KR20230027062A - Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element - Google Patents

Abstract

(Ar 은 페닐렌기를 나타내고, Q 는 적어도 1 개의 나프탈렌 고리를 포함하는 2 가의 유기기를 나타내고, Q 와 2 개의 산소 원자의 각각은, 상기 적어도 1 개의 나프탈렌 고리를 구성하는 벤젠 고리 상에서 결합하고, 일방의 산소 원자와 결합하는 벤젠 고리와 타방의 산소 원자와 결합하는 벤젠 고리는 상이하다. 상기 페닐렌기 상의 임의의 수소 원자는, 탄소수 1 ∼ 3 의 알킬기, 탄소수 1 ∼ 3 의 알콕시기, 탄소수 1 ∼ 3 의 불소 함유 알킬기, 탄소수 1 ∼ 3 의 불소 함유 알콕시기 및 불소 원자로 이루어지는 군에서 선택되는 적어도 1 종으로 치환되어 있어도 된다.)The liquid crystal aligning agent containing the polymer (P) containing at least 1 sort(s) chosen from the group which consists of a polyimide precursor obtained using the diamine component containing the diamine (1) represented by following formula (1), and a polyimide.

(Ar represents a phenylene group, Q represents a divalent organic group containing at least one naphthalene ring, Q and each of the two oxygen atoms are bonded on the benzene ring constituting the at least one naphthalene ring, and one The benzene ring bonded to the oxygen atom of and the benzene ring bonded to the other oxygen atom are different. Any hydrogen atom on the phenylene group is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, or a benzene ring of 1 to 3 carbon atoms. It may be substituted with at least one selected from the group consisting of a fluorine-containing alkyl group of 3, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, and a fluorine atom.)

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element

The present invention relates to a liquid crystal display element having a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and the liquid crystal aligning film.

BACKGROUND OF THE INVENTION Liquid crystal display elements are widely used from small applications such as mobile phones and smart phones to relatively large applications such as televisions and monitors. A liquid crystal display element is generally constructed by arranging a pair of electrode substrates so as to face each other with a predetermined gap (several micrometers) between them, and encapsulating a liquid crystal between the electrode substrates. And display in a liquid crystal display element is performed by applying a voltage between the transparent conductive films which comprise each electrode of an electrode substrate. These liquid crystal display elements have an indispensable liquid crystal alignment film in order to control the alignment of liquid crystal molecules.

On the other hand, as a liquid crystal display element, various driving methods having different electrode structures, physical properties of liquid crystal molecules to be used, and the like have been developed. For example, various modes such as a twisted nematic (TN) method, a super twisted nematic (STN) method, a vertical alignment (VA) method, an in-plane switching (IPS) method, and a fringe field switching (FFS) method are known.

Among them, VA (vertical alignment) type liquid crystal display elements have a wide viewing angle, fast response speed, high contrast, and can also eliminate the need for rubbing treatment in terms of production processes. It is widely used mainly for televisions and monitors where demand is high.

International Publication No. 2008/117615 Japanese Unexamined Patent Publication No. 2008-76950

By the way, although the above-mentioned transparent conductive film in a liquid crystal display element is usually formed with the composition (ITO) which has indium oxide as a main component and doped several % of tin oxide to this (ITO), the refractive index is the refractive index of a liquid crystal aligning film. Unlike , it has a high value. For this reason, when it is going to transmit the light from a display light source to an electrode substrate, light will be reflected by the boundary surface of the transparent conductive film and the liquid crystal aligning film in each electrode substrate. As a result, the light transmittance of the electrode substrate cannot be sufficiently obtained, causing a problem that the display luminance is lowered.

In particular, recently, ultra-high resolution panels such as 4K and 8K have been developed, but in these panels, the share of black matrix (BM) and TFT (Thin Film Transistor) increases, and the aperture ratio of the panel decreases. Improvement of the transmittance of the display unit is considered important.

Then, the present inventors studied variously about the formation material in order to raise the refractive index of a liquid crystal aligning film from a viewpoint that the said problem can be solved if the difference of the refractive index of a transparent conductive film and the refractive index of a liquid crystal aligning film is made small. In order to specifically, raise the refractive index of a liquid crystal aligning film, the kind of polymer contained in the liquid crystal aligning agent which forms a liquid crystal aligning film was searched for variously.

As a result, a liquid crystal aligning film having a refractive index approximating the refractive index of the transparent conductive film was obtained by selecting a specific polymer, but on the other hand, the polymer forming the liquid crystal aligning film having a high refractive index has solubility to the solvent component of the liquid crystal aligning agent. Since this is not so good, there is a tendency to be inferior in terms of the storage stability of the liquid crystal aligning agent and the applicability (printability) to the substrate, and it has become clear that there is room for further improvement.

The objective of this invention is the liquid crystal aligning agent which can form the liquid crystal aligning film which the solubility of the containing component of a liquid crystal aligning agent is good, and which has a high refractive index in view of the said situation, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and It is providing the liquid crystal display element which has this liquid crystal aligning film.

As a result of earnestly researching in order to achieve the said subject, this inventor discovered that the liquid crystal aligning agent containing the polymer which has a specific structure is effective in order to achieve the said objective, and came to complete this invention.

This invention contains at least 1 sort(s) chosen from the group which consists of a polyimide precursor obtained using the diamine component containing diamine (1) (henceforth, a specific diamine) represented by following formula (1), and a polyimide. It exists in the liquid crystal display element which has the liquid crystal aligning agent characterized by containing the polymer (P) which does, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film.

[Formula 1]

(Ar represents a phenylene group, Q represents a divalent organic group containing at least one naphthalene ring, Q and each of the two oxygen atoms are bonded on the benzene ring constituting the at least one naphthalene ring, and one The benzene ring bonded to the oxygen atom of and the benzene ring bonded to the other oxygen atom are different. Any hydrogen atom on the phenylene group is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, or a benzene ring of 1 to 3 carbon atoms. It may be substituted with at least one selected from the group consisting of a fluorine-containing alkyl group of 3, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, and a fluorine atom.)

ADVANTAGE OF THE INVENTION According to this invention, the solubility of the containing component of a liquid crystal aligning agent is favorable and the liquid crystal aligning agent which can form the liquid crystal aligning film which has a high refractive index is obtained. Since the liquid crystal aligning film formed from such a liquid crystal aligning agent has a high refractive index, the difference between the refractive index of the transparent conductive film and the refractive index of the liquid crystal aligning film in a liquid crystal display element can be reduced, and a liquid crystal display element excellent in display quality can be obtained. there is.

Although the mechanism by which the said effect of this invention is acquired is not necessarily clear, it is thought that the following is one factor. That is, in the polymer of the present invention, since the naphthalene ring is arranged not at the bonding position of the amino group but at the center of the diamine molecule, the packing property of the polymer is lowered and the solubility is improved, and the refractive index of the liquid crystal alignment film obtained by introduction of the naphthalene ring is thought to have increased.

Hereinafter, although the liquid crystal display element which has the liquid crystal aligning agent of this invention, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film is demonstrated in detail, description of the structural requirements described below is one embodiment of this invention It is an example as , and is not specified by these contents.

