JPWO2010074269A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal aligning agent which causes little film abrasion due to rubbing treatment and has a small decrease in voltage holding ratio even after being exposed to a backlight for a long time. Component (A), a compound having a structure in which a group represented by formula [i] is bonded to an aromatic ring, and component (B), at least one kind selected from the group consisting of polyimide and a polyimide precursor A liquid crystal aligning agent comprising a molecular compound. In the formula [i], X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. (Chemical formula 1)

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element containing polyimide and / or a polyimide precursor.

  Liquid crystal display elements are currently widely used as display devices that are thin and light. Usually, in this liquid crystal display element, a liquid crystal alignment film is used to determine the alignment state of the liquid crystal. Most of the liquid crystal alignment films, except for some vertical alignment liquid crystal display elements, are produced by subjecting the surface of the polymer film formed on the electrode substrate to some alignment treatment.

As the polymer used for the liquid crystal alignment film, polyimide, polyamide, polyamideimide and the like are known, and a liquid crystal aligning agent obtained by dissolving these polymers and their precursors in a solvent is generally used. A polyamic acid is generally used as a polyimide precursor.
The most widely used method for orienting a polymer film formed on an electrode substrate is a method of rubbing the surface of the film by applying pressure with a cloth made of rayon or the like. is there. However, in the rubbing process, a part of the film may be peeled off, or the surface of the liquid crystal alignment film may be damaged due to the rubbing process, so-called “film scraping” may occur. This abnormality is considered to be one of the causes of deteriorating the characteristics of the liquid crystal display element and further reducing the yield.

In order to deal with the problem of film abrasion associated with such rubbing treatment, a method of using a liquid crystal aligning agent containing a specific thermally crosslinkable compound together with at least one polymer of polyamic acid or polyimide (for example, Patent Document 1). And a method of improving rubbing resistance by using a curing agent, such as a method of using a liquid crystal aligning agent containing an epoxy group-containing compound (see, for example, Patent Document 2).
Furthermore, in recent years, large-screen and high-definition liquid crystal televisions have been widely put into practical use, and liquid crystal display elements for such applications are required to have characteristics that can withstand long-term use in harsh usage environments. Therefore, the liquid crystal alignment film used there is required to have a higher reliability than before, and the electrical characteristics of the liquid crystal alignment film are not only good in initial characteristics but also, for example, over a long period of time. Excellent light resistance is required because it is exposed to a backlight.

Japanese Patent Laid-Open No. 9-185065 JP-A-9-146100

The present invention has been made in view of the above circumstances.
That is, the problem to be solved by the present invention is to provide a liquid crystal aligning agent with little film scraping due to rubbing treatment and a small decrease in voltage holding ratio even after being exposed to a backlight for a long time. An object of the present invention is to provide a highly reliable liquid crystal display device that can withstand long-term use in harsh usage environments.

The present invention has the following gist.
(1) at least selected from the group consisting of a compound having a structure in which the group represented by formula [i], which is component (A), is bonded to an aromatic ring, and polyimide and polyimide precursor, which is component (B) A liquid crystal aligning agent comprising a kind of polymer compound.

(X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
(2) The liquid crystal aligning agent as described in said (1) whose X in Formula [i] is a hydrogen atom.
(3) The component (A) is at least one selected from the group consisting of a compound represented by the following formula [1] and a compound represented by the formula [2], according to the above (1) or (2) Liquid crystal aligning agent.

〔式中、Ｘ_１、Ｘ_２、及びＸ_３は、それぞれ独立に水素原子又は炭素原子数１〜３のアルキル基であり、Ｙ_１、Ｙ_２、及びＹ_３はそれぞれ独立に芳香環を表し、該芳香環の任意の水素原子は、水酸基、炭素原子数１〜３のアルキル基、ハロゲン原子、炭素原子数１〜３のアルコキシ基又はビニル基で置換されていてもよい。Ｚ_１は、単結合、全部又は一部が結合して環状構造を形成してもよい炭素原子数１〜１０の飽和炭化水素基であり任意の水素原子はフッ素原子で置換されていてもよい、−ＮＨ−、−Ｎ（ＣＨ_３）−又は式［３］で表される基である。

[Wherein, X ₁ , X ₂ , and X ₃ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ₁ , Y ₂ , and Y ₃ each independently represent an aromatic ring. Any hydrogen atom of the aromatic ring may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group. Z ₁ is a single bond, a saturated hydrocarbon group having 1 to 10 carbon atoms, which may be bonded to all or part of it to form a cyclic structure, and any hydrogen atom may be substituted with a fluorine atom. , —NH—, —N (CH ₃ ) —, or a group represented by the formula [3].

（式中、Ｐ_１及びＰ_２はそれぞれ独立に炭素原子数１〜５のアルキル基であり、Ｑ_１は芳香環を表す。）
ｔ_１は２〜４の整数であり、ｔ_２及びｔ_３はそれぞれ独立に１〜３の整数であり、ａ及びｂはそれぞれ独立に１〜３の整数である。〕
（４）式［１］におけるＸ_１及び式［２］におけるＸ_２及びＸ_３が、水素原子である上記（３）に記載の液晶配向剤。
（５）式［１］におけるＹ_１及び式［２］におけるＹ_２及びＹ_３がそれぞれ独立に、ベンゼン環又はピリジン環である上記（３）又は（４）に記載の液晶配向剤。
（６）（Ａ）成分が下記の化合物からなる群から選ばれる少なくとも一種の化合物である上記（１）〜（５）のいずれかに記載の液晶配向剤。

(In the formula, P ₁ and P ₂ are each independently an alkyl group having 1 to 5 carbon atoms, and Q ₁ represents an aromatic ring.)
t ₁ is an integer of 2 to 4, an integer from _{t 2} and _{t 3} are each independently 1 to 3, a and b are each independently 1 to 3 integers. ]
(4) it is _{X 2} and _{X 3} in _{X 1} and equation [2] in [1], the liquid crystal alignment agent according to the above (3) is a hydrogen atom.
(5) The liquid crystal aligning agent according to (3) or (4), wherein Y ₁ in formula [1] and Y ₂ and Y ₃ in formula [2] are each independently a benzene ring or a pyridine ring.
(6) The liquid crystal aligning agent in any one of said (1)-(5) whose (A) component is at least 1 type of compound chosen from the group which consists of the following compound.

（７）（Ａ）成分が下記の化合物からなる群から選ばれる少なくとも一種の化合物である上記（１）〜（５）のいずれかに記載の液晶配向剤。

(7) The liquid crystal aligning agent in any one of said (1)-(5) whose (A) component is at least 1 type of compound chosen from the group which consists of the following compound.

（８）（Ｂ）成分が、ジアミン成分とテトラカルボン酸二無水物成分とを反応させて得られるポリアミック酸及び該ポリアミック酸を脱水閉環させて得られるポリイミドからなる群より選ばれる少なくとも一種の高分子化合物である上記（１）〜（７）のいずれかに記載の液晶配向剤。
（９）さらに、有機溶媒を含有する上記（１）〜（８）のいずれかに記載の液晶配向剤。
（１０）有機溶媒を除いた質量（固形分の濃度）が、１〜２０質量％である上記（１）〜（９）のいずれかに記載の液晶配向剤。
（１１）上記（１）〜（１０）のいずれかに記載の液晶配向剤を用いて得られる液晶配向膜。
（１２）上記（１１）に記載の液晶配向膜を具備する液晶表示素子。

(8) The component (B) is at least one kind selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic dianhydride component and a polyimide obtained by dehydrating and ring-closing the polyamic acid. The liquid crystal aligning agent in any one of said (1)-(7) which is a molecular compound.
(9) The liquid crystal aligning agent according to any one of (1) to (8), further containing an organic solvent.
(10) The liquid crystal aligning agent in any one of said (1)-(9) whose mass (concentration of solid content) except an organic solvent is 1-20 mass%.
(11) A liquid crystal alignment film obtained using the liquid crystal aligning agent according to any one of (1) to (10).
(12) A liquid crystal display device comprising the liquid crystal alignment film according to (11).

  The liquid crystal alignment treatment agent of the present invention can obtain a liquid crystal alignment film with little film scraping due to rubbing treatment and a small decrease in voltage holding ratio even after being exposed to a backlight for a long time. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.

  The liquid crystal aligning agent of the present invention comprises (A) component, a compound having a structure in which a group represented by formula [i] is bonded to an aromatic ring (hereinafter also referred to as a specific compound), and (B) component. It contains at least one polymer compound selected from the group consisting of a polyimide and a polyimide precursor (hereinafter also referred to as a specific polymer).

式［ｉ］において、Ｘは水素原子又は炭素原子数１〜３のアルキル基を表す。なかでも、Ｘが水素原子である場合、均一な液晶の配向を保ったまま、液晶のプレチルト角を 上げることができるとともに、液晶表示素子に蓄積した電荷の抜けを速くすることができるので好ましい。
本発明の液晶配向剤は、通常は、（Ａ）成分と、（Ｂ）成分とを含有し、それらが有機溶媒に溶解した溶液状態である。

In the formula [i], X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In particular, it is preferable that X is a hydrogen atom because the pretilt angle of the liquid crystal can be increased while maintaining uniform liquid crystal orientation, and the discharge of charge accumulated in the liquid crystal display element can be accelerated.
The liquid crystal aligning agent of the present invention usually contains a component (A) and a component (B) and is in a solution state in which they are dissolved in an organic solvent.

<(A) component>
The specific compound as the component (A) has a structure in which the group represented by the above formula [i] is bonded to the aromatic ring, but the group represented by the formula [i] (—CH ₂ —OX group) is an aromatic ring. The structure directly bonded to the compound facilitates the bonding reaction between the polyimide and the polyamic acid and also facilitates the self-reaction between specific compounds. This is presumed to be a factor that exerts the effect of the present invention.
Among the specific compounds, at least one compound selected from the group consisting of a compound represented by the following formula [1] and a compound represented by the formula [2] is preferable.

