JP5240207B2 - Liquid crystal aligning agent and liquid crystal display element using the same - Google Patents

Description

  The present invention relates to a liquid crystal alignment treatment agent used when producing a liquid crystal alignment film and a liquid crystal display element using the same.

  Currently, as a liquid crystal alignment film of a liquid crystal display element, a liquid crystal alignment treatment agent (also referred to as a liquid crystal alignment agent) mainly composed of a polyimide precursor such as polyamic acid or a solution of soluble polyimide is applied to a glass substrate and fired. A so-called polyimide-based liquid crystal alignment film is mainly used.

  The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, as liquid crystal display elements have become higher in definition, the liquid crystal alignment film used in the liquid crystal alignment film has a high voltage holding ratio and a direct current voltage due to demands such as a reduction in contrast of the liquid crystal display elements and a reduction in the afterimage phenomenon. The characteristics that the residual charge when applied is small and / or the residual charge accumulated by the DC voltage is quickly relaxed have become increasingly important.

  In a polyimide-based liquid crystal alignment film, a liquid crystal aligning agent containing a tertiary amine having a specific structure in addition to polyamic acid or an imide group-containing polyamic acid was used as a short time until the afterimage generated by direct current voltage disappears. There are known ones (for example, see Patent Document 1) and those using a liquid crystal aligning agent containing a soluble polyimide using a specific diamine having a pyridine skeleton as a raw material (for example, see Patent Document 2). In addition to polyamic acid and its imidized polymer, a compound containing one carboxylic acid group in the molecule, assuming that the voltage holding ratio is high and the time until the afterimage generated by direct current voltage disappears is short , Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic anhydride group in the molecule and a compound containing one tertiary amine group in the molecule (for example, a patent Document 3) is known.

  However, in recent years, large-screen, high-definition liquid crystal televisions have been widely put into practical use, and liquid crystal display elements in such applications are more effective against afterimages than conventional displays that mainly display characters and still images. The requirements are becoming stricter, and characteristics that can withstand long-term use in harsh usage environments are required. Therefore, the liquid crystal alignment film used there is required to have a higher reliability than before, and the electrical characteristics of the liquid crystal alignment film not only have good initial characteristics, but also, for example, at high temperatures. There is a need to maintain good properties even after prolonged exposure.

JP 9-316200 A JP-A-10-104633 JP-A-8-76128

  It is an object of the present invention to provide a liquid crystal alignment film that has a high voltage holding ratio when the liquid crystal alignment film is formed and that can quickly relieve residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time. Providing a liquid crystal aligning agent that can be obtained, and further having a liquid crystal aligning film obtained by using the liquid crystal aligning agent, and a highly reliable liquid crystal display element that can withstand long-term use in harsh use environments Is to provide.

The present inventor has intensively studied to achieve the above object, and has found a liquid crystal aligning agent that achieves this. The present invention is based on such knowledge and has the following gist.
(1) A liquid crystal aligning agent containing a copolymer obtained by reacting a diamine component (A) and a diamine compound (B) and a tetracarboxylic dianhydride component.
Diamine compound (A): a diamine compound represented by the following formula [1],
Diamine compound (B): a diamine compound having a carboxyl group in the molecule.

（式［１］中、Ｘ_１は−Ｏ−、−ＮＱ^１−、−ＣＯＮＱ^１−、−ＮＱ^１ＣＯ−、−ＣＨ_２Ｏ−、及び−ＯＣＯ−からなる群より選ばれる少なくとも１種の２価の有機基であり、Ｑ^１は水素原子又は炭素数１から３のアルキル基であり、Ｘ_２は単結合、又は炭素数１から２０の脂肪族炭化水素基、非芳香族環式炭化水素基、及び芳香族炭化水素基からなる群より選ばれる少なくとも１種の２価の有機基であり、Ｘ_３は単結合、又は−Ｏ−、−ＮＱ^２−、−ＣＯＮＱ^２−、−ＮＱ^２ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、及び−Ｏ（ＣＨ_２）_ｍ−（ｍは１から５の整数である）からなる群より選ばれる少なくとも１種の２価の有機基であり、Ｑ^２は水素原子又は炭素数１から３のアルキル基（ただし、Ｘ _３ が−ＮＱ ^２ −である場合は、Ｑ ^２ は炭素数１から３のアルキル基）であり、Ｘ_４は窒素含有芳香族複素環であり、ｎは１から４の整数である）。
（２）式［１］が、下記の式［１ａ］から式［１ｆ］で表される化合物からなる群より選ばれる少なくとも１種である上記（１）に記載の液晶配向処理剤。

(Wherein [1], _{X 1} is ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one selected from the group consisting of -OCO- A divalent organic group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic cyclic carbonization hydrogen radicals, and at least one divalent organic group selected from the group consisting of an aromatic hydrocarbon group, _{X 3} is a single bond or ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ ² CO—, —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5), and at least one divalent organic group selected from the group consisting of Q ² is an alkyl group (having one to three the number of hydrogen atoms or carbon, _{X 3} is -NQ ² - if it is , Q ² is an alkyl group) having 1 to 3 carbon atoms, X ₄ is a nitrogen-containing aromatic heterocyclic ring, n is an integer from 1 to 4).
(2) The liquid crystal aligning agent according to the above (1), wherein the formula [1] is at least one selected from the group consisting of compounds represented by the following formulas [1a] to [1f].

（式中、Ｑ^１は水素原子又は炭素数１から３のアルキル基であり、Ｘ_２は単結合、又は炭素数１から２０の脂肪族炭化水素基、非芳香族環式炭化水素基、及び芳香族炭化水素基からなる群より選ばれる少なくとも１種の２価の有機基であり、Ｘ_３は単結合、又は−Ｏ−、−ＮＱ^２−、−ＣＯＮＱ^２−、−ＮＱ^２ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、及び−Ｏ（ＣＨ_２）_ｍ−（ｍは１から５の整数である）からなる群より選ばれる少なくとも１種の２価の有機基であり、Ｑ^２は水素原子又は炭素数１から３のアルキル基（ただし、Ｘ _３ が−ＮＱ ^２ −である場合は、Ｑ ^２ は炭素数１から３のアルキル基）であり、Ｘ_４は窒素含有芳香族複素環であり、ｎは１から４の整数である）。
（３）式［１ａ］から式［１ｆ］中のＸ_２が単結合、炭素数１から３の直鎖アルキレン基、又はベンゼン環である上記（２）に記載の液晶配向処理剤。
（４）式［１ａ］から式［１ｆ］中のＸ_３が単結合、−ＯＣＯ−、又は−ＯＣＨ_２−である上記（２）又は上記（３）に記載の液晶配向処理剤。
（５）式［１ａ］から式［１ｆ］中のＸ_４がイミダゾール環、ピリジン環、又はピリミジン環である上記（２）から上記（４）のいずれかに記載の液晶配向処理剤。
（６）式［１ａ］から式［１ｆ］中のｎが１又は２の整数である上記（２）から上記（５）のいずれかに記載の液晶配向処理剤。
（７）式［１ａ］から式［１ｆ］中のＸ_２が炭素数１から１０の直鎖又は分岐アルキレン基、シクロへキサン環、ベンゼン環、及びナフタレン環からなる群より選ばれる少なくとも１種であり、Ｘ_３が単結合、−Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、及び−Ｏ（ＣＨ_２）_ｍ−（ｍは１から５の整数である）からなる群より選ばれる少なくとも１種であり、Ｘ_４がピロール環、イミダゾール環、ピラゾール環、ピリジン環、ピリミジン環、ピリダジン環、トリアジン環、トリアゾール環、ピラジン環、ベンズイミダゾール環、及びベンゾイミダゾール環からなる群より選ばれる少なくとも１種であり、ｎが１又は２の整数である上記（２）記載の液晶配向処理剤。
（８）式［１ａ］から式［１ｆ］中のＸ_２が単結合、炭素数１から５の直鎖又は分岐アルキレン基、及びベンゼン環からなる群より選ばれる少なくとも１種であり、Ｘ_３が単結合、−Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、及び−Ｏ（ＣＨ_２）_ｍ−（ｍは１から５の整数である）からなる群より選ばれる少なくとも１種であり、Ｘ_４がピロール環、イミダゾール環、ピラゾール環、ピリジン環、及びピリミジン環からなる群より選ばれる少なくとも１種であり、ｎが１又は２の整数である上記（２）に記載の液晶配向処理剤。
（９）式［１ａ］から式［１ｆ］中のＸ_２が単結合、炭素数１から３の直鎖アルキレン基、及びベンゼン環からなる群より選ばれる少なくとも１種であり、Ｘ_３が単結合、−ＯＣＯ−、及び−ＯＣＨ_２−からなる群より選ばれる少なくとも１種であり、Ｘ_４がイミダゾール環、ピリジン環、及びピリミジン環からなる群より選ばれる少なくとも１種であり、ｎが１又は２の整数である上記（２）に記載の液晶配向処理剤。
（１０）分子内にカルボキシル基を有するジアミン化合物が、下記の式［２］で表されるジアミンである上記（１）から上記（９）のいずれかに記載の液晶配向処理剤。

(Wherein Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and at least one divalent organic group selected from the group consisting of an aromatic hydrocarbon group, _{X 3} is a single bond or ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO-, At least one divalent organic group selected from the group consisting of —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5), and Q ² is hydrogen. An atom or an alkyl group having 1 to 3 carbon atoms (provided that when X ₃ is —NQ ² —, Q ² is an alkyl group having 1 to 3 carbon atoms) , and X ₄ is a nitrogen-containing aromatic heterocyclic ring. And n is an integer from 1 to 4.
(3) The liquid crystal aligning agent according to the above (2), wherein X ₂ in the formulas [1a] to [1f] is a single bond, a linear alkylene group having 1 to 3 carbon atoms, or a benzene ring.
(4) The liquid crystal aligning agent according to the above (2) or (3), wherein X ₃ in the formulas [1a] to [1f] is a single bond, —OCO—, or —OCH ₂ —.
(5) The liquid crystal aligning agent according to any one of (2) to (4) above, wherein X ₄ in the formulas [1a] to [1f] is an imidazole ring, a pyridine ring, or a pyrimidine ring.
(6) The liquid crystal aligning agent according to any one of (2) to (5) above, wherein n in the formulas [1a] to [1f] is an integer of 1 or 2.
(7) At least one selected from the group consisting of a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring, and a naphthalene ring, wherein X ₂ in the formulas [1a] to [1f] is And X ₃ is a single bond, —O—, —CONH—, —NHCO—, —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5). is at least one selected from the group consisting, X ₄ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and a benzimidazole ring The liquid-crystal aligning agent of said (2) description which is at least 1 sort (s) chosen from the group which consists of, and n is an integer of 1 or 2.
(8) X ₂ in the formulas [1a] to [1f] is at least one selected from the group consisting of a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, and a benzene ring, and X ₃ Is selected from the group consisting of a single bond, —O—, —CONH—, —NHCO—, —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer from 1 to 5). In the above (2), at least one is selected, X ₄ is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring, and n is an integer of 1 or 2. The liquid crystal aligning agent of description.
(9) X ₂ in the formulas [1a] to [1f] is at least one selected from the group consisting of a single bond, a linear alkylene group having 1 to 3 carbon atoms, and a benzene ring, and X ₃ is a single group. And at least one selected from the group consisting of a bond, —OCO—, and —OCH ₂ —, X ₄ is at least one selected from the group consisting of an imidazole ring, a pyridine ring, and a pyrimidine ring, and n is 1. Or the liquid-crystal aligning agent as described in said (2) which is an integer of 2.
(10) The liquid-crystal aligning agent in any one of said (1) to said (9) whose diamine compound which has a carboxyl group in a molecule | numerator is diamine represented by following formula [2].

（式［２］中、Ｘ_５は炭素数６から３０の芳香族環を有する有機基であり、ｎは１から４の整数である。）
（１１）式［２］のジアミン化合物が、下記の式［３］から式［７］からなる群より選ばれる少なくとも１種のジアミン化合物である上記（１０）に記載の液晶配向処理剤。

(In the formula [2], X ₅ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.)
(11) The liquid crystal aligning agent according to the above (10), wherein the diamine compound of the formula [2] is at least one diamine compound selected from the group consisting of the following formulas [3] to [7].