In the following description, Boc represents a tert-butoxycarbonyl group. Moreover, as a "halogen atom", a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

(liquid crystal alignment agent)

The liquid crystal aligning agent of this invention contains a polymer (P) and further contains other components as needed.

(Polymer (P))

Polymer (P) contains at least 1 sort(s) chosen from the group which consists of a polyimide precursor obtained using a diamine component, and a polyimide.

The polymer (P) is at least one selected from the group consisting of a polyimide precursor and a polyimide, and may be one component or two or more components.

(diamine component)

A diamine component contains diamine (1) represented by following formula (1).

[Formula 2]

(In the above formula (1), Ar and Q are as defined above, respectively.)

Especially, from the viewpoint of obtaining the effect of the present invention, Q preferably has 10 to 40 carbon atoms, and Q is more preferably a divalent organic group having 10 to 40 carbon atoms represented by the following formula (f).

[Formula 3]

(A ₁ and A ₂ are each independently a naphthalene ring which may have a substituent. X ₁ and X ₂ are each independently a single bond, an oxygen atom or a sulfur atom. Y is a compound having 1 to 8 carbon atoms. It is a divalent organic group containing an oxygen atom or a sulfur atom between the carbon-carbon bonds of an alkylene group or an alkylene group of 1 to 8 carbon atoms, m is an integer of 0 to 2, and n is an integer of 0 or 1. * indicates a bonding hand.)

The naphthalene ring may have a substituent. As a substituent which a naphthalene ring may have, a C1-C4 alkyl group, a C1-C4 alkoxy group, a halogen atom, etc. are mentioned. X ₁ and X ₂ are preferably oxygen atoms.

As a preferable specific example of the diamine (1) represented by the said formula (1), the following formula (d-1) - (d-2) is mentioned.

[Formula 4]

When the polymer (P) contained in the liquid crystal aligning agent of the present invention is applied to the liquid crystal aligning agent for liquid crystal display elements of TN method, STN method, VA method, PSA method, and SC-PVA mode, the above formula (1) In addition to the diamine represented by , it is preferable to include, as a constituent component, diamine (s) having at least one kind selected from the group consisting of partial structures represented by the following formulas (S1) to (S3). In the polymer (P), the diamine (s) may be at least one component selected from the group consisting of a polyimide precursor and a polyimide containing diamine (1) as a component, and constitutes diamine (1). At least 1 type of structural component selected from the group which consists of a polyimide precursor and polyimide different from at least 1 type selected from the group which consists of a polyimide precursor and polyimide contained as a component may be sufficient.

[Formula 5]

In formula (S1), X ¹ and X ² are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON( CH ₃ )-, -N(CH ₃ )CO-, -NH-, -O-, -COO-, -OCO-, -((CH ₂ ) _a1 -A ₁ ) _m1 -, or -(A ₁ - (CH ₂ ) _a1 ) _m1 -[a1 is an integer of 1 to 15, A ₁ represents an oxygen atom, -COO-, or -OCO-, and m1 is an integer of 1 to 2. When m1 is 2, a plurality of a1s are each independent, and a plurality of _A1s are each independent.]. G ¹ and G ² each independently represent a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen atom on the cyclic group is selected from the group consisting of an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, and a fluorine atom. may be substituted with at least one type. m and n are each independently an integer of 0 to 3, and the sum of m and n is 1 to 6. From a viewpoint of improving liquid-crystal orientation, 2-6 are preferable and, as for the sum total of m and n, 2-4 are more preferable. R ¹ represents an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group of 2 to 20 carbon atoms, and any hydrogen atom forming R ¹ may be substituted with a fluorine atom.

Moreover, as a divalent cyclic group in ^G1 and ^G2 , a cyclopropylene group, a cyclohexylene group, and a phenylene group are mentioned. Arbitrary hydrogen atoms on these cyclic groups may be substituted with an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, or a fluorine atom.

[Formula 6]

In formula (S2), X ³ is a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -NH-, -O-, -CH ₂ represents O-, -COO- or -OCO-. R ² represents an alkyl group of 1 to 20 carbon atoms or an alkoxyalkyl group of 2 to 20 carbon atoms, and any hydrogen atom forming R ² may be substituted with a fluorine atom.

In addition, R ² is preferably an alkyl group of 3 to 20 carbon atoms or an alkoxyalkyl group of 2 to 20 carbon atoms from the viewpoint of improving the liquid crystal orientation.

[Formula 7]

In formula (S3), X ⁴ is -CONH-, -NHCO-, -O-, -COO-, -OCO-, -((CH ₂ ) _a1 -A ₁ ) _m1 -, or -(A ₁ -(CH ₂ ) _a1 ) _m1 -[a1 is an integer of 1 to 15, A ₁ represents an oxygen atom, -COO-, or -OCO-, and m1 is an integer of 1 to 2. When m1 is 2, a plurality of a1s are each independent, and a plurality of _A1s are each independent.]. R ³ represents a structure having a steroid skeleton. Further, R ³ preferably has a structure containing a cholestanyl group, a cholesteryl group or a lanostanyl group.

As a preferable specific example of formula (S1), the following formulas [S1-x1] - [S1-x7] are mentioned.

[Formula 8]

In the above formula, R ¹ represents an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group of 2 to 20 carbon atoms. X ^p is -(CH ₂ ) _a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O -, -CH ₂ OCO-, -COO-, or -OCO-. A ₁ is an oxygen atom or -COO-* (provided that the bond attached with "*" bonds to (CH ₂ ) _a2 ), A ₂ is an oxygen atom or *-COO- (provided that "*" is The attached bond represents (CH ₂ ) bonded to _a2 ), a1 and a3 are each independently an integer of 0 or 1, a2 is an integer of 1 to 10, and Cy is 1,4-cyclohexylene group or a 1,4-phenylene group.

As a preferable specific example of the said formula (S3), the following formula [S3-x] is mentioned. In formula [S3-x], X represents formula [X1], formula [X2] or -CH ₂ -O-, and Col represents formula [Col1], formula [Col2] or formula [Col3] and G represents formula [G1], formula [G2], formula [G3] or formula [G4]. In formula, "Me" represents a methyl group. * represents a bonding hand.

[Formula 9]

Preferred diamine (s) having a partial structure represented by the above formulas (S1) to (S3) is preferably a diamine having a partial structure represented by the above formulas (S1) to (S3) and having at least one benzene ring. . Diamine represented by the following formula (d1) or formula (d2) as diamine (s) is mentioned.

[Formula 10]

In formulas (d1) and (d2), Y represents a side chain structure represented by the formulas (S1) to (S3). X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -COO-, -CONH-, -(CH ₂ )m-, -SO ₂ -, -O-(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -CO-(CH ₂ ) _m -CO-, -NH-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -NH-, -SO ₂ -(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -SO ₂ -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, or -COO-(CH ₂ ) _m -OCO-. m is an integer of 1 to 8; In the formula (d2), two Y's may be the same or different.

