WO2023074570A1

WO2023074570A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: WO2023074570A1
Application number: PCT/JP2022/039298
Authority: WO
Inventors: 里枝軍司; 佳和原田; 雄介山本; 亮一芦澤; 奈穂国見
Original assignee: 日産化学株式会社
Priority date: 2021-10-28
Filing date: 2022-10-21
Publication date: 2023-05-04
Also published as: JPWO2023074570A1; TW202328409A

Abstract

Provided is a liquid crystal alignment agent capable of forming a liquid crystal alignment film that has little in-plane variations (non-uniformity) in the liquid crystal twist angle, and that demonstrates an excellent layer separation property even when two or more types of polymers are used. Also provided is a liquid crystal display element comprising said liquid crystal alignment film.　The liquid crystal alignment agent is characterized by containing at least one polymer (P) selected from the group consisting of a polyimide precursor obtained by using a diamine component that includes a diamine (0) represented by formula (DA), and a polyimide that is an imidization product of said polyimide precursor. (The definitions of symbols are as stated in the specification.)

Description

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

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, a liquid crystal display element comprising the liquid crystal aligning film, and a novel diamine and polymer suitable for them.

Liquid crystal display elements are used in a wide range of applications, from small applications such as mobile phones and smartphones to relatively large applications such as televisions and monitors. In addition, various driving methods with different electrode structures and physical properties of the liquid crystal molecules used have been developed. -Plane Switching), FFS (Fringe Field Switching), and other liquid crystal display devices using various modes are known. These liquid crystal display elements generally have a liquid crystal alignment film that is indispensable for controlling the alignment state of liquid crystal molecules. Polyamic acid and polyimide are generally used as materials for liquid crystal alignment films because of their excellent properties such as heat resistance, mechanical strength, and affinity with liquid crystals.

Currently, the liquid crystal alignment film that is most widely used industrially is a so-called rubbing alignment treatment in which the surface of a resin film such as polyimide formed on an electrode substrate is rubbed in one direction with a cloth such as cotton, nylon, or polyester. It is made by doing. The rubbing orientation treatment is a useful method that is simple and excellent in productivity. As an alignment treatment method that replaces the rubbing alignment treatment, a photo-alignment treatment method is known in which polarized radiation is applied to impart liquid crystal alignment ability. As the photo-alignment treatment method, a method using a photoisomerization reaction, a method using a photocrosslinking reaction, a method using a photodecomposition reaction, etc. have been proposed (for example, Non-Patent Document 1, Patent Document 1, Patent Document 2).

Japanese Patent Laid-Open No. 9-297313 Japanese Patent Application Laid-Open No. 2004-206091

In recent years, as the performance of liquid crystal display elements has improved, in addition to large-screen, high-definition liquid crystal televisions, it has been applied to in-vehicle applications such as car navigation systems, meter panels, surveillance cameras, and medical camera monitors. is being considered. Therefore, the demand for higher performance, particularly higher definition, of liquid crystal display elements is increasing, and a liquid crystal alignment film capable of further improving various characteristics of liquid crystal display elements is desired.

In addition, as the size of the liquid crystal display element has increased, there has been a problem that the twist angle of the liquid crystal within the plane of the liquid crystal display element varies slightly due to variations in the manufacturing process. Such variations lead to non-uniform brightness in the plane of the liquid crystal display element when black is displayed, leading to deterioration of the quality of the liquid crystal display element.

Furthermore, from the viewpoint of simultaneously satisfying the various properties described above, it is possible to mix two or more types of polymers having different properties. polymer moves to the upper layer, so-called layer separation does not function sufficiently, and a product that fully satisfies the required requirements may not be obtained.

The present invention has been made in view of the above circumstances, and when the variation (non-uniformity) of the twist angle of the liquid crystal in the plane of the liquid crystal alignment film is small and two or more types of polymers are used Another object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal aligning film with high layer separability, and a liquid crystal display element having the liquid crystal aligning film.

As a result of intensive research to achieve the above object, the present inventors found that a liquid crystal aligning agent containing a polymer using a novel diamine having a specific structure is effective for achieving the above object. We found a certain thing and came to complete the present invention.

The present invention provides at least one selected from the group consisting of a polyimide precursor obtained using a diamine component containing a diamine (0) represented by the following formula (D _A ) and a polyimide that is an imidized product of the polyimide precursor. A liquid crystal aligning agent characterized by containing a polymer (P) of No., a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal aligning film.

(Z ₁ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms, and the above alkyl group, alkenyl group, or A hydrogen atom of the alkynyl group may be substituted with a monovalent group Any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded may be substituted with a monovalent group.
A represents a divalent organic group (a) in which any carbon-carbon bond in an alkylene group having 4 to 10 carbon atoms satisfies either of the following conditions (1) and (2). In the following conditions (1) and (2), *1 is bonded to a carbon atom possessed by an alkylene group, and the carbon-carbon bond is a carbon-carbon bond forming the main chain of the polymer (P). selected from
(1) "*1-N(Boc)-*1" is inserted between two or more carbon-carbon bonds.
(2) "*1-N(Boc)-C(=O)-N(R)-*1" is inserted between one or more carbon-carbon bonds. R represents a hydrogen atom or a monovalent organic group. Boc represents a tert-butoxycarbonyl group. )
In addition, in this invention, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom. Boc represents a tert-butoxycarbonyl group.

According to the present invention, the liquid crystal that has a small variation (non-uniformity) in the twist angle of the liquid crystal in the plane of the liquid crystal alignment film and that can obtain high layer separation even when two or more types of polymers are used. A liquid crystal aligning agent forming an alignment film, a liquid crystal aligning film obtained from the liquid crystal aligning agent, a high-performance liquid crystal display element provided with the liquid crystal aligning film, and a novel diamine and polymer used for their production can get.

Although the mechanism by which the above effects of the present invention are obtained is not necessarily clear, it is estimated as follows. Due to the oxyaniline structure contained in the diamine (0) of the present invention, a liquid crystal alignment film having a small variation in the twist angle of the liquid crystal can be obtained. It is considered that the above effect was obtained because the hydrophobicity of the Boc group makes it easy to be unevenly distributed on the membrane surface, thereby achieving high layer separation.

<Specific diamine>
The liquid crystal aligning agent of the present invention is, as described above, a polyimide precursor obtained using a diamine component containing a diamine (0) represented by the following formula (D _A ) (also referred to as a specific diamine in the present invention) and at least one polymer (P) selected from the group consisting of polyimide which is an imidized product of the polyimide precursor.

In the above formula (D _A ), A and Z ₁ are each as defined above.

The number of carbon atoms in the alkylene group of A in the above formula (D _A ) is preferably 6 to 10 from the viewpoint of obtaining high liquid crystal orientation.
The alkylene group for A in the above formula (D _A ) may be either a linear or branched alkylene group, but a linear alkylene group is preferred from the viewpoint of favorably obtaining the effects of the present invention.

