JP5939157B2 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using the same - Google Patents

Description

  The present invention relates to a novel diamine compound useful as a raw material for a polymer used in a liquid crystal alignment film, a polyamic acid and a polyimide obtained using the same, and a liquid crystal alignment treatment agent. Furthermore, it is related with the liquid crystal display element which has a liquid crystal aligning film obtained from the said liquid-crystal aligning agent. More specifically, a liquid crystal alignment treatment agent capable of forming a liquid crystal alignment film for vertical alignment by polarized or non-polarized radiation with a small dose, such a liquid crystal alignment film and a method for forming the same, and a liquid crystal comprising such a liquid crystal alignment film The present invention relates to a display element and an optical member.

The liquid crystal alignment film is a constituent member of a liquid crystal display element that is widely used as a display device, and plays a role of aligning liquid crystals in a certain direction. Currently, the main liquid crystal alignment film that is industrially used is formed from a liquid crystal alignment treatment agent comprising a polyimide precursor, polyamic acid (also referred to as polyamic acid), a polyamic acid ester, or a polyimide solution. The In general, after applying a liquid crystal alignment treatment agent to a substrate, heating and baking, an alignment treatment for aligning the liquid crystal in parallel or with respect to the substrate surface is performed. As this alignment treatment, the surface of the organic film is rubbed with a cloth such as cotton, nylon, rayon or the like, a so-called rubbing surface treatment method, a method of obliquely depositing silicon oxide on the substrate surface, a Langmuir brochette method on the substrate surface ( A method of forming a monomolecular film having a long-chain alkyl group using the LB method is known. Among these, the provision of liquid crystal alignment ability by rubbing is generally used from the viewpoints of substrate size, liquid crystal alignment uniformity, processing time, cost, and the like.
However, in providing liquid crystal alignment ability by rubbing treatment, defects in the liquid crystal alignment film occur due to rubbing, resulting in display defects, dust generation, or generation of static electricity TFT (Thin Film Transistor). There was a problem that the circuit of the element was destroyed.

In vertical alignment type liquid crystal display elements, MVA (Multi Vertical Alignment) method is used to form protrusions on the TFT substrate or color filter substrate to control the direction in which the liquid crystal is tilted. A PVA (Patterned Vertical Alignment) system that controls the direction in which the liquid crystal tilts by an electric field, a liquid crystal panel using a substrate with a slit formed in an ITO electrode, and a liquid crystal to which a photopolymerizable compound is added to produce an electric field A PSA (Polymer Sustained Alignment) system is known in which UV is applied and ultraviolet rays (UV) are irradiated in a state where the liquid crystal is tilted to fix the alignment of the liquid crystal.
Problems with these conventional vertical alignment methods include an increase in the cost of the panel due to the use of a complex substrate and a decrease in the transmittance of the panel due to protrusions and slits.
On the other hand, as another means for imparting liquid crystal alignment ability to the liquid crystal alignment film in the liquid crystal cell, by irradiating the photosensitive thin film such as polyvinyl cinnamate and polyimide formed on the substrate surface with polarized or non-polarized radiation, A photo-alignment method that imparts liquid crystal alignment ability is known. (See Patent Documents 1 to 8)
This photo-alignment method is known to be useful as a method of controlling the tilt direction of liquid crystal molecules in a vertical alignment mode liquid crystal display element. That is, it is known that the tilt direction of the liquid crystal molecules at the time of voltage application can be uniformly controlled by using a vertical alignment film imparted with an alignment regulating force by a photo-alignment method (see Patent Documents 9 to 11).
As described above, by using the vertical alignment film to which the alignment regulating force is applied by the photo-alignment method, the liquid crystal molecules can be slightly tilted from the normal direction of the substrate toward one direction in the substrate surface.
Thus, the liquid crystal aligning film manufactured by the photo-alignment method is preferable for liquid crystal display elements. However, when a liquid crystal aligning agent containing cinnamate or polyimide known so far is used in the photo-alignment method, there is a problem that the radiation dose required to obtain the liquid crystal alignment ability is large. It was. Problems caused by a large amount of irradiation include an increase in the tact time of the liquid crystal display device, a defect in the liquid crystal alignment film caused by prolonged irradiation, and a corresponding decrease in the reliability of the liquid crystal panel. It was.
Further, in the vertical alignment type liquid crystal display element, when an unreacted photoreactive group is present in the liquid crystal alignment film, unreacted light is generated by long-time exposure of the backlight (BL) light of the liquid crystal panel. There has been a problem that the reactive group reacts and the pretilt angle of the liquid crystal changes.

Japanese Unexamined Patent Publication No. 6-287453 Japanese Unexamined Patent Publication No. 10-251646 Japanese Unexamined Patent Publication No. 11-2815 Japanese Unexamined Patent Publication No. 11-152475 Japanese Unexamined Patent Publication No. 2000-144136 Japanese Unexamined Patent Publication No. 2000-319510 Japanese Unexamined Patent Publication No. 2000-281724 Japanese Unexamined Patent Publication No. 9-297313 Japanese Unexamined Patent Publication No. 2003-307736 Japanese Patent No. 4088156 Japanese Unexamined Patent Publication No. 2004-163646

  An object of the present invention is to provide a liquid crystal alignment for vertical alignment that can develop a pretilt angle with a small dose of polarized or non-polarized radiation and can maintain a stable pretilt angle even when exposed to backlight for a long time. An object of the present invention is to provide a liquid crystal alignment treatment agent used for forming a film, a formed liquid crystal alignment film, and a liquid crystal display element including the liquid crystal alignment film.

（Ａ）：式［１］中、Ｘ¹は単結合、−ＣＨ_２Ｏ−、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、又は−ＣＯＮＨ−を表し、Ｘ^２は炭素数１〜３のアルキレン基を表し、Ｘ^３は−Ｏ−、−ＮＨ−、又は−Ｎ（Ｒ^１）−を表し、Ｘ^４は単結合、−Ｏ−、−Ｓ−、又は−ＮＨ−を表す。Ｘ^５は単結合を表し、Ｘ^６は炭素数１〜１８の直鎖又は分岐状のアルキル基を表し、Ｘ^７は水素原子、−Ｒ^２、−ＯＲ^３、−ＮＨＲ^４、−Ｎ（Ｒ^５）_２、又は−ＳＲ^６を表す。ここでＲ^１〜Ｒ^６はそれぞれ独立して炭素数１〜５のアルキル基を表す。ｎは１又は２の整数を表す。
（Ｂ）：式［１］中、Ｘ¹は単結合を表し、Ｘ^２は炭素数１〜３のアルキレン基を表し、Ｘ^３は−Ｏ−、−ＮＨ−、又は−Ｎ（Ｒ^１）−を表し、Ｘ^４ は−Ｏ−を表す。Ｘ^５は単結合又は下記式[Ｘ^５−１]〜[Ｘ^５−５]の群から選択される炭素環を表し、Ｘ^６は炭素数１〜１８の直鎖又は分岐状のアルキル基を表し、Ｘ^７は水素原子、−Ｒ^２、−ＯＲ^３、−ＮＨＲ^４、−Ｎ（Ｒ^５）_２、又は−ＳＲ^６を表す。ここでＲ^１〜Ｒ^６はそれぞれ独立して炭素数１〜５のアルキル基を表す。ｎは１又は２の整数を表す。

（ただし、上記の炭素環構造において、任意の水素原子はＣＨ_３にて置換されていてもよい。）
（Ｃ）：式［１］中、Ｘ¹は単結合、−ＣＨ_２Ｏ−、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、又は−ＣＯＮＨ−を表し、Ｘ^２は−ＣＨ_２−を表し、Ｘ^３は−Ｏ−、−ＮＨ−、又は−Ｎ（Ｒ^１）−を表し、Ｘ^４は単結合、−Ｏ−、−Ｓ−、又は−ＮＨ−を表す。Ｘ^５は単結合又は下記式[Ｘ^５−１]〜[Ｘ^５−５]の群から選択される炭素環を表し、Ｘ^６は炭素数８〜１２の直鎖又は分岐状のアルキル基を表し、Ｘ^７は水素原子、−Ｒ^２、−ＯＲ^３、−ＮＨＲ^４、−Ｎ（Ｒ^５）_２、又は−ＳＲ^６を表す。ここでＲ^１〜Ｒ^６はそれぞれ独立して炭素数１〜５のアルキル基を表す。ｎは１又は２の整数を表す。

（ただし、上記の炭素環構造において、任意の水素原子はＣＨ_３にて置換されていてもよい。）
（２）前記ジアミン成分中の式［１］のジアミン化合物の含有量が、３０〜１００モル％である上記（１）に記載の液晶配向処理剤。
（３）前記式［１］のｎが１である上記（１）又は（２）に記載の液晶配向処理剤。 As a result of diligent research to achieve the above object, the present inventors have found that a liquid crystal aligning agent containing a polymer obtained by using a diamine compound having a specific structure achieves the above object. . The present invention is based on such knowledge and has the following gist.
(1) A reaction of a diamine component containing a diamine compound represented by the following formula [1] and satisfying any of the following (A), (B) or (C) with a tetracarboxylic dianhydride component: The liquid crystal aligning agent containing the polyamic acid obtained and the at least 1 polymer chosen from the group which consists of a polyimide obtained by imidating this polyamic acid.

(A): In formula [1], X ¹ represents a single bond, —CH ₂ O—, —O—, —COO—, —OCO—, —NHCO—, or —CONH—, and X ² represents the number of carbon atoms. 1 to 3 alkylene groups, X ³ represents —O—, —NH—, or —N (R ¹ ) —, and X ⁴ represents a single bond, —O—, —S—, or —NH—. Represent. X ⁵ represents a single bond, X ⁶ represents a linear or branched alkyl group having 1 to 18 carbon atoms, X ⁷ represents a hydrogen atom, —R ² , —OR ³ , —NHR ⁴ , —N (R ⁵⁾ _2, or an -SR ^6. Here, R ^{1 to} R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 or 2.
(B): In the formula [1], X ¹ represents a single bond, X ² represents an alkylene group having 1 to 3 carbon atoms, and X ³ represents —O—, —NH—, or —N (R ¹ ). - represents, ^{X 4} represents -O-. X ⁵ represents a single bond or a carbocycle selected from the group of the following formulas [X ⁵ -1] to [X ⁵ -5], and X ⁶ represents a linear or branched alkyl group having 1 to 18 carbon atoms. It represents, ^{X 7} is a hydrogen ^{atom, -R 2, -OR 3, -NHR} 4, -N (R 5) 2, or an -SR ^6. Here, R ^{1 to} R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 or 2.

(However, in the above carbocyclic structure, any hydrogen atom may be substituted with CH _3. )
(C): In Formula [1], X ¹ represents a single bond, —CH ₂ O—, —O—, —COO—, —OCO—, —NHCO—, or —CONH—, and X ² represents —CH ^2. _2- represents, X ³ represents —O—, —NH—, or —N (R ¹ ) —, and X ⁴ represents a single bond, —O—, —S—, or —NH—. X ⁵ represents a single bond or a carbocycle selected from the group of the following formulas [X ⁵ -1] to [X ⁵ -5], and X ⁶ represents a linear or branched alkyl group having 8 to 12 carbon atoms. It represents, ^{X 7} is a hydrogen ^{atom, -R 2, -OR 3, -NHR} 4, -N (R 5) 2, or an -SR ^6. Here, R ^{1 to} R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 or 2.

(However, in the above carbocyclic structure, any hydrogen atom may be substituted with CH _3. )
(2) The liquid-crystal aligning agent as described in said (1) whose content of the diamine compound of Formula [1] in the said diamine component is 30-100 mol%.
(3) The liquid-crystal aligning agent as described in said (1) or (2) whose n of said Formula [1] is 1.

(4) The liquid crystal aligning film obtained from the liquid-crystal aligning agent as described in any one of said (1)-(3).
(5) above (1) to apply the liquid crystal alignment treating agent according to any one of (3) on a substrate and baked, then imparting the liquid crystal alignment capability by irradiating radiation polarization or unpolarized A method for producing a liquid crystal alignment film.
(6) A liquid crystal display device comprising the liquid crystal alignment film according to (4).

  According to the liquid crystal aligning agent of this invention, the liquid crystal aligning film for expressing a pretilt angle can be obtained with the irradiation amount of a small radiation compared with the conventional photo-alignment method. In addition, the liquid crystal display element having the liquid crystal alignment film of the present invention exhibits a stable pretilt angle even when exposed to backlight for a long time, and is useful as a highly reliable liquid crystal display element.

式中、Ｘ¹は単結合、−ＣＨ_２Ｏ−、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、又は−ＣＯＮＨ−を表す。
Ｘ²は炭素数１〜３のアルキレン基を表す。
Ｘ^３は−Ｏ−、−ＮＨ−、又は−Ｎ（Ｒ^１）−を表す。
Ｘ^４は単結合、−Ｏ−、−Ｓ−、又は−ＮＨ−を表す。
Ｘ^５は単結合又は下記式[Ｘ^５−１]〜[Ｘ^５−５]の群から選択される炭素環を表す。
Ｘ^６は炭素数１〜１８の直鎖又は分岐状のアルキル基を表す。
Ｘ^７は水素原子、−Ｒ^２、−ＯＲ^３、−ＮＨＲ^４、−Ｎ（Ｒ^５）_２、又は−ＳＲ^６を表す。ここでＲ^１〜Ｒ^６は、それぞれ独立して炭素数１〜５のアルキル基を表す。
ｎは１又は２の整数を表す。

上記式[Ｘ^５−１]〜[Ｘ^５−５]の炭素環構造においては、任意の水素原子はＣＨ_３にて置換されていてもよい。<Diamine compound represented by Formula [1]>
The diamine compound of the present invention (hereinafter sometimes referred to as a specific diamine compound) is represented by the following formula [1].

In the formula, X ¹ represents a single bond, —CH ₂ O—, —O—, —COO—, —OCO—, —NHCO—, or —CONH—.
X ² represents an alkylene group having 1 to 3 carbon atoms.
X ³ represents —O—, —NH—, or —N (R ¹ ) —.
X ⁴ represents a single bond, —O—, —S—, or —NH—.
X ⁵ represents a single bond or a carbocyclic ring selected from the group of the following formulas [X ⁵ -1] to [X ⁵ -5].
X ⁶ represents a linear or branched alkyl group having 1 to 18 carbon atoms.
X ⁷ represents a hydrogen atom, —R ² , —OR ³ , —NHR ⁴ , —N (R ⁵ ) ₂ , or —SR ⁶ . Here, R ^{1 to} R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms.
n represents an integer of 1 or 2.

In the carbocyclic structures of the above formulas [X ⁵ -1] to [X ⁵ -5], any hydrogen atom may be substituted with CH ₃ .

The bonding position of the two amino groups (—NH ₂ ) in the formula [1] is not limited. Specifically, with respect to the linking group (X 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, or 3, 5 positions. Among these, from the viewpoint of the reactivity when synthesizing the polyamic acid and the ease when synthesizing the diamine compound, the bonding position of the two amino groups is the position of 2, 4 or the position of 2, 5 or The positions 3, 5 are particularly preferred.

式［２］中、Ｘ¹は単結合、−ＣＨ_２Ｏ−、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、又は−ＣＯＮＨ−の結合基であり、Ｘ^２は炭素数１〜３のアルキレン基である。
Ｘ^２のアルキレン鎖の長さが、少ない照射量でプレチルト角を発現するためには重要であり、このアルキレン鎖が長すぎると、プレチルト角を発現するまでの照射量が多くなってしまう。これは垂直配向用の液晶配向膜を形成する重合体中に含有されるアミンの側鎖（上記式［２］のＸ^３に結合したカルボニル基からの部位）の根元の部位で光反応が起こることで、光反応による異方性が側鎖全体に影響し、側鎖が液晶へ与える配向規制力が大きくなるためである。この結果、少ない照射量でも液晶のプレチルト角を発現させることが可能となる。The diamine compound of the present invention, when used as a liquid crystal alignment film for vertical alignment, is intended to give a pretilt angle by irradiation with ultraviolet rays, and is represented by the following formula [2] included in the formula [1]. This is the part that determines the expression of the pretilt angle. By optimizing this structure, a preferable pretilt angle can be obtained.

In the formula [2], X ¹ is a single bond, —CH ₂ O—, —O—, —COO—, —OCO—, —NHCO—, or —CONH—, and X ² has 1 carbon atom. ~ 3 alkylene groups.
The length of the alkylene chain X ² is important in order to express a pretilt angle with a small radiation dose, this alkylene chain is too long, it becomes much irradiation dose until express pretilt angle. This is because a photoreaction occurs at the base of the side chain of the amine contained in the polymer forming the liquid crystal alignment film for vertical alignment (the site from the carbonyl group bonded to X ³ in the above formula [2]). This is because the anisotropy due to the photoreaction affects the entire side chain, and the alignment regulating force exerted on the liquid crystal by the side chain is increased. As a result, the pretilt angle of the liquid crystal can be expressed even with a small irradiation amount.