As a preferable specific example of the diamine of the said formula (d1), the following formula (d1-1) - (d1-18) are mentioned.

[Formula 11]

(n is an integer from 1 to 20.)

[Formula 12]

As diamine represented by the said formula (d2), the structure chosen from the group which consists of following formula (d2-1) - (d2-6) is mentioned.

[Formula 13]

In the above formula, X ^p1 to X ^p8 are -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-. X ^s1 to X ^s4 each independently represent -O-, -COO- or -OCO-. X _a to X _f represent a single bond, -O-, -NH-, or -O-(CH ₂ ) _m -O- (m is an integer of 1 to 8). R ^1a to R ^1h each independently represent an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group of 2 to 20 carbon atoms.

(Preparation of Polymer (P))

The polymer (P) contained in the liquid crystal aligning agent of this invention may be comprised from polyimide which is the imidized thing of the polyimide precursor of 1 component or 2 or more components, and this polyimide precursor. Here, a polyimide precursor is a polymer from which a polyimide can be obtained by imidating, such as a polyamic acid and polyamic acid ester. More preferable specific aspects of the polymer (P) are listed below, but the present invention is not limited thereto.

At least one polymer selected from the group consisting of a polyimide precursor obtained by using the diamine (1) and a diamine component containing the diamine (s), and a polyimide that is an imide of the polyimide precursor (hereinafter, Also referred to as a copolymer);

At least one polymer (p-1) selected from the group consisting of a polyimide precursor obtained by using a diamine component containing the diamine (1) and a polyimide that is an imide of the polyimide precursor, and the diamine ( s) and a mixture with at least one polymer (p-2) selected from the group consisting of a polyimide precursor obtained using a diamine component containing the polyimide precursor and a polyimide that is an imide of the polyimide precursor (hereinafter also referred to as a polymer blend) do), etc.

These copolymers or polymer blends may be used alone or in combination.

The polyamic acid (P), which is the polyimide precursor of the polymer (P), is a diamine component containing the diamine (1) (preferably a diamine component containing diamine (s) in addition to the diamine (1)) and tetra It can be obtained by a polymerization reaction with a carboxylic acid component.

In this case, the amount of diamine (1) used is preferably 1 to 100 mol%, more preferably 1 to 99 mol%, and further 5 to 95 mol%, relative to the diamine component to be reacted with the tetracarboxylic acid component. desirable.

When using diamine (s) in addition to the diamine (1), the amount of diamine (s) used is preferably 1 to 99 mol%, and 1 to 95 mol, based on the tetracarboxylic acid component and the diamine component to be reacted. % is more preferable.

The diamine component used for manufacture of the said polyamic acid (P) may contain diamine (Hereinafter, these are also called other diamine.) other than diamine (1) and diamine (s). Although the example of other diamine is given below, this invention is not limited to these.

p-phenylenediamine, m-phenylenediamine, 4-(2-(methylamino)ethyl)aniline, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and Diamine which has a carboxy group, such as a diamine compound represented by the following formula (3b-1) - a formula (3b-4); 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether; 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-aminophenoxy ) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,2-bis (4-aminophenoxy) ethane, 1,2-bis (4-amino-2-methylphenoxy) ethane, 1 ,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-amino Phenoxy)hexane, 4-(2-(4-aminophenoxy)ethoxy)-3-fluoroaniline, di(2-(4-aminophenoxy)ethyl)ether, 4-amino-4'-( 2-(4-aminophenoxy)ethoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4 ,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7- Diaminonaphthalene, diamine represented by the following formulas (nh-1) to (nh-6), 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4- (4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 1,3-bis(4-aminophenethyl)urea, diamine having a urea bond, meta Diamine having a photopolymerizable group at the terminal such as 2-(2,4-diaminophenoxy)ethyl acrylate, 2,4-diamino-N,N-diallylaniline, the following formulas (R1) to (R5), etc. of diamine having a radical initiating function, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 9,9-bis(4-aminophenyl)fluorene, etc. Diamine having a photosensitizing function, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6- Diaminocarbazole, diamine having a heterocyclic ring such as the following formulas (z-1) to (z-18), diamines having a diphenylamine skeleton such as the following formulas (Dp-1) to (Dp-9), and the following Diamine having a group "-N (Boc)" such as formulas (5-1) to (5-10), the following formula (Ox-1 ) to (Ox-2), diamines having an oxazoline structure, etc., diamines described in International Publication No. 2016/125870, and the like.

[Formula 14]

(In formula (3b-1), A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON( CH ₃ )- or -N(CH ₃ )CO-, m1 and m2 each independently represent an integer of 0 to 4, and m1 + m2 represent an integer of 1 to 4. Formula (3b-2 ), m3 and m4 each independently represent an integer of 1 to 5. In formula (3b-3), A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 represents an integer of 1 to 5 In formula (3b-4), A ³ and A ⁴ are each independently a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO -, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-, and m6 represents an integer of 1 to 4.)

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

(n is an integer from 1 to 6.)

[Formula 19]

[Formula 20]

[Formula 21]

Especially, as other diamines, p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'-dialysis from the viewpoint of obtaining the effect of the present invention preferably. Minodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminobiphenyl, methacrylic acid 2-(2 ,4-diaminophenoxy)ethyl, 2,4-diamino-N,N-diallylaniline, diamines represented by the formulas (R1) to (R5), and formulas (z-1) to (z-18) ), diamines represented by the formulas (5-1) to (5-10), and diamines represented by the formulas (Ox-1) to (Ox-2) are preferable.

When using other diamines in addition to the diamine (1), the amount of the other diamines used is preferably 1 to 99 mol%, more preferably 5 to 95 mol%, based on the total diamine components used am.

When using other diamines in addition to the diamine (1) and diamine (s), the amount of diamine (s) used is preferably 98 mol% or less with respect to the tetracarboxylic acid component and the diamine component to be reacted, and 94 mol% or less is more preferable.

The amount of diamine represented by the above formulas (5-1) to (5-10) is preferably 5 to 40 mol% based on the total amount of diamine components used for production of the polyamic acid (P), more preferably It is 10-40 mol%.

In the liquid crystal display element using the PSA method or the SC-PVA mode, from the viewpoint of increasing the response speed, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, diamine having a photopolymerizable group at the terminal, The diamines represented by the formulas (R1) to (R5) and the diamines represented by the formulas (z-1) to (z-18) can be used at least one in the case of producing the polyamic acid (P), and the amount thereof is used. Silver is preferably 1 to 40 mol%, more preferably 5 to 40 mol%, based on all the diamine components used for production of the polyamic acid (P).

(Tetracarboxylic acid component)

In the case of producing the polyamic acid (P), the tetracarboxylic acid component to be reacted with the diamine component is not only tetracarboxylic dianhydride, but also tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, Alternatively, derivatives of tetracarboxylic dianhydride such as tetracarboxylic acid dialkyl ester dihalide can also be used.

Examples of the tetracarboxylic dianhydride or derivative thereof include aromatic, aliphatic or alicyclic tetracarboxylic dianhydride or derivatives thereof. Here, aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an aromatic ring. Aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it is not necessary to be constituted only of a chain-like hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in part.