The hydrogen atom of the alkyl group, alkenyl group, or alkynyl group of Z ₁ in the above formula (D _A ) may be substituted with a monovalent group, and the monovalent group includes a halogen atom, a carboxy group, hydroxy group, cyano group, nitro group and the like. Among them, a halogen atom is preferable.
Z ₁ in the above formula (D _A ) is preferably a hydrogen atom or a methyl group.

The monovalent organic group for R in the above "*1-N(Boc)-C(=O)-N(R)-*1" includes an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, Alkoxy group, alkenyl group having 2 to 3 carbon atoms, acyl group having 2 to 3 carbon atoms, alkylsilyl group having 1 to 3 carbon atoms, alkoxysilyl group having 1 to 3 carbon atoms, Boc group, or these groups possess Monovalent organic groups in which a portion of hydrogen atoms are substituted with at least one of halogen atoms and hydroxy groups can be mentioned.
R is preferably a hydrogen atom or a Boc group.

The hydrogen atoms on the benzene ring to which the amino groups at both ends in the above formula (D _A ) are bonded may be substituted with a monovalent group, and the monovalent group includes a halogen atom, a methyl group, a methoxy group, carboxy group, hydroxy group, cyano group, nitro group and the like. Among them, a halogen atom, a methyl group, or a methoxy group is preferable.

From the viewpoint of obtaining high liquid crystal orientation, the two amino groups in the above formula (D _A ) are preferably para-positions with respect to the divalent organic group connecting the benzene rings.

From the viewpoint of suitably obtaining the effects of the present invention, A in the above formula (D _A ) preferably has the following aspects. Note that n1, n1′, n1″, n2, n2′, n3, n3′ and n3″ are each independently an integer of 1 or more, and the sum of n1, n1′ and n1″ is 4 to 10. , the sum of n2 and n2′ is 4-10, and the sum of n3, n3′ and n3″ is 4-10. In the following embodiments, R has the same definition as R in "*1-N(Boc)-C(=O)-N(R)-*1" above. When R is present more than once, it has the above definition independently of each other.
*—(CH ₂ ) _n1 —N(Boc)—(CH ₂ ) _n1′ —N(Boc)—(CH ₂ ) _n1″ —*,
*-( _CH2 ) _n2 -N(Boc)-C(=O)-N(R)-( _CH2 ) _n2' -*,
*-( _CH2 ) _n3 -N(Boc)-C(=O)-N(R)-( _CH2 ) _n3' -N(R)-C(=O)-N(Boc)-( _CH2 ) _n3″ -*.

Preferred examples of the above formula (D _A ) include the following formulas (d _A -1) to (d _A -2).

(In the above formula, Z ₁ , R, n1, n1′, n1″, n2 and n2′ are as defined above. Any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded may be substituted with a monovalent group, and the monovalent group includes a monovalent group capable of substituting the hydrogen atom on the benzene ring to which the amino groups at both ends in the above formula (D _A ) are bonded. groups can be mentioned.)

(Polymer (P))
The polymer (P) contained in the liquid crystal aligning agent of the present invention is a polyimide precursor obtained using a diamine component containing the diamine (0), or a polyimide that is an imidized product of the polyimide precursor. Here, the polyimide precursor is a polymer from which a polyimide can be obtained by imidating polyamic acid, polyamic acid ester, or the like. A polymer (P) may be used individually by 1 type, and may be used in combination of 2 or more types.
The polymer (P) is a polymer having at least one repeating unit selected from the group consisting of repeating units (p1) represented by the following formula (1) and imidized structural units of the repeating units (p1). may be

(In formula (1), X ₁ represents a tetravalent organic group. Y ₁ is a divalent organic group obtained by removing two amino groups from the specific diamine. R and Z each independently represent a hydrogen atom. Or represents a monovalent organic group.)
The monovalent organic group for R and Z in the above formula (1) includes a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the methylene group of the hydrocarbon group is -O-, -S-, -CO -, -COO-, -COS-, -NR ³ -, -CO-NR ³ -, -Si(R ³ ) ₂ - (where R ³ is a hydrogen atom or a monovalent carbon atom having 1 to 6 carbon atoms) is a hydrogen group), a monovalent group A substituted with —SO ₂ —, etc., the above monovalent hydrocarbon group, or at least one hydrogen atom bonded to a carbon atom of the above monovalent group A is a halogen Atoms, hydroxy groups, alkoxy groups, nitro groups, amino groups, mercapto groups, nitroso groups, alkylsilyl groups, alkoxysilyl groups, silanol groups, sulphino groups, phosphino groups, carboxy groups, cyano groups, sulfo groups, acyl groups, etc. Examples include a substituted monovalent group and a monovalent group having a heterocyclic ring.
The monovalent organic group for R and Z in the above formula (1) includes, among others, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a tert A -butoxycarbonyl group is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred.
From the viewpoint of suitably obtaining the effects of the present invention, R and Z are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
X ₁ in the above formula (1) includes, for example, a tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof, which will be described later. Preferred embodiments of the tetracarboxylic dianhydride or derivative thereof in X ₁ above include preferred embodiments of the tetracarboxylic dianhydride or derivative thereof that can be used for synthesizing the polymer (P) described later.
A polyamic acid (P′), which is a polyimide precursor of the polymer (P), can be obtained by a polymerization reaction between a diamine component containing the diamine (0) and a tetracarboxylic acid component. The diamine (0) may be used alone or in combination of two or more.
The amount of diamine (0) used is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more, relative to the total diamine component.

The diamine component used for producing the polyamic acid (P') may contain diamines other than diamine (0) (hereinafter also referred to as other diamines). When other diamines are used in addition to the diamine (0), the amount of the diamine (0) used is preferably 90 mol % or less, more preferably 80 mol % or less, relative to the diamine component.