式中、Ｘ_１、Ｘ_２、及びＸ_３は、それぞれ独立に水素原子又は炭素原子数１〜３のアルキル基であり、Ｙ_１、Ｙ_２、及びＹ_３はそれぞれ独立に芳香環を表わす。該芳香環の任意の水素原子は、水酸基、炭素原子数１〜３のアルキル基、ハロゲン原子、炭素原子数１〜３のアルコキシ基又はビニル基で置換されていてもよい。Ｚ_１は、単結合、全部又は一部が結合して環状構造を形成してもよい炭素原子数１〜１０の２価の飽和炭化水素基であり任意の水素原子はフッ素原子で置換されていてもよい、−ＮＨ−、−Ｎ（ＣＨ_３）−、式［３］で表される基である。ｔ_１は２〜４の整数であり、ｔ_２及びｔ_３はそれぞれ独立に１〜３の整数であり、ａ及びｂはそれぞれ独立に１〜３の整数である。

In the formula, X ₁ , X ₂ , and X ₃ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ₁ , Y ₂ , and Y ₃ each independently represent an aromatic ring. Any hydrogen atom in the aromatic ring may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group. Z ₁ is a single bond, a divalent saturated hydrocarbon group having 1 to 10 carbon atoms, which may be bonded to all or part of it to form a cyclic structure, and any hydrogen atom is substituted with a fluorine atom. Or —NH—, —N (CH ₃ ) —, or a group represented by the formula [3]. t ₁ is an integer of 2 to 4, an integer from _{t 2} and _{t 3} are each independently 1 to 3, a and b are each independently 1 to 3 integers.

式〔３〕中、Ｐ_１及びＰ_２はそれぞれ独立に炭素原子数１〜５のアルキル基であり、Ｑ_１は芳香環を表す。
式［１］及び式［２］の−ＣＨ_２−ＯＸ_１基、−ＣＨ_２−ＯＸ_２基及び、−ＣＨ_２−ＯＸ_３基は芳香環に直接結合しているので、Ｙ_１、Ｙ_２、及びＹ_３は、それぞれ独立に芳香環である。

In formula [3], P ₁ and P ₂ are each independently an alkyl group having 1 to 5 carbon atoms, and Q ₁ represents an aromatic ring.
Since the —CH ₂ —OX ₁ group, —CH ₂ —OX ₂ group, and —CH ₂ —OX ₃ group of the formula [1] and the formula [2] are directly bonded to the aromatic ring, Y ₁ , Y ₂ , And Y ₃ are each independently an aromatic ring.

  Specific examples thereof include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine Ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline Ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, acridine ring, oxazole ring and the like. Specific examples of more preferable aromatic rings include benzene ring, naphthalene ring, fluorene ring, anthracene ring, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring, carbazole ring, pyridazine ring, pyrazine. Ring, benzimidazole ring, benzimidazole ring, indole ring, quinoxaline ring, acridine ring and the like. More preferred are a benzene ring, a naphthalene ring, a pyridine ring and a carbazole ring, and most preferred are a benzene ring and a pyridine ring.

In addition, the hydrogen atom of these aromatic rings may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group.
T ₂ and t ₃ in the formula [2] are more preferably integers of 1 or 2. Moreover, a and b are more preferably 1 or 2.
X ₁ in the formula [1] and X ₂ and X ₃ in the formula [2] are each independently preferably one group selected from a hydrogen atom, CH ₃ , C ₂ H ₅ , and C ₃ H ₇ . The smaller the number of carbons, the better the bonding reaction with polyimide and polyamic acid, or the easier the self-reaction between the compounds. On the other hand, when the number of carbon atoms increases, the reactivity of the —CH ₂ —OX ₁ group, —CH ₂ —OX ₂ group, and —CH ₂ —OX ₃ group decreases, so that the storage stability of the solution containing the compound is decreased. Increase. In particular, when X ₁ in Formula [1] and X ₂ and X ₃ in Formula [2] are hydrogen atoms, the pretilt angle of the liquid crystal can be increased while maintaining uniform liquid crystal orientation, and the liquid crystal This is preferable because the charge stored in the display element can be discharged quickly.
Z ₁ in the formula [2] is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which may be bonded to all or part thereof to form a cyclic structure. Any hydrogen atom that it has may be substituted with a fluorine atom.

Examples of Z ₁ include an alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, a combination of an alkylene group and an alicyclic hydrocarbon group, and 1 carbon atom. -10 groups. In addition, a group in which any hydrogen atom of the above-described group is substituted with a fluorine atom is exemplified.

Q ₁ in the formula [3] is an aromatic ring, and specific examples thereof include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole. Ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, Examples include a pyrazine ring, a benzimidazole ring, a benzimidazole ring, a thionoline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an acridine ring, and an oxazole ring. Specific examples of more preferable aromatic rings include benzene ring, naphthalene ring, fluorene ring, anthracene ring, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring, carbazole ring, pyridazine ring, pyrazine. Ring, benzimidazole ring, benzimidazole ring, indole ring, quinoxaline ring, acridine ring and the like. More preferably, a benzene ring, a naphthalene ring, a pyridine ring, a carbazole ring, a fluorene ring, etc. are mentioned.
In the present invention, it is also possible to use at least one compound selected from the group consisting of formula [1] and formula [2].
Specific examples of the specific compound used in the present invention include [P1] to [P45], but are not limited thereto.

上記（Ａ）成分である特定化合物は、［Ｐ１５］、［Ｐ１７］、［Ｐ１９］、［Ｐ２９］、［Ｐ３１］、［Ｐ４１］で表される化合物が好ましく、なかでも、［Ｐ１５］、［Ｐ１７］、［Ｐ２９］、［Ｐ３１］、［Ｐ４１］で表される化合物がより好ましい。

The specific compound as the component (A) is preferably a compound represented by [P15], [P17], [P19], [P29], [P31], [P41], and among them, [P15], [P41] The compounds represented by P17], [P29], [P31], and [P41] are more preferable.

<(B) component>
The component (B) is a specific polymer, and the specific polymer is as defined above. In the present invention, the polyimide precursor means a polyamic acid and / or a polyamic acid ester. As the specific polymer, polyimide and polyamic acid are preferable.
In the present invention, the method for synthesizing the specific polymer is not particularly limited.
The specific polymer is usually obtained by reacting a diamine component and a tetracarboxylic dianhydride component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds, and the formula [5] A polyamic acid having the structural formula of the repeating unit represented is obtained. In order to obtain polyamic acid ester, the method of converting the carboxyl group of polyamic acid into ester is used. Furthermore, in order to obtain a polyimide, the method of imidating the said polyamic acid and making it a polyimide is used.

式［５］中、Ｒ_１は４価の有機基であり、Ｒ_２は２価の有機基であり、ｎは正の整数を表す。
原料であるテトラカルボン酸成分とジアミン成分は、所望により、適宜選択される。ここで言うテトラカルボン酸及びその誘導体とは、テトラカルボン酸、テトラカルボン酸ジハライド及びテトラカルボン酸二無水物である。なかでも、テトラカルボン酸二無水物はジアミン化合物との反応性が高いので好ましい。
上記Ｒ_１の具体例は、下記のＡ−１〜Ａ−４６の構造が挙げられる。

In Formula [5], R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, and n represents a positive integer.
The raw material tetracarboxylic acid component and diamine component are appropriately selected as desired. The tetracarboxylic acid and its derivatives mentioned here are tetracarboxylic acid, tetracarboxylic acid dihalide and tetracarboxylic dianhydride. Of these, tetracarboxylic dianhydrides are preferred because of their high reactivity with diamine compounds.
Specific examples of R ₁ include the following structures A-1 to A-46.

また、Ｒ_２の具体例は、後述するＢ−１〜Ｂ−１１３の構造が挙げられる。

Specific examples of R ₂ include the structures B-1 to B-113 described later.

上記Ｂ−１１２及びＢ−１１３において、Ｑは−ＣＯＯ−，−ＯＣＯ−，−ＣＯＮＨ−，−ＮＨＣＯ−，−ＣＨ_２−，−Ｏ−，−ＣＯ−，又は−ＮＨ−のいずれかを表す。
特定重合体の製造方法としては、例えば、式［６］で表されるテトラカルボン酸二無水物の少なくとも一種を含むテトラカルボン酸成分と、式［７］で表されるジアミン化合物の少なくとも一種を含むジアミン成分とを、Ｎ−メチルピロリドン、Ｎ，Ｎ’−ジメチルアセトアミド、Ｎ，Ｎ’−ジメチルホルムアミド、γ−ブチルラクトンなどの有機溶媒中で重縮合反応させる方法が挙げられる。

In the above B-112 and B-113, Q represents any of —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, and —NH—. .
Examples of the method for producing the specific polymer include a tetracarboxylic acid component containing at least one tetracarboxylic dianhydride represented by the formula [6] and at least one diamine compound represented by the formula [7]. Examples thereof include a method of subjecting the diamine component to be contained to a polycondensation reaction in an organic solvent such as N-methylpyrrolidone, N, N′-dimethylacetamide, N, N′-dimethylformamide, and γ-butyllactone.

なお、式［６］中のＲ_１は、式［５］における定義と同意義であり、その具体例は、上記のＡ−１〜Ａ−４６である。また、式［７］中のＲ_２は、式［５］における定義と同意義であり、その具体例は、上記のＢ−１〜Ｂ−１１３である。

Incidentally, _{R 1} in the formula [6] are the same meanings as defined in the formula [5], its specific example is the above-mentioned A-1~A-46. Also, _{R 2} in the formula [7] is the same meanings as defined in the formula [5], its specific example is the above-mentioned B-1~B-113.

The tetracarboxylic dianhydride and its derivative used for obtaining the specific polymer are not particularly limited. Tetracarboxylic dianhydride can be used alone or in combination of two or more. Among these, when importance is attached to the voltage holding characteristic, it is preferable to use a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure such as A-1 to A-25 and A-46. . In particular, it is preferable to use at least one selected from the group consisting of A-1 to A-6, A-8, A-16, A-18 to A-24, and A-46.
Further, when at least 10 to 100 mol% of the tetracarboxylic dianhydride component is a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, it is effective for voltage holding characteristics.