Further, alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxyl groups are bonded to an aromatic ring. Moreover, it is not necessary to be comprised only of an alicyclic structure, and may have a chain-like hydrocarbon structure or an aromatic ring structure in part.

Especially, what the said tetracarboxylic dianhydride or its derivative(s) is represented by a following formula (T) is preferable. That is, it is preferable that a polymer (P) contains the tetracarboxylic acid component containing the tetracarboxylic dianhydride represented by Formula (T) as a structural component.

[Formula 22]

However, in Formula (T), X represents a structure selected from the group consisting of the following (x-1) to (x-13).

[Formula 23]

R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, and a fluorine-containing carbon atom of 1 to 6 carbon atoms. represents a monovalent organic group or a phenyl group. R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group. j and k are integers of 0 or 1, and A ₁ and A ₂ are each independently a single bond, ether (-O-), carbonyl (-CO-), ester (-COO- or -OCO- ), a phenylene group, a sulfonyl group (-SO ₂ -) or an amide group (-CONH- or -NHCO-). *1 is a binding hand bonded to one acid anhydride group, and *2 is a bond hand bonded to the other acid anhydride group. In formula (x-13), two A ₂ may be the same as or different from each other.

As more preferable specific examples of the formula (x-1), the following formulas (X1-1) to (X1-6) are exemplified. In the formula, * represents a bonding hand.

[Formula 24]

Preferred specific examples of the above formulas (x-12) and (x-13) include the following formulas (x-14) to (x-29). In the formula, * represents a bonding hand.

[Formula 25]

[Formula 26]

As a preferable specific example of the tetracarboxylic dianhydride represented by the said formula (T) or its derivative(s), X is the said formula (x-1) - (x-7), and (x-11) - (x- 13).

The usage ratio of the tetracarboxylic dianhydride or derivative thereof represented by the formula (T) is preferably 1 mol% or more, more preferably 5 mol% or more, based on 1 mol of all tetracarboxylic acid components used. , 10 mol% or more is more preferable.

The tetracarboxylic dianhydride and its derivative used for manufacture of polyamic acid (P) may contain tetracarboxylic dianhydride other than the said formula (T) or its derivative(s).

Manufacture of a polyamic acid (P) is performed by making the said diamine component and tetracarboxylic-acid component react (condensation polymerization) in a solvent. The solvent is not particularly limited as long as the resulting polymer dissolves therein.

Specific examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, Dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, etc. are mentioned. Moreover, when the solvent solubility of a polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1] - [D-3 ] The solvent represented by can be used.

[Formula 27]

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms).

These solvents may be used alone or in combination. Moreover, even if it is a solvent which does not dissolve a polymer, you may mix with the said solvent and use it in the range in which the produced|generated polymer does not precipitate.

When reacting the diamine component and the tetracarboxylic acid component in a solvent, the reaction can be carried out at any concentration, but the total amount of the diamine component and the tetracarboxylic acid component relative to the reaction solution is preferably 1 to 50% by mass , More preferably, it is 5-30 mass %. At the initial stage of the reaction, a high concentration may be carried out, and then a solvent may be added.

In reaction, it is preferable that ratio of the total number of moles of a diamine component and the total number of moles of a tetracarboxylic acid component is 0.8-1.2. As with conventional polycondensation reactions, the closer this molar ratio is to 1.0, the higher the molecular weight of the specific polymer produced.

The polyamic acid ester, which is a polyimide precursor, is, for example, [I] a method of reacting the polyamic acid obtained by the above synthetic reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with diamine, [III] It can be obtained by a known method such as a method of reacting a tetracarboxylic acid diester dihalide compound with diamine.

[Polyimide]

The polyimide contained in the liquid crystal aligning agent of this invention is a polyimide obtained by ring-closing the said polyimide precursor. In polyimide, the ring closure rate of amic acid groups (also referred to as imidization rate) does not necessarily need to be 100%, and can be arbitrarily adjusted depending on the use or purpose.

As a method of obtaining a polyimide by imidating a polyimide precursor, thermal imidation in which a solution of a polyimide precursor is heated as it is or catalyst imidation in which a catalyst is added to a solution of a polyimide precursor is exemplified. The temperature in the case of thermal imidation of the polyimide precursor in the solution is 100 to 400°C, preferably 120 to 250°C, and it is preferable to carry out the imidization reaction while removing water generated by the reaction to the outside of the system.

Catalytic imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 mole times, preferably 2 to 20 mole times the amount of the amide acid group, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times the amount of the amide acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, and tributylamine trioctylamine, and among these, pyridine is preferable because it has appropriate basicity to advance the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferable because purification after completion of the reaction becomes easy. The imidation rate by catalyst imidation is controllable by adjusting the catalyst amount, reaction temperature, and reaction time.

What is necessary is just to throw in the reaction solution into a solvent and just to precipitate, when collect|recovering the polyimide produced|generated from the reaction solution of imidation of a polyimide precursor. Examples of solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by being put into a solvent can be collected by filtration and then dried by heating or at room temperature under normal pressure or reduced pressure. In addition, the impurities in the polymer can be reduced by re-dissolving the polymer recovered by precipitation in a solvent and repeating the operation of re-precipitation and recovery 2 to 10 times. Examples of the solvent at this time include alcohols, ketone hydrocarbons, and the like, and it is preferable to use three or more solvents selected from among these, since purification efficiency is further increased.

The weight average molecular weight (Mw) of the polyimide precursor and polyimide in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 150,000. Further, the molecular weight distribution (Mw/Mn) expressed as the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, more preferably 10 or less. By existing in such a molecular weight range, favorable orientation of a liquid crystal display element is securable.

<Terminal sealing agent>

When synthesize|combining the polymer (P) in this invention, it is good also as synthesizing an end-capping type|mold polymer using the above tetracarboxylic acid component and a diamine component using a suitable terminal capping agent. The polymer of terminal capping has the effect of the improvement of the film hardness of the liquid crystal aligning film obtained by a coating film, and the improvement of the adhesion|attachment characteristic of a sealing compound and a liquid crystal aligning film.

Examples of the terminal of the polymer (P) in the present invention include an amino group, a carboxy group, an acid anhydride group, an isocyanate group, or derivatives thereof. The said terminal can be obtained by a normal condensation reaction, or by sealing a terminal using the following terminal blocker.

As the terminal blocker, for example, acetic anhydride, maleic anhydride, nadic acid anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, the following formula (m -1) The compound represented by - (m-6), 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoro Acid 1 anhydrides, such as a leuisobenzofuran 1, 3-dione and 4-ethynyl phthalic anhydride;

[Formula 28]

bicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; Chlorocarbonyl compounds, such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride; Aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine , monoamine compounds such as n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; Monoisocyanate compounds, such as ethyl isocyanate, phenyl isocyanate, and naphthyl isocyanate, etc. are mentioned.

The use ratio of the terminal blocker is preferably 0.01 to 20 parts by mole, more preferably 0.01 to 10 parts by mole, based on 100 parts by mole in total of the diamine component to be used.

