JP5382372B2 - Liquid crystal alignment treatment 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 so-called polyimide liquid crystal alignment film obtained by applying and baking a liquid crystal alignment treatment agent mainly composed of a polyimide precursor such as polyamic acid or a soluble polyimide solution is mainly used. ing.

  One of the characteristics required for the liquid crystal alignment film is so-called pre-tilt angle control of the liquid crystal in which the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained at an arbitrary value. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film.

  Among the technologies for controlling the pretilt angle depending on the polyimide structure, the method using a diamine having a side chain as a part of the polyimide raw material increases the pretilt angle depending on the proportion of the diamine used, so the target pretilt angle is controlled. This is relatively easy and is useful as a means for increasing the pretilt angle. As the side chain structure of the diamine that increases the pretilt angle of the liquid crystal, a structure containing a steroid skeleton (see, for example, Patent Document 1) and a ring structure (see, for example, Patent Document 2) such as a phenyl group or a cyclohexyl group has been proposed. Furthermore, a diamine having 3 to 4 such ring structures in the side chain has also been proposed (see, for example, Patent Document 3).

  On the other hand, in the process of preparing the liquid crystal alignment film, when applying a solution of polyamic acid or a solvent-soluble polyimide to a substrate, it is generally industrially performed by flexographic printing, and the solvent of the coating liquid is In addition to N-methyl-2-pyrrolidone and γ-butyrolactone having excellent polymer solubility, butyl cellosolve and the like are mixed for the purpose of forming a uniform and defect-free thin film. However, since a solvent such as butyl cellosolve is inferior in the ability to dissolve polyamic acid or polyimide, it has a problem that precipitation occurs when mixed in a large amount (see, for example, Patent Document 4). In particular, this problem appears remarkably in a solvent-soluble polyimide solution.

  Moreover, since the polyimide obtained by using the diamine having a side chain as described above tends to reduce the coating uniformity of the solution, it is necessary to increase the mixing amount of the coating property improving solvent such as butyl cellosolve. Also, the mixing tolerance of such a solvent is an important characteristic of polyimide.

  In addition, as liquid crystal display elements are becoming higher in definition, liquid crystal alignment films used in the liquid crystal alignment films used in the liquid crystal display elements have a high voltage holding ratio and a direct current voltage from the viewpoint of suppressing contrast reduction and afterimage phenomenon. The characteristics that the accumulated charge when applied is small and the residual charge accumulated by the DC voltage is quickly relaxed are becoming increasingly important.

  In a polyimide-based liquid crystal alignment film, a liquid crystal alignment treatment agent containing a tertiary amine with a specific structure in addition to polyamic acid or imide group-containing polyamic acid is used as a short time until the afterimage generated by direct current voltage disappears. (For example, see Patent Document 5), and those using a liquid crystal aligning agent containing a soluble polyimide using a specific diamine having a pyridine skeleton as a raw material (see, for example, Patent Document 6). In addition to polyamic acid and its imidized polymer, etc., one carboxylic acid group is contained 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. Liquid crystal aligning agent containing a very small amount of a compound selected from a compound, a compound containing one carboxylic anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (for example, Patent Document 7) See).

  However, in recent years, large-screen, high-definition liquid crystal televisions have been widely put into practical use, and in such liquid crystal display elements, there are more demands for afterimages than displays that mainly display characters and still images. There is a demand for characteristics that can withstand long-term use in harsh usage environments. Therefore, the liquid crystal alignment film to be used has to be more reliable than conventional liquid crystal alignment films. The electrical characteristics of the liquid crystal alignment film are not only good in initial characteristics but also, for example, at a high temperature for a long time. There is a need to maintain good properties even after exposure.

JP-A-4-281427 JP-A-9-278724 JP 2004-67589 A Tokukaihei 2-37324 JP 9-316200 A JP-A-10-104633 JP-A-8-76128

  The object of the present invention is to prevent precipitation even when a poor solvent is mixed with a liquid crystal alignment treatment coating solution, and to increase the pretilt angle of the liquid crystal. Liquid crystal alignment treatment agent that can be aligned vertically, has a high voltage holding ratio, and provides a liquid crystal alignment film that can quickly relieve residual charges accumulated by DC voltage even after being exposed to a high temperature for a long time. Is to provide. Furthermore, an object of the present invention is to provide a highly reliable liquid crystal display element that can withstand long-term use in a severe use environment by using this liquid crystal alignment treatment agent.

The present inventor conducted intensive studies to achieve the above object, and found a novel liquid crystal aligning agent that achieves this. The present invention is based on such knowledge and has the following gist.
(1) A diamine compound (A) represented by the following formula [1], a diamine compound (B) represented by the following formula [2], and a diamine compound having a carboxyl group in the molecule A liquid crystal aligning agent comprising a copolymer obtained by reacting a diamine component containing (C) with tetracarboxylic dianhydride.

（式［１］中、ｐは、０又は１の整数であり、Ｘ_１はフェニレンであり、Ｘ_２はフェニレン又はシクロヘキシレンであり、Ｘ_３はシクロヘキシレンであり、Ｘ_４は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基である。式［２］中、Ｙ_１は−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−であり、Ｙ_２は単結合、炭素数１〜２０の脂肪族炭化水素基、非芳香族環式炭化水素基、又は芳香族炭化水素基であり、Ｙ_３は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、又は−Ｏ（ＣＨ_２）_ｍ−（ｍは１〜５の整数である）であり、Ｙ_４は窒素含有芳香族複素環であり、ｎは１〜４の整数である。）
（２）前記ジアミン化合物（Ａ）が、下記式［１'］で表されるジアミン化合物（Ａ'）である上記（１）に記載の液晶配向処理剤。

(In the formula [1], p is an integer of 0 or 1, X ₁ is phenylene, X ₂ is phenylene or cyclohexylene, X ₃ is cyclohexylene, and X ₄ has 3 to 3 carbon atoms. And an alkyl group having 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms, wherein Y ₁ is —O—, _{-NH -, - N (CH 3} ) -, - CONH -, - NHCO -, - CH 2 O -, - OCO -, - CON (CH 3) -, or -N _(CH 3) a CO-, Y 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, and Y ₃ is a single bond, —O—, —NH—, _{-N (CH 3) -, -} CONH -, - NHCO -, - COO -, - OCO -, - _{ON (CH 3) -, -} N (CH 3) CO-, or -O _{(CH 2)} m - is (m is an integer of 1 to 5), _{Y 4} is a nitrogen-containing aromatic heterocyclic , N is an integer from 1 to 4.)
(2) The liquid-crystal aligning agent as described in said (1) whose said diamine compound (A) is a diamine compound (A ') represented by following formula [1'].

（式［１'］中、Ｘ_１、Ｘ_２、Ｘ_３、及びＸ_４は前記式［１］と同義である。）
（３）前記ジアミン化合物（Ａ）が、下記式［１''］で表されるジアミン化合物（Ａ''）である上記（１）に記載の液晶配向処理剤。

(In the formula [1 ′], X ₁ , X ₂ , X ₃ and X ₄ have the same meanings as those in the formula [1].)
(3) The liquid-crystal aligning agent as described in said (1) whose said diamine compound (A) is a diamine compound (A '') represented by following formula [1 ''].

（式［１''］中、Ｘ''_１は１，４−フェニレン又は１，４−シクロへキシレンであり、Ｘ''_２は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基である。）
（４）ジアミン化合物（Ａ'）が、下記の式［１'ａ］で表されるジアミン化合物である上記（２）に記載の液晶配向処理剤。

(In the formula [1 ″], X ″ ₁ is 1,4-phenylene or 1,4-cyclohexylene, X ″ ₂ is an alkyl group having 3 to 12 carbon atoms, and 3 to 12 carbon atoms. A fluoroalkyl group, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms.)
(4) The liquid-crystal aligning agent as described in said (2) whose diamine compound (A ') is a diamine compound represented by following formula [1'a].

（式［１'ａ］中、Ｘ_５は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基であり、１，４−シクロへキシレンのシス−トランス異性は、それぞれトランス異性体である。）
（５）ジアミン化合物（Ａ'）が、下記の式［１'ｂ］で表されるジアミン化合物である上記（２）に記載の液晶配向処理剤。

(In the formula [1′a], X ₅ is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. And the cis-trans isomerism of 1,4-cyclohexylene is each a trans isomer.)
(5) The liquid-crystal aligning agent as described in said (2) whose diamine compound (A ') is a diamine compound represented by following formula [1'b].

（式［１'ｂ］中、Ｘ_６は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基であり、１，４−シクロへキシレンのシス−トランス異性は、トランス異性体である。）
（６）ジアミン化合物（Ａ''）が、下記の式［１''ａ］で表されるジアミン化合物である上記（３）に記載の液晶配向処理剤。

(In the formula [1′b], X ₆ is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. And the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer.)
(6) The liquid-crystal aligning agent as described in said (3) whose diamine compound (A '') is a diamine compound represented by following formula [1''a].

（式［１''ａ］中、Ｘ''_３は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基であり、１，４−シクロへキシレンのシス−トランス異性は、それぞれトランス異性体である）。
（７）ジアミン化合物（Ａ''）が、下記の式［１''ｂ］で表されるジアミン化合物である上記（３）に記載の液晶配向処理剤。

(In the formula [1 ″ a], X ″ ₃ is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. It is a fluoroalkoxy group, and the cis-trans isomerism of 1,4-cyclohexylene is each a trans isomer).
(7) The liquid-crystal aligning agent as described in said (3) whose diamine compound (A '') is a diamine compound represented by following formula [1''b].

（式［１''ｂ］中、Ｘ''_４は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基であり、１，４−シクロへキシレンのシス−トランス異性は、トランス異性体である）。
（８）式［２］中のＹ_１が−Ｏ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＮ（ＣＨ_３）−、又は−ＣＨ_２Ｏ−である上記（２）〜（７）のいずれか一項に記載の液晶配向処理剤。
（９）式［２］中のＹ_２が単結合、炭素数１〜５の直鎖又は分岐アルキル基、又はベンゼン環である上記（２）〜（８）のいずれか一項に記載の液晶配向処理剤。
（１０）式［２］中のＹ_３が単結合、−Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、又は−Ｏ（ＣＨ_２）_ｍ−（ｍは１〜５の整数である）である上記（２）〜（９）のいずれか一項に記載の液晶配向処理剤。

(In the formula [1 ″ b], X ″ ₄ is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. It is a fluoroalkoxy group, and the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer).
(8) The above (2) to (2), wherein Y ₁ in the formula [2] is —O—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) —, or —CH ₂ O—. The liquid crystal aligning agent as described in any one of 7).
(9) The liquid crystal according to any one of (2) to (8), wherein Y ₂ in formula [2] is a single bond, a linear or branched alkyl group having 1 to 5 carbon atoms, or a benzene ring. Alignment treatment agent.
(10) [2] _{Y 3} is a single bond in the, -O -, - CONH -, - NHCO -, - COO -, - OCO-, or _{-O (CH 2) m - (} m is 1-5 The liquid crystal aligning agent according to any one of the above (2) to (9).

(11) The liquid crystal alignment treating agent according to any one of Y ₄ pyrrole rings in [2], an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring in the above (2) to (10).
(12) The liquid-crystal aligning agent as described in any one of said (2)-(11) whose n in Formula [2] is an integer of 1-3.
(13) [2] _{Y 1} in the -O -, - NH -, - CONH -, - NHCO -, - CON (CH 3) -, or _-CH 2 is O-, _{Y 2} carbon atoms 1 to 5 linear or branched alkyl groups, Y ₃ is a single bond, Y ₄ is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, or pyrimidine ring, and n is an integer of 1 to 3. The liquid-crystal aligning agent as described in any one of said (2)-(7).
(14) In Formula [2], Y ₁ is —O—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) —, or —CH ₂ O—, and Y ₂ is a benzene ring. Y ₃ is —O—, —CONH—, —NHCO—, —COO—, —OCO—, or —O (CH ₂ ) _m — (m is an integer of 1 to 5), and Y The liquid-crystal aligning agent as described in any one of said (2)-(7) whose ₄ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring, and n is an integer of 1.
(15) The liquid-crystal aligning agent as described in any one of said (2)-(14) whose diamine compound (C) is a diamine compound represented by following formula [3].