（式［３］中、ｍ１は１から４の整数であり、式［４］中、Ｘ_６は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ２及びｍ３はそれぞれ０から４の整数であり、かつｍ２＋ｍ３は１から４の整数を示し、式［５］中、ｍ４及びｍ５はそれぞれ１から５の整数であり、式［６］中、Ｘ_７は炭素数１から５の直鎖又は分岐アルキル基であり、ｍ６は１から５の整数であり、式［７］中、Ｘ_８は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_７は１から４の整数である。）
（１２）式［３］中、ｍ１が１から２の整数である上記（１１）に記載の液晶配向処理剤。
（１３）式［４］中、Ｘ_６が単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、又は−ＯＣＯ−であり、ｍ２及びｍ３は共に１の整数である上記（１１）に記載の液晶配向処理剤。
（１４）式［７］中、Ｘ_８は単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、又は−ＯＣＯ−であり、ｍ_７は１から２の整数である上記（１１）に記載の液晶配向処理剤。
（１５）ジアミン成分中、式［１］で表されるジアミンの１モルに対して、分子内にカルボキシル基を有するジアミンが、０．０１から９９モルである上記（１）から上記（１４）のいずれかに記載の液晶配向処理剤。
（１６）液晶配向処理剤中に含まれる溶媒中の５から８０質量％が貧溶媒である上記（１）から上記（１５）のいずれかに記載の液晶配向処理剤。
（１７）液晶配向処理剤中の共重合体がポリアミド酸を脱水閉環させて得られるポリイミドである上記（１）から上記（１６）のいずれかに記載の液晶配向処理剤。
（１８）上記（１）から上記（１７）のいずれかに記載の液晶配向処理剤を用いて得られる液晶配向膜。
（１９）上記（１８）に記載の液晶配向膜を有する液晶表示素子。

(In formula [3], m1 is an integer of 1 to 4, and in formula [4], X ₆ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH _2- , -COO-, -OCO-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-, m2 and m3 are each an integer of 0 to 4, and m2 + m3 is 1 to 4 It indicates the integer, wherein [5], m4 and m5 is an integer of from respectively 1 5, wherein [6], X ₇ is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, m6 an integer from 1 to 5, wherein [7], _{X 8} is a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 - _{-C (CF 3) 2 -,} - O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH 3) -, or -N _(CH 3) a CO-, _{m 7} is an integer of 1 to 4).
(12) The liquid-crystal aligning agent as described in said (11) whose m1 is an integer of 1 to 2 in Formula [3].
(13) In Formula [4], X ₆ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —NH—, —N. _{(CH 3) -, - CONH} -, - NHCO -, - COO-, or a -OCO-, liquid crystal alignment treating agent according to (11) m2 and m3 are both the integer 1.
(14) In formula [7], X ₈ is a single bond, —CH ₂ —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —. , —COO—, or —OCO—, and m ₇ is an integer of 1 to 2, according to (11) above.
(15) In the diamine component, the diamine having a carboxyl group in the molecule is 0.01 to 99 mol with respect to 1 mol of the diamine represented by the formula [1]. The liquid-crystal aligning agent in any one of.
(16) The liquid crystal aligning agent according to any one of (1) to (15) above, wherein 5 to 80% by mass in the solvent contained in the liquid crystal aligning agent is a poor solvent.
(17) The liquid crystal aligning agent according to any one of (1) to (16), wherein the copolymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and ring-closing polyamic acid.
(18) A liquid crystal alignment film obtained using the liquid crystal alignment treatment agent according to any one of (1) to (17).
(19) A liquid crystal display device having the liquid crystal alignment film according to (18).

  The liquid crystal aligning agent of the present invention can be obtained by a relatively simple method. By using the liquid crystal aligning agent, the voltage holding ratio is high and even after being exposed to a high temperature for a long time. Thus, a liquid crystal alignment film can be obtained in which the residual charge accumulated by the direct current voltage is quickly relaxed. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.

The present invention is described in detail below.
The present invention uses a liquid crystal aligning agent containing a copolymer obtained by reacting a diamine component (A) and a diamine component containing the diamine compound (B) with tetracarboxylic dianhydride, and the liquid crystal aligning agent. And a liquid crystal display element having the liquid crystal alignment film.
In that case, a diamine compound (A) is a diamine compound represented by Formula [1], and a diamine compound (B) is a diamine compound which has a carboxyl group in a molecule | numerator.

The diamine compound (A) used in the present invention has a nitrogen-containing aromatic heterocycle in the side chain. The nitrogen-containing aromatic heterocycle functions as an electron hopping site due to its conjugated structure, and therefore, the movement of electric charges can be promoted in the liquid crystal alignment film. Furthermore, the nitrogen-containing aromatic heterocycle is bonded to the carboxyl group of the diamine compound (B) by an electrostatic interaction such as salt formation or hydrogen bond, so that the carboxyl group and the nitrogen-containing aromatic heterocycle There is a charge transfer between them. Therefore, the charge transferred to the nitrogen-containing aromatic heterocyclic moiety can efficiently move within and between the molecules of the copolymer.
As described above, the liquid crystal aligning agent of the present invention has a high voltage holding ratio when formed into a liquid crystal alignment film, and the residual charge accumulated by a DC voltage even after being exposed to a high temperature for a long time. There is an effect that relaxation is fast.

<Diamine component>
[Diamine compound (A)]
The diamine compound (A) used in the present invention is a diamine compound represented by the following formula [1].

式［１］中、Ｘ_１は−Ｏ−、−ＮＱ^１−、−ＣＯＮＱ^１−、−ＮＱ^１ＣＯ−、−ＣＨ_２Ｏ−、及び−ＯＣＯ−からなる群より選ばれる少なくとも１種の２価の有機基であり、Ｑ^１は水素原子又は炭素数１から３のアルキル基であり、Ｘ_２は単結合、又は炭素数１から２０の脂肪族炭化水素基、非芳香族環式炭化水素基、及び芳香族炭化水素基からなる群より選ばれる少なくとも１種の２価の有機基であり、Ｘ_３は単結合、又は−Ｏ−、−ＮＱ^２−、−ＣＯＮＱ^２−、−ＮＱ^２ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、及び−Ｏ（ＣＨ_２）_ｍ−（ｍは１から５の整数である）からなる群より選ばれる少なくとも１種の２価の有機基であり、Ｑ^２は水素原子又は炭素数１から３のアルキル基（ただし、Ｘ _３ が−ＮＱ ^２ −である場合は、Ｑ ^２ は炭素数１から３のアルキル基）であり、Ｘ_４は窒素含有芳香族複素環であり、ｎは１から４の整数である。

Wherein [1], _{X 1} is ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one 2 selected from the group consisting of -OCO- A valent organic group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic cyclic hydrocarbon group, and at least one divalent organic group selected from the group consisting of an aromatic hydrocarbon group, _{X 3} is a single bond or ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO-, and _{-O (CH 2) m - (} m is from 1 5 is an integer) at least one divalent organic group selected from the group consisting of, Q ² is an alkyl group (having one to three the number of hydrogen atoms or carbon, _{X 3} is -NQ ² - if it is the Q ² is an alkyl group) having 1 to 3 carbon atoms, X ₄ is a nitrogen-containing aromatic heterocyclic ring, n is an integer from 1 to 4.

The bonding position of the two amino groups (—NH ₂ ) in the formula [1] is not limited. Specifically, when n is an integer of _{1, with} respect to the side chain linking group (X ₁ ), 2, 3 positions, 2, 4 positions, 2, 5 positions on the benzene ring, 2, 6 positions, 3 and 4 positions, and 3 and 5 positions. When n is an integer of 2, the following positions are listed. When the side chain linking group (X ₁ ) is located at 2 positions on the benzene ring with respect to the side chain linking group (X ₁ ), the bonding positions of the two amino groups are the positions 3 and 4, 3 , 5 position, 3, 6 position, and 4, 5 position. In addition, when there is a side chain linking group (X ₁ ) at position 3 on the benzene ring with respect to the side chain linking group (X ₁ ), the bonding positions of the two amino groups are positions 2 and 4 , 2, 5 positions, 4, 5 positions, and 4, 6 positions. Furthermore, when there is a side chain linking group (X ₁ ) at position 4 on the benzene ring with respect to the side chain linking group (X ₁ ), the two amino groups are bound at positions 2, 3 , 2, 5 position, 2, 6 position, 3, 5 position. When n is an integer of 3, the following positions are listed. When the side chain linking group (X ₁ ) is located at 2, 3 positions on the benzene ring with respect to the side chain linking group (X ₁ ), the bonding positions of the two amino groups are positions 4 and 5 , 4, 6 positions. In addition, when the side chain linking group (X ₁ ) is located at 2, 4 positions on the benzene ring with respect to the side chain linking group (X ₁ ), the bonding positions of the two amino groups are 3, 5 , 3, 6 and 5, 6 positions. Furthermore, when there are side chain bonding groups (X ₁ ) at positions 3 and 5 on the benzene ring with respect to the side chain bonding group (X ₁ ), the bonding positions of the two amino groups are 2, 4 Position. When n is an integer of 4, the following positions are listed. When there are side chain bonding groups (X ₁ ) at positions 2, 3, and 4 on the benzene ring with respect to the side chain bonding group (X ₁ ), the bonding positions of the two amino groups are 5, 6 Position. In addition, when there are side chain bonding groups (X ₁ ) at positions 2, 4, and 5 on the benzene ring with respect to the side chain bonding group (X ₁ ), the bonding positions of the two amino groups are 3 , 6 positions. Further, when the side chain linking group (X ₁ ) is located at positions 2, 4, 6 on the benzene ring with respect to the side chain linking group (X ₁ ), the bonding positions of the two amino groups are 3 , 5 positions. Among these, taking into consideration the reactivity when synthesizing the polyamic acid and the ease when synthesizing the diamine compound, when n is an integer of 1, the bonding positions of the two amino groups are 2,4. , 2, 5 position, 3, 5 position, or side chain linking group (X ₁ ) when n is an integer of 2, side chain linking group at position 3 on the benzene ring In the case where (X ₁ ) is present, the positions where the binding positions of the two amino groups are 4, 6 are particularly preferable.

Wherein [1], _{X 1} is ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one 2 selected from the group consisting of -OCO- Valent organic group. Among ^{them, -O -, - NQ 1 -} , - CONQ 1 -, - NQ 1 CO- is preferred. Q ¹ has the same meaning as defined in formula [1].

More specific structures of X ₁ include the following formulas [1a] to [1f].

Among these, the formula [1a], the formula [1b], the formula [1c], and the formula [1d] are preferable. Q ¹ has the same meaning as defined in formula [1].
In the formula [1], X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. An aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferred.

Specific examples of the non-aromatic cyclic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, Cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydro A naphthalene ring, a norbornene ring, an adamantane ring, etc. are mentioned.
Specific examples of the aromatic hydrocarbon group include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, and phenalene ring.

Preferred X ₂ in the formula [1] is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, or a cyclopentane ring. , Cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, and anthracene ring, more preferably a single bond, linear or branched alkylene having 1 to 10 carbon atoms Group, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a fluorene ring, and an anthracene ring, and more preferably a single bond and a straight chain having 1 to 10 carbon atoms. Chain or branched alkylene group, cyclohexane ring, benzene ring, naphtha A len ring, particularly preferably a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, and a benzene ring. Most preferably, they are a single bond, a linear alkylene group having 1 to 3 carbon atoms, or a benzene ring.

Wherein [1], _{X 3} is a single bond or ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO-, and -O _{(CH 2) m} - (M is an integer of 1 to 5) is at least one divalent organic group selected from the group consisting of a single bond, —O—, —CONQ ² —, —NQ ² CO—, —COO—, —OCO—, —O (CH ₂ ) _m — (m is an integer of 1 to 5). Most preferably, a single bond, -OCO-, or -OCH ₂ - is. Q ² has the same meaning as defined in formula [1].

