JP5229236B2 - Liquid crystal aligning agent and liquid crystal display element using the same - Google Patents

Description

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

At present, as a liquid crystal alignment film of a liquid crystal display element, a so-called polyimide type liquid crystal alignment treatment agent (also referred to as a liquid crystal alignment agent) mainly composed of a polyimide precursor such as polyamide acid or a solution of soluble polyimide is applied and baked. A liquid crystal alignment film is mainly used.
One of the characteristics required for the liquid crystal alignment film is so-called pre-tilt angle control of the liquid crystal in which the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained at an arbitrary value. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film.

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

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

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

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

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

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

  The object of the present invention is to have a property of increasing the pretilt angle of the liquid crystal when it is used as a liquid crystal alignment film, so that the liquid crystal can be vertically aligned even at a small usage rate, and the liquid crystal alignment treatment agent can be applied. An object of the present invention is to provide a liquid crystal aligning agent that hardly causes precipitation even when a poor solvent is mixed with the liquid. In addition to these characteristics, the voltage holding ratio is high, and even after being exposed to a high temperature for a long time, the residual charge accumulated by the DC voltage is quickly relaxed and exposed to the ultraviolet light of the backlight for a long time. An object of the present invention is to provide a liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio even afterward. It is another object of the present invention to provide a highly reliable liquid crystal display element that can withstand long-term use in a harsh use environment.

The present inventor conducted intensive studies to achieve the above object, and found a novel liquid crystal aligning agent that achieves this. The present invention is based on such knowledge and has the following gist.
(1) A liquid crystal aligning agent comprising the following component (A) and the following component (B).
Component (A): A polyimide obtained by imidizing a polyamic acid having a structural formula of a repeating unit represented by the following formula [1], and having a carboxyl group in the molecule of the polymer.
Component (B): It has one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Amine compound.

（式［１］中、Ｒ_１は４価の有機基であり、Ｒ_２は下記の式［２］を含む２価の有機基である。）

(In Formula [1], R ₁ is a tetravalent organic group, and R ₂ is a divalent organic group including the following Formula [2].)

（式［２］中、Ｘ_１はフェニレンであり、Ｘ_２はシクロヘキシレン又はフェニレンであり、Ｘ_３はシクロヘキシレンである。Ｘ_４は炭素数３〜１２のアルキル基、炭素数３〜１２のアルコキシ基、炭素数３〜１２のフルオロアルキル基、又は炭素数３〜１２のフルオロアルコキシ基である。）
（２）式［２］のＸ_２はシクロヘキシレン又はフェニレンであり、Ｘ_４は炭素数３〜６のアルキル基、炭素数３〜６のアルコキシ基、炭素数３〜６のフルオロアルキル基、又は炭素数３〜６のフルオロアルコキシ基である上記（１）に記載の液晶配向処理剤。
（３）式［１］中のＲ_２が下記の式［３］を含む２価の有機基である上記（１）に記載の液晶配向処理剤。

(In the formula [2], X ₁ is phenylene, X ₂ is cyclohexylene or phenylene, and X ₃ is cyclohexylene. X ₄ is an alkyl group having 3 to 12 carbon atoms and 3 to 12 carbon atoms. An alkoxy group, a C3-C12 fluoroalkyl group, or a C3-C12 fluoroalkoxy group.)
(2) X _{2 in} formula [2] is cyclohexylene or phenylene, and X ₄ is an alkyl group having 3 to 6 carbon atoms, an alkoxy group having 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 6 carbon atoms, or The liquid-crystal aligning agent as described in said (1) which is a C3-C6 fluoro alkoxy group.
(3) type liquid crystal alignment treating agent according to the above [1] R ₂ in is a divalent organic group containing the formula [3] (1).

（式［３］中、ｎは２〜１１の整数であり、１，４−シクロヘキシレンのシス−トランス異性は、トランス異性体である。）
（４）式［１］中のＲ_２が下記の式［４］を含む２価の有機基である上記１に記載の液晶配向処理剤。

(In the formula [3], n is an integer of 2 to 11, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)
(4) The liquid crystal aligning agent according to the above 1, wherein R ₂ in the formula [1] is a divalent organic group containing the following formula [4].

（式［４］中、ｎは２〜１１の整数であり、１，４−シクロヘキシレンのシス−トランス異性は、トランス異性体である。）
（５）（Ａ）成分が、式［１］で表される繰り返し単位の構造式を有するポリアミド酸をイミド化させた重合体であり、該重合体の有するカルボキシル基の量が、該重合体の繰り返し単位に対する平均値で０．１〜３個である上記（１）〜（４）のいずれかに記載の液晶配向処理剤。
（６）（Ａ）成分が、前記の式［１］で表される繰り返し単位の構造式中、繰り返し単位の一部又は全てが下記の式［５］で表される単位を有する構造式を有するポリアミド酸をイミド化させた重合体であり、該重合体の有するカルボキシル基の量が、該重合体の繰り返し単位に対する平均値で０．１〜３個である上記（１）〜（５）のいずれかに記載の液晶配向処理剤。

(In the formula [4], n is an integer of 2 to 11, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)
(5) The component (A) is a polymer obtained by imidizing polyamic acid having the structural formula of the repeating unit represented by the formula [1], and the amount of the carboxyl group of the polymer is The liquid-crystal aligning agent in any one of said (1)-(4) which is 0.1-3 by the average value with respect to the repeating unit.
(6) In the structural formula of the repeating unit represented by the formula [1], the component (A) has a structural formula in which a part or all of the repeating units have a unit represented by the following formula [5]. (1) to (5) above, wherein the polymer has an imidized polyamic acid, and the amount of carboxyl groups of the polymer is 0.1 to 3 on average with respect to the repeating unit of the polymer. The liquid-crystal aligning agent in any one of.

（式中、Ｒ_３は４価の有機基であり、Ｒ_４は２価の有機基であり、Ｒ_３又はＲ_４の少なくとも一方はカルボキシル基を有する。）
（７）（Ｂ）成分が、下記の式［６］で表されるアミン化合物である上記（１）〜（６）のいずれかに記載の液晶配向処理剤。

(In the formula, R ₃ is a tetravalent organic group, R ₄ is a divalent organic group, and at least one of R _{3 and} R ₄ has a carboxyl group.)
(7) The liquid-crystal aligning agent in any one of said (1)-(6) whose (B) component is an amine compound represented by following formula [6].

（式［６］中、Ｙ_１は脂肪族炭化水素基又は非芳香族環式炭化水素基を有する２価の有機基であり、Ｙ_２は窒素含有芳香族複素環である）
（８）（Ｂ）成分が、下記の式［７］で表されるアミン化合物である上記（１）〜（６）のいずれかに記載の液晶配向処理剤。

(In Formula [6], Y ₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₂ is a nitrogen-containing aromatic heterocycle)
(8) The liquid-crystal aligning agent in any one of said (1)-(6) whose (B) component is an amine compound represented by following formula [7].

（式［７］中、Ｙ_３は炭素数１〜１０の２価の脂肪族炭化水素基又は非芳香族環式炭化水素基であり、Ｙ_４は、単結合、若しくは−Ｏ−、−ＮＨ−、−Ｓ−、−ＳＯ_２−又は炭素数１〜１９の２価の有機基である。また、Ｙ_３とＹ_４が有する炭素原子の合計は１〜２０である。Ｙ_５は窒素含有芳香族複素環である。）
（９）（Ｂ）成分が、式［７］におけるＹ_３、Ｙ_４、及びＹ_５がそれぞれ下記に記載の基又は環から選択される組み合わせからなるアミン化合物である上記（８）に記載の液晶配向処理剤。

(Wherein [7], _{Y 3} is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, _{Y 4} represents a single bond or -O -, - NH —, —S—, —SO ₂ — or a divalent organic group having 1 to 19 carbon atoms, and the total number of carbon atoms of Y ₃ and Y ₄ is 1 to 20. Y ₅ contains nitrogen. Aromatic heterocycle.)
(9) The component (B) is an amine compound comprising a combination in which Y ₃ , Y ₄ , and Y ₅ in the formula [7] are each selected from the following groups or rings: Liquid crystal aligning agent.

However, Y ₃ represents a linear or branched alkylene group having 1 to 10 carbon atoms, unsaturated alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane Ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricyclo One selected from the group consisting of an eicosane ring, a tricyclodecosan ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, and an adamantane ring;
Y ₄ is a single bond, —O—, —NH—, —S—, —SO ₂ —, a hydrocarbon group having 1 to 19 carbon atoms, —CO—O—, —O—CO—, —CO—NH. _{-, - NH-CO -,} - CO -, - CF 2 -, - C (CF 3) 2 -, - CH (OH) -, - C (CH 3) 2 -, - Si (CH 3) 2 - , —O—Si (CH ₃ ) ₂ —, —Si (CH ₃ ) ₂ —O—, —O—Si (CH ₃ ) ₂ —O—, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane Ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, 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, One selected from the group consisting of an enothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, and a morpholine ring;
Y ₅ is a pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine From the group consisting of ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thioline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, and acridine ring One kind to be chosen.
(10) Any one of (1) to (9) above, wherein the component (B) is contained in an amount of 0.01 to 2 moles per 1 mole of the carboxyl group of the component (A) polyimide. Liquid crystal aligning agent as described in.
(11) Liquid crystal aligning agent in any one of said (1)-(10) obtained by mixing the organic solvent containing the polyimide of (A) component, and the amine compound of (B) component under a heating. .
(12) A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of (1) to (11).
(13) A liquid crystal display device having the liquid crystal alignment film according to (12).