（式［３］中、Ｚ_１は炭素数６〜３０の芳香族環を有する有機基であり、ｋは１〜４の整数である。）
（１６）式［３］のジアミン化合物が、下記の式［３ａ］、式［３ｂ］、式［３ｃ］、式［３ｄ］及び式［３ｅ］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（１５）に記載の液晶配向処理剤。

(In Formula [3], Z ₁ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and k is an integer of 1 to 4).
(16) The diamine compound of the formula [3] is at least one diamine compound selected from the group consisting of the following formula [3a], formula [3b], formula [3c], formula [3d] and formula [3e] The liquid-crystal aligning agent as described in said (15) which is.

（式［３ａ］中、ｍ_１は１〜４の整数である。式［３ｂ］中、Ｚ_２は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_２及びｍ_３はそれぞれ０〜４の整数を示し、かつｍ_２＋ｍ_３は１〜４の整数を示す。式［３ｃ］中、ｍ_４及びｍ_５はそれぞれ１〜５の整数である。式［３ｄ］中、Ｚ_３は炭素数１〜５の直鎖又は分岐アルキル基であり、ｍ_６は１〜５の整数である。式［３ｅ］中、Ｚ_４は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_７は１〜４の整数である。）

(In the formula [3a], m ₁ is an integer of ₁ to 4. In the formula [3b], Z ₂ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —. , —CF ₂ —, —C (CF ₃ ) —, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH _2- , -COO-, -OCO-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-, m ₂ and m ₃ each represent an integer of 0 to 4, and m ₂ + m ₃ represents an integer of 1 to 4. In formula [3c], m ₄ and m ₅ are each an integer of 1 to 5. In formula [3d], Z ₃ is a straight chain or branched chain having 1 to 5 carbon atoms. M ₆ is an alkyl group and m ₆ is an integer of 1 to 5. In formula [3e], Z ₄ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —. CF ₂ - _{-C (CF 3) -, -} 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).

In equation (17) [3a], the liquid crystal alignment treating agent according to the above (16) _{m 1} is an integer of 1-2.
(18) In the formula [3b], Z ₂ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —NH—, —N. (CH ₃ ) —, —CONH—, —NHCO—, —COO—, or —OCO—, wherein m ₂ and m ₃ are both integers of 1, the liquid crystal aligning agent according to (16) above.
(19) In the formula [3e], Z ₄ represents 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, and the liquid crystal aligning agent according to (16) above.
(20) In the diamine component, the diamine compound (A) is 0.5 to 50 mol with respect to 1 mol of the diamine compound (C), and the diamine compound (B) is 1 mol of the diamine compound (C). The liquid-crystal aligning agent as described in any one of said (2)-(19) which is 0.5-10 mol with respect to.
(21) The liquid-crystal aligning agent as described in any one of said (2)-(20) containing 5-70 mass% poor solvent in a liquid-crystal aligning agent.
(22) The liquid crystal aligning agent according to any one of (2) to (21), wherein the copolymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and cyclizing polyamic acid.
(23) A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of (2) to (22).
(24) A liquid crystal display device comprising the liquid crystal alignment film according to (23).

The liquid crystal alignment treatment agent of the present invention can be obtained by a relatively simple method, and has a characteristic of increasing the pretilt angle of the liquid crystal when formed into a liquid crystal alignment film. Can be made.
In addition, even when a poor solvent is mixed with the liquid crystal aligning agent coating solution, precipitation is unlikely to occur, and therefore a uniform liquid crystal alignment film can be formed even when coating on a large substrate.
Furthermore, it is possible to obtain a liquid crystal alignment film that has a high voltage holding ratio and can quickly relieve residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time. Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in 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 relates to a liquid crystal aligning agent containing a copolymer obtained by reacting a diamine component (A), a diamine compound (B) and a diamine component (C) with a tetracarboxylic dianhydride, A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and further a liquid crystal display element having the liquid crystal alignment film.

  At that time, the diamine compound (A) is a diamine compound represented by the formula [1], the diamine compound (B) is a diamine compound represented by the formula [2], and the diamine compound (C) is: It is a diamine compound having a carboxyl group in the molecule.

The diamine compound (A) used in the present invention is a specific diamine having a substituent having a characteristic of increasing the pretilt angle in the side chain (hereinafter, also referred to as a specific diamine (A)).
Therefore, the liquid crystal aligning agent obtained using this specific diamine (A) can align a liquid crystal perpendicularly even if the specific diamine (A) is used in a small proportion. Further, by reducing the use ratio, the solubility of the polymer in the organic solvent increases, and precipitation hardly occurs even when a poor solvent is mixed in the coating liquid of the liquid crystal alignment treatment agent.

  The diamine compound (B) used in the present invention (hereinafter sometimes referred to as a specific diamine (B)) has a nitrogen-containing aromatic heterocycle in the side chain. This nitrogen-containing aromatic heterocycle functions as an electron hopping site due to its conjugated structure, so that it is possible to promote charge transfer in the liquid crystal alignment film. Further, this nitrogen-containing aromatic heterocyclic ring is bonded to the carboxyl group of the diamine compound (C) (hereinafter sometimes referred to as a specific diamine (C)) by electrostatic interaction such as salt formation or hydrogen bonding. Thus, charge transfer occurs between the carboxyl group and the nitrogen-containing aromatic heterocycle. 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 the property of increasing the pretilt angle of the liquid crystal when formed into a liquid crystal alignment film, and can align the liquid crystal vertically even with a small use ratio. In addition, precipitation is unlikely to occur when a poor solvent is mixed in the liquid crystal aligning agent coating solution. Furthermore, it is possible to obtain a liquid crystal alignment film that has a high voltage holding ratio and can quickly relieve residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time.

Hereinafter, the compounds used in the present invention will be described.
<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、式［１］中、ｐは、０又は１の整数であり、Ｘ_１はフェニレン、好ましくは１,４−フェニレンであり、Ｘ_２はフェニレン、好ましくは１,４−フェニレン、又はシクロヘキシレンフェニレン好ましくは１,４−シクロヘキシレンであり、Ｘ_３はシクロヘキシレンフェニレン好ましくは１,４−シクロヘキシレンである。フェニレン及びシクロヘキシレンは、必要に応じて置換基を有していてもよい。Ｘ_４は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基である。
アルキル基、フルオロアルキル基、アルコキシ基、及びフルオロアルコキシ基は直鎖状又は分岐状でもよいが、直鎖状が好ましく、また、置換基を有していてもよい。
ジアミン化合物（Ａ）は、なかでも、下記式［１'］で表されるジアミン化合物（Ａ'）、又は、下記式［１''］で表されるジアミン化合物（Ａ''）が好ましい。

In formula [1], in formula [1], p is an integer of 0 or 1, X ₁ is phenylene, preferably 1,4-phenylene, and X ₂ is phenylene, preferably 1,4-phenylene. Or cyclohexylenephenylene, preferably 1,4-cyclohexylene, and X ₃ is cyclohexylenephenylene, preferably 1,4-cyclohexylene. Phenylene and cyclohexylene may have a substituent as necessary. X ₄ is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms.
The alkyl group, fluoroalkyl group, alkoxy group, and fluoroalkoxy group may be linear or branched, but are preferably linear, and may have a substituent.
Among them, the diamine compound (A) is preferably a diamine compound (A ′) represented by the following formula [1 ′] or a diamine compound (A ″) represented by the following formula [1 ″].

以下に、ジアミン化合物（Ａ'）及びジアミン化合物（Ａ''）について説明する。
＜ジアミン化合物（Ａ'）＞
本発明に用いるジアミン化合物（Ａ'）は、下記の式［１'］で表されるジアミン化合物である。

Hereinafter, the diamine compound (A ′) and the diamine compound (A ″) will be described.
<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、Ｘ_２、Ｘ_３、及びＸ_４は前記式［１］と同義である。）

(In the formula [1 ′], X ₁ , X ₂ , X ₃ and X ₄ have the same meanings as those in the formula [1].)

The bonding position of the amino group in the benzene ring to which the amino group in Formula [1 ′] is bonded is not limited. As specific examples, with respect to the side chain linking group (—CH ₂ O—), 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions on the benzene ring, 3 , 4 and 3 and 5 positions. Among these, from the viewpoint of reactivity when synthesizing the polyamic acid, the positions 2, 4, 2, 5, and 3, 5 are preferable. Considering the ease of synthesis of the diamine compound, the positions 2, 4 or 2, 5 are preferred.

  Among the diamine compounds of the formula [1 ′], the diamine compounds represented by the following formulas [1′a] and [1′b] have the effect of increasing the pretilt angle of the liquid crystal with a small use ratio. It is preferable because it is large. In particular, the diamine represented by the formula [1′a] is more preferable because of its excellent effect.

式［１'ａ］におけるＸ_５は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基である。中でも、Ｘ_５が炭素数３〜１２のアルキル基又は炭素数３〜１２のフルオロアルキル基が好ましく、より好ましくは炭素数３〜１２のアルキル基であり、特には、炭素数３〜７のアルキル基である。更には、式［１'ａ］における１，４ーシクロへキシレンのシス−トランス異性は、それぞれトランス異性体が好ましい。

X ₅ in the formula [1′a] is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. . Among them, X ₅ is preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, and particularly an alkyl group having 3 to 7 carbon atoms. It is a group. Furthermore, the cis-trans isomerism of 1,4-cyclohexylene in the formula [1′a] is preferably a trans isomer.

式［１'ｂ］におけるＸ_６は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基である。中でも、Ｘ_４が炭素数３〜１２のアルキル基又は炭素数３〜１２のフルオロアルキル基が好ましく、より好ましくは炭素数３〜１２のアルキル基であり、特には、炭素数３〜７のアルキル基である。更には、式［１'ｂ］における１，４ーシクロへキシレンのシス−トランス異性は、トランス異性体が好ましい。

X ₆ in Formula [1′b] is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. . Among them, X ₄ is preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, and particularly an alkyl group having 3 to 7 carbon atoms. It is a group. Further, the cis-trans isomerism of 1,4-cyclohexylene in the formula [1′b] is preferably a trans isomer.

Preferable specific examples of the diamine compound represented by the formula [1 ′] of the present invention are diamine compounds represented by the following formula [1′c] to formula [1′f]. X _{5 to} X ₈ in the following formulas are each independently an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or 3 to 3 carbon atoms. 12 fluoroalkoxy groups. Among them, X _{5 to} X ₈ are each independently preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, , An alkyl group having 3 to 7 carbon atoms. Moreover, all the cis-trans isomerisms of 1,4-cyclohexylene in the following formulas are trans isomers.

式［１'］で表されるジアミン化合物を製造する方法は特に限定されないが、好ましい方法としては以下の方法が挙げられる。

The method for producing the diamine compound represented by the formula [1 ′] is not particularly limited, but preferred methods include the following methods.

上記の式［１'ｇ］のジニトロ化合物を合成し、通常の方法でニトロ基を還元してアミノ基に変換することで得られる。ジニトロ化合物を還元する方法には、特に制限はなく、通常、パラジウム-炭素、酸化白金、ラネーニッケル、白金黒、ロジウム-アルミナ、硫化白金炭素などを触媒として用い、酢酸エチル、トルエン、テトラヒドロフラン、ジオキサン、アルコール系などの溶媒中、水素ガス、ヒドラジン、塩化水素などによって還元を行う方法がある。式［１'ｇ］中のＸ_１、Ｘ_２、Ｘ_３、及びＸ_４は、式［１］で定義したのと同じである。

It is obtained by synthesizing the dinitro compound of the above formula [1′g] and reducing the nitro group to convert it to an amino group by an ordinary method. The method for reducing the dinitro compound is not particularly limited. 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 of performing reduction with hydrogen gas, hydrazine, hydrogen chloride, or the like in an alcohol-based solvent. X ₁ , X ₂ , X ₃ and X ₄ in the formula [1′g] are the same as defined in the formula [1].

The dinitro compound of the formula [1′g] can be obtained by reacting a hydroxyl group-containing compound represented by the following formula [1′h] with dinitrochlorobenzene or the like. X ₁ , X ₂ , X ₃ and X ₄ in the formula [1′h] are the same as defined in the formula [1].

式［１'ｈ］で表される水酸基含有化合物を製造する方法は、下記の反応式（１）ないし、反応式（２）に示される方法により製造できるが、本発明はこれに限定されるものではない。

The method for producing the hydroxyl group-containing compound represented by the formula [1′h] can be produced by the method represented by the following reaction formula (1) or reaction formula (2), but the present invention is limited to this. It is not a thing.