On the other hand, when importance is attached to liquid crystal orientation and accumulated charge reduction, it is preferable to use an aromatic acid dianhydride such as A-26 to A-45. In particular, it is preferable to use at least one selected from the group consisting of A-26, A-27, A-32, A-34, and A-39 to A-43.
Further, when at least 20 to 100 mol% of the tetracarboxylic dianhydride component is an aromatic dianhydride, it is effective for reducing the liquid crystal alignment and the accumulated charge.
The preferred composition ratio (mol%) when a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure in the tetracarboxylic dianhydride component is used in combination with an aromatic dianhydride is the former. 10-80 mol%, the latter is 20-90 mol%.
In particular, among tetracarboxylic dianhydrides, when at least one selected from the group consisting of A-6, A-16, A-18, A-19 to A-22, and A-46 is used, these are used. The solubility of the specific polymer is high, and the solubility when the polymer is dehydrated and closed to form a soluble polyimide is good.

  The diamine represented by the formula [7] is not particularly limited, and only one kind may be used in the present invention, but a plurality of kinds may be used. Among these, when a part or all of the diamine component used for obtaining the specific polymer is B-80 to B-101 or the like, the pretilt angle of the liquid crystal can be increased. Examples of the diamine component that increases the pretilt angle of the liquid crystal include diamine compounds represented by the following formula.

なお、式中、Ａ_４は、フッ素原子で置換されていてもよい、炭素数３〜２０のアルキル基であり、Ａ_３は、１，４シクロへキシレン基、又は１，４−フェニレン基であり、Ａ_２は、酸素原子、又は−ＣＯＯ−＊（ただし、「＊」を付した結合手がＡ_３と結合する）であり、Ａ_１は酸素原子、又は−ＣＯＯ−＊（ただし、「＊」を付した結合手が（ＣＨ_２）ａ２と結合する。である。また、ａ_１は０、又は１の整数であり、ａ２は２〜１０の整数であり、ａ３は０、又は１の整数である。
液晶を特に垂直配向させる場合は、ジアミン成分の好ましくは５〜１００モル％、より好ましくは１０〜８０モル％をＢ−８０〜Ｂ−１０１などが使用される。

In the formula, A ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group. A ₂ is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A ₃ ), and A ₁ is an oxygen atom or —COO— * (where “ The bond marked with “*” binds to (CH ₂ ) a2. Further, a ₁ is 0 or an integer of 1, a 2 is an integer of 2 to 10, and a 3 is 0 or 1. Is an integer.
When the liquid crystal is particularly vertically aligned, B-80 to B-101 or the like is preferably used in an amount of 5 to 100 mol%, more preferably 10 to 80 mol% of the diamine component.

In the polymerization reaction between the tetracarboxylic acid component and the diamine component, the reaction temperature can be selected from -20 ° C to 150 ° C, preferably in the range of -5 ° C to 100 ° C.
The degree of polymerization of the specific polymer is affected by the raw material charge ratio. Therefore, the ratio between the total number of moles of the compound constituting the tetracarboxylic acid component and the total number of moles of the diamine compound constituting the diamine component is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. The closer this molar ratio is to 1.0, the greater the degree of polymerization of the polymer produced.
As a method for imidizing polyamic acid, thermal imidization by heating and catalyst imidization using a catalyst are generally used, but the catalyst imidation in which the imidization reaction proceeds at a relatively low temperature is obtained. It is preferable that the molecular weight does not decrease.

  Catalytic imidation can be performed by stirring polyamic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature at this time is -20 ° C to 250 ° C, preferably 0 to 180 ° C. The higher the reaction temperature, the faster the imidization proceeds, but if it is too high, the molecular weight of the polyimide may decrease. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. If the amount of the basic catalyst or acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too large, it becomes difficult to completely remove the reaction after completion of the reaction. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The organic solvent is not limited as long as it dissolves polyamic acid, and specific examples thereof include N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, Examples thereof include N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, dimethyl sulfone, hexamethyl sulfoxide, and γ-butyrolactone. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

  The produced polyimide can be obtained by collecting the reaction solution in a poor solvent and collecting the produced precipitate. In that case, the poor solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like. The polyimide that has been poured into a poor solvent and precipitated is filtered, and then can be powdered by drying at normal temperature or under reduced pressure at normal temperature or under reduced pressure. The polyimide can also be refine | purified by repeating the operation which melt | dissolves the polyimide powder further in an organic solvent, and reprecipitates 2-10 times. When the impurities cannot be removed by a single precipitation recovery operation, it is preferable to perform this purification step.

  The molecular weight of the specific polyimide used in the present invention is not particularly limited, but is preferably 2,000 to 200,000 in terms of weight average molecular weight, more preferably 4 from the viewpoint of easy handling and stability of characteristics when a film is formed. , 50,000 to 50,000. The molecular weight is determined by GPC (gel permeation chromatography).

<Liquid crystal alignment agent>
The liquid-crystal aligning agent of this invention is normally obtained by mixing the specific compound which is above-mentioned (A) component, the specific polymer which is (B) component, and the other component mentioned later in an organic solvent if desired. It is done. One type of specific compound may be sufficient and multiple types may be used together.
Examples of the mixing method include a method of adding the component (A) and, if desired, other components described later to a solution obtained by dissolving the component (B) in an organic solvent. The organic solvent used in that case will not be specifically limited if it is a solvent which melt | dissolves a polyimide. Specific examples are given below.

  For example, N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethyl Urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, Examples include propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. Two or more kinds of these solvents may be mixed and used.

When dissolving polyimide in an organic solvent, heating may be performed for the purpose of promoting dissolution of polyimide. If the heating temperature is too high, the molecular weight of the polyimide may decrease, so the temperature is preferably 30 to 100 ° C, more preferably 50 to 90 ° C. Although the density | concentration of the solution of a polyimide is not specifically limited, 1-20 mass% is preferable as a density | concentration of the polyimide in a solution, More preferably, it is 3-15 mass%, Most preferably, it is 3-10 mass%.
The specific compound may be added directly to the solution of the polyamic acid and the solvent-soluble polyimide, but is added after a solution having a concentration of 0.1 to 50% by mass, preferably 5 to 20% by mass with an appropriate solvent. It is preferable. Examples of the solvent include the above-described polyimide solvents.

<Other ingredients>
In addition to the specific polymer and the specific compound, the liquid crystal alignment treatment agent of the present invention is a solvent or substance that improves the film thickness uniformity or surface smoothness when the liquid crystal alignment treatment agent is applied as another component, a liquid crystal alignment film A substance that improves the adhesion between the substrate and the substrate may be contained. These components may be added during the mixing of the specific polymer and the specific compound, or may be added later to the mixed solution.

[Solvent that improves film thickness uniformity and surface smoothness]
Specific examples of the solvent for improving the film thickness uniformity and the surface smoothness include the following.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene Glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, 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, 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, 3-methoxy Ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy- 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl acetate Low surface tension such as ter-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 A solvent etc. are mentioned.
These solvents may be used alone or in combination. When using the above solvent, it is preferable that it is 5-80 mass% of the whole solvent contained in a liquid-crystal aligning agent, More preferably, it is 20-60 mass%.

[Substances that improve film thickness uniformity and surface smoothness]
Examples of substances that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, EFTOP EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these substances 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 component (B) contained in the liquid crystal aligning agent. .

[Substance for improving adhesion between liquid crystal alignment film and substrate]
Specific examples of the substance 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.
When these substances are added, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the specific polymer component contained in the liquid crystal alignment treatment agent. . If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

  In addition to the above, the liquid crystal alignment treatment agent of the present invention has a polymer component other than the specific polymer and electrical characteristics 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. Substances to be changed (dielectrics, conductive substances, etc.), and further, crosslinkable substances for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.

[Substances that change electrical characteristics]
Specific examples of the substance that promotes charge transfer in the liquid crystal alignment film and promotes charge release of the liquid crystal cell using the liquid crystal alignment film include amines such as M1 to M158 (hereinafter also referred to as added amine). It is done. The added amine may be added directly to the solution of the specific polymer, but it is preferably added after a suitable solvent is used to make a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. Examples of the solvent include the above-described polyimide solvents.

  The concentration of the solid content in the liquid crystal alignment treatment agent of the present invention can be appropriately changed depending on the film thickness of the target liquid crystal alignment film. Is preferably 1 to 20% by mass, more preferably 2 to 10% by mass. Solid content here means the mass of the component remove | excluding the solvent from the liquid-crystal aligning agent.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like. The substrate 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 particular, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed from the viewpoint of simplifying the process. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light, such as aluminum, can also be used.
A method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of performing screen printing, offset printing, flexographic printing, ink jet, or the like is common. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.

  Firing after applying the liquid crystal aligning agent on the substrate can form a coating film by evaporating the solvent at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate. If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. 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 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 a method for manufacturing a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are scattered on the liquid crystal alignment film on one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure and sealed, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the 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.
The liquid crystal display element produced using the liquid crystal aligning agent of this invention becomes the thing excellent in reliability, and can be utilized suitably for a large-screen, high-definition liquid crystal television.

Examples (Synthesis examples) will be described below together with comparative examples to explain the present invention in more detail. However, the present invention should not be construed as being limited thereto.
<Synthesis Examples 1-14, Examples 1-27, and Comparative Examples 1-6>
The abbreviations used in these Examples (Synthesis Examples) and Comparative Examples are as follows. Moreover, the molecular weight measurement of the polyimide and the measurement of the imidization rate were according to the following methods.
<Tetracarboxylic dianhydride>
A-1: 4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride A-2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride A-3: Pyromellitic dianhydride A-4: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride A-5: 2,3,5-tricarboxycyclopentylacetic acid-1, 4: 2,3-dianhydride

＜ジアミン＞
Ｂ−２：１，３−ジアミノ−４−オクタデシルオキシベンゼン
Ｂ−４：ｐ−フェニレンジアミン
Ｂ−５：４−｛４−（４−ヘプチルシクロヘキシル）フェノキシ｝−１，３−ジアミノベンゼン
Ｂ−８：４，４'−ジアミノジフェニルメタン
Ｂ−１３：３，５−ジアミノ安息香酸
Ｂ−１４：ｍ−フェニレンジアミン
Ｂ−１５：下記式Ｂ−１５で表されるジアミン化合物
Ｂ−１６：１，３−ジアミノ−５−{４−〔トランス−４−（トランス−４−ｎ−ペンチルシクロへキシル）シクロへキシル〕フェノキシメチル}ベンゼン

<Diamine>
B-2: 1,3-diamino-4-octadecyloxybenzene B-4: p-phenylenediamine B-5: 4- {4- (4-heptylcyclohexyl) phenoxy} -1,3-diaminobenzene B-8 : 4,4'-diaminodiphenylmethane B-13: 3,5-diaminobenzoic acid B-14: m-phenylenediamine B-15: diamine compound represented by the following formula B-15 B-16: 1,3- Diamino-5- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxymethyl} benzene

（特定化合物）
Ｐ１５、Ｐ１７、Ｐ２９、Ｐ３１及びＰ４１の意味は、前記したとおりである。

(Specific compounds)
The meanings of P15, P17, P29, P31 and P41 are as described above.