In the formula [1], X ₄ is a nitrogen-containing aromatic heterocyclic ring, and nitrogen containing at least one structure selected from the group consisting of the following formulas [[2a], formulas [2b] and formulas [2c] Containing aromatic heterocycle.

式［２ｃ］中、Ｙ_１は炭素数１から５の直鎖又は分岐アルキル基である。

In formula [2c], Y ₁ is a linear or branched alkyl group having 1 to 5 carbon atoms.

Preferable X ₄ in the formula [1] is a pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring. , Pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring Acridine ring, more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring , Triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benz An imidazole ring and a benzimidazole ring are preferable, and a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring are particularly preferable. Most preferred is an imidazole ring, a pyridine ring, or a pyrimidine ring.

Further, _{X 3} is formulas contained in _{X 4} [2a], it is preferably bonded to a substituent not adjacent to Equation [2b] and the formula [2c].
In the formula [1], n is an integer of 1 to 4, and preferably an integer of 1 to 3 from the viewpoint of reactivity with tetracarboxylic dianhydride. Most preferably, n is an integer of 1 or 2.

A preferred combination of _{X 1, X 2, X 3} , X 4 and n in the formula [1], _{X 1} is ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O -And -OCO-, and at least one selected from the group consisting of -OCO-, wherein X ₂ is a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, and cyclobutane X ₃ is at least one selected from the group consisting of a ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, and an anthracene ring. single ^{bond, -O -, - NQ 2 -} , - CONQ 2 -, - NQ 2 CO -, - COO -, - OCO-, and -O _{(CH 2)} m - ₍ m is at least one selected from the group consisting of 1 to 5), and X ₄ is a pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline Ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, tinoline ring, phenanthroline ring, indole ring, quinoxaline It is at least one selected from the group consisting of a ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridine ring, and n is an integer of 1 or 2.

More preferably _X 1 in the formula _{[1], X 2, X} 3, X 4 and n combinations of, _{X 1} is ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO-, and -CH _And at least one selected from the group consisting of ₂ O—, wherein X ₂ is a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring a benzene ring, a naphthalene ring, a fluorene ring, and at least one selected from the group consisting of an anthracene ring, _{X 3} is a single ^{bond, -O -, - NQ 2 -} , - CONQ 2 -, - NQ 2 CO- , -COO -, - OCO-, and _{-O (CH 2) m - (} m is from 1 5 is an integer) is at least one selected from the group consisting of, _{X 4} is a pyrrole ring, an imidazole ring At least one selected from the group consisting of pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, and benzimidazole ring And n is an integer of 1 or 2.

Further preferred compounds of formula _X 1 in _{[1], X 2, X} 3, the combination of _{X 4} and n, _{X 1} is ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 It is at least one selected from the group consisting of O- and -OCO-, and X ₂ is selected from the group consisting of a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring, and a naphthalene ring. is at least one selected, _{X 3} is a single ^{bond, -O -, - CONQ 2 -} , - NQ 2 CO -, - COO -, - OCO-, and _{-O (CH 2) m - (} m is 1 is at least one selected from the group consisting of 5 of an integer) from, X ₄ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, Baie 'S imidazole ring, and at least one selected from the group consisting of benzimidazole ring, n is an integer of 1 or 2.

Particularly preferred _{X 1, X 2, X 3} , the combination of _{X 4} and n in the formula [1], _{X 1} is ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO-, and -CH ₂ is at least one selected from the group consisting of O-, X ₂ is a single bond, at least one selected from the group consisting of linear or branched alkylene group, and benzene rings having 1 to 5 carbon atoms, X ₃ is a single ^{bond, -O -, - CONQ 2 -} , - NQ 2 CO -, - COO -, - OCO-, and -O _{(CH 2)} m - consists of (m is an integer from 1 to 5) At least one selected from the group, X ₄ is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring, and n is an integer of 1 or 2.

The most preferred _X 1 in the formula _{[1], X 2, X} 3, X 4 and n combinations of, _{X 1} is ^{-O -, - NQ 1 -,} - CONQ 1 -, and the group consisting of ^-NQ 1 CO- is at least one more selected, X ₂ is a single bond, a straight-chain alkylene group having 1 to 3 carbon atoms, and at least one selected from the group consisting of benzene ring, X ₃ is a single bond, -OCO- And at least one selected from the group consisting of —OCH ₂ —, X ₄ is at least one selected from the group consisting of an imidazole ring, a pyridine ring, and a pyrimidine ring, and n is an integer of 1 or 2. is there.

Particularly preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ and n in the formula [1] are as shown in Tables 1 to 3 below. Q ¹ and Q ² are the same as defined in formula [1].

[Synthesis Method of Diamine Compound (A)]
Although the method to manufacture the diamine compound represented by Formula [1] of this invention is not specifically limited, The following method is mentioned as a preferable method.

The specific diamine compound of the present invention can be obtained by synthesizing a dinitro compound represented by the formula [4], further reducing the nitro group and converting it to an amino group. There is no particular limitation on the method for reducing the dinitro compound, and usually palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran, dioxane, There is a method in which hydrogen gas, hydrazine, hydrogen chloride, or the like is used in an alcohol-based solvent. X ₁ , X ₂ , X ₃ , X ₄ and n in the formula [4] are as defined in the formula [1].

In the dinitro compound of the formula [4], X ₂ and X ₄ are bonded via X ₃ and then the dinitro moiety is bonded via X ₁ , and the dinitro moiety is bonded to X ₂ via the linking moiety X _1. It can be obtained by, for example, a method of bonding to X ₄ via X ₃ .

X ₁ represents —O— (ether bond), —NQ ¹ — (amino bond), —CONQ ¹ — (amide bond), —NQ ¹ CO— (reverse amide bond), —CH ₂ O— (methylene ether bond). And at least one linking group selected from the group consisting of —OCO— (reverse ester bond), and these linking groups can be formed by ordinary organic synthetic techniques. Q ^{1 of} each linking group is as defined in the formula [1].

For example, when X ₁ is an ether or methylene ether bond, a corresponding dinitro group-containing halogen derivative is reacted with a hydroxyl group derivative containing X ₂ , X ₃ and X ₄ in the presence of an alkali, or a dinitro group-containing hydroxyl group derivative , X ₂ , X ₃ and X ₄ may be reacted in the presence of an alkali.
In the case of an amino bond, a method of reacting a corresponding dinitro group-containing halogen derivative with an amino group-substituted derivative containing X ₂ , X ₃ and X ₄ in the presence of an alkali can be mentioned.

In the case of a reverse ester bond, a method of reacting a corresponding dinitro group-containing hydroxyl group derivative with an acid chloride containing X ₂ , X ₃ and X ₄ in the presence of an alkali can be mentioned.
Examples of the amide bond include a method in which a corresponding dinitro group-containing acid chloride is reacted with an amino group-substituted product containing X ₂ , X ₃ and X ₄ in the presence of an alkali.
In the case of a reverse amide bond, a method in which a corresponding dinitro group-containing amino group-substituted product and an acid chloride product containing X ₂ , X ₃ and X ₄ are reacted in the presence of an alkali can be mentioned.

  Specific examples of dinitro group-containing halogen derivatives and dinitro group-containing derivatives include 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrofluorobenzene, 3,5-dinitrobenzoic acid chloride, 3,5 -Dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, 3,5-dinitrobenzyl chloride, 2,4-dinitrobenzyl chloride, 3,5-dinitrobenzyl alcohol, 2,4- Dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol, 2,4- And dinitrophenylacetic acid. In consideration of availability of raw materials and reaction, one or more kinds can be selected and used.

[Diamine compound (B)]
The diamine compound (B) used in the present invention is a diamine compound having a carboxyl group in the molecule. Although the specific structure is not particularly limited, the compound represented by the formula [2] is preferable.

式［２］中、Ｘ_５は炭素数６から３０の芳香族環を有する有機基であり、ｎは１から４の整数である。

In formula [2], X ₅ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.

  If formula [2] is specifically shown, the following formulas [3] to [7] are exemplified.

In Formula [3], m1 is an integer of 1 to 4, and in Formula [4], X ₆ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —. _{CF 2 -, - C (CF} 3) 2 -, - O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH2- , -COO-, -OCO-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-, m2 and m3 are each an integer from 0 to 4, and m2 + m3 is an integer from 1 to 4 are shown, wherein [5], an integer of 5 from each m4 and m5 1, wherein [6], _{X 7} is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, m6 from 1 5 is an integer, wherein [7], _{X 8} is a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 -, - _{(CF 3) 2 -, -} O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH2 -, - COO -, - OCO—, —CON (CH ₃ ) —, or —N (CH ₃ ) CO—, and m ₇ represents an integer of 1 to 4.

In the structure of formula [3] to formula [7], preferably, in formula [3], m1 is an integer of 1 to 2, in formula [4], X ₆ is a single bond, —CH ₂ —, _{-C 2 H 4 -, - C} (CH 3) 2 -, - O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO -, - COO-, or - A structure in which both m2 and m3 are integers of 1, and in formula [7], X ₈ is a single bond, —CH ₂ —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, or —OCO—, and m ₇ is a structure that is an integer of 1 to 2.

  Specific examples of the diamine compound (B) include compounds of the following formulas [8] to [18].

In the formula [17], X ₉ is a single bond, —CH ₂ —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO. -, or a -OCO-, where _{[18], X 10} is a single _{bond, -CH 2 -, - O -} , - CO -, - NH -, - CONH -, - NHCO -, - CH 2 O _{-, - OCH 2 -, -} COO-, or -OCO-.

[Other diamine compounds]
In this invention, unless the effect of this invention is impaired, other diamine compounds other than a diamine compound (A) and a diamine compound (B) can be used together as a diamine component. Specific examples are given below.

  p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 , 6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy -4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'- Lifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl, 4,4′-diamino Diphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, 2,3′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane Bis (3-aminophenyl) silane , Dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, 3,3′-thiodianiline, 4,4′-diaminodiphenylamine, 3,3 ′ -Diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3 ' -Diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4, 4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzo Phenone, 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8- Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3 -Aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4aminophenyl) butane, 1,4-bis ( 3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) ) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4- Aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′-[1,4-phenylenebis (methylene)] dianiline, 4,4 ′-[1,3-phenylenebis (methylene) )] Dianiline, 3,4 ′-[1,4-phenylenebis (methylene)] dianiline, 3,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,3 ′-[1,4- Phenylenebis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylene [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis ( 4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-amino Phenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-amino) Benzamide), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1, 4-phenylene) bis (3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenzamide), N, N′-bis (4-aminophenyl) terephthalamide, N, N '-Bis (3-aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4- Aminophenyl) anthracene, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4 -Aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) Nyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-amino) Phenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, , 9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane. Bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and the like.

  Examples of the diamine include a diamine having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a macrocyclic substituent composed of these in the side chain of the diamine. Examples include diamine compounds represented by the formula [DA26] from DA1].

（式［ＤＡ１］から式［ＤＡ５］中、Ｒ_１は、炭素数１以上２２以下のアルキル基又はフッ素含有アルキル基である。）

(In Formula [DA1] to Formula [DA5], R ₁ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.)

In the formula [DA6] to formula [DA9], R ₂ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, or —NH—. , R ₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group. )

(In Formula [DA10] and Formula [DA11], R ₄ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—, and R ₅ represents the number of carbon atoms. 1 to 22 alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups.)

(In formula [DA12] to formula [DA14], R ₆ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, — OCH ₂ — or —CH ₂ — is shown, and R ₇ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.

(In Formula [DA15] and Formula [DA16], R ₈ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, — OCH ₂ —, —CH ₂ —, —O—, or —NH—, wherein R ₉ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group .)

加えて、下記の式［ＤＡ２７］で示されるようなジアミノシロキサンなども挙げることができる。

In addition, diaminosiloxanes represented by the following formula [DA27] can also be exemplified.