Examples of other diamines are listed below, but are not limited to these. The other diamines may be used singly or in combination of two or more. p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4 ,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diamino biphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,3′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl represented by the following formulas (d _AL -1) to (d _AL -10) diamine, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3- aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis( 3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12- bis(3-aminophenoxy)dodecane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4′-bis(4-aminophenoxy)biphenyl, 4 , 4′-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthyloxy)ethane, 1, 2-bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylene Bis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl) Terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate (hereinafter, these diamines are also referred to as other diamines (a). ); a diamine having a photoalignable group such as 4,4′-diaminoazobenzene or diaminotran; 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N,N-diallylaniline Diamines terminated with photopolymerizable groups; 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone, 2-(4-(2-hydroxy -2-methylpropanoyl)phenoxy)ethyl diamines having a radical polymerization initiator function such as 3,5-diaminobenzoate; diamines having an amide bond such as 4,4'-diaminobenzanilide, 1,3-bis(4 -aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,3-bis(4-aminophenethyl)urea and other diamines having a urea bond; 3,3′-diaminodiphenyl ether, 3,4 '-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane , 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-amino-4-methylphenyl)propane, 4,4'-diaminobenzophenone , 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene; 2,6-diaminopyridine, 3,4 -diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine , N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-[3-(1H-imidazol-1-yl)propyl] 3,5-diaminobenzamide, 4-[4 -[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-benzenamine, diamines represented by the following formulas (z-1) to (z-13), etc. or 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis (4-aminophenyl)-N,N'-dimethylbenzidine or diamines having a diphenylamine structure such as N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-benzenediamine At least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group and a tertiary amino group (hereinafter also referred to as a specific nitrogen atom-containing structure). ) (provided that the molecule does not have an amino group bonded with a protective group that is eliminated by heating and replaced with a hydrogen atom.); 2,4-diaminophenol, 3,5-diaminophenol, 3,5- diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamino-3,3'-dihydroxybiphenyl; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 1,2-bis(4-aminophenyl)ethane-3,3'- dicarboxylic acids, diamines having a carboxyl group such as 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1 -(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene -6-amine; groups such as the following formulas (5-1) to (5-6) "-N(D)-" (D represents a protecting group that is eliminated by heating and replaced with a hydrogen atom, preferably carbamate-based protection a tert-butoxycarbonyl group, more preferably a tert-butoxycarbonyl group, excluding the above specific diamines), cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, Cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate and 3,6-bis(4-aminobenzoyloxy) Diamines having a steroid skeleton such as cholestane, diamines represented by the following formulas (V-1) to (V-2); 1,3-bis(3-aminopropyl)-tetramethyldisiloxane having a siloxane bond Diamine; metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), a diamine in which two amino groups are bonded to a group represented by any one of formulas (Y-1) to (Y-167) described in WO 2018/117239, and the like.

(In formulas (d _AL -6) and (d _AL -8), m1 and m2 each independently have the above definition.)

In the above formula (V-1), m and n are each independently an integer of 0 to 3 and satisfy 1≦m+n≦4. j is an integer of 0 or 1; X ¹ is -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, represents -CH ₂ O-, -CH ₂ -OCO-, -COO- or -OCO-; R ¹ is a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and It represents a monovalent group such as an alkoxyalkyl group having 2 to 10 carbon atoms. In formula (V-2) above, X ² represents -O-, -CH ₂ O-, -CH ₂ -OCO-, -COO- or -OCO-. When two of m, n, X ¹ and R ¹ are present, each independently has the above definition.

From the viewpoint of suitably obtaining the effects of the present invention, the diamine component used in the production of the polyamic acid (P′) should contain at least one diamine selected from the group consisting of the above other diamines (a). is preferred.　　

When other diamines are used in addition to the diamine (0), the amount of the other diamines used is preferably 10 to 90 mol% with respect to the total diamine components used in the production of the polymer (P). and more preferably 20 to 80 mol %.

(Tetracarboxylic acid component)
When 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, or tetracarboxylic acid. Derivatives of tetracarboxylic dianhydrides such as carboxylic acid dialkyl ester dihalides can also be used.

The tetracarboxylic dianhydride or derivative thereof includes an acyclic aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or derivatives thereof. . Among them, it is more preferable to contain a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring, or a derivative thereof. In particular, it is more preferable to contain a tetracarboxylic dianhydride having at least one structure selected from the group consisting of a cyclobutane ring, a cyclopentane ring and a cyclohexane ring, or a derivative thereof.
The tetracarboxylic dianhydrides or derivatives thereof may be used singly or in combination of two or more.
The acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not need to be composed only of a chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure in part thereof.
An 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 carboxy groups are bonded to the aromatic ring. Moreover, it is not necessary to consist only of an alicyclic structure, and a part thereof may have a chain hydrocarbon structure or an aromatic ring structure.
An 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. However, it is not necessary to consist only of an aromatic ring structure, and a part thereof may have a chain hydrocarbon structure or an alicyclic structure.

The tetracarboxylic acid component that can be used in the production of the polyamic acid (P′) preferably includes the following tetracarboxylic dianhydrides or derivatives thereof (in the present invention, these are collectively referred to as specific tetracarboxylic acids Also called derivatives.).
Acyclic aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3 ,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3′,4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5 ,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho [1,2-c]furan-1,3-dione, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2. 2] octane-2,3,5,6-tetracarboxylic dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride alicyclic tetracarboxylic dianhydrides such as; Carboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ether tetra Carboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, 4,4′-bis(3 ,4-dicarboxyphenoxy)-2,2-diphenylpropane dianhydride, ethylene glycol bisanhydrotrimellitate, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 4,4′-carbonyldi phthalic anhydride, 4,4'-(1,4-phenylenedioxy)bis(phthalic anhydride), or 4,4'-(1,4-phenylenedimethylene)bis(phthalic anhydride), etc. Aromatic tetracarboxylic dianhydrides; In addition, tetracarboxylic dianhydrides described in JP-A-2010-97188.

Preferred examples of the above specific tetracarboxylic acid derivatives include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3, 3′,4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4, 5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydro naphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, pyromellit acid dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8- naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3′,4,4 '-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, or derivatives thereof.

The proportion of the above-mentioned specific tetracarboxylic acid derivative used is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, relative to the total tetracarboxylic acid components used.

(Liquid crystal aligning agent)
The liquid crystal aligning agent of the present invention is a liquid composition in which the polymer (P) and optionally other components are preferably dispersed or dissolved in a suitable solvent.
The total content of the polymer components contained in the liquid crystal aligning agent of the present invention can be appropriately changed by setting the thickness of the coating film to be formed. 1 mass % or more is preferable with respect to the total mass of a liquid crystal aligning agent, and 10 mass % or less is preferable from the point of the storage stability of a solution.
The content of the polymer (P) used in the present invention is preferably 1 to 100 parts by mass, more preferably 10 to 100 parts by mass, with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. 20 to 100 parts by weight is particularly preferred.

The liquid crystal aligning agent of the present invention may contain polymers other than the polymer (P). Specific examples of other polymers include at least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component that does not have the specific diamine and a polyimide that is an imidized product of the polyimide precursor. (Also referred to as polymer (B) in the present invention.), polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly( isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, polymers selected from the group consisting of poly(meth)acrylates, and the like. .

Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac Manufacturing Co., Ltd.) and the like. Anhydride) copolymers include Isoban-600 (manufactured by Kuraray Co., Ltd.). A specific example of the poly(vinyl ether-maleic anhydride) copolymer is Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland).
Among them, the polymer (B) is more preferable from the viewpoint of reducing afterimages derived from residual DC.
These other polymers may be used singly or in combination of two or more. The content of the other polymer is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and further 20 to 80 parts by mass with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. preferable.
90 mass parts or less may be sufficient as content of the said polymer (P) with respect to a total of 100 mass parts of the polymers contained in a liquid crystal aligning agent, and 80 mass parts or less may be sufficient.