<Amine compound>
C-1: 3-aminomethylpyridine C-2: 3-aminopropylimidazole (organic solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve GBL: γ-butyrolactone

<Measurement of molecular weight of polyimide>
The molecular weight of the polyimide in the synthesis example was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Science 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) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran ( THF) is 10 ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight of about 9,000,150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight about 12,000, 4,000, 1,000).

<Measurement of imidization ratio>
The imidation ratio of polyimide in the synthesis example was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Kagaku Co., Ltd.), add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. 500 MHz proton NMR was measured for this solution with the NMR measuring device by the JEOL datum company (JNW-ECA500). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing near 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100
In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, α is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%) 1 This is the ratio of the number of reference protons to one.

(Synthesis Example 1)
A-4 (13.5 g, 54 mmol), B-4 (5.4 g, 50 mmol), and B-5 (8.2 g, 22 mmol) were mixed in NMP (80.1 g) at 40 ° C. for 3 hours. After the reaction, A-2 (3.3 g, 17 mmol) and NMP (41.8 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (104.2 g) and diluting to 6% by mass, acetic anhydride (12.5 g) and pyridine (9.7 g) were added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was put into methanol (1300 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (A). The imidation ratio of this polyimide was 55%, the number average molecular weight was 19,100, and the weight average molecular weight was 54,300.

(Synthesis Example 2)
A-4 (127.6 g, 510 mmol), B-13 (51.8 g, 340 mmol), and B-5 (129.4 g, 340 mmol) were mixed in NMP (1096 g) and reacted at 80 ° C. for 5 hours. Then, A-2 (33.0 g, 168 mmol) and NMP (272 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (510.2 g) and diluting to 6% by mass, acetic anhydride (54.3 g) and pyridine (42.2 g) were added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was put into methanol (6500 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (B). The imidation ratio of this polyimide was 57%, the number average molecular weight was 22,800, and the weight average molecular weight was 79,200.

(Synthesis Example 3)
A-4 (127.6 g, 510 mmol), B-13 (51.8 g, 340 mmol), and B-5 (129.4 g, 340 mmol) were mixed in NMP (1096 g) and reacted at 80 ° C. for 5 hours. Then, A-2 (33.0 g, 168 mmol) and NMP (272 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (101.2 g) and diluting to 6% by mass, acetic anhydride (21.4 g) and pyridine (16.0 g) were added as an imidization catalyst and reacted at 90 ° C. for 3 hours. It was. This reaction solution was put into methanol (650 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (C). The imidation ratio of this polyimide was 81%, the number average molecular weight was 21,400, and the weight average molecular weight was 65,400.

(Synthesis Example 4)
A-4 (37.3 g, 148.8 mmol), B-13 (21.1 g, 138.9 mmol), and B-16 (25.9 g, 59.5 mmol) were mixed in NMP (203.5 g). After reacting at 80 ° C. for 5 hours, A-2 (9.5 g, 48.3 mmol) and NMP (171.4 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (125.6 g) and diluting to 6% by mass, acetic anhydride (27.0 g) and pyridine (20.9 g) were added as imidization catalysts, and the mixture was heated at 90 ° C. for 3.5 hours. Reacted. This reaction solution was poured into methanol (1600 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (D). The imidation ratio of this polyimide was 80%, the number average molecular weight was 21,200, and the weight average molecular weight was 64,500.

(Synthesis Example 5)
A-1 (30.3 g, 100.0 mmol), B-4 (9.7 g, 90.0 mmol), and B-2 (3.8 g, 10.0 mmol) were mixed in NMP (246.7 g). And a reaction at 50 ° C. for 24 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (120.8 g) and diluting to 6% by mass, acetic anhydride (35.0 g) and pyridine (16.2 g) were added as an imidization catalyst and reacted at 35 ° C. for 3 hours. It was. This reaction solution was poured into methanol (1420 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (E). The imidation ratio of this polyimide was 83%, the number average molecular weight was 12,700, and the weight average molecular weight was 29,200.

(Synthesis Example 6)
A-2 (11.8 g, 60.0 mmol), A-3 (11.5 g, 52.8 mmol), and B-8 (23.8 g, 120.0 mmol) were mixed in NMP (266.4 g). The polyamic acid solution (F) was prepared by reacting at room temperature for 5 hours. The number average molecular weight of this polyamic acid was 11,700, and the weight average molecular weight was 29,400.

(Synthesis Example 7)
A-2 (39.2 g, 200.0 mmol) and B-4 (20.5 g, 190.0 mmol) were mixed in NMP (537.9 g) and reacted at room temperature for 5 hours to obtain a polyamic acid solution (G). Prepared. The number average molecular weight of this polyamic acid was 13,600, and the weight average molecular weight was 38,400.

(Synthesis Example 8)
A-5 (22.2 g, 99.0 mmol) and B-8 (19.8 g, 100.0 mmol) were mixed in NMP (168.1 g) and reacted at 40 ° C. for 15 hours to obtain a polyamic acid solution (H ) The number average molecular weight of this polyamic acid was 25,500, and the weight average molecular weight was 92,100.

(Synthesis Example 9)
A-5 (22.2 g, 99.0 mmol) and B-8 (19.8 g, 100.0 mmol) were mixed in NMP (168.1 g) and reacted at 40 ° C. for 15 hours to obtain a polyamic acid solution. It was. After adding NMP to this polyamic acid solution (50.0 g) and diluting to 4.5% by mass, acetic anhydride (6.0 g) and pyridine (4.7 g) were added as imidization catalysts and reacted at 100 ° C. for 3 hours. I let you. This reaction solution was poured into methanol (620 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (I). The imidation ratio of this polyimide was 64%, the number average molecular weight was 21,200, and the weight average molecular weight was 75,900.

(Synthesis Example 10)
A-5 (3.3 g, 15 mmol), B-4 (1.3 g, 12 mmol) and B-15 (1.5 g, 3 mmol) were mixed in NMP (24.5 g) and reacted at 40 ° C. for 8 hours. To obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.5 g) and pyridine (1.9 g) were added as an imidization catalyst and reacted at 90 ° C. for 3 hours. . This reaction solution was poured into methanol (330 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (J). The imidation ratio of this polyimide was 50%, the number average molecular weight was 18,100, and the weight average molecular weight was 52,300.

(Synthesis Example 11)
A-5 (4.5 g, 20 mmol), B-14 (1.5 g, 14 mmol), B-5 (2.3 g, 6 mmol) were mixed in NMP (33.0 g) and reacted at 40 ° C. for 8 hours. To obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (3.7 g) and pyridine (2.9 g) were added as an imidization catalyst and reacted at 90 ° C. for 3 hours. . This reaction solution was put into methanol (370 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (K). The imidation ratio of this polyimide was 51%, the number average molecular weight was 18,600, and the weight average molecular weight was 72,600.

(Synthesis Example 12)
A-4 (85.1 g, 340 mmol), B-13 (39.6 g, 260 mmol) and B16 (60.9 g, 140 mmol) were mixed in NMP (556.3 g) and reacted at 80 ° C. for 5 hours. Thereafter, A-2 (11.5 g, 58 mmol) and NMP (231.4 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (200.0 g) and diluting to 6% by mass, acetic anhydride (26.4 g) and pyridine (13.7 g) were added as an imidization catalyst and reacted at 100 ° C. for 2.5 hours. I let you. This reaction solution was put into methanol (2500 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (L). The imidation ratio of this polyimide was 71%, the number average molecular weight was 21,300, and the weight average molecular weight was 54,700.

(Synthesis Example 13)
A-4 (112.6 g, 450 mmol), B-4 (19.5 g, 180 mmol), B-13 (18.3, 120 mmol), B-5 (114.2 g, 300 mmol) and NMP (793.5 g) After mixing at 80 ° C. for 5 hours, A-2 (28.6 g, 145 mmol) and NMP (378.5 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (300.0 g) and diluting to 6% by mass, acetic anhydride (31.3 g) and pyridine (24.2 g) were added as an imidization catalyst and reacted at 80 ° C. for 4 hours. . This reaction solution was poured into methanol (3700 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (M). The imidation ratio of this polyimide was 52%, the number average molecular weight was 19,800, and the weight average molecular weight was 53,800.

(Synthesis Example 14)
A-4 (138.2 g, 552 mmol), B-13 (39.6 g, 260 mmol) and B-5 (74.2 g, 195 mmol) were mixed in NMP (819 g) and reacted at 80 ° C. for 5 hours. Then, A-2 (18.1 g, 92 mmol) and NMP (346 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (500.0 g) and diluting to 6% by mass, acetic anhydride (68.1 g) and pyridine (35.2 g) were added as an imidization catalyst and reacted at 100 ° C. for 2.5 hours. I let you. This reaction solution was poured into methanol (6200 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (N). The imidation ratio of this polyimide was 68%, the number average molecular weight was 22,100, and the weight average molecular weight was 77,200.

Liquid crystal aligning agents (1) to (27) were prepared as follows, and the rubbing resistance of each of these liquid crystal aligning agents was evaluated as follows. The results are summarized in Table 1.
[Rubbing resistance evaluation]
The liquid crystal aligning agent of the present invention obtained above was spin coated on a glass substrate with a transparent electrode, dried on an 80 ° C. hot plate for 5 minutes, and then baked in a hot air circulation oven at 220 ° C. for 30 minutes, A coating film having a thickness of 100 nm was formed. The coated surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.4 mm to obtain a substrate with a liquid crystal alignment film.
The surface of the liquid crystal alignment film in the vicinity of the center of the substrate was randomly observed with a laser microscope set at a magnification of 100 times, and the rubbing scratches and rubbing residue (about the observation visual field of about 6.5 mm square) The rubbing resistance was evaluated from the average value of the amount of deposits). The results are shown in Table 1 described later. The evaluation criteria were determined as follows.
Evaluation criteria A: 20 or less rubbing scratches or rubbing residues B: 20 to 40 rubbing scratches or rubbing residues C: 40 to 60 rubbing scratches or rubbing residues D: 60 or more rubbing scratches or rubbing residues

Example 1
NMP (29.5 g) was added to the polyimide powder (A) (5.2 g) obtained in Synthesis Example 1, and dissolved by stirring at 80 ° C. for 30 hours. Add 10.0 mass% NMP solution (5.2 g) of P15 (0.52 g as P15), NMP (3.4 g), and BCS (43.3 g) to this solution and stir at room temperature for 2 hours. Thus, a liquid crystal aligning agent (1) was obtained.