（式［ＤＡ２７］中、ｍは、１から１０の整数である。）
その他のジアミン化合物は、液晶配向膜とした際の液晶配向性、電圧保持特性、蓄積電荷などの特性に応じて、１種類または２種類以上を混合して使用することもできる。

(In the formula [DA27], m is an integer of 1 to 10.)
Other diamine compounds may be used alone or in combination of two or more depending on properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when the liquid crystal alignment film is formed.

<Tetracarboxylic dianhydride>
The tetracarboxylic dianhydride used in the present invention is not particularly limited. Specific examples are given below.
Pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic Acid dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3 3,3- Oxafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4, 5-pyridinetetracarboxylic dianhydride, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,4,9 , 10-perylenetetracarboxylic dianhydride, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, oxydiphthaltetracarboxylic dianhydride, 1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cycloheptanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetra Carboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3 4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo [4,3,0] nonane-2, 4,7,9- Tracarboxylic dianhydride, bicyclo [4,4,0] decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo [4,4,0] decane-2,4,8,10- Tetracarboxylic dianhydride, tricyclo [6.3.0.0 <2,6>] undecane-3,5,9,11-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic Acid dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydraphthalene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2 ] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid Acid dianhydride, tetracyclo [6,2,1,1,0,2,7] Dodeca-4,5,9,10-tetracarboxylic dianhydride, 3,5,6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic dianhydride, 1,2,4,5-cyclohexanetetra Examples thereof include carboxylic dianhydrides.

  Tetracarboxylic dianhydride can be used singly or in combination of two or more according to properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when formed into a liquid crystal alignment film.

<Copolymer>
The copolymer of the present invention comprises a polyamic acid obtained by reacting a diamine component containing the diamine compound (A) and the diamine compound (B) with tetracarboxylic dianhydride, and dehydrating and ring-closing the polyamic acid. It is a polyimide obtained. Any of these polyamic acids and polyimides is useful as a copolymer for obtaining a liquid crystal alignment film.

  The liquid crystal alignment film obtained by using the copolymer of the present invention has a higher voltage holding ratio as the content ratio of the specific diamine compound in the diamine component increases, and even after being exposed to a high temperature for a long time. The residual charge accumulated by the DC voltage is alleviated faster.

  Therefore, in the diamine component, the content of the diamine compound (B) is preferably 0.01 to 99 mol with respect to 1 mol of the diamine compound (A). More preferably, it is 0.1-50 mol, More preferably, it is 0.5-20 mol, Most preferably, it is 0.5-10 mol.

  In obtaining the polyamic acid of the present invention by the reaction of the diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. In general, tetracarboxylic dianhydride and diamine are reacted in an organic solvent. The reaction of tetracarboxylic dianhydride and diamine is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.

  The organic solvent used for the reaction between tetracarboxylic dianhydride and diamine is not particularly limited as long as the produced polyamic acid can be dissolved. Specific examples are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, isopropyl alcohol, Methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene Glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether , Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n- Pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3 -Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, Propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used alone or in combination. Further, even a solvent that does not dissolve the polyamic acid may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
Moreover, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use a dehydrated and dried organic solvent.

  When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent. A method of adding by dispersing or dissolving, a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component. Any of these methods may be used. In addition, when the tetracarboxylic dianhydride or diamine component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed and reacted to form a high molecular weight product.

  The polymerization temperature at that time can be selected from an arbitrary temperature of -20 ° C to 150 ° C, preferably in the range of -5 ° C to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight copolymer, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. Since it becomes difficult, the total concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

  In the polyamic acid polymerization reaction, the ratio of the total number of moles of tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.

The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the above polyamic acid, and is useful as a copolymer for obtaining a liquid crystal alignment film.
In the polyimide of the present invention, the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
Examples of the method for imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.

  The temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.

  Catalytic imidation of polyamic acid can be performed by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 ° C to 250 ° C, preferably 0 ° C to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

  When the produced polyamic acid or polyimide is recovered from the polyamic acid or polyimide reaction solution, the reaction solution may be poured into a poor solvent and precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating. Moreover, when the operation of re-dissolving the precipitated and recovered copolymer in an organic solvent and re-precipitation and recovery is repeated 2 to 10 times, impurities in the copolymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.

  The molecular weight of the polyamic acid and the polyimide contained in the liquid crystal aligning agent of the present invention is determined by considering the strength of the coating film obtained therefrom, the workability when forming the coating film, and the uniformity of the coating film. The weight average molecular weight measured by the Permeation Chromatography method is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Liquid crystal alignment agent>
The liquid crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution which the resin component for forming a resin film melt | dissolved in the organic solvent. Here, the said resin component is a resin component containing the at least 1 sort (s) of polymer chosen from the copolymer of this invention mentioned above. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

  In the present invention, all of the above resin components may be copolymers used in the present invention, and other polymers may be mixed with the copolymer of the present invention. At that time, the content of the polymer other than the copolymer of the present invention in the resin component is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.

  Examples of such other polymers include polyamic acid or polyimide obtained by using a diamine compound other than the diamine compound (A) and the diamine compound (B) as a diamine component to be reacted with tetracarboxylic dianhydride. It is done.

  The organic solvent used for the liquid-crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which the resin component mentioned above is dissolved. Specific examples are given below.

  N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4 -Hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination.

The liquid crystal aligning agent of this invention may contain components other than the above. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
Specific examples of the solvent (poor solvent) that improves the uniformity of the film thickness and the surface smoothness include the following.

  For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Low surface such as monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester Examples thereof include a solvent having tension.

These poor solvents may be used alone or in combination. When using the above solvent, it is preferable that it is 5 to 80 mass% of the whole solvent contained in a liquid-crystal aligning agent, More preferably, it is 20 to 60 mass%.
Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

More specifically, for example, EFTOP EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent. .
Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

  For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like.

  When using a compound that improves the adhesion to the substrate, the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent. The amount is preferably 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

  In addition to the above, the liquid crystal alignment treatment agent of the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. A substance, and further, a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like. In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.

  A method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of performing screen printing, offset printing, flexographic printing, ink jet, or the like is common. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.

  Firing after applying the liquid crystal aligning agent on the substrate can be performed at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, and the solvent can be evaporated to form a coating film. . If the thickness of the coating film formed after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. It is preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
To give an example of liquid crystal cell production, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside. Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like. . The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.
As described above, the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the interpretation of the present invention is not limited to these examples.
[Synthesis of diamine compound]
<Synthesis Example 1>
Synthesis of diamine compound (4)

化合物（２）（２９．９２ｇ，２７７ｍｍｏｌ）、及びトリエチルアミン（２８．０３ｇ，２７７ｍｍｏｌ）のテトラヒドロフラン（３００ｇ）溶液を１０℃以下に冷却し、化合物（１）（６０．７６ｇ，２６３ｍｍｏｌ）のテトラヒドロフラン（１５０ｇ）溶液を発熱に注意しながら滴下した。滴下終了後、反応温度を２３℃に上げ、さらに反応を行った。ＨＰＬＣ（高速液体クロマトグラフ）にて反応の終了を確認後、蒸留水（２Ｌ）に反応液を空け、析出した固体をろ過、水洗後、エタノール（４５０ｇ）で分散洗浄し、化合物（３）を得た（得量：７２．９１ｇ，得率：９２％）。
1H-NMR（400MHz，DMSO-d6，δppm）：9.79（1H，t），9.10-9.09（2H，m），9.00-8.96（1H，m），8.61（1H，broad），8.50-8.48（1H，m），7.79-7.76（1H，m），
7.40-7.36（1H，m），4.57（2H，s）．

A solution of compound (2) (29.92 g, 277 mmol) and triethylamine (28.03 g, 277 mmol) in tetrahydrofuran (300 g) was cooled to 10 ° C. or lower, and compound (1) (60.76 g, 263 mmol) in tetrahydrofuran (150 g) was cooled. ) The solution was added dropwise taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and further reaction was performed. After confirming the completion of the reaction by HPLC (High Performance Liquid Chromatograph), the reaction solution is poured into distilled water (2 L), the precipitated solid is filtered, washed with water, then dispersed and washed with ethanol (450 g) to obtain Compound (3). Obtained (yield: 72.91 g, yield: 92%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.79 (1H, t), 9.10-9.09 (2H, m), 9.00-8.96 (1H, m), 8.61 (1H, broad), 8.50-8.48 (1H , M), 7.79-7.76 (1H, m),
7.40-7.36 (1H, m), 4.57 (2H, s).

Next, a mixture of compound (3) (72.00 g, 238 mmol), 5% palladium carbon (hydrous type, 7.2 g, 10 wt%), and 1,4-dioxane (720 g) was added in the presence of hydrogen in the presence of 60 Stir at ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was dispersed and washed with ethanol (360 g) to obtain a diamine compound (4) (amount obtained: 43.62 g, yield: 76%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.64 (1H, t), 8.50 (1H, d), 8.44 (1H, d), 7.67 (1H, d), 7.34 (1H, q), 6.23 ( 2H, d), 5.94 (1H, s), 4.87 (4H, s), 4.39 (2H, d).

<Synthesis Example 2>
Synthesis of diamine compound (7)

化合物（５）（４０．００ｇ，３２８ｍｍｏｌ）、及びトリエチルアミン（３３．１８ｇ，３２８ｍｍｏｌ）のテトラヒドロフラン（４００ｇ）溶液を１０℃以下に冷却し、化合物（１）（７２．００ｇ、３１２ｍｍｏｌ）のテトラヒドロフラン（１７６ｇ）溶液を発熱に注意しながら滴下した。滴下終了後、反応温度を２３℃に上げ、さらに反応を行った。ＨＰＬＣにて反応の終了を確認後、蒸留水（３．５Ｌ）に反応液を空け、析出した固体をろ過、水洗後、メタノール（２００ｇ）で分散洗浄し、化合物（６）を得た（得量：８１．４ｇ，得率：８２％）。
1H-NMR（400MHz，DMSO-d6，δppm）：8.83-8.34（5H，m)，7.83-7.66（1H，m），7.39-7.33（1H，m），4.69-4.49（2H，m），2.91-2.85（3H，m）．

A solution of compound (5) (40.00 g, 328 mmol) and triethylamine (33.18 g, 328 mmol) in tetrahydrofuran (400 g) was cooled to 10 ° C. or lower, and compound (1) (72.00 g, 312 mmol) in tetrahydrofuran (176 g). ) The solution was added dropwise taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and further reaction was performed. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3.5 L), the precipitated solid was filtered, washed with water, and then dispersed and washed with methanol (200 g) to obtain compound (6) (obtained). (Amount: 81.4 g, yield: 82%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.83-8.34 (5H, m), 7.83-7.66 (1H, m), 7.39-7.33 (1H, m), 4.69-4.49 (2H, m), 2.91 -2.85 (3H, m).

Next, a mixture of compound (6) (80.00 g, 253 mmol), palladium hydroxide carbon (hydrous type, 8.0 g, 10 wt%), and 1,4-dioxane (1200 g) was added in the presence of hydrogen in the presence of 23 Stir at ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was uniformly dissolved in tetrahydrofuran (150 g), and the solution was dropped into hexane (660 g) at −20 ° C. to precipitate a solid. Then, the diamine compound (7) was obtained by filtration and cold hexane washing (amount obtained: 74.98 g, yield: 98%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.46-8.34 (2H, m), 7.63-7.54 (1H, broad), 7.36-7.33 (1H, m), 5.86-5.76 (3H, m), 4.86 (4H, s), 4.57-4.53 (2H, broad), 2.80 (3H, broad).