In formula [2], X ³ represents —O—, —NH—, or —N (R ¹ ) —, and X ⁴ represents a single bond, —O—, —S—, or —NH—.
R ¹ represents an alkyl group having 1 to 5 carbon atoms.
X ³ and X ⁴ are a linking group of a photoreactive moiety, and X ³ and X ⁴ are particularly preferably —O— because of the length of the light absorption wavelength of the photoreactive group and the ease of synthesis.
In formula [2], X ⁵ is a single bond or a carbocyclic ring selected from the group of the following formulas [X ⁵ -1] to [X ⁵ -5], and X ⁶ is a straight chain having 1 to 18 carbon atoms or It is a branched alkyl group.
X ⁵ and X ⁶ are important for vertically aligning the liquid crystal. When X ⁵ is a single bond, X ⁶ is preferably a long-chain alkyl group from the viewpoint of vertical alignment ability. In this case, the number of carbon atoms of X ⁶ is preferably 6 to 18, and more preferably 8 to 12.
In addition, when X ⁵ is a carbocycle selected from the group of the following formulas [X ⁵ -1] to [X ⁵ -5], X ⁴ is preferably a slightly short alkyl group because the vertical alignment ability is improved. In this case, the number of carbon atoms of X ⁴ is preferably 1 to 12, and more preferably 3 to 8.

式［２］中、Ｘ^７は水素原子、−Ｒ^２、−ＯＲ^３、−ＮＨＲ^４、−Ｎ（Ｒ^５）_２、又は−ＳＲ^６を表す。ここで、Ｒ^２〜Ｒ^６は、それぞれ独立して炭素数１〜５のアルキル基を表す。 ｎは１又は２の整数を表す。
Ｘ^７及びｎは、光反応性基の感光波長を決定するために重要であり、Ｘ^７に電子供与性の置換基を用いると、光反応性基の吸収波長が長波長化する。また、ｎが２であると、同様の効果が得られる。Ｘ^７及びｎは、光反応性基の感光波長を好ましい波長にすることができる。

Wherein [2], ^{X 7} is a hydrogen ^{atom, -R 2, -OR 3, -NHR} 4, -N (R 5) 2, or an -SR ^6. Here, R < ² > -R < ⁶ > represents a C1-C5 alkyl group each independently. n represents an integer of 1 or 2.
X ⁷ and n are important for determining the photosensitive wavelength of the photoreactive group. When an electron donating substituent is used for X ⁷ , the absorption wavelength of the photoreactive group becomes longer. When n is 2, the same effect can be obtained. X ⁷ and n can make the photosensitive wavelength of the photoreactive group a preferable wavelength.

上記に例示するジアミン化合物に記載のＣ_ｎＨ_２ｎ+１部分において、ｎは１〜１８の整数を表す。From the viewpoint of photosensitive wavelength and photoreactive sensitivity when used as a liquid crystal alignment film for vertical alignment, preferred specific combinations of X ^{1 to} X ⁷ in formula [1] are shown below.

In the C _n H _{2n + 1} portion described in the diamine compound exemplified above, n represents an integer of 1 to 18.

<Method for synthesizing specific diamine compound>
Manufacturing method 1
A dinitro body 4 having a cinnamic acid moiety in the side chain is produced by a reaction between an acrylic ester body 2 obtained from the dinitro body 1 and a benzene derivative 3 having a leaving functional group Y. The obtained dinitro compound 4 can be converted to the target diamine 5 by selecting and carrying out a reduction method that does not affect the double bond portion of the side chain.

Ｘ^３が−Ｏ−である化合物１ａ’の水酸基を、ハロゲンやスルホン酸エステルなどの脱離基に変換した後、アジ化物と反応させて得られる、対応するアジド誘導体を還元しても、Ｘ^３が−ＮＨ−である化合物１ａ’’を得ることができる。また、脱離基に変換後に、コハク酸イミドやフタルイミドと反応させた後、生成したＮ-アルキルイミドをヒドラジンで分解する、いわゆる、ガブリエル合成によるアミンの合成でも、Ｘ^３が−ＮＨ−である化合物１ａ’’を得ることができる。
Ｘ^３が−ＮＨ−である化合物１ａ’’に対して、アルキルハライドやアルキルスルホン酸エステルを塩基の共存下で反応させて、Ｘ^３が−ＮＲ^１（Ｒ^１は炭素数１〜５のアルキル基を表す。）である化合物１ａ’’得ることができる。また、アルデヒド化合物を作用させて対応するイミン化合物とし、そのイミン部分をボラン系の還元剤などで還元する、いわゆる、還元的アミノ化反応を利用することで、Ｘ^３が−ＮＲ^１（Ｒ^１は炭素数１〜５のアルキル基を表す。）である化合物１ａ’’’を得ることができる。前者のアルキル化の場合は、アルキル基が複数個導入された副生成物が得られるが、後者の方法では副生成物がなく、アルキル基の導入に有効である。Production Method of Compound 1 <When X ¹ is a single bond (m is an integer of 1 to 3, and X ³ represents —O—, —NH—, or —NR ¹ —)>
Some raw materials can be purchased as commercial products. In the case where it is difficult to obtain a commercially available product, when a carboxylic acid as shown in Compound 6 is subjected to a reduction reaction with a borane reducing agent, a raw material in which X ³ corresponds to —O— can be synthesized. Further, if a borane reducing agent is allowed to act on the compound 6 in which the carboxylic acid moiety of the compound 6 is a cyano group, that is, the compound 7, a raw material of a diamine compound in which X ³ is —NH— can be synthesized.

Even if the corresponding azide derivative obtained by converting the hydroxyl group of compound 1a ′ in which X ³ is —O— into a leaving group such as halogen or sulfonic acid ester and then reacting with an azide is reduced, Compound 1a ″ in which ³ is —NH— can be obtained. Further, after conversion to a leaving group, after reacting with succinimide or phthalimide, the produced N-alkylimide is decomposed with hydrazine, so that X ³ is —NH— in the synthesis of amine by so-called Gabriel synthesis. Compound 1a ″ can be obtained.
The compound 1a ″ in which X ³ is —NH— is reacted with an alkyl halide or an alkyl sulfonate in the presence of a base, and X ³ is —NR ¹ (R ¹ is an alkyl having 1 to 5 carbon atoms). A compound 1a ″, which represents a group). Further, by using a so-called reductive amination reaction in which an aldehyde compound is allowed to act to form a corresponding imine compound and the imine portion is reduced with a borane-based reducing agent or the like, X ³ becomes —NR ¹ (R ¹ Represents an alkyl group having 1 to 5 carbon atoms.) Can be obtained. In the former alkylation, a by-product in which a plurality of alkyl groups are introduced is obtained, but in the latter method, there is no by-product and it is effective for introducing an alkyl group.

化合物９において、ＹはＦ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、又は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、トルエンスルホニルオキシ基、トリフルオロメタンスルホニル基などのスルホン酸エステル類を表す。
保護基であるＰは、ホルミル基、アセチル基、プロピオニル基、ベンゾイル基などのエステル系の保護基、メトキシメチル基、エトキシエチル基、テトラヒドロピラニル基、テトラヒドロフリル基などのアセタール系の保護基、トリメチルシリル基、トリエチルシリル基、トリ（イソプロピル）シリル基、トリフェニルシリル基、ｔｅｒｔ−ブチルジメチルシリル基、ｔｅｒｔ−ブチルジフェニルシリル基、クミルジフェニルシリル基などのシリル系の保護基、メトキシカルボニル基、エトキシカルボニル基、ベンジロキシカルボニル基、フェノキシカルボニル基、ｔｅｒｔ−ブトキシカルボニル基などの炭酸エステル系の保護基が挙げられる。副反応を制御する観点から、アセタール系又はシリル系の保護基が好ましい。
化合物８と化合物９からジニトロ体１０を得る反応の際に塩基を共存させるが、使用する塩基としては、炭酸カリウム、炭酸水素ナトリウム、水素化ナトリウム、水素化カリウムなどの無機塩基、トリエチルアミン、ジ（イソプロピル）エチルアミンなどのアミン類などが使用できる。本反応を行う際に、反応を円滑に進行させるために、ヨウ化ナトリウム, ヨウ化カリウム、又はテトラ−ｎ−ブチルアンモニウムヨーダイドを添加するのが好ましい。<When X ¹ is —O— (m is an integer of 1 to 3, and X ³ represents —O—, —NH—, or —NR ¹ —)>
Dinitrophenol 8 having a side chain is obtained by alkylation of commercially available dinitrophenol 8 with compound 9 having protecting group P. By deprotecting the protecting group P contained in the dinitro body 10, the dinitro intermediate 1b can be produced.

In Compound 9, Y represents a halogen atom such as F, Cl, Br, or I, or a sulfonic acid ester such as a methanesulfonyloxy group, a benzenesulfonyloxy group, a toluenesulfonyloxy group, or a trifluoromethanesulfonyl group.
P, which is a protective group, is an ester-type protective group such as formyl group, acetyl group, propionyl group, or benzoyl group; an acetal-type protective group such as methoxymethyl group, ethoxyethyl group, tetrahydropyranyl group, or tetrahydrofuryl group; Silyl-based protective groups such as trimethylsilyl group, triethylsilyl group, tri (isopropyl) silyl group, triphenylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, cumyldiphenylsilyl group, methoxycarbonyl group, Examples thereof include carbonate-based protecting groups such as ethoxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, and tert-butoxycarbonyl group. From the viewpoint of controlling the side reaction, an acetal type or silyl type protecting group is preferred.
In the reaction for obtaining the dinitro compound 10 from the compound 8 and the compound 9, a base is allowed to coexist. Examples of the base used include inorganic bases such as potassium carbonate, sodium hydrogen carbonate, sodium hydride, potassium hydride, triethylamine, di ( Amines such as isopropyl) ethylamine can be used. In carrying out this reaction, it is preferable to add sodium iodide, potassium iodide, or tetra-n-butylammonium iodide to facilitate the reaction.

The deprotection reaction of compound 10 is carried out by selecting deprotection conditions suitable for the protecting group used. When an ester-based or carbonate-based protecting group is used, both acidic and alkaline liquid hydrolysis reactions are effective. Deprotection can also be achieved by utilizing a transesterification reaction with a lower alcohol. When an acetal type protecting group is used, a deprotection reaction using a catalytic amount of an organic acid such as mineral acid, formic acid, acetic acid or toluenesulfonic acid is preferred. When a silyl protecting group is used, deprotection using a fluoride such as tetra-n-butylammonium fluoride is preferred under the same conditions as the deprotection of an acetal protecting group.
By carrying out reductive amination reaction on the compound obtained above with X ³ being —NH—, X ³ represents —NR ¹ (R ¹ represents an alkyl group having 1 to 5 carbon atoms). ) Can be synthesized.
In addition, a compound in which the OH group and the Y group of the compound 8 and the compound 9 are interchanged, that is, a compound in which the hydroxyl group of the compound 8 is fluorine or chlorine and the compound 9 has an OH group is represented by the presence of a base. Compound 10 can also be obtained by reaction under the following conditions.

化合物１１において、ＨａｌはＯＨ基、もしくは、ハロゲン原子を示すが、安定性を考えると、ＯＨ基又はクロロ基である化合物１１を使用することが好ましい。
化合物１２中の保護基Ｐは、好ましい保護基についても前記と同義である。
化合物１２中のＺは、水酸基、アミノ基、ハロゲン、又はスルホニル基を表す。<When X ¹ is —COO— or —CONH— (m is an integer of 1 to 3, and X ³ represents —O—, —NH—, or —NR ¹ —)>
In the reaction of the carboxylic acid or its derivative 11 and the compound 12 having a protecting group P, a dinitro-ester 13 (Q═O) or dinitro-amide 13 (Q is —NH—) having a side chain. ) By deprotecting the protecting group contained in the dinitro-ester compound 13 (Q is —O—) or the dinitro-amide compound 13 (Q is —NH—), the ester bond group is removed. The dinitro intermediate 1c can be produced.

In Compound 11, Hal represents an OH group or a halogen atom, but considering stability, it is preferable to use Compound 11 which is an OH group or a chloro group.
The protecting group P in the compound 12 is as defined above for the preferred protecting groups.
Z in the compound 12 represents a hydroxyl group, an amino group, a halogen, or a sulfonyl group.

Q in the compound 13 represents —O— or —NH—. The functional group represented by Z in compound 12 is selected in consideration of the structure of the Hal portion of compound 11 to be used. For example, when Hal is an OH group and OH group or NH ₂ group is selected as Z, a condensing agent such as dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, or carbonyldiimidazole is used. The compound 13 having an ester (Q is —O—) or an amide bond (Q is —NH—) is obtained. When Hal is an OH group and a halogen or sulfonyl group is selected as Z, inorganic bases such as potassium carbonate, sodium hydrogen carbonate, sodium hydride and potassium hydride, amines such as triethylamine and di (isopropyl) ethylamine To give ester compound 13 (Q is —O—). In order to make the reaction proceed smoothly, it is also effective to add sodium iodide, potassium iodide, or tetra-n-butylammonium iodide.

When Hal is a halogen atom typified by a chloro group, an ester compound 13 (Q is —O—) or an amide compound 13 (Q Is —NH—. In this reaction, amines such as triethylamine and pyridine are added as a base.
The compound 1c can be obtained by deprotecting the protecting group P of the obtained compound 13. The deprotection conditions are the same as the deprotection conditions for the compound 10.
The compound 1a ″ in which X ³ is —NH— is reacted with an alkyl halide or an alkyl sulfonate in the presence of a base, and X ³ is NR ¹ (R ¹ is an alkyl group having 1 to 5 carbon atoms). Can be obtained. Further, by utilizing a so-called reductive amination reaction in which an aldehyde compound is allowed to act to form a corresponding imine compound and the imine portion is reduced with a borane-based reducing agent or the like, X ³ becomes NR ¹ (R ¹ is A compound 1c which is an alkyl group having 1 to 5 carbon atoms can be obtained. In the former alkylation, a by-product in which a plurality of alkyl groups are introduced is obtained, but in the latter method, there is no by-product and it is effective for introducing an alkyl group.

化合物１４とジニトロ体１６とジニトロ中間体１ｄ中のＱは、−Ｏ−又は−ＮＨ−を表す。
カルボン酸誘導体１５において、ＨａｌはＯＨ基、もしくは、ハロゲン原子を示すが、安定性を考えるとＯＨ基又はクロロ基である化合物１５を使用することが好ましい。 保護基Ｐは、好ましい保護基についても前記と同義である。<When X ¹ is —OCO— or —NHCO— (m is an integer of 1 to 3, and X ³ represents —O—, —NH—, or —NR —)>
Esterification or amidation is carried out by reacting dinitrophenol (Q is —O—) or dinitroaniline (Q is —NH—) 14 with a carboxylic acid derivative 15 having a protecting group P, Alternatively, a dinitro intermediate 1d having an ester bond or an amide bond can be produced by making the dinitro body 16 having an amide side chain and then deprotecting the protecting group contained in the dinitro body 16.

Q in the compound 14, the dinitro body 16 and the dinitro intermediate 1d represents —O— or —NH—.
In the carboxylic acid derivative 15, Hal represents an OH group or a halogen atom, but it is preferable to use the compound 15 which is an OH group or a chloro group in view of stability. The protecting group P is as defined above for the preferred protecting groups.

When Hal is an OH group, ie, when carboxylic acid 15 is reacted with dinitrophenol 14 (Q is —O—) or dinitroaniline 14 (Q is —NH—), dicyclohexylcarbodiimide, 1 Generally, a condensing agent such as ethyl-3- (3-dimethylaminopropyl) carbodiimide or carbonyldiimidazole is used. Furthermore, it is preferable for the progress of the reaction to add a catalytic amount of acid or N, N-dimethylaminopyridine. A method in which Hal is used for the reaction using an acid halide derivative typified by a chloro group or the like is also preferred. At this time, the reaction is carried out by adding a base such as an amine such as triethylamine or pyridine.
The dinitro intermediate 1d can be obtained by deprotecting P, which is a protecting group of the obtained compound 16, and the deprotection conditions are the same as the deprotection conditions for the compound 10 described above.