When X ₂ is 1,4-cyclohexylene, a synthesis route of reaction formula (1) can be mentioned. X ₁ , X ₃ and X ₄ in the reaction formula (1) are the same as defined in the formula [1], R ₁ represents a protecting group such as a methyl group or a benzyl group, and R ₂ represents MgBr. , MgCl or Li.
Examples of the reagent used in the dehydration reaction include inorganic acids such as hydrochloric acid or sulfuric acid, organic acids such as p-toluenesulfonic acid, and acid anhydrides such as acetic anhydride or trifluoroacetic anhydride.

Examples of the reduction reaction include a hydrogenation reaction using palladium (Pd) or platinum (Pt) as a catalyst, or a catalytic reduction reaction using a metal such as iron, tin, or zinc.
Examples of the reaction of the deprotecting group include a methyl group elimination reaction using boron tribromide (BBr ₃ ), a debenzylation reaction by hydrogenation using a Pd catalyst, and the like.

Ｘ_２が１,４−フェニレンの場合、反応式（２）の合成経路が挙げられる。反応式（２）中のＸ_１、Ｘ_３、及びＸ_４は、式［１］で定義したのと同じであり、Ｔ_１はメチル基又はベンジル基などの保護基を表し、Ｔ_２はハロゲン原子、メタンスルホニルオキシ基、ベンゼンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、Ｂ（ＯＨ）_２、ＭｇＢｒ、ＭｇＣｌ又はＬｉなどを表し、Ｔ_３はハロゲン原子、メタンスルホニルオキシ基、ベンゼンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、Ｂ（ＯＨ）_２、ＭｇＢｒ、ＭｇＣｌ又はＬｉなどを表す。
脱保護基の反応としては、ＢＢｒ_３を用いたメチル基の脱離反応又はＰｄ触媒などを用いた水素添加による脱ベンジル化反応などが挙げられる。

When X ₂ is 1,4-phenylene, a synthesis route of the reaction formula (2) can be mentioned. X ₁ , X ₃ and X ₄ in the reaction formula (2) are the same as defined in the formula [1], T ₁ represents a protecting group such as a methyl group or a benzyl group, and T ₂ represents a halogen atom. Represents an atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a trifluoromethanesulfonyloxy group, B (OH) ₂ , MgBr, MgCl or Li, and T ₃ represents a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a trifluoro It represents a lomethanesulfonyloxy group, B (OH) ₂ , MgBr, MgCl or Li.
Examples of the deprotecting group reaction include a methyl group elimination reaction using BBr ₃ or a debenzylation reaction by hydrogenation using a Pd catalyst or the like.

<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１，４−フェニレン又は１，４−シクロへキシレンである。１，４−フェニレン及び１，４−シクロへキシレンは、必要に応じて置換基を有していてもよい。Ｘ''_２は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基である。アルキル基、フルオロアルキル基、アルコキシ基、及びフルオロアルコキシ基は直鎖状又は分岐状でもよいが、直鎖状が好ましく、置換基を有していてもよい。
式［１''］中のアミノ基が結合しているベンゼン環におけるアミノ基の結合位置は限定されない。具体例としては、側鎖の結合基（−Ｏ−）に対して、ベンゼン環上の２，３の位置、２，４の位置、２，５の位置、２，６の位置、３，４の位置、３，５の位置が挙げられる。なかでも、ポリアミド酸を合成する際の反応性の観点から、２，４の位置、２，５の位置、３，５の位置が好ましい。ジアミン化合物の合成の容易性も加味すると、２，４の位置、又は２，５の位置が好ましい。

In the formula [1 ″], X ″ ₁ is 1,4-phenylene or 1,4-cyclohexylene. 1,4-phenylene and 1,4-cyclohexylene may have a substituent, if necessary. X ″ ₂ is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. The alkyl group, fluoroalkyl group, alkoxy group and fluoroalkoxy group may be linear or branched, but are preferably linear and may have a substituent.
The bonding position of the amino group in the benzene ring to which the amino group in Formula [1 ″] is bonded is not limited. Specific examples include 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 on the benzene ring with respect to the side chain linking group (—O—). And positions 3, 5 and the like. Among these, from the viewpoint of reactivity when synthesizing the polyamic acid, the positions 2, 4, 2, 5, and 3, 5 are preferable. Considering the ease of synthesis of the diamine compound, the positions 2, 4 or 2, 5 are preferred.

Among the diamine compounds of formula [1 ″], diamines represented by the following formula [1 ″ a] and formula [1 ″ b] in which X ″ ₁ is 1,4-trans-cyclohexylene A compound is preferable because it has a large effect of increasing the pretilt angle of the liquid crystal with a small use ratio. In particular, the diamine compound represented by the formula [1 ″ a] is more preferable because of its excellent effect.

式［１''ａ］におけるＸ''_３は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基である。中でも、Ｘ''_３が炭素数３〜１２のアルキル基又は炭素数３〜１２のフルオロアルキル基が好ましく、より好ましくは炭素数３〜１２のアルキル基であり、特には、炭素数３〜７のアルキル基である。更には、式［１''ａ］における１，４ーシクロへキシレンのシス−トランス異性は、それぞれトランス異性体が好ましい。

X ″ ₃ in the formula [1 ″ a] is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy having 3 to 12 carbon atoms. It is a group. Among these, X ″ ₃ is preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, and particularly 3 to 7 carbon atoms. It is an alkyl group. Furthermore, the cis-trans isomerism of 1,4-cyclohexylene in the formula [1 ″ a] is preferably a trans isomer.

式［１''ｂ］におけるＸ''_４は炭素数３〜１２のアルキル基、炭素数３〜１２のフルオロアルキル基、炭素数３〜１２のアルコキシ基、又は炭素数３〜１２のフルオロアルコキシ基である。中でも、Ｘ''_４が炭素数３〜１２のアルキル基又は炭素数３〜１２のフルオロアルキル基が好ましく、より好ましくは炭素数３〜１２のアルキル基であり、特には、炭素数３〜７のアルキル基である。更には、式［１''ｂ］における１，４ーシクロへキシレンのシス−トランス異性は、トランス異性体が好ましい。

X ″ ₄ in the formula [1 ″ b] is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy having 3 to 12 carbon atoms. It is a group. Among these, X ″ ₄ is preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms, and particularly 3 to 7 carbon atoms. It is an alkyl group. Furthermore, the cis-trans isomerism of 1,4-cyclohexylene in the formula [1 ″ b] is preferably a trans isomer.

Preferable specific examples of the diamine compound represented by the formula [1 ″] of the present invention are diamine compounds represented by the following formula [1 ″ c] to formula [1 ″ f]. In addition, X ″ _{5 to} X ″ ₈ in the following formula are each independently an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, Or it is a C3-C12 fluoro alkoxy group. Among these, X ″ _{5 to} X ″ ₈ are each independently preferably an alkyl group having 3 to 12 carbon atoms or a fluoroalkyl group having 3 to 12 carbon atoms, more preferably an alkyl group having 3 to 12 carbon atoms. In particular, an alkyl group having 3 to 7 carbon atoms. Moreover, all the cis-trans isomerisms of 1,4-cyclohexylene in the following formulas are trans isomers.

式［１''］で表されるジアミン化合物を製造する方法は特に限定されないが、好ましい方法としては以下の方法が挙げられる。

Although the method to manufacture the diamine compound represented by Formula [1 ''] is not specifically limited, As a preferable method, the following method is mentioned.

上記の式［１''ｇ］のジニトロ化合物を合成し、通常の方法でニトロ基を還元してアミノ基に変換することで得られる。ジニトロ化合物を還元する方法には、特に制限はなく、通常、パラジウム-炭素、酸化白金、ラネーニッケル、白金黒、ロジウム-アルミナ、硫化白金炭素などを触媒として用い、酢酸エチル、トルエン、テトラヒドロフラン、ジオキサン、アルコール系などの溶媒中、水素ガス、ヒドラジン、塩化水素などによって還元を行う方法がある。式［１''ｇ］中のＸ''_１、及びＸ''_２は、式［１''］で定義したのと同じである。
式［１''ｇ］ののジニトロ化合物は、下記の式［１''ｈ］で表わされる水酸基含有化合物とジニトロクロロベンゼンなどとの反応により得ることができる。なお、式［１''ｈ］中のＸ''_１、及びＸ''_２は式［１''］で定義したのと同じである。

It is obtained by synthesizing the dinitro compound of the above formula [1 ″ g] and reducing the nitro group to convert it to an amino group by a usual method. The method for reducing the dinitro compound is not particularly limited. 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 of performing reduction with hydrogen gas, hydrazine, hydrogen chloride, or the like in an alcohol-based solvent. X ″ ₁ and X ″ ₂ in the formula [1 ″ g] are the same as defined in the formula [1 ″].
The dinitro compound of the formula [1 ″ g] can be obtained by reacting a hydroxyl group-containing compound represented by the following formula [1 ″ h] with dinitrochlorobenzene or the like. X ″ ₁ and X ″ ₂ in the formula [1 ″ h] are the same as defined in the formula [1 ″].

式［１''ｈ］で表される水酸基含有化合物を製造する方法は、下記の反応式（１）ないし、反応式（２）に示される方法により製造できるが、本発明はこれに限定されるものではない。
Ｘ''_１が１，４ーシクロへキシレンの場合、反応式（１）の合成経路が挙げられる。反応式（１）中のＸ''_２は、式［１''］で定義したのと同じであり、Ｒ_１はメチル基又はベンジル基などの保護基を表し、Ｒ_２はＭｇＢｒ、ＭｇＣｌ又はＬｉなどを表す。
脱水反応に用いられる試剤としては、塩酸又は硫酸などの無機酸類、ｐ−トルエンスルホン酸などの有機酸類、無水酢酸又は無水トリフルオロ酢酸などの酸無水物類などが挙げられる。

The method for producing the hydroxyl group-containing compound represented by the formula [1 ″ h] can be produced by the method represented by the following reaction formula (1) or reaction formula (2), but the present invention is limited to this. It is not something.
In the case where X ″ ₁ is 1,4-cyclohexylene, the synthesis route of the reaction formula (1) can be mentioned. X ″ ₂ in the reaction formula (1) is the same as defined in the formula [1 ″], R ₁ represents a protecting group such as a methyl group or a benzyl group, and R ₂ represents MgBr, MgCl or Li etc. are represented.
Examples of the reagent used in the dehydration reaction include inorganic acids such as hydrochloric acid or sulfuric acid, organic acids such as p-toluenesulfonic acid, and acid anhydrides such as acetic anhydride or trifluoroacetic anhydride.

Examples of the reduction reaction include a hydrogenation reaction using palladium (Pd) or platinum (Pt) as a catalyst, or a catalytic reduction reaction using a metal such as iron, tin, or zinc.
Examples of the reaction of the deprotecting group include a methyl group elimination reaction using boron tribromide (BBr ₃ ), a debenzylation reaction by hydrogenation using a Pd catalyst, and the like.

Ｘ''_１が１，４−フェニレンの場合、反応式（２）の合成経路が挙げられる。反応式（２）中のＸ''_２は、式［１''］で定義したのと同じであり、Ｔ_１はメチル基又はベンジル基などの保護基を表し、Ｔ_２はハロゲン原子、メタンスルホニルオキシ基、ベンゼンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、Ｂ（ＯＨ）_２、ＭｇＢｒ、ＭｇＣｌ又はＬｉなどを表し、Ｔ_３はハロゲン原子、メタンスルホニルオキシ基、ベンゼンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基、Ｂ（ＯＨ）_２、ＭｇＢｒ、ＭｇＣｌ又はＬｉなどを表す。
脱保護基の反応としては、ＢＢｒ_３を用いたメチル基の脱離反応又はＰｄ触媒などを用いた水素添加による脱ベンジル化反応などが挙げられる。

When X ″ ₁ is 1,4-phenylene, a synthesis route of the reaction formula (2) can be mentioned. X 'in the reaction formula (2)' ₂ has the formula [1 'is the same as defined'], T ₁ represents a protecting group such as a methyl group or a benzyl group, T ₂ represents a halogen atom, methane Represents a sulfonyloxy group, a benzenesulfonyloxy group, a trifluoromethanesulfonyloxy group, B (OH) ₂ , MgBr, MgCl or Li, and T ₃ represents a halogen atom, a methanesulfonyloxy group, a benzenesulfonyloxy group, a trifluoromethanesulfonyloxy group. Group, B (OH) ₂ , MgBr, MgCl, Li or the like.
Examples of the deprotecting group reaction include a methyl group elimination reaction using BBr ₃ or a debenzylation reaction by hydrogenation using a Pd catalyst or the like.