<Synthesis Example 3>
Synthesis of diamine compound (10)

化合物（８）（１６．６９ｇ，１３７ｍｍｏｌ）、及びトリエチルアミン（１３．８２ｇ，１３７ｍｍｏｌ）のテトラヒドロフラン（２００ｇ）溶液を１０℃以下に冷却し、化合物（１）（３０．００ｇ、１３０ｍｍｏｌ）のテトラヒドロフラン（１５０ｇ）溶液を発熱に注意しながら滴下した。滴下終了後、反応温度を２３℃に上げ、さらに反応を行った。ＨＰＬＣにて反応の終了を確認後、蒸留水（２．８Ｌ）に反応液を空け、析出した固体をろ過、水洗後、エタノール（２００ｇ）で分散洗浄し、化合物（９）を得た（得量：３４．５３ｇ，得率：８４％）。
1H-NMR（400MHz，DMSO-d6，δppm）：9.30（1H，t），9.01-9.00（2H，m），8.95-8.93（1H，m），8.47（1H，d），8.42（1H，dd），7.69（2H，d），7.32（1H，q），3.64-3.58（2H，m），2.92（2H，t）．

A tetrahydrofuran (200 g) solution of compound (8) (16.69 g, 137 mmol) and triethylamine (13.82 g, 137 mmol) was cooled to 10 ° C. or lower, and tetrahydrofuran (150 g) of compound (1) (30.00 g, 130 mmol) was cooled. ) The solution was added dropwise taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and further reaction was performed. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (2.8 L), the precipitated solid was filtered, washed with water, and then dispersed and washed with ethanol (200 g) to obtain compound (9) (obtained). (Amount: 34.53 g, yield: 84%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.30 (1H, t), 9.01-9.00 (2H, m), 8.95-8.93 (1H, m), 8.47 (1H, d), 8.42 (1H, dd ), 7.69 (2H, d), 7.32 (1H, q), 3.64-3.58 (2H, m), 2.92 (2H, t).

Next, a mixture of compound (9) (32.00 g, 101 mmol), 5% palladium carbon (hydrated type, 3.2 g, 10 wt%), and 1,4-dioxane (320 g) was added in the presence of hydrogen in the presence of 60 Stir at ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was dispersed and washed with tetrahydrofuran (150 g) to obtain a diamine compound (10) (yield: 19.21 g, yield: 74%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.43-8.39 (2H, m), 8.09 (1H, t), 7.63 (1H, d), 7.30 (1H, dd), 6.16 (2H, d), 5.92 (1H, d), 4.84 (4H, s), 3.44-3.28 (3H, m), 2.82 (3H, t).

<Synthesis Example 4>
Synthesis of diamine compound (14)

A solution of compound (11) (29.84 g, 160 mmol) in tetrahydrofuran (60 g) was added dropwise to a solution of compound (12) (35.00 g, 321 mmol) and triethylamine (97.39 g, 962 mmol) in tetrahydrofuran (240 g). After completion of the dropwise addition, the reaction was followed by HPLC. After confirming the completion of the reaction, dichloromethane (1 L) was added, followed by washing with distilled water (600 mL) three times. The organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated to give a crude compound (13). The obtained crude product was recrystallized from ethyl acetate (500 g) / hexane (1 L) to obtain compound (13) (amount: 38.74 g, yield: 88%).
1H-NMR (400 MHz, CDCl3, δ ppm): 8.79 (1H, d), 8.71 (1H, d), 8.66 (1H, dd), 8.46 (1H, dd), 7.88-7.85 (1H, m), 7.40 ( 1H, q), 7.30 (1H, d), 5.38 (2H, s).

Compound (13) (20.00 g, 72.7 mmol), platinum (IV) oxide (hydrated, 2.0 g, 10 wt%), and ethyl acetate / ethanol (200 g, 100/50 (v / v%)) ) Was stirred at 40 ° C. in the presence of hydrogen. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product of compound (14). The obtained crude product was purified by silica gel column chromatography (the effluent solvent was hexane / ethyl acetate (100/50 v / v%)) to obtain the diamine compound (14) (yield: 15.27 g, obtained). (Rate: 98%).
1H-NMR (400MHz, CDCl3, δppm): 8.66 (1H, d), 8.57 (1H, dd), 7.77-7.73 (1H, m), 7.33-7.29 (1H, m), 6.67 (1H, d), 5.00 (2H, s), 3.37 (4H, s).

<Synthesis Example 5>
Synthesis of diamine compound (16)

化合物（２）（２９．９８ｇ，２７７ｍｍｏｌ）、炭酸水素ナトリウム（２９．１２ｇ，３４７ｍｍｏｌ）、及び蒸留水（６３０ｇ）の混合溶液に、２３℃下、化合物（１１）（４３．００ｇ，２３１ｍｍｏｌ）のエタノール（８３０ｇ）溶液を滴下して加えた。滴下終了後、ＨＰＬＣにて反応の終了を確認した後、ジクロロメタン（２Ｌ）を加え水層を除去した。その後、有機層を飽和食塩水（５００ｍＬ）で３回洗浄し、無水硫酸マグネシウムで有機層を乾燥した後、溶媒留去を行った。得られた粗物を酢酸エチル（５００ｇ）/ヘキサン（１Ｌ）で再結晶することで化合物（１５）を得た（得量：５５．２８ｇ、得率：８７％）。
1H-NMR（400MHz，CDCl3，δppm）：9.18（1H，d），9.17（1H，broad），8.66-8.62（2H，m），8.29-8.25（1H，m），7.69-7.66（1H，m），7.37-7.33（1H，m），6.90（1H，d），4.68（2H，m）．

Compound (11) (43.00 g, 231 mmol) was added to a mixed solution of compound (2) (29.98 g, 277 mmol), sodium hydrogen carbonate (29.12 g, 347 mmol), and distilled water (630 g) at 23 ° C. Ethanol (830 g) solution was added dropwise. After completion of the dropwise addition, after confirming the completion of the reaction by HPLC, dichloromethane (2 L) was added and the aqueous layer was removed. Thereafter, the organic layer was washed three times with saturated brine (500 mL), dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The obtained crude product was recrystallized from ethyl acetate (500 g) / hexane (1 L) to obtain compound (15) (amount: 55.28 g, yield: 87%).
1H-NMR (400MHz, CDCl3, δppm): 9.18 (1H, d), 9.17 (1H, broad), 8.66-8.62 (2H, m), 8.29-8.25 (1H, m), 7.69-7.66 (1H, m ), 7.37-7.33 (1H, m), 6.90 (1H, d), 4.68 (2H, m).

Next, a mixture of compound (15) (3.0 g, 10.9 mmol), platinum (IV) oxide (hydrated type, 0.3 g, 10 wt%), and 1,4-dioxane (30 g) was added in the presence of hydrogen. And stirred at 23 ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a diamine compound (16) (amount obtained: 2.30 g, yield: 98%).
1H-NMR (400MHz, CDCl3, δppm): 8.63 (1H, d), 8.52 (1H, dd), 7.71-7.66 (1H, m), 7.28-7.24 (1H, m), 6.53 (1H, d), 6.18-6.11 (2H, m), 4.22 (2H, s), 3.70 (1H, s), 3.56-3.34 (4H, broad).

<Synthesis Example 6>
Synthesis of diamine compound (19)

  Compound (17) (50.00 g, 170 mmol), potassium carbonate (47.01 g, 340 mmol), copper (I) iodide (6.48 g, 34.0 mmol), N-methylglycine (6.06 g, 68.0 mmol) ) And DMSO (dimethyl sulfoxide) (1 L), Compound (2) (36.78 g, 340 mmol) was added dropwise at 40 ° C. After completion of the dropwise addition, after confirming the completion of the reaction by HPLC, ethyl acetate (4 L) / distilled water (5 L) was added, and then insoluble matters were removed by filtration. Thereafter, the aqueous layer removed by liquid separation was extracted twice with ethyl acetate (500 g), and the organic layers were combined and dried over anhydrous magnesium sulfate. After the solvent was distilled off by an evaporator to obtain a crude product, recrystallization was performed with ethyl acetate (700 mL) / hexane (2 L) to obtain a compound (18) (yield: 23.04 g, yield: 49%). ).

1H-NMR (400 MHz, CDCl3, δ ppm): 8.63 (1H, broad), 8.50-8.49 (1H, broad), 7.95 (1H, t), 7.80-7.76 (3H, m), 7.67 (1H, t), 7.39 (1H, q), 4.52 (2H, d).
Next, a mixture of compound (18) (1.0 g, 3.65 mmol), platinum (IV) oxide (water-containing type, 0.1 g, 10 wt%), and methanol (10 g) was mixed at 23 ° C. in the presence of hydrogen. And stirred. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a diamine compound (19) (amount obtained: 0.97 g, yield: 97%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.52 (1H, d), 8.41 (1H, dd), 7.69 (1H, d), 7.32 (1H, q), 5.60 (1H, t), 5.17 ( 2H, s), 4.37-4.14 (4H, m).

<Synthesis Example 7>
Synthesis of diamine compound (23)

Under a nitrogen atmosphere, a solution of compound (21) (51.43 g, 281 mmol) in tetrahydrofuran (300 g) was kept at 10 ° C. or lower to obtain compound (20) (50.00 g, 281 mmol), triethylamine (170.5 g, 1.69 mol). , And a solution of DMAP (4-dimethylaminopyridine) (6.87 g, 56.2 mmol) in tetrahydrofuran (500 g) was added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C., and the mixture was stirred for 1 hour and further heated to reflux. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (6.4 L), filtered and washed with water to obtain a crude product. The obtained crude product was recrystallized from tetrahydrofuran (243 g) / hexane (1458 g) to obtain compound (22) (amount obtained: 72.58 g, yield: 89%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 11.25 (1H, s), 9.18 (1H, d), 9.09 (2H, dd), 8.82 (1H, dd), 8.57 (1H, t), 8.38- 8.35 (1H, m), 7.64 (1H, q).

Next, a mixture of compound (22) (20.00 g, 69.4 mmol), 5% palladium carbon (hydrous type, 2.0 g, 10 wt%), and 1,4-dioxane (400 g) was added in the presence of hydrogen. , And stirred at 90 ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was dispersed and washed with ethanol (75 g) to obtain a diamine compound (23) (amount obtained: 10.14 g, yield: 64%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.87 (1H, s), 9.03-9.01 (1H, m), 8.72-8.70 (1H, m), 8.23-8.19 (1H, m), 7.54-7.50 (1H, m), 6.27-6.26 (2H, m), 5.63-5.61 (1H, m), 4.75-4.73 (2H, m).

<Synthesis Example 8>
Synthesis of diamine compound (26)

Under a nitrogen atmosphere, a solution of compound (21) (20.00 g, 112 mmol) in tetrahydrofuran (120 g) was cooled to 10 ° C. or lower, and compound (24) (20.57 g, 112 mmol), triethylamine (68.18 g, 674 mmol), Then, a solution of DMAP (2.74 g, 22.5 mmol) in tetrahydrofuran (200 g) was added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C., and the mixture was stirred for 1 hour and further heated to reflux for 17 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (2.6 L), filtered and washed with water to obtain a crude product. The obtained crude product was dispersed and washed with ethanol (40 g), and then filtered and dried to obtain compound (25) (yield: 16.45 g, yield: 51%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 11.4 (1H, s), 9.15-9.14 (1H, m), 8.86 (1H, d), 8.77 (1H, d), 8.64-8.60 (1H, m ), 8.33 (1H, d), 8.06 (1H, d), 7.66 (1H, q), 2.92 (2H, t).

Next, a mixture of compound (25) (15.00 g, 52.0 mmol), 5% palladium carbon (hydrous type, 1.5 g, 10 wt%), and 1,4-dioxane (150 g) was added in the presence of hydrogen. And stirred at 60 ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product of compound (26). The resulting crude product was purified by silica gel column chromatography (the effluent solvent was hexane / ethyl acetate (100/50 v / v%)), and further purified by recrystallization from tetrahydrofuran (400 g) / hexane (600 g). Compound (26) was obtained (yield: 6.11 g, yield: 51%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.54 (1H, s), 9.10 (1H, d), 8.72 (1H, dd), 8.30-8.27 (1H, m), 7.90 (1H, s), 7.52 (1H, q), 6.75 (1H, d), 6.61 (1H, d), 5.99 (1H, m), 4.65 to 4.59 (4H, m).