The liquid crystal aligning agent of the present invention can be obtained by a relatively simple method. Moreover, the liquid crystal aligning agent of this invention has the characteristic which enlarges the pretilt angle of a liquid crystal, when it makes it a liquid crystal aligning film, and can align a liquid crystal vertically even with a small usage rate. Also, precipitation is unlikely to occur when a poor solvent is mixed in the liquid crystal aligning agent coating solution. Furthermore, it is possible to obtain a liquid crystal alignment film that has a high voltage holding ratio and can quickly relieve residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time.
Moreover, the liquid crystal display element which has the liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention becomes the thing excellent in reliability, and can be suitably utilized for a high-definition liquid crystal television etc. with a large screen.

The liquid-crystal aligning agent of this invention is a polymer which imidated the polyamic acid which has structural formula of the repeating unit represented by said Formula [1] which is (A) component, and is a molecule | numerator of this polymer A polyimide having a carboxyl group therein (hereinafter also referred to as a specific polyimide), and (B) component having one amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and It is a liquid crystal aligning agent containing an amine compound (hereinafter also referred to as a specific amine compound) in which an amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. In the present specification, the above-described amino group (—NH ₂ ) is synonymous with a primary amino group, and is hereinafter also referred to as a primary amino group.

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

  In the liquid crystal aligning agent of the present invention, the amino group in the specific amine compound forms a salt with the carboxyl group in the specific polyimide, or water or alcohol is removed from the carboxyl group or carboxy ester group in the specific polyimide. It is thought that it has an amide bond accompanied by separation or a bonding reaction involving ring opening of the imide group with respect to the imide group in the specific polyimide. Furthermore, it is considered that the amino group that forms a salt with the carboxyl group in the specific polyimide forms an amide bond by elimination of water in the baking step in producing the liquid crystal alignment film. As a result, the liquid crystal aligning agent of the present invention is efficiently combined with the specific amine compound and the specific polyimide in the obtained liquid crystal alignment film despite the simple means of mixing in an organic solvent. Think.

  On the other hand, the nitrogen-containing aromatic heterocycle in the specific amine compound functions as an electron hopping site due to its conjugated structure, and therefore promotes the movement of charges in the obtained liquid crystal alignment film. In addition, when the liquid crystal alignment film is used, the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide are linked by an electrostatic interaction such as salt formation or hydrogen bond, so that the specific carboxyl group in the specific polyimide is identified. Charge transfer occurs between the nitrogen-containing aromatic heterocycle in the amine compound. Furthermore, since the specific amine compound is chemically bonded to the specific polyimide, the charge transferred to the nitrogen-containing aromatic heterocyclic moiety can efficiently move within and between the polyimide molecules.

  As described above, the liquid crystal aligning agent of the present invention has the property of increasing the pretilt angle of the liquid crystal when formed into a liquid crystal alignment film, and can align the liquid crystal vertically even with a small use ratio. In addition, precipitation is unlikely to occur when a poor solvent is mixed in the liquid crystal aligning agent coating solution. Furthermore, it is possible to obtain a liquid crystal alignment film that has a high voltage holding ratio and can quickly relieve residual charges accumulated by a DC voltage even after being exposed to a high temperature for a long time.

<(A) component / specific polyimide>
In the present invention, the specific polyimide as the component (A) is a polymer obtained by imidizing polyamic acid having the structural formula of the repeating unit represented by the formula [1], and a carboxyl group is present in the molecule of the polymer. The structure is not particularly limited as long as it has polyimide. Since this polyimide can be obtained relatively simply by using tetracarboxylic dianhydride and diamine as raw materials, a polyamic acid having a structural formula of a repeating unit represented by the formula [1] is imidized. Polymers are preferred.

（式［１］中、Ｒ_１は４価の有機基であり、Ｒ_２は下記の式［２］を含む２価の有機基である。）

(In Formula [1], R ₁ is a tetravalent organic group, and R ₂ is a divalent organic group including the following Formula [2].)

In the formula [2], X ₁ is phenylene, X ₂ is cyclohexylene or phenylene, and X ₃ is cyclohexylene. Phenylene or cyclohexylene may have a substituent as necessary. X ₄ is an alkyl group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, or A fluoroalkoxy group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms. The alkyl group, fluoroalkyl group, alkoxy group, and fluoroalkoxy group may be linear or branched, but are preferably linear, and may have an appropriate substituent.

The bonding position of the amino group in the benzene ring of the main chain in the formula [2] is not limited. As specific examples, with respect to Z ₁ in the following formula [8], positions 2, 3; positions 2, 4; positions 2, 5; positions 2, 6; positions 3, 4; 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, the positions 2, 4, 2, 5, and 3, 5 are preferable. Considering the ease of diamine synthesis, the positions 2, 4 or 2, 5 are preferred.

Among the formulas [2], X ₁ is preferably 1,4-phenylene. X ₂ is preferably 1,4-phenylene or 1,4-cyclohexylene, more preferably 1,4-phenylene or 1,4-trans-cyclohexylene. 4-trans-cyclohexylene is preferred. X ₃ is preferably 1,4-cyclohexylene, particularly 1,4-trans-cyclohexylene.

  Preferred specific examples of the structure represented by the formula [2] of the present invention are as follows. In addition, n in the following formulas [9] to [12] is each independently preferably an integer of 2 to 11, particularly preferably an integer of 2 to 6. Moreover, the cis-trans isomerism of 1,4-cyclohexylene in the formula is a trans isomer.

式［２］の構造を含む特定ポリイミドは、下記の式［１３］に示す特定ジアミンを原料に用いることで得ることができる。

The specific polyimide including the structure of the formula [2] can be obtained by using a specific diamine represented by the following formula [13] as a raw material.

（式［１３］中、Ｘ_１、Ｘ_２、Ｘ_３及びＸ_４は式［２］で定義したものと同定義である。）
式［１３］で表されるジアミンを製造する方法は特に限定されないが、好ましい方法としては以下の方法が挙げられる。

(In formula [13], X ₁ , X ₂ , X ₃ and X ₄ have the same definitions as those defined in formula [2].)
Although the method of manufacturing diamine represented by Formula [13] is not specifically limited, The following method is mentioned as a preferable method.

（式［１４］中、Ｘ_１、Ｘ_２、Ｘ_３及びＸ_４は式［２］で定義したものと同定義である。）
式［１４］のジニトロ化合物を合成し、通常の方法でニトロ基を還元してアミノ基に変換することで得られる。
式［１４］のジニトロ化合物は、下記の式［１５］で表わされる水酸基含有化合物とジニトロクロロベンゼンなどとの反応により得ることができる。

(In Formula [14], X ₁ , X ₂ , X ₃ and X ₄ have the same definitions as those defined in Formula [2].)
It is obtained by synthesizing a dinitro compound of the formula [14] and reducing the nitro group to convert it to an amino group by a usual method.
The dinitro compound of the formula [14] can be obtained by reacting a hydroxyl group-containing compound represented by the following formula [15] with dinitrochlorobenzene or the like.

（式［１５］中、Ｘ_１、Ｘ_２、Ｘ_３及びＸ_４は式［２］で定義したものと同定義である。）
式［３］、［４］、及び［９］〜［１２］の構造を含む特定ポリイミドも、上記と同様の手法で得ることができる。
式［１］中においてＲ_１及びＲ_２はそれぞれ１種類であっても、それぞれ異なったＲ_１及びＲ_２を有し、繰り返し単位として異なった複数種を組み合わせたものでもよい。
液晶のプレチルト角を大きくするという目的では、式［２］の構造を１モル％以上用いることが好ましい。液晶を垂直に配向させるという目的では、１０モル％以上用いることが好ましく、より好ましくは、１５モル％以上である。式［３］、［４］、及び［９］〜［１２］の構造を含む特定ポリイミドも同様である。
特定ポリイミドは、上記ポリアミド酸をイミド化させる際のイミド化率を通常は１００％未満に制御することで得ることができる。

(In formula [15], X ₁ , X ₂ , X ₃ and X ₄ have the same definitions as those defined in formula [2].)
The specific polyimide containing the structures of the formulas [3], [4], and [9] to [12] can also be obtained by the same method as described above.
In the formula [1], R ₁ and R ₂ may be one type or may have different R ₁ and R ₂ and a combination of different types as repeating units.
For the purpose of increasing the pretilt angle of the liquid crystal, it is preferable to use 1 mol% or more of the structure of the formula [2]. For the purpose of aligning the liquid crystal vertically, it is preferably used in an amount of 10 mol% or more, more preferably 15 mol% or more. The same applies to the specific polyimide containing the structures of the formulas [3], [4], and [9] to [12].
The specific polyimide can be obtained by controlling the imidization ratio when imidating the polyamic acid to usually less than 100%.

  The specific polyimide can also be obtained by imidizing a polyamic acid containing a structural unit represented by the following formula [5] in the repeating unit in the structural formula of the repeating unit represented by the formula [1]. it can.