<Diamine compound (B)>
The diamine compound (B) used in the present invention is a diamine compound represented by the following formula [2].

式［２］中、Ｙ_１は−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−であり、Ｙ_２は単結合、炭素数１〜２０の脂肪族炭化水素基、非芳香族環式炭化水素基、又は芳香族炭化水素基であり、Ｙ_３は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−、又は−Ｏ（ＣＨ_２）_ｍ−（ｍは１〜５の整数である）であり、Ｙ_４は窒素含有芳香族複素環であり、ｎは１〜４の整数である。
式［２］における２つのアミノ基（−ＮＨ_２）の結合位置は限定されない。具体的には、側鎖の結合基（Ｙ_１）に対して、ベンゼン環上の２，３の位置、２，４の位置、２，５の位置、２，６の位置、３，４の位置、３，５の位置が挙げられる。なかでも、ポリアミック酸を合成する際の反応性の観点から、２，４の位置、２，５の位置、３，５の位置が好ましい。ジアミン化合物を合成する際の容易性も加味すると、２，４の位置、又は２，５の位置がより好ましい。

In Formula [2], Y ₁ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) —. Or —N (CH ₃ ) CO—, Y 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; ₃ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ) —, —N (CH ₃ ) CO— or —O (CH ₂ ) _m — (m is an integer of 1 to 5), Y ₄ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4.
The bonding position of the _two amino groups (—NH ₂ ) in Formula [2] is not limited. Specifically, with respect to the linking group (Y ₁ ) of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring Position, 3, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, the positions 2, 4, 2, 5, and 3, 5 are preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 2, 5 are more preferable.

In Formula [2], Y ₁ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) —. Or —N (CH ₃ ) CO—. Among them, -O -, - NH -, - CONH -, - NHCO -, - CON (CH 3) -, - CH 2 O-, or -OCO- are preferred because it is easy to synthesize the diamine compound. Particularly preferred is —O—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) —, or —CH ₂ O—.

In Formula [2], Y 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. A C1-C20 aliphatic hydrocarbon group may be linear, may be branched, and may have an unsaturated bond. Preferably it is a C1-C10 aliphatic hydrocarbon group. Specific examples of the non-aromatic 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. Decane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring , Norbornene ring, adamantane ring and the like.
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 Y ₂ in the formula [2] 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, a cyclopentane ring, Examples include 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, and more preferably a single bond, a linear or branched alkyl having 1 to 10 carbon atoms. Group, an unsaturated alkyl 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 carbon number of 1 to 10 Examples include linear or branched alkyl groups, cyclohexane rings, benzene rings, and naphthalene rings. Particularly preferable examples include a single bond, a linear or branched alkyl group having 1 to 5 carbon atoms, and a benzene ring.

In Formula [2], Y ₃ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ). —, —N (CH ₃ ) CO—, or —O (CH ₂ ) _m — (m is an integer of 1 to 5), preferably a single bond, —O—, —NH—, —CONH. —, —NHCO—, —COO—, —OCO—, or —O (CH ₂ ) _m — (m is an integer of 1 to 5), more preferably a single bond, —O—, —NH. -, - CONH -, - NHCO -, - COO -, - OCO-, or -O _{(CH 2)} m - is (m is an integer of 1 to 5), more preferably a single bond, -O -, - CONH -, - NHCO -, - COO -, - OCO-, or -O _{(CH 2)} m - is (m is an integer of 1 to 5)
In the formula [2], Y 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], [2b], and [2c] Containing aromatic heterocycle.

（式［２ｃ］中、Ａ_１は炭素数１〜５の直鎖又は分岐アルキル基である）。

(In Formula [2c], A ₁ is a linear or branched alkyl group having 1 to 5 carbon atoms).

  Specific examples of the nitrogen-containing aromatic heterocycle include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, and a 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, oxa A diazole ring, an acridine ring, etc. can be mentioned.

Preferred Y ₄ in the formula [2] 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 ring, benzothiazole ring, phenothiazine ring, oxadiazole ring An acridine ring, and more preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, a carbazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, and a pyrazolidine. Ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, and more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, Examples thereof include a benzimidazole ring and a benzimidazole ring, and particularly preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring.
Further, _{Y 3} is formula contained in _{Y 4} [2a], wherein [2b], and is preferably bonded with a substituent nonadjacent the formula [2c].

In the formula [2], n is an integer of 1 to 4, and preferably 1 to 3 from the viewpoint of reactivity with tetracarboxylic dianhydride.
A preferred combination of Y ₁ , Y ₂ , Y ₃ , Y ₄ , and n in the formula [2] is such that Y ₁ is —O—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) —. , —CH ₂ O—, or —OCO—, wherein Y ₂ is a linear or branched alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, or cyclopentane. Ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring, or anthracene ring, and Y ₃ is a single bond, —O—, —NH—, —CONH. -, - NHCO -, - COO -, - OCO-, or -O _{(CH 2)} m - is (m is an integer of 1 to 5), _{Y 4} is a pyrrole ring, an imidazole ring, oxa 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 A ring, a benzimidazole ring, a benzimidazole ring, a thionoline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, or an acridine ring, and n is 1 to 2.

In a more preferable formula [2], Y ₁ , Y ₂ , Y ₃ , Y ₄ , and n have a combination in which Y ₁ is —O—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, Or -OCO-, wherein Y ₂ is a linear or branched alkyl group having 1 to 10 carbon atoms, unsaturated alkyl group having 1 to 10 carbon atoms, cyclohexane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, fluorene A ring or an anthracene ring, and Y ₃ is a single bond, —O—, —NH—, —CONH—, —NHCO—, —COO—, —OCO—, or —O (CH ₂ ) _m — (m is is 1-5 for an integer), Y ₄ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, a carbazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, Pirazoriji Ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzimidazole ring, n is 1-2.

In a more preferable combination of Y ₁ , Y ₂ , Y ₃ , Y ₄ , and n in the formula [2], Y ₁ is —O—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ). -, - _CH 2 O-, or a -OCO-, _{Y 2} is a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclohexane ring, a benzene ring, or a naphthalene ring cycloheteroalkyl, _{Y 3} is a single bond , —O—, —CONH—, —NHCO—, —COO—, —OCO—, or —O (CH ₂ ) _m — (m is an integer of 1 to 5), and Y 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, or a benzimidazole ring, and n is 1 or 2.

Particularly preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , and n in the formula [2] are as follows: Y ₁ is —O—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ). -, or _-CH 2 is O-, _{Y 2} is a single bond, a straight-chain or branched alkyl group having 1 to 5 carbon atoms, a benzene ring, _{Y 3} is a single bond, -O -, - CONH -, - NHCO -, - COO -, - OCO-, or -O _{(CH 2)} m - is (m is an integer of 1 to 5), _{Y 4} is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or It is a pyrimidine ring, and n is 1 to 3.
The most preferable combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , and n in the formula [2] are as shown in Tables 1 to 8 below.

本発明の式［２］で表されるジアミン化合物を製造する方法は特に限定されないが、好ましい方法としては以下の方法が挙げられる。

Although the method to manufacture the diamine compound represented by Formula [2] of this invention is not specifically limited, The following method is mentioned as a preferable method.

上記の式［２ｄ］で示すジニトロ化合物を合成し、通常の方法でニトロ基を還元してアミノ基に変換することで得られる。ジニトロ化合物を還元する方法には、特に制限はなく、通常、パラジウム-炭素、酸化白金、ラネーニッケル、白金黒、ロジウム-アルミナ、硫化白金炭素などを触媒として用い、酢酸エチル、トルエン、テトラヒドロフラン、ジオキサン、アルコール系などの溶媒中、水素ガス、ヒドラジン、塩化水素などによって還元を行う方法がある。式［２ｄ］中のＹ_１、Ｙ_２、Ｙ_３、Ｙ_４、及びｎは、式［２］の定義と同意義である。
式［２ｄ］のジニトロ化合物は、Ｙ_３を介してＹ_２及びＹ_４を結合させ、その後、ジニトロ部をＹ_１を介して結合させる方法、ジニトロ部を連結部Ｙ_１を介してＹ_２を結合させ、その後、Ｙ_３を介してＹ_４と結合させる方法などで得ることができる。

It can be obtained by synthesizing the dinitro compound represented by the above formula [2d] and reducing the nitro group to convert it to an amino group by an ordinary method. The method for reducing the dinitro compound is not particularly limited. 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 of performing reduction with hydrogen gas, hydrazine, hydrogen chloride, or the like in an alcohol-based solvent. Y ₁ , Y ₂ , Y ₃ , Y ₄ , and n in the formula [2d] are as defined in the formula [2].
Dinitro compound of formula [2d], via a _{Y 3} is bound to _{Y 2} and _{Y 4,} then, a method of attaching dinitro section through the _{Y 1,} the _{Y 2} via a connecting portion _{Y 1} dinitro portion It can be obtained by, for example, a method of bonding to Y ₄ via Y ₃ .

Y ₁ represents —O— (ether bond), —NH— (amino bond), —N (CH ₃ ) — (methylated amino bond), —CONH— (amide bond), —NHCO— (reverse amide bond), -CH ₂ O-(methylene ether bond), - OCO- (reverse ester _{bond), - CON (CH 3)} - (N- methyl-amide bond), or _-N (CH 3) CO- (N- methylation Linking groups such as reverse amide bonds), and these linking groups can be formed by conventional organic synthetic techniques.
For example, when Y ₁ is an ether or methylene ether bond, a corresponding dinitro group-containing halogen derivative is reacted with a hydroxyl group derivative containing Y ₂ , Y ₃ and Y ₄ in the presence of an alkali, or a dinitro group-containing hydroxyl group derivative And a halogen-substituted derivative containing Y ₂ , Y ₃ and Y ₄ 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 Y ₂ , Y ₃ and Y ₄ in the presence of an alkali can be mentioned.
In the case of an ester bond, a method of reacting a corresponding dinitro group-containing acid chloride and a hydroxyl group-substituted derivative containing Y ₂ , Y ₃ and Y 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 Y ₂ , Y ₃ and Y ₄ in the presence of an alkali can be mentioned.

In the case of an amide bond, a method of reacting a corresponding dinitro group-containing acid chloride and an amino group-substituted product containing Y ₂ , Y ₃ and Y ₄ in the presence of an alkali can be mentioned.
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 Y ₂ , Y ₃ and Y 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.
The dinitro group-containing halogen derivative and the dinitro group-containing derivative can be used by selecting one or more kinds in consideration of the availability of raw materials and the point of reaction.

<Diamine compound (C)>
The diamine compound (C) 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 [3] is preferable.

式［３］中、Ｚ_１は炭素数６〜３０の芳香族環を有する有機基であり、ｋは１〜４の整数である。
式［３］で表される化合物を具体的に示すと、下記の式［３ａ］、式［３ｂ］、式［３ｃ］、式［３ｄ］及び式［３ｅ］のジアミン化合物が挙げられる。

In the formula [3], Z ₁ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and k is an integer of 1 to 4.
Specific examples of the compound represented by the formula [3] include diamine compounds represented by the following formula [3a], formula [3b], formula [3c], formula [3d] and formula [3e].

式［３ａ］中、ｍ_１は１〜４の整数である。
式［３ｂ］中、Ｚ_２は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_２及びｍ_３はそれぞれ０〜４の整数を示し、かつｍ_２＋ｍ_３は１〜４の整数を示す。
式［３ｃ］中、ｍ_４及びｍ_５はそれぞれ１〜５の整数である。
式［３ｄ］中、Ｚ_３は炭素数１〜５の直鎖又は分岐アルキル基であり、ｍ_６は１〜５の整数である。
式［３ｅ］中、Ｚ_４は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、又は−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_７は１〜４の整数を示す。

In the formula [3a], m ₁ is an integer of ₁ to 4.
In formula [3b], Z ₂ represents a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) —, —O—, _{-CO -, - NH -, -} N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH2 -, - COO -, - OCO -, - CON (CH 3) -, or -N _(CH 3) a CO-, _{m 2} and _{m 3} are each an integer of 0 to 4, and _m 2 + _{m 3} is an integer of 1-4.
In formula [3c], m ₄ and m ₅ are each an integer of 1 to 5.
In formula [3d], Z ₃ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m ₆ is an integer of 1 to 5.
In formula [3e], Z ₄ represents a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) —, —O—, _{-CO -, - NH -, -} N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH2 -, - COO -, - OCO -, - CON (CH 3) -, or -N _(CH 3) a CO-, _{m 7} represents an integer of 1-4.

