、保護異硫氰酸酯基、含有噁唑啉環結構的基、含有麥芽糖酸結構的基、環碳酸酯基及下述式(d)所示基所成群的至少1種基的化合物,或下述式(e)所示化合物的化合物(以下將此等總稱為化合物(C))為佳。 (式中,Q31 為氫原子、碳數1~3的烷基或「*-CH2 -OH」,Q32 及Q33 各獨立為氫原子、碳數1~3的烷基或「*-CH2 -OH」。*表示鍵結手。A表示具有芳香環之(m+n)價有機基。m表示1~6的整數,n表示0~4的整數)The crosslinking compound is selected from the group consisting of an oxirane group, an oxetanyl group, and a protective At least one type of group consisting of an isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a maltobionic acid structure, a cyclic carbonate group, and a group represented by the following formula (d) Compounds, or compounds represented by the following formula (e) (hereinafter these are collectively referred to as compounds (C)) are preferred. (In the formula, Q 31 is a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, or "*-CH 2 -OH", and Q 32 and Q 33 are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, or "* -CH 2 -OH". * represents the bonding hand. A represents a (m+n)-valent organic group having an aromatic ring. m represents an integer from 1 to 6, and n represents an integer from 0 to 4)
作為具有環氧乙烷基的化合物之具體例子,例如可舉出在日本特開平10-338880號公報之段落[0037]所記載的化合物,或在WO2017/170483號所記載的具有三嗪環作為骨架之化合物等具有2個以上環氧乙烷基之化合物。此等之中,以N,N,N’,N’,-四縮水甘油基-m-二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N’,N’,-四縮水甘油基-4、4’-二胺基二苯基甲烷、N,N,N’,N’-四縮水甘油基-p-伸苯基二胺、下述式(r-1)~(r-3)中任一所示化合物等含氮原子之化合物為特佳。 Specific examples of compounds having an oxirane group include compounds described in paragraph [0037] of Japanese Patent Application Laid-Open No. 10-338880, and compounds having a triazine ring described in WO2017/170483. Compounds with two or more ethylene oxide groups such as skeleton compounds. Among these, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane Alkane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-p-phenylene Compounds containing nitrogen atoms such as diamines and compounds represented by any one of the following formulas (r-1) to (r-3) are particularly preferred.
作為具有氧雜環丁烷基之化合物的具體例子,例如可舉出在WO2011/132751號之段落[0170]~[0175]所記載的具有2個以上氧雜環丁烷基之化合物等。Specific examples of the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of WO2011/132751.
作為具有保護異氰酸酯基之化合物的具體例子,例如可舉出在日本特開2014-224978號公報之段落[0046]~[0047]所記載的具有2個以上保護異氰酸酯基的化合物、在WO2015/141598號的段落[0119]~[0120]所記載的具有3個以上保護異氰酸酯基之化合物等。此等中以下述式(bi-1)~(bi-3)中任一所示化合物為佳。 Specific examples of the compound having a protected isocyanate group include compounds having two or more protected isocyanate groups described in paragraphs [0046] to [0047] of Japanese Patent Application Laid-Open No. 2014-224978, and compounds having two or more protected isocyanate groups described in WO2015/141598 Compounds having three or more protected isocyanate groups described in paragraphs [0119] to [0120] of No. 1, etc. Among these, compounds represented by any one of the following formulas (bi-1) to (bi-3) are preferred.
作為具有保護異硫氰酸酯基之化合物的具體例子,例如可舉出日本特開2016-200798號公報所記載的具有2個以上保護異硫氰酸酯基的化合物。 作為具有含噁唑啉環結構的基之化合物的具體例子,例如可舉出日本特開2007-286597號公報之段落[0115]所記載的含有2個以上噁唑啉結構之化合物。Specific examples of the compound having a protected isothiocyanate group include compounds having two or more protected isothiocyanate groups described in Japanese Patent Application Laid-Open No. 2016-200798. Specific examples of compounds having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures described in paragraph [0115] of Japanese Patent Application Laid-Open No. 2007-286597.
作為具有含麥芽糖酸結構的基之化合物的具體例子,例如可舉出在WO2012/091088號所記載的具有2個以上麥芽糖酸結構之化合物。 作為具有環碳酸酯基之化合物的具體例子,例如可舉出在WO2011/155577號所記載的化合物。Specific examples of compounds having a maltobionic acid structure-containing group include compounds having two or more maltobionic acid structures described in WO2012/091088. Specific examples of the compound having a cyclic carbonate group include compounds described in WO2011/155577.
作為前述式(d)所示基之R1 、R2 、R3 的碳數1~3的烷基,可舉出在上述式(l)、(n)所例示之基。 作為具有前述式(d)所示基之化合物的具體例子,例如可舉出在WO2015/072554號或在日本特開2016-118753號公報之段落[0058]所記載的具有2個以上前述式(d)所示基的化合物、在日本特開2016-200798號公報所記載的化合物等。此等中以下述式(hd-1)~(hd-8)所示化合物為佳。 Examples of the alkyl groups having 1 to 3 carbon atoms in R 1 , R 2 and R 3 of the group represented by the formula (d) include the groups exemplified by the formulas (l) and (n). Specific examples of compounds having a group represented by the aforementioned formula (d) include compounds having two or more of the aforementioned formulas ( Compounds of the group represented by d), compounds described in Japanese Patent Application Laid-Open No. 2016-200798, etc. Among these, compounds represented by the following formulas (hd-1) to (hd-8) are preferred.