（式［５］中、Ｒ_３は４価の有機基であり、Ｒ_４は２価の有機基であり、Ｒ_３又はＲ_４の少なくとも一方はカルボキシル基を有する。）
その際、イミド化率は１００％であってもよい。
特定ポリイミドのイミド化率は、高い電圧保持率が得られるという理由から２０％以上であることが好ましく、より好ましくは４０％以上である。
特定ポリイミド中のカルボキシル基の量は、本発明の効果が効率よく得られるという理由から、ポリイミドとしての構造式の繰り返し単位に対する平均値で０．１〜３個であることが好ましく、より好ましくは０．３〜２．０個であり、特に好ましくは０．５〜１．８個である。この場合の繰り返し単位とは、イミド化されていないアミド酸基を含んでいる単位も合わせたものである。例えば、式［１］で表される繰り返し単位からなるポリアミド酸をイミド化して得られるポリイミドの場合、イミド化率が１００％未満では下記の式［１６ａ］〜［１６ｄ］の構造の組合せから構成されることが考えられるが、上記でカルボキシル基の量を算出する場合の繰り返し単位には式［１６ａ］〜［１６ｄ］の全てが含まれる。

(In Formula [5], R ₃ is a tetravalent organic group, R ₄ is a divalent organic group, and at least one of R ₃ or R ₄ has a carboxyl group.)
At that time, the imidization ratio may be 100%.
The imidization ratio of the specific polyimide is preferably 20% or more, and more preferably 40% or more, because a high voltage holding ratio can be obtained.
The amount of the carboxyl group in the specific polyimide is preferably 0.1 to 3, more preferably an average value with respect to the repeating unit of the structural formula as a polyimide, because the effect of the present invention can be obtained efficiently. 0.3 to 2.0, and particularly preferably 0.5 to 1.8. The repeating unit in this case is a combination of units containing an imidized amic acid group. For example, in the case of a polyimide obtained by imidizing a polyamic acid composed of a repeating unit represented by the formula [1], when the imidization ratio is less than 100%, the composition is composed of a combination of the structures of the following formulas [16a] to [16d]. Although it is conceivable that the repeating unit for calculating the amount of carboxyl group as described above includes all of the formulas [16a] to [16d].

In the present invention, the amount of the carboxyl group in the specific polyimide (hereinafter also referred to as the average value of the carboxyl group) is determined as the sum of P in (i) below and Q in (ii).
(I) Average value of carboxyl group derived from unimided amide acid with respect to repeating unit of structural formula as polyimide: P
(Ii) Average value of the carboxyl groups contained in R ₃ and R ₄ of the formula [5] with respect to the repeating unit of the structural formula as polyimide: Q
And P of said (i) is computable from following formula (1) using imidation rate (z). In addition, the imidation rate (z) is calculated | required from <measurement of an imidation rate> mentioned later, for example.

P = 2 × (1−z / 100) (1)

On the other hand, Q in the above (ii) is an average value of the carboxyl group contained in R ₃ of the formula [5] with respect to the repeating unit of the structural formula as polyimide: Q ₁ and the polyimide of the carboxyl group contained in R ₄ mean values for structural formula repeating units as: determined by the sum of the Q _2.
Said R < ₃ >, R < ₄ > is the tetracarboxylic dianhydride residue (R < ₃ >) and the diamine residue (R < ₄ >) which are 1 part or all of the raw material used in order to obtain a specific polyimide, respectively.
Therefore, the above Q ₁ uses the molar fraction of the tetracarboxylic dianhydride represented by the following formula [V1] in the total molar amount of the tetracarboxylic dianhydride used to obtain the specific polyimide, It is calculated from the following equation (2).

（式［Ｖ１］中、Ｒ_３は式［５］で定義したものと同じである。）
Ｑ_１＝β_１×Ｗ_１／Ｗ_２ （２）
ここで、β_１はＲ_３に含有されるカルボキシル基の個数を表し、Ｗ_１は式[Ｖ１]のテトラカルボン酸二無水物のモル量であり、Ｗ_２はテトラカルボン酸二無水物の合計モル量を表す。
また、上記Ｑ_２は、特定ポリイミドを得るために用いるジアミンの合計モル量における下記の式[Ｖ２]で表されるジアミンのモル分率を用いて、下記の式（３）から算出される。

(In formula [V1], R ₃ is the same as defined in formula [5].)
Q ₁ = β ₁ × W ₁ / W ₂ (2)
Here, β ₁ represents the number of carboxyl groups contained in R ₃ , W ₁ is the molar amount of tetracarboxylic dianhydride of the formula [V1], and W ₂ is the total of tetracarboxylic dianhydrides. Represents molar amount.
Further, the Q ₂ are using the molar fraction of the diamine represented by the formula [V2] below in the total molar amount of the diamine used to obtain a specific polyimide, is calculated from the following equation (3).

（式[Ｖ２]中、Ｒ_３は式［５］で定義したものと同じある。）
Ｑ_２＝β_２×Ｗ_３／Ｗ_４ （３）
ここで、β_２はＲ_４に含有されるカルボキシル基の個数を表し、Ｗ_３は式[Ｖ２]で表されるジアミンのモル量であり、Ｗ_４はジアミンの合計モル量を表す。
かくして、カルボキシル基の量は下記の式（４）で求められる。
特定ポリイミド中のカルボキシル基の量
＝Ｐ＋Ｑ_１＋Ｑ_２
＝２×（１−ｚ／１００）＋β_１×Ｗ_１／Ｗ_２＋β_２×Ｗ_３／Ｗ_４ （４）

(In formula [V2], R ₃ is the same as defined in formula [5].)
Q ₂ = β ₂ × W ₃ / W ₄ (3)
Here, β ₂ represents the number of carboxyl groups contained in R ₄ , W ₃ represents the molar amount of the diamine represented by the formula [V2], and W ₄ represents the total molar amount of the diamine.
Thus, the amount of the carboxyl group can be obtained by the following formula (4).
Amount of carboxyl group in specific polyimide = P + Q ₁ + Q ₂
= 2 × (1−z / 100) + β ₁ × W ₁ / W ₂ + β ₂ × W ₃ / W ₄ (4)

In the present invention, adjustment of the amount of carboxyl group in the specific polyimide,
(1) Means for adjusting by controlling the imidization rate,
(2) Means of adjusting by the number of carboxyl groups contained in R ₃ or R ₄ of formula [5] and the ratio of formula [5] in the structural formula of the repeating unit represented by formula [1],
Any of these may be used. Furthermore, the means (1) and (2) can be used in combination.

From the viewpoint of the degree of freedom in selecting R ₁ and R ₂ in the formula [1], the means (1) is preferable. From the viewpoint of the degree of freedom in selecting the imidization ratio of the specific polyimide, the means (2) is preferable. The means (2) is preferred from the viewpoint that the specific amine compound is not likely to be detached or the polyimide chain is cleaved by the imidization reaction in the baking step when the liquid crystal alignment film is produced.

When adjusting the amount of carboxyl groups in a particular polyimide by means of (1), R ₁ and R ₂ in the formula [1] is not particularly limited. In addition, R ₁ and R ₂ may each be one type in the formula [1], or may have different R ₁ and R ₂ structures, and a combination of different types as repeating units.
Specific examples of R ₁ in the formula [1] are as follows.

これらのうち、Ａ−６、Ａ−１６、Ａ−１８〜Ａ−２２、Ａ−２５、Ａ−３７、又はＡ−３８は、イミド化率が高いポリイミドであっても有機溶媒に対する溶解性が高いので好ましい。

Among these, even if A-6, A-16, A-18 to A-22, A-25, A-37, or A-38 is a polyimide with a high imidation rate, it has solubility in an organic solvent. It is preferable because it is high.

Moreover, more than 10 mole% of R ₁ is, if having an alicyclic structure or aliphatic structure as A-1 to A-25 preferably improved voltage holding ratio. In particular, those in which R ₁ is used in combination of two types selected from A-1, A-16, and A-19 are preferable because a liquid crystal alignment film with faster charge relaxation can be obtained.
In the formula [1], R ₂ may contain an organic group other than the structure represented by the formula [2]. Specific examples are as follows.

(In B-112 and B-113, Q represents any of —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, —NH—. )
When the amount of the carboxyl group in the specific polyimide is adjusted by the means (2), the structure is not particularly limited as long as it has a carboxyl group in either R ₃ or R ₄ . The number of carboxyl groups is preferably 0 to 2 for R ₃ and R ₄ (however, either one of R ₃ or R ₄ has at least one carboxyl group).

From the viewpoint of easy synthesis of polyimide and availability of raw materials, it is preferable that R ₄ has a carboxyl group. Examples of R ₄ having a carboxyl group include B-102 to B-113. At that time, R ₄ may also be used in combination of two or more even one having a carboxyl group. Further, when R ₄ has a carboxyl group, the structure of R ₃ is not particularly limited, and specific examples include A-1 to A-45.

<Production method of specific polyimide>
Although the manufacturing method of the specific polyimide which is (A) component used for this invention is not specifically limited, In general, the tetracarboxylic acid component which consists of 1 type or multiple types chosen from tetracarboxylic acid and its derivative (s), and 1 type Alternatively, a method is used in which a polyamic acid having a structural formula of a repeating unit represented by the formula [1] is synthesized by reacting with a diamine component composed of a plurality of types of diamine compounds, and the polyamic acid is imidized to form a polyimide. It is done.
In that case, the obtained polyamic acid can be made into a homopolymer (homopolymer) or a copolymer (copolymer) by appropriately selecting a tetracarboxylic acid component and a diamine component as raw materials.
The term “tetracarboxylic acid” and derivatives thereof as used herein refers to tetracarboxylic acid, tetracarboxylic acid dihalide, or tetracarboxylic dianhydride. Of these, tetracarboxylic dianhydrides are preferred because of their high reactivity with diamine compounds.