In the diamine compounds of the above formula [3a], formula [3b], formula [3c], formula [3d] and formula [3e], preferably, in formula [3a], m ₁ is an integer of ₁ to 2 In the formula [3b], Z ₂ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —NH—, —N. (CH ₃ ) —, —CONH—, —NHCO—, —COO—, or —OCO—, wherein m ₂ and m ₃ are both integers of 1, and in formula [3e], Z ₄ is A single bond, —CH ₂ —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, or —OCO—, m ₇ is a structure which is an integer of 1-2.

  Specific examples of the diamine compound (C) include compounds of the following formula [3f] to formula [3n] and formula [3p].

式［３ｎ］中、Ｂ_１は単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、又は−ＯＣＯ−である。
式［３ｐ］中、Ｂ_２は単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、又は−ＯＣＯ−である。

In formula [3n], B ₁ is a single bond, —CH ₂ —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO. -Or -OCO-.
In the formula [3p], B ₂ 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), a diamine compound (B), and a diamine compound (C) 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.

  In addition to the diamine compound (A), the diamine compound (B), and the diamine compound (C), the side chain includes an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a macrocyclic substitution composed thereof. A diamine compound having a body can be used. Specifically, diamines represented by the following formulas [DA1] to [DA26] can be exemplified.

式［ＤＡ１］〜式［ＤＡ５］中、Ｒ_１は、炭素数１以上２２以下のアルキル基又は炭素数１以上２２以下の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 having 1 to 22 carbon atoms.

式［ＤＡ６］〜式［ＤＡ９］中、Ｒ_２は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−、又は−ＮＨ−を示し、Ｒ_３は炭素数１以上２２以下のアルキル基又は炭素数１以上２２以下のフッ素含有アルキル基を示す。

In 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 having 1 to 22 carbon atoms.

式［ＤＡ１０］及び式［ＤＡ１１］中、Ｒ_４は、−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−、又は−ＣＨ_２ＯＣＯ−を示し、Ｒ_５は炭素数１以上２２以下のアルキル基、炭素数１以上２２以下のアルコキシ基、炭素数１以上２２以下のフッ素含有アルキル基又は炭素数１以上２２以下のフッ素含有アルコキシ基である。

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 1 carbon atom. These are an alkyl group having 22 or less, an alkoxy group having 1 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

式［ＤＡ１２］〜式［ＤＡ１４］中、Ｒ_６は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、又は−ＣＨ_２−を示し、Ｒ_７は炭素数１以上２２以下のアルキル基、炭素数１以上２２以下のアルコキシ基、炭素数１以上２２以下のフッ素含有アルキル基又は炭素数１以上２２以下のフッ素含有アルコキシ基である。

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- , wherein R ₇ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, or 1 or more carbon atoms. 22 or less fluorine-containing alkoxy group.

式［ＤＡ１５］及び式［ＤＡ１６］中、Ｒ_８は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−、−Ｏ−、又は−ＮＨ−を示し、Ｒ_９はフッ素基、シアノ基、トリフルオロメタル基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基、又は水酸基である。

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 trifluorometal group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group It is.

さらに、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。

Furthermore, the diaminosiloxane etc. which are shown by the following formula [DA27] can be mentioned.

式［ＤＡ２７］中、ｍは、１〜１０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 formula [DA27], m is an integer of 1-10.
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 of carboxylic acid for obtaining tetracarboxylic dianhydride are given below.
Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetracarboxylic acid, bis ( 3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2 , 2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bi (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxy) Phenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid Acid, oxydiphthaltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1 , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Boronic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3 , 4-Dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [3 , 3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane -2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2,6>] Undecane-3, 5, 9 11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydraphthalene-1,2 -Dicarboxylic acid, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Hexane-1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane- 2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and the like.

  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 is a polyamic acid obtained by reacting a diamine compound (A), a diamine compound (B), a diamine component containing the diamine compound (C), and a tetracarboxylic dianhydride, And a polyimide obtained by dehydrating and ring-closing this polyamic acid. Both the polyamic acid and the polyimide are useful as a copolymer for obtaining a liquid crystal alignment film.

In the liquid crystal alignment film obtained using the copolymer of the present invention, the pretilt angle of the liquid crystal increases as the content ratio of the diamine compound (A) in the diamine component increases. Therefore, in the diamine component, the content of the diamine compound (A) is preferably 0.01 to 99 mol with respect to 1 mol of the diamine compound (C). More preferably, it is 0.1-75 mol, More preferably, it is 0.5-50 mol.
In addition, the liquid crystal alignment film obtained by using the copolymer of the present invention has a higher voltage holding ratio and is exposed to a high temperature for a long time as the content ratio of the diamine compound (B) in the diamine component increases. Even so, 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 (C). 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 diamine and tetracarboxylic dianhydride 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 diamine component and the tetracarboxylic dianhydride 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.

  Although the polymerization temperature in that case can select arbitrary temperature of -20-150 degreeC, Preferably it is the range of -5-100 degreeC. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total of the diamine component and the tetracarboxylic dianhydride is preferably 1 to 50% by mass, more preferably 5 to 30% by mass with respect to the entire reaction solution (100% 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, catalytic imidization in which a catalyst is added to the polyamic acid solution, and the like. The temperature at which the polyamic acid is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and a method in which water generated by the imidation reaction is removed from the system is preferable.

The catalytic imidation of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amidic 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, the process of re-dissolving the precipitated and recovered copolymer in an organic solvent and repeating the reprecipitation and recovery can be repeated 2 to 10 times to reduce impurities in the copolymer. 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 weights of the polyamic acid and the polyimide contained in the liquid crystal alignment treatment agent of the present invention are determined by considering the strength of the obtained coating film, workability at the time of coating film formation, and uniformity of the coating film, GPC (Gel Permeation Chromatography). ) Is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000 in terms of weight average molecular weight measured by the method.

<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 at least 1 type of copolymer chosen from the copolymer of this invention mentioned above.
At that time, the content of the resin component is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass with respect to the entire liquid crystal alignment treatment agent (100% by mass). is there.

In the present invention, all of the resin components may be the copolymer of the present invention, and other copolymers may be mixed with the copolymer of the present invention. In that case, content of the other copolymer in a resin component is 0.5-15 mass%, Preferably it is 1-10 mass%.
Such other copolymer is, for example, a polyamide obtained by using a diamine other than the diamine compound (A), the diamine compound (B), and the diamine compound (C) as a diamine component to be reacted with tetracarboxylic dianhydride. An acid or a polyimide is mentioned.
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.

The liquid crystal aligning agent of this invention may contain components other than the above. Examples thereof include a solvent or compound that improves the film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied, and a compound that improves the adhesion between the liquid crystal alignment film and the substrate.
Specific examples of the solvent for improving the film thickness uniformity and 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, hexane, n-pentane, n-octane, di Cyl 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, 3 -Ethyl 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-1- Low surface tension such as no ethyl 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 And the like.

These solvents may be used alone or in combination. When using the above solvent, it is preferable that it is 5-80 mass% of the whole solvent contained in a liquid-crystal aligning agent, More preferably, it is 20-60 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, F-top 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 the compound which improves adhesiveness with a board | substrate, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of the resin component contained in a liquid-crystal aligning agent, More preferably, 1- 20 parts by mass. If the amount is less than 0.1 part 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. 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 form a coating film by evaporating the solvent at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate. If the thickness of the coating film 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, so it is preferably 5 to 300 nm, more preferably 10-100 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.

The present invention will be described in more detail with reference to the following examples, but should not be construed as being limited thereto.
"Synthesis of polyamic acid or polyimide"
The abbreviations of the compounds used in the examples are shown below.
<Tetracarboxylic dianhydride>
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

<Diamine compound (A ')>
m-PBCH5DABz: 1,3-diamino-5- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxymethyl} benzene m-PBCH7DABz: 1,3-diamino-5- {4 -[Trans-4- (trans-4-n-heptylcyclohexyl) cyclohexyl] phenoxymethyl} benzene p-PBCH5DABz: 1,4-diamino-5- {4- [trans-4- (trans-4-n-pentyl) Cyclohexyl) cyclohexyl] phenoxymethyl} benzene m-BPCH5DABz: 1,3-diamino-5- {4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxymethyl} benzene

<Diamine compound (A '')>
PBCH5DAB: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene PBCH7DAB: 1,3-diamino-4- {4- [trans-4 -(Trans-4-n-heptylcyclohexyl) cyclohexyl] phenoxy} benzene BPCH5DAB: 1,3-diamino-4- {4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxy} benzene

<Diamine compound (B)>
Diamine (B1) to Diamine (B12)

<Diamine compound (C)>
DBA: 3,5-diaminobenzoic acid

<Other diamines>
p-PDA: p-phenylenediamine m-PBCH5DABEs: 3,5-diamino- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenyl} benzoate PBP5DABz: 1,3-diamino- 4-[(4-n-pentylphenyl) phenoxymethyl] benzene PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene PBP5DAB: 1,3-diamino-4 -[(4-n-pentylphenyl) phenoxy] benzenediamine (S1)

<Organic solvent>
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve

<Molecular weight measurement of polyamic acid and 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: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight 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.) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture). The solution was completely dissolved by applying ultrasonic waves.
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 by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears near 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.

<Example 1>
BODA (3.50 g, 14.0 mmol), m-PBCH5DABz (1.87 g, 4.20 mmol), diamine (B1) (2.03 g, 8.39 mmol), and DBA (2.34 g, 15.4 mmol). After mixing in NMP (20.8 g) and reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (16.4 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.

After NMP was added to this polyamic acid solution (20.1 g) and diluted so that the content of polyamic acid was 6% by mass, acetic anhydride (2.50 g) and pyridine (1.92 g) were used as an imidization catalyst. And reacted at 80 ° C. for 4 hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 54%, the number average molecular weight was 18,500, and the weight average molecular weight was 47,100.
NMP (19.5g) and BCS (27.5g) were added to this polyimide powder (3.00g), and liquid crystal aligning agent [1] was obtained. 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 aligning agent [1] obtained above was spin-coated on the ITO surface of the substrate with 3 cm × 4 cm ITO electrode, and baked at 80 ° C. for 5 minutes and in a 210 ° C. hot air circulating oven for 1 hour. A polyimide coating was prepared.
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. After bonding the liquid crystal alignment film surface of another substrate to the inside and the rubbing direction being reversed, the sealing agent was cured to prepare an empty cell. A nematic liquid crystal was injected into this empty cell by a reduced pressure injection method to obtain an antiparallel aligned nematic liquid crystal cell.

<Evaluation of pretilt angle>
The pretilt angle of the liquid crystal cell produced above was measured at room temperature using a pretilt angle measuring device (ELSICON model: PAS-301). The results are shown in Table 11.
Moreover, when the liquid crystal cell produced similarly to the above except having not rubbed was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Evaluation of voltage holding ratio>
A voltage of 4 V was applied to the liquid crystal cell after measuring the pretilt angle at a temperature of 80 ° C. at 60 μm, the voltage after 16.67 ms and 1667 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio. . The results are shown in Table 12.
<Evaluation of residual charge relaxation>
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 12.
<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 12 and Table 13 described later.

<Example 2>
BODA (3.51 g, 14.0 mmol), m-PBCH5DABz (3.76 g, 8.42 mmol), diamine (B1) (1.36 g, 5.61 mmol), and DBA (2.13 g, 14.0 mmol). After mixing in NMP (22.0 g) and reacting at 80 ° C. for 5 hours, CBDA (2.75 g, 14.0 mmol) and NMP (17.6 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to this polyamic acid solution (20.0 g) and diluting the polyamic acid content to 6 mass%, acetic anhydride (4.32 g) and pyridine (3.35 g) as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 80%, the number average molecular weight was 18,800, and the weight average molecular weight was 48,900.