(Example 2)
NMP (27.3 g) was added to the polyimide powder (B) (5.6 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 30 hours. To this solution, 5.0 mass% NMP solution (5.6 g) of C-1 (0.28 g as C-1), NMP (8.1 g), and BCS (46.6 g) were added, and at 50 ° C. Stir for 15 hours. A 10.0% by mass NMP solution (5.6 g) of P15 (0.56 g as P15) was added to this solution, followed by stirring at room temperature for 2 hours to obtain a liquid crystal aligning agent (2).

Example 3
NMP (27.3 g) was added to the polyimide powder (B) (5.6 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 30 hours. To this solution, 5.0 mass% NMP solution (5.6 g) of C-1 (0.28 g as C-1), NMP (8.1 g), and BCS (46.6 g) were added, and at 50 ° C. Stir for 15 hours. A 10.0% by mass NMP solution (3.9 g) of P15 (0.39 g as P15) was added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (3).

Example 4
NMP (27.3 g) was added to the polyimide powder (B) (5.6 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 30 hours. To this solution, 5.0 mass% NMP solution (5.6 g) of C-1 (0.28 g as C-1), NMP (8.1 g), and BCS (46.6 g) were added, and at 50 ° C. Stir for 15 hours. A 10.0% by mass NMP solution (2.8 g) of P15 (0.28 g as P15) was added to this solution, followed by stirring at room temperature for 2 hours to obtain a liquid crystal aligning agent (4).

(Example 5)
NMP (27.3 g) was added to the polyimide powder (B) (5.6 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 30 hours. To this solution, 5.0 mass% NMP solution (5.6 g) of C-1 (0.28 g as C-1), NMP (8.1 g), and BCS (46.6 g) were added, and at 50 ° C. Stir for 15 hours. A 10.0% by mass NMP solution (1.7 g) of P15 (0.17 g as P15) was added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (5).

(Example 6)
NMP (35.2 g) was added to the polyimide powder (C) (7.2 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 30 hours. To this solution was added 5.0 mass% NMP solution (7.2 g) of C-1 (0.36 g as C-1), NMP (10.4 g), and BCS (60.0 g) at 50 ° C. Stir for 15 hours. A 10.0% by mass NMP solution (7.2 g) of P15 (0.72 g as P15) was added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (6).

(Example 7)
NMP (25.4 g) was added to the polyimide powder (D) (5.2 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 ° C. for 30 hours. To this solution was added 5.0 wt% NMP solution (5.2 g) of C-1 (0.26 g as C-1), NMP (7.5 g), and BCS (43.4 g) at 50 ° C. Stir for 15 hours. A 10.0% by mass NMP solution (5.2 g) of P15 (0.52 g as P15) was added to this solution, followed by stirring at room temperature for 2 hours to obtain a liquid crystal aligning agent (7).

(Example 8)
A liquid crystal aligning agent (8) was obtained in the same manner as in Example 7 except that P15 was changed to P31.

Example 9
NMP (5.0 g) and BCS (5.0 g) were added to the polyamic acid (G) (15.0 g) obtained in Synthesis Example 7, and the mixture was stirred at room temperature for 2 hours. A 10.0% by mass NMP solution (1.5 g) of P15 (0.15 g as P15) was added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (9).

(Example 10)
A liquid crystal aligning agent (10) was obtained in the same manner as in Example 9 except that P15 was changed to P17.
(Example 11)
A liquid crystal aligning agent (11) was obtained in the same manner as in Example 9 except that P15 was changed to P29.
(Example 12)
A liquid crystal aligning agent (12) was obtained in the same manner as in Example 9 except that P15 was changed to P41.
(Example 13)
GBL (45.0 g) was added to the polyimide powder (E) (5.0 g) obtained in Synthesis Example 5 and dissolved by stirring at 50 ° C. for 20 hours. GBL (33.3 g) was added to this solution and stirred at room temperature for 2 hours to obtain a polyimide solution. Next, GBL (112.5 g) and BCS (37.5 g) were added to the polyamic acid solution (F) (100.0 g) obtained in Synthesis Example (6), and the mixture was stirred at room temperature for 2 hours. An acid solution was obtained. Furthermore, the said polyimide solution (20.0g) and the polyamic acid solution (80.0g) were mixed, and the polyimide and the polyamic acid mixed solution were obtained by stirring at room temperature for 20 hours. Finally, 10.0 mass% GBL solution (6.0 g) of P15 (0.6 g as P15) was added to this mixed solution, and the liquid crystal aligning agent (13) was obtained by stirring at room temperature for 2 hours.
(Example 14)
NMP (8.5 g) in the polyamic acid (H) (20.0 g) obtained in Synthesis Example 8, 10.0 mass% NMP solution (1.5 g) of P17 (0.15 g as P17), BCS (20. 0 g) was added, and the liquid crystal aligning agent (14) was obtained by stirring at room temperature for 2 hours.

(Example 15)
NMP (28.3 g) was added to the polyimide powder (I) (5.0 g) obtained in Synthesis Example 9, and dissolved by stirring at 70 ° C. for 30 hours. By adding 10.0 mass% NMP solution (2.5 g) of P17 (0.25 g as P17), NMP (11.7 g), and BCS (33.3 g) to this solution, and stirring at room temperature for 2 hours A liquid crystal aligning agent (15) was obtained.
(Example 16)
NMP (28.3 g) was added to the polyimide powder (J) (5.0 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 ° C. for 30 hours. By adding 10.0 mass% NMP solution (2.5 g) of P17 (0.25 g as P17), NMP (11.7 g), and BCS (33.3 g) to this solution, and stirring at room temperature for 2 hours A liquid crystal aligning agent (16) was obtained.
(Example 17)
NMP (28.3 g) was added to the polyimide powder (K) (5.0 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 ° C. for 30 hours. By adding 10.0 mass% NMP solution (2.5 g) of P17 (0.25 g as P17), NMP (11.7 g), and BCS (33.3 g) to this solution, and stirring at room temperature for 2 hours A liquid crystal aligning agent (17) was obtained.
(Example 18)
NMP (48.8 g) was added to the polyimide powder (L) (10.0 g) obtained in Synthesis Example 12, and dissolved by stirring at 70 ° C. for 30 hours. To this solution, a 5.0 mass% NMP solution (10.0 g) of C-1 (0.5 g as C-1), NMP (22.8 g), and BCS (75.0 g) were added, and 15 ° C. at 15 ° C. Stir for hours. A 10.0 mass% NMP solution (5.0 g) of P17 (0.5 g as P17) was added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (18).

(Example 19)
NMP (48.8 g) was added to the polyimide powder (M) (10.0 g) obtained in Synthesis Example 13 and dissolved by stirring at 70 ° C. for 30 hours. To this solution, a 5.0 mass% NMP solution (10.0 g) of C-2 (0.5 g as C-2), NMP (22.8 g), and BCS (75.0 g) were added, and 20 ° C. was added at 20 ° C. Stir for hours. A 10.0 mass% NMP solution (5.0 g) of P17 (0.5 g as P17) was added to this solution and stirred at room temperature for 2 hours to obtain a polyimide solution (O). Next, NMP (48.8 g) was added to the polyimide powder (N) (10.0 g) obtained in Synthesis Example 14, and dissolved by stirring at 70 ° C. for 30 hours. To this solution, 5.0 mass% NMP solution (5.9 g) of C-2 (0.6 g as C-2), NMP (26.9 g) and BCS (75.0 g) were added, and 20 ° C. was added at 20 ° C. Stir for hours. A 10.0 mass% NMP solution (5.0 g) of P17 (0.5 g as P17) was added to this solution and stirred at room temperature for 2 hours to obtain a polyimide solution (P). Furthermore, the said polyimide solution (O) (30.0g) and the polyimide solution (P) (30.0g) were mixed, and the liquid-crystal aligning agent (19) was obtained by stirring for 20 hours.

(Example 20)
NMP (9.8 g) was added to the polyimide powder (A) (2.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 80 ° C. for 30 hours. By adding 10.0 mass% NMP solution (1.0 g) of P17 (0.1 g as P17), NMP (3.9 g), and BCS (16.7 g) to this solution, and stirring at room temperature for 2 hours A liquid crystal aligning agent (20) was obtained.
(Example 21)
NMP (9.8 g) was added to the polyimide powder (B) (2.0 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 30 hours. NMP (2.9 g) and BCS (16.7 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours. A 10.0% by mass NMP solution (2.0 g) of P17 (0.2 g as P17) was added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (21).

(Example 22)
NMP (9.8 g) was added to the polyimide powder (B) (2.0 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 30 hours. To this solution was added a 5.0 mass% NMP solution (2.0 g) of C-1 (0.1 g as C-1), NMP (1.5 g), and BCS (16.7 g). Stir for hours. A 10.0% by mass NMP solution (1.4 g) of P17 (0.14 g as P17) was added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (22).
(Example 23)
NMP (9.8 g) was added to the polyimide powder (B) (2.0 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 30 hours. NMP (2.9 g) and BCS (16.7 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours. A 10.0 mass% NMP solution (1.0 g) of P17 (0.1 g as P17) was added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (23).
(Example 24)
NMP (9.8 g) was added to the polyimide powder (B) (2.0 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 30 hours. To this solution, a 5.0 mass% NMP solution (2.0 g) of C-1 (0.1 g as C-1), NMP (2.3 g), and BCS (16.7 g) were added, and 15 ° C. at 15 ° C. Stir for hours. A 10.0 mass% NMP solution (0.6 g) of P17 (0.06 g as P17) was added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (24).