作為於前述式(e)之A中具有芳香環之(m+n)價有機基,可舉出碳數5~30的(m+n)價芳香族烴基、碳數5~30的芳香族烴基直接或隔著連結基而進行鍵結之(m+n)價有機基,或具有芳香族雜環之(m+n)價的基。作為前述芳香族烴基,例如可舉出苯、萘等。作為芳香族雜環,例如可舉出吡咯環、咪唑環、吡唑環、吡啶環、嘧啶環、喹啉環、異喹啉環、咔唑環、噠嗪環、吡嗪環、苯並咪唑環、苯並咪唑環、吲哚環、喹喔啉環、吖啶環等。作為前述連結基,可舉出碳數1~10的伸烷基,或自前述伸烷基除去1個氫原子之基、2價或3價環己烷環等。且,前述伸烷基之任意氫原子可由氟原子或三氟甲基等有機基所取代。若要舉出具體例子,可舉出在WO2010/074269號所記載的化合物等。作為較佳具體例子,可舉出下述式(e-1)~(e-11)。 Examples of the (m+n)-valent organic group having an aromatic ring in A of the aforementioned formula (e) include (m+n)-valent aromatic hydrocarbon groups having 5 to 30 carbon atoms, and aromatic hydrocarbon groups having 5 to 30 carbon atoms. A (m+n)-valent organic group in which a hydrocarbon group is bonded directly or via a linking group, or a (m+n)-valent group having an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon group include benzene, naphthalene, and the like. Examples of the aromatic heterocyclic ring include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a pyridazine ring, a pyrazine ring, and a benzimidazole ring. ring, benzimidazole ring, indole ring, quinoxaline ring, acridine ring, etc. Examples of the connecting group include an alkylene group having 1 to 10 carbon atoms, a group obtained by removing one hydrogen atom from the alkylene group, a divalent or trivalent cyclohexane ring, and the like. Furthermore, any hydrogen atom in the aforementioned alkylene group may be substituted by a fluorine atom or an organic group such as trifluoromethyl. Specific examples include compounds described in WO2010/074269. Preferable specific examples include the following formulas (e-1) to (e-11).
上述化合物為交聯性化合物的一例,但並未限定於此等者。例如可舉出在WO2015/060357號之[0105]~[0116]所揭示的上述以外的成分等。又,在本發明之液晶配向劑所含有之交聯性化合物可組合2種類以上。 本發明之液晶配向劑中,交聯性化合物之含有量對於液晶配向劑所含之聚合物成分100重量份而言,以0.5~20重量份者為佳,以進行交聯反應而表現目的效果,且AC殘像特性較少的觀點來看,較佳為1~15重量份。The above-mentioned compounds are examples of cross-linked compounds, but are not limited thereto. Examples include components other than the above disclosed in WO2015/060357 No. [0105] to [0116]. In addition, two or more types of crosslinking compounds contained in the liquid crystal alignment agent of the present invention may be combined. In the liquid crystal alignment agent of the present invention, the content of the cross-linking compound is preferably 0.5 to 20 parts by weight based on 100 parts by weight of the polymer component contained in the liquid crystal alignment agent, so as to carry out the cross-linking reaction and achieve the desired effect. , and from the viewpoint of less AC afterimage characteristics, 1 to 15 parts by weight is preferred.
作為前述密著助劑,例如可舉出3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基二乙氧基甲基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲丙基三甲氧基矽烷、3-脲丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽基丙基三伸乙基三胺、N-三甲氧基矽基丙基三伸乙基三胺、10-三甲氧基矽基-1,4,7-三氮雜癸烷、10-三乙氧基矽基-1,4,7-三氮雜癸烷、9-三甲氧基矽基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽基-3,6-二氮雜壬基乙酸酯、N-苯甲基-3-胺基丙基三甲氧基矽烷、N-苯甲基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(氧乙烯)-3-胺基丙基三甲氧基矽烷、N-雙(氧乙烯)-3-胺基丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、p-苯乙烯三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、參-(三甲氧基矽基丙基)異氰脲酸酯、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷等矽烷偶合劑。使用此等矽烷偶合劑時,由AC殘像較少的觀點來看,對於液晶配向劑中所含的聚合物成分100重量份而言以0.1~30重量份者為佳,較佳為0.1~20重量份。Examples of the adhesion aid include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, and 2-aminopropyltriethoxysilane. Aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl) Ethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-amino Propyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilyl Propyl triethylene triamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3 -Aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3 -Aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-benzene Ethylene trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, ginseng-(trimethoxysilylpropyl)isocyanurea Acid ester, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane and other silane coupling agents. When using such a silane coupling agent, from the viewpoint of less AC afterimage, 0.1 to 30 parts by weight is preferred for 100 parts by weight of the polymer component contained in the liquid crystal alignment agent, and 0.1 to 30 parts by weight is preferred. 20 parts by weight.
<液晶配向膜・液晶顯示元件> 液晶配向膜為使上述液晶配向劑塗布於基板,並經乾燥、燒成而得之膜。作為塗布液晶配向劑之基板,若為透明性高之基板即可,並無特別限定,可使用玻璃基板、氮化矽基板、丙烯酸基板或聚碳酸酯基板等塑質基板等。此時,若使用可使液晶驅動的ITO電極等所形成的基板時,由製程的簡單化之觀點來看為佳。又,在反射型之液晶顯示元件中,不僅為單側基板,亦可使用矽晶圓等不透明物,此時的電極中亦可使用鋁等反射光之材料。<Liquid crystal alignment film・Liquid crystal display element> The liquid crystal alignment film is a film obtained by coating the above-mentioned liquid crystal alignment agent on a substrate, drying, and firing. The substrate on which the liquid crystal alignment agent is coated is not particularly limited as long as it is a highly transparent substrate. Plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates, or polycarbonate substrates can be used. In this case, it is preferable from the viewpoint of simplification of the manufacturing process to use a substrate formed of ITO electrodes that can drive liquid crystals. In addition, in a reflective liquid crystal display element, not only a single-sided substrate can be used, but also opaque materials such as silicon wafers can be used. In this case, light-reflecting materials such as aluminum can also be used in the electrodes.
對於液晶配向劑之基板的塗布方法,並無特別限定,但在工業上一般進行絲網印刷、膠版印刷、柔版印刷或噴墨法等方法。作為其他塗布方法,有浸漬法、輥塗法、狹縫塗布法、旋轉器法或噴霧法等,可配合目的而使用。The coating method of the liquid crystal alignment agent substrate is not particularly limited, but in industry, methods such as screen printing, offset printing, flexographic printing, or inkjet are generally used. As other coating methods, there are dipping method, roll coating method, slit coating method, spinner method, spray method, etc., which can be used according to the purpose.