The content ratio of the polymer (P) in the liquid crystal aligning agent of the present invention is preferably 30 parts by mass or more, more preferably 30 to 100 parts by mass, relative to 100 parts by mass in total of the polymers contained in the liquid crystal aligning agent. 50 to 100 parts by mass is more preferred.

(other ingredients)

The liquid crystal aligning agent of this invention is a liquid composition in which a polymer (P) and other components used as needed are disperse|distributed or melt|dissolved preferably in a suitable solvent, for example.

In the liquid crystal aligning agent of the present invention, polymers other than the polymer (P) (hereinafter also referred to as other polymers) for the purpose of, for example, improving electrical properties, homeotropic alignment, and solution characteristics. may be included.

90 mass parts or less is preferable with respect to 100 mass parts of the total of the polymer contained in a liquid crystal aligning agent, as for the content rate of another polymer, 10-90 mass parts are more preferable, and 20-80 mass parts are still more preferable.

The other polymer is not particularly limited, and examples thereof include polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, and poly(meth). ) main skeletons such as acrylate. Especially, it is preferable that it is at least 1 sort(s) chosen from the group which consists of polyamide, polyurea, polyorganosiloxane, poly(meth)acrylate, and polyester. In addition, you may use other polymers in combination of 2 or more types.

In addition, the liquid crystal aligning agent of this invention may contain components other than the above as needed. As the component, for example, an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a block isocyanate group, a crosslinkable compound having at least one substituent selected from a hydroxyl group and an alkoxy group, and polymerizable unsaturated At least one compound selected from the group consisting of crosslinkable compounds having a group, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film compounds for

Preferred specific examples of the crosslinkable compound include compounds represented by the following formulas (CL-1) to (CL-11).

[Formula 29]

As a compound for adjusting the dielectric constant or electric resistance of a liquid crystal aligning film, the monoamine which has nitrogen-containing aromatic heterocycles, such as 3-picolylamine, is mentioned. When using the monoamine which has a nitrogen-containing aromatic heterocyclic ring, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polymer components contained in a liquid crystal aligning agent, More preferably, it is 0.1-20 mass parts.

Preferable specific examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltriethoxysilane. Propyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxy Silane, 3-ureidopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl Methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, and the like. When using a functional silane compound, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polymer components contained in a liquid crystal aligning agent, More preferably, it is 0.1-20 mass parts.

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if a polymer component melt|dissolves uniformly. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, Dimethylsulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N- Dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)- 2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxy Ethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone (these are collectively referred to as "good solvent") and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide or γ -Butyrolactone is preferred. It is preferable that it is 20-99 mass % of the whole solvent contained in a liquid crystal aligning agent, as for content of a good solvent, 20-90 mass % is more preferable, and it is 30-80 mass % especially preferable.

In addition, the organic solvent contained in the liquid crystal aligning agent is used in combination with a solvent (also referred to as a poor solvent) that improves the coating property at the time of applying the liquid crystal aligning agent and the surface smoothness of the coating film in addition to the above solvent. desirable. Although the specific example of the organic solvent used together is shown below, it is not limited to these.

For example, diisopropyl ether, diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1 ,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3- Ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl Ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate , Propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2 -(2-Ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether, 3-methoxymethylpropionate, 3-ethoxyethylpropionate, 3- Ethyl methoxypropionate, 3-methoxypropylpropionate, 3-methoxybutylpropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-hep) Thanon), etc.

Among them, diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2 - Pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferred.

1-80 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable, as for content of a poor solvent, 10-80 mass % is more preferable, and 20-70 mass % is especially preferable. The type and content of the poor solvent are appropriately selected depending on the application device, application conditions, and application environment of the liquid crystal aligning agent.

Preferable combinations of solvents of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether. , N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4 -Hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone and propylene glycol diacetate, N,N-dimethyllactoamide and diisobutyl ketone, N-methyl-2-pyrrolidone and 3-ethoxyethylpropionate, N-ethyl-2-pyrrolidone and 3-ethoxyethylpropionate, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate, N-ethyl-2-pyrroly Money and dipropylene glycol dimethyl ether, N,N-dimethyl lactoamide and ethylene glycol monobutyl ether, N,N-dimethyl lactoamide and propylene glycol diacetate, N-ethyl-2-pyrrolidone and diethylene glycol diethyl Ether, N,N-dimethyllactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl Ethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone and 4-hydroxy Roxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, N-methyl-2- Pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monomethyl ether Butyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone Diisobutyl ketone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol diacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, and propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-p Rolidone, γ-butyrolactone, propylene glycol monobutyl ether, diisobutyl carbinol, N-methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, N-methyl-2-p Rolidone with propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone with propylene glycol monobutyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone with propylene glycol Monobutyl ether with propylene glycol diacetate, N-ethyl-2-pyrrolidone with propylene glycol monobutyl ether with diisobutyl ketone, N-ethyl-2-pyrrolidone with γ-butyrolactone and diisobutyl ketone , N-ethyl-2-pyrrolidone, N,N-dimethyllactoamide, and diisobutyl ketone.

The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferably 1 to 10 It is the range of mass %. The range of a particularly preferable solid content concentration differs according to the method used when apply|coating a liquid crystal aligning agent to a board|substrate. For example, in the case of the spinner method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. In the case of using the printing method, it is particularly preferable to set the solid content concentration in the range of 3 to 9% by mass, thereby setting the solution viscosity in the range of 12 to 50 mPa·s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration in the range of 1 to 5% by mass, thereby setting the solution viscosity in the range of 3 to 15 mPa·s.

(liquid crystal alignment film/liquid crystal display element)

The liquid crystal aligning film of this invention is obtained from the said liquid crystal aligning agent. Although the liquid crystal aligning film of this invention can be used for a liquid crystal aligning film of a horizontal alignment type or a vertical alignment type, it is a liquid crystal aligning film suitable especially for liquid crystal display elements of vertical alignment types, such as a VA system or a PSA mode mentioned later. The liquid crystal display element of this invention is equipped with the said liquid crystal aligning film.

The liquid crystal display element of this invention is equipped with the liquid crystal aligning film of this invention.

An example of the manufacturing method of the liquid crystal display element of this invention contains process (A), (B), and (C).

Process (A): process of applying the liquid crystal aligning agent of this invention on a pair of board|substrates which have a conductive film, and forming a coating film

Step (B): A step of forming a liquid crystal cell by arranging the liquid crystal molecules so that the coating films face each other through a layer of liquid crystal molecules

Step (C): Step of irradiating light to the liquid crystal cell in a state where a voltage is applied between the conductive films of the pair of substrates

The liquid crystal display element of this invention can be manufactured by the method including the following process (1)-(3) or process (1)-(4), for example.

(1) Process of applying a liquid crystal aligning agent on a substrate

The liquid crystal aligning agent of the present invention is applied to one surface of a substrate on which a patterned transparent conductive film is formed, for example, by a suitable coating method such as a roll coater method, a spin coat method, a printing method, or an inkjet method. Here, the substrate is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to a glass substrate or a silicon nitride substrate. Further, in the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is used for only one substrate, and a material that reflects light such as aluminum can be used for the electrode in this case.