(Example 25)
NMP (9.8 g) was added to the polyimide powder (C) (2.0 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 30 hours. To this solution, a 5.0 mass% NMP solution (2.0 g) of C-1 (0.1 g as C-1), NMP (1.9 g), and BCS (16.7 g) were added, and 15 ° C. at 15 ° C. Stir for hours. A 10.0% by mass NMP solution (1.0 g) of P17 (0.1 g as P17) was added to this solution, followed by stirring at room temperature for 2 hours to obtain a liquid crystal aligning agent (25).
(Example 26)
NMP (9.8 g) was added to the polyimide powder (D) (2.0 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 ° C. for 30 hours. To this solution, a 5.0 mass% NMP solution (2.0 g) of C-1 (0.1 g as C-1), NMP (1.9 g), and BCS (16.7 g) were added, and 15 ° C. at 15 ° C. Stir for hours. A 10.0% by mass NMP solution (1.0 g) of P17 (0.1 g as P17) was added to this solution, followed by stirring at room temperature for 2 hours to obtain a liquid crystal aligning agent (26).

(Example 27)
GBL (18.0 g) was added to the polyimide powder (E) (2.0 g) obtained in Synthesis Example 5 and dissolved by stirring at 50 ° C. for 20 hours. GBL (13.3g) was added to this solution, and it stirred at room temperature for 2 hours, and obtained the polyimide solution. Next, GBL (112.5 g) and BCS (37.5 g) were added to the polyamic acid solution (F) (100.0 g) obtained in Synthesis Example (6), and the mixture was stirred at room temperature for 2 hours. A solution was obtained. Furthermore, the said polyimide solution (20.0g) and the polyamic acid solution (80.0g) were mixed, and the polyimide and the polyamic acid mixed solution were obtained by stirring at room temperature for 20 hours. Finally, 10.0 mass% GBL solution (6.0 g) of P17 (0.6 g as P17) was added to this mixed solution, and the liquid crystal aligning agent (27) was obtained by stirring at room temperature for 2 hours.

(Comparative Example 1)
NMP (32.2 g) was added to the polyimide powder (A) (6.6 g) obtained in Synthesis Example 1 and dissolved by stirring at 80 ° C. for 30 hours. NMP (16.1 g) and BCS (55.0 g) were added to this solution, and the liquid crystal aligning agent (28) was obtained by stirring at room temperature for 2 hours.
(Comparative Example 2)
NMP (22.5 g) was added to the polyimide powder (B) (4.6 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 30 hours. To this solution, 5.0 mass% NMP solution of C-1 (4.6 g) (0.23 g as C-1), NMP (6.7 g), and BCS (38.4 g) were added, and at 50 ° C. The liquid crystal aligning agent (29) was obtained by stirring for 15 hours.
(Comparative Example 3)
A liquid crystal aligning agent (30) was prepared in the same manner as in Comparative Example 2 except that the polyimide powder (C) obtained in Synthesis Example 3 was used.
(Comparative Example 4)
A liquid crystal aligning agent (31) was obtained in the same manner as in Comparative Example 2 except that the polyimide powder (D) obtained in Synthesis Example 4 was used.
(Comparative Example 5)
Γ-BL (18.0 g) was added to the polyimide powder (E) (2.0 g) obtained in Synthesis Example 5 and dissolved by stirring at 50 ° C. for 20 hours. GBL (8.3g) and BCS (5.0g) were added to this solution, and the liquid-crystal aligning agent (32) was obtained by stirring at room temperature for 2 hours.
(Comparative Example 6)
NMP (5.0 g) and BCS (5.0 g) were added to the polyamic acid (G) (15.0 g) obtained in Synthesis Example 7, and the mixture was stirred at room temperature for 2 hours to obtain a liquid crystal alignment treatment agent (33). Got.

(Examples 28 to 38 and Comparative Examples 7 and 8)
About each liquid crystal aligning agent obtained by the said Example and comparative example, this was spin-coated on the glass substrate with an ITO electrode, and after drying for 5 minutes on an 80 degreeC hotplate, 210 degreeC hot-air circulation type Baking was performed for 1 hour in an oven to prepare a liquid crystal alignment film having a thickness of 100 nm. After preparing two substrates with a liquid crystal alignment film and spraying a spacer of 6 μm on the surface of one liquid crystal alignment film, a sealant is printed and bonded together, and then the sealant is cured to be emptied. A cell was produced. A liquid crystal MLC-6608 (manufactured by Merck Japan Co., Ltd.) was injected into this empty cell by a reduced pressure injection method, and the inlet was sealed to obtain a nematic liquid crystal cell.
When each liquid crystal cell was observed with a polarizing microscope, the liquid crystal was uniformly vertically aligned and no alignment defects were observed. About each liquid crystal cell, the voltage holding rate after UV-vis irradiation (light resistance) was evaluated with the voltage holding rate at the time of liquid crystal cell preparation, and the result was put together in Table 2.

<Voltage holding ratio during liquid crystal cell production>
A voltage of 1 V was applied to the liquid crystal cell produced above at a temperature of 80 ° C. for 60 μs, the voltage after 16.67 ms and 50 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio. . As a result, the voltage holding ratio at 16.67 ms was 97.0%, and the voltage holding ratio at 50 ms was 94.2%.
The measurement was performed using a VHR-1 voltage holding ratio measuring device manufactured by Toyo Technica Co., Ltd., with settings of Voltage: ± 1 V, Pulse Width: 60 μs, Frame Period: 16.67 ms or 50 ms.

<Voltage holding ratio after UV-vis irradiation>
The same measurement was performed after irradiating each liquid crystal cell having completed the voltage holding ratio measurement with light of 50 J / cm ^{2 in} terms of 365 nm. The UV-vis (high pressure mercury lamp) irradiation was performed using a SEN LIGHT CORPORATION desktop type UV curing device (HCT3B28HEX-1). As a result, the voltage holding ratio at 16.67 ms was 92.3%, and the voltage holding ratio at 50 ms was 88.9%.

<実施例３９〜５４及び比較例９〜２０>
下記のようにしてそれぞれ液晶配向処理剤を調製した。得られた各液晶配向処理剤の組成をまとめて表３に示す。また、各液晶配向処理剤を用いて液晶セルを作製し、下記するように、それぞれのチルト角、ラビング耐性及びＲＤＣを評価した。結果をまとめて表４に示す。
なお、これらの実施例及び比較例で使用する略号は、以下のとおりである。なお、特に、説明のない略号の意味は、前記したとおりである。

（特定化合物）
Ｐ１３、Ｐ１７、Ｐ４６、Ｐ４７、Ｐ３１及びＰ４９の意味は、前記したとおりである。

<Examples 39 to 54 and Comparative Examples 9 to 20>
Liquid crystal aligning agents were prepared as follows. The compositions of the obtained liquid crystal alignment treatment agents are summarized in Table 3. Moreover, a liquid crystal cell was produced using each liquid crystal aligning agent, and each tilt angle, rubbing resistance, and RDC were evaluated as described below. The results are summarized in Table 4.
The abbreviations used in these examples and comparative examples are as follows. In particular, the meanings of the abbreviations that are not described are as described above.

(Specific compounds)
The meanings of P13, P17, P46, P47, P31 and P49 are as described above.

（ジアミン）
Ｂ−１：２，４−ジアミノ−Ｎ，Ｎ−ジアリルアニリン
Ｂ−３：４−（トランス−４−ペンチルシクロへキシル）ベンズアミド−２’,４’−フェニレンジアミン
Ｂ−６：４−アミノベンジルアミン
Ｂ−７：３−アミノベンジルアミン
Ｂ−９：１，３−ジアミノ−４−ドデシルオキシ−ベンゼン
Ｂ−１０：１，３−ジアミノ−４−テトラデシルオキシベンゼン
Ｂ−１１：１，４−ビス(4−アミノフェノキシ)ペンタン
Ｂ−１２：４，４‘−ジアミノジフェニルアミン

(Diamine)
B-1: 2,4-Diamino-N, N-diallylaniline B-3: 4- (trans-4-pentylcyclohexyl) benzamide-2 ′, 4′-phenylenediamine B-6: 4-aminobenzyl Amine B-7: 3-aminobenzylamine B-9: 1,3-diamino-4-dodecyloxy-benzene B-10: 1,3-diamino-4-tetradecyloxybenzene B-11: 1,4- Bis (4-aminophenoxy) pentane B-12: 4,4'-diaminodiphenylamine

<Production of liquid crystal cell>
A liquid crystal alignment treatment agent is spin-coated on a glass substrate with a transparent electrode, dried on an 80 ° C. hot plate for 5 minutes, and then baked on a 210 ° C. hot plate for 10 minutes to form a coating film having a thickness of 70 nm. I let you. This coating film surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film. Prepare two substrates with a liquid crystal alignment film, spray a 6μm spacer on the surface of one liquid crystal alignment film, print a sealant on it, and face the other substrate with the liquid crystal alignment film surface After laminating so that the rubbing direction was perpendicular, the sealing agent was cured to produce an empty cell. Liquid crystal MLC-2003 (Merck Japan Co., Ltd.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a twisted nematic liquid crystal cell.
<Measurement of pretilt angle>
The prepared twisted nematic liquid crystal cell was heated at 105 ° C. for 5 minutes, and then the pretilt angle was measured. The pretilt angle was measured using a crystal rotation method.

<Measurement of accumulated charge (RDC)>
A DC voltage was applied from 0 V to 1.0 V at a temperature of 23 ° C. at a temperature of 23 ° C. to the twisted nematic liquid crystal cell manufactured by the method described in <Preparation of Liquid Crystal Cell> above, and the flicker amplitude at each voltage. Levels were measured and a calibration curve was created. After grounding for 5 minutes, after applying AC voltage 3.0V and DC voltage 5.0V for 1 hour, measure the flicker amplitude level immediately after setting only DC voltage to 0N and compare it with the calibration curve prepared in advance. Estimated. (This RDC estimation method is called a flicker reference method.)
Here, RDC (before OFF) indicates values immediately after application of AC voltage 3.0V and DC voltage 5.0V for 1 hour, and RDC (after 10 minutes) indicates accumulated charge 10 minutes after the AC voltage is turned OFF. Indicates the value of.