將液晶配向劑塗布於基板上後,藉由加熱板、熱循環型烤箱或IR(紅外線)型烤箱等加熱手段,可使溶劑蒸發而成為液晶配向膜。塗布液晶配向劑後之乾燥、燒成步驟可選擇任意溫度與時間。通常欲充分除去所含有的溶劑時,在50~120℃進行1~10分鐘燒成後,在150~300℃進行5~120分鐘燒成之條件可舉出。燒成後的液晶配向膜之厚度若過薄時液晶顯示元件之信賴性會有降低之情況產生,故以5~300nm為佳,以10~200nm為較佳。After the liquid crystal alignment agent is coated on the substrate, the solvent can be evaporated by heating means such as a hot plate, thermal cycle oven or IR (infrared) oven to form a liquid crystal alignment film. Any temperature and time can be selected for the drying and firing steps after coating the liquid crystal alignment agent. Generally, in order to fully remove the contained solvent, the conditions include calcining at 50 to 120°C for 1 to 10 minutes and then calcining at 150 to 300°C for 5 to 120 minutes. If the thickness of the liquid crystal alignment film after firing is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, 5 to 300 nm is preferred, and 10 to 200 nm is preferred.
使由本發明之液晶配向劑所得之液晶配向膜進行配向處理的方法可使用摩擦處理法,但以使用光配向處理法為佳。 藉由摩擦處理或光配向處理進行配向處理時,欲改善液晶配向性,視情況以在150~250℃的溫度進行加熱處理後進行配向處理亦佳,又亦可將液晶配向膜經塗膜的基板在50~250℃一邊加熱一邊進行配向處理。The method for aligning the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can be a rubbing treatment method, but it is better to use a photo alignment treatment method. When alignment treatment is performed by rubbing treatment or photo-alignment treatment, in order to improve the alignment of the liquid crystal, it is better to conduct the alignment treatment after heat treatment at a temperature of 150 to 250°C, or the liquid crystal alignment film can also be coated. The substrate is aligned while being heated at 50 to 250°C.
進一步在前述方法中,亦可對於經配向處理的液晶配向膜使用水或溶劑,進行接觸處理而除去附著於液晶配向膜之雜質。 作為使用於上述接觸處理的溶劑,雖無特別限定,作為具體例子,可舉出水、甲醇、乙醇、2-丙醇、丙酮、甲基乙基酮、1-甲氧基-2-丙醇、1-甲氧基-2-丙醇乙酸酯、丁基溶纖劑、乳酸乙酯、乳酸甲酯、二丙酮醇、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙酸丙酯、乙酸丁酯或乙酸環己酯等。Furthermore, in the aforementioned method, water or a solvent may also be used for the alignment-treated liquid crystal alignment film to perform contact treatment to remove impurities attached to the liquid crystal alignment film. The solvent used in the contact treatment is not particularly limited, but specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, and 1-methoxy-2-propanol. , 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate , propyl acetate, butyl acetate or cyclohexyl acetate, etc.
本發明之液晶配向膜可適合作為IPS方式或FFS方式等橫向電場方式之液晶顯示元件的液晶配向膜使用,特別可作為FFS方式之液晶顯示元件的液晶配向膜而有用。液晶顯示元件由本發明之液晶配向劑得到附有液晶配向膜之基板後,以既知方法製作液晶單元後可使用該液晶單元。The liquid crystal alignment film of the present invention can be suitably used as a liquid crystal alignment film for a lateral electric field liquid crystal display element such as an IPS method or an FFS method, and is particularly useful as a liquid crystal alignment film for an FFS method liquid crystal display element. After the liquid crystal display element obtains a substrate with a liquid crystal alignment film from the liquid crystal alignment agent of the present invention, the liquid crystal cell can be used after producing a liquid crystal cell by a known method.
作為液晶單元之製作方法的一例子,可將被動矩陣結構的液晶顯示元件作為例子說明。且亦可為構成圖像顯示的各畫素部分中設有TFT(Thin Film Transistor)等開關元件的主動矩陣結構之液晶顯示元件。 具體而言,準備透明玻璃製基板,一方基板上設置普通電極,另他一方基板上設置分段電極。此等電極例如可作為ITO電極,而製圖成所望圖像顯示。其次,於各基板上設置絕緣膜而覆蓋普通電極與分段電極。絕緣膜例如可為藉由溶膠-凝膠法所形成之SiO2 -TiO2 膜。As an example of a method of manufacturing a liquid crystal cell, a liquid crystal display element with a passive matrix structure can be used as an example. Moreover, it can also be an active matrix liquid crystal display element with switching elements such as TFT (Thin Film Transistor) provided in each pixel portion of the image display. Specifically, transparent glass substrates are prepared, a common electrode is provided on one substrate, and a segmented electrode is provided on the other substrate. These electrodes can be used as ITO electrodes, for example, and can be patterned into desired image displays. Secondly, an insulating film is provided on each substrate to cover the common electrode and the segmented electrode. The insulating film may be, for example, a SiO 2 -TiO 2 film formed by a sol-gel method.