Below, the specific example of the manufacturing method of specific polyimide is shown.
For example, a tetracarboxylic acid component containing at least one selected from tetracarboxylic dianhydrides represented by the formula [18] and a diamine component containing at least one selected from diamine compounds represented by the formula [19] Polyamide acid can be obtained by polycondensation reaction in an organic solvent such as N-methylpyrrolidone, N, N′-dimethylacetamide, N, N′-dimethylformamide, and γ-butyrolactone.

なお、式［１８］中のＲ_１は、式［１］で定義したものと同じである。

R ₁ in formula [18] is the same as that defined in formula [1].

なお、式［１９］中のＲ_２は、式［１］で定義したものと同じである。
その際、反応温度は、−２０℃から１５０℃の任意の温度を選択することができるが、好ましくは−５℃から１００℃の範囲である。
テトラカルボン酸成分を構成する化合物の合計モル数と、ジアミン成分を構成するジアミン化合物の合計モル数との比は、好ましくは０．８：１〜１．２：１、特に好ましくは０．９：１〜１．１：１である。このモル比が１．０に近いほど生成する重合体の重合度は大きくなる。

R ₂ in formula [19] is the same as that defined in formula [1].
In this case, the reaction temperature can be selected from -20 ° C to 150 ° C, preferably in the range of -5 ° C to 100 ° C.
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: 1 to 1.2: 1, particularly preferably 0.9. : 1 to 1.1: 1. The closer this molar ratio is to 1.0, the greater the degree of polymerization of the polymer produced.

In addition, in order to obtain a polyamic acid having a unit represented by the formula [5] in a part or all of the repeating units in the structural formula of the repeating unit represented by the formula [1], a carboxyl group is added to R _1. A tetracarboxylic dianhydride having a diamine and / or a diamine having a carboxyl group at R ₂ may be used.
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 -20-250 degreeC, Preferably it is 0-180 degreeC. 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 used in this case 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 the polyamic acid is soluble, 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, and water. 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).

<(B) component / specific amine compound>
The specific amine compound as the component (B) used in the present invention has one amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the amino group is a divalent aliphatic hydrocarbon group or a non-valent group. It is an amine compound bonded to an aromatic cyclic hydrocarbon group.
Since this specific amine compound has only one amino group in the molecule, problems such as polymer precipitation and gelation may occur when preparing the liquid crystal aligning agent or during storage of the liquid crystal aligning agent. Can be avoided.
The primary amino group contained in the specific amine compound contains a divalent aliphatic hydrocarbon group or non-aromatic hydrocarbon in the molecule from the viewpoint of salt formation with the specific polyimide and the ease of the bonding reaction. It must be bonded to an aromatic cyclic hydrocarbon group.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1-20, more preferably 1-15, and still more preferably 1-10.
Specific examples of the divalent non-aromatic cyclic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane Ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, Examples include a decahydronaphthalene ring, a norbornene ring, an adamantane ring, and the like. Preferably, it is a ring having 3 to 20 carbon atoms, more preferably a ring having 3 to 15 carbon atoms, and still more preferably a non-aromatic cyclic hydrocarbon group having 3 to 10 carbon atoms. It is.
The nitrogen-containing aromatic heterocyclic ring contained in the specific amine compound is an aromatic cyclic hydrocarbon containing at least one structure selected from the group consisting of the following formula [20a], formula [20b] and formula [20c]. And more preferably 1 to 4.

（式中、Ｚ_２は炭素数１〜５の直鎖または分岐アルキル基である。）

(In the formula, Z ₂ is a linear or branched alkyl group having 1 to 5 carbon atoms.)

Specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, List triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Can do. Furthermore, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom.
A more preferred specific amine compound is an amine compound represented by the following formula [6].

（式中、Ｙ_１は脂肪族炭化水素基又は非芳香族環式炭化水素基を有する２価の有機基であり、Ｙ_２は窒素含有芳香族複素環である。）
式［６］において、Ｙ_１は脂肪族炭化水素基又は非芳香族環式炭化水素基を有する２価の有機基であれば特に限定されない。

(In the formula, Y ₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₂ is a nitrogen-containing aromatic heterocyclic ring.)
In the formula [6], Y ₁ is not particularly limited as long as Y ₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Preferred Y ₁ in the formula [6] is a divalent organic group having one kind selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. . Examples of the non-aromatic cyclic hydrocarbon group include the structures described above. Y ₁ is more preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring. , Cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring, adamantane ring and the like. Y ₁ is particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

In addition, —CH ₂ — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y ₁ is —O—, —NH—, —CO—O—. , -O-CO -, - CO -NH -, - NH-CO -, - CO -, - S -, - S (O) 2 -, - CF 2 -, - C (CF 3) 2 -, - _{C (CH 3) 2 -,} - Si (CH 3) 2 -, - O-Si (CH 3) 2 -, - Si (CH 3) 2 -O -, - O-Si (CH 3) 2 -O -It may be replaced by a divalent cyclic hydrocarbon group or a heterocyclic ring. Further, the hydrogen atom bonded to any carbon atom is a linear or branched alkylene group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group.

  Specific examples of the divalent cyclic hydrocarbon group include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, cyclobutane ring, cyclopentane ring. , Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring Ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like.

  Specific examples of the divalent heterocyclic ring include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole. Ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, tinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole Ring, acridine ring and the like.

Y ₂ in the formula [6] is a nitrogen-containing aromatic heterocycle, and similarly to the above, at least one structure selected from the group consisting of the formula [20a], the formula [20b], and the formula [20c]. Is an aromatic cyclic hydrocarbon containing Specific examples thereof include the structure described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring , A phenazine ring and a phthalazine ring are preferable.

From the viewpoint of ease of electrostatic interaction such as salt formation and hydrogen bonding between the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide, Y ₁ is represented by the formula [20a] and formula contained in Y _2. It is preferably bonded to a substituent not adjacent to [20b] and formula [20c].
Furthermore, the carbon atom of the nitrogen-containing aromatic heterocyclic ring that is Y ₂ in Formula [6] may have a halogen atom and / or a substituent of an organic group, and the organic group includes an oxygen atom, a sulfur atom, You may contain hetero atoms, such as a nitrogen atom.

A preferred combination of Y ₁ and Y ₂ in the formula [6], Y ₁ is selected from the group consisting of non-aromatic cyclic hydrocarbon group having an aliphatic hydrocarbon group and having 3 to 20 carbon atoms having 1 to 20 carbon atoms Y ₂ is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole A ring, a quinoxaline ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocycle of Y ₂ may have a halogen atom and / or a substituent of an organic group, and the organic group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
A more preferred specific amine compound is an amine compound represented by the following formula [7].

（式中、Ｙ_３は炭素数１〜１０の２価の脂肪族炭化水素基又は非芳香族環式炭化水素基であり、Ｙ_４は、単結合、若しくは−Ｏ−、−ＮＨ−、−Ｓ−、−ＳＯ_２−又は炭素数１〜１９の２価の有機基である。また、Ｙ_３とＹ_４が有する炭素原子の合計は１〜２０である。Ｙ_５は窒素含有芳香族複素環である。）

(Wherein Y ₃ is a C 1-10 divalent aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group, and Y ₄ is a single bond, or —O—, —NH—, — S—, —SO ₂ — or a divalent organic group having 1 to 19 carbon atoms, and the total number of carbon atoms of Y ₃ and Y ₄ is 1 to 20. Y ₅ is a nitrogen-containing aromatic complex. Ring.)

Y ₃ in Formula [7] is a C 1-10 divalent aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclo Octane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, trio A cycloeicosane ring, a tricyclodecosan ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring, and the like. More preferably, a linear or branched alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane And a ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, and an adamantane ring. Particularly preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.

—CH ₂ — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y ₃ is —O—, —NH—, —CO—O—, — O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, —C ( _{CH 3) 2 -, - Si} (CH 3) 2 -, - O-Si (CH 3) 2 -, - Si (CH 3) 2 -O -, - O-Si (CH 3) 2 -O-, It may be replaced with a divalent cyclic hydrocarbon group or a heterocyclic ring. Further, the hydrogen atom bonded to any carbon atom is a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom, It may be replaced with a hydroxyl group. The cyclic hydrocarbon group and the heterocyclic ring referred to here have the same meaning as defined for Y ₁ in the formula [6].
Y ₄ in Formula [7] is a single bond, —O—, —NH—, —S—, —SO ₂ — or a divalent organic group having 1 to 19 carbon atoms. The divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. Specific examples of such Y ₄ are given below.

For example, a single bond, —O—, —NH—, —S—, —SO ₂ —, a hydrocarbon group having 1 to 19 carbon atoms, —CO—O—, —O—CO—, —CO—NH—, _{-NH-CO -, - CO -} , - CF 2 -, - C (CF 3) 2 -, - CH (OH) -, - C (CH 3) 2 -, - Si (CH 3) 2 -, - O—Si (CH ₃ ) ₂ —, —Si (CH ₃ ) ₂ —O—, —O—Si (CH ₃ ) ₂ —O—, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane Ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane Ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, 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, an oxadiazole ring, an acridine ring, an oxazole ring, piperazine ring, piperidine ring, dioxane ring, morpholine ring and the like. Y ₄ may contain two or more of these.