Production Method of Compound 2 Compound 2 can be produced by esterification between corresponding raw material 1 such as dinitrobenzyl alcohol and an acrylic acid derivative.
As the acrylic acid derivative, it is preferable to use acid halides such as acrylic acid chloride and acrylic acid bromide, acrylic acid anhydride and the like.
In the esterification reaction, inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, NaH, KaH are used as the base. , Trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, amines such as pyridine, quinoline, collidine, and organic bases such as tert-sodium butoxide and tert-potassium butoxide.

The solvent can be appropriately selected as long as it is inert and stable under the reaction conditions and does not interfere with the reaction. For example, amines, aprotic polar organic solvents (dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane Etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogenated hydrocarbons (Chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles Acetonitrile, propionitrile, etc. butyronitrile) can be used. These solvents can be appropriately selected in consideration of the reaction conditions and the easiness of the reaction, and can be used singly or in combination of two or more. Moreover, depending on the case, it can also use as a non-aqueous solvent using a dehydrating agent or a desiccant.
The reaction temperature is preferably in the range of −100 ° C. to the boiling point of the solvent used, and more preferably in the range of −50 to 150 ° C.
The reaction time is preferably 0.1 to 1,000 hours.
Compound 2 obtained as described above may be purified by recrystallization, distillation, silica gel column chromatography, activated carbon or the like.
Compound 2 can also be synthesized by transesterification of acrylic acid esters such as methyl acrylate and ethyl acrylate with dinitrobenzyl alcohol, or reaction of acrylic acid with dinitrobenzyl halides such as dinitrobenzyl chloride and dinitrobromide. be able to.

上記化合物１７と化合物１８において、ＵはＦ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、−ＯＨ、−ＳＨ、又は−ＮＨ_２を表し、Ｘ^５は単結合又は前記[Ｘ^５−１]〜[Ｘ^５−５]の群から選択される炭素環を表し、Ｘ^６は炭素数１〜１８の直鎖又は分岐状のアルキル基を表す。
Ｘ^７は水素原子、−Ｒ^２、−ＯＲ^３、−ＮＨＲ^４、−Ｎ（Ｒ^５）_２、又は−ＳＲ^６を表す。ここで、Ｒ²〜Ｒ^６は、それぞれ独立して炭素数１〜５のアルキル基を表す。
ｎは１又は２の整数を表す。
Ｙ及びＬは、それぞれ独立してハロゲン又は擬ハロゲン基であり、例えば、Ｆ、Ｃｌ、Ｂｒ、Ｉ、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、トルエンスルホニルオキシ基、トリフルオロメタンスルホニル基などのアルキルスルホニルオキシ基、又は芳香族スルホニルオキシ基を示す。
化合物３の製法は、例えば１７で示した化合物と１８で示した化合物との反応により製造することができる。また、化合物１７と化合物１８の幾つかは容易に市販品として入手することが可能である。Production method of compound 3

In the compounds 17 and 18, U represents a halogen atom such as F, Cl, Br, or I, —OH, —SH, or —NH ₂ , and X ⁵ is a single bond or the above [X ⁵ -1] to [[ X ⁵ -5] represents a carbocyclic ring selected from the group, and X ⁶ represents a linear or branched alkyl group having 1 to 18 carbon atoms.
X ⁷ represents a hydrogen atom, —R ² , —OR ³ , —NHR ⁴ , —N (R ⁵ ) ₂ , or —SR ⁶ . Here, R < ² > -R < ⁶ > represents a C1-C5 alkyl group each independently.
n represents an integer of 1 or 2.
Y and L are each independently a halogen or pseudohalogen group, and examples thereof include alkylsulfonyl such as F, Cl, Br, I, methanesulfonyloxy group, benzenesulfonyloxy group, toluenesulfonyloxy group, and trifluoromethanesulfonyl group. An oxy group or an aromatic sulfonyloxy group is shown.
Compound 3 can be produced, for example, by reacting the compound represented by 17 with the compound represented by 18. Some of the compounds 17 and 18 can be easily obtained as commercial products.

<When X ⁴ is —O—, —S—, or —NH—>
The substituent U of the compound 17 is —OH, —SH, or —NH ₂ , and X ^{5 of the} compound 18 is a single bond or selected from the group of [X ⁵ -1] to [X ⁵ -5]. In the case of the carbocyclic ring, compound 3 is obtained by reacting both compounds in the presence of a base. Examples of the base to be used include organic aliphatics such as alkali metal hydroxides and carbonates such as lithium, sodium and potassium, triethylamine, diazabicyclooctane, diazabicycloundecene, pyridine and 4-dimethylaminopyridine. , Aromatic, and heterocyclic organic bases. Mixtures of these bases can also be used. Particularly preferred is potassium carbonate.
The solvent can be appropriately selected as long as it is stable under the reaction conditions and is inert and does not interfere with the reaction. For example, ketone solvents (acetone, 2-butanone, methyl isobutyl ketone, etc.), aprotic polar organic solvents (dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, Dichlorobenzene, nitrobenzene, tetralin, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, Ethyl, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.) can be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used alone or in combination of two or more. Moreover, depending on the case, it can also use as a non-aqueous solvent using a dehydrating agent or a desiccant.
The reaction temperature is preferably from −100 ° C. to the boiling point of the solvent used, more preferably from −50 to 150 ° C.
The reaction time is preferably 0.1 to 1,000 hours.
Compound 3 obtained as described above can be purified by recrystallization, distillation, silica gel column chromatography or the like.

When the substituent U of the compound 17 is —OH, —SH, or —NH ₂ , and X ^{5 of the} compound 18 is a single bond or [X ⁵ -5], a metal complex is present in the presence of a suitable base. Compound 3 can be synthesized by utilizing a coupling reaction using a ligand as a catalyst. As the metal complex, it is preferable to use a copper complex, a palladium complex, or a nickel complex. In particular, it is preferable to use a zero-valent complex having tertiary phosphine or tertiary phosphite as a ligand. In addition, an appropriate precursor that can be easily converted into a zero-valent complex in the reaction system can also be used. Furthermore, in the reaction system, a complex containing no tertiary phosphine or tertiary phosphite as a ligand is mixed with a tertiary phosphine or tertiary phosphite, and the tertiary phosphine or tertiary phosphite is used as a ligand. Low valence complexes can also be generated.

Examples of the tertiary phosphine or tertiary phosphite as a ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc. Complexes containing a mixture of two or more of these ligands are also preferably used. As the catalyst, a copper complex or a palladium complex containing no tertiary phosphine or tertiary phosphite is used. It is also preferable to use a combination of a tertiary phosphine or tertiary phosphite complex and the above-described ligand. As a complex that does not contain tertiary phosphine or tertiary phosphite used in combination with the above ligand, Cu catalyst, CuCl, CuBr, CuI, Cu ₂ O, CuCN, CuO, etc., and palladium catalyst, Bis (benzylideneacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzonitrile) dichloropalladium, palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon and the like. Examples of the complex containing tertiary phosphine or tertiary phosphite as a ligand include dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, (ethylene) bis (triphenylphosphine) palladium, tetrakis. Examples thereof include (triphenylphosphine) palladium and bis (triphenylphosphine) dichloropalladium, but are not limited thereto. The amount of the copper complex, palladium complex, nickel complex or the like used as the catalyst may be a so-called catalytic amount. Generally, 20 mol% or less of the compound to be reacted is sufficient, and usually 10 mol% or less.

  Bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, methylamine, dimethylamine, trimethylamine Amines such as ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, collidine In addition, sodium acetate, potassium acetate, lithium acetate and the like can also be used.

The solvent can be appropriately selected as long as it is stable under the reaction conditions and is inert and does not interfere with the reaction. For example, water, alcohols, amines, aprotic polar organic solvents (dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl) Ethers, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.) , Halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate) Etc.), nitriles (acetonitrile, propionitrile, etc. butyronitrile) can be mentioned. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. Moreover, depending on the case, it can also use as a non-aqueous solvent using a dehydrating agent or a desiccant.
The reaction temperature is from -100 ° C to the boiling point of the solvent used, and is preferably in the range of -50 to 150 ° C.
The reaction time is preferably 0.1 to 1,000 hours.
Compound 3 obtained as described above may be purified by recrystallization, distillation, silica gel column chromatography or the like.

<When X ⁴ is a single bond>
When the substituent U of the compound 17 is F, Cl, Br, or I and X ^{4 of the} compound 3 is a single bond, the coupling is carried out using a metal complex and a ligand as a catalyst in the presence of an appropriate base. Compound 3 can be synthesized using the reaction. As a metal complex, an iron complex, a palladium complex, or a nickel complex is preferable. In particular, it is preferable to use a zero-valent complex having tertiary phosphine or tertiary phosphite as a ligand. In addition, an appropriate precursor that can be easily converted into a zero-valent complex in the reaction system can also be used. Furthermore, in the reaction system, a complex containing no tertiary phosphine or tertiary phosphite as a ligand is mixed with a tertiary phosphine or tertiary phosphite, and the tertiary phosphine or tertiary phosphite is used as a ligand. Low valence complexes can also be generated.
Examples of the tertiary phosphine or tertiary phosphite as a ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc. Complexes containing a mixture of two or more of these ligands are also preferably used. As the catalyst, an iron complex or a palladium complex containing no tertiary phosphine or tertiary phosphite is used. It is also preferable to use a combination of a tertiary phosphine or tertiary phosphite complex and the above-described ligand. As a complex that does not contain tertiary phosphine or tertiary phosphite used in combination with the above ligands, FeBr ₃ , FeBr _2, FeCl ₃ , FeCl ₂ , FeF ₃ , FeF ₂ , Fe (acetyl) Acetonato) ₃ , Fe (acetylacetonate) _{2 and the} like, and palladium catalysts include bis (benzylideneacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzonitrile) dichloropalladium, Palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon and the like. Examples of the complex containing tertiary phosphine or tertiary phosphite as a ligand include dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, (ethylene) bis (triphenylphosphine) palladium, tetrakis. Examples thereof include (triphenylphosphine) palladium and bis (triphenylphosphine) dichloropalladium, but are not limited thereto. The amount of the iron complex, palladium complex, nickel complex, etc. used as the catalyst may be a so-called catalytic amount, and generally 20 mol% or less of the compound to be reacted is sufficient, and usually 10 mol% or less.

Examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, and other inorganic bases, N, N-dimethylethylenediamine, Methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, In addition to amines such as quinoline and collidine, sodium acetate, potassium acetate, lithium acetate and the like can also be used.
The solvent can be appropriately selected as long as it is stable under the reaction conditions and is inert and does not interfere with the reaction. For example, water, alcohols, amines, aprotic polar organic solvents (dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl) Ethers, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.) , Halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate) Etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.) can be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. Moreover, depending on the case, it can also use as a non-aqueous solvent using a dehydrating agent or a desiccant.
The reaction temperature is from -100 ° C to the boiling point of the solvent used, and is preferably in the range of -50 to 150 ° C.
The reaction time is preferably 0.1 to 1,000 hours.
Compound 3 obtained as described above may be purified by recrystallization, distillation, silica gel column chromatography or the like.

Production Method of Compound 4 Compound 4 can be synthesized by coupling reaction such as Heck reaction between Compound 2 and Compound 3 in the presence of a metal complex catalyst, a ligand, and a base.
Y in compound 3 may be any substituent having a leaving ability, such as halogen atoms such as F, Cl, Br, and I, methanesulfonyloxy group, benzenesulfonyloxy group, toluenesulfonyloxy group, trifluoro An alkylsulfonyloxy group such as a lomethanesulfonyl group, an aromatic sulfonyloxy group, or the like is used, and considering reactivity, a Br, I, or trifluoromethanesulfonyl group is preferable.
The coupling reaction preferably uses a metal complex and a ligand as a catalyst. Usually, a palladium complex, a nickel complex, etc. are used as a metal complex.
As the catalyst, those having various structures can be used, but it is preferable to use a so-called low-valent palladium complex or nickel complex, particularly a zero-valent complex having a tertiary phosphine or tertiary phosphite as a ligand. Is preferred. In addition, an appropriate precursor that can be easily converted into a zero-valent complex in the reaction system can also be used. Furthermore, in the reaction system, a complex containing no tertiary phosphine or tertiary phosphite as a ligand is mixed with a tertiary phosphine or tertiary phosphite, and the tertiary phosphine or tertiary phosphite is converted into a ligand. It is also possible to generate a low valence complex.

  Examples of the tertiary phosphine or tertiary phosphite as a ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc. Complexes containing a mixture of two or more of these ligands are also preferably used. It is also a preferred embodiment to use a combination of a palladium complex not containing tertiary phosphine or tertiary phosphite and / or a complex containing tertiary phosphine or tertiary phosphite and the above-mentioned ligand as a catalyst. Complexes containing no tertiary phosphine or tertiary phosphite used in combination with the above ligands include bis (benzylideneacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzo Nitrile) dichloropalladium, palladium acetate, palladium chloride, palladium-activated carbon and the like. Examples of the complex containing tertiary phosphine or tertiary phosphite as a ligand include dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, (ethylene) bis (triphenylphosphine) palladium, tetrakis. Examples thereof include (triphenylphosphine) palladium and bis (triphenylphosphine) dichloropalladium, but are not limited thereto. The amount of these palladium complexes used may be a so-called catalytic amount, generally 20 mol% or less of the compound to be reacted is sufficient, and usually 10 mol% or less.

Bases include inorganic bases, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, In addition to amines such as diisopropylethylamine, pyridine, imidazole, quinoline and collidine, sodium acetate, potassium acetate, lithium acetate and the like can also be used.
The solvent can be appropriately selected as long as it is stable under the reaction conditions and is inert and does not interfere with the reaction. For example, water, alcohols, amines, aprotic polar organic solvents (dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl) Ethers, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.) , Halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate) Etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.) can be used. These solvents can be appropriately selected in consideration of the reaction conditions and the easiness of the reaction. In this case, one kind can be used alone, or two or more kinds can be used in combination. Moreover, depending on the case, it can also use as a non-aqueous solvent using a dehydrating agent or a desiccant.
The reaction temperature is from −100 ° C. to the boiling point of the solvent used, and is preferably in the range of −50 to 150 ° C.
The reaction time is preferably 0.1 to 1,000 hours.
Compound 4 obtained as described above may be purified by recrystallization, distillation, silica gel column chromatography, activated carbon or the like.

Production method of compound 5 The dinitro compound 4 obtained above is converted to the target diamine compound 5 by selecting reduction reaction conditions that do not impair the double bond of the side chain, reducing the nitro group. Can do.
For reduction of the nitro group while leaving the double bond of the side chain as it is, it is preferable to use a metal such as Fe, Sn, Zn, or a metal salt thereof together with a proton source. Metals and metal salts may be used alone or jointly.
As the proton source, acids such as hydrochloric acid, ammonium salts such as ammonium chloride, and protic solvents such as methanol and ethanol can be used.
The solvent is not particularly limited as long as it can withstand an environment under a reducing atmosphere, such as an aprotic polar organic solvent (dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, Dichlorobenzene, nitrobenzene, tetralin, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyroni) Lil, etc.) can be used. These solvents can be appropriately selected in consideration of the reaction conditions and the easiness of the reaction, and can be used alone or in combination of two or more. In some cases, an appropriate dehydrating agent or desiccant can be used as a non-aqueous solvent.
The reaction temperature is from −100 ° C. to the boiling point of the solvent used. Preferably, it is the range of -50-150 degreeC.
The reaction time is preferably 0.1 to 1,000 hours.
Compound 5 obtained as described above may be purified by recrystallization, distillation, silica gel column chromatography, activated carbon or the like.

Manufacturing method 2
A dinitro body 4 having a cinnamic acid moiety in the side chain can be produced by reacting the dinitro body 1 with the acrylic acid derivative 19 or the compound 20 which is an acid halide. The obtained dinitro compound 4 can be converted to the target diamine compound 5 by selecting and carrying out a reduction method that does not affect the double bond portion of the side chain.