其次於各基板上形成液晶配向膜,於一方基板上重疊另一方基板而使彼此液晶配向膜面呈面對面,將周邊以密封劑進行接著。欲控制基板間隙,通常於密封劑中可混入間隔物,又對於未設置密封劑的面內部分中,散布基板間隙控制用間隔物者為佳。於密封劑之一部分,設置自外部可填充液晶之開口部。其次,通過設有於密封劑之開口部,以2片基板與密封劑所包圍的空間內注入液晶材料後,將該開口部以接著劑密封。注入可使用真空注入法,亦可使用在大氣中利用毛細管現象的方法。液晶材料可使用正型液晶材料或負型液晶材料中任一種,較佳為負型液晶材料。其次進行偏光板之設置。具體而言,在2片基板之液晶層的反面上貼合一對偏光板。 如上述,藉由使用本發明之液晶配向劑,可得到來自殘留DC之殘像或AC殘像的產生少,重工容易且透過率高的液晶配向膜。 [實施例]Next, a liquid crystal alignment film is formed on each substrate, and the other substrate is overlapped on one substrate so that the liquid crystal alignment film surfaces face each other, and the periphery is bonded with a sealant. In order to control the substrate gap, spacers can usually be mixed into the sealant, and it is better to spread spacers for substrate gap control in the in-plane portions where the sealant is not provided. An opening that can be filled with liquid crystal from the outside is provided in a part of the sealant. Next, through the opening provided in the sealant, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant, and then the opening is sealed with the adhesive. For injection, a vacuum injection method may be used, or a method utilizing capillary phenomena in the atmosphere may be used. As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material can be used, and a negative liquid crystal material is preferred. Next, set up the polarizing plate. Specifically, a pair of polarizing plates are bonded to the opposite surfaces of the liquid crystal layers of the two substrates. As described above, by using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film with less residual DC or AC afterimages, easy rework, and high transmittance can be obtained. [Example]
在以下舉出實施例,更具體說明本發明,但本發明並未限定於此等。以下中之化合物的簡稱及各特性測定方法如以下所示。 (二胺) l-1、n-1、DA-1~DA-7:各為下述式(l-1)、(n-1)、(DA-1)~(DA-7)所示化合物 (四羧酸二酐) CA-1~CA-5:各為下述式(CA-1)~(CA-5)所示化合物 (化合物C) C-1:下述式(C-1)所示化合物 (化合物D) D-1:下述式(D-1)所示化合物 (化合物E) E-1:下述式(E-1)所示化合物 (有機溶劑) NMP:N-甲基-2-吡咯啶酮、 GBL:γ-丁內酯、 BCS:丁基溶纖劑、BCA:丁基溶纖劑乙酸酯The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The abbreviations of the following compounds and the methods for measuring each characteristic are as follows. (diamine) l-1, n-1, DA-1 to DA-7: each is a compound represented by the following formula (l-1), (n-1), (DA-1) to (DA-7) (tetracarboxylic dianhydride) CA-1 to CA-5: Each is a compound represented by the following formulas (CA-1) to (CA-5) (Compound C) C-1: Compound represented by the following formula (C-1) (Compound D) D-1: Compound represented by the following formula (D-1) (Compound E) E-1: Compound represented by the following formula (E-1) (organic solvent) NMP: N-methyl-2-pyrrolidinone, GBL: γ-butyrolactone, BCS: Butyl Cellosolve, BCA: Butyl Cellosolve Acetate
[黏度] 使用E型黏度計TVE-22H(東機產業公司製),以試樣量1.1mL、錐形轉子TE-1(1˚34’、R24)、溫度25℃進行測定。[viscosity] The measurement was performed using an E-type viscometer TVE-22H (manufactured by Toki Industrial Co., Ltd.) with a sample volume of 1.1 mL, a conical rotor TE-1 (1˚34’, R24), and a temperature of 25°C.
<醯亞胺化率之測定> 將聚醯亞胺粉末20mg放入於NMR試樣管(NMR取樣試管標準,φ5(草野科學公司製)),添加重氫化二甲基亞碸(DMSO-d6,0.05%TMS(四甲基矽烷)混合品)(0.53ml),經超音波使其完全溶解。將該溶液以NMR測定機(JNW-ECA500)(日本電子數據公司製)測定500MHz之質子NMR。醯亞胺化率取決於將來自在醯亞胺化前後無變化的結構之質子作為基準質子時,使用該質子的吸收峰積分值,與來自出現於9.5ppm~10.0ppm附近的醯胺酸之NH基的質子吸收峰積分值而藉由以下式求得。 醯亞胺化率(%)=(1-α・x/y)×100 對於上述式,x為來自醯胺酸的NH基之質子吸收峰積分值,y為基準質子之吸收峰積分值,α為對於1個聚醯胺酸(醯亞胺化率為0%)時醯胺酸的NH基質子之基準質子的個數比例。<Measurement of acyl imidization rate> Put 20 mg of polyimide powder into an NMR sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), and add deuterated dimethylsulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) ) mixture) (0.53ml), completely dissolved by ultrasonic wave. This solution was measured for proton NMR at 500 MHz with an NMR measuring machine (JNW-ECA500) (manufactured by Japan Electronics Data Corporation). The rate of imidization is determined by using the proton from a structure that does not change before and after imidization as a reference proton, and using the integrated value of the absorption peak of this proton, and the NH from amide acid that appears around 9.5 ppm to 10.0 ppm. The integrated value of the proton absorption peak of the base is calculated by the following formula. Ethylene imidization rate (%) = (1-α・x/y)×100 Regarding the above formula, x is the integrated value of the proton absorption peak derived from the NH group of amide, y is the integrated value of the absorption peak of the reference proton, and α is the value for one polyamide (imidization rate 0%). The ratio of the number of base protons of the NH base proton of amide.
[聚合物之合成] <合成例1> 於附有攪拌裝置及氮導管的1L四口燒瓶中,秤出DA-2(46.35g,189.8mmol)、DA-4(28.81g,51.75mmol)、DA-3(41.25g,103.5mmol),加入NMP至固體成分濃度成為15%,一邊送入氮一邊攪拌使其溶解。將該二胺溶液在水冷下一邊攪拌,一邊添加CA-1(50.27g,224.3mmol),進一步添加NMP至固體成分濃度成為18%,在氮環境下40℃中進行1小時攪拌。其後水冷下一邊攪拌,一邊添加CA-3(14.21g,72.5mmol),進一步添加NMP至固體成分濃度成為18%,在氮環境下且23℃下進行2小時攪拌,得到聚醯胺酸溶液。 於放有攪拌子之3L三角燒瓶中,放入在上述所得之聚醯胺酸溶液1000.0g,加入NMP(500.0g)、乙酸酐(105.99g)、吡啶(27.37g),在室溫進行30分鐘攪拌後,在50℃進行2小時反應。將該反應溶液投入於6500g之甲醇中,過濾分離所得之沈澱物。將該沈澱物以甲醇洗淨後,在溫度80℃下減壓乾燥後得到聚醯亞胺之粉末。該聚醯亞胺的粉末之醯亞胺化率為75%。 於放有攪拌子之1000mL三角燒瓶中,放入該聚醯亞胺之粉末(100.00g),加入NMP(400.0g),在70℃進行24小時攪拌而使其溶解後得到固體成分濃度為20%之聚醯亞胺(PI-A-1)的溶液。[Synthesis of polymers] <Synthesis example 1> In a 1L four-necked flask equipped with a stirring device and a nitrogen tube, weigh out DA-2 (46.35g, 189.8mmol), DA-4 (28.81g, 51.75mmol), and DA-3 (41.25g, 103.5mmol). NMP was added until the solid content concentration became 15%, and stirred while adding nitrogen to dissolve it. CA-1 (50.27 g, 224.3 mmol) was added to the diamine solution while stirring under water cooling, NMP was further added until the solid content concentration became 18%, and stirring was performed at 40° C. for 1 hour in a nitrogen atmosphere. Thereafter, while stirring under water cooling, CA-3 (14.21 g, 72.5 mmol) was added, NMP was further added until the solid content concentration became 18%, and stirring was carried out for 2 hours at 23°C in a nitrogen environment to obtain a polyamic acid solution. . In a 3L Erlenmeyer flask equipped with a stirrer, put 1000.0g of the polyamide solution obtained above, add NMP (500.0g), acetic anhydride (105.99g), and pyridine (27.37g), and proceed at room temperature for 30 After stirring for 2 minutes, the reaction was carried out at 50°C for 2 hours. The reaction solution was added to 6500 g of methanol, and the resulting precipitate was separated by filtration. After washing the precipitate with methanol, it was dried under reduced pressure at a temperature of 80° C. to obtain polyimide powder. The polyimide powder had an imidization rate of 75%. In a 1000mL Erlenmeyer flask equipped with a stirrer, put the polyimide powder (100.00g), add NMP (400.0g), stir at 70°C for 24 hours to dissolve, and obtain a solid content concentration of 20 % solution of polyimide (PI-A-1).