Specific examples including two or more of these include —NH—CH ₂ —, —NH—C ₂ H ₄ —, —NH—C ₃ H ₆ —, —NH—C ₄ H ₈ —, —S—CH _{2. -, - S-C 2 H} 4 -, - S-C 3 H 6 -, - S-C 4 H 8 -, - O-CH 2 -, - O-C 2 H 4 -, - O-C 3 _{H 6 -, - O-C} 4 H 8 -, - NH-CO-CH 2 -, - NH-CO-C 2 H 4 -, - NH-CO-C 3 H 6 -, - NH-CO-C _{4 H 8 -, - CO-} CH 2 -, - CO-C 2 H 4 -, - CO-C 3 H 6 -, - CO-C 4 H 8 -, - CO-NH-CH 2 -, - CO _{-NH-C 2 H 4 -,} - CO-NH-C 3 H 6 -, - CO-NH-C 4 H 8 -, - NH-CH 2 -CH (CH 3) -, - NH-C 2 H ₄ -CH _(CH 3) - , —NH—C ₃ H ₆ —CH (CH ₃ ) —, —NH—C ₄ H ₈ —CH (CH ₃ ) —, —S—CH ₂ —CH (CH ₃ ) —, —S—C ₂ H _{4 -CH (CH 3) -,} - S-C 3 H 6 -CH (CH 3) -, - S-C 4 H 8 -CH (CH 3) -, - O-CH 3 -CH (CH 3) _{-, - O-C 2 H} 4 -CH (CH 3) -, - O-C 3 H 6 -CH (CH 3) -, - O-C 4 H 8 -CH (CH 3) -, - NH- _{CO-CH 2 -CH (CH 3} ) -, - NH-CO-C 2 H 4 -CH (CH 3) -, - NH-CO-C 3 H 6 -CH (CH 3) -, - NH-CO _{-C 4 H 8 -CH (CH 3} ) -, - CH (OH) -CH 2 -, - CH (OH) -C 2 H 4 -, - CH (OH) -C 3 H 6 -, - CH ( OH) -C _{4 H 8 -, - CH (} CH 2 OH) -CH 2 -, - CH (CH 2 OH) -C 2 H 4 -, - CH (CH 2 OH) -C 3 H 6 -, - CH (CH 2 _{OH) -C 4 H 8 -,} - NH-CH (CH 2 OH) -CH 2 -, - CO-NH-CH (CH 2 OH) -CH 2 -, - NH-CO-CH (CH 2 OH) _{-CH 2 -, - CO-CH} (CH 2 OH) -CH 2 -, - S-CH (CH 2 OH) -CH 2 -, - O-CH (CH 2 OH) -CH 2 -, - CH ( _{N (CH 3) 2) -} , - C 6 H 4 -O -, - C 6 H 4 -NH -, - C 6 H 4 -CO-NH -, - C 6 H 4 -NH-CO -, - C ₆ H ₄ —CO—, —C ₆ H ₄ —CH 2 —, —C ₆ H ₄ —S— and the like can be mentioned.

Y ₅ in Formula [7] is a nitrogen-containing aromatic heterocyclic ring, and is the same as the definition of Y _{2 in} Formula [6]. Specific examples thereof include the same structure as Y ₂ described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring , A phenazine ring, or a phthalazine ring is preferable.

From the viewpoint of ease of electrostatic interaction such as salt formation or hydrogen bonding between the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide, Y ₄ is a formula [20a] or formula included in Y _5. It is preferably bonded to a carbon atom that is not adjacent to [20b] or formula [20c].
Further, the carbon atom of the nitrogen-containing aromatic heterocyclic ring represented by Y ₅ in the formula [7] may have a halogen atom and / or a substituent of an organic group, and the organic group is an oxygen atom, a sulfur atom, nitrogen You may contain hetero atoms, such as an atom.

In the preferable combination of Y ₃ , Y ₄ and Y ₅ in the formula [7], Y ₃ is a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclo A heptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring or an adamantane ring, and Y ₄ is a single bond, having 1 to 10 carbon atoms. A linear or branched alkylene group, -O-, -NH-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CO-, -S-, -SO _{2 -, - CF 2 -,} - C (CF 3) 2 -, - Si (CH 3) 2 -, - O-Si (CH 3) 2 -, - Si (CH 3) 2 -O -, - O -Si _{CH 3) 2 -O -, -} CH (OH) -, - NH-CH 2 -, - NH-C 2 H 4 -, - NH-C 3 H 6 -, - NH-C 4 H 8 -, - _{S-CH 2 -, - S} -C 2 H 4 -, - S-C 3 H 6 -, - S-C 4 H 8 -, - O-CH 2 -, - O-C 2 H 4 -, - O—C ₃ H ₆ —, —O—C ₄ H ₈ —, —NH—CO—CH ₂ —, —NH—CO—C ₂ H ₄ —, —NH—CO—C ₃ H ₆ —, —NH _{-CO-C 4 H 8 -,} - CO-CH 2 -, - CO-C 2 H 4 -, - CO-C 3 H 6 -, - CO-C 4 H 8 -, - CO-NH-CH 2 _{-, - CO-NH-C} 2 H 4 -, - CO-NH-C 3 H 6 -, - CO-NH-C 4 H 8 -, - NH-CH 2 -CH (CH 3) -, - NH -C ₂ H ₄ -CH (CH _{3 -, - NH-C 3 H} 6 -CH (CH 3) -, - NH-C 4 H 8 -CH (CH 3) -, - S-CH 2 -CH (CH 3) -, - S-C 2 H ₄ —CH (CH ₃ ) —, —S—C ₃ H ₆ —CH (CH ₃ ) —, —S—C ₄ H ₈ —CH (CH ₃ ) —, —O—CH ₃ —CH (CH _{3) ) -, - O-C 2} H 4 -CH (CH 3) -, - O-C 3 H 6 -CH (CH 3) -, - O-C 4 H 8 -CH (CH 3) -, - NH _{-CO-CH 2 -CH (CH 3} ) -, - NH-CO-C 2 H 4 -CH (CH 3) -, - NH-CO-C 3 H 6 -CH (CH 3) -, - NH- _{CO-C 4 H 8 -CH (} CH 3) -, - CH (OH) -CH 2 -, - CH (OH) -C 2 H 4 -, - CH (OH) -C 3 H 6 -, - CH (OH) _{C 4 H 8 -, - CH} (CH 2 OH) -CH 2 -, - CH (CH 2 OH) -C 2 H 4 -, - CH (CH 2 OH) -C 3 H 6 -, - CH (CH _{2 OH) -C 4 H 8 -} , - NH-CH (CH 2 OH) -CH 2 -, - CO-NH-CH (CH 2 OH) -CH 2 -, - NH-CO-CH (CH 2 OH _{) -CH 2 -, - CO-} CH (CH 2 OH) -CH 2 -, - S-CH (CH 2 OH) -CH 2 -, - O-CH (CH 2 OH) -CH 2 -, - CH _{(N (CH 3) 2)} -, - C 6 H 4 -O -, - C 6 H 4 -NH -, - C 6 H 4 -CO-NH -, - C 6 H 4 -NH-CO-, _{-C 6 H 4 -CO -, -} C 6 H 4 -CH 2 -, - C 6 H 4 -S-, cyclopropane ring, cyclobutane ring, cyclopentane , Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring , Anthracene ring, phenanthrene ring, phenalene ring, and Y ₅ is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring Quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring, or phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocycle of Y ₅ may have a halogen atom and / or a substituent of an organic group, and the organic group is a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.

In a more preferable combination of Y ₃ , Y ₄ and Y ₅ in the formula [7], Y ₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, A cycloheptane ring, a norbornene ring, or an adamantane ring, and Y ₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, —O—. CO -, - CO-NH - , - NH-CO -, - CO -, - S -, - S (O) 2 -, - CH (OH) -, - NH-CH 2 -, - S-CH 2 _{-, - O-CH 2 -} , - O-C 2 H 4 -, - NH-CO-CH 2 -, - CO-CH 2 -, - CO-NH-CH 2 -, - NH-CH 2 -CH _{(CH 3) -, - S} -CH 2 -CH (CH 3) -, - O-CH 3 -CH _{(CH 3) -, - NH} -CO-CH 2 -CH (CH 3) -, - CH (OH) -CH 2 -, - CH (OH) -C 2 H 4 -, - CH (CH 2 OH) _{-CH 2 -, - NH-CH} (CH 2 OH) -CH 2 -, - CO-NH-CH (CH 2 OH) -CH 2 -, - NH-CO-CH (CH 2 OH) -CH 2 - _{, -CO-CH (CH 2 OH} ) -CH 2 -, - S-CH (CH 2 OH) -CH 2 -, - O-CH (CH 2 OH) -CH 2 -, - CH (N (CH 3 _{) 2) -, - C 6} H 4 -O -, - C 6 H 4 -NH -, - C 6 H 4 -CO-NH -, - C 6 H 4 -NH-CO -, - C 6 H 4 _{-CO -, - C 6 H 4} -CH2 -, - C 6 H 4 -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohex Ring, cycloheptane ring, a norbornene ring, adamantane ring, a benzene ring, a naphthalene ring, tetrahydronaphthalene ring, azulene ring, an indene ring, a fluorene ring, an anthracene ring, phenanthrene ring, or phenalene ring, Y _5, pyrrole ring, Imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring, or phthalazine ring It is. The carbon atom of the nitrogen-containing aromatic heterocycle of Y ₅ may have a halogen atom and / or a substituent of an organic group, and the organic group is a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.