<Synthesis Example 9>
Synthesis of diamine compound (29)

Under a nitrogen atmosphere, compound (12) (21.39 g, 196 mmol) is gradually added dropwise to a tetrahydrofuran (100 g) solution of compound (27) (10.00 g, 49.0 mmol) and triethylamine (59.50 g, 588 mmol). did. After completion of the reaction, the reaction solution was added to distilled water (1 L), filtered and washed with water to obtain a crude compound (28). The obtained crude product was recrystallized from acetonitrile (200 g) / ethyl acetate (300 g) to obtain compound (28) (amount: 11.35 g, yield: 61%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.74-8.73 (3H, m), 8.61 (2H, dd), 7.93 (2H, d), 7.50 (2H, q), 7.44 (1H, s), 5.56 (4H, s).

Next, a mixture of compound (28) (8.00 g, 20.1 mmol), platinum (IV) oxide (hydrous type, 0.8 g, 10 wt%), and 1,4-dioxane (80 g) was added in the presence of hydrogen. And stirred at 60 ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was recrystallized from tetrahydrofuran (200 g) / hexane (600 g) to obtain a diamine compound (29) (yield: 4.66 g, yield: 72%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.65 (2H, d), 8.52 (2H, dd), 7.88-7.85 (2H, m), 7.40 (2H, q), 6.68 (1H, s), 6.07 (1H, s), 4.96 (4H, s), 4.25 (4H, s).

<Synthesis Example 10>
Synthesis of diamine compound (34)

  A mixture of compound (31) (81.60 g, 74.1 mmol), calcium hydroxide (18.29 g, 24.7 mmol), and DMSO (375 g) was heated to 50 ° C. under a nitrogen atmosphere, and then compound (30) A solution of (50.00 g, 24.7 mmol) in DMSO (125 g) was added dropwise. After completion of the dropwise addition, the completion of the reaction was confirmed by HPLC, and then the reaction solution was poured into 5% by mass hydrochloric acid ice water (4 L), and the solid was filtered and washed with water to obtain a wet product of compound (32). Thereafter, recrystallization was performed with 2-propanol (205 g) / hexane (335 g) to obtain a compound (32) (amount: 49.0 g, yield: 72%).

  1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.73 (1H, s), 8.86 (1H, d), 8.42 (1H, dd), 7.11-7.05 (3H, m), 6.90-6.87 (2H, m ).

Next, a tetrahydrofuran (180 g) solution of the compound (21) (19.34 g, 109 mmol) is cooled to 10 ° C. or lower under a nitrogen atmosphere, and the compound (31) (30.0 g, 109 mmol), triethylamine (33.0 g, 324 mmol) is cooled. ), And DMAP (2.65 g, 21.7 mmol) in DMSO (300 g) were added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C., stirred for 1 hour, and further heated to reflux for 19 hours. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (3.9 L), filtered, washed with water, and washed with methanol to obtain a crude product. The obtained crude product was dissolved in chloroform, and the insoluble material was filtered off. Thereafter, the filtrate was concentrated and purified by silica gel column chromatography (the effluent solvent was 1,2-dichloroethane / ethyl acetate (100/40 v / v%)) to obtain compound (33) (yield: 35). .8 g, yield: 86%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.29 (1H, dd), 8.92-8.91 (2H, m), 8.52-8.48 (2H, m), 7.69-7.66 (1H, m), 7.53-7.51 (2H, m), 7.44-7.40 (2H, m), 7.24 (1H, d).

Next, a toluene (170 g) solution of the compound (33) (30.00 g, 78.7 mmol) and iron powder (26.36 g, 472 mmol) was heated to 70 ° C. under a nitrogen atmosphere, and then ammonium chloride (12.63 g) was used. , 236 mmol) of 10% by mass aqueous solution was added dropwise. After completion of the reaction, the solid was filtered through celite. Thereafter, the aqueous layer was removed from the filtrate, and then the organic layer was concentrated with an evaporator to obtain a crude product. Next, the obtained crude product was dissolved in ethyl acetate (1 L) and washed three times with distilled water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The crude product (34) thus obtained was recrystallized from methanol (100 g) / 2-propanol (100 g) to obtain a diamine compound (34) (amount: 15.4 g, yield: 61%). .
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.20 (1H, dd), 8.85 (1H, dd), 8.43-8.40 (1H, m), 7.62-7.59 (1H, m), 7.19-7.16 (2H , M), 6.88-6.84 (2H, m), 6.53 (1H, d), 6.02 (1H, d), 5.81 (1H, dd), 4.69 (2H, s), 4.57 (2H, s).

<Synthesis Example 11>
Synthesis of diamine compound (37)

Compound (32) (17.00 g, 61.6 mmol), Compound (35) (6.57 mL, 67.7 mmol), and triphenylphosphine (20.99 g, 80.0 mmol) in tetrahydrofuran (340 g) under nitrogen atmosphere The solution was cooled in an ice bath, and a solution of DEAD (diethyl azodicarboxylate) (40 mass% toluene solution, 34.84 mL, 80.0 mmol) was gradually added dropwise. After completion of the dropwise addition, the reaction temperature was gradually raised to 23 ° C. to carry out the reaction. After confirming the completion of the reaction by HPLC, the solvent was distilled off with an evaporator to obtain a crude product. Thereafter, recrystallization was performed twice with 2-propanol (450 g) to obtain a compound (36) (amount obtained: 17.77 g, yield: 79%).
1H-NMR (400 MHz, CDCl3, δ ppm): 8.84 (1H, d), 8.71 (1H, broad), 8.63 (1H, dd), 8.30 (1H, dd), 7.80 (1H, d), 7.36 (1H, q), 7.12-7.08 (4H, m), 7.01 (1H, d), 5.04 (2H, s).

Next, under a nitrogen atmosphere, a mixture of compound (36) (15.00 g, 40.8 mmol), platinum (IV) oxide (hydrated, 1.5 g, 10 wt%), and 1,4-dioxane (230 g) The mixture was stirred at 23 ° C. in the presence of hydrogen. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The resulting crude product was recrystallized from 2-propanol (60 g) to obtain a diamine compound (37) (yield: 9.66 g, yield 77%).
1H-NMR (400 MHz, CDCl3, δ ppm): 8.66 (1H, d), 8.57 (1H, dd), 7.77 (1H, m), 7.34 (1H, q), 6.87 (4H, s), 6.69 (1H, d), 6.16 (1H, d), 6.07 (1H, dd), 5.02 (2H, s), 3.65-3.48 (4H, broad).

<Synthesis Example 12>
Synthesis of diamine compound (40)

A solution of compound (38) (23.45 g, 190 mmol) and triethylamine (19.23 g, 277 mmol) in tetrahydrofuran (230 g) was cooled to 10 ° C. or lower, and compound (1) (41.68 g, 180 mmol) in tetrahydrofuran (110 g) was cooled. ) The solution was added dropwise taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and further reaction was performed. After confirming the completion of the reaction by HPLC (high performance liquid chromatograph), the reaction solution was poured into distilled water (1.5 L), and the precipitated solid was filtered and washed with water. Thereafter, the solid was dispersed and washed with ethanol (380 g) to obtain compound (39) (yield: 50.82 g, yield: 89%).
1H-NMR (400MHz, DMSO-d6, δppm): 9.76 (1H, t), 9.09-9.02 (2H, m), 8.99-8.93 (1H, m), 8.50 (1H, broad), 7.64-7.60 (1H , M), 7.36-7.32 (1H, m), 7.20-7.14 (1H, m), 4.57 (2H, s), 3.35 (2H, s).

Next, a mixture of compound (39) (48.00 g, 151 mmol), 5% palladium carbon (hydrous type, 4.8 g, 10 wt%), and 1,4-dioxane (490 g) was added in the presence of hydrogen in the presence of 60. Stir at ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was dispersed and washed with ethanol (300 g) to obtain a diamine compound (40) (amount: 27.20 g, yield: 70%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.64 (1H, t), 8.50 (1H, d), 8.44 (1H, d), 7.67 (1H, d), 7.34 (1H, q), 6.23 ( 2H, d), 5.94 (1H, s), 4.87 (4H, s), 4.39 (2H, d).

<Synthesis Example 13>
Synthesis of diamine compound (43)

A solution of compound (41) (15.22 g, 142 mmol) and triethylamine (15.09 g, 149 mmol) in tetrahydrofuran (150 g) was cooled to 10 ° C. or lower, and compound (1) (31.1 g, 135 mmol) in tetrahydrofuran (50 g) ) The solution was added dropwise taking care of the exotherm. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and further reaction was performed. After confirming the completion of the reaction by HPLC, the reaction solution was poured into distilled water (1 L), and the precipitated solid was filtered and washed with water. Thereafter, the solid was dispersed and washed with ethanol (300 g) to obtain compound (42) (yield: 36.92 g, yield: 90%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 9.75 (1H, broad), 9.10 (2H, s), 8.97-8.92 (1H, m), 7.40-7.22 (5H, m), 4.59-4.52 (2H , M).

Next, a mixture of compound (42) (36.00 g, 119 mmol), 5% palladium carbon (hydrous type, 3.6 g, 10 wt%), and 1,4-dioxane (300 g) was added in the presence of hydrogen in the presence of 60 Stir at ° C. After completion of the reaction, the catalyst was filtered through celite, and then the solvent was distilled off with an evaporator to obtain a crude product. The obtained crude product was recrystallized from methanol (200 g) to obtain a diamine compound (43) (yield: 21.5 g, yield: 72%).
1H-NMR (400 MHz, DMSO-d6, δ ppm): 8.55 (1H, broad), 7.34-7.17 (5H, m), 6.28 (2H, s), 6.98-6.94 (1H, m), 4.85-4.74 (4H , Broad), 4.42-4.35 (2H, m).

[Synthesis of polyimide]
Abbreviations of compounds such as tetracarboxylic dianhydride used are shown below.
(Tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

（ジアミン）
ＤＢＡ：３，５−ジアミノ安息香酸
ｐ−ＰＤＡ：ｐ−フェニレンジアミン
ＰＣＨ７ＤＡＢ：１，３−ジアミノ−４−〔４−（トランス−４−ｎ−ヘプチルシクロへキシル）フェノキシ〕ベンゼン

(Diamine)
DBA: 3,5-diaminobenzoic acid p-PDA: p-phenylenediamine PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

（有機溶媒）
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＢＣＳ：ブチルセロソルブ
＜ポリイミドの分子量測定＞
合成例におけるポリイミドの分子量は、昭和電工社製 常温ゲル浸透クロマトグラフィー（ＧＰＣ）装置（ＧＰＣ−１０１）、Ｓｈｏｄｅｘ社製カラム（ＫＤ−８０３、ＫＤ−８０５）を用い以下のようにして測定した。

(Organic solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve <Molecular weight measurement of polyimide>
The molecular weight of the polyimide in the synthesis example was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Showa Denko KK and a column (KD-803, KD-805) manufactured by Shodex.

Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) 10ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight manufactured by Polymer Laboratory) About 12,000, 4,000, 1,000).

<Measurement of imidization ratio>
The imidation ratio of polyimide in the synthesis example was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 by Kusano Kagaku Co., Ltd.), add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture), and apply ultrasonic waves. And completely dissolved. 500 MHz proton NMR was measured for this solution with the NMR measuring device by the JEOL datum company (JNW-ECA500). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

<Synthesis Example 14>
BODA (3.83 g, 15.3 mmol), DBA (1.09 g, 7.17 mmol), PCH7DAB (3.88 g, 10.2 mmol), and diamine compound (4) (0.74 g, 3.06 mmol) were added to NMP. (17.5 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (1.00 g, 5.10 mmol) and NMP (14.0 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Got.
After adding NMP to this polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.67 g) and pyridine (0.90 g) were added as imidization catalysts, and 3.5 hours at 90 ° C. Reacted. This reaction solution was poured into methanol (130 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (A). The imidation ratio of this polyimide was 55%, the number average molecular weight was 18,500, and the weight average molecular weight was 48,200.

<Synthesis Example 15>
After adding NMP to the polyamic acid solution (10.0 g) obtained in Synthesis Example 14 and diluting to 6% by mass, acetic anhydride (2.17 g) and pyridine (1.68 g) were added as imidization catalysts, and 90% The reaction was carried out at 3.5 ° C. for 3.5 hours. This reaction solution was poured into methanol (140 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (B). The imidation ratio of this polyimide was 80%, the number average molecular weight was 17,100, and the weight average molecular weight was 46,900.