<合成例2> 如下述表1所示,使用二胺、四羧酸衍生物及有機溶劑,各與合成例1同樣程序下實施後,得到下述表1所示組成的聚醯胺酸。取出如此所得之聚醯胺酸溶液1000.0g,放入化合物E-1(45.32g,207.63mmol)再進行12小時攪拌後,與合成例1同樣地使用NMP、乙酸酐與吡啶,得到聚醯亞胺(PI-A-2)之溶液。表1中,括弧內的數值對四羧酸成分而言,表示對於使用於合成的二胺之合計量100莫耳份的各化合物之配合比例(莫耳份),對二胺成分而言,表示對於使用於合成的二胺之合計量100莫耳份的各化合物之配合比例(莫耳份)。對於有機溶劑,對使用於合成的有機溶劑之合計量100重量份的各有機溶劑之配合比例(重量份)。<Synthesis example 2> As shown in Table 1 below, a diamine, a tetracarboxylic acid derivative and an organic solvent were used, and the same procedure as in Synthesis Example 1 was carried out to obtain a polyamic acid having a composition shown in Table 1 below. Take out 1000.0g of the polyamide solution thus obtained, add compound E-1 (45.32g, 207.63mmol) and stir for 12 hours. Then, use NMP, acetic anhydride and pyridine in the same manner as in Synthesis Example 1 to obtain polyamide. Solution of amine (PI-A-2). In Table 1, the numerical values in parentheses represent, for the tetracarboxylic acid component, the blending ratio (mol parts) of each compound per 100 mol parts of the total amount of diamine used for synthesis. For the diamine component, Indicates the blending ratio (mol parts) of each compound relative to 100 mol parts of the total amount of diamine used for synthesis. Regarding the organic solvent, the mixing ratio (parts by weight) of each organic solvent is 100 parts by weight of the total amount of organic solvents used for synthesis.
<合成例3> 於附有攪拌裝置及氮導管的1L四口燒瓶中,秤出DA-2(24.12g,98.8mmol)、DA-1(22.74g,98.8mmol)、l-1(42.12g,197.5mmol),添加NMP(464.9g)、GBL(185.7g)至固體成分濃度為12%,一邊送入氮一邊攪拌使其溶解。將該二胺溶液在水冷下一邊攪拌,一邊使脂肪族酸二酐的CA-3(50.0g,255.0mmol)與GBL(237.7g)同時添加,成為固體成分濃度為13.5%,在氮環境下水冷下進行2小時攪拌。進一步添加芳香族酸二酐之CA-5(25.84g,118.5 mmol),再添加GBL至固體成分濃度為15%,在氮環境下50℃中進行15小時攪拌,得到固體成分成為15%之NMP/GBL=50/50的聚醯胺酸(PAA-B-1)之溶液。<Synthesis Example 3> In a 1L four-necked flask equipped with a stirring device and a nitrogen tube, weigh out DA-2 (24.12g, 98.8mmol), DA-1 (22.74g, 98.8mmol), and l-1 (42.12g, 197.5mmol). NMP (464.9g) and GBL (185.7g) were added until the solid content concentration became 12%, and they were stirred and dissolved while feeding nitrogen. While stirring the diamine solution under water cooling, aliphatic acid dianhydride CA-3 (50.0g, 255.0mmol) and GBL (237.7g) were added simultaneously to achieve a solid content concentration of 13.5% in a nitrogen environment. Stir for 2 hours under water cooling. Further add aromatic acid dianhydride CA-5 (25.84g, 118.5 mmol), then add GBL until the solid content concentration is 15%, and stir for 15 hours at 50°C in a nitrogen environment to obtain NMP with a solid content of 15%. /GBL=50/50 solution of polyamide (PAA-B-1).
<合成例4~10> 如下述表1所示,使用二胺、四羧酸衍生物及有機溶劑,各與合成例3同樣程序下實施後,得到下述表1所示之聚醯胺酸(PAA-B-2)~(PAA-B-8)之溶液。表1中,括弧內之數值表示,對於四羧酸成分,將合成時使用的二胺之合計量作為100莫耳份時的各化合物之配向比例(莫耳份),對於二胺成分,將合成時使用的二胺之合計量100莫耳份時的各化合物之配合比例(莫耳份)。對於有機溶劑,表示對於合成時使用的有機溶劑之合計量100重量份的各有機溶劑之配合比例(重量份)。<Synthesis Examples 4 to 10> As shown in Table 1 below, a diamine, a tetracarboxylic acid derivative and an organic solvent were used, and the same procedures as in Synthesis Example 3 were carried out to obtain the polyamic acid (PAA-B-2) shown in Table 1 below. ~(PAA-B-8) solution. In Table 1, the numerical values in parentheses represent the alignment ratio (mol parts) of each compound when the total amount of diamines used in the synthesis is taken as 100 mol parts for the tetracarboxylic acid component, and the diamine component is The mixing ratio (mol parts) of each compound when the total amount of diamines used in the synthesis is 100 mol parts. The organic solvent indicates the blending ratio (parts by weight) of each organic solvent based on 100 parts by weight of the total amount of organic solvents used during synthesis.