化合物１９と化合物２０において、ＸはハロゲンのＦ、Ｃｌ、Ｂｒ、又はＩを表し、Ｘ^４は単結合、−Ｏ−、−Ｓ−、又は−ＮＨ−を表す。
Ｘ^５、Ｘ^６、Ｘ^７、及びｎは前記と同義である。
化合物２０の製法は、化合物１９と酸ハロゲン化剤とを反応する方法である。Ｘは試薬の入手性、反応性の観点から、Ｃｌ、又はＢｒが好ましい。使用される酸ハロゲン化剤としては、例えば、塩化チオニル、オギザリルクロライド、ホスゲン、塩素、オキシ塩化リン、三塩化リン、五塩化リン、Ｎ−クロロコハク酸イミド、三塩化ホウ素、臭化チオニル、オギザリルブロミド、臭素、オキシ臭化リン、三臭化リン、五臭化リン、Ｎ−ブロモコハク酸イミドなどが挙げられる。好ましくは、塩化チオニル、又は臭化チオニルが用いられる。酸ハロゲン化剤としては、化合物１９に対して、通常２〜１００倍モル、好ましくは２〜３０倍モル、より好ましくは２〜３倍モル使用される。
上記の反応は、塩化チオニルなどの酸ハロゲン化剤中でも行うことができるが、必要に応じて溶媒を使用することができる。Production method of compound 20

In the compounds 19 and 20, X represents a halogen such as F, Cl, Br, or I, and X ⁴ represents a single bond, —O—, —S—, or —NH—.
X ⁵ , X ⁶ , X ⁷ and n are as defined above.
The production method of compound 20 is a method of reacting compound 19 with an acid halogenating agent. X is preferably Cl or Br from the viewpoint of reagent availability and reactivity. Examples of the acid halogenating agent used include thionyl chloride, oxalyl chloride, phosgene, chlorine, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, N-chlorosuccinimide, boron trichloride, thionyl bromide, ogi. Examples include zalyl bromide, bromine, phosphorus oxybromide, phosphorus tribromide, phosphorus pentabromide, and N-bromosuccinimide. Preferably, thionyl chloride or thionyl bromide is used. The acid halogenating agent is generally used in an amount of 2 to 100 times mol, preferably 2 to 30 times mol, more preferably 2 to 3 times mol, of Compound 19.
The above reaction can be carried out in an acid halogenating agent such as thionyl chloride, but a solvent can be used if necessary.

  The solvent is not particularly limited as long as it is inert to the reaction. For example, aprotic polar organic solvents (dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), ethers (diethyl ether, diisopropyl ether) , Tetrabutyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, Dichlorobenzene, nitrobenzene, tetralin, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, Propionic acid methyl etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.) can be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. In some cases, an appropriate dehydrating agent or desiccant can be used as a non-aqueous solvent.

In addition, the above reaction proceeds even without a catalyst, but by adding a catalyst, the amount of chlorinating agent used can be reduced and the reaction can be accelerated. The catalyst is not particularly limited. For example, organic bases such as triethylamine, pyridine, quinoline, N, N-dimethylaniline, dimethylformamide, metals such as sodium methoxide, potassium methoxide, or potassium t-butoxide Examples include alkoxides. Preferable examples include triethylamine pyridine and dimethylformamide. More preferably, pyridine is used. These catalysts are generally used in an amount of 0 to 100 times mol, preferably 0.01 to 10 times mol for the acid halide.
The reaction temperature is from −100 ° C. to the boiling point of the solvent used, and is preferably in the range of −50 to 150 ° C.
The reaction time is usually 0.1 to 1,000 hours.
The compound 20 obtained as described above may be purified by operations such as recrystallization, distillation, silica gel column chromatography and the like.

化合物２１において、Ａはアルキル基、シリル基又は水素を表し、例えば、メチル基、エチル基、プロピル基、ｎ−ブチル基、イソプロピル基、ｔｅｒｔ−ブチル基、ｓｅｃ−ブチル基、フェニル基、ベンジル基、シリル基、テトラヒドロピラニル基、テトラヒドロフラニル基、メトキシメチル基、メトキシエトキシ基、ビニル基等である。
上記反応は、化合物３と２１を金属錯体触媒、配位子及び塩基の共存下、ヘック反応などのカップリング反応により、化合物１９を合成できる。反応条件は、製法１の化合物４の合成法で示した方法と同様である。
Ａがアルキル基、又はシリル基の場合は、反応後、酸、又は塩基存在下、エステル基−ＣＯＯＡを水により加水分解することで、対応する化合物１９へと誘導することができる。用いる酸としては、希硫酸などの鉱酸や、p-トルエンスルホン酸、蟻酸、酢酸などの有機酸が挙げられる。また、塩基としては、炭酸水素カリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸ナトリウム等の炭酸塩類、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物、水酸化カルシウム、水酸化マグネシウム等のアルカリ土類金属の水酸化物、リン酸二水素ナトリウムやリン酸二水素カリウム等のリン酸塩類、酢酸ナトリウムや酢酸カリウム等のカルボン酸塩類、トリエチルアミン、ピリジン等の有機塩基類、ナトリウムメトキシド、ナトリウムエトキシド等の金属アルコキシド類、水素化ナトリウム等の金属水素化物類等が挙げられる。Production Method 1 of Compound 19

In the compound 21, A represents an alkyl group, a silyl group or hydrogen, for example, methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, tert-butyl group, sec-butyl group, phenyl group, benzyl group. Silyl group, tetrahydropyranyl group, tetrahydrofuranyl group, methoxymethyl group, methoxyethoxy group, vinyl group and the like.
In the above reaction, compound 19 can be synthesized from compound 3 and 21 by a coupling reaction such as Heck reaction in the presence of a metal complex catalyst, a ligand and a base. The reaction conditions are the same as those shown in the synthesis method of compound 4 in production method 1.
When A is an alkyl group or a silyl group, the ester group —COOA can be hydrolyzed with water in the presence of an acid or a base after the reaction to derive the corresponding compound 19. Examples of the acid used include mineral acids such as dilute sulfuric acid and organic acids such as p-toluenesulfonic acid, formic acid and acetic acid. Examples of the base include carbonates such as potassium bicarbonate, sodium bicarbonate, potassium carbonate and sodium carbonate, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkalis such as calcium hydroxide and magnesium hydroxide. Earth metal hydroxides, phosphates such as sodium dihydrogen phosphate and potassium dihydrogen phosphate, carboxylates such as sodium acetate and potassium acetate, organic bases such as triethylamine and pyridine, sodium methoxide, sodium Examples thereof include metal alkoxides such as ethoxide and metal hydrides such as sodium hydride.

Hydrolysis may be carried out in a solvent mixed with water in order to facilitate the reaction. Examples of the solvent used include aprotic polar organic solvents such as dimethylformamide, dimethylsulfoxide, and dimethylacetamide, acetonitrile, propionitrile, Nitriles such as butyronitrile, weak organic solvents such as pyridine, and alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol. Moreover, reaction can be performed more rapidly by heating.
The reaction temperature is from −100 ° C. to the boiling point of the solvent used, and is preferably in the range of −50 to 150 ° C.
The reaction time is usually 0.1 to 1,000 hours.
Further, the compound 19 obtained as described above may be purified by operations such as recrystallization, distillation, silica gel column chromatography and the like.

化合物２２と化合物２３において、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、ｎ、及びＡは前記と同義である。また、Ａの例示の基についても、前記と同様である。
化合物１９の製法は、例えば、Ａがアルキル基、又はシリル基の場合は、化合物２２と化合物２３とを塩基の存在下、脱水縮合させた後、ジエステル部分を加水分解し、脱炭酸させる方法である。また、Ａが水素の場合は、化合物２２と化合物２３とを塩基の存在下、脱水縮合させた後、脱炭酸させる方法である。
Ａが水素の場合、特に限定されないが、例えばピリジン溶媒中、ピペリジン存在下、６０〜１００℃にて反応させることにより、アルデヒド基とマロン酸を脱水縮合させ、その後、１００〜１５０℃に加熱することで、脱炭酸反応を進行させて、化合物１９を得ることができる。Production method 2 of compound 19

In the compounds 22 and 23, X ⁴ , X ⁵ , X ⁶ , X ⁷ , n, and A are as defined above. The same applies to the exemplified group A.
For example, when A is an alkyl group or a silyl group, the compound 19 is prepared by dehydrating and condensing the compound 22 and the compound 23 in the presence of a base, followed by hydrolysis of the diester moiety and decarboxylation. is there. When A is hydrogen, the compound 22 and the compound 23 are dehydrated and condensed in the presence of a base and then decarboxylated.
When A is hydrogen, it is not particularly limited. For example, aldehyde group and malonic acid are subjected to dehydration condensation by reacting at 60 to 100 ° C. in the presence of piperidine in a pyridine solvent, and then heated to 100 to 150 ° C. Thus, the compound 19 can be obtained by advancing the decarboxylation reaction.

  The base used for the dehydration condensation reaction is not particularly limited as long as it has a base strength (basicity) that allows the reaction to proceed smoothly. For example, alkali metal hydroxides and carbonates such as lithium, sodium and potassium, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride Alkaline earth metal, sodium or potassium, methylate, ethylate, n-propylate, isopropylate, n-butyrate, sec-butyrate, tert-butyrate, 2-methyl-2-butyrate, 2-methyl-2-pentylate, Alkali metal alcoholates derived from primary, secondary or tertiary aliphatic alcohols having 1 to 10 carbon atoms such as 3-methyl-3-pentylate, 3-ethyl-3-pentylate, diazabicyclooctane, diaza Bicycloundecene 4-dimethylaminopyridine, pyrrolidine, a piperidine, organic aliphatic, aromatic, nitrogenous base heterocycles. These bases can also be used as a mixture. As the base, sodium ethoxide and sodium hydride are preferable. The amount of the base used is usually 0.1 to 10 times mol, preferably 0.1 to 5 times mol for the compound 22.

As the solvent, any solvent that does not react with the compound 22 and the compound 23 can be used. For example, aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, ethers such as diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, pentane, Aliphatic hydrocarbons such as xane, heptane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, nitriles such as acetonitrile, propionitrile, butyronitrile, An organic weak basic solvent such as pyridine and quinoline can be used. In addition, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol can also be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. In some cases, an appropriate dehydrating agent or desiccant can be used as a non-aqueous solvent.
The conditions for hydrolysis with water are the same as the method shown in Production Method-1 for Compound 19.
The reaction temperature is from −100 ° C. to the boiling point of the solvent used, and is preferably in the range of −50 to 150 ° C.
The reaction time is usually 0.1 to 1,000 hours.
Further, the compound 19 obtained as described above may be purified by operations such as recrystallization, distillation, silica gel column chromatography and the like.

化合物２４において、Ｕ、及びｎは前記と同義である。
化合物２２の製法は、例えば、化合物２４と化合物１８とを反応する方法である。また、化合物２４と化合物１８の幾つかは、容易に市販品として入手することが可能である。
化合物２４の置換基Ｕが、−ＯＨ、−ＳＨ、又は−ＮＨ_２であり、化合物１８のＸ^５が、単結合、又は前記[Ｘ^５−１]〜[Ｘ^５−４]の群から選択される炭素環である場合は、塩基の存在下で、化合物２４と化合物１８を反応させることで化合物２２が得られる。反応条件は、製法１の化合物３の合成法における、Ｘ^５が前記[Ｘ^５−１]〜[Ｘ^５−４]の群から選択される構造である場合の方法を適用することができる。
化合物２４の置換基Ｕが、−ＯＨ、−ＳＨ、又は−ＮＨ_２であり、化合物１８のＸ^５が、単結合、又は前記[Ｘ^５−５]の炭素環である場合は、塩基の存在下、金属錯体と配位子を触媒としたカップリング反応により合成することができる。反応条件は、製法１の化合物３の合成法における、Ｘ^５が前記[Ｘ^５−５]である場合の方法を適用することができる。
化合物２４の置換基Ｕが、ハロゲンＦ、Ｃｌ、Ｂｒ、又はＩであり、化合物２２のＸ^４が、単結合の場合は、塩基の存在下、金属錯体と配位子を触媒としたカップリング反応により合成することができる。反応条件は、製法１の化合物３の合成法における、Ｘ^４が単結合の場合の方法を適用することができる。Production method of compound 22

In compound 24, U and n are as defined above.
The method for producing compound 22 is, for example, a method in which compound 24 and compound 18 are reacted. Some of the compound 24 and the compound 18 can be easily obtained as commercial products.
The substituent U of the compound 24 is —OH, —SH, or —NH ₂ , and X ^{5 of the} compound 18 is a single bond or selected from the group of [X ⁵ -1] to [X ⁵ -4]. In the case of a carbocyclic ring, compound 22 is obtained by reacting compound 24 and compound 18 in the presence of a base. As the reaction conditions, the method in the case where X ⁵ in the synthesis method of Compound 3 in Production Method 1 is a structure selected from the group of [X ⁵ -1] to [X ⁵ -4] can be applied.
Substituents U of compounds 24, -OH, -SH, or a -NH _2, if the ^{X 5} compound 18 is a carbocyclic ring of a single bond, or a ^[X 5 -5], the presence of a base It can be synthesized by a coupling reaction using a metal complex and a ligand as a catalyst. As the reaction conditions, the method in which X ⁵ in the method for synthesizing compound 3 in production method 1 is the above [X ⁵ -5] can be applied.
When the substituent U of the compound 24 is halogen F, Cl, Br, or I and X ^{4 of the} compound 22 is a single bond, the coupling is carried out using a metal complex and a ligand as a catalyst in the presence of a base. It can be synthesized by reaction. As the reaction conditions, the method in the case where X ⁴ is a single bond in the synthesis method of Compound 3 in Production Method 1 can be applied.

化合物２５において、Ａは前記と同義であり、例示の基についても、前記と同様である。
化合物１９の製法は、例えば、化合物２２と化合物２５とを塩基の存在下、脱水縮合反応させた後、エステル基−ＣＯＯＡを水によって加水分解する方法である。
上記反応に使用する塩基は、反応を円滑に進行させる塩基の強さ（塩基度）を有する塩基を用いればよく、特に限定されない。例えば、リチウム、ナトリウム、カリウムのようなアルカリ金属の水酸化物、リチウムアミド、ナトリウムアミド、カリウムアミドのようなアルカリ金属アミド、リチウムヒドリド、ナトリウムヒドリド、カリウムヒドリドのようなアルカリ金属水素化物、アルカリ土類金属、ナトリウムやカリウムの、メチラート、エチラート、ｎ−プロピラート、イソプロピラート、ｎ−ブチラート、ｓｅｃ−ブチラート、ｔｅｒｔ−ブチラート、２−メチル−２−ブチラート、２−メチル−２−ペンチラート、３−メチル−３−ペンチラート、３−エチル−３−ペンチラートのような一級、二級もしくは三級の炭素数１〜１０の脂肪族アルコールから誘導されるアルカリ金属アルコラート等である。これらの塩基は、混合物としても使用することができる。塩基としては、ナトリウムエトキシド、ナトリウムヒドリドが好ましい。これらの塩基は、通常、化合物２２に対して０．１〜１０倍モル、好ましくは０．１〜５倍モル使用される。Production Method 3 for Compound 19

In compound 25, A has the same meaning as described above, and the exemplified groups are also the same as described above.
The compound 19 is produced, for example, by subjecting the compound 22 and the compound 25 to a dehydration condensation reaction in the presence of a base, and then hydrolyzing the ester group —COOA with water.
The base used for the reaction is not particularly limited as long as it has a base strength (basicity) that allows the reaction to proceed smoothly. For example, alkali metal hydroxides such as lithium, sodium and potassium, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride, alkaline earth Metals such as sodium and potassium, methylate, ethylate, n-propylate, isopropylate, n-butyrate, sec-butyrate, tert-butyrate, 2-methyl-2-butyrate, 2-methyl-2-pentylate, 3-methyl And alkali metal alcoholates derived from primary, secondary or tertiary aliphatic alcohols having 1 to 10 carbon atoms such as -3-pentylate and 3-ethyl-3-pentylate. These bases can also be used as a mixture. As the base, sodium ethoxide and sodium hydride are preferable. These bases are generally used in an amount of 0.1 to 10 mol, preferably 0.1 to 5 mol per mol of Compound 22.

The solvent can be used as long as it does not react with compound 22 and compound 25. For example, aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, ethers such as diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, pentane, Aliphatic hydrocarbons such as xane, heptane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, nitriles such as acetonitrile, propionitrile, butyronitrile, An organic weak basic solvent such as pyridine and quinoline can be used. In addition, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol can also be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. Moreover, depending on the case, it can also be used as a nonaqueous solvent using a suitable dehydrating agent or a desiccant.
The conditions for hydrolysis with water are the same as the method shown in Production Method-1 for Compound 19.
The reaction temperature is from −100 ° C. to the boiling point of the solvent used, and is preferably in the range of −50 to 150 ° C.
The reaction time is usually 0.1 to 1,000 hours.
The compound 19 obtained as described above may be purified by operations such as recrystallization, distillation, silica gel column chromatography.