<Synthesis Example 16>
BODA (2.41 g, 9.64 mmol), DBA (1.37 g, 9.01 mmol), PBCH7DAB (0.48 g, 1.27 mmol), and diamine compound (7) (0.66 g, 2.72 mmol) were added to NMP. (9.00 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (0.63 g, 3.21 mmol) and NMP (7.80 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Got.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.60 g) and pyridine (0.90 g) were added as imidization catalysts, The reaction was allowed for 5 hours. This reaction solution was poured into methanol (140 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (C). The imidation ratio of this polyimide was 56%, the number average molecular weight was 17,300, and the weight average molecular weight was 46,000.

<Synthesis Example 17>
BODA (4.59 g, 18.4 mmol), DBA (1.30 g, 8.55 mmol), PCH7DAB (4.66 g, 12.2 mmol), and diamine compound (10) (0.94 g, 3.88 mmol) were mixed with NMP. (21.5 g), and after reacting at 80 ° C. for 5 hours, CBDA (1.20 g, 6.12 mmol) and NMP (17.0 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Got.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.68 g) and pyridine (0.92 g) were added as an imidization catalyst, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (130 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (D). The imidation ratio of this polyimide was 60%, the number average molecular weight was 18,100, and the weight average molecular weight was 47,800.

<Synthesis Example 18>
After adding NMP to the polyamic acid solution (10.0 g) obtained in Synthesis Example 17 and diluting to 6% by mass, acetic anhydride (2.16 g) and pyridine (1.75 g) were added as imidization catalysts, The reaction was carried out at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (130 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (E). The imidation ratio of this polyimide was 83%, the number average molecular weight was 17,300, and the weight average molecular weight was 45,900.

<Synthesis Example 19>
BODA (2.56 g, 10.3 mmol), DBA (0.94 g, 6.18 mmol), PCH7DAB (1.56 g, 4.10 mmol), and diamine compound (14) (0.74 g, 3.04 mmol) were added to NMP. (10.50 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (0.67 g, 3.42 mmol) and NMP (9.00 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. Got.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.16 g) and pyridine (0.88 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (140 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (F). The imidation ratio of this polyimide was 55%, the number average molecular weight was 19,100, and the weight average molecular weight was 49,100.

<Synthesis Example 20>
BODA (2.49 g, 9.94 mmol), DBA (1.11 g, 7.30 mmol), PCH7DAB (0.75 g, 1.97 mmol), and diamine compound (16) (0.85 g, 3.52 mmol) were mixed with NMP. (9.50 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (0.65 g, 3.31 mmol) and NMP (8.10 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Got.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.12 g) and pyridine (0.90 g) were added as an imidization catalyst, and 2 at 80 ° C. Reacted for hours. This reaction solution was poured into methanol (120 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (G). The imidation ratio of this polyimide was 53%, the number average molecular weight was 18,800, and the weight average molecular weight was 47,900.

<Synthesis Example 21>
BODA (2.53 g, 10.1 mmol), DBA (0.72 g, 4.74 mmol), PCH7DAB (2.56 g, 6.73 mmol), and diamine compound (19) (0.43 g, 1.79 mmol) were added to NMP. (12.1 g), and after reacting at 80 ° C. for 5 hours, CBDA (0.66 g, 3.37 mmol) and NMP (9.20 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Got.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.16 g) and pyridine (1.00 g) were added as an imidization catalyst, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (140 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (H). The imidation ratio of this polyimide was 55%, the number average molecular weight was 16,900, and the weight average molecular weight was 46,500.

<Synthesis Example 22>
BODA (2.60 g, 10.4 mmol), DBA (0.74 g, 4.87 mmol), PCH7DAB (2.64 g, 6.93 mmol), and diamine compound (23) (0.47 g, 1.96 mmol) were mixed with NMP. (11.1 g), and the mixture was reacted at 80 ° C. for 5 hours. Then, CBDA (0.68 g, 3.47 mmol) and NMP (9.50 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Got.
After adding NMP to the obtained polyamic acid solution (10.1 g) and diluting to 6% by mass, acetic anhydride (1.15 g) and pyridine (1.01 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (120 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (I). The imidation ratio of this polyimide was 54%, the number average molecular weight was 18,100, and the weight average molecular weight was 48,100.

<Synthesis Example 23>
BODA (2.49 g, 9.94 mmol), DBA (1.11 g, 7.30 mmol), PCH7DAB (0.50 g, 1.31 mmol), and diamine compound (26) (1.06 g, 4.37 mmol) were mixed with NMP. (9.50 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (0.65 g, 3.31 mmol) and NMP (8.10 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Got.
After adding NMP to the obtained polyamic acid solution (10.2 g) and diluting to 6% by mass, acetic anhydride (1.17 g) and pyridine (0.99 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (130 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (J). The imidation ratio of this polyimide was 57%, the number average molecular weight was 18,100, and the weight average molecular weight was 47,000.

<Synthesis Example 24>
BODA (2.45 g, 9.79 mmol), DBA (1.59 g, 10.5 mmol), PCH7DAB (0.49 g, 1.29 mmol), and diamine compound (29) (0.42 g, 1.74 mmol) were mixed with NMP. (8.50 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (0.64 g, 3.26 mmol) and NMP (7.50 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. Got.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.16 g) and pyridine (1.00 g) were added as an imidization catalyst, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (130 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (K). The imidation ratio of this polyimide was 55%, the number average molecular weight was 18,400, and the weight average molecular weight was 47,900.

<Synthesis Example 25>
BODA (2.49 g, 9.94 mmol), DBA (0.61 g, 4.01 mmol), PCH7DAB (2.52 g, 6.63 mmol), and diamine compound (34) (0.85 g, 3.52 mmol) were mixed with NMP. (12.5 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (0.65 g, 3.31 mmol) and NMP (10.5 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Got.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.16 g) and pyridine (1.01 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was put into methanol (150 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (L). The imidation ratio of this polyimide was 55%, the number average molecular weight was 18,400, and the weight average molecular weight was 47,400.

<Synthesis Example 26>
BODA (4.40 g, 17.6 mmol), DBA (1.25 g, 8.22 mmol), PCH7DAB (4.46 g, 11.7 mmol), and diamine compound (37) (1.08 g, 4.46 mmol) were added to NMP. (21.0 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (1.15 g, 5.86 mmol) and NMP (16.5 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Got.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (1.15 g) and pyridine (1.00 g) were added as an imidization catalyst, and The reaction was allowed for 5 hours. This reaction solution was put into methanol (150 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (M). The imidation ratio of this polyimide was 55%, the number average molecular weight was 19,800, and the weight average molecular weight was 48,800.

<Synthesis Example 27>
After adding NMP to the polyamic acid solution obtained in Synthesis Example 26 and diluting to 6% by mass, acetic anhydride (2.17 g) and pyridine (1.66 g) were added as an imidization catalyst, and 3.5% at 90 ° C. Reacted for hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (N). The imidation ratio of this polyimide was 82%, the number average molecular weight was 16,800, and the weight average molecular weight was 46,300.

<Synthesis Example 28>
BODA (2.45 g, 9.79 mmol), DBA (0.70 g, 4.61 mmol), PCH7DAB (2.48 g, 6.53 mmol), and diamine compound (40) (0.50 g, 2.08 mmol) were added to NMP. (11.5 g), and after reacting at 80 ° C. for 5 hours, CBDA (0.64 g, 3.26 mmol) and NMP (8.50 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Got.
After adding NMP to the obtained polyamic acid solution (10.1 g) and diluting to 6% by mass, acetic anhydride (2.15 g) and pyridine (1.67 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (O). The imidation ratio of this polyimide was 80%, the number average molecular weight was 16,900, and the weight average molecular weight was 47,200.

<Synthesis Example 29>
BODA (2.49 g, 9.94 mmol), p-PDA (0.50 g, 4.64 mmol), PCH7DAB (2.52 g, 6.63 mmol), and diamine compound (40) (0.51 g, 2.11 mmol) Was mixed in NMP (11.3 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.65 g, 3.31 mmol) and NMP (8.30 g) were added, and reacted at 40 ° C. for 6 hours. An acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (2.16 g) and pyridine (1.67 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (P). The imidation ratio of this polyimide was 79%, the number average molecular weight was 17,100, and the weight average molecular weight was 47,900.

<Synthesis Example 30>
BODA (2.53 g, 10.1 mmol), DBA (0.72 g, 4.74 mmol), PCH7DAB (2.56 g, 6.73 mmol), and diamine compound (43) (0.49 g, 2.01 mmol) were added to NMP. (11.8 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (0.66 g, 3.37 mmol) and NMP (8.60 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. Got.
After adding NMP to the obtained polyamic acid solution (10.0 g) and diluting to 6% by mass, acetic anhydride (2.15 g) and pyridine (1.65 g) were added as imidization catalysts, The reaction was allowed for 5 hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (Q). The imidation ratio of this polyimide was 81%, the number average molecular weight was 17,900, and the weight average molecular weight was 48,100.

<Synthesis Example 31>
BODA (2.49 g, 9.94 mmol), p-PDA (0.50 g, 4.64 mmol), PCH7DAB (2.51 g, 6.63 mmol), and diamine compound (43) (0.48 g, 1.98 mmol) Was mixed in NMP (10.5 g) and reacted at 80 ° C. for 5 hours, then CBDA (0.65 g, 3.31 mmol) and NMP (8.10 g) were added, and reacted at 40 ° C. for 6 hours. An acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (10.1 g) and diluting to 6% by mass, acetic anhydride (2.18 g) and pyridine (1.68 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (R). The imidation ratio of this polyimide was 80%, the number average molecular weight was 17,700, and the weight average molecular weight was 47,600.

[Preparation and evaluation of liquid crystal aligning agent]
<Example 1>
NMP (22.1 g) was added to the polyimide powder [A] (5.1 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 40 hours. NMP (11.1 g) and BCS (46.8 g) were added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent [1]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

[Production of liquid crystal cell]
The liquid crystal alignment treatment agent [1] obtained above was spin coated on the ITO surface of the substrate with 3 cm × 4 cm (vertical × horizontal) ITO electrode, and heated at 80 ° C. for 5 minutes and 210 ° C. hot air circulating oven Was baked for 1 hour to prepare a polyimide coating film having a thickness of 100 nm.
This substrate with a liquid crystal alignment film is subjected to a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm. Got.
Two substrates with this liquid crystal alignment film were prepared, and a 6 μm bead spacer was sprayed on the surface of one liquid crystal alignment film, and then a sealant was printed thereon. Another substrate was bonded so that the liquid crystal alignment film surface was inward and the rubbing direction was reversed, and then the sealing agent was cured to produce an empty cell. Liquid crystal MLC-6608 (manufactured by Merck Japan Ltd.) was injected into this empty cell by a reduced pressure injection method to obtain an antiparallel aligned nematic liquid crystal cell.

[Evaluation of voltage holding ratio]
A voltage of 4 V was applied to the liquid crystal cell obtained above at a temperature of 80 ° C. for 60 μs, the voltages after 16.67 ms and 1667 ms were measured, and the voltage holding ratio was calculated as the voltage holding ratio. . The results are shown in Table 7 described later.

[Evaluation of relaxation of residual charge]
A DC voltage of 10 V was applied to the liquid crystal cell after measuring the voltage holding ratio for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. The residual charges after 50 seconds and 1000 seconds were measured. For measurement, a 6254 type liquid crystal property evaluation apparatus manufactured by Toyo Corporation was used. The results are shown in Table 8 described later.

[Evaluation after leaving at high temperature]
The liquid crystal cell after the residual charge measurement was left in a high-temperature bath set at 100 ° C. for 7 days, and then the voltage holding ratio and the residual charge were measured. The results are shown in Table 7 and Table 8 described later.