(Polymer (B))
Specific examples of the tetracarboxylic acid component used in the production of the polymer (B) include the same compounds as those exemplified for the polymer (P), including preferred specific examples. The tetracarboxylic acid component used for producing the polymer (B) is more preferably a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring. or derivatives thereof, more preferably the above-mentioned specific tetracarboxylic acid derivative, and most preferably using more preferred specific examples of the above-mentioned specific tetracarboxylic acid derivative.
The amount of the specific tetracarboxylic acid derivative used is preferably 10 mol % or more, more preferably 20 mol % or more, more preferably 50 mol % or more, relative to the total tetracarboxylic acid component used in the production of the polymer (B). More preferably mol% or more.

Examples of the diamine component for obtaining the polymer (B) include the diamines exemplified for the polymer (P) above. Among them, diamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 having at least one group selected from the group consisting of urea bond, amide bond, carboxy group and hydroxy group in the molecule '-Diaminodiphenyl ether, at least one diamine selected from the group consisting of diamines represented by the above formulas (d _AL -1) to (d _AL -10), and diamines having the above specific nitrogen atom-containing structure ( In the present invention, these are also referred to as specific diamines (b).) are preferably included. As the diamine component, one type of diamine may be used alone, or two or more types may be used in combination.
When the specific diamine (b) is used, the amount used is preferably 10 mol % or more, more preferably 20 mol % or more, of the total diamine component used in the production of the polymer (B). When using a diamine other than the specific diamine (b), the amount used is preferably 90 mol% or less, more preferably 80 mol% or less, of the total diamine component used in the production of the polymer (B).

(Production of polyamic acid)
A polyamic acid is produced by reacting a diamine component and a tetracarboxylic acid component in an organic solvent. The ratio of the tetracarboxylic acid component and the diamine component used in the polyamic acid production reaction is 0.5 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid component per 1 equivalent of the amino group of the diamine component. is preferably 0.8 to 1.2 equivalents. As in ordinary polycondensation reactions, the closer the equivalent of the acid anhydride group of the tetracarboxylic acid component is to 1 equivalent, the greater the molecular weight of the resulting polyamic acid.
The reaction temperature in the production of polyamic acid is preferably -20 to 150°C, more preferably 0 to 100°C. Also, the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. Polyamic acid can be produced at any concentration. The concentration of polyamic acid is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then the solvent can be added.

Specific examples of the organic solvent include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone. In addition, when the solvent solubility of the polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Solvents such as glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used.

(Production of Polyamic Acid Ester)
Polyamic acid esters are produced by, for example, [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [III] a tetracarboxylic acid It can be obtained by a known method such as a method of reacting a diester dihalide and a diamine.

(Manufacturing of polyimide)
A polyimide can be obtained by ring-closing (imidizing) a polyimide precursor such as the above polyamic acid or polyamic acid ester. As used herein, the imidization ratio is the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or derivatives thereof and carboxy groups (or derivatives thereof). The imidization rate does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, and catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.
When the polyimide precursor is thermally imidized in the solution, the temperature is preferably 100 to 400° C., more preferably 120 to 250° C., and water produced by the imidization reaction is removed from the system. is preferred.

Catalytic imidization of the polyimide precursor is carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, preferably -20 to 250°C, more preferably stirring at 0 to 180°C. can be done. The amount of the basic catalyst is preferably 0.5 to 30 times the molar amount of the amic acid group, more preferably 2 to 20 times the molar amount, and the amount of the acid anhydride is preferably 1 to 50 times the molar amount of the amic acid group. It is preferably 3 to 30 molar times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferable because it has appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferably used because it facilitates purification after the reaction is completed. The imidization rate by catalytic imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

When recovering the generated polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be put into a solvent to precipitate. 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 adding it to the solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure. In addition, the impurities in the polymer can be reduced by repeating the operation of redissolving the recovered polymer in an organic solvent and recovering it by reprecipitation 2 to 10 times. Solvents in this case include, for example, alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more solvents selected from these, because the efficiency of purification is further increased.

When producing a polyimide precursor or polyimide in the present invention, a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride or a derivative thereof, and a diamine component containing the diamine, together with an appropriate terminal blocker to end block A polymer of the type may be produced. The end-blocking polymer has effects of improving the film hardness of the liquid crystal alignment film obtained by the coating film and improving the adhesion properties between the sealing agent and the liquid crystal alignment film.
Examples of the terminal of the polyimide precursor or polyimide in the present invention include an amino group, a carboxyl group, an acid anhydride group, or a group derived from a terminal blocking agent to be described later. An amino group, a carboxyl group, and an acid anhydride group can be obtained by a normal condensation reaction, or can be obtained by terminal blocking using the following terminal blocking agents.

Terminal blockers include, for example, acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, and trimellitic anhydride. 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthal acid anhydrides such as acid anhydrides; dicarbonic acid 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, n-pentylamine, n - monoamine compounds such as hexylamine, n-heptylamine, n-octylamine; Examples include isocyanates having unsaturated bonds.
The proportion of the terminal blocker used is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, per 100 mol parts of the total diamine component used.

The polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyimide precursor and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. is. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By being in this molecular weight range, it is possible to ensure good liquid crystal orientation of the liquid crystal display element.

The organic solvent contained in the liquid crystal aligning agent according to the present invention is not particularly limited as long as it uniformly dissolves the polymer (P) and other polymers added as necessary. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N,N-dimethylpropionamide, tetramethylurea, N,N-diethylformamide, N-methyl-2-pyrrolidone , N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethyl Propanamide, 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-(3-methoxypropyl)-2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-( 4-methoxybutyl)-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (these are collectively referred to as good solvents), and the like. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.

Further, the organic solvent contained in the liquid crystal aligning agent is a mixture of the above solvents and a solvent (also referred to as a poor solvent) that improves the coatability and the surface smoothness of the coating film when applying the liquid crystal aligning agent. The use of solvents is preferred. Specific examples of the poor solvent are given below, but are not limited thereto. The content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, particularly preferably 20 to 70% by mass, of the total solvent contained in the liquid crystal aligning agent. The type and content of the poor solvent are appropriately selected according to the liquid crystal aligning agent coating device, coating conditions, coating environment, and the like.

Examples of poor solvents include diisopropyl ether, diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, -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 mono Acetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy) -2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, Diethylene glycol monopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol diacetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl acetate ether, cyclohexyl acetate, 4-methyl-2-pentyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, lactic acid n-butyl, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone) and the like.

Among them, diisobutyl carbinol, 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 are preferred.