化合物２６において、Ａは前記と同義であり、例示の基についても、前記と同様である。Ｗは、トリフェニルホスフィン、又はホスホン酸エステルである。
化合物１９の製法は、例えば、化合物２２と化合物２６とをウィティッヒ反応、又はＨｏｒｎｅｒ−Ｗａｄｓｗｏｒｔｈ−Ｅｍｍｏｎｓ反応させた後、エステル基−ＣＯＯＡを加水分解する方法である。反応は、溶媒中で、塩基を使用して行なうことが好ましい。
反応に使用する塩基は、ホスホニウムイリドを円滑に発生させる強さの塩基を用いるのが好ましい。塩基として、例えば、リチウム、ナトリウム、カリウムのようなアルカリ金属の水酸化物や炭酸塩、ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウムのようなアルキルリチウム、リチウムアミド、ナトリウムアミド、カリウムアミドのようなアルカリ金属アミド、リチウムヒドリド、ナトリウムヒドリド、カリウムヒドリドのようなアルカリ金属水素化物、リチウムヘキサメチルジシラジド、ナトリウムヘキサメチルジシラジド、カリウムヘキサメチルジシラジドのようなアルカリ金属ジシラジド類、アルカリ土類金属、ナトリウムやカリウムの、メチラート、エチラート、ｎ−プロピラート、イソプロピラート、ｎ−ブチラート、ｓｅｃ−ブチラート、ｔｅｒｔ−ブチラート、２−メチル−２−ブチラート、２−メチル−２−ペンチラート、３−メチル−３−ペンチラート、３−エチル−３−ペンチラートのような一級、二級もしくは三級の炭素数１〜１０の脂肪族アルコールから誘導されるアルカリ金属アルコラート、ジアザビシクロオクタン、ジアザビシクロウンデセン、４−ジメチルアミノピリジン、ピロリジン、ピペリジンなどの、有機脂肪族、芳香族、複素環の窒素塩基などが使用できる。特には、ブチルリチウム、ｔｅｒｔ−ブチルリチウムが好ましい。Production Method 4 of Compound 19

In compound 26, A has the same meaning as described above, and the exemplified groups are also the same as described above. W is triphenylphosphine or a phosphonate.
The compound 19 is produced by, for example, a method in which the compound 22 and the compound 26 are subjected to a Wittig reaction or Horner-Wadsworth-Emmons reaction, and then the ester group —COOA is hydrolyzed. The reaction is preferably performed using a base in a solvent.
The base used for the reaction is preferably a strong base that smoothly generates phosphonium ylide. Examples of bases include alkali metal hydroxides and carbonates such as lithium, sodium, and potassium, alkyl lithiums such as butyl lithium, sec-butyl lithium, and tert-butyl lithium, lithium amides, sodium amides, and potassium amides. Alkali metal amides, lithium hydride, sodium hydride, alkali metal hydrides such as potassium hydride, lithium hexamethyldisilazide, sodium hexamethyldisilazide, alkali metal disilazides such as potassium hexamethyldisilazide, Alkaline earth metal, sodium and potassium, methylate, ethylate, n-propylate, isopropylate, n-butyrate, sec-butyrate, tert-butyrate, 2-methyl-2-butyrate, 2-methylate Alkali metal alcoholates derived from primary, secondary or tertiary aliphatic alcohols having 1 to 10 carbon atoms such as 2-pentylate, 3-methyl-3-pentylate, 3-ethyl-3-pentylate, diaza Organic aliphatic, aromatic and heterocyclic nitrogen bases such as bicyclooctane, diazabicycloundecene, 4-dimethylaminopyridine, pyrrolidine and piperidine can be used. In particular, butyl lithium and tert-butyl lithium are preferable.

As the solvent, any solvent that does not react with the compound 22 and the compound 26 can be used. For example, ethers (diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aprotic polar organic solvents (dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), fat Aromatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), nitriles (acetonitrile, propionitrile, etc.) , Butyronitrile, etc.) can be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. Moreover, depending on the case, it can also use as a non-aqueous solvent using a dehydrating agent or a desiccant.
The conditions for hydrolysis with water are the same as the method shown in Production Method-1 for Compound 19.
The reaction temperature is from −100 ° C. to the boiling point of the solvent used, and is preferably in the range of −50 to 150 ° C.
The reaction time is 0.1 to 1,000 hours.
Further, the compound 19 obtained as described above may be purified by operations such as recrystallization, distillation, silica gel column chromatography and the like.

化合物２７と化合物２８において、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、及びｎは前記と同義である。
ＭはＬｉ、ＭｇＣｌ、ＭｇＢｒ、又はＭｇＩの有機金属反応剤である。
Ａは前記と同義であり、例示の基についても、前記と同様である。
化合物１９の製法は、例えば、溶媒中、化合物２７と、銅塩、亜鉛塩、又はジアルキル亜鉛を混合させ、銅キュプラート、もしくはジアリール亜鉛化合物を調製し、化合物２８で示した化合物との１,４−付加反応を行った後、エステル基−ＣＯＯＡを水によって加水分解する方法である。
この反応に使用する銅塩、亜鉛塩、又はジアルキル亜鉛は、単独で使用しても良く、また、これらの銅塩、亜鉛塩、ジアルキル亜鉛を組み合わせて使用しても良い。Production Method of Compound 19-5

In the compounds 27 and 28, X ⁴ , X ⁵ , X ⁶ , X ⁷ , and n are as defined above.
M is an organometallic reactant of Li, MgCl, MgBr, or MgI.
A has the same meaning as described above, and the same applies to the exemplified groups.
The compound 19 is prepared by, for example, mixing a compound 27 with a copper salt, a zinc salt, or a dialkylzinc in a solvent to prepare a copper cuprate or a diarylzinc compound, and 1,4 of the compound represented by the compound 28. -After the addition reaction, the ester group -COOA is hydrolyzed with water.
The copper salt, zinc salt, or dialkylzinc used in this reaction may be used alone, or these copper salts, zinc salts, dialkylzinc may be used in combination.

Examples of the copper salt used in the reaction include CuCl, CuBr, CuI, CuCN, or a mixed salt of CuCl ₂ and LiCl, and CuI is particularly preferable.
Examples of the zinc salt used in the reaction are ZnCl ₂ , ZnBr ₂ , or ZnI ₂ , and ZnCl ₂ is particularly preferable.
Examples of the dialkyl zinc used in the reaction are dibutyl zinc, diethyl zinc, or dibutenyl zinc, with diethyl zinc being particularly preferred.

As the solvent, any solvent that does not react with the organometallic reactant can be used.
For example, ethers (diethyl ether, diisopropyl ether, tetrabutyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.), aprotic polar organic solvents (dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), fat Aromatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.) and aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.) can be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. In some cases, an appropriate dehydrating agent or desiccant can be used as a non-aqueous solvent.
The conditions for hydrolysis with water are the same as the method shown in Production Method-1 for Compound 19.
The reaction temperature is from −100 ° C. to the boiling point of the solvent used, and is preferably in the range of −50 to 150 ° C.
The reaction time is 0.1 to 1,000 hours.
The compound 10 obtained as described above may be purified by operations such as recrystallization, distillation, silica gel column chromatography and the like.

化合物２９と化合物３０において、Ｕ、Ｘ、Ｘ^４、Ｘ^５、Ｘ^６、Ｘ^７、及びｎは前記と同義である。
化合物２７の製法は、例えば、化合物２９と化合物１８との反応により化合物３０を合成し、その後、化合物３０と金属マグネシウム、又はリチオ化剤とを反応させる方法である。化合物２９と化合物１８の幾つかは、容易に市販品として入手することが可能である。
化合物２９の置換基Ｕが、−ＯＨ、−ＳＨ、又は−ＮＨ_２であり、化合物１８のＸ^５が、単結合、又は前記[Ｘ^５−１]〜[Ｘ^５−４]の群から選択される炭素環である場合は、塩基の存在下で、化合物２９と化合物１８とを反応させることで化合物３０が得られる。反応条件は、製法１の化合物３の合成法における、Ｘ^５が前記[Ｘ^５−１]〜[Ｘ^５−４]の群から選択される炭素環である場合の方法を適用することができる。
化合物２９の置換基Ｕが、−ＯＨ、−ＳＨ、又は−ＮＨ_２であり、化合物１８のＸ^５が、単結合、又は前記[Ｘ^５−５]の炭素環である場合は、塩基の存在下、金属錯体と配位子を触媒としたカップリング反応により合成することができる。反応条件は、製法１の化合物３の合成法における、Ｘ^５が前記[Ｘ^５−５]である場合の方法を適用することができる。
化合物２９の置換基Ｕが、ハロゲンＦ、Ｃｌ、Ｂｒ、又はＩであり、化合物２７のＸ^４が単結合の場合は、塩基の存在下、金属錯体と配位子を触媒としたカップリング反応により合成することができる。反応条件は、製法１の化合物３の合成法における、Ｘ^４が単結合の場合の方法を適用することができる。
得られた化合物３０に、エーテル溶媒中、金属Ｍｇを加えて反応させ、グリニャール反応に用いることのできる化合物２７(Ｍ＝ＭｇＦ、ＭｇＣｌ、ＭｇＢｒ、ＭｇＩ)を得る。また、溶媒中、金属リチウムを反応させて、ＭがＬｉの化合物２７を得ることができる。Production method of compound 27

In Compound 29 and Compound 30, U, X, X ⁴ , X ⁵ , X ⁶ , X ⁷ and n are as defined above.
The production method of compound 27 is, for example, a method in which compound 30 is synthesized by reaction of compound 29 and compound 18, and then compound 30 is reacted with magnesium metal or a lithiating agent. Some of Compound 29 and Compound 18 can be easily obtained as commercial products.
The substituent U of Compound 29 is —OH, —SH, or —NH ₂ , and X ^{5 of} Compound 18 is a single bond or selected from the group of [X ⁵ -1] to [X ⁵ -4]. In the case of a carbocyclic ring, compound 30 is obtained by reacting compound 29 with compound 18 in the presence of a base. As the reaction conditions, the method in the case where X ⁵ is a carbocyclic ring selected from the group of [X ⁵ -1] to [X ⁵ -4] in the synthesis method of compound 3 of production method 1 can be applied. .
Substituents U of compounds 29, -OH, -SH, or a -NH _2, if the ^{X 5} compound 18 is a carbocyclic ring of a single bond, or a ^[X 5 -5], the presence of a base It can be synthesized by a coupling reaction using a metal complex and a ligand as a catalyst. As the reaction conditions, the method in which X ⁵ in the method for synthesizing compound 3 in production method 1 is the above [X ⁵ -5] can be applied.
Substituents U compound 29 is a halogen F, Cl, Br, or I, if X ⁴ of compound 27 is a single bond, the presence of a base, coupling reaction using metal complex and a ligand as a catalyst Can be synthesized. As the reaction conditions, the method in the case where X ⁴ is a single bond in the synthesis method of Compound 3 in Production Method 1 can be applied.
Compound 30 (M = MgF, MgCl, MgBr, MgI) that can be used for the Grignard reaction is obtained by reacting the obtained compound 30 with metal Mg in an ether solvent. Alternatively, compound 27 in which M is Li can be obtained by reacting metallic lithium in a solvent.

化合物３１において、Ｕ、及びｎは前記と同義である。
化合物１９の製法は、例えば、化合物３１と化合物１８とを反応させ、反応後、エステル基−ＣＯＯＡを水によって加水分解する方法である。また、化合物３１と化合物１８の幾つかは容易に市販品として入手することが可能である。
化合物３１の置換基Ｕが、−ＯＨ、−ＳＨ、又は−ＮＨ_２であり、化合物１８のＸ^５が、単結合、又は前記[Ｘ^５−１]〜[Ｘ^５−４]の群から選択される炭素環である場合は、塩基の存在下で、化合物３１と化合物１８とを反応させ、反応後、化合物１９の製法−１で示した水による加水分解を行い、化合物１９が得られる。反応条件は、製法１の化合物３の合成法における、Ｘ^５が前記[Ｘ^５−１]〜[Ｘ^５−４]の群から選択される炭素環である場合の方法を適用することができる。
化合物３１の置換基Ｕが、−ＯＨ、−ＳＨ、又は−ＮＨ_２であり、化合物１８のＸ^５が、単結合、又は前記[Ｘ^５−５]である場合は、塩基の存在下、金属錯体と配位子を触媒としてカップリング反応させ、反応後、化合物１９の製法−１で示した水による加水分解を実施することにより、化合物１９が得られる。反応条件は、製法１の化合物３の合成法における、Ｘ^５が前記[Ｘ^５−５]である場合の方法を適用することができる。
化合物３１の置換基Ｕが、ハロゲンＦ、Ｃｌ、Ｂｒ、又はＩであり、化合物１９のＸ^４が単結合の場合は、塩基の存在下、金属錯体と配位子を触媒としてカップリング反応させ、反応後、化合物１９の製法−１で示した水による加水分解を実施することにより、化合物１９が得られる。反応条件は、製法１の化合物３の合成法における、Ｘ^４が単結合の場合の方法を適用することができる。Production Method of Compound 19-6

In compound 31, U and n are as defined above.
The compound 19 is produced, for example, by reacting the compound 31 and the compound 18 and hydrolyzing the ester group —COOA with water after the reaction. Some of the compound 31 and the compound 18 can be easily obtained as commercial products.
The substituent U of the compound 31 is —OH, —SH, or —NH ₂ , and X ^{5 of the} compound 18 is a single bond or selected from the group of [X ⁵ -1] to [X ⁵ -4]. In the case of a carbocyclic ring, compound 31 and compound 18 are reacted in the presence of a base, and after the reaction, hydrolysis with water shown in production method-1 of compound 19 is performed to obtain compound 19. As the reaction conditions, the method in the case where X ⁵ is a carbocyclic ring selected from the group of [X ⁵ -1] to [X ⁵ -4] in the synthesis method of compound 3 of production method 1 can be applied. .
When the substituent U of the compound 31 is —OH, —SH, or —NH ₂ , and X ^{5 of the} compound 18 is a single bond or the above [X ⁵ -5], a metal is present in the presence of a base. A compound 19 is obtained by performing a coupling reaction using a complex and a ligand as a catalyst, and carrying out hydrolysis with water shown in Production Method-1 of Compound 19 after the reaction. As the reaction conditions, the method in which X ⁵ in the method for synthesizing compound 3 in production method 1 is the above [X ⁵ -5] can be applied.
Substituents U of Compound 31 is a halogen F, Cl, Br, or I, if X ⁴ of compound 19 is a single bond, the presence of a base, by a coupling reaction with a metal complex and a ligand as a catalyst After the reaction, compound 19 is obtained by carrying out hydrolysis with water as shown in Production method 1 of compound 19. As the reaction conditions, the method in the case where X ⁴ is a single bond in the synthesis method of Compound 3 in Production Method 1 can be applied.

Production Method of Compound 4 Compound 4 can be produced by an esterification reaction between Compound 1 and compound 19 or 20 of an acrylic acid derivative in a solvent.
In particular, in the reaction of an acid halide with Compound 1, such as Compound 20, the acid halide is preferably an acid halide such as an acid chloride or an acid bromide, and further in the presence of a base. It is preferable to carry out the reaction because the reaction proceeds smoothly. Examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium hydride, potassium hydride and the like. An inorganic base, amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, collidine, and organic bases such as sodium tert-butoxide and potassium tert-butoxide can be used.

The solvent can be appropriately selected as long as it is stable under the reaction conditions and is inert and does not interfere with the reaction. For example, amines, aprotic polar organic solvents (dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, etc.), ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane ), Aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogenated hydrocarbons (Chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles Acetonitrile, propionitrile, etc. butyronitrile) can be used. These solvents can be appropriately selected in consideration of the reaction conditions and the easiness of the reaction, and can be used singly or in combination of two or more. Moreover, depending on the case, it can also use as a non-aqueous solvent using a dehydrating agent or a desiccant.
The reaction temperature is from −100 ° C. to the boiling point of the solvent used, and is preferably in the range of −50 to 150 ° C.
The reaction time is preferably 0.1 to 1,000 hours.
Compound 4 obtained as described above may be purified by recrystallization, distillation, silica gel column chromatography, activated carbon or the like.
In the reaction of Compound 19 and Compound 1, a condensing agent such as dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide, carbonyldiimidazole and the like is generally used. At this time, addition of a catalytic amount of acid or N, N-dimethylaminopyridine is preferable because it has an effect on the progress of the reaction.

Production Method of Compound 5 Production of Compound 5 using Compound 4 can be carried out by the method described in Production Method 1.
<Polyamic acid, polyamic acid ester, polyimide>
The diamine compound of the present invention can obtain a polyamic acid having a specific structure in the side chain by reacting with a tetracarboxylic acid or a derivative thereof such as tetracarboxylic acid, tetracarboxylic acid dihalide, or tetracarboxylic dianhydride. it can. In addition to tetracarboxylic acid and its derivatives, a precursor of polyimide by reacting tetracarboxylic acid diester dichloride with a diamine compound, or reacting tetracarboxylic acid diester and diamine compound in the presence of a condensing agent, base, etc. The polyamic acid ester which is a body can be obtained. Furthermore, a polyimide having a specific structure in the side chain can be obtained by dehydrating and cyclizing the polyamic acid or heating the polyamic acid ester at a high temperature to promote dealcoholization and cyclization.