<Example 2>
NMP (21.7 g) was added to the polyimide powder [B] (5.0 g) obtained in Synthesis Example 15, and dissolved by stirring at 70 ° C. for 40 hours. NMP (10.8g) and BCS (45.8g) were added to this solution, and the liquid-crystal aligning agent [2] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [2], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 3>
NMP (29.4 g) was added to the polyimide powder [C] (4.9 g) obtained in Synthesis Example 16, and dissolved by stirring at 70 ° C. for 40 hours. NMP (14.8g) and BCS (32.5g) were added to this solution, and the liquid crystal aligning agent [3] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [3], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 4>
NMP (21.6 g) was added to the polyimide powder [D] (5.0 g) obtained in Synthesis Example 17 and dissolved by stirring at 70 ° C. for 40 hours. NMP (10.5g) and BCS (45.4g) were added to this solution, and the liquid crystal aligning agent [4] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [4], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 5>
NMP (27.2 g) was added to the polyimide powder [E] (5.0 g) obtained in Synthesis Example 18 and dissolved by stirring at 70 ° C. for 40 hours. NMP (13.5g) and BCS (37.6g) were added to this solution, and the liquid-crystal aligning agent [5] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [5], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 6>
NMP (25.0 g) was added to the polyimide powder [F] (5.1 g) obtained in Synthesis Example 19, and dissolved by stirring at 70 ° C. for 40 hours. NMP (12.5g) and BCS (42.5g) were added to this solution, and the liquid-crystal aligning agent [6] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [6], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 7>
NMP (24.4 g) was added to the polyimide powder [G] (5.0 g) obtained in Synthesis Example 20, and dissolved by stirring at 70 ° C. for 40 hours. NMP (12.2g) and BCS (41.8g) were added to this solution, and the liquid-crystal aligning agent [7] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [7], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 8>
NMP (30.1 g) was added to the polyimide powder [H] (5.0 g) obtained in Synthesis Example 21, and dissolved by stirring at 70 ° C. for 40 hours. NMP (14.7g) and BCS (33.5g) were added to this solution, and the liquid crystal aligning agent [8] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [8], a liquid crystal cell was prepared in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 9>
NMP (32.7 g) was added to the polyimide powder [I] (5.0 g) obtained in Synthesis Example 22, and dissolved by stirring at 70 ° C. for 40 hours. NMP (16.5g) and BCS (29.2g) were added to this solution, and the liquid crystal aligning agent [9] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [9], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 10>
NMP (31.5 g) was added to the polyimide powder [J] (4.8 g) obtained in Synthesis Example 23 and dissolved by stirring at 70 ° C. for 40 hours. NMP (15.5g) and BCS (28.1g) were added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained liquid-crystal aligning agent [10]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [10], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 11>
NMP (38.3 g) was added to the polyimide powder [K] (5.0 g) obtained in Synthesis Example 24, and dissolved by stirring at 70 ° C. for 40 hours. NMP (19.2g) and BCS (20.7g) were added to this solution, and the liquid crystal aligning agent [11] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [11], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 12>
NMP (32.2 g) was added to the polyimide powder [L] (4.9 g) obtained in Synthesis Example 25, and dissolved by stirring at 70 ° C. for 40 hours. NMP (16.1 g) and BCS (28.5 g) were added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent [12]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [12], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 13>
NMP (30.0 g) was added to the polyimide powder [M] (5.0 g) obtained in Synthesis Example 26, and dissolved by stirring at 70 ° C. for 40 hours. NMP (14.8g) and BCS (33.3g) were added to this solution, and the liquid-crystal aligning agent [13] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [13], a liquid crystal cell was prepared in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of residual charge relaxation, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Example 14>
NMP (32.6 g) was added to the polyimide powder [N] (5.0 g) obtained in Synthesis Example 27, and dissolved by stirring at 70 ° C. for 40 hours. NMP (16.6g) and BCS (29.2g) were added to this solution, and the liquid-crystal aligning agent [14] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [14], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Comparative Example 1>
NMP (24.5 g) was added to the polyimide powder [O] (4.5 g) obtained in Synthesis Example 28 and dissolved by stirring at 70 ° C. for 40 hours. NMP (12.3g) and BCS (33.8g) were added to this solution, and the liquid-crystal aligning agent [15] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [15], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Comparative example 2>
NMP (35.3 g) was added to the polyimide powder [P] (4.6 g) obtained in Synthesis Example 29, and dissolved by stirring at 70 ° C. for 40 hours. NMP (17.6g) and BCS (19.3g) were added to this solution, and the liquid-crystal aligning agent [16] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [16], a liquid crystal cell was prepared in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Comparative Example 3>
NMP (27.1 g) was added to the polyimide powder [Q] (4.5 g) obtained in Synthesis Example 30, and dissolved by stirring at 70 ° C. for 40 hours. NMP (13.3g) and BCS (30.1g) were added to this solution, and the liquid-crystal aligning agent [17] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [17], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

<Comparative example 4>
NMP (37.1 g) was added to the polyimide powder [R] (4.5 g) obtained in Synthesis Example 31, and dissolved by stirring at 70 ° C. for 40 hours. NMP (18.5g) and BCS (35.0g) were added to this solution, and the liquid-crystal aligning agent [18] was obtained by stirring at 25 degreeC for 2 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved. Using the obtained liquid crystal aligning agent [18], a liquid crystal cell was produced in the same manner as in Example 1, and evaluation of voltage holding ratio, evaluation of relaxation of residual charge, and evaluation after standing at high temperature were performed. The results are shown in Table 7 and Table 8 described later.

The liquid crystal alignment treatment agent of the present invention has a high voltage holding ratio when formed into a liquid crystal alignment film, and even after being exposed to a high temperature for a long time, the liquid crystal alignment film has a quick relaxation of charges accumulated by a DC voltage. Is obtained. Furthermore, a highly reliable liquid crystal display element that can withstand long-term use in a harsh use environment can be provided. As a result, it is useful for TN elements, STN elements, TFT liquid crystal elements, and liquid crystal display elements of vertical alignment type and horizontal alignment type (IPS).

It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-014970 filed on January 25, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (19)

The liquid-crystal aligning agent containing the copolymer obtained by making the diamine component and tetracarboxylic dianhydride component containing a diamine compound (A) and a diamine compound (B) react.
Diamine compound (A): a diamine compound represented by the following formula [1],
Diamine compound (B): a diamine compound having a carboxyl group in the molecule.

(Wherein [1], _{X 1} is ^{-O -, - NQ 1 -,} - CONQ 1 -, - NQ 1 CO -, - CH 2 O-, and at least one selected from the group consisting of -OCO- A divalent organic group, Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a non-aromatic cyclic carbonization hydrogen radicals, and at least one divalent organic group selected from the group consisting of an aromatic hydrocarbon group, _{X 3} is a single bond or ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ ² CO—, —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5), and at least one divalent organic group selected from the group consisting of Q ² is an alkyl group (having one to three the number of hydrogen atoms or carbon, _{X 3} is -NQ ² - if it is , Q ² is an alkyl group) having 1 to 3 carbon atoms, X ₄ is a nitrogen-containing aromatic heterocyclic ring, n is an integer from 1 to 4). The liquid crystal aligning agent according to claim 1, wherein the formula [1] is at least one selected from the group consisting of compounds represented by the following formulas [1a] to [1f].

(Wherein Q ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and at least one divalent organic group selected from the group consisting of an aromatic hydrocarbon group, _{X 3} is a single bond or ^{-O -, - NQ 2 -,} - CONQ 2 -, - NQ 2 CO-, At least one divalent organic group selected from the group consisting of —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5), and Q ² is hydrogen. An atom or an alkyl group having 1 to 3 carbon atoms (provided that when X ₃ is —NQ ² —, Q ² is an alkyl group having 1 to 3 carbon atoms) , and X ₄ is a nitrogen-containing aromatic heterocyclic ring. And n is an integer from 1 to 4. The liquid crystal aligning agent according to claim 2, wherein X ₂ in the formulas [1a] to [1f] is a single bond, a linear alkylene group having 1 to 3 carbon atoms, or a benzene ring. The liquid crystal aligning agent according to claim 2 or ₃ , wherein X ₃ in the formulas [1a] to [1f] is a single bond, —OCO—, or —OCH ₂ —. The liquid crystal aligning agent according to any one of claims 2 to ₄ , wherein X ₄ in the formulas [1a] to [1f] is an imidazole ring, a pyridine ring, or a pyrimidine ring.   The liquid crystal aligning agent according to any one of claims 2 to 5, wherein n in the formulas [1a] to [1f] is an integer of 1 or 2. X ₂ in the formula [1a] to the formula [1f] is at least one selected from the group consisting of a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring, a benzene ring, and a naphthalene ring, X ₃ is a group consisting of a single bond, —O—, —CONH—, —NHCO—, —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5). is at least one selected, X ₄ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and from the group consisting of benzimidazole ring The liquid-crystal aligning agent of Claim 2 which is at least 1 sort chosen, and n is an integer of 1 or 2. X ₂ in the formulas [1a] to [1f] is at least one selected from the group consisting of a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, and a benzene ring, and X ₃ is a single bond. , —O—, —CONH—, —NHCO—, —COO—, —OCO—, and —O (CH ₂ ) _m — (m is an integer of 1 to 5). The liquid crystal alignment according to claim 2, wherein X ₄ is at least one selected from the group consisting of a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring, and n is an integer of 1 or 2. Processing agent. X ₂ in the formulas [1a] to [1f] is at least one selected from the group consisting of a single bond, a linear alkylene group having 1 to 3 carbon atoms, and a benzene ring, and X ₃ is a single bond, Is at least one selected from the group consisting of OCO- and -OCH _2- , X ₄ is at least one selected from the group consisting of an imidazole ring, a pyridine ring, and a pyrimidine ring, and n is 1 or 2 The liquid-crystal aligning agent of Claim 2 which is an integer. The liquid crystal aligning agent according to any one of claims 1 to 9, wherein the diamine compound having a carboxyl group in the molecule is a diamine represented by the following formula [2].

(In the formula [2], X ₅ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and n is an integer of 1 to 4.) The liquid crystal aligning agent according to claim 10, wherein the diamine compound of the formula [2] is at least one diamine compound selected from the group consisting of the following formulas [3] to [7].

(In formula [3], m1 is an integer of 1 to 4, and in formula [4], X ₆ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH _2- , -COO-, -OCO-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-, m2 and m3 are each an integer of 0 to 4, and m2 + m3 is 1 to 4 It indicates the integer, wherein [5], m4 and m5 is an integer of from respectively 1 5, wherein [6], X ₇ is a straight-chain or branched alkyl group having 1 to 5 carbon atoms, m6 an integer from 1 to 5, wherein [7], _{X 8} is a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 - _{-C (CF 3) 2 -,} - O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH 3) -, or -N _(CH 3) a CO-, _{m 7} is an integer of 1 to 4).   The liquid-crystal aligning agent of Claim 11 whose m1 is an integer of 1 to 2 in Formula [3]. In Formula [4], X ₆ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —NH—, —N (CH ₃ The liquid crystal aligning agent according to claim 11, wherein m 2 and m 3 are integers of 1 in the formula:-), —CONH—, —NHCO—, —COO—, or —OCO—. In the formula [7], X ₈ is a single bond, —CH ₂ —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO. -, or a -OCO-, liquid crystal alignment treating agent according to claim 11 _{m 7} is an integer from 1 to 2.   The diamine which has a carboxyl group in a molecule | numerator is 0.01-99 mol with respect to 1 mol of diamine represented by Formula [1] in a diamine component, The claim 1 any one of Claims 14-14. Liquid crystal alignment treatment agent.   The liquid crystal aligning agent according to any one of claims 1 to 15, wherein 5 to 80% by mass of the solvent contained in the liquid crystal aligning agent is a poor solvent.   The liquid crystal aligning agent according to any one of claims 1 to 16, wherein the copolymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and ring-closing polyamic acid.   The liquid crystal aligning film obtained using the liquid-crystal aligning agent in any one of Claims 1-17.   The liquid crystal display element which has a liquid crystal aligning film of Claim 18.