NMP (22.0 g) and BCS (25.0 g) were added to this polyimide powder (3.00 g) to obtain a liquid crystal aligning agent [2]. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 3>
BODA (3.50 g, 14.0 mmol), m-PBCH5DABz (3.75 g, 8.39 mmol), diamine (B2) (2.87 g, 11.2 mmol), and DBA (1.28 g, 8.39 mmol). After mixing in NMP (23.5 g) and reacting at 80 ° C. for 5 hours, CBDA (2.78 g, 14.2 mmol) and NMP (18.8 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to this polyamic acid solution (25.1 g) and diluting the polyamic acid content to 6 mass%, acetic anhydride (3.13 g) and pyridine (2.42 g) were used as imidization catalysts. In addition, the mixture was reacted at 80 ° C. for 4 hours. This reaction solution was put into methanol (350 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 56%, the number average molecular weight was 17,400, and the weight average molecular weight was 46,600.

NMP (21.2g) and BCS (25.8g) were added to this polyimide powder (3.00g), and liquid crystal aligning agent [3] was obtained. 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 the pretilt angle was evaluated. The results are shown in Table 11 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 4>
BODA (3.48 g, 13.9 mmol), m-PBCH5DABz (3.73 g, 8.35 mmol), diamine (B3) (0.75 g, 2.78 mmol), and DBA (2.54 g, 16.7 mmol). After mixing in NMP (22.0 g) and reacting at 80 ° C. for 5 hours, CBDA (2.73 g, 13.9 mmol) and NMP (17.7 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained. This polyamic acid solution had a number average molecular weight of 24,100 and a weight average molecular weight of 57,200.
NMP (10.2 g) and BCS (25.0 g) were added to the obtained polyamic acid solution (15.1 g) to obtain a liquid crystal aligning agent [4]. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 5>
BODA (3.50 g, 14.0 mmol), m-PBCH5DABz (1.87 g, 4.20 mmol), diamine (B4) (1.81 g, 8.39 mmol), and DBA (2.34 g, 15.4 mmol). After mixing in NMP (20.4 g) and reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (16.3 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to this polyamic acid solution (25.1 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (5.39 g) and pyridine (4.18 g) were used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (330 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 81%, the number average molecular weight was 17,500, and the weight average molecular weight was 47,500.
NMP (22.7g) and BCS (25.8g) were added to this polyimide powder (3.10g), and liquid crystal aligning agent [5] was obtained. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 6>
BODA (3.50 g, 14.0 mmol), m-PBCH5DABz (1.87 g, 4.20 mmol), diamine (B5) (0.60 g, 2.80 mmol), and DBA (3.19 g, 21.0 mmol). After mixing in NMP (19.8 g) and reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (15.6 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to this polyamic acid solution (20.1 g) and diluting the polyamic acid content to 6% by mass, acetic anhydride (2.51 g) and pyridine (1.93 g) are used as imidization catalysts. And reacted at 80 ° C. for 4 hours. This reaction solution was put into methanol (270 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 55%, the number average molecular weight was 18,800, and the weight average molecular weight was 48,300.

NMP (22.1g) and BCS (25.0g) were added to this polyimide powder (3.00g), and liquid crystal aligning agent [6] was obtained. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 7>
BODA (3.50 g, 14.0 mmol), m-PBCH5DABz (2.50 g, 5.60 mmol), diamine (B6) (1.20 g, 5.60 mmol), and DBA (2.55 g, 16.8 mmol). After mixing in NMP (20.7 g) and reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (16.6 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to this polyamic acid solution (20.0 g) and diluting the polyamic acid content to 6 mass%, acetic anhydride (2.50 g) and pyridine (1.95 g) were used as imidization catalysts. In addition, the mixture was reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 56%, the number average molecular weight was 17,800, and the weight average molecular weight was 48,100.

NMP (26.1 g) and BCS (24.1 g) were added to this polyimide powder (3.21 g) to obtain a liquid crystal aligning agent [7]. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 8>
BODA (3.51 g, 14.0 mmol), m-PBCH5DABz (2.51 g, 5.61 mmol), diamine (B7) (1.28 g, 5.60 mmol), and DBA (2.56 g, 16.8 mmol). After mixing in NMP (20.9 g) and reacting at 80 ° C. for 5 hours, CBDA (2.75 g, 14.0 mmol) and NMP (16.7 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to this polyamic acid solution (25.2 g) and diluting the polyamic acid content to 6% by mass, acetic anhydride (5.39 g) and pyridine (4.18 g) were used as imidization catalysts. In addition, the mixture was reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (330 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 80%, the number average molecular weight was 17,200, and the weight average molecular weight was 47,100.

NMP (19.5g) and BCS (27.5g) were added to this polyimide powder (3.00g), and liquid crystal aligning agent [8] was obtained. 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 produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 9>
BODA (3.51 g, 14.0 mmol), m-PBCH5DABz (3.76 g, 8.42 mmol), diamine (B8) (0.64 g, 2.81 mmol), and DBA (2.56 g, 16.8 mmol). After mixing in NMP (22.1 g) and reacting at 80 ° C. for 5 hours, CBDA (2.75 g, 14.0 mmol) and NMP (17.6 g) were added and reacted at 40 ° C. for 6 hours to polyamic acid. A solution was obtained. This polyamic acid solution had a number average molecular weight of 20,900 and a weight average molecular weight of 50,900.
NMP (10.0 g) and BCS (36.5 g) were added to the obtained polyamic acid solution (20.0 g) to obtain a liquid crystal aligning agent [9]. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 10>
BODA (3.51 g, 14.0 mmol), m-PBCH5DABz (3.76 g, 8.42 mmol), diamine (B9) (1.44 g, 5.61 mmol), and DBA (2.13 g, 14.0 mmol). After mixing in NMP (22.6 g) and reacting at 80 ° C. for 5 hours, CBDA (2.75 g, 14.0 mmol) and NMP (18.1 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to this polyamic acid solution (25.0 g) to dilute the polyamic acid content to 6 mass%, acetic anhydride (5.39 g) and pyridine (4.18 g) as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (330 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 79%, the number average molecular weight was 18,100, and the weight average molecular weight was 48,900.
NMP (19.5g) and BCS (27.5g) were added to this polyimide powder (3.01g), and liquid crystal aligning agent [10] was obtained. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 11>
BODA (3.48 g, 13.9 mmol), m-PBCH5DABz (2.49 g, 5.56 mmol), diamine (B10) (0.90 g, 2.78 mmol), and DBA (2.96 g, 19.5 mmol). After mixing in NMP (20.8 g) and reacting at 80 ° C. for 5 hours, CBDA (2.73 g, 13.9 mmol) and NMP (16.7 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained. The number average molecular weight of this polyamic acid solution was 23,500, and the weight average molecular weight was 55,800.
NMP (13.3 g) and BCS (33.4 g) were added to the obtained polyamic acid solution (20.0 g) to obtain a liquid crystal aligning agent [11]. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 12>
BODA (3.50 g, 14.0 mmol), m-PBCH5DABz (3.75 g, 8.39 mmol), diamine (B11) (1.80 g, 5.60 mmol), and DBA (2.13 g, 14.0 mmol). After mixing in NMP (23.1 g) and reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (18.5 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.

After NMP was added to this polyamic acid solution (20.1 g) and diluted so that the content of polyamic acid was 6% by mass, acetic anhydride (4.30 g) and pyridine (3.35 g) were used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 80%, the number average molecular weight was 18,500, and the weight average molecular weight was 48,900.
NMP (19.5g) and BCS (27.5g) were added to this polyimide powder (3.04g), and liquid crystal aligning agent [12] was obtained. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 13>
BODA (3.50 g, 14.0 mmol), m-PBCH5DABz (3.75 g, 8.39 mmol), diamine (B12) (2.58 g, 8.39 mmol), and DBA (1.70 g, 11.2 mmol). After mixing in NMP (23.7 g) and reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (19.0 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After NMP was added to this polyamic acid solution (20.0 g) and diluted so that the content of polyamic acid was 6% by mass, acetic anhydride (4.30 g) and pyridine (3.35 g) were used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 81%, the number average molecular weight was 17,800, and the weight average molecular weight was 47,500.
NMP (20.8g) and BCS (29.3g) were added to this polyimide powder (3.21g), and liquid crystal aligning agent [13] was obtained. 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 produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 14>
BODA (3.51 g, 14.0 mmol), m-PBCH7DABz (4.00 g, 8.42 mmol), diamine (B1) (1.36 g, 5.61 mmol), and DBA (2.13 g, 14.0 mmol). After mixing in NMP (22.8 g) and reacting at 80 ° C. for 5 hours, CBDA (2.75 g, 14.0 mmol) and NMP (18.3 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
NMP was added to this polyamic acid solution (20.2 g) to dilute the polyamic acid content to 6% by mass, and then acetic anhydride (4.30 g) and pyridine (3.33 g) as an imidization catalyst. And reacted at 90 ° C. for 3.5 hours. This reaction solution was put into methanol (270 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 80%, the number average molecular weight was 17,900, and the weight average molecular weight was 47,300.
NMP (19.5g) and BCS (27.5g) were added to this polyimide powder (3.00g), and liquid crystal aligning agent [14] was obtained. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 15>
BODA (3.50 g, 14.0 mol), m-BPCH5DABz (3.98 g, 8.39 mmol), diamine (B1) (2.03 g, 8.39 mmol), and DBA (1.70 g, 11.2 mmol). After mixing in NMP (23.2 g) and reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (18.5 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
NMP was added to this polyamic acid solution (20.0 g) to dilute the polyamic acid content to 6% by mass, and then acetic anhydride (4.29 g) and pyridine (3.35 g) as an imidization catalyst. And reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (290 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 54%, the number average molecular weight was 17,800, and the weight average molecular weight was 48,100.
NMP (22.8 g) and BCS (32.0 g) were added to this polyimide powder (3.50 g) to obtain a liquid crystal aligning agent [15]. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Example 16>
BODA (3.48 g, 13.9 mmol), p-PBCH5DABz (3.73 g, 8.35 mmol), diamine (B1) (2.02 g, 8.35 mmol), and DBA (1.69 g, 11.1 mmol). After mixing in NMP (22.7 g) and reacting at 80 ° C. for 5 hours, CBDA (2.73 g, 13.9 mmol) and NMP (18.1 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to this polyamic acid solution (20.5 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (4.35 g) and pyridine (3.35 g) are used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 79%, the number average molecular weight was 16,900, and the weight average molecular weight was 46,800.
NMP (22.7g) and BCS (25.8g) were added to this polyimide powder (3.30g), and liquid crystal aligning agent [16] was obtained. 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 produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Comparative Example 1>
BODA (3.51 g, 14.0 mmol), PCH7DAB (1.60 g, 4.21 mmol), diamine (B1) (2.04 g, 8.42 mmol), and DBA (2.35 g, 15.4 mmol) were added to NMP ( 20.3 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (2.75 g, 14.0 mmol) and NMP (16.3 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After adding NMP to this polyamic acid solution (20.3 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (2.50 g) and pyridine (1.94 g) are used as imidization catalysts. And reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 54%, the number average molecular weight was 17,000, and the weight average molecular weight was 46,700.
NMP (24.2g) and BCS (27.5g) were added to this polyimide powder (3.30g), and the liquid-crystal aligning agent [17] was obtained. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Comparative example 2>
BODA (3.50 g, 14.0 mmol), PCH7DAB (5.31 g, 14.0 mmol), diamine (B1) (1.36 g, 5.60 mmol), and DBA (1.28 g, 8.39 mmol) were added to NMP ( 23.4 g), and after reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (18.8 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After NMP was added to this polyamic acid solution (20.0 g) and diluted so that the content of polyamic acid was 6% by mass, acetic anhydride (2.48 g) and pyridine (1.94 g) were used as an imidization catalyst. And reacted at 80 ° C. for 4 hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 55%, the number average molecular weight was 16,600, and the weight average molecular weight was 46,100.
NMP (23.5g) and BCS (26.7g) were added to this polyimide powder (3.21g), and liquid crystal aligning agent [18] was obtained. 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 the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Comparative Example 3>
BODA (3.50 g, 14.0 mmol), m-PBCH5DABEs (3.87 g, 8.39 mmol), diamine (B1) (1.36 g, 5.60 mmol), and DBA (2.13 g, 14.0 mmol). After mixing in NMP (22.6 g) and reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (18.1 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After adding NMP to this polyamic acid solution (20.0 g) and diluting the polyamic acid content to 6 mass%, acetic anhydride (2.51 g) and pyridine (1.95 g) as imidization catalysts. And reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 54%, the number average molecular weight was 17,400, and the weight average molecular weight was 47,900.
When NMP (27.1 g) and BCS (20.0 g) were added to this polyimide powder (3.01 g), precipitation of the resin component occurred, and a liquid crystal aligning agent could not be obtained.
Therefore, a liquid crystal cell could not be produced.