<Polyamic acid>
The polyamic acid of the present invention is a polyamic acid obtained by a reaction between a diamine component containing a diamine compound represented by the formula [1] and tetracarboxylic dianhydride.
The polyamic acid ester of the present invention reacts a diamine component containing a diamine compound represented by the formula [1] with a tetracarboxylic acid diester dichloride in the presence of a base, or a tetracarboxylic acid diester and a diamine compound as a condensing agent. , A polyamic acid ester obtained by reacting in the presence of a base or the like.
The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing this polyamic acid or by heating and ring-closing the polyamic acid ester.
Any of polyamic acid, polyamic acid ester, and polyimide is useful as a polymer for obtaining a liquid crystal alignment film.

  In the diamine component (hereinafter also referred to as a diamine component) for obtaining a polyamic acid by reaction with tetracarboxylic dianhydride, the content ratio of the diamine compound represented by the formula [1] is not limited. The content rate of the diamine compound represented by Formula [1] is 10 mol% or more of a diamine component, for example, Preferably it is 20 mol% or more, More preferably, it is 30 mol% or more. The diamine compound represented by Formula [1] may be sufficient as 100 mol% of a diamine component. The larger the content ratio of the diamine compound represented by the formula [1], the higher the ability to stand the liquid crystal vertically when the liquid crystal alignment film is used, and the higher the efficiency of the photo-alignment treatment. In order to obtain a desired pretilt angle, the pretilt angle during the photo-alignment treatment varies depending on the structure of the side chain of the diamine compound represented by the formula [1] and the vertical alignment ability of the liquid crystal used. The content ratio of the diamine compound represented by can be selected within a preferred range.

In the diamine component, a diamine compound other than the diamine compound represented by the formula [1] used when the diamine compound represented by the formula [1] is less than 100 mol% (sometimes referred to as other diamine compounds). .) Is not particularly limited, but specific examples thereof are as follows.
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone Examples include diamines.
Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino. 2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 '-Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4′-diamino-3,3′-dimethyldiphenylmethane, 2,2′-diaminostilbene, 4,4′-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis (4-aminophenoxy) ) Benzoic acid, 4,4′-bis (4-aminophenoxy) bibenzyl, 2,2-bis [(4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenyl) Enoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, α, α′-bis (4-aminophenyl) -1,4- Diisopropylbenzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′ -Diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6-diaminopyrene, 1,8- Diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) tetramethyldisi Xanthine, benzidine, 2,2′-dimethylbenzidine, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis (4-aminophenyl) ) Octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4- Aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, di (4-aminophenyl) propane-1, 3-dioate, di (4-aminophenyl) butane-1,4-dioate, di (4-aminophenyl) pentane-1,5-dioate, di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8-dioate, di (4-aminophenyl) nonane-1,9-dioate, di (4-aminophenyl) ) Decane-1,10-dioate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4-bis [4- (4-aminopheno) Phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] hexane, 1,7-bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-aminophenoxy) phenoxy] nonane, 1,10- And bis [4- (4-aminophenoxy) phenoxy] decane.

  Examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4- Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4-methyl) Aminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopentyl) Niline, 3- (5-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- (6 -Aminonaphthyl) ethylamine, 3- (6-aminonaphthyl) ethylamine and the like.

Examples of heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diamino. Examples thereof include carbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole.
Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane. 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diamino Examples include dodecane, 1,18-diaminooctadecane, and 1,2-bis (3-aminopropoxy) ethane.

（Ｒ_６は、炭素数１〜２２の、アルキル基又はフッ素含有アルキル基である。）

（Ｓ_５は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−、又は−ＮＨ−を示し、Ｒ_６は炭素数１〜２２の、アルキル基又はフッ素含有アルキル基を示す。）You may use together the diamine compound which has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and the macrocyclic substituent which consists of them in a side chain. Specifically, diamines represented by the following formulas [DA-1] to [DA-26] can be exemplified.

(R ₆ is an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms.)

(S ₅ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, or —NH—, and R ₆ represents one having 1 to 22 carbon atoms. Represents an alkyl group or a fluorine-containing alkyl group.)

（Ｓ_６は、−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−、又は−ＣＨ_２ＯＣＯ−を示し、Ｒ_７は炭素数１〜２２の、アルキル基、アルコキシ基、フッ素含有アルキル基又はフッ素含有アルコキシ基である。）

（Ｓ_７は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、又は−ＣＨ_２−を示し、Ｒ_８は炭素数１〜２２の、アルキル基、アルコキシ基、フッ素含有アルキル基又はフッ素含有アルコキシ基である。）

(S ₆ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—, and R ₇ represents an alkyl group, alkoxy group having 1 to 22 carbon atoms, A fluorine-containing alkyl group or a fluorine-containing alkoxy group.)

(S ₇ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, or —CH ₂ —. R ₈ is an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.)

（Ｓ_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、トリフルオロメタン基、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。）

（Ｒ_１０は炭素数３〜１２のアルキル基であり、１，４−シクロへキシレンのシス−トランス異性は、それぞれトランス体である。）

(S ₈ is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ —, —O -Represents-or -NH-, and R ₉ represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.

(R ₁₀ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

  For the purpose of supplementing the vertical alignment ability simultaneously with the diamine compound represented by the general formula [1], the diamine compounds of [DA-1] to [DA-26] can be used in combination. As a more preferred diamine that can be used in combination, formulas [DA-10] to [DA-26] are preferable from the viewpoint of voltage holding ratio, residual accumulated voltage, and the like, and more preferably, [DA-10] to [DA-16] It is a diamine compound. The preferable content of these diamine compounds is not particularly limited, but is preferably 5 to 50 mol%, more preferably 5 to 30 mol% in the diamine component.

（ｍは０〜３の整数であり、ｎは１〜５の整数である）。
[ＤＡ−２７]や[ＤＡ−２８]を含有させることにより、電圧保持率（ＶＨＲ）を向上させることができ、[ＤＡ−２９]〜［ＤＡ−３４］は、蓄積電荷の低減に効果があるので好ましい。Further, the following diamine compounds may be used in combination.

(M is an integer from 0 to 3, and n is an integer from 1 to 5).
By containing [DA-27] and [DA-28], the voltage holding ratio (VHR) can be improved, and [DA-29] to [DA-34] are effective in reducing the accumulated charge. This is preferable.

（ｍは、１から１０の整数である。）
その他のジアミン化合物は、液晶配向膜とした際の液晶配向性、電圧保持特性、蓄積電荷などの特性に応じて、１種類又は２種類以上を混合して使用することもできる。In addition, diaminosiloxanes represented by the following formula [DA-27] can also be cited as other diamine compounds.

(M is an integer from 1 to 10.)
Other diamine compounds may be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.

The tetracarboxylic dianhydride that is reacted with the diamine component to obtain the polyamic acid (polyamic acid) of the present invention is not particularly limited. Specific examples are given below.
Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1, , 3,4-Butanetetracarboxylic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetra Carboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride , Tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo [6.6.0.1 ^{2 , 7} . 0 ^3,6 . 1 ^9,14 . 0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dianhydride, 4- (2,5-di-oxo-tetrahydrofuran-3-yl) -1,2 3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the like.

  In addition to the tetracarboxylic dianhydride having the alicyclic structure or aliphatic structure, the use of aromatic tetracarboxylic dianhydride improves the liquid crystal alignment and reduces the accumulated charge of the liquid crystal cell. Is preferable. As aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4-benzophenonetetra Carboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride Products, 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.

The tetracarboxylic acid dialkyl ester reacted with the diamine component to obtain the polyamic acid ester of the present invention is not particularly limited. Specific examples are given below.
Examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, and 1,3-dimethyl- 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-cyclo Pentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl Ester, 3,4-dicarboxy-1,2,3 -Tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2, 5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dialkyl ester, hexacyclo [ 6.6.0.1 ^2,7 . 0 ^3,6 . 1 ^9,14 . 0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4- (2,5-di-oxo-tetrahydrofuran-3-yl) -1,2, Examples include 3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester.

  As the aromatic tetracarboxylic acid dialkyl ester, pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyltetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-biphenyltetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-benzophenone tetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7- Naphthalene tetracarboxylic acid dialkyl ester And the like.

  The dicarboxylic acid to be reacted with the diamine component in order to obtain a polyamide from the diamine compound of the present invention is not particularly limited. Specific examples of the aliphatic dicarboxylic acid of dicarboxylic acid or its derivative include malonic acid, succinic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelin Examples thereof include dicarboxylic acids such as acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid.

  Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, and 1,3-cyclobutanedicarboxylic acid. Acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid Acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4- (2-nor Lunene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1,4-dicarboxylic acid, bicyclo [2.2.2] octane-2,3-dicarboxylic acid, 2, 5-dioxo-1,4-bicyclo [2.2.2] octanedicarboxylic acid, 1,3-adamantane dicarboxylic acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro [3. 3] Heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid and the like.

As aromatic dicarboxylic acids, o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid Acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4 Anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4 "-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4′-diphenylethanedicarboxylic acid, 4,4′-diphenylpropyl Pandicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-tolane Dicarboxylic acid, 4,4′-carbonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 4,4′-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3′-p-phenylenedipropionic acid 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3 ′-[4,4 ′-(methylenedi-p-phenylene)] dipropionic acid, 4,4 ′-[4,4 ′-(oxydi) -P-phenylene)] dipropionic acid, 4,4 '-[4,4'-(oxydi-p-phenylene)] butyric acid, (isopropylidenedi-p-phenylenedioxy) dibutyric acid, bis (p- Carbo And xylphenyl) dimethylsilane.
Examples of the dicarboxylic acid containing a heterocyclic ring include 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2, Examples thereof include 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid.

The various dicarboxylic acids may be acid dihalides or anhydrides. Among these dicarboxylic acids, a dicarboxylic acid capable of giving a polyamide having a linear structure is particularly preferable in terms of maintaining the orientation of liquid crystal molecules. Among them, terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylethanedicarboxylic acid, 4,4′- Diphenylpropanedicarboxylic acid, 4,4′-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propanedicarboxylic acid, 4,4 cast terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5 -Pyridine dicarboxylic acid or these acid dihalides are preferably used. Some of these compounds have isomers, but may be a mixture containing them. Two or more compounds may be used in combination.
The dicarboxylic acids used in the present invention are not limited to the above exemplary compounds.

The tetracarboxylic dianhydride can be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
In obtaining the polyamic acid of the present invention by reaction of tetracarboxylic dianhydride and a diamine component, a known synthesis method can be used. In general, tetracarboxylic dianhydride and a diamine component are reacted in an organic solvent. The reaction between the tetracarboxylic dianhydride and the diamine compound 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 the tetracarboxylic dianhydride and the diamine compound is not particularly limited as long as the produced polyamic acid dissolves. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , 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, ethyl 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, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion , 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like can be mentioned. 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.
In addition, 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 as much as possible.

  When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent. A method of adding by dispersing or dissolving, a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component. Any of these methods may be used. Further, 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 concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is performed at a high concentration, and then an organic solvent can be added.
In the above reaction, the ratio of the total number of moles of tetracarboxylic dianhydride and the total number of moles of the diamine component is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. . 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 polymer 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.

<Polyimide>
Examples of the method for imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
The temperature at which the polyamic acid is thermally imidized in the solution is 100 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 amic acid group, and the amount of the acid anhydride is 1 to 50 mol times of the amido group, preferably 3 to 3 times. 30 mole times.
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 easy. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

<Polyamic acid ester>
As a method for synthesizing a polyamic acid ester, a kind of a precursor of a polyimide is obtained by reacting a tetracarboxylic acid diester dichloride with a diamine compound, or by reacting the tetracarboxylic acid diester with a diamine compound in the presence of a condensing agent or a base. The polyamic acid ester which is can be obtained. Alternatively, the polyamic acid ester can be obtained by polymerizing the polyamic acid in advance and esterifying the carboxylic acid in the amic acid using a polymer reaction.
Specifically, tetracarboxylic acid diester dichloride and a diamine compound in the presence of a base and an organic solvent are -20 to 150 ° C, preferably 0 to 50 ° C, 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.
As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently. The addition amount of the base is preferably 2 to 4 moles with respect to the tetracarboxylic acid diester dichloride, from the viewpoint of easy removal and easy obtaining of a high molecular weight product.

When the condensation polymerization reaction is performed in the presence of a condensing agent, examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, and N, N′-carbonyldioxide. Imidazole, dimethoxy-1,3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O— (Benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholium chloride n-hydrate Can be used.
In addition, in the method using a condensing agent, when a Lewis acid is added as an additive, the reaction proceeds efficiently. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0.1 to 1.0 mol times with respect to the tetracarboxylic acid diester.

As the solvent, the above-described solvents used for polymerization to obtain a polyamic acid can be used, but N-methyl-2-pyrrolidone, γ-butyrolactone, and the like are preferable in view of the solubility of the monomer and polymer. These solvents may be used alone or in combination of two or more. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible.
The total concentration of the tetracarboxylic acid diester dichloride and the diamine component in the reaction solution is preferably 1 to 30% by mass, and preferably 5 to 20% by mass from the viewpoint that the polymer is hardly precipitated and a high molecular weight product is easily obtained. Is more preferable.
Furthermore, the reaction is preferably performed in a nitrogen atmosphere to prevent outside air from being mixed.

<Polyamide>
Polyamide can also be synthesized in the same manner as the polyamic acid ester.

<Recovery of polymer>
When recovering the generated polyamic acid, polyamic acid ester, polyimide, etc. from the reaction solution such as polyamic acid (polyamic acid), polyamic acid ester, polyimide, etc., the reaction solution is put into a poor solvent to precipitate the polymer. You can do it. 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 deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
The molecular weight of the polyamic acid and polyimide contained in the liquid crystal alignment treatment agent of the present invention is determined by considering the strength of the obtained coating film, the workability at the time of coating film formation, and the uniformity of the coating film. ) The weight average molecular weight measured by the method is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.

<Liquid crystal alignment agent>
The liquid crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution which the resin component for forming a resin film melt | dissolved in the organic solvent. Here, the said resin component is a resin component containing at least 1 type of polymer chosen from the polymer of this invention mentioned above. In that case, as for content of a resin component, 1-20 mass% is preferable, More preferably, it is 3-15 mass%, Most preferably, it is 3-10 mass%.
In the present invention, all of the resin components may be the polymer of the present invention, and other polymers may be mixed with the polymer of the present invention. In that case, content of polymers other than the polymer of this invention in a resin component is 0.5-15 mass%, Preferably it is 1-10 mass%.
Examples of such other polymers include polyamic acid or polyimide obtained by using a diamine compound other than the specific diamine compound as a diamine component to be reacted with the tetracarboxylic dianhydride component.

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 a resin component is dissolved. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4 Such as methyl-2-pentanone and the like. These may be used alone or in combination.

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

The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Low 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester Examples include solvents having surface tension.
These poor 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-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene 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-tetra Glycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N Examples include ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane.

基板との密着性を向上させる化合物を使用する場合、その使用量は、液晶配向処理剤に含有される樹脂成分の１００質量部に対して０．１〜３０質量部であることが好ましく、より好ましくは１〜２０質量部である。使用量が０．１質量部未満であると密着性向上の効果は期待できず、３０質量部よりも多くなると液晶の配向性が悪くなる場合がある。
本発明の液晶配向処理剤には、上記の他、本発明の効果が損なわれない範囲であれば、液晶配向膜の誘電率や導電性などの電気特性を変化させる目的で、誘電体や導電物質、さらには、液晶配向膜にした際の膜の硬度や緻密度を高める目的で、架橋性化合物を添加してもよい。Furthermore, in addition to improving the adhesion between the substrate and the film, the following phenoplast-based additive may be included in the liquid crystal alignment treatment agent for the purpose of preventing deterioration of electrical characteristics due to the backlight. Specific phenoplast additives are shown below, but are not limited to this structure.

When using the compound which improves adhesiveness with a board | substrate, it is preferable that the usage-amount is 0.1-30 mass parts with respect to 100 mass parts of the resin component contained in a liquid-crystal aligning agent, and more. Preferably it is 1-20 mass parts. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
In addition to the above, the liquid crystal alignment treatment agent of the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. A crosslinkable compound may be added for the purpose of increasing the hardness and density of the substance and, further, the liquid crystal alignment film.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without alignment treatment after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment, light irradiation or the like, or in vertical alignment applications. it can. 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. In the reflective liquid crystal display element, an opaque object such as a silicon wafer can be used as long as it is only on one side of the substrate. In this case, a material that reflects light such as aluminum can be used as the electrode.