<Evaluation of rubbing resistance>
The liquid crystal aligning agent of the present invention obtained above was spin-coated on a glass substrate with a transparent electrode, dried on an 80 ° C. hot plate for 5 minutes, and then baked in a hot air circulation oven at 210 ° C. for 10 minutes, A coating film having a thickness of 100 nm was formed. This coating film surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.5 mm to obtain a substrate with a liquid crystal alignment film.
The surface of the liquid crystal alignment film in the vicinity of the center of the substrate was randomly observed with a laser microscope set at a magnification of 100 times, and the rubbing scratches and rubbing residue (about the observation visual field of about 6.5 mm square) The rubbing resistance was evaluated from the average value of the amount of deposits). The evaluation criteria were determined as follows.
Evaluation criteria ○: 20 or less rubbing scratches or rubbing residues Δ: 20 to 60 rubbing scratches or rubbing residues ×: 60 or more rubbing scratches or rubbing residues

(Example 39)
30.03 g (100 mmol) of A-1 was used as the tetracarboxylic dianhydride component, 9.73 g (90 mmol) of B-4 and 3.77 g (10 mmol) of B-2 were used as the diamine component, and in 247 g of NMP, The reaction was carried out at 40 degrees for 3 hours to obtain a polyamic acid solution.
50 g of this polyamic acid solution was diluted to 5% by weight with NMP, and 17.6 g of acetic anhydride and 8.2 g of pyridine were added as an imidization catalyst and reacted at 40 ° C. for 3 hours to prepare a soluble polyimide resin solution. This solution was poured into 0.6 L of methanol, and the resulting precipitate was filtered off and dried to obtain a white soluble polyimide (SPI-1). As a result of measuring the molecular weight of this soluble polyimide, the number average molecular weight was 13,430, and the weight average molecular weight was 26,952. The imidation ratio was 85%.
1 g of this polyimide powder was dissolved in 11.8 g of GBL and 4.8 g of BCS to obtain a uniform polyimide solution. To 10 g of this solution, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Example 40)
As a tetracarboxylic dianhydride component, 9.80 g (50 mmol) of A-2, 9.60 g (44 mmol) of A-3, and 19.8 g (100 mmol) of B-8 as a diamine component, 222 g of NMP, The mixture was reacted at room temperature for 5 hours to obtain a polyamic acid solution (PAA-1). The number average molecular weight of this polyamic acid was 11,153, and the weight average molecular weight was 29,487. 10.5 g of NMP and 7.5 g of BCS were added to 8 g of this solution, followed by stirring at room temperature for 20 hours to obtain a uniform liquid crystal aligning agent.
To 10 g of a solution in which SPI-1 and PAA-1 were mixed at a mass ratio of 2: 8, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Example 41)
To 10 g of a solution in which SPI-1 and PAA-1 were mixed at a mass ratio of 2: 8, 0.03 g of P19 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.
(Example 42)
To 10 g of a solution in which SPI-1 and PAA-1 were mixed at a mass ratio of 2: 8, 0.03 g of P13 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.
(Example 43)
To 10 g of a solution in which SPI-1 and PAA-1 were mixed at a mass ratio of 2: 8, 0.03 g of P49 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.
(Example 44)
To 10 g of the solution in which SPI-1 and PAA-1 were mixed at a mass ratio of 2: 8, 0.03 g of P48 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.
(Example 45)
To 10 g of a solution in which SPI-1 and PAA-1 were mixed at a mass ratio of 2: 8, 0.03 g of P46 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Example 46)
To 10 g of a solution in which SPI-1 and PAA-1 were mixed at a mass ratio of 2: 8, 0.03 g of P47 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.
(Example 47)
A mixture of 30.03 g (100 mmol) of A-1, 8.56 g (80 mmol) of B-4, and 5.85 g (20 mmol) of B-9 in 252 g of NMP at 50 ° C. for 24 hours to give a polyamic acid A solution was prepared. 50 g of this polyamic acid solution was diluted to 5% by mass with NMP, and 8.0 g of pyridine and 17.2 g of acetic anhydride were further added as an imidization catalyst, followed by reaction at 40 ° C. for 3 hours. This solution was put into 0.6 L of methanol, and the resulting precipitate was filtered off and dried to obtain white polyimide powder (SPI-2). The obtained solvent-soluble polyimide had a number average molecular weight of 9,111 and a weight average molecular weight of 18,045. The imidation ratio was 83%.
To 10 g of a solution in which SPI-2- and PAA-1 were mixed at a mass ratio of 2: 8, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Example 48)
As tetracarboxylic dianhydride component, A-2 was used as 8.18 g (42 mmol), A-3 was used as 1.63 g (7.5 mmol), and diamine component was used as B-7 as 1.22 g (10 mmol). , B-1 (5.08 g, 25 mmol) and B-3 (6.11 g, 15 mmol) were reacted in NMP (88.96 g) at room temperature for 24 hours to obtain a polyamic acid solution. 228.5 g of NMP was added to 95.8 g of this polyamic acid solution for dilution, 15.1 g of acetic anhydride and 6.4 g of pyridine were added, and the mixture was reacted at 50 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 1259.1 ml of methanol to recover the precipitated solid. The solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of soluble polyimide (SPI-3). The number average molecular weight of this polyimide was 18,195, and the weight average molecular weight was 57,063. Moreover, the imidation ratio was 93%. 10.8 g of GBL was added to 1.2 g of this polyimide powder and stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring. After 12 g of this solution was cooled to 23 ° C., 2 g of GBL and 6 g of BCS were added and stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
To 10 g of this solution, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Example 49)
As a tetracarboxylic dianhydride component, A-2 is 13.53 g (69 mmol), A-3 is 6.54 g (30 mmol), and as a diamine component, B-1 is 8.13 g (40 mmol), and B-6 is 3.67 g (30 mmol) and 8.77 g (30 mmol) of B-9 were used and reacted at room temperature in 161.8 g of NMP for 24 hours to obtain a polyamic acid solution.
To 34.81 g of this polyamic acid solution, 62.65 g of NMP was added for dilution, and 5.15 g of acetic anhydride and 2.19 g of pyridine were added and reacted at a temperature of 50 ° C. for 3 hours to imidize.
The reaction solution was cooled to about room temperature and then poured into 366.8 ml of methanol to recover the precipitated solid. Further, the solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of polyimide (SPI-4). The number average molecular weight of this polyimide was 12,016, and the weight average molecular weight was 35,126. Moreover, the imidation ratio was 90%.
10.8 g of GBL was added to 1.2 g of this polyimide powder and stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring. After 12 g of this solution was cooled to 23 ° C., 2 g of GBL and 6 g of BCS were added and stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
To 10 g of this solution, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Example 50)
As a tetracarboxylic dianhydride component, 13.2 g (68 mmol) of A-2, 6.54 g (30 mmol) of A-3, 3.81 g (10 mmol) of B-5 as a diamine component, and B-1 Using 8.13 g (40 mmol) and 7.64 g (50 mmol) of B-6, NMP151.7 g was reacted at room temperature for 24 hours to obtain a polyamic acid solution. 59.61 g of NMP was added to 33.38 g of this polyamic acid solution for dilution, 5.26 g of acetic anhydride and 2.24 g of pyridine were added, and the mixture was reacted at 50 ° C. for 3 hours to imidize.
The reaction solution was cooled to about room temperature and then poured into 351.7 ml of methanol to recover the precipitated solid. Further, the solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of polyimide (SPI-5). The number average molecular weight of this polyimide was 10,111, and the weight average molecular weight was 33,653. Moreover, the imidation ratio was 90%.
10.8 g of GBL was added to 1.2 g of this polyimide powder and stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring. After 12 g of this solution was cooled to 23 ° C., 2 g of GBL and 6 g of BCS were added and stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.
To 10 g of this solution, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Example 51)
As tetracarboxylic dianhydride component, 6.86 g (35 mmol) of A-2, 3.27 g (15 mmol) of A-3, and 2.44 g (20 mmol) of B-7 as a diamine component, B The polyamic acid solution (PAA-2) was obtained by reacting for 3 hours at room temperature in 87.0 g of NMP using 3.04 g (15 mmol) of -1 and 6.11 g (15 mmol) of B-3. The number average molecular weight of this polyamic acid was 15,539, and the weight average molecular weight was 47,210. 10.5 g of NMP and 7.5 g of BCS were added to 8 g of this solution, followed by stirring at room temperature for 20 hours to obtain a uniform liquid crystal aligning agent.
To 10 g of this solution, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.
(Example 52)
To 10 g of a solution in which SPI-3- and PAA-4 were mixed at a mass ratio of 3: 7, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Example 53)
Using 4.05 g (18 mmol) of A-3 as the tetracarboxylic dianhydride component, 5.15 g (18 mmol) of B-11 and 0.75 g (2 mmol) of B-2 as the diamine component, NMP73. The reaction was carried out in 07 g at room temperature for 16 hours to obtain a 12% by mass polyamic acid solution. The number average molecular weight of this polyamic acid was 12,180, and the weight average molecular weight was 25,160. 50 g of this polyamic acid solution was diluted with 115 g of NMP and 50 g of BCS to obtain a polyamic acid solution (PAA-3).
To 10 g of this solution, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Example 54)
As a tetracarboxylic dianhydride component, 7.15 g (37 mmol) of A-2, 3.00 g (10 mmol) of A-1 as a diamine component, 7.97 g (40 mmol) of B-12, 1 of B-8 .98 g (10 mmol) was used and reacted in 181 g of NMP at room temperature for 16 hours to obtain a 10% by mass polyamic acid solution. The number average molecular weight of this polyamic acid was 12,180, and the weight average molecular weight was 30,160. 100.0 g of this polyamic acid solution was diluted with 230 g of NMP and 100 g of BCS to obtain a polyamic acid solution (PAA-4).
0.03 g of P17 was added to 10 g of a solution in which PAA-3- and PAA-4 were mixed at a mass ratio of 2: 8, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Comparative Example 9)
30.03 g (100 mmol) of A-1 was used as the tetracarboxylic dianhydride component, 9.73 g (90 mmol) of B-4 and 3.77 g (10 mmol) of B-2 were used as the diamine component, and in 247 g of NMP, The reaction was carried out at 40 degrees for 3 hours to obtain a polyamic acid solution.
50 g of this polyamic acid solution was diluted to 5% by weight with NMP, and 17.6 g of acetic anhydride and 8.2 g of pyridine were added as an imidation catalyst and reacted at 40 ° C. for 3 hours to prepare a soluble polyimide resin solution. This solution was poured into 0.6 L of methanol, and the resulting precipitate was filtered off and dried to obtain a white soluble polyimide (SPI-1). As a result of measuring the molecular weight of this soluble polyimide, the number average molecular weight was 13,430, and the weight average molecular weight was 26,952. The imidation ratio was 85%. 1 g of this polyimide powder was dissolved in 11.8 g of GBL and 4.8 g of BCS to obtain a uniform polyimide solution.
(Comparative Example 10)
SPI-1 and PAA-1 were mixed at a mass ratio of 2: 8, and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.
(Comparative Example 11)
SPI-2 and PAA-1 were mixed at a mass ratio of 2: 8 and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Comparative Example 12)
As tetracarboxylic dianhydride component, A-2 was used as 8.18 g (42 mmol), A-3 was used as 1.63 g (7.5 mmol), and diamine component was used as B-7 as 1.22 g (10 mmol). , B-1 (5.08 g, 25 mmol) and B-3 (6.11 g, 15 mmol) were reacted in NMP (88.96 g) at room temperature for 24 hours to obtain a polyamic acid solution. 228.5 g of NMP was added to 95.8 g of this polyamic acid solution for dilution, 15.1 g of acetic anhydride and 6.4 g of pyridine were added, and the mixture was reacted at 50 ° C. for 3 hours to imidize. The reaction solution was cooled to about room temperature and then poured into 1259.1 ml of methanol to recover the precipitated solid. The solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of soluble polyimide (SPI-3). The number average molecular weight of this polyimide was 18,195, and the weight average molecular weight was 57,063. Moreover, the imidation ratio was 93%. 10.8 g of GBL was added to 1.2 g of this polyimide powder and stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring. After 12 g of this solution was cooled to 23 ° C., 2 g of GBL and 6 g of BCS were added and stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.