<實施例1> [液晶配向劑之調製] 使用在合成例1所得之聚醯亞胺(PI-A-1)的溶液及在合成例3所得之聚醯胺酸(PAA-B-1)的溶液,藉由NMP、GBL及BCS進行稀釋,再添加化合物(C-1)至對於全聚合物100重量份成為3重量份,而添加化合物(D-1)至對全聚合物100重量份為1重量份,並在室溫下攪拌。其次,藉由將該所得的溶液以孔徑0.5μm的濾器進行過濾,得到聚合物之成分比率為(PI-A-1):(PAA-B-1)=20:80(固體成分換算重量比),溶劑組成比為固體成分:NMP:GBL:BCS=4.5:30:45.5:20(重量比),化合物(C-1)與化合物(D-1)的配合比例各成為固體成分比3重量份與1重量份之液晶配向劑(1)(下述表2)。確認到於該液晶配向劑中未見到混濁或析出等異常現像,而得到均勻溶液。<Example 1> [Preparation of liquid crystal alignment agent] The solution of polyimide (PI-A-1) obtained in Synthesis Example 1 and the solution of polyamide (PAA-B-1) obtained in Synthesis Example 3 were used and diluted with NMP, GBL and BCS. , then add the compound (C-1) to 3 parts by weight based on 100 parts by weight of the whole polymer, and add the compound (D-1) so that it becomes 1 part by weight based on 100 parts by weight of the whole polymer, and stir at room temperature. Next, the obtained solution was filtered through a filter with a pore size of 0.5 μm to obtain a polymer component ratio of (PI-A-1): (PAA-B-1)=20:80 (solid content converted weight ratio ), the solvent composition ratio is solid content: NMP: GBL: BCS = 4.5: 30: 45.5: 20 (weight ratio), and the mixing ratio of compound (C-1) and compound (D-1) is each solid content ratio 3 wt. parts and 1 part by weight of liquid crystal alignment agent (1) (Table 2 below). It was confirmed that no abnormal phenomena such as turbidity or precipitation were observed in the liquid crystal alignment agent, and a uniform solution was obtained.
<實施例2~11,比較例1~4> 使用下述表2的聚合物及化合物(C)、化合物(D)以外,藉由實施與實施例1之同樣步驟,得到液晶配向劑(2)~(15)。表2中,括弧內之數值表示,對於聚合物及化合物(C)、化合物(D)的使用於各液晶配向劑之調製的聚合物成分之合計100重量份而言,各聚合物成分或化合物(C)、化合物(D)之配合比例(重量份)。對於有機溶劑,表示對於使用於液晶配向劑之調製的有機溶劑之合計量100重量份而言的各有機溶劑之配合比例(重量份)。<Examples 2 to 11, Comparative Examples 1 to 4> Liquid crystal alignment agents (2) to (15) were obtained by carrying out the same steps as in Example 1 except using the polymer, compound (C) and compound (D) in Table 2 below. In Table 2, the numerical values in parentheses represent the amount of each polymer component or compound based on 100 parts by weight of the total polymer component of the polymer, compound (C), and compound (D) used in the preparation of each liquid crystal alignment agent. (C), the mixing ratio of compound (D) (parts by weight). The organic solvent represents the blending ratio (parts by weight) of each organic solvent based on 100 parts by weight of the total amount of organic solvents used to prepare the liquid crystal alignment agent.
[液晶顯示元件之製作] 製作出邊緣場開關(Fringe Field Switching:FFS)模式液晶顯示元件之構成的液晶單元。 首先準備附有電極之基板。基板為30mm×50mm尺寸且厚度0.7mm之玻璃基板。於基板上形成具備作為第1層之構成對向電極之扁平形狀圖型的ITO電極。於第1層的對向電極上作為第2層,藉由CVD法形成成膜的SiN(氮化矽)膜。第2層之SiN膜的膜厚為500nm,作為層間絕緣膜而發揮其功能。於第2層之SiN膜上,配置作為第3層而製圖ITO膜所形成的梳齒狀畫素電極,形成第1畫素及第2畫素之2種畫素。各畫素之尺寸為縱10mm且橫約5mm。此時,所謂第1層之對向電極與第3層之畫素電極表示藉由第2層之SiN膜的作用而成為電絕緣。[Production of liquid crystal display components] A liquid crystal cell composed of a Fringe Field Switching (FFS) mode liquid crystal display element was produced. First prepare the substrate with electrodes attached. The substrate is a glass substrate with a size of 30mm×50mm and a thickness of 0.7mm. An ITO electrode having a flat-shaped pattern constituting the counter electrode as the first layer is formed on the substrate. A SiN (silicon nitride) film is formed as a second layer on the counter electrode of the first layer by a CVD method. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning an ITO film as the third layer is arranged to form two types of pixels: a first pixel and a second pixel. The size of each pixel is 10mm vertically and approximately 5mm horizontally. At this time, the counter electrode of the first layer and the pixel electrode of the third layer mean that they are electrically insulated by the SiN film of the second layer.
第3層之畫素電極為,具有使中央部分彎曲成「く」之字形狀的電極要素以複數配列所構成的梳齒狀形狀。各電極要素之橫向方向的寬為3μm,電極要素間之間隔為6μm。形成各畫素之畫素電極因使中央部分彎曲成「く」之字形狀的電極要素以複數配列所構成,故各畫素之形狀並非長方形狀,與電極要素同樣地在中央部分具備彎曲成粗體的與「く」相似的形狀。然後各畫素係將該中央彎曲部分作為界境而分割為上下,具有彎曲部分之上側第1區域與下側第2區域。The pixel electrode of the third layer has a comb-shaped shape in which a plurality of electrode elements are arranged in a "く" zigzag shape at the center. The width of each electrode element in the lateral direction is 3 μm, and the distance between electrode elements is 6 μm. The pixel electrode forming each pixel is composed of a plurality of electrode elements arranged in a zigzag shape with the central part bent into a "く" shape. Therefore, the shape of each pixel is not a rectangular shape. Like the electrode elements, it has a bent shape in the central part. Bold shapes similar to 「く」. Then, each pixel is divided into upper and lower parts with the central curved portion as a boundary, and has a first region above the curved portion and a second region below the curved portion.