The application method of the liquid crystal alignment treatment agent is not particularly limited, but industrially, screen printing, offset printing, flexographic printing, ink jet, and the like are common. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
Firing after applying the liquid crystal aligning agent on the substrate can be performed at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, and the solvent can be evaporated to form a coating film. . If the thickness of the coating film formed after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Preferably it is 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. A method of bonding the other substrate and injecting liquid crystal under reduced pressure, or a method in which a liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed, and then the substrate is bonded and sealed. It can be illustrated. 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 examples below, but the present invention is not limited to these examples.

<Example 1>
4-Iodophenol 1 (22.0 g, 0.100 mol), potassium carbonate (20.7 g, 0.150 mol) and 130 ml (ml) of dimethylformamide were added to a four-necked flask and stirred in a nitrogen atmosphere, then heated to 80 ° C. did. After reaching 80 ° C., 1-bromodecane (17.9 g, 0.0809 mol) was added dropwise over 30 minutes. After completion of the addition, the mixture was further stirred for 1 hour. After confirming disappearance of 1-bromodecane by GC (gas chromatography), the solvent was distilled off, 120 ml of toluene and 150 g of pure water were added for extraction, and the aqueous layer was removed. Thereafter, 100 ml of 1N NaOH was added to the organic layer, extraction was performed, and the aqueous layer was removed. The obtained organic layer was dried over anhydrous magnesium sulfate, and then magnesium sulfate was collected by filtration. The obtained organic layer was evaporated under reduced pressure to obtain a compound 2 (yield 26.9 g, 0.0747 mol, yield 92.3%). The structure of Compound 2 was confirmed by ¹ H-NMR (nuclear magnetic resonance) analysis.
¹ H-NMR (CDCl ₃ ): δ7.55-7.52 (m, 2H, Ar—H), 6.69-6.65 (m, 2H, Ar—H), 3.90 (t, 2H, J = 6.8 Hz, Ar— _{O-CH 2), 1.79-1.72 (} m, 2H, Ar-O-CH 2 -CH 2 -), 1.47-1.27 (m, 14H, Ar-O-CH 2 -CH 2 -C 7 H 14 -) , 0.87 (t, 3H, J = 6.8Hz, -CH ₂ -CH ₃ )

<Example 2>
A solution prepared by mixing 3,5-dinitrobenzyl alcohol 3 (39.6 g, 0.200 mol), triethylamine (26.3 g, 0.260 mol) and 200 ml of tetrahydrofuran was stirred at 0 ° C. in a nitrogen atmosphere, and acrylic acid was added to the solution. A solution prepared by mixing acid chloride (21.7 g, 0.240 mol) and 40 ml of tetrahydrofuran was added dropwise over 30 minutes. Furthermore, after dropping, the mixture was stirred for 4 hours. After the reaction was completed, the solvent was distilled off, 300 g of water was added to the obtained crude product, and the mixture was stirred at 25 ° C. for 30 minutes in a slurry state. Thereafter, the reaction solution was filtered, and the solid content was dried at 70 ° C. under reduced pressure for 3 hours to obtain Compound 4 (amount 48.7 g 0.193 mol, yield 96.5%). The structure of Compound 4 was confirmed by ¹ H-NMR analysis.
¹ H-NMR (CDCl ₃ ): δ9.02 (t, 1H, J = 2.4Hz, Ar-H), 8.58 (m, 2H, Ar-H), 6.54 (dd, 1H, J = 17.6, 1.2Hz , -CH = CH ₂ ), 6.27-6.20 (m, 1H, -CH = CH ₂ ), 5.99 (dd, 1H, J = 10.8Hz, 1.2Hz, -CH = CH ₂ ), 5.40 (s, 2H, Ar-CH ₂ -O)

<Example 3>
Compound 2 (25.3 g, 0.0702 mol), Compound 4 (21.1 g, 0.0837 mol), palladium chloride-acetonitrile complex (0.572 g, 2.21 mmol), tris (o-tolyl) phosphine (1 .28 g, 4.21 mmol), tripotassium phosphate (22.7 g, 0.107 mol), and 170 g of dimethylacetamide were decompressed to 50 Torr with a diaphragm pump at room temperature, and then reconstituted with nitrogen. The operation of pressurizing was repeated 10 times to remove oxygen contained in the reactor and dimethylacetamide. The temperature was then raised, and the mixture was stirred at 110 ° C. for 3 hours under a nitrogen atmosphere. After completion of the reaction, the solvent was distilled off and extracted with 200 g of water and 250 g of chloroform. The separated aqueous layer was further extracted twice with 250 g of chloroform, and the obtained organic layer was dried over anhydrous magnesium sulfate. The organic layer obtained by filtering magnesium sulfate was distilled off the solvent under reduced pressure, and the resulting crude product was washed with 170 g of acetonitrile. Thereafter, the crystals were filtered, and the obtained solid content was dried under reduced pressure to obtain Compound 5 (amount 32.5 g, 0.0671 mol, yield 95.6%). The structure of Compound 5 was confirmed by ¹ H-NMR analysis.
¹ H-NMR (CDCl ₃ ): δ 9.01 (t, 1H, Ar—H), 8.61 (d, 2H, J = 1.6 Hz, Ar—H), 7.74 (d, 1H, J = 16.0 Hz, − CH = CH-Ar), 7.49 (d, 2H, J = 7.6Hz, Ar-H), 6.91 (d, 2H, J = 7.6Hz, Ar-H), 6.39 (d, 1H, J = 16.0Hz, -CH = CH-Ar), 5.42 (s, 2H, Ar-CH ₂ -O), 3.99 (t, 2H, J = 6.4Hz, Ar-O-CH ₂ ), 1.83-1.76 (m, 2H, Ar _{-O-CH 2 -CH 2 -)} , 1.49-1.28 (m, 14H, Ar-O-CH 2 -CH 2 -C 7 H 14 -), 0.89 (t, 3H, J = 6.4Hz, -CH 2 -CH ₃ )

２、４−ジニトロフェニル酢酸（５６．６ｇ、２５０ｍｍｏｌ）のテトラヒドロフラン（４５２ｇ）溶液に、ボランジメチルスルフィド錯体（５７．０ｇ、７５０ｍｍｏｌ）のテトラヒドロフラン（２８１ｇ）溶液を１時間かけて滴下し、２２時間室温で攪拌した。その後、水（１１２ｇ）を０℃で２時間かけて滴下し、室温で２時間攪拌後、酢酸エチルと水で抽出を行い、水層を分離し、有機層を硫酸マグネシウムで乾燥した。硫酸マグネシウムをろ過で除去して、得られた有機層を濃縮し、得られた粗物を酢酸エチルとヘキサンから再結晶を行い、２，４―ジニトロフェニルエチルアルコール１を得た（４２．１ｇ、７９%収率）。
¹H-NMR (CDCl₃): δ 8.79 (d, 1H, J=2.4 Hz, Ar-H), 8.40 (dd, 1H, J=8.4, 2.4Hz, Ar-H), 7.70 (d, 1H, J=8.4Hz, Ar-H), 4.01 (dt, 2H, J=5.2, 6.0 Hz, CH₂-OH), 3.29 (t, 2H, J=6.0 Hz, Ar-CH₂), 1.63 (t, 1H, J=5.2Hz, -OH).

<Example 4>
A solution of ammonium chloride (9.9 g, 0.185 mol) dissolved in 90.0 g of pure water was heated to 55 ° C. and stirred. After reaching 55 ° C., iron powder (51.1 g, 0.915 mol) was added, and the temperature was further raised to 80 ° C. After reaching 80 ° C., Compound 5 (29.0 g, 0.0599 mol) dissolved in 145 g of toluene heated to 80 ° C. was added dropwise. After completion of the dropwise addition, the mixture was further stirred for 2 hours. After completion of the reaction, hot filtration was performed under a heating condition of 80 ° C., and the obtained reaction solution was separated to remove the aqueous layer. Activated carbon 1.2g was put into the obtained organic layer, and it stirred at 80 degreeC on heating conditions for 30 minutes. Thereafter, the mixture was filtered while heated at 80 ° C. under heating, and the obtained organic layer was washed twice with pure water previously heated to 80 ° C. The obtained organic layer was dried over anhydrous magnesium sulfate, and then magnesium sulfate was collected by filtration. The solvent was distilled off from the obtained organic layer under reduced pressure to obtain Compound 6 (yield 18.7 g, 0.0440 mol). ) Yield 73.5%). The structure of Compound 6 was confirmed by ¹ H-NMR analysis.
¹ H-NMR (CDCl ₃ ): δ 7.67 (d, 1H, J = 16.0 Hz, -CH = CH-Ar), 7.45 (d, 2H, J = 8.4Hz, Ar-H), 6.88 (d, 2H, J = 8.4Hz, Ar-H), 6.34 (d, 1H, J = 16.0Hz, -CH = CH-Ar), 6.15 (d, 2H, J = 1.6Hz, Ar-H), 5.98 (t , 1H, J = 1.6Hz, Ar -H), 5.05 (s, 2H, Ar-CH 2 -O), 3.97 (t, 2H, J = 6.4Hz, Ar-O-CH 2), 3.62 (b, _{4H, NH 2), 1.82-1.76 (} m, 2H, Ar-O-CH 2 -CH 2 -), 1.46-1.27 (m, 14H, Ar-O-CH 2 -CH 2 -C 7 H 14 -) , 0.88 (t, 3H, J = 7.2Hz, -CH ₂ -CH ₃ )

To a solution of 2,4-dinitrophenylacetic acid (56.6 g, 250 mmol) in tetrahydrofuran (452 g), a solution of borane dimethyl sulfide complex (57.0 g, 750 mmol) in tetrahydrofuran (281 g) was added dropwise over 1 hour, and the mixture was stirred for 22 hours at room temperature. And stirred. Thereafter, water (112 g) was added dropwise at 0 ° C. over 2 hours, stirred at room temperature for 2 hours, extracted with ethyl acetate and water, the aqueous layer was separated, and the organic layer was dried over magnesium sulfate. Magnesium sulfate was removed by filtration, the obtained organic layer was concentrated, and the resulting crude product was recrystallized from ethyl acetate and hexane to obtain 2,4-dinitrophenylethyl alcohol 1 (42.1 g). 79% yield).
¹ H-NMR (CDCl ₃ ): δ 8.79 (d, 1H, J = 2.4 Hz, Ar-H), 8.40 (dd, 1H, J = 8.4, 2.4 Hz, Ar-H), 7.70 (d, 1H, J = 8.4Hz, Ar-H), 4.01 (dt, 2H, J = 5.2, 6.0 Hz, CH ₂ -OH), 3.29 (t, 2H, J = 6.0 Hz, Ar-CH ₂ ), 1.63 (t, 1H, J = 5.2Hz, -OH).

エーテル化合物２（３６．２ｇ、１３１ｍｍｏｌ）、アクリル酸（１３．０ｇ、１８０ｍｍｏｌ）、酢酸パラジウム（０．２６９ｇ、１．２０ｍｍｏｌ）、トリス（ｏ−トリル）ホスフィン（０．７３０ｇ、２．４０ｍｍｏｌ）、及びトリブチルアミン（６７．９ｇ、３６６ｍｍｏｌ）にジメチルアセトアミド（３６２ｇ）を加え、１４０℃で２時間攪拌した。その後、酢酸エチルと水で抽出を行い、水層を分離し、有機層を硫酸マグネシウムで乾燥した。ろ過により硫酸マグネシウムを除去して、得られた有機層を濃縮し、得られた粗物を酢酸エチルとヘキサンで再結晶を行い、桂皮酸誘導体３を得た（２１．１ｇ、７３％収率）。
¹H-NMR (DMSO): δ 12.2 (s, 1H, CO₂H), 7.62 (d, 2H, Ｊ=8.8 Hz, Ar-H), 7.54 (d, 1H, Ｊ=16.0 Hz, CO-CH=CH), 6.95 (d, 2H, Ｊ=8.8 Hz, Ar-H), 6.36 (d, 1H, J=16.0 Hz, CO-CH=CH), 4.01 (t, 2H,Ｊ=6.6 Hz, O-CH₂), 1.69 (m, 2H, O-CH₂-CH₂), 1.44 (m, 2H, CH₂-CH₃), 0.93 ( t, 3H, J=7.4 Hz, -CH₃).

Dimethylformamide (90.1 g) was added to iodobutane (30.0 g, 163 mmol), 4-iodophenol (39.4 g, 179 mmol), and potassium carbonate (27.0 g, 196 mmol), and the mixture was stirred at 85 ° C. for 2 hours. Thereafter, potassium carbonate was removed by filtration. Subsequently, extraction was performed with toluene and a 1N aqueous sodium hydroxide solution. The aqueous layer was separated, and the obtained organic layer was dried over magnesium sulfate. After removing magnesium sulfate by filtration, the organic layer was concentrated to obtain ether compound 2 (36.2 g, 81% yield). .
¹ H-NMR (CDCl ₃ ): δ 7.53 (d, 2H, J = 8.8 Hz, Ar-H), 6.66 (d, 2H, J = 8.8 Hz, Ar-H), 3.90 (t, 2H, J = 6.6 Hz, O-CH ₂ ), 1.76 (m, 2H, O-CH ₂ -CH ₂ ), 1.47 (m, 2H, CH ₂ -CH ₃ ), 0.96 (t, 3H, J = 7.6 Hz,- CH ₃ ).

Ether compound 2 (36.2 g, 131 mmol), acrylic acid (13.0 g, 180 mmol), palladium acetate (0.269 g, 1.20 mmol), tris (o-tolyl) phosphine (0.730 g, 2.40 mmol), Dimethylacetamide (362 g) was added to tributylamine (67.9 g, 366 mmol), and the mixture was stirred at 140 ° C. for 2 hours. Thereafter, extraction was performed with ethyl acetate and water, the aqueous layer was separated, and the organic layer was dried over magnesium sulfate. Magnesium sulfate was removed by filtration, the obtained organic layer was concentrated, and the obtained crude product was recrystallized with ethyl acetate and hexane to obtain cinnamic acid derivative 3 (21.1 g, 73% yield). ).
¹ H-NMR (DMSO): δ 12.2 (s, 1H, CO ₂ H), 7.62 (d, 2H, J = 8.8 Hz, Ar-H), 7.54 (d, 1H, J = 16.0 Hz, CO-CH = CH), 6.95 (d, 2H, J = 8.8 Hz, Ar-H), 6.36 (d, 1H, J = 16.0 Hz, CO-CH = CH), 4.01 (t, 2H, J = 6.6 Hz, O -CH ₂ ), 1.69 (m, 2H, O-CH ₂ -CH ₂ ), 1.44 (m, 2H, CH ₂ -CH ₃ ), 0.93 (t, 3H, J = 7.4 Hz, -CH ₃ ).