In a more preferable combination of Y ₃ , Y ₄ and Y ₅ in the formula [7], Y ₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or a cyclohexane ring. Y ₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms, —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—, — NH—CO—, —CO—, —CH (OH) —, —NH—CH ₂ —, —S—CH ₂ —, —O—CH ₂ —, —NH—CO—CH ₂ —, —CO—CH _{2 -, - CO-NH-} CH 2 -, - NH-CH 2 -CH (CH 3) -, - S-CH 2 -CH (CH 3) -, - O-CH 3 -CH (CH 3) - _{, -NH-CO-CH 2 -CH} (CH 3) -, - CH (OH) -CH 2 -, - CH ( _{H) -C 2 H 4 -,} - CH (CH 2 OH) -CH 2 -, - NH-CH (CH 2 OH) -CH 2 -, - CO-NH-CH (CH 2 OH) -CH 2 - _{, -NH-CO-CH (CH} 2 OH) -CH 2 -, - CO-CH (CH 2 OH) -CH 2 -, - S-CH (CH 2 OH) -CH 2 -, - O-CH ( _{CH 2 OH) -CH 2 -,} - CH (N (CH 3) 2) -, - C 6 H 4 -O -, - C 6 H 4 -NH -, - C 6 H 4 -CO-NH-, _{-C 6 H 4 -NH-CO -} , - C 6 H 4 -CO -, - C 6 H 4 -CH2 -, - C 6 H 4 -S-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane Ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydro A Futaren ring, fluorene ring, or an anthracene ring, Y ₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or benzimidazole It is a ring. The carbon atom of the nitrogen-containing aromatic heterocycle of Y ₅ may have a halogen atom and / or a substituent of an organic group, and the organic group is a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.

A particularly preferred combination of Y ₃ , Y ₄ and Y ₅ in the formula [7] is that Y ₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclobutane ring, or a cyclohexane ring, and Y ₄ is a simple group. A bond, —O—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CH (OH) —, a benzene ring, a naphthalene ring, a fluorene ring, or an anthracene ring. Y ₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring. The carbon atom of the nitrogen-containing aromatic heterocycle of Y ₅ may have a halogen atom and / or a substituent of an organic group, and the organic group is a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain.
Specific examples of the specific amine compound used in the present invention include M1 to M156 compounds.

  More preferable compounds include M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M108 to M125, M128-M137, M139-M143, M149-M156 are mentioned. More preferable are M6 to M8, M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114 to M116. M118 to M121, M125, M134 to M136, M139, M140, M143, M150, and M152 to M156.

<Liquid crystal alignment agent>
The liquid-crystal aligning agent of this invention is normally obtained by mixing the above-mentioned specific polyimide which is (A) component, and the specific amine compound which is (B) component in an organic solvent. Each of the specific polyimide and the characteristic amine compound to be mixed may be one kind or a plurality of kinds may be used in combination.

  As a mixing method, a reaction solution (specific polyimide solution) obtained by imidizing polyamic acid, which is a precursor of the specific polyimide, may be used. Preferably, the powder of the specific polyimide obtained by purification is used as an organic solvent. The method of adding a specific amine compound to the solution dissolved in (1) is mentioned. The organic solvent used in that case will not be specifically limited if it is a solvent which dissolves specific polyimide. Specific examples of such organic solvents 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 the specific polyimide is dissolved in the organic solvent, the specific polyimide may be heated for the purpose of promoting the dissolution of the specific polyimide. Since the molecular weight of a polyimide may fall when the temperature to heat is too high, the temperature of 30-100 degreeC is preferable. The concentration of the specific polyimide solution is not particularly limited. However, since it is easy to uniformly mix with the specific amine compound, the specific polyimide concentration in the solution is preferably 1 to 20% by mass, more preferably 3 to 15% by mass. Preferably it is 3-10 mass%.
The specific amine compound may be added directly to the solution of the specific polyimide, but it is preferable to add the specific amine compound after forming a solution having a concentration of 0.1 to 10% by mass with an appropriate solvent. As this solvent, the solvent of the specific polyimide mentioned above is mentioned.

  It is preferable to heat after mixing a specific polyimide and a specific amine compound in an organic solvent. By heating, the ratio of the specific amine compound and the specific polyimide that are already bonded in the state of the liquid crystal alignment treatment agent is increased, and the charge can be transferred more efficiently when the liquid crystal alignment film is formed. The temperature in the case of heating after mixing is preferably 10 to 100 ° C, more preferably 20 to 80 ° C.

  The content of the specific amine compound in the liquid crystal aligning agent of the present invention is one of the carboxyl groups contained in the specific polyimide because the effects of the present invention can be obtained efficiently and the stability of the liquid crystal aligning agent is not impaired. 0.01-2 mol times is preferable with respect to molar amount, More preferably, it is 0.05-1 mol times, Especially preferably, it is 0.08-0.8 mol times.

  In addition to the specific polyimide and specific amine compound, the liquid crystal alignment treatment agent of the present invention is a solvent or compound that improves the film thickness uniformity and surface smoothness when the liquid crystal alignment treatment agent is applied as other components, a liquid crystal alignment film A compound that improves the adhesion between the substrate and the substrate may be contained. Other components may be added during the mixing of the specific polyimide and the specific amine compound, or may be added later to these mixed solutions.

Specific examples of the solvent for improving the film thickness uniformity and surface smoothness include the following.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 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 lu-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactyl 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%.

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, EFTOP EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the component (A) contained in the liquid crystal aligning agent. It is.

  Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

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

  It is preferable that the usage-amount of the compound which improves the adhesiveness with these board | substrates is 0.1-30 mass parts with respect to 100 mass parts of the specific polyimide component contained in a liquid-crystal aligning agent, More preferably, 1 ˜20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

In addition to the above, the liquid crystal alignment treatment agent of the present invention changes the polymer components other than the specific polyimide, and the 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. It is also possible to add a target dielectric material or conductive material, and a crosslinkable compound for the purpose of increasing the hardness and density of the film when the liquid crystal alignment film is formed.
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, but a film having no defect is formed, and the film thickness is suitable as a liquid crystal alignment film. It is preferable to set it as 1-20 mass% from the reason that can be obtained, More preferably, it is 2-10 mass%.

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

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

Firing after applying the liquid crystal aligning agent on the substrate can form a coating film by evaporating the solvent at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate. If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 300 nm, more preferably 10-100 nm. When the liquid crystal is aligned horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.

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

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the interpretation of the present invention is not limited to these examples.
The explanation of the abbreviations used in this example is as follows.
(Tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

(Diamine)
DBA: 3,5-diaminobenzoic acid m-PBCH5DABz: 1,3-diamino-5- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxymethyl} benzene m -BPCH5DABz: 1,3-diamino-5- {4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxymethyl} benzene p-PBCH5DABz: 1,4-diamino-5- {4- [Trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxymethyl} benzene PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) Phenoxy] benzene

（特定アミン化合物）
３−ＡＭＰ：３−アミノメチルピリジン
４−ＡＭＰ：４−アミノメチルピリジン
ＡＥＰ：４−（２−アミノエチル）ピリジン
ＡＰＩ：１−（３−アミノプロピル）イミダゾール
２−ＡＭＭＰ：２−（アミノメチル）−５−メチルピラジン

(Specific amine compounds)
3-AMP: 3-aminomethylpyridine 4-AMP: 4-aminomethylpyridine AEP: 4- (2-aminoethyl) pyridine API: 1- (3-aminopropyl) imidazole 2-AMMP: 2- (aminomethyl) -5-methylpyrazine

（比較化合物）
Ｐｙ：ピリジン
ＡＰ：３−アミノピリジン
ＨＡ：へキシルアミン

(Comparative compound)
Py: pyridine AP: 3-aminopyridine HA: hexylamine

（有機溶媒）
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＢＣＳ：ブチルセロソルブ

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

<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 / 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 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 (JNW-ECA500) by JEOL datum. The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100
In the above formula, x is 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 one NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
<Calculation method of carboxyl group amount>
It was calculated by the method described above.

<Synthesis Example 1>
BODA (4.41 g, 17.6 mmol), DBA (2.86 g, 18.8 mmol) and m-PBCH5DABz (2.11 g, 4.70 mmol) as side chain diamine were mixed in NMP (23.0 g). After reacting at 80 ° C. for 5 hours, CBDA (1.01 g, 5.15 mmol) and NMP (18.0) 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 (20.0 g) and diluting to 6% by mass, acetic anhydride (2.53 g) and pyridine (1.96 g) were added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was put into methanol (270 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 40%, the number average molecular weight was 17,300, and the weight average molecular weight was 46,800. The amount of carboxyl groups in this polyimide is 2.0 with respect to the repeating unit.

<Synthesis Example 2>
BODA (32.28 g, 129.2 mmol), DBA (18.32 g, 120.4 mmol), and m-PBCH5DABz (23.16 g, 51.6 mmol) as side chain diamine were mixed in NMP (172.1 g). After reacting at 80 ° C. for 5 hours, CBDA (8.20 g, 42.0 mmol) and NMP (152.0) 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 (150.0 g) and diluting to 6% by mass, acetic anhydride (16.13 g) and pyridine (12.45 g) are added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was poured into methanol (1900 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (B). The imidation ratio of this polyimide was 80%, the number average molecular weight was 19,700, and the weight average molecular weight was 52,200. The amount of carboxyl groups in this polyimide is 1.1 with respect to the repeating unit.