(Comparative Example 13)
As tetracarboxylic dianhydride components, 13.2 g (69 mmol) of A-2, 6.54 g (30 mol) of A-3, 8.13 g (40 mmol) of B-1 as a diamine component, and B-6 3.67 g (30 mmol) and 8.77 g (30 mmol) of B-9 were used and reacted at room temperature in 161.8 g of NMP for 24 hours to obtain a polyamic acid solution.
To 34.81 g of this polyamic acid solution, 62.65 g of NMP was added for dilution, and 5.15 g of acetic anhydride and 2.19 g of pyridine were added and reacted at a temperature of 50 ° C. for 3 hours to imidize.
The reaction solution was cooled to about room temperature and then poured into 366.8 ml of methanol to recover the precipitated solid. Further, this solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of polyimide (SPI-4). The number average molecular weight of this polyimide was 12,016, and the weight average molecular weight was 35,126. Moreover, the imidation ratio was 90%.
10.8 g of GBL was added to 1.2 g of this polyimide powder and stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring. After 12 g of this solution was cooled to 23 ° C., 2 g of GBL and 6 g of BCS were added and stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.

(Comparative Example 14)
As a tetracarboxylic dianhydride component, 13.2 g (68 mmol) of A-2, 6.54 g (30 mmol) of A-3, 3.81 g (10 mmol) of B-5 as a diamine component, and B-1 Using 8.13 g (40 mmol) and 7.64 g (50 mmol) of B-6, NMP151.7 g was reacted at room temperature for 24 hours to obtain a polyamic acid solution. 59.61 g of NMP was added to 33.38 g of this polyamic acid solution for dilution, 5.26 g of acetic anhydride and 2.24 g of pyridine were added, and the mixture was reacted at 50 ° C. for 3 hours to imidize.
The reaction solution was cooled to about room temperature and then poured into 351.7 ml of methanol to recover the precipitated solid. Further, the solid was washed several times with methanol and then dried under reduced pressure at a temperature of 100 ° C. to obtain a white powder of polyimide (SPI-5). The number average molecular weight of this polyimide was 10,111, and the weight average molecular weight was 33,653. Moreover, the imidation ratio was 90%.
10.8 g of GBL was added to 1.2 g of this polyimide powder and stirred at a temperature of 50 ° C. for 24 hours. The polyimide was completely dissolved at the end of stirring. After 12 g of this solution was cooled to 23 ° C., 2 g of GBL and 6 g of BCS were added and stirred at a temperature of 50 ° C. for 20 hours. After stirring, the mixture was cooled to 23 ° C. to obtain a uniform liquid crystal aligning agent.

(Comparative Example 15)
As a tetracarboxylic dianhydride component, A-2 6.86 g (35 mmol), A-3 3.27 g (15 mmol), diamine component B-7 2.44 g (20 mmol), B The polyamic acid solution (PAA-2) was obtained by reacting for 3 hours at room temperature in 87.0 g of NMP using 3.04 g (15 mmol) of -1 and 6.11 g (15 mmol) of B-3. The number average molecular weight of this polyamic acid was 15,539, and the weight average molecular weight was 47,210. 10.5 g of NMP and 7.5 g of BCS were added to 8 g of this solution, followed by stirring at room temperature for 20 hours to obtain a uniform liquid crystal aligning agent.
(Comparative Example 16)
SPI-3 and PAA-4 were mixed at a mass ratio of 3: 7 and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.
(Comparative Example 17)
Using 4.05 g (18 mmol) of A-3 as the tetracarboxylic dianhydride component, 5.15 g (18 mmol) of B-11 and 0.75 g (2 mmol) of B-2 as the diamine component, NMP73. The reaction was carried out in 07 g at room temperature for 16 hours to obtain a 12% by mass polyamic acid solution. The number average molecular weight of this polyamic acid was 12,180, and the weight average molecular weight was 25,160. 50 g of this polyamic acid solution was diluted with 115 g of NMP and 50 g of BCS to obtain a polyamic acid solution (PAA-3).

(Comparative Example 18)
As a tetracarboxylic dianhydride component, 9.80 g (50 mmol) of A-2, 9.60 g (44 mmol) of A-3, and 19.8 g (100 mmol) of B-8 as a diamine component, 222 g of NMP, The mixture was reacted at room temperature for 5 hours to obtain a polyamic acid solution (PAA-1). The number average molecular weight of this polyamic acid was 11,153, and the weight average molecular weight was 29,487. 10.5 g of NMP and 7.5 g of BCS were added to 8 g of this solution, followed by stirring at room temperature for 20 hours to obtain a uniform liquid crystal aligning agent.
To 10 g of this solution, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

(Comparative Example 19)
As a tetracarboxylic dianhydride component, 7.15 g (37 mmol) of A-2, 3.00 g (10 mmol) of A-1 as a diamine component, 7.97 g (40 mmol) of B-12, 1 of B-8 .98 g (10 mmol) was used and reacted in 181 g of NMP at room temperature for 16 hours to obtain a 10% by mass polyamic acid solution. The number average molecular weight of this polyamic acid was 12,180, and the weight average molecular weight was 30,160. 100.0 g of this polyamic acid solution was diluted with 230 g of NMP and 100 g of BCS to obtain a polyamic acid solution (PAA-4).
To 10 g of this solution, 0.03 g of P17 was added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.
(Comparative Example 20)
PAA-3 and PAA-4 were mixed at a mass ratio of 2: 8 and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent.

By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film with little film scraping due to rubbing treatment and a small decrease in voltage holding ratio even after being exposed to a backlight for a long time, The obtained liquid crystal display element having a liquid crystal alignment film has excellent reliability, and can be used for LCDs such as large-screen and high-definition liquid crystal televisions and monitors.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-334248 filed on Dec. 26, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (12)

Component (A), a compound having a structure in which a group represented by formula [i] is bonded to an aromatic ring, and component (B), at least one kind selected from the group consisting of polyimide and a polyimide precursor A liquid crystal aligning agent comprising a molecular compound.

(X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)   The liquid crystal aligning agent according to claim 1, wherein X in the formula [i] is a hydrogen atom. The liquid crystal aligning agent according to claim 1 or 2, wherein the component (A) is at least one selected from the group consisting of a compound represented by the following formula [1] and a compound represented by the formula [2].

[Wherein, X ₁ , X ₂ , and X ₃ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y ₁ , Y ₂ , and Y ₃ each independently represent an aromatic ring. Any hydrogen atom of the aromatic ring may be substituted with a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a vinyl group. Z ₁ is a single bond, a saturated hydrocarbon group having 1 to 10 carbon atoms, which may be bonded to all or part of it to form a cyclic structure, and any hydrogen atom may be substituted with a fluorine atom. , —NH—, —N (CH ₃ ) —, or a group represented by the formula [3].

(In the formula, P ₁ and P ₂ are each independently an alkyl group having 1 to 5 carbon atoms, and Q ₁ represents an aromatic ring.)
t ₁ is an integer of 2 to 4, an integer from _{t 2} and _{t 3} are each independently 1 to 3, a and b are each independently 1 to 3 integers. ] The liquid crystal aligning agent according to claim 3, wherein X ₁ in the formula [1] and X ₂ and X ₃ in the formula [2] are hydrogen atoms. The liquid crystal aligning agent according to claim 3 or 4, wherein Y ₁ in the formula [1] and Y ₂ and Y ₃ in the formula [2] are each independently a benzene ring or a pyridine ring. The liquid crystal aligning agent according to claim 1, wherein the component (A) is at least one compound selected from the group consisting of the following compounds.

The liquid crystal aligning agent according to claim 1, wherein the component (A) is at least one compound selected from the group consisting of the following compounds.

  The component (B) is at least one polymer compound selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic dianhydride component and a polyimide obtained by dehydrating and ring-closing the polyamic acid. The liquid crystal aligning agent in any one of Claims 1-7.   Furthermore, the liquid crystal aligning agent in any one of Claims 1-8 containing an organic solvent.   The liquid crystal aligning agent in any one of Claims 1-9 whose mass (concentration of solid content) except an organic solvent is 1-20 mass%.   The liquid crystal aligning film obtained using the liquid crystal aligning agent in any one of Claims 1-10.   A liquid crystal display device comprising the liquid crystal alignment film according to claim 11.