比較各畫素之第1區域與第2區域時,成為構成此等的畫素電極之電極要素的形成方向相異者。即,將後述液晶配向膜的摩擦方向作為基準時,在畫素之第1區域,使畫素電極之電極要素成為+10˚之角度(順時鐘)而形成,在畫素之第2區域,使畫素電極之電極要素成為-10˚之角度(順時鐘)而形成。即,在各畫素之第1區域與第2區域,藉由於畫素電極與對向電極之間輸入電壓,進而引起的液晶在基板面內進行轉動之動作(面對面切換)而使彼此方向成為反方向而構成。When comparing the first region and the second region of each pixel, the formation directions of the electrode elements constituting the electrodes of these pixels are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, in the first area of the pixel, the electrode element of the pixel electrode is formed at an angle of +10˚ (clockwise), and in the second area of the pixel, It is formed by making the electrode elements of the pixel electrode have an angle of -10˚ (clockwise). That is, in the first area and the second area of each pixel, the input voltage between the pixel electrode and the counter electrode causes the liquid crystal to rotate within the substrate surface (face-to-face switching), so that the mutual directions become Constructed in the opposite direction.
其次,將液晶配向劑以孔徑1.0μm的濾器進行過濾後,對於準備好的上述附有電極之基板與在裏面具有成膜為ITO膜之高度4μm之柱狀間隔物的玻璃基板,以旋塗塗布進行塗布。在80℃之加熱板上進行5分鐘乾燥後,在230℃之熱風循環式烤箱進行20分鐘燒成,得到膜厚60nm之聚醯亞胺膜。將該聚醯亞胺膜以人造纖維布進行摩擦(輥直徑:120mm,輥轉動數:500rpm,移動速度:30mm/sec,推入長度:0.3mm,摩擦方向:對於3層IZO梳齒電極傾斜10˚之方向)後,在純水中進行1分鐘超音波照射而洗淨,經吹氣而除去水滴。其後,在80℃進行15分鐘乾燥,得到附有液晶配向膜之基板。將此等2片附有液晶配向膜之基板作為1組,於基板上留下液晶注入口之形狀下塗布(印刷)密封劑,將另1片基板貼合成面向液晶配向膜面,且使摩擦方向成為逆平行方向。其後使密封劑硬化,製作出單元間隙為4μm之空胞。藉由對該空胞進行減壓注入法,注入液晶MLC-3019(默克公司製),密封注入口,得到FFS方式之液晶單元。其後將所得之液晶單元在120℃進行1小時加熱,在23℃放置一晩後使用於液晶配向性之評估上。Next, after filtering the liquid crystal alignment agent through a filter with a pore size of 1.0 μm, spin coating was performed on the prepared substrate with electrodes and a glass substrate having columnar spacers with a height of 4 μm formed as an ITO film inside. Apply to apply. After drying on a hot plate at 80°C for 5 minutes, it was fired in a hot air circulation oven at 230°C for 20 minutes to obtain a polyimide film with a film thickness of 60 nm. The polyimide film was rubbed with artificial fiber cloth (roller diameter: 120mm, roller rotation number: 500rpm, moving speed: 30mm/sec, pushing length: 0.3mm, rubbing direction: inclined for the 3-layer IZO comb electrode 10˚ direction), perform ultrasonic irradiation in pure water for 1 minute to wash, and blow air to remove water droplets. Thereafter, drying was performed at 80° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film. Take these two substrates with liquid crystal alignment films as a set, apply (print) sealant on the substrate to leave the liquid crystal injection port, and attach the other substrate so that it faces the liquid crystal alignment film surface, and rub it The direction becomes anti-parallel. The sealant was then hardened to produce empty cells with a cell gap of 4 μm. By performing a reduced-pressure injection method on this air cell, liquid crystal MLC-3019 (manufactured by Merck & Co., Ltd.) was injected, and the injection port was sealed to obtain an FFS-type liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120°C for 1 hour and left at 23°C overnight before being used for evaluation of liquid crystal alignment.
[評估] 1.藉由長期交流驅動之殘像評估 準備與上述使用於殘像評估之液晶單元同樣之結構的液晶單元。 在將該液晶單元放置於高亮度背光上之狀態下,輸入頻率60Hz之±5V的交流電壓168小時。其後,使液晶單元之畫素電極與對向電極之間成短路狀態,在室溫中直接放置一天。 放置後,將液晶單元配置在與偏光軸呈直交的2片偏光板之間,在電壓無輸入之狀態下開背光燈,調整液晶單元的配置角度使透過光之亮度至最小。然後,自第1畫素的第2區域變得最暗的角度,使液晶單元轉動至第1區域變得最暗的角度時,該轉動角度作為角度Δ而算出。對於第2畫素亦同樣,比較第2區域與第1區域而算出同樣的角度Δ。 該角度Δ未達0.15˚時,表示良好液晶配向性。評估結果如表3所示。[evaluate] 1. Afterimage evaluation driven by long-term communication A liquid crystal cell having the same structure as the liquid crystal cell used for afterimage evaluation was prepared. With the liquid crystal unit placed on a high-brightness backlight, an AC voltage of ±5V with a frequency of 60Hz was input for 168 hours. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left directly at room temperature for one day. After placement, place the liquid crystal unit between two polarizing plates perpendicular to the polarization axis, turn on the backlight with no voltage input, and adjust the arrangement angle of the liquid crystal unit to minimize the brightness of the transmitted light. Then, when the liquid crystal cell is rotated from the angle at which the second area of the first pixel becomes darkest to the angle at which the first area becomes darkest, the rotation angle is calculated as the angle Δ. The same applies to the second pixel. The second area and the first area are compared to calculate the same angle Δ. When the angle Δ is less than 0.15˚, it indicates good liquid crystal alignment. The evaluation results are shown in Table 3.