Preferred solvent combinations 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-dimethyllactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N- Methyl-2-pyrrolidone and ethyl 3-ethoxypropionate and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and 3-ethoxyethyl propionate and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 3-ethoxy Ethyl Propionate and Diethylene Glycol Monopropyl Ether, N-Ethyl-2-Pyrrolidone and 3-Ethoxy Ethyl Propionate and Diethylene Glycol Monopropyl Ether, N-Methyl-2-Pyrrolidone and Ethylene Glycol Monobutyl Ether Acetate, N-Ethyl-2- Pyrrolidone and dipropylene glycol dimethyl ether, N,N-dimethyl lactamide and ethylene glycol monobutyl ether, N,N-dimethyl lactamide and propylene glycol diacetate, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether, N-ethyl-2 - pyrrolidone and diethylene glycol monoethyl ether and butyl cellosolve acetate, N-methyl-2-pyrrolidone and diethylene glycol monomethyl ether and butyl cellosolve acetate, N,N-dimethyllactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2- pyrrolidone and 4-hydroxy-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 monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol dimethyl ether, γ-butyrolactone and 4-hydroxy -4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether Diisobutyl ketone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutylcarbinol, N-methyl-2- pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol monomethyl ether, N- ethyl-2-pyrrolidone and diethylene glycol diethyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and propylene glycol diacetate, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and diisobutyl ketone, N-ethyl-2-pyrrolidone and γ-butyrolactone and diisobutyl ketone, N-ethyl-2-pyrrolidone and N,N-dimethyllactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether and ethylene glycol monobutyl ketone Butyl ether acetate, γ-butyrolactone and ethylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate and propylene glycol dimethyl ether, N-methyl-2-pyrrolidone and acetic acid 4- methyl-2-pentyl and ethylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and cyclohexyl acetate and 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and propylene glycol monomethyl ether, cyclopentanone and propylene glycol monomethyl ether, Examples include N-methyl-2-pyrrolidone, cyclohexanone and propylene glycol monomethyl ether.

(Liquid crystal aligning agent)
The liquid crystal aligning agent of the present invention may contain other components (hereinafter also referred to as additive components) in addition to the polymer (P), the other polymer, and the organic solvent. Such additive components include, for example, a crosslinkable compound having at least one substituent selected from an oxiranyl group, an oxetanyl group, a blocked isocyanate group, an oxazoline group, a cyclocarbonate group, a hydroxy group and an alkoxy group; At least one crosslinkable compound selected from the group consisting of crosslinkable compounds having saturated groups, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, and compounds for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film.

Preferred specific examples of the crosslinkable compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, Epicoat 828 (manufactured by Mitsubishi Chemical Corporation), etc. Bisphenol A type epoxy resin, bisphenol F type epoxy resin such as Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A type epoxy resin such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), YX6954BH30 (manufactured by Mitsubishi Chemical Corporation) and the like biphenyl skeleton-containing epoxy resins, phenol novolac type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), (o, m, p-) cresol novolac type epoxy resins such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), Triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.), alicyclic epoxy resins such as Celoxide 2021P (manufactured by Daicel), N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1, Compounds containing a tertiary nitrogen atom represented by 3-bis(N,N-diglycidylaminomethyl)cyclohexane or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, compounds having two or more oxiranyl groups such as tetrakis(glycidyloxymethyl)methane; compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of WO2011/132751; Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B- Compounds having a blocked isocyanate group such as 870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.); 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2 -oxazoline), 2,2'-bis(5-methyl-2-oxazoline), 1,2,4-tris(2-oxazolinyl)-benzene, compounds having an oxazoline group such as Epocross (manufactured by Nippon Shokubai Co., Ltd.) WO2011/155577, paragraphs [0025] to [0030] and [0032] having a cyclocarbonate group; N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide, 2, 2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, 2,2-bis(4-hydroxy-3,5 -Dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane and other compounds having a hydroxyl group or an alkoxy group; glycerin mono (meth) acrylate, glycerin di (meth) acrylate (1,2- , 1,3-body mixture), glycerin tris (meth) acrylate, glycerin 1,3-diglycerolate di (meth) acrylate, pentaerythritol tri (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono Compounds represented by (meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate, and hexaethylene glycol mono(meth)acrylate can be mentioned. The content of the crosslinkable compound is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

Examples of compounds for adjusting the dielectric constant and electrical resistance include monoamines having a nitrogen atom-containing aromatic heterocycle such as 3-picolylamine. The content of the monoamine having a nitrogen atom-containing aromatic heterocyclic ring is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. part by mass.

Preferred specific examples of the above functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane. Ethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltri ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane silane, 3-isocyanatopropyltriethoxysilane, and the like. The content of the functional silane compound is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass based on 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.

The solid content concentration in the liquid crystal aligning agent (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 preferably It is 1 to 10% by mass.
A particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when a spin coating method is used, the solid content concentration is particularly preferably 1.5 to 4.5% by mass. When the printing method is used, it is particularly preferable to set the solid content concentration to 3 to 9% by mass and thereby the solution viscosity to 12 to 50 mPa·s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration to 1 to 5% by mass and thereby the solution viscosity to 3 to 15 mPa·s. The temperature for preparing the liquid crystal aligning agent is preferably 10 to 50°C, more preferably 20 to 30°C.

(Liquid crystal alignment film and liquid crystal display element)
A liquid crystal display element according to the present invention comprises a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display element is not particularly limited. , an optically compensated bend method (OCB method), and various other operation modes.

The liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (4), a method including steps (1) to (2) and (4), steps (1) to (3), ( 4-2) and (4-4), or by a method including steps (1) to (3), (4-3) and (4-4).

<Step (1): Step of applying a liquid crystal aligning agent onto a substrate>
A process (1) is a process of apply|coating a liquid crystal aligning agent on a board|substrate. A specific example of step (1) is as follows.
A liquid crystal aligning agent is applied to one surface of the substrate provided with the patterned transparent conductive film by an appropriate coating method such as a roll coater method, a spin coat method, a printing method, an inkjet method, or a spray method. Here, the material of the substrate is not particularly limited as long as it is highly transparent, and glass, silicon nitride, plastic such as acrylic, polycarbonate, etc., can also be used. In addition, in a reflective liquid crystal display element, if only one substrate is used, an opaque material such as a silicon wafer can be used, and in this case, a light-reflecting material such as aluminum can be used for the electrodes. In the case of manufacturing an IPS or FFS liquid crystal display element, a substrate provided with electrodes made of a transparent conductive film or a metal film patterned in a comb shape and a counter substrate provided with no electrodes are used. and
An IPS substrate, which is a comb-teeth electrode substrate used in an IPS-type liquid crystal display element, includes, for example, a substrate, a plurality of linear electrodes formed on the substrate and arranged in a comb-teeth shape, and and a liquid crystal alignment film formed to cover the linear electrodes.
The FFS substrate, which is a comb-teeth electrode substrate used in an FFS mode liquid crystal display element, includes, for example, a base material, a plane electrode formed on the base material, an insulating film formed on the plane electrode, It has a plurality of linear electrodes formed on an insulating film and arranged in a comb shape, and a liquid crystal alignment film formed on the insulating film so as to cover the linear electrodes.

More preferable examples of the method of applying the liquid crystal aligning agent to the substrate to form a film include a printing method such as screen printing, offset printing, or flexo printing, a spin coating method, an inkjet method, or a spray method. Among them, flexographic printing, spin coating, or ink-jet coating and film-forming methods can be preferably used.