(2) Process of firing the coating film

After application of the liquid crystal aligning agent, for the purpose of preventing liquid drop of the applied alignment agent, etc., preheating (prebaking) is preferably performed first. The prebaking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. And, in order to evaporate the solvent, it is preferable that a further heating (post-bake) process is performed. This post-baking temperature is preferably 80 to 300°C, more preferably 120 to 250°C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 5 to 300 nm, and more preferably 10 to 200 nm.

Although the coating film formed in the said process (1) can be used as a liquid crystal aligning film as it is, you may give an orientation ability provision process with respect to the coating film. Examples of the orientation ability imparting treatment include a rubbing treatment in which a coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and an optical alignment treatment in which polarized or non-polarized radiation is irradiated to the coating film, and the like. can

In the photo-alignment treatment, as the radiation applied to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. In addition, when the radiation used is linearly polarized light or partially polarized light, irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or a combination of these may be performed. In the case of irradiating unpolarized radiation, the direction of irradiation is oblique.

(3) Step of forming a liquid crystal layer

(3-1) In case of VA type liquid crystal display element

As mentioned above, two board|substrates on which the liquid crystal aligning film was formed are prepared, and a liquid crystal is arrange|positioned between the board|substrates of 2 sheets opposingly arranged. Specifically, the following two methods are mentioned. The first method is a conventionally known method. First, the board|substrates of 2 sheets are opposingly arranged with a clearance gap (cell gap) so that each liquid crystal aligning film may oppose. Next, the peripheral portions of the two substrates are bonded together using a sealant, and a liquid crystal composition is injected and filled into the substrate surface and the cell gap partitioned by the sealant to bring them into contact with the film surfaces, and then the injection hole is sealed.

In addition, the second method is a method called ODF (One Drop Fill) method.

For example, ultraviolet curable sealing agent is apply|coated to a predetermined place on one board|substrate among two board|substrates on which the liquid crystal aligning film was formed, and also the liquid crystal composition is dripped at several predetermined points on the liquid crystal aligning film surface. Then, the other board|substrate is bonded together so that the liquid crystal aligning film may oppose, and the liquid crystal composition is pressed and spread|spread on the whole surface of a board|substrate, and it is made to contact a film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing compound. In either case, it is preferable to further remove the flow alignment during liquid crystal charging by slowly cooling to room temperature after heating to a temperature at which the used liquid crystal composition takes an isotropic phase.

The liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and contains a polymerizable compound that polymerizes by at least one of active energy rays and heat between the pair of substrates. A liquid crystal display device (hereinafter, also referred to as a PSA type liquid crystal display device). ) is also preferably used.

Moreover, the liquid crystal aligning agent of this invention has a liquid crystal layer between a pair of board|substrates provided with electrodes, and the polymeric group which superposes|polymerizes by at least one of an active energy ray and heat between said pair of board|substrates is formed. You may use it also for the liquid crystal display element (henceforth SC-PVA mode type|mold liquid crystal display element.) manufactured through the process of arrange|positioning the containing liquid crystal aligning film and applying a voltage between electrodes.

(3-2) In the case of manufacturing a PSA type liquid crystal display element

It is the same as the above (3-1) except for injecting or dropping the liquid crystal composition containing the polymerizable compound. As a polymeric compound, the polymeric compound represented by the following formula (M-1) - (M-7) is mentioned, for example.

[Formula 30]

(3-3) Case of manufacturing SC-PVA mode type liquid crystal display element

After carrying out similarly to the said (3-1), you may employ|adopt the method of manufacturing a liquid crystal display element through the process of irradiating an ultraviolet-ray mentioned later. According to this method, a liquid crystal display element excellent in response speed can be obtained with a small light irradiation amount, similarly to the case of manufacturing the PSA type liquid crystal display element. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group represented by the above formulas (M-1) to (M-7) in a molecule, and the content thereof is It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polymer components, More preferably, it is 1-20 mass parts. Moreover, the said polymeric group may have the polymer used for a liquid crystal aligning agent, and as such a polymer, the polymer obtained by using for reaction the diamine component containing the diamine which has the said photopolymerizable group at the terminal, for example is mentioned. there is.

(4) Step of irradiating ultraviolet rays

The liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates obtained in the above (3-2) or (3-3). The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. Further, as the light to be irradiated, for example, ultraviolet rays and visible rays containing light with a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light with a wavelength of 300 to 400 nm are preferable. As the light source for irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. As an irradiation amount of light, Preferably it is 1,000-200,000 J/m<2>, More preferably, it is 1,000-100,000 J/m<2>.

And a liquid crystal display element can be obtained by bonding a polarizing plate together to the outer surface of a liquid crystal cell. Examples of the polarizing plate bonded to the outer surface of the liquid crystal cell include a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is stretched and oriented is sandwiched between protective films of cellulose acetate or a polarizing plate made of the H film itself. there is.

The liquid crystal display device of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, and smart phones. , It can be used for various display devices such as various monitors, liquid crystal televisions, and information displays. In addition, the polymer composition contained in the liquid crystal aligning agent is a liquid crystal aligning film for retardation films, a liquid crystal aligning film for scanning antennas or liquid crystal array antennas, or a liquid crystal aligning film for transmission scattering type liquid crystal light control elements, or uses other than these, examples For example, it can be used for the protective film of color filters, the gate insulating film of flexible displays, and substrate materials.

Example

Examples The present invention will be specifically described below with reference to examples, but the present invention is not construed as being limited to these examples. The symbol of the compound and the method for measuring each characteristic are as follows.

(tetracarboxylic dianhydride)

DC-1 to DC-3: Compounds represented by the following formulas (DC-1) to (DC-3)

[Formula 31]

(diamine)

DA-1 to DA-11: Compounds represented by the following formulas (DA-1) to (DA-11).

[Formula 32]

The compound represented by formula (DA-1) was synthesized by the synthesis method described in non-patent literature (High Performance Polymers, vol. 31 (9-10), p 1043-1053 (2019)).

The compound represented by formula (DA-2) was synthesized by the synthesis method described in non-patent literature (Separation and Purification Technology, vol. 235, 116218 (2020)).

The compound represented by Formula (DA-3) was synthesized by the synthesis method described in non-patent literature (Polymer Science, Series B: Polymer Chemistry, vol. 60 (3), 273-282 (2018)).

(menstruum)

NMP: N-methyl-2-pyrrolidone

BCS: Butyl cellosolve (ethylene glycol monobutyl ether)

[viscosity]

The measurement was performed using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) at a sample amount of 1.1 mL (milliliter), cone rotor TE-1 (1° 34', R24), and a temperature of 25°C.

[Measurement of Molecular Weight]

It was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101, manufactured by Showa Denko) and a column (GPC KD-803, GPC KD-805, manufactured by Showa Denko).