2.累積電荷之緩和速度測定 將與上述(液晶單元之製作)同樣地所製作之液晶單元,設置於偏光軸配置成直交的2片偏光板之間,在將畫素電極與對向電極呈短路的同電位之狀態下,自2片偏光板下方照射LED背光,在2片偏光板上面,調節液晶單元的角度使所測定的LED背光透過光之亮度變成最小。其次,於該液晶單元一邊輸入頻率60Hz之交流電壓,一邊測定V-T曲線(電壓-透過率曲線),將相對透過率成為23%時的交流電壓作為驅動電壓而算出。 在殘像評估中,一邊使相對透過率成為23%而輸入頻率60Hz之交流電壓,一邊使液晶單元進行驅動,同時輸入1V之直流電壓,進行120分鐘驅動。其後,僅停止直流電壓之輸入,僅以交流電壓進一步進行15分鐘驅動。 自停止直流電壓之輸入的時間點,經過10分鐘後,若緩和至相對透過率為25%以下時評估定義為「良好」,若降低至相對透過率為26%以下需要10分鐘以上時,評估定義為「不良」。 然後,依據上述方法的殘像評估為在液晶單元之溫度為40℃之狀態的溫度條件下進行。2. Measurement of relaxation speed of accumulated charge A liquid crystal cell fabricated in the same manner as above (Preparation of a liquid crystal cell) is placed between two polarizing plates with polarization axes arranged at right angles, and the pixel electrode and the counter electrode are short-circuited and at the same potential. The LED backlight is illuminated from below the two polarizing plates, and the angle of the liquid crystal unit is adjusted above the two polarizing plates to minimize the measured brightness of the LED backlight transmitted light. Next, the V-T curve (voltage-transmittance curve) was measured while inputting an AC voltage with a frequency of 60 Hz to the liquid crystal cell, and the AC voltage when the relative transmittance became 23% was calculated as the driving voltage. In the afterimage evaluation, the liquid crystal cell was driven while the relative transmittance was set to 23% and an AC voltage with a frequency of 60 Hz was input. At the same time, a DC voltage of 1 V was input and the driving was performed for 120 minutes. Thereafter, only the input of DC voltage was stopped, and driving was continued for a further 15 minutes with only AC voltage. If the relative transmittance eases to less than 25% after 10 minutes from the time when the DC voltage input is stopped, the evaluation is defined as "good". If it takes more than 10 minutes to reduce the relative transmittance to less than 26%, the evaluation is Defined as "bad". Then, the afterimage evaluation based on the above method was performed under the temperature condition of the state where the temperature of the liquid crystal cell was 40°C.
3.黑水準評估 將與上述(液晶單元之製作)同樣地所製作之液晶單元,設置於偏光軸配置成直交的2片偏光板之間,在電壓無輸入的狀態下開背光燈,調整液晶單元的配置角度至透過光之亮度變成最小。將該液晶單元使用Hamamatsu Photonics公司製之Digital CCD camera「C8800-21C」進行觀察,將攝入的圖像使用同公司的解析軟體「ExDcam Image capture Software」,進行亮度之數值化。若該液晶單元之亮度值為580以下時評估為「良好」,在此以上者評估為「不良」。3. Black level assessment The liquid crystal cell produced in the same manner as above (preparation of liquid crystal cell) is placed between two polarizing plates with polarization axes arranged at right angles. The backlight is turned on with no voltage input, and the arrangement angle of the liquid crystal cell is adjusted to The brightness of the transmitted light becomes minimal. This liquid crystal cell was observed using a Digital CCD camera "C8800-21C" manufactured by Hamamatsu Photonics, and the brightness of the captured image was quantified using the company's analysis software "ExDcam Image capture Software". If the brightness value of the liquid crystal unit is 580 or less, it is evaluated as "good", and if it is above this, it is evaluated as "poor".
4.重工性之評估 將本發明之液晶配向劑以旋塗塗布方式塗布於ITO基板上。在60℃之加熱板上進行1分鐘30秒的乾燥後,在230℃之熱風循環式烤箱中進行20分鐘燒成,形成膜厚100nm之塗膜。其後將加熱至35℃之重工材(KR-31)所製作的基板進行600秒之浸漬而使其顯像後,以超純水進行30秒的流水洗淨。其後經吹氣乾燥後觀察其殘膜量。此時將殘膜時的情況評估為「良好」,將有殘膜之情況評估為「不良」。4. Evaluation of heavy workability The liquid crystal alignment agent of the present invention is coated on the ITO substrate by spin coating. After drying on a hot plate at 60°C for 1 minute and 30 seconds, it was fired in a hot air circulation oven at 230°C for 20 minutes to form a coating film with a thickness of 100nm. Thereafter, the substrate made of heavy industry material (KR-31) heated to 35°C was immersed for 600 seconds to develop, and then rinsed with ultrapure water for 30 seconds. After air blowing and drying, the remaining film amount was observed. At this time, the condition with residual film is evaluated as "good", and the condition with residual film is evaluated as "poor".
將上述1~4的實驗之結果記載於表3。 [產業上可利用性]The results of the above-mentioned experiments 1 to 4 are shown in Table 3. [Industrial availability]
本發明之液晶配向劑在IPS驅動方式或FFS驅動方式等廣範圍的液晶顯示元件中之液晶配向膜的形成上為有用。 且,在2019年2月13日申請的日本專利申請2019-023807號及在2019年4月23日申請的日本專利申請2019-082233號之說明書、申請專利範圍、圖面及發明摘要的所有內容皆引用於此,作為本發明之說明書的揭示內容而記載。The liquid crystal alignment agent of the present invention is useful in the formation of liquid crystal alignment films in a wide range of liquid crystal display elements such as IPS drive systems or FFS drive systems. Furthermore, all contents of the specification, patent scope, drawings and abstract of the Japanese Patent Application No. 2019-023807 filed on February 13, 2019 and the Japanese Patent Application No. 2019-082233 filed on April 23, 2019 All are cited here and are described as the disclosure content of the specification of the present invention.
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