<Step (2): Step of firing the applied liquid crystal aligning agent>
A process (2) is a process of baking the liquid crystal aligning agent apply|coated on the board|substrate, and forming a film|membrane. A specific example of step (2) is as follows.
After applying the liquid crystal aligning agent on the substrate in step (1), the solvent is evaporated by heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven, or polyimide typified by polyamic acid Thermal imidization of the precursor can be performed. Drying after applying a liquid crystal aligning agent and a baking process can select arbitrary temperature and time, and may be performed in multiple times. The temperature for baking the liquid crystal aligning agent can be, for example, 40 to 180.degree. From the viewpoint of shortening the process, it may be carried out at 40 to 150°C. The firing time is not particularly limited, but may be 1 to 10 minutes or 1 to 5 minutes. When a polyimide precursor represented by polyamic acid is thermally imidized, a step of baking at 150 to 300° C. or 150 to 250° C. may be added after the above step. The firing time is not particularly limited, but is, for example, 5 to 40 minutes, preferably 5 to 30 minutes.
The thickness of the film after baking is preferably 5 to 300 nm, more preferably 10 to 200 nm, because if it is too thin, the reliability of the liquid crystal display element may deteriorate.

<Step (3): Step of subjecting the film obtained in Step (2) to orientation treatment>
Step (3) is a step of subjecting the film obtained in step (2) to orientation treatment. That is, in a horizontally aligned liquid crystal display element such as an IPS system or an FFS system, the coating film is subjected to an alignment ability imparting treatment. On the other hand, in a liquid crystal display element of a vertical alignment type such as a VA system or a PSA (Polymer Sustained Alignment) system, the formed coating film can be used as it is as a liquid crystal alignment film. may be applied. Examples of the alignment treatment method for the liquid crystal alignment film include a rubbing alignment treatment method and a photo-alignment treatment method. As a photo-alignment treatment method, the surface of the film is irradiated with radiation polarized in a certain direction, and in some cases, preferably, heat treatment is performed to impart liquid crystal alignment (also referred to as liquid crystal alignment ability). method. As radiation, ultraviolet light or visible light having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm, more preferably 200 to 400 nm are preferred.

The radiation dose is preferably 1 to 10,000 mJ/cm ² , more preferably 100 to 5,000 mJ/cm ² . In addition, when irradiating with radiation, the substrate having the film-like material may be irradiated with heating at 50 to 250° C. in order to improve liquid crystal orientation. The liquid crystal alignment film thus produced can stably orient liquid crystal molecules in a fixed direction.

Furthermore, the coating film irradiated with polarized radiation or the coating film subjected to rubbing alignment treatment by the above method may be subjected to contact treatment using water or a solvent. Further, the film subjected to the alignment treatment may be subjected to heat treatment without being subjected to contact treatment. Furthermore, the film subjected to the contact treatment may be further subjected to heat treatment.

The solvent used in the contact treatment is not particularly limited as long as it dissolves the decomposed product produced from the film-like material by irradiation with radiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, 3- methyl methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate and the like. Solvents may be used singly or in combination of two or more.

The temperature of the heat treatment for the above radiation-irradiated coating film is more preferably 50 to 300°C, more preferably 120 to 250°C. The heat treatment time is preferably 1 to 30 minutes.

<Step (4): Step of producing a liquid crystal cell>
Two substrates on which liquid crystal alignment films are formed as described above are prepared, and liquid crystal is arranged between the two substrates facing each other. Specifically, the following two methods are mentioned.
In the first method, first, two substrates are arranged to face each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other. Next, the peripheries of the two substrates are bonded together using a sealing agent, and a liquid crystal composition is injected and filled into the cell gap defined by the substrate surface and the sealing agent to contact the film surface, and then the injection hole is sealed. stop.
The liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used. In the following description, a liquid crystal composition with a positive dielectric anisotropy is also referred to as a positive liquid crystal, and a liquid crystal composition with a negative dielectric anisotropy is also referred to as a negative liquid crystal.
The above liquid crystal composition contains a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocyclic ring, a cycloalkane, A liquid crystal compound having a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring may be included, and a compound having two or more rigid sites (mesogenic skeleton) exhibiting liquid crystallinity in the molecule (for example, two rigid biphenyl structure, or a bimesogenic compound in which a terphenyl structure is linked by an alkyl group). The liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase.
In addition, the liquid crystal composition may further contain an additive from the viewpoint of improving liquid crystal orientation. Such additives include photopolymerizable monomers such as compounds having a polymerizable group ((meth)acryloyl group, etc.); optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); oxidation Antifoaming agents; UV absorbers; dyes; antifoaming agents; polymerization initiators;
Positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019 and MLC-7081 manufactured by Merck.
As the negative liquid crystal, for example, MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, or MLC- 7029 and the like.
In addition, in the PSA mode, MLC-3023 manufactured by Merck Co., Ltd. can be used as a liquid crystal containing a compound having a polymerizable group.

The second method is a method called ODF (One Drop Fill) method. A predetermined place on one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, an ultraviolet light-curing sealant, and a liquid crystal composition is applied to several predetermined places on the surface of the liquid crystal alignment film. drip. Thereafter, the other substrate is attached so that the liquid crystal alignment films face each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant. In any method, it is desirable to remove the flow orientation at the time of liquid crystal filling by heating the liquid crystal composition to a temperature at which the used liquid crystal composition assumes an isotropic phase and then slowly cooling to room temperature.
When the coating film is subjected to the rubbing alignment treatment, the two substrates are arranged opposite to each other so that the rubbing directions of the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.
As the sealant, for example, an epoxy resin or the like containing a curing agent and aluminum oxide spheres as spacers can be used. Liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.

The liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates. A liquid crystal display element (PSA type liquid crystal display element) manufactured through a process of polymerizing a polymerizable compound by at least one of irradiating an active energy ray and heating while placing an object and applying a voltage between electrodes. is also preferably used.
Further, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group polymerized by at least one of active energy rays and heat is placed between the pair of substrates. It is also preferably used in a liquid crystal display element (SC-PVA type liquid crystal display element) manufactured through a process of arranging a liquid crystal alignment film containing the liquid crystal and applying a voltage between electrodes.

<Step (4-2): For PSA liquid crystal display device>
It is carried out in the same manner as in (4) above, except that the liquid crystal composition containing a polymerizable compound is injected or dropped. Examples of the polymerizable compound include polymerizable compounds having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule.

<Step (4-3): For SC-PVA liquid crystal display element>
A method of manufacturing a liquid crystal display element may be employed in which a step of irradiating ultraviolet rays, which will be described later, is performed after performing the same as in the above (4). According to this method, a liquid crystal display device having an excellent response speed can be obtained with a small amount of light irradiation, as in the case of manufacturing the PSA type liquid crystal display device. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups in the molecule, and its content is 0.1 to 30 per 100 parts by mass of all polymer components. It is preferably parts by mass, more preferably 1 to 20 parts by mass. Further, the polymerizable group may be present in the polymer used for the liquid crystal alignment agent, and such a polymer includes, for example, a diamine component containing a diamine having a photopolymerizable group at the end thereof, which is used in the reaction. The polymer obtained is mentioned.