<Comparative Example 4>
BODA (3.49 g, 14.0 mmol), PBP5DAB (3.54 g, 8.37 mmol), diamine (B1) (1.35 g, 5.58 mmol), and DBA (2.12 g, 14.0 mmol) were added to NMP ( 22.0 g) and reacted at 80 ° C. for 5 hours. Then, CBDA (2.74 g, 14.0 mmol) and NMP (17.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After NMP was added to this polyamic acid solution (20.0 g) and diluted so that the content of polyamic acid was 6% by mass, acetic anhydride (2.50 g) and pyridine (1.93 g) were used as an imidization catalyst. And reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (290 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 55%, the number average molecular weight was 16,400, and the weight average molecular weight was 46,900.
When NMP (28.8 g) and BCS (21.3 g) were added to this polyimide powder (3.20 g), precipitation of the resin component occurred and a liquid crystal aligning agent could not be obtained.
Therefore, a liquid crystal cell could not be produced.

<Comparative Example 5>
BODA (3.48 g, 13.9 mmol), PBCH5DAB (3.61 g, 8.35 mmol), diamine (B1) (1.35 g, 5.56 mmol), and p-PDA (1.50 g, 13.9 mmol). After mixing in NMP (21.0 g) and reacting at 80 ° C. for 5 hours, CBDA (2.73 g, 13.9 mmol) and NMP (16.8 g) were added and reacted at 40 ° C. for 6 hours. A solution was obtained.
After NMP was added to this polyamic acid solution (20.0 g) and diluted so that the content of polyamic acid was 6% by mass, acetic anhydride (2.48 g) and pyridine (1.94 g) were used as an imidization catalyst. And reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 55%, the number average molecular weight was 17,800, and the weight average molecular weight was 48,100.
NMP (22.1g) and BCS (25.0g) were added to this polyimide powder (3.20g), and the liquid-crystal aligning agent [19] was obtained. 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 [19], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.

<Comparative Example 6>
BODA (3.50 g, 14.0 mmol), PBCH5DAB (3.63 g, 8.39 mmol), diamine (S1) (1.35 g, 5.60 mmol), and DBA (2.13 g, 14.0 mmol) were added to NMP ( 22.2 g) and the mixture was reacted at 80 ° C. for 5 hours. Then, CBDA (2.74 g, 14.0 mmol) and NMP (17.7 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
NMP was added to this polyamic acid solution (20.1 g) to dilute the polyamic acid content to 6% by mass, and then acetic anhydride (2.50 g) and pyridine (1.95 g) as an imidization catalyst. And reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (290 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 54%, the number average molecular weight was 18,100, and the weight average molecular weight was 47,800.
NMP (22.7g) and BCS (25.8g) were added to this polyimide powder (3.11g), and liquid crystal aligning agent [20] was obtained. 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 [20], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 11. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 12 and Table 13.
<Example 21>
BODA (3.51 g, 14.0 mmol), PBCH5DAB (1.82 g, 4.21 mmol), diamine (B1) (2.04 g, 8.42 mmol), and DBA (2.35 g, 15.4 mmol) were added to NMP ( 20.7 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (2.75 g, 14.0 mmol) and NMP (16.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After NMP was added to this polyamic acid solution (20.0 g) and diluted so that the content of polyamic acid was 6% by mass, acetic anhydride (2.51 g) and pyridine (1.93 g) were used as imidization catalysts. And reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 55%, the number average molecular weight was 19,100, and the weight average molecular weight was 48,100.
NMP (19.5g) and BCS (27.5g) were added to this polyimide powder (3.01g), and liquid crystal aligning agent [21] was obtained. 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 aligning agent [21] obtained above was spin-coated on the ITO surface of the 3 cm × 4 cm ITO electrode substrate, and baked at 80 ° C. for 5 minutes in a 210 ° C. hot air circulating oven for 1 hour. A polyimide coating was prepared.
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. After bonding the liquid crystal alignment film surface of another substrate to the inside and the rubbing direction being reversed, the sealing agent was cured to prepare an empty cell. A nematic liquid crystal was injected into this empty cell by a reduced pressure injection method to obtain an antiparallel aligned nematic liquid crystal cell.

<Evaluation of pretilt angle>
The pretilt angle of the liquid crystal cell produced above was measured at room temperature using a pretilt angle measuring device (ELSICON model: PAS-301). The results are shown in Table 15.
Moreover, when the liquid crystal cell produced similarly to the above except having not rubbed was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.
<Evaluation of voltage holding ratio>
A voltage of 4 V was applied to the liquid crystal cell after measuring the pretilt angle at a temperature of 80 ° C. at 60 μm, the voltage after 16.67 ms and 1667 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio. . The results are shown in Table 16.
<Evaluation of residual charge relaxation>
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 17.
<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 16 and Table 17.

<Example 22>
BODA (3.49 g, 14.0 mmol), PBCH5DAB (3.62 g, 8.37 mmol), diamine (B1) (1.35 g, 5.58 mmol), and DBA (2.12 g, 14.0 mmol) were added to NMP ( 22.1 g) and reacted at 80 ° C. for 5 hours. Then, CBDA (2.74 g, 14.0 mmol) and NMP (17.7 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After adding NMP to this polyamic acid solution (25.1 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (5.40 g) and pyridine (4.18 g) are used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (330 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 81%, the number average molecular weight was 19,500, and the weight average molecular weight was 49,500.
NMP (22.0 g) and BCS (25.1 g) were added to this polyimide powder (3.01 g) to obtain a liquid crystal aligning agent [22]. 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 [22], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 23>
BODA (3.55 g, 14.2 mmol), PBCH5DAB (3.68 g, 8.51 mmol), diamine (B2) (2.91 g, 11.4 mmol), and DBA (1.30 g, 8.51 mmol) were added to NMP ( 23.6 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (2.78 g, 14.2 mmol) and NMP (18.9 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After NMP was added to this polyamic acid solution (20.0 g) and diluted so that the content of polyamic acid was 6% by mass, acetic anhydride (2.51 g) and pyridine (1.93 g) were used as imidization catalysts. And reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 55%, the number average molecular weight was 18,200, and the weight average molecular weight was 47,200.
NMP (22.7 g) and BCS (25.8 g) were added to this polyimide powder (3.11 g) to obtain a liquid crystal aligning agent [23]. 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 [23], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 24>
BODA (3.51 g, 14.0 mmol), PBCH5DAB (3.64 g, 8.42 mmol), diamine (B3) (0.76 g, 2.81 mmol), and DBA (2.56 g, 16.8 mmol) were added to NMP ( 22.0 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (2.75 g, 14.0 mmol) and NMP (17.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained. The number average molecular weight of this polyamic acid solution was 22,600, and the weight average molecular weight was 54,600.
NMP (10.1 g) and BCS (25.0 g) were added to the obtained polyamic acid solution (15.0 g) to obtain a liquid crystal aligning agent [24]. 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 [24], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 25>
BODA (3.48 g, 13.9 mmol), PBCH5DAB (1.81 g, 4.17 mmol), diamine (B4) (1.80 g, 8.35 mmol), and DBA (2.33 g, 15.3 mmol) were added to NMP ( 20.2 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (2.73 g, 13.9 mmol) and NMP (16.1 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After adding NMP to this polyamic acid solution (20.0 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (4.31 g) and pyridine (3.34 g) are used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (260 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 80%, the number average molecular weight was 17,100, and the weight average molecular weight was 46,000.
NMP (22.1g) and BCS (25.3g) were added to this polyimide powder (3.00g), and liquid crystal aligning agent [25] was obtained. 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 [25], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 26>
BODA (3.50 g, 14.0 mmol), PBCH5DAB (1.82 g, 4.20 mmol), diamine (B5) (0.60 g, 2.80 mmol), and DBA (3.19 g, 21.0 mmol) were added to NMP ( In 19.7 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (15.7 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After adding NMP to this polyamic acid solution (25.0 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (3.13 g) and pyridine (2.42 g) are used as imidization catalysts. And reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (340 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 53%, the number average molecular weight was 19,400, and the weight average molecular weight was 49,300.
NMP (29.3g) and BCS (33.3g) were added to this polyimide powder (4.01g), and the liquid-crystal aligning agent [26] was obtained. 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 [26], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 27>
BODA (3.52 g, 14.1 mmol), PBCH5DAB (2.43 g, 5.63 mmol), diamine (B6) (1.21 g, 5.63 mmol), and DBA (2.57 g, 16.9 mmol) were added to NMP ( 20.7 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (2.76 g, 14.1 mmol) and NMP (16.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After NMP was added to this polyamic acid solution (20.0 g) and diluted so that the content of polyamic acid was 6% by mass, acetic anhydride (2.51 g) and pyridine (1.93 g) were used as imidization catalysts. And reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 55%, the number average molecular weight was 18,300, and the weight average molecular weight was 48,300.
NMP (32.7 g) and BCS (30.1 g) were added to this polyimide powder (4.00 g) to obtain a liquid crystal aligning agent [27]. 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 [27], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 28>
BODA (3.50 g, 14.0 mmol), PBCH5DAB (2.42 g, 5.60 mmol), diamine (B7) (1.28 g, 5.60 mmol), and DBA (2.55 g, 16.8 mmol) were added to NMP ( 20.8 g), and after reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (16.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After adding NMP to this polyamic acid solution (20.0 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (4.31 g) and pyridine (3.34 g) are used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (260 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 81%, the number average molecular weight was 16,300, and the weight average molecular weight was 46,300.
NMP (22.8 g) and BCS (32.1 g) were added to this polyimide powder (3.51 g) to obtain a liquid crystal aligning agent [28]. 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 [28], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 29>
BODA (3.51 g, 14.0 mmol), PBCH5DAB (3.64 g, 8.42 mmol), diamine (B8) (0.64 g, 2.81 mmol), and DBA (2.56 g, 16.8 mmol) were added to NMP ( 20.8 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (2.75 g, 14.0 mmol) and NMP (16.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained. This polyamic acid solution had a number average molecular weight of 21,500 and a weight average molecular weight of 52,300.

NMP (10.0 g) and BCS (36.7 g) were added to the obtained polyamic acid solution (20.1 g) to obtain a liquid crystal aligning agent [29]. 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 [29], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 30>
BODA (3.50 g, 14.0 mmol), PBCH5DAB (3.63 g, 8.39 mmol), diamine (B9) (1.44 g, 5.60 mmol), and DBA (2.13 g, 14.0 mmol) were added to NMP ( 22.3 g), and after reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (17.9 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After adding NMP to this polyamic acid solution (20.0 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (4.31 g) and pyridine (3.35 g) are used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was put into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 78%, the number average molecular weight was 17,900, and the weight average molecular weight was 49,100.
NMP (20.8 g) and BCS (29.3 g) were added to this polyimide powder (3.20 g) to obtain a liquid crystal aligning agent [30]. 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 [30], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 31>
BODA (3.48 g, 13.9 mmol), PBCH5DAB (2.41 g, 5.56 mmol), diamine (B10) (0.90 g, 2.78 mmol), and DBA (2.96 g, 19.5 mmol) were added to NMP ( 20.7 g), and after reacting at 80 ° C. for 5 hours, CBDA (2.73 g, 13.9 mmol) and NMP (16.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained. This polyamic acid solution had a number average molecular weight of 20,100 and a weight average molecular weight of 50,100.