Column temperature: 50 ℃

Eluent: N,N-dimethylformamide (as an additive, 30 mmol/L (liter) of lithium bromide monohydrate (LiBr H ₂ O), 30 mmol/L of phosphoric acid/anhydrous crystal (o-phosphoric acid), tetrahydro Furan (THF) is 10 mL/L)

Flow rate: 1.0 mL/min

Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

[Synthesis of polyamic acid]

<Synthesis Example 1>

2.05 g (6.0 mmol) of DA-1 and 2.80 g (14.0 mmol) of DA-7 were weighed and put into a 100 mL four-neck flask equipped with a stirrer, and 19.4 g of NMP was added, stirred, and dissolved. While stirring this diamine solution, 4.26 g (19.0 mmol) of DC-1 was added as a tetracarboxylic dianhydride component, 17.0 g of NMP was further added, stirred at 60°C for 15 hours, and polyamic acid (A-1, viscosity : 625 mPa·s, number average molecular weight: 7,094) was obtained.

<Synthesis Examples 2 to 7>

Of the polyamic acids (A-2) to (A-7) shown in Table 1 below by carrying out in the same manner as in Synthesis Example 1, except that the diamine component and the tetracarboxylic dianhydride component were changed to those shown in Table 1 below. got a solution. The viscosity and molecular weight of the obtained polyamic acid are shown in Table 1 below.

[Preparation of liquid crystal aligning agent]

<Example 1>

NMP (6.0 g) and BCS (8.0 g) were added to the solution (6.0 g) of the polyamic acid (A-1) obtained above, stirred at room temperature for 10 hours, and the polyamic acid (A-1) occupied in the liquid crystal aligning agent The concentration of 6 mass % and the density|concentration of NMP obtained the liquid crystal aligning agent (PAA-1) whose density|concentration of 54 mass % and BCS is 40 mass %.

<Examples 2 to 3 and Comparative Examples 1 to 3 and Preparation Example 1>

The liquid crystal aligning agent (PAA-2) shown in following Table 2 - (PAA-7) were obtained by carrying out similarly to Example 1 except having changed the polyamic-acid solution into what is shown in following Table 2.

<Example 4>

NMP (0.6 g) and BCS (1.4 g) were added to the liquid crystal aligning agent (PAA-1) (4.0 g) obtained above, and the concentration of the polyamic acid (A-1) occupied in the liquid crystal aligning agent was stirred at room temperature for 10 hours. 4 mass % and the density|concentration of NMP obtained the liquid crystal aligning agent (PAA-r-1) whose density|concentration of 46 mass % and BCS is 50 mass %.

<Examples 5 to 6 and Comparative Examples 4 to 6>

The liquid crystal aligning agent (PAA-r-2) shown in following Table 3 - (PAA-r-6) were obtained by carrying out similarly to Example 4 except having changed the polyamic-acid solution into what is shown in following Table 3.

<Examples 7 to 9 and Comparative Examples 7 to 9>

The liquid crystal aligning agent (PAA-1) obtained in Example 1 and the liquid crystal aligning agent (PAA-7) obtained in Preparation Example 1 were mixed so that each mass ratio would be 3:7 (PAA-7:PAA-1), It stirred at room temperature for 3 hours, and prepared the liquid crystal aligning agent (PAA-b-1) of Example 7.

Moreover, the liquid crystal of Examples 8-9 and Comparative Examples 7-9 shown in following Table 4 respectively by carrying out similarly to Example 7 except having changed the combination of the liquid crystal aligning agent used to what is shown in following Table 4. Alignment agents (PAA-b-2) to (PAA-b-6) were prepared.

[Solubility of Liquid Crystal Aligning Agent in Poor Solvent]

The liquid crystal aligning agent prepared in the said Examples 4-6 and Comparative Examples 4-6 was left still in the -20 degreeC freezer for 14 hours. Then, it was taken out to room temperature and visually confirmed whether or not polymer solid content had precipitated. A result is shown in Table 5. The case where the polymer was dissolved was set to "○", and the case where the polymer was precipitated was set to "x".

[Measurement of Refractive Index of Liquid Crystal Alignment Film]

After spin-coating the liquid crystal aligning agent prepared in the said Examples 1-3 and Comparative Examples 1-3 to a silicon wafer, and drying for 90 seconds with a 70 degreeC hot plate, baking in a 230 degreeC hot air circulation type oven for 20 minutes It performed and formed the liquid crystal aligning film of 100 nm of film thickness. Next, using a spectroscopic ellipsometer (M-2000, manufactured by J. A. Woollam), fitting by the CAUCHY model was performed, and the refractive index in a wavelength of 250 to 800 nm was measured. A result is shown in Table 6. Table 6 shows the refractive index at a wavelength of 550 nm. The case where the refractive index was 1.630 or more was regarded as "excellent", and the case of less than 1.630 was regarded as "unacceptable".

[Production of Liquid Crystal Alignment Film and Liquid Crystal Cell]

Using the liquid crystal aligning agent prepared in the said Examples 7-9 and Comparative Examples 7-9, the liquid crystal cell was produced as follows.

Each liquid crystal aligning agent is spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm is formed, and dried for 90 seconds with a hot plate at 70 ° C. After carrying out, it baked for 30 minutes with a 230 degreeC hot-air circulation type oven, and the liquid crystal aligning film of 100 nm of film thickness was formed.

Moreover, after spin-coating a liquid crystal aligning agent on the ITO surface in which an electrode pattern is not formed, and drying with a 70 degreeC hot plate for 90 seconds, it bakes in a 230 degreeC hot-air circulation oven for 20 minutes, and a film thickness of 100 The liquid crystal aligning film of nm was formed.

After spread|dispersing a 4 micrometer bead spacer on the liquid crystal aligning film of one board|substrate with respect to said 2 board|substrate, the sealing compound (solvent-type thermosetting type epoxy resin) was printed from it. Then, after making the surface of the other board|substrate on the side where the liquid crystal aligning film was formed inside, and bonding together with the previous board|substrate, the sealing compound was thermosetted and the empty cell was produced. A liquid crystal (MLC-3023, manufactured by Merck & Co., Ltd.) containing a polymerizable compound was injected into the empty cell by a vacuum injection method to prepare a liquid crystal cell.

Then, 10 J/cm<2> of ultraviolet rays which let the filter which cuts out the wavelength of 325 nm or less from the outer side of this liquid crystal cell were irradiated in the state which applied the DC voltage of 15V to this liquid crystal cell. In addition, the illuminance of ultraviolet rays was measured using UV-MO3A manufactured by ORC. Thereafter, for the purpose of inactivating the unreacted polymerizable compound remaining in the liquid crystal cell, ultraviolet rays (UV lamp: FLR40SUV32/ A-1) was irradiated for 30 minutes.

[Evaluation of Vertical Orientation]

Evaluation of the vertical orientation of each liquid crystal cell produced as mentioned above is shown in Table 7. The evaluation method is as follows. Each liquid crystal cell was sandwiched between cross nicol polarizing plates, and the liquid crystal cell was rotated in a state where the backlight was irradiated from the rear, and whether or not the liquid crystal was vertically aligned due to a change in brightness was visually observed. As for the evaluation criteria, the case where the liquid crystal was vertically aligned was "○", and the case where the liquid crystal was not vertically aligned was "x". A result is shown in Table 7.