<Step (4-4): Step of irradiating with ultraviolet rays>
The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (4-2) or (4-3) above. The voltage applied here can be, for example, 5 to 50 V direct current or alternating current. As the light for irradiation, for example, ultraviolet light containing light with a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferable. 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 the light source for the irradiation light. The irradiation amount of light is preferably 1,000 to 200,000 J/m ² , more preferably 1,000 to 100,000 J/m ² .

Then, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell as necessary. As the polarizing plate to be attached to the outer surface of the liquid crystal cell, a polarizing film called "H film" in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate consisting of

Although the present invention will be described in more detail with reference to examples below, the present invention should not be construed as being limited to these examples. The abbreviations of the compounds used and methods for measuring physical properties are as follows.

(organic solvent)
NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve (ethylene glycol monobutyl ether)
THF: Tetrahydrofuran DMF: N,N-dimethylformamide

(Acid dianhydride)
CA-1 to CA-2: compounds represented by the following formulas (CA-1) to (CA-2), respectively

(diamine)
DA-1 to DA-10: compounds represented by the following formulas (DA-1) to (DA-10), respectively. Diamines included in the scope of the specific diamine of the present invention are compounds represented by the following formulas (DA-1) to (DA-2).

(reaction reagent)
Boc ₂ O: di-tert-butyl dicarbonate

[Measurement of molecular weight]
Measurement was performed using the following normal temperature GPC (gel permeation chromatography) apparatus, and Mn and Mw were calculated as values converted to polyethylene glycol and polyethylene oxide.
GPC apparatus: GPC-101 (manufactured by Showa Denko), column: GPC KD-803, GPC KD-805 (manufactured by Showa Denko) in series, column temperature: 50 ° C., eluent: N,N-dimethylformamide (addition As agents, lithium bromide monohydrate (LiBr.H ₂ O) is 30 mmol/L, phosphoric acid/anhydride crystals (o-phosphoric acid) is 30 mmol/L, and tetrahydrofuran (THF) is 10 mL/L), flow rate: 1.0 mL/min Standard sample for creating a calibration curve: 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; 000, 4,000 and 1,000) (manufactured by Polymer Laboratories).

[Synthesis of Monomer]
DA-1 and DA-2 are novel compounds that have not been published in literature, etc., and their synthesis methods are described in detail below. -OTMS represents a tetramethylsiloxy group.

The products described in the monomer synthesis examples below were identified by ¹ H-NMR analysis (analysis conditions are as follows).
Apparatus: Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) "AVANCE III" (manufactured by BRUKER) 500 MHz.
Solvent: deuterated dimethyl sulfoxide (DMSO-d ₆ , standard: tetramethylsilane)

(Monomer Synthesis Example 1 Synthesis of DA-1)
DA-1 was synthesized according to the route shown below.

After THF (200 g) was added to N,N'-bis(2-hydroxyethyl)ethylenediamine (25.0 g, 0.169 mol), the mixture was stirred at 50°C. A solution of Boc ₂ O (75.5 g, 0.346 mol) diluted with THF (50 g) was added dropwise thereto, and the mixture was heated and stirred for 20 hours to react. After completion of the reaction, the solution was cooled to room temperature (25°C), concentrated, added with acetonitrile (118 g), stirred at room temperature (25°C) for 30 minutes, and precipitated crystals were separated by filtration. The obtained crystals were dried at 40° C. to obtain DA-1-1. On the other hand, the filtrate was concentrated, acetonitrile (59 g) was added again, the mixture was stirred for 30 minutes, and the precipitated crystals were collected by filtration. The obtained crystals were dried to obtain DA-1-1 (total yield: 54.4 g, 0.156 mol, yield: 92%). From ^{the 1} H-NMR results shown below, this solid was confirmed to be DA-1-1.
¹ H-NMR (500 MHz) in DMSO-d ₆ : δ (ppm) = 4.65 (br, 2H), 3.45 (s, 4H), 3.28 (s, 4H), 3.18-3 .16 (m, 4H), 1.39-1.38 (m, 18H).

After sodium hydride (13.8 g, 60%-dispersed in liquid paraffin) and DMF (200 g) were added to the flask, the mixture was stirred while cooling at 0° C. in an ice bath. A solution of DA-1-1 (50.0 g, 0.143 mol) obtained above dissolved in DMF (300 g) was added dropwise thereto and stirred for 30 minutes. Furthermore, a solution of 4-fluoronitrobenzene (42.5 g, 0.301 mol) dissolved in DMF (50 g) was added dropwise, and after completion of the dropwise addition, the mixture was stirred at room temperature (25° C.) for 6 hours for reaction. Methanol (100 g) was added to the reaction solution to deactivate excess sodium hydride, and the reaction solution was added to methanol (1550 g) and stirred to precipitate crystals. Crystals were separated by filtration, washed with methanol (150 g), and dried at 40° C. to obtain DA-1-2 (yield: 66.0 g, 0.112 mol, yield: 78%). . From ^{the 1} H-NMR results shown below, this solid was confirmed to be DA-1-2.
¹ H-NMR (500 MHz) in DMSO-d ₆ : δ (ppm) = 8.18 (d, J = 7.5 Hz, 4H), 7.15 (d, J = 9.0 Hz, 4H), 4. 23 (s, 4H), 3.55 (t, 4H), 3.38 (s, 4H), 1.38 (s, 9H), 1.35 (s, 9H).

To DA-1-2 (65.9 g, 0.112 mol) obtained above, THF (989 g) was added and nitrogen-substituted, and then carbon-supported palladium (5% Pd carbon powder (hydrous product) K type, N E Chemcat Co.) (5.27 g) was added and the mixture was replaced with nitrogen again, a Tedlar bag filled with hydrogen was attached, and the mixture was heated and stirred at 45° C. for 18 hours to react. As the reaction progressed, the crystals dissolved, and then a large amount of crystals precipitated again from the solution. Supported palladium was removed. By concentrating the filtrate, crude DA-1 was obtained.
Methanol (200 g) was added to the crude DA-1, stirred at room temperature (25° C.) in a slurry state, and filtered. The obtained crystals were dried to obtain DA-1 (yield: 45.2 g, 0.0852 mol, yield: 76%). From the ¹ H-NMR results shown below, this solid was confirmed to be DA-1.
¹ H-NMR (500 MHz) in DMSO-d ₆ : δ (ppm) = 6.64 (d, J = 7.5 Hz, 4H), 6.49 (d, J = 7.5 Hz, 4H), 4. 59 (s, 4H), 3.90 (s, 4H), 3.43 (s, 4H), 3.35 (s, 4H), 1.39 (s, 9H), 1.37 (s, 9H) ).

(Monomer Synthesis Example 2 Synthesis of DA-2)
DA-2 was synthesized according to the route shown below.