NMP (10.1 g) and BCS (25.0 g) were added to the obtained polyamic acid solution (15.0 g) to obtain a liquid crystal aligning agent [31]. 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 [31], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 32>
BODA (3.49 g, 14.0 mmol), PBCH5DAB (3.62 g, 8.37 mmol), diamine (B11) (1.79 g, 5.58 mmol), and DBA (2.12 g, 14.0 mmol) were added to NMP ( 22.9 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (2.74 g, 14.0 mmol) and NMP (18.3 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After adding NMP to this polyamic acid solution (20.0 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (4.31 g) and pyridine (3.35 g) are used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (290 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 81%, the number average molecular weight was 18,200, and the weight average molecular weight was 48,400.
NMP (21.5g) and BCS (30.3g) were added to this polyimide powder (3.31g), and liquid crystal aligning agent [32] was obtained. 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 [32], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 33>
BODA (3.50 g, 14.0 mmol), PBCH5DAB (3.63 g, 8.39 mmol), diamine (B12) (2.58 g, 8.39 mmol), and DBA (1.70 g, 11.2 mmol) were added to NMP ( 23.5 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (2.74 g, 14.0 mmol) and NMP (18.8 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After NMP was added to this polyamic acid solution (20.2 g) and diluted so that the content of polyamic acid was 6% by mass, acetic anhydride (4.32 g) and pyridine (3.34 g) were used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 80%, the number average molecular weight was 17,100, and the weight average molecular weight was 47,100.
NMP (22.8 g) and BCS (32.1 g) were added to this polyimide powder (3.50 g) to obtain a liquid crystal aligning agent [33]. 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 [33], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, 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 16 and Table 17.

<Example 34>
BODA (3.48 g, 13.9 mmol), PBCH7DAB (3.84 g, 8.35 mmol), diamine (B1) (1.35 g, 5.56 mmol), and DBA (2.12 g, 13.9 mmol) were added to NMP ( 22.4 g), and the mixture was reacted at 80 ° C. for 5 hours. Then, CBDA (2.73 g, 13.9 mmol) and NMP (18.0 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After adding NMP to this polyamic acid solution (20.0 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (4.31 g) and pyridine (3.34 g) are used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was put into methanol (270 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 81%, the number average molecular weight was 18,900, and the weight average molecular weight was 48,900.
NMP (20.2g) and BCS (28.4g) were added to this polyimide powder (3.11g), and the liquid-crystal aligning agent [34] was obtained. 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 [34], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 35>
BODA (3.51 g, 14.0 mol), PBCH7DAB (3.88 g, 8.42 mmol), diamine (B1) (2.04 g, 8.42 mmol), and DBA (1.71 g, 11.2 mmol) were added to NMP ( 23.1 g), and reacted at 80 ° C. for 5 hours. Then, CBDA (2.75 g, 14.0 mmol) and NMP (18.4 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After adding NMP to this polyamic acid solution (20.2 g) and diluting so that the content of polyamic acid is 6% by mass, acetic anhydride (4.52 g) and pyridine (3.61 g) are used as imidization catalysts. And reacted at 90 ° C. for 5 hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 92%, the number average molecular weight was 17,100, and the weight average molecular weight was 46,900.
NMP (22.8 g) and BCS (32.1 g) were added to this polyimide powder (3.51 g) to obtain a liquid crystal aligning agent [35]. 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 [35], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Example 36>
BODA (3.50 g, 14.0 mmol), BPCH5DAB (3.59 g, 8.39 mmol), diamine (B1) (2.03 g, 8.39 mmol), and DBA (1.70 g, 11.2 mmol) were added to NMP ( 22.5 g), and after reacting at 80 ° C. for 5 hours, CBDA (2.74 g, 14.0 mmol) and NMP (18.0 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. Obtained.
After adding NMP to this polyamic acid solution (20.0 g) to dilute the polyamic acid content to 6% by mass, acetic anhydride (4.31 g) and pyridine (3.34 g) are used as imidization catalysts. And reacted at 90 ° C. for 3.5 hours. This reaction solution was put into methanol (270 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder. The imidation ratio of this polyimide was 81%, the number average molecular weight was 18,900, and the weight average molecular weight was 48,900.
NMP (22.7g) and BCS (25.8g) were added to this polyimide powder (3.11g), and the liquid-crystal aligning agent [36] was obtained. 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 [36], a liquid crystal cell was produced in the same manner as in Example 21, and the pretilt angle was evaluated. The results are shown in Table 15. In addition, when the liquid crystal cell produced like Example 21 was observed with the polarizing microscope except not having rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell manufactured in the same manner as in Example 21, 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 16 and Table 17.

<Printability test>
Printing was performed using the liquid crystal alignment treatment agents obtained in Examples 1 to 16, 21 to 36, and Comparative Examples 1, 2, 5, and 6. A simple printing machine (S15 type) manufactured by Nissha Printing Co., Ltd. was used as the printing machine. Printing was performed on a cleaned chromium vapor deposition substrate at a printing area of 8 cm × 8 cm, a printing pressure of 0.2 mm, five discarded substrates, a time from printing to temporary drying of 90 seconds, and a temporary drying temperature of 70 ° C. for 5 minutes. .
The pinholes were confirmed by visual observation under a sodium lamp. Tables 11 and 15 show the number of pinholes as printability.

＊１：液晶配向処理剤中の溶媒全体に占めるＢＣＳの使用割合。
＊２：ポリアミド酸。
＊３：樹脂成分の析出により、評価不可能。

* 1: BCS usage ratio in the total solvent in the liquid crystal alignment treatment agent.
* 2: Polyamic acid.
* 3: Cannot be evaluated due to precipitation of resin components.

＊１：樹脂成分の析出により、評価不可能。

* 1: Cannot be evaluated due to precipitation of resin components.

＊１：樹脂成分の析出により、評価不可能。

* 1: Cannot be evaluated due to precipitation of resin components.

＊１：液晶配向処理剤中の溶媒全体に占めるＢＣＳの使用割合。
＊２：ポリアミド酸。

* 1: BCS usage ratio in the total solvent in the liquid crystal alignment treatment agent.
* 2: Polyamic acid.

A liquid crystal display element produced using a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be suitably used for a large-screen, high-definition liquid crystal television, etc. Useful.

The specification, claims, and abstract of Japanese Patent Application No. 2008-245037 filed on September 24, 2008 and Japanese Patent Application No. 2008-245038 filed on September 24, 2008. Is hereby incorporated by reference as a disclosure of the specification of the present invention.

Claims (24)

Diamine compound (A) represented by the following formula [1], diamine compound (B) represented by the following formula [2], and diamine compound (C) which is a diamine compound having a carboxyl group in the molecule A liquid crystal aligning agent characterized by containing a copolymer obtained by reacting a diamine component containing a tetracarboxylic dianhydride.

(In the formula [1], p is an integer of 0 or 1, X ₁ is phenylene, X ₂ is phenylene or cyclohexylene, X ₃ is cyclohexylene, and X ₄ has 3 to 3 carbon atoms. And an alkyl group having 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms, wherein Y ₁ is —O—, _{-NH -, - N (CH 3} ) -, - CONH -, - NHCO -, - CH 2 O -, - OCO -, - CON (CH 3) -, or -N _(CH 3) a CO-, Y 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, and Y ₃ is a single bond, —O—, —NH—, _{-N (CH 3) -, -} CONH -, - NHCO -, - COO -, - OCO -, - _{ON (CH 3) -, -} N (CH 3) CO-, or -O _{(CH 2)} m - is (m is an integer of 1 to 5), _{Y 4} is a nitrogen-containing aromatic heterocyclic , N is an integer from 1 to 4.) The liquid crystal aligning agent according to claim 1, wherein the diamine compound (A) is a diamine compound (A ') represented by the following formula [1'].

(In the formula [1 ′], X ₁ , X ₂ , X ₃ and X ₄ have the same meanings as those in the formula [1].) The liquid crystal aligning agent according to claim 1, wherein the diamine compound (A) is a diamine compound (A ″) represented by the following formula [1 ″].

(In the formula [1 ″], X ″ ₁ is 1,4-phenylene or 1,4-cyclohexylene, X ″ ₂ is an alkyl group having 3 to 12 carbon atoms, and 3 to 12 carbon atoms. A fluoroalkyl group, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms.) The liquid-crystal aligning agent of Claim 2 whose diamine compound (A ') is a diamine compound represented by following formula [1'a].

(In the formula [1′a], X ₅ is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. And the cis-trans isomerism of 1,4-cyclohexylene is each a trans isomer.) The liquid-crystal aligning agent of Claim 2 whose diamine compound (A ') is a diamine compound represented by following formula [1'b].

(In the formula [1′b], X ₆ is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms. And the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer.) The liquid crystal aligning agent according to claim 3, wherein the diamine compound (A ″) is a diamine compound represented by the following formula [1 ″ a].

(In the formula [1 ″ a], X ″ ₃ is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. It is a fluoroalkoxy group, and the cis-trans isomerism of 1,4-cyclohexylene is each a trans isomer). The liquid-crystal aligning agent of Claim 3 whose diamine compound (A '') is a diamine compound represented by following formula [1''b].

(In the formula [1 ″ b], X ″ ₄ is an alkyl group having 3 to 12 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. It is a fluoroalkoxy group, and the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer). _{Y 1} in the formula [2] is -O -, - NH -, - CONH -, - NHCO -, - CON (CH 3) -, or any claims 2 to 7 _-CH 2 O-a is The liquid crystal aligning agent according to claim 1. Equation [2] Y ₂ is a single bond in the liquid crystal alignment treating agent according to any one of claims 2 to 8 is a linear or branched alkyl group, or a benzene ring having 1 to 5 carbon atoms. Y ₃ in the formula [2] is a single bond, —O—, —CONH—, —NHCO—, —COO—, —OCO—, or —O (CH ₂ ) _m — (m is an integer of 1 to 5. The liquid-crystal aligning agent as described in any one of Claims 2-9. The liquid crystal aligning agent according to any one of claims 2 to 10, wherein Y ₄ in the formula [2] is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring.   N in Formula [2] is an integer of 1-3, The liquid-crystal aligning agent as described in any one of Claims 2-11. Y ₁ in Formula [2] is —O—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) —, or —CH ₂ O—, and Y ₂ has 1 to 5 carbon atoms. A linear or branched alkyl group, Y ₃ is a single bond, Y ₄ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring, and n is an integer of 1 to 3. The liquid-crystal aligning agent as described in any one of Claims 2-7. Y ₁ in the formula [2] is —O—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) —, or —CH ₂ O—, Y ₂ is a benzene ring, Y ₃ is —O—, —CONH—, —NHCO—, —COO—, —OCO—, or —O (CH ₂ ) _m — (m is an integer of 1 to 5), and Y ₄ is pyrrole. It is a ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring, and n is an integer of 1, The liquid crystal aligning agent as described in any one of Claims 2-7. The liquid crystal aligning agent according to any one of claims 2 to 14, wherein the diamine compound (C) is a diamine compound represented by the following formula [3].

(In Formula [3], Z ₁ is an organic group having an aromatic ring having 6 to 30 carbon atoms, and k is an integer of 1 to 4). The diamine compound of the formula [3] is at least one diamine compound selected from the group consisting of the following formula [3a], formula [3b], formula [3c], formula [3d] and formula [3e] Item 16. A liquid crystal aligning agent according to Item 15.

(In the formula [3a], m ₁ is an integer of ₁ to 4. In the formula [3b], Z ₂ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —. , —CF ₂ —, —C (CF ₃ ) —, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH _2- , -COO-, -OCO-, -CON (CH ₃ )-, or -N (CH ₃ ) CO-, m ₂ and m ₃ each represent an integer of 0 to 4, and m ₂ + m ₃ represents an integer of 1 to 4. In formula [3c], m ₄ and m ₅ are each an integer of 1 to 5. In formula [3d], Z ₃ is a straight chain or branched chain having 1 to 5 carbon atoms. M ₆ is an alkyl group and m ₆ is an integer of 1 to 5. In formula [3e], Z ₄ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —. CF ₂ - _{-C (CF 3) -, -} 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). Wherein [3a], the liquid crystal alignment treating agent according to claim 16 _{m 1} is an integer of 1-2. In Formula [3b], Z ₂ 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 claim 16 _{m 2} and _{m 3} are both the integer 1. In the formula [3e], Z ₄ represents 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 16 _{m 7} is an integer of 1-2.   In a diamine component, a diamine compound (A) is 0.5-50 mol with respect to 1 mol of diamine compounds (C), and a diamine compound (B) is with respect to 1 mol of diamine compounds (C). The liquid crystal aligning agent according to any one of claims 2 to 19, which is 0.5 to 10 mol.   The liquid-crystal aligning agent as described in any one of Claims 2-20 containing 5-70 mass% poor solvent in a liquid-crystal aligning agent.   The liquid crystal aligning agent according to any one of claims 2 to 21, wherein the copolymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and ring-closing polyamic acid.   A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of claims 2 to 22.   24. A liquid crystal display element comprising the liquid crystal alignment film according to claim 23.