<Synthesis Example 3>
After adding NMP to the polyamic acid solution (30.2 g) obtained in Synthesis Example 2 and diluting to 6% by mass, acetic anhydride (6.41 g) and triethylamine (2.27 g) were added as an imidization catalyst, and 100 ° C. For 4 hours. The reaction solution was neutralized by adding oxalic acid (2.82 g), and then poured into methanol (350 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 98%, the number average molecular weight was 19,200, and the weight average molecular weight was 51,200. The amount of carboxyl groups in this polyimide is 0.74 with respect to the repeating unit.

<Synthesis Example 4>
BODA (3.90 g, 15.6 mmol), DBA (2.16 g, 14.2 mmol) and m-BPCH5DABz (2.65 g, 6.10 mmol) as side chain diamine were mixed in NMP (18.0 g). After reacting at 80 ° C. for 5 hours, CBDA (0.93 g, 4.74 mmol) and NMP (14.4 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 (30.0 g) and diluting to 6% by mass, acetic anhydride (3.23 g) and pyridine (2.49 g) were added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was poured into methanol (380 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 82%, the number average molecular weight was 17,100, and the weight average molecular weight was 48,400. The amount of carboxyl groups in this polyimide is 1.06 with respect to the repeating unit.

<Synthesis Example 5>
BODA (3.28 g, 13.1 mmol), DBA (2.42 g, 15.9 mmol), and p-PBCH5DABz (2.26 g, 5.03 mmol) as side chain diamine were mixed in NMP (14.0 g). After reacting at 80 ° C. for 5 hours, CBDA (0.72 g, 3.68 mmol) and NMP (11.3 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 (30.1 g) and diluting to 6% by mass, acetic anhydride (3.22 g) and pyridine (2.51 g) were added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was poured into methanol (380 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 80%, the number average molecular weight was 18,400, and the weight average molecular weight was 49,900. The amount of carboxyl groups in this polyimide is 1.1 with respect to the repeating unit.

<Synthesis Example 6>
BODA (15.0 g, 60.0 mmol), DBA (9.74 g, 64.0 mmol) and PCH7DAB (6.09 g, 16.0 mmol) as side chain diamine were mixed in NMP (131 g) at 80 ° C. After reacting for 5 hours, CBDA (3.88 g, 19.8 mmol) and NMP (30 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 (10.0 g) and diluting to 6% by mass, acetic anhydride (1.27 g) and pyridine (0.98 g) were added as an imidization catalyst and reacted at 80 ° C. for 3 hours. It was. This reaction solution was poured into methanol (140 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (F). The imidation ratio of this polyimide was 46%, the number average molecular weight was 20,200, and the weight average molecular weight was 62,500. The amount of carboxyl groups in this polyimide is 1.88 with respect to the repeating unit.

<Synthesis Example 7>
BODA (150.1 g, 600 mmol), DBA (60.9 g, 400 mmol) and PCH7DAB (152.2 g, 400 mmol) as side chain diamine were mixed in NMP (1290 g) and reacted at 80 ° C. for 5 hours. CBDA (38.8 g, 198 mmol) and NMP (320 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 (21.3 g) and pyridine (16.5 g) were added as an imidization catalyst and reacted at 90 ° 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 (G). The imidation ratio of this polyimide was 81%, the number average molecular weight was 20,400, and the weight average molecular weight was 63,000. The amount of carboxyl groups in this polyimide is 0.88 with respect to the repeating unit.

<Example 1>
NMP (9.34 g) was added to the polyimide powder (A) (1.65 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added 10 mass% NMP solution (0.50 g) of 3-AMP (0.050 g as 3-AMP), NMP (3.43 g), and BCS (12.5 g), and 15 hours at 50 ° C. The liquid crystal aligning agent [1] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

<Production of liquid crystal cell>
The liquid crystal aligning agent [1] obtained above was spin-coated on the ITO surface of the substrate with 3 cm × 4 cm ITO electrode, and baked at 80 ° C. for 5 minutes and in a 210 ° C. hot air circulating oven for 1 hour. A polyimide coating was prepared.
This substrate with a liquid crystal alignment film is subjected to a rubbing treatment with a roll diameter 120 mm, a rayon cloth rubbing device under the conditions of a rotation speed of 300 rpm, a roll traveling speed of 20 mm / sec, and an indentation amount of 0.3 mm. Got.
Two substrates with this liquid crystal alignment film were prepared, and a 6 μm bead spacer was sprayed on the surface of one liquid crystal alignment film, and then a sealant was printed thereon. Another substrate was bonded so that the liquid crystal alignment film surface was inside and the rubbing direction was reversed, and then the sealing agent was cured to produce an empty cell. An antiparallel aligned nematic liquid crystal cell was obtained by vacuum injection into this empty cell.

<Evaluation of pretilt angle>
The pretilt angle of the liquid crystal cell produced above was measured at room temperature using a pretilt angle measuring device (ELSICON model: PAS-301). The results are shown in Table 2 described later.
Moreover, when the liquid crystal cell produced similarly to the above except having not rubbed was observed with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Evaluation of voltage holding ratio>
A voltage of 4 V was applied to the liquid crystal cell after the pretilt angle measurement at a temperature of 80 ° C. for 60 μs, the voltage after 16.67 ms and 1667 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio. . The results are shown in Table 3 described later.
<Evaluation of residual charge relaxation>
A DC voltage of 10 V was applied to the liquid crystal cell after measuring the voltage holding ratio for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. The residual charges after 50 seconds and 1000 seconds were measured. For measurement, a 6254 type liquid crystal physical property evaluation apparatus manufactured by Toyo Technica Co., Ltd. was used. The results are shown in Table 4 described later.

<Evaluation after leaving at high temperature>
The liquid crystal cell after the residual charge measurement was left in a high-temperature bath set at 100 ° C. for 7 days, and then the voltage holding ratio and the residual charge were measured. The results are shown in Tables 3 and 4 below.
<Evaluation of voltage holding ratio after UV irradiation>
A voltage of 4 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 after 1667 ms was measured, and the voltage holding ratio was calculated as the voltage holding ratio. Furthermore, after the measurement, the liquid crystal cell was irradiated with ultraviolet rays having a dose of 10 J / cm ² at 365 nm by a desktop UV curing device (HCT3 B28 HEX-1 (manufactured by Sen Special Light Source)), and the voltage was maintained under the same conditions. The rate was measured. The results are shown in Table 5 described later.