Claims (15)

A liquid crystal characterized by containing a polymer (P) containing at least one kind selected from the group consisting of polyimide precursors and polyimides obtained using a diamine component containing diamine (1) represented by the following formula (1) orientation agent.

(Ar represents a phenylene group, Q represents a divalent organic group containing at least one naphthalene ring, Q and each of the two oxygen atoms are bonded on the benzene ring constituting the at least one naphthalene ring, and one The benzene ring bonded to the oxygen atom of and the benzene ring bonded to the other oxygen atom are different. Any hydrogen atom on the phenylene group is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, or a benzene ring of 1 to 3 carbon atoms. It may be substituted with at least one selected from the group consisting of a fluorine-containing alkyl group of 3, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, and a fluorine atom.) According to claim 1,
A liquid crystal aligning agent in which Q represents a divalent organic group having 10 to 40 carbon atoms represented by the following formula (f).

(A ₁ and A ₂ are each independently a naphthalene ring which may have a substituent. X ₁ and X ₂ are each independently a single bond, an oxygen atom or a sulfur atom. Y is a compound having 1 to 8 carbon atoms. It is a divalent organic group containing an oxygen atom or a sulfur atom between the carbon-carbon bonds of an alkylene group or an alkylene group of 1 to 8 carbon atoms, m is an integer of 0 to 2, and n is an integer of 0 or 1. * indicates a bonding hand.) According to claim 1 or 2,
The liquid crystal aligning agent which is any diamine chosen from the group which the said diamine (1) consists of following formula (d-1) - (d-2).

According to any one of claims 1 to 3,
The liquid crystal aligning agent in which the said polymer (P) contains as a structural component the diamine (s) which has at least 1 sort(s) chosen from the group which consists of partial structures represented by following formula (S1) - (S3).

(X ¹ and X ² are each independently a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, - N(CH ₃ )CO-, -NH-, -O-, -COO-, -OCO-, -((CH ₂ ) _a1 -A ₁ ) _m1 -, or -(A ₁ -(CH ₂ ) _a1 ) _m1 -[a1 is an integer of 1 to 15, A ₁ represents an oxygen atom, -COO-, or -OCO-, and m1 is an integer of 1 to 2. When m1 is 2, a plurality of a1s are independently G ¹ and ^{G 2} _are each independently a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen atom on the cyclic group is an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxy group of 1 to 3 carbon atoms, and fluorine. may be substituted with at least one member selected from the group consisting of atoms, m and n are each independently an integer of 0 to 3, and the sum of m and n is 1 to 6. R ¹ is 1 to 20 carbon atoms; It represents an alkyl group, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group of 2 to 20 carbon atoms, and any hydrogen atom forming R ¹ may be substituted with a fluorine atom.)

(X ³ is a single bond, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -NH-, -O-, -CH ₂ O-, -COO- or -OCO-. R ² represents an alkyl group of 1 to 20 carbon atoms or an alkoxyalkyl group of 2 to 20 carbon atoms, and any hydrogen atom forming R ² may be substituted with a fluorine atom.)

(X ⁴ is -CONH-, -NHCO-, -O-, -COO-, -OCO-, -((CH ₂ ) _a1 -A ₁ ) _m1 -, or -(A ₁ -(CH ₂ ) _a1 ) _m1 -[a1 is an integer of 1 to 15, A ₁ represents an oxygen atom, -COO-, or -OCO-, and m1 is an integer of 1 to 2. When m1 is 2, a plurality of a1's are each independent, and a plurality of A ₁ are each independent]. R ³ represents a structure having a steroid skeleton.) According to claim 4,
The liquid crystal aligning agent whose said diamine (s) is diamine represented by a following formula (d1) or formula (d2).

(X is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -COO-, -CONH-, -(CH ₂ ) _m -, -SO ₂ -, - O-(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -CO-(CH ₂ ) _m -CO-, -NH-(CH ₂ ) _m -, -NH-(CH ₂ ) _m -NH-, -SO ₂ -(CH ₂ ) _m -, -SO ₂ -(CH ₂ ) _m -SO ₂ -, -CONH-(CH ₂ ) _m -, - represents CONH-(CH ₂ ) _m -NHCO- or -COO-(CH ₂ ) _m -OCO- m is an integer of 1 to 8. Y is each independently represented by the formulas (S1) to (S3) ) represents a substructure of any of ). According to claim 5,
The liquid crystal aligning agent whose diamine represented by the said formula (d1) is any diamine chosen from the group which consists of following formula (d1-1) - (d1-18).

(n is an integer from 1 to 20.)

According to claim 5,
The liquid crystal aligning agent whose diamine represented by the said formula (d2) is any diamine chosen from the group which consists of following formula (d2-1) - (d2-6).

(X ^p1 to X ^p8 are -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O- _{X a} ^{_ _} _{_} ~ _Xf represents a single bond, -O-, -NH-, or -O-(CH ₂ ) _m -O- (m is an integer of 1 to 8.) R ^1a to R ^1h are each independently , which represents an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, or an alkoxyalkyl group of 2 to 20 carbon atoms.) According to any one of claims 1 to 7,
The liquid crystal aligning agent in which the said polymer (P) contains the tetracarboxylic-acid component containing tetracarboxylic dianhydride represented by following formula (T) as a structural component.

(X represents a structure selected from the following (x-1) to (x-13).)

(R ¹ to R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkynyl group of 2 to 6 carbon atoms, and a fluorine-containing carbon atom of 1 to 6 represents a monovalent organic group or a phenyl group, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, j and k are integers of 0 or 1, and A ₁ and A ₂ are each independently , single bond, ether (-O-), carbonyl (-CO-), ester (-COO- or -OCO-), phenylene group, sulfonyl group (-SO ₂ -) or amide group (-CONH- or -NHCO-) *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group. In the formula (x-13), two A ₂ are , which may be the same or different.) According to claim 8,
A liquid crystal aligning agent in which X in the formula (T) is any of (x-1) to (x-7) and (x-11) to (x-13). According to any one of claims 1 to 9,
The liquid crystal aligning agent in which the said diamine (1) is contained 1-100 mol% in all the diamine components of the said polymer (P). According to any one of claims 4 to 9,
The liquid crystal aligning agent in which the said diamine (s) contains 1-99 mol% in all the diamine components of the said polymer (P). The liquid crystal aligning film formed using the liquid crystal aligning agent in any one of Claims 1-11. According to claim 12,
A liquid crystal alignment film for vertical alignment. The liquid crystal display element provided with the liquid crystal aligning film of Claim 12 or 13. The manufacturing method of the liquid crystal display element containing the following process (A), (B), and (C).
Step (A): Step of applying the liquid crystal aligning agent according to any one of claims 1 to 11 on a pair of substrates having a conductive film to form a coating film
Step (B): A step of forming a liquid crystal cell by arranging the coating films to face each other through a layer of liquid crystal molecules
Step (C): Step of irradiating the liquid crystal cell with light in a state where a voltage is applied between the conductive films of the pair of substrates