ジニトロ化合物４（１９．９ｇ、４８．０ｍｍｏｌ）、還元鉄（３２．２ｇ、５８３ｍｍｏｌ）、及び塩化アンモニウム（１５．４ｇ、２８８ｍｍｏｌ）を酢酸エチル（２００ｇ）と水（７７．１ｇ）に溶解し、７０℃で１４時間攪拌した。その後、７０℃のままセライトを用いてろ過を行い、得られたろ液の有機層を硫酸マグネシウムにより乾燥した。ろ過により硫酸マグネシウムを除去して、得られた有機層を濃縮し、粗物を得た。得られた粗物をテトラヒドロフラン（２００ｇ）に溶解し、活性炭（２．００ｇ）を加え、室温で１８時間撹拌した。ろ過により活性炭を除去し、有機層を濃縮して目的物であるジアミン化合物５を得た（１５．５ｇ、９１％収率）。
¹H-NMR (CDCl₃): δ 7.65 (d, 1H, J=16.0 Hz, CO-CH=CH), 7.41 (d, 2H, J=8.4 Hz, Ar-H,), 6.89 (d, 2H,J=8.4 Hz, Ar-H), 6.85 (d, 1H, J=8.0 Hz, Ar-H), 6.30 (d, 1H, J=16.0 Hz, CO-CH=CH), 6.10 (dd, 1H, J=8.0, 2.4 Hz, Ar-H), 6.07 (d, 1H, J=2.4 Hz Ar-H), 4.30 (t, 2H, J=7.6 Hz, CH₂-OCO), 4.00 (t, 2H, J=6.4 Hz, C₆H₄-O-CH₂), 3.88 (br-s, 2H, NH₂), 3.56 (br-s, 2H, NH₂), 2.81 (m, 2H, J=7.6 Hz, Ar-CH₂), 1.78 (m, 2H, O-CH₂-CH₂), 1.49(m, 2H, CH₂-CH₃), 0.98 ( t, 3H, J=7.2 Hz, -CH₃).Cinnamic acid compound 3 (16.2 g, 73.5 mmol), 2,4-dinitrophenylethyl alcohol 1 (15.6 g, 73.5 mmol), and dimethylaminopyridine (0.895 g, 7.32 mmol) were added to tetrahydrofuran (232 g). 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (16.2 g, 84.5 mmol) was added at 0 ° C., and the mixture was stirred at room temperature for 15 hours. Thereafter, the mixture was extracted with ethyl acetate and water, the aqueous layer was separated, and the organic layer was dried over magnesium sulfate. Magnesium sulfate was removed by filtration, the obtained organic layer was concentrated, and the resulting crude product was purified by column chromatography to obtain dinitro compound 4 (19.9 g, 65% yield).
¹ H-NMR (CDCl ₃ ): δ 8.83 (d, 1H, J = 2.4 Hz, Ar-H), 8.40 (dd, 1H, J = 8.8, 2.4 Hz, Ar-H), 7.66 (d, 1H, J = 8.8 Hz, Ar-H), 7.60 (d, 1H, J = 16.0 Hz, CO-CH = CH), 7.46 (d, 2H, J = 8.4 Hz, Ar-H), 6.89 (d, 2H, J = 8.4 Hz, Ar-H), 6.21 (d, 1H, J = 16.0 Hz, CO-CH = CH) 4.53 (t, 2H, J = 6.4 Hz, CH ₂ -OCO), 4.00 (t, 2H, J = 6.6 Hz, C ₆ H ₄ -O-CH ₂ ), 3.45 (m, 2H, J = 6.4 Hz, Ar-CH ₂ ), 1.78 (m, 2H, O-CH ₂ -CH ₂ ), 1.52 ( m, 2H, CH ₂ -CH ₃ ), 0.98 (t, 3H, J = 7.4 Hz, -CH ₃ ).

Dinitro compound 4 (19.9 g, 48.0 mmol), reduced iron (32.2 g, 583 mmol), and ammonium chloride (15.4 g, 288 mmol) were dissolved in ethyl acetate (200 g) and water (77.1 g). The mixture was stirred at 70 ° C. for 14 hours. Then, it filtered using cerite with 70 degreeC, and the organic layer of the obtained filtrate was dried with magnesium sulfate. Magnesium sulfate was removed by filtration, and the obtained organic layer was concentrated to obtain a crude product. The obtained crude product was dissolved in tetrahydrofuran (200 g), activated carbon (2.00 g) was added, and the mixture was stirred at room temperature for 18 hours. The activated carbon was removed by filtration, and the organic layer was concentrated to obtain the target diamine compound 5 (15.5 g, 91% yield).
¹ H-NMR (CDCl ₃ ): δ 7.65 (d, 1H, J = 16.0 Hz, CO-CH = CH), 7.41 (d, 2H, J = 8.4 Hz, Ar-H,), 6.89 (d, 2H , J = 8.4 Hz, Ar-H), 6.85 (d, 1H, J = 8.0 Hz, Ar-H), 6.30 (d, 1H, J = 16.0 Hz, CO-CH = CH), 6.10 (dd, 1H , J = 8.0, 2.4 Hz, Ar-H), 6.07 (d, 1H, J = 2.4 Hz Ar-H), 4.30 (t, 2H, J = 7.6 Hz, CH ₂ -OCO), 4.00 (t, 2H , J = 6.4 Hz, C ₆ H ₄ -O-CH ₂ ), 3.88 (br-s, 2H, NH ₂ ), 3.56 (br-s, 2H, NH ₂ ), 2.81 (m, 2H, J = 7.6 Hz, Ar-CH ₂ ), 1.78 (m, 2H, O-CH ₂ -CH ₂ ), 1.49 (m, 2H, CH ₂ -CH ₃ ), 0.98 (t, 3H, J = 7.2 Hz, -CH ₃ ).

（有機溶媒）
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＢＣ：ブチルセロソルブ[Synthesis of polyamic acid]
The abbreviations such as tetracarboxylic dianhydride and diamine compound used for the synthesis of polyamic acid are shown below.
(Tetracarboxylic dianhydride)
PMDA: pyromellitic dianhydride CBDA: 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride (diamine compound)
p-PDA: p-phenylenediamine DA1: 3,5-diaminobenzyl 3- (4- (4-decyloxy) phenyl) acrylate

(Organic solvent)
NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve

<Measurement of molecular weight of polyimide>
The molecular weight of polyimide was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Kagaku Co., Ltd. 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) 10 ml / L).
Flow rate: 1.0 ml / min Standard sample for preparation of 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).

<Example 5>
DA1 (0.637 g, 1.50 mmol) and p-PDA (0.162 g, 1.50 mmol) were mixed in NMP (8.13 g) and stirred for 1 hour at room temperature to dissolve, then PMDA ( 0.635 g, 2.91 mmol) was added and reacted at room temperature for 12 hours to obtain a polyamic acid solution. NMP (9.56 g) and BC (4.78 g) were added to this polyamic acid solution (9.56 g), and the mixture was stirred for 5 hours to obtain 6% by mass of a liquid crystal aligning agent (A).
The number average molecular weight of this polyamic acid was 7,000, and the weight average molecular weight was 17,000.

<Example 6>
DA1 (0.743 g, 1.75 mmol) and p-PDA (0.081 g, 0.75 mmol) were mixed in NMP (7.67 g) and stirred at room temperature for 1 hour to dissolve, then PMDA ( 0.529 g, 2.43 mmol) was added and reacted at room temperature for 12 hours to obtain a polyamic acid solution. NMP (9.02 g) and BC (4.51 g) were added to this polyamic acid solution (9.02 g) and stirred for 5 hours to obtain 6% by mass of a liquid crystal aligning agent (B).
The number average molecular weight of this polyamic acid was 6,500, and the weight average molecular weight was 16,000.

<Example 7>
DA1 (0.849 g, 2.0 mmol) was mixed in NMP (7.21 g) and dissolved by stirring for 1 hour at room temperature, then PMDA (0.424 g, 1.94 mmol) was added, and 12 at room temperature. It was made to react for time and the polyamic acid solution was obtained. NMP (8.48 g) and BC (4.24 g) were added to this polyamic acid solution (8.48 g), and the mixture was stirred for 5 hours to obtain 6% by mass of a liquid crystal aligning agent (C).
The number average molecular weight of this polyamic acid was 6,000, and the weight average molecular weight was 16,000.

<Example 8>
DA1 (0.509 g, 1.20 mmol) and p-PDA (0.194 g, 1.80 mmol) were mixed in NMP (7.22 g) and stirred for 1 hour at room temperature to dissolve, then CBDA ( 0.571 g, 2.91 mmol) was added and reacted at room temperature for 12 hours to obtain a polyamic acid solution. NMP (9.02 g) and BC (4.51 g) were added to this polyamic acid solution (9.02 g) and stirred for 5 hours to obtain 6% by mass of a liquid crystal aligning agent (D).
The number average molecular weight of this polyamic acid was 8000, and the weight average molecular weight was 21,000.

<Example 9>
DA1 (0.637 g, 1.50 mmol) and p-PDA (0.163 g, 1.50 mmol) were mixed in NMP (7.76 g) and stirred for 1 hour at room temperature to dissolve, then CBDA ( 0.571 g, 2.91 mmol) was added and reacted at room temperature for 12 hours to obtain a polyamic acid solution. NMP (9.13 g) and BC (4.57 g) were added to this polyamic acid solution (9.13 g) and stirred for 5 hours to obtain 6% by mass of a liquid crystal aligning agent (E).
The number average molecular weight of this polyamic acid was 7000, and the weight average molecular weight was 19000.

<Example 10>
Using the liquid crystal aligning agent (A) obtained in Example 5, a liquid crystal cell was produced according to the procedure shown below.

[Production of liquid crystal cell]
The liquid crystal aligning agent (A) obtained in Example 5 was spin-coated on the ITO surface of a glass substrate with a transparent electrode made of an ITO film, dried for 90 seconds on an 80 ° C. hot plate, and then heated at 200 ° C. for circulating hot air. Baking was performed for 30 minutes in a type oven to form a liquid crystal alignment film having a thickness of 100 nm.
This substrate was irradiated with 100 mJ of 313 nm linearly polarized light UV having an irradiation intensity of 8.0 mW / cm ² . The direction of the incident light was inclined by 40 ° with respect to the normal direction of the substrate. The linearly polarized light UV was adjusted by passing a 313 nm band pass filter through the ultraviolet light of a high pressure mercury lamp and then passing it through a 313 nm polarizing plate.
Two substrates were prepared, and a 6 μm bead spacer was sprayed on the liquid crystal alignment film of one substrate, and then a sealant was printed thereon. Next, the liquid crystal alignment surfaces of the two substrates are made to face each other, pressure-bonded so that the projection direction of the optical axis of the linearly polarized light UV on each substrate is antiparallel, and the sealant is thermally cured at 150 ° C. for 105 minutes. It was. A negative liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell.
A similar liquid crystal cell was produced by changing the exposure amount of the polarized UV light to be irradiated from 0 mJ to 1000 mJ by the above method.

[Liquid crystal cell evaluation]
When a voltage of 8 V was applied to and released from the liquid crystal cell at 25 ° C., the presence or absence of an abnormal domain was observed with a polarizing microscope, and the case where there was no abnormal domain was evaluated as “good liquid crystal alignment”. The liquid crystal cell produced above showed good vertical alignment when no voltage was applied, and the liquid crystal alignment was good when a voltage was applied.

[Evaluation of pretilt angle]
The pretilt angle of the liquid crystal cell was measured by the Mueller matrix method using “Axo Scan” manufactured by AxoMetrix.

<Example 11>
A liquid crystal cell was prepared in the same manner as in Example 10 except that the liquid crystal aligning agent (A) was changed to the liquid crystal aligning agent (B), and the orientation of the liquid crystal and the pretilt angle were measured.

<Example 12>
A liquid crystal cell was prepared in the same manner as in Example 10 except that the liquid crystal aligning agent (A) was changed to the liquid crystal aligning agent (C), and the orientation of the liquid crystal and the pretilt angle were measured.

<Example 13>
A liquid crystal cell was prepared in the same manner as in Example 10 except that the liquid crystal aligning agent (A) was changed to the liquid crystal aligning agent (D), and the orientation of the liquid crystal and the pretilt angle were measured.

<Example 14>
A liquid crystal cell was prepared in the same manner as in Example 10 except that the liquid crystal aligning agent (A) was changed to the liquid crystal aligning agent (E), and the orientation of the liquid crystal and the pretilt angle were measured.
Table 1 shows the composition ratios of the acid dianhydride and the diamine compound used in the production of the liquid crystal aligning agents (A) to (E). In Table 1,% in parentheses indicates the content ratio (mol%) of the corresponding acid dianhydride or diamine compound in the total acid dianhydride component or in the total diamine component.
Table 2 shows the pretilt angles of the liquid crystal cells manufactured in each example.

From the results of Table 2, the liquid crystal display device obtained by using the novel diamine compound of the present invention exhibits a good vertical alignment property, and aligns the liquid crystal even with a dose as small as 100 mJ by irradiating polarized ultraviolet rays. It was confirmed that a large pretilt angle was developed. Furthermore, it was confirmed that the liquid crystal alignment film using the novel diamine compound of the present invention can keep the pretilt angle constant regardless of the amount of ultraviolet irradiation. This indicates that the pretilt angle can be stably maintained even after being exposed to light such as a backlight for a long time.
From these facts, the novel diamine compound of the present invention can be used in a liquid crystal alignment film for a liquid crystal display element of a vertical alignment method, and is preferably used also in a photo alignment method that imparts liquid crystal alignment ability by ultraviolet irradiation. it can.

<Comparative Example 1>

1.11 g (2.70 mmol) of DA2 and 0.11 g (0.30 mmol) of DA3 were mixed in NMP (10.22 g) and stirred at room temperature for 1 hour to dissolve, then 0.58 g of CBDA ( 2.94 mmol) was added and reacted at room temperature for 12 hours to obtain a polyamic acid solution. NMP (9.0 g) and BC (9.0 g) were added to this polyamic acid solution (12.0 g), and the mixture was stirred for 5 hours to obtain 6% by mass of a liquid crystal aligning agent (F). The number average molecular weight of this polyamic acid was 12,000, and the weight average molecular weight was 29000.
A liquid crystal cell was prepared in the same manner as in Example 10 except that the liquid crystal aligning agent (A) was changed to the liquid crystal aligning agent (F) in Example 10 above, and the liquid crystal orientation and pretilt angle were measured. went.
Table 3 shows the composition ratios of the acid dianhydride and the diamine compound used in the synthesis of the liquid crystal aligning agent (F). Table 4 shows the pretilt angle of the liquid crystal cell manufactured in Comparative Example 1.

The liquid crystal display element having a liquid crystal alignment film obtained from the novel diamine compound of the present invention has a stable pretilt angle even when exposed to light such as a backlight for a long time, has excellent reliability, and has a large screen. And can be suitably used for high-definition liquid crystal televisions.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2010-153075 filed on July 5, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (6)

Obtained by the reaction of a diamine component containing a diamine compound represented by the following formula [1] and satisfying any of the following (A), (B) or (C) with a tetracarboxylic dianhydride component: A liquid crystal aligning agent containing a polyamic acid and at least one polymer selected from the group consisting of polyimides obtained by imidizing the polyamic acid.

(A): In formula [1], X ¹ represents a single bond, —CH ₂ O—, —O—, —COO—, —OCO—, —NHCO—, or —CONH—, and X ² represents the number of carbon atoms. 1 to 3 alkylene groups, X ³ represents —O—, —NH—, or —N (R ¹ ) —, and X ⁴ represents a single bond, —O—, —S—, or —NH—. Represent. X ⁵ represents a single bond, X ⁶ represents a linear or branched alkyl group having 1 to 18 carbon atoms, X ⁷ represents a hydrogen atom, —R ² , —OR ³ , —NHR ⁴ , —N (R ⁵⁾ _2, or an -SR ^6. Here, R ^{1 to} R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 or 2.
(B): In the formula [1], X ¹ represents a single bond, X ² represents an alkylene group having 1 to 3 carbon atoms, and X ³ represents —O—, —NH—, or —N (R ¹ ). - represents, ^{X 4} represents -O-. X ⁵ represents a single bond or a carbocycle selected from the group of the following formulas [X ⁵ -1] to [X ⁵ -5], and X ⁶ represents a linear or branched alkyl group having 1 to 18 carbon atoms. It represents, ^{X 7} is a hydrogen ^{atom, -R 2, -OR 3, -NHR} 4, -N (R 5) 2, or an -SR ^6. Here, R ^{1 to} R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 or 2.

(However, in the carbocyclic structure, any hydrogen atom may be substituted with CH _3. )
(C): In Formula [1], X ¹ represents a single bond, —CH ₂ O—, —O—, —COO—, —OCO—, —NHCO—, or —CONH—, and X ² represents —CH ^2. _2- represents, X ³ represents —O—, —NH—, or —N (R ¹ ) —, and X ⁴ represents a single bond, —O—, —S—, or —NH—. X ⁵ represents a single bond or a carbocycle selected from the group of the following formulas [X ⁵ -1] to [X ⁵ -5], and X ⁶ represents a linear or branched alkyl group having 8 to 12 carbon atoms. It represents, ^{X 7} is a hydrogen ^{atom, -R 2, -OR 3, -NHR} 4, -N (R 5) 2, or an -SR ^6. Here, R ^{1 to} R ⁶ each independently represents an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 or 2.

(However, in the above carbocyclic structure, any hydrogen atom may be substituted with CH _3. )   The liquid-crystal aligning agent of Claim 1 whose content of the diamine compound of Formula [1] in the said diamine component is 30-100 mol%.   N of said Formula [1] is 1, The liquid-crystal aligning agent of Claim 1 or 2.   The liquid crystal aligning film obtained from the liquid-crystal aligning agent as described in any one of Claims 1-3. The manufacturing method of the liquid crystal aligning film which apply | coats and bakes the liquid-crystal aligning agent as described in any one of Claims 1-3 on a board | substrate, and then irradiates polarized or non-polarized radiation, and provides liquid crystal aligning ability. .   A liquid crystal display device comprising the liquid crystal alignment film according to claim 4.