<Example 2>
NMP (9.46 g) was added to the polyimide powder (B) (1.67 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added 10 mass% NMP solution (0.50 g) of 3-AMP (0.050 g as 3-AMP), NMP (3.47 g), and BCS (12.5 g), and the mixture was stirred at 50 ° C. for 15 hours. The liquid crystal aligning agent [2] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [2], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Example 3>
NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added 10 mass% NMP solution (0.83 g) of 3-AMP (0.083 g as 3-AMP), NMP (3.14 g), and BCS (12.4 g), and the mixture was stirred at 50 ° C. for 15 hours. The liquid crystal aligning agent [3] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [3], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Example 4>
NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added 10 mass% NMP solution (1.16 g) of 3-AMP (0.116 g as 3-AMP), NMP (2.84 g), and BCS (12.4 g), and 15 hours at 50 ° C. The liquid crystal aligning agent [4] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [4], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Example 5>
NMP (9.29 g) was added to the polyimide powder (B) (1.64 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added 10 mass% NMP solution (1.64 g) of 3-AMP (0.164 g as 3-AMP), NMP (2.38 g), and BCS (12.3 g), and 15 hours at 50 ° C. The liquid crystal aligning agent [5] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [5], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Example 6>
NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added a 10 wt% NMP solution (1.16 g) of 4-AMP (0.116 g as 4-AMP), NMP (2.84 g), and BCS (12.4 g), and 15 hours at 50 ° C. By stirring, a liquid crystal aligning agent [6] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [6], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Example 7>
NMP (9.41 g) was added to the polyimide powder (B) (1.66 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours. A 10 mass% NMP solution (1.16 g) of AEP (0.116 g as AEP), NMP (2.86 g), and BCS (12.5 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours. A liquid crystal aligning agent [7] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [7], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Example 8>
NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours. A 10% by mass NMP solution (1.16 g) of API (0.116 g as API), NMP (2.84 g), and BCS (12.4 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours. A liquid crystal aligning agent [8] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [8], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Example 9>
NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours. To this solution, a 10% by mass NMP solution (1.16 g) of 2-AMMP (0.116 g as 2-AMMP), NMP (2.84 g), and BCS (12.4 g) were added, and the mixture was stirred at 50 ° C. for 15 hours. The liquid crystal aligning agent [9] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [9], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Example 10>
NMP (9.29 g) was added to the polyimide powder (C) (1.64 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added 10 mass% NMP solution (1.64 g) of 3-AMP (0.164 g as 3-AMP), NMP (2.38 g), and BCS (12.3 g), and 15 hours at 50 ° C. By stirring, a liquid crystal aligning agent [10] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [10], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Example 11>
NMP (9.34 g) was added to the polyimide powder (D) (1.65 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added 10 mass% NMP solution (1.16 g) of 3-AMP (0.116 g as 3-AMP), NMP (2.85 g), and BCS (12.4 g), and 15 hours at 50 ° C. By stirring, a liquid crystal aligning agent [11] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [11], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Example 12>
NMP (9.34 g) was added to the polyimide powder (E) obtained in Synthesis Example 5 (1.65 g), and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added 10 mass% NMP solution (1.16 g) of 3-AMP (0.116 g as 3-AMP), NMP (2.84 g), and BCS (12.5 g), and 15 hours at 50 ° C. By stirring, a liquid crystal aligning agent [12] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [12], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Comparative Example 1>
NMP (9.34 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 40 hours. NMP (3.88g) and BCS (12.4g) were added to this solution, and the liquid-crystal aligning agent [13] was obtained by stirring at 50 degreeC for 15 hours. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [13], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Comparative example 2>
NMP (9.24 g) was added to the polyimide powder (C) (1.63 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 40 hours. NMP (3.83g) and BCS (12.2g) were added to this solution, and it stirred at 50 degreeC for 15 hours, and obtained liquid-crystal aligning agent [14]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [14], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Comparative Example 3>
NMP (9.34 g) was added to the polyimide powder (D) (1.65 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 40 hours. NMP (3.88g) and BCS (12.3g) were added to this solution, and it stirred at 50 degreeC for 15 hours, and obtained liquid-crystal aligning agent [15]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [15], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Comparative example 4>
NMP (9.31 g) was added to the polyimide powder (E) (1.65 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 40 hours. NMP (3.88g) and BCS (12.4g) were added to this solution, and it stirred at 50 degreeC for 15 hours, and obtained liquid-crystal aligning agent [16]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [16], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Comparative Example 5>
NMP (9.23 g) was added to the polyimide powder (F) (1.63 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C. for 40 hours. NMP (3.83g) and BCS (12.2g) were added to this solution, and it stirred at 50 degreeC for 15 hours, and obtained liquid-crystal aligning agent [17]. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [17], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Comparative Example 6>
NMP (9.23 g) was added to the polyimide powder (B) (1.63 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours. By adding 10 mass% PMP of NMP solution (1.14 g) (0.114 g as Py), NMP (2.80 g), and BCS (12.3 g) to this solution, and stirring at 50 ° C. for 15 hours. A liquid crystal aligning agent [18] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [18], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Comparative Example 7>
NMP (9.33 g) was added to the polyimide powder (B) (1.65 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours. A 10 mass% NMP solution (1.16 g) of AP (0.116 g as AP), NMP (2.83 g), and BCS (12.3 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours. A liquid crystal aligning agent [19] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [19], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Comparative Example 8>
NMP (9.23 g) was added to the polyimide powder (B) (1.63 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 40 hours. A 10 mass% NMP solution (1.14 g) of HA (0.114 g as HA), NMP (2.78 g), and BCS (12.3 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours. A liquid crystal aligning agent [20] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [20], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Comparative Example 9>
NMP (9.34 g) was added to the polyimide powder (F) (1.65 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added 10 mass% NMP solution (0.50 g) of 3-AMP (0.05 g as 3-AMP), NMP (3.43 g), and BCS (12.4 g), and 15 hours at 50 ° C. The liquid crystal aligning agent [21] was obtained by stirring. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [21], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced like Example 1 was observed with the polarization microscope except having not rubbed, the liquid crystal was not vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

<Comparative Example 10>
NMP (9.34 g) was added to the polyimide powder (G) (1.65 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C. for 40 hours. To this solution was added 10 mass% NMP solution (1.16 g) of 3-AMP (0.116 g as 3-AMP), NMP (2.83 g), and BCS (12.4 g), and 15 hours at 50 ° C. By stirring, a liquid crystal aligning agent [22] was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.
Using the obtained liquid crystal aligning agent [22], a liquid crystal cell was produced in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. In addition, when the liquid crystal cell produced similarly to Example 1 was observed with the polarization microscope except having not rubbed, it was confirmed that the liquid crystal was uniformly vertically aligned.
Further, using the liquid crystal cell produced in the same manner as in Example 1, evaluation of voltage holding ratio, evaluation of relaxation of residual charge, evaluation after standing at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Table 3, Table 4 and Table 5 described later.

The liquid crystal aligning agent of the present invention has the effect of increasing the pretilt angle of the liquid crystal when formed into a liquid crystal aligning film, and can align the liquid crystal vertically even with a small use ratio. Precipitation does not easily occur when a poor solvent is mixed with the coating solution. In addition to these characteristics, the voltage holding ratio is high, and even after being exposed to high temperatures for a long time, the charge accumulated by the DC voltage is quickly relaxed, and after being exposed to the ultraviolet light of the backlight for a long time. However, the liquid crystal aligning agent from which the liquid crystal aligning film which can suppress the fall of a voltage holding rate is obtained is obtained. Furthermore, a highly reliable liquid crystal display element that can withstand long-term use in a harsh use environment can be provided. As a result, it is useful for TN elements, STN elements, TFT liquid crystal elements, and vertical alignment type liquid crystal display elements.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-004992 filed on January 11, 2008 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (13)

The liquid crystal aligning agent characterized by containing the following (A) component and the following (B) component.
Component (A): A polyimide obtained by imidizing a polyamic acid having a structural formula of a repeating unit represented by the following formula [1], and having a carboxyl group in the molecule of the polymer.
Component (B): It has one primary amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Amine compound.

(In Formula [1], R ₁ is a tetravalent organic group, and R ₂ is a divalent organic group including the following Formula [2].)

(In the formula [2], X ₁ is phenylene, X ₂ is cyclohexylene or phenylene, and X ₃ is cyclohexylene. X ₄ is an alkyl group having 3 to 12 carbon atoms and 3 to 12 carbon atoms. An alkoxy group, a C3-C12 fluoroalkyl group, or a C3-C12 fluoroalkoxy group.) X _{2 in the} formula [2] is cyclohexylene or phenylene, and X ₄ is an alkyl group having 3 to 6 carbon atoms, an alkoxy group having 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 6 carbon atoms, or 3 carbon atoms. The liquid-crystal aligning agent of Claim 1 which is a fluoro alkoxy group of -6. The liquid crystal aligning agent according to claim 1, wherein R ₂ in the formula [1] is a divalent organic group containing the following formula [3].

(In the formula [3], n is an integer of 2 to 11, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.) The liquid crystal aligning agent according to claim 1, wherein R ₂ in the formula [1] is a divalent organic group containing the following formula [4].

(In the formula [4], n is an integer of 2 to 11, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)   The component (A) is a polymer obtained by imidizing polyamic acid having the structural formula of the repeating unit represented by the formula [1], and the amount of the carboxyl group of the polymer is the repeating unit of the polymer. The liquid crystal aligning agent according to any one of claims 1 to 4, wherein the average value is 0.1 to 3 for the liquid crystal. In the structural formula of the repeating unit represented by the formula [1], the component (A) has a structural formula in which a part or all of the repeating units have a unit represented by the following formula [5]. The amount of carboxyl groups of the polymer is 0.1 to 3 on an average value with respect to the repeating unit of the polymer. Liquid crystal aligning agent.

(In the formula, R ₃ is a tetravalent organic group, R ₄ is a divalent organic group, and at least one of R _{3 and} R ₄ has a carboxyl group.) (B) A component is an amine compound represented by following formula [6], The liquid-crystal aligning agent in any one of Claims 1-6.

(In Formula [6], Y ₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₂ is a nitrogen-containing aromatic heterocycle) (B) A component is an amine compound represented by following formula [7], The liquid-crystal aligning agent in any one of Claims 1-6.

(Wherein [7], _{Y 3} is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, _{Y 4} represents a single bond or -O -, - NH —, —S—, —SO ₂ — or a divalent organic group having 1 to 19 carbon atoms, and the total number of carbon atoms of Y ₃ and Y ₄ is 1 to 20. Y ₅ contains nitrogen. Aromatic heterocycle.) The liquid crystal aligning agent according to claim 8, wherein the component (B) is an amine compound comprising a combination in which Y ₃ , Y ₄ and Y ₅ in the formula [7] are each selected from the following groups or rings. .
However, Y ₃ represents a linear or branched alkylene group having 1 to 10 carbon atoms, unsaturated alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane Ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricyclo One selected from the group consisting of an eicosane ring, a tricyclodecosan ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, and an adamantane ring;
Y ₄ is a single bond, —O—, —NH—, —S—, —SO ₂ —, a hydrocarbon group having 1 to 19 carbon atoms, —CO—O—, —O—CO—, —CO—NH. _{-, - NH-CO -,} - CO -, - CF 2 -, - C (CF 3) 2 -, - CH (OH) -, - C (CH 3) 2 -, - Si (CH 3) 2 - , —O—Si (CH ₃ ) ₂ —, —Si (CH ₃ ) ₂ —O—, —O—Si (CH ₃ ) ₂ —O—, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane Ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, 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, One selected from the group consisting of an enothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a dioxane ring, and a morpholine ring;
Y ₅ is a pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine From the group consisting of ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thioline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, and acridine ring One kind to be chosen.   The liquid crystal aligning process in any one of Claims 1-9 which contain (B) component in the ratio of 0.01-2 mole times amount with respect to 1 mol amount of the carboxyl group which the polyimide of (A) component has. Agent.   The liquid-crystal aligning agent in any one of Claims 1-10 obtained by mixing the organic solvent containing the polyimide of (A) component, and the amine compound of (B) component under a heating.   The liquid crystal aligning film obtained from the liquid-crystal aligning agent in any one of Claims 1-11.   The liquid crystal display element which has a liquid crystal aligning film of Claim 12.