In a nitrogen atmosphere, 3-amino-1-propanol (30.0 g, 399 mmol), methylene chloride (600 g) and triethylamine (60.7 g, 600 mmol) were added to a 1 L four-necked flask, and after cooling to 0° C., trimethylsilyl chloride ( 47.8 g, 440 mmol) was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at 0° C. for 1 hour, and then carbonyldiimidazole (31.1 g, 192 mmol) was added to carry out the reaction. After stirring at 0° C. for 1 hour, the mixture was further stirred at room temperature for 48 hours to complete the reaction. The reaction solution was transferred to a separatory funnel, washed twice with water (300 g), the organic layer was dried over magnesium sulfate (40.0 g), and the magnesium sulfate was removed by filtration. After concentrating the resulting filtrate, it was vacuum-dried (40° C.) to obtain oily DA-2-1 (60.3 g, 188 mmol, yield 98.0%, colorless and transparent oil).

Under a nitrogen atmosphere, DA-2-1 (41.2 g, 129 mmol), 4-nitrofluorobenzene (39.8 g, 282 mmol), potassium hydroxide (17.2 g, 307 mmol), and NMP ( 380 g) was added, and the mixture was stirred at 0° C. for 24 hours to react. After the reaction, water (460 g) cooled to 0° C. was added to the reaction solution, and the wet product obtained by filtering the precipitated solid was washed with water (300 g) three times and then with acetonitrile (300 g) three times. gone. The resulting solid was dried to give DA-2-2 (38.9 g, 93.0 mmol, 72.1% yield, yellow solid).

Under a nitrogen atmosphere, DA-2-2 (34.0 g, 81.3 mmol), di-tert-butyl dicarbonate (28.0 g, 128 mmol), THF (169 g), and 4-dimethylamino were placed in a 500 mL four-necked flask. Pyridine (99.8 mg, 0.82 mmol) was added and reacted at 60° C. for 24 hours. After the reaction, the mixture was concentrated until the content weight reached 117 g, and then isopropyl alcohol (156 g) was added to precipitate crystals. Thereafter, the mixture was cooled to 0° C., stirred for 5 hours, filtered, and the cake was washed once with a mixed solution of isopropyl alcohol (39 g) and tetrahydrofuran (18 g). The obtained crystals were vacuum-dried (50° C.) to obtain 26.5 g of crude DA-2-3. Next, in a nitrogen atmosphere, DA-2-3 crude (26.5 g) and toluene (160 g) were added to a 500 mL four-necked flask and dissolved at 80 ° C., and then heated to 45 ° C. to precipitate impurities. was removed by filtration. After concentrating until the mass of the obtained filtrate reached 40.0 g, the precipitated crystals were separated by filtration and vacuum-dried (50° C.) to obtain DA-2-3 (18. 9 g, 36.5 mmol, 44.9% yield, yellow solid).

In a nitrogen atmosphere, DA-2-3 (17.9 g, 34.5 mmol), tetrahydrofuran (151 g), carbon-supported palladium (5% Pd carbon powder (50% water content) K type, N・E Chemcat Co., Ltd., 1.89 g) was added, and after substituting a hydrogen atmosphere, the mixture was reacted at room temperature. After completion of the reaction, carbon-supported palladium was removed by filtration, and the resulting wet product obtained by concentrating the filtrate was vacuum-dried at 50° C. to obtain DA-2 (12.8 g, 27.9 mmol, yield 80 .9%, brown solid). From the ¹ H-NMR results shown below, this solid was confirmed to be DA-2.
¹ H-NMR (500 MHz, DMSO-d6): δ (ppm) = 8.66 (t, 1H, J = 5.5 Hz), 6.65 (d, 2H, J = 9.0 Hz), 6.60 (d, 2H, J = 9.0Hz), 6.48 (dd, 4H, J = 9.0Hz, 2.1Hz), 4.54 (d, 4H, J = 7.0Hz), 3.85- 3.75 (m, 6H,), 3.29 (q, 2H, J=7.0Hz), 1.87-1.81 (m, 4H), 1.44 (s, 9H).

[Synthesis of polymer]
(Synthesis example 1)
DA-3 (0.541 g, 5.00 mmol), DA-1 (2.65 g, 5.00 mmol) and NMP (23.4 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at 60° C. while supplying nitrogen. Then, after cooling to room temperature, CA-1 (2.15 g, 9.60 mmol) and NMP (15.8 g) were added and stirred at 40 ° C. for 24 hours to obtain a polyamic acid with a solid content concentration of 12% by mass. A solution of (PAA-1) was obtained. This polyamic acid had an Mn of 10,600 and an Mw of 31,900.

(Synthesis example 2)
DA-3 (0.541 g, 5.00 mmol), DA-2 (2.29 g, 5.00 mmol) and NMP (20.8 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. After that, CA-1 (2.16 g, 9.65 mmol) and NMP (15.9 g) were added and stirred at 40 ° C. for 24 hours to obtain polyamic acid (PAA-2) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 14,400 and an Mw of 46,300.

(Synthesis Example 3)
DA-3 (0.541 g, 5.00 mmol), DA-6 (1.71 g, 5.00 mmol) and NMP (16.5 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. After that, CA-1 (2.19 g, 9.78 mmol) and NMP (16.1 g) were added and stirred at 40 ° C. for 24 hours to obtain polyamic acid (PAA-3) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 16,700 and an Mw of 52,800.

(Synthesis Example 4)
DA-3 (0.541 g, 5.00 mmol), DA-7 (1.99 g, 5.00 mmol) and NMP (18.5 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. After that, CA-1 (2.16 g, 9.65 mmol) and NMP (15.9 g) were added and stirred at 40 ° C. for 24 hours to obtain polyamic acid (PAA-4) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 13,000 and an Mw of 37,800.

(Synthesis Example 5)
DA-3 (0.541 g, 5.00 mmol), DA-8 (1.79 g, 5.00 mmol) and NMP (17.1 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. After that, CA-1 (2.15 g, 9.60 mmol) and NMP (15.8 g) were added and stirred at 40 ° C. for 24 hours to obtain a polyamic acid (PAA-5) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 16,100 and an Mw of 52,300.

(Synthesis Example 6)
DA-3 (0.324 g, 3.00 mmol), DA-4 (0.733 g, 3.00 mmol), DA-5 (0.641 g, 2.00 mmol), DA-1 (1.06 g, 2.00 mmol) and NMP (20.2 g) were added and dissolved by stirring at 60° C. while purging with nitrogen. Then, after cooling to room temperature, CA-1 (2.15 g, 9.57 mmol) and NMP (15.7 g) were added and stirred at 40 ° C. for 24 hours to obtain a polyamic acid with a solid content concentration of 12% by mass. A solution of (PAA-6) was obtained. This polyamic acid had an Mn of 14,600 and an Mw of 37,500.

(Synthesis Example 7)
DA-3 (0.324 g, 3.00 mmol), DA-4 (0.733 g, 3.00 mmol), DA-5 (0.641 g, 2.00 mmol), DA-2 (0.917 g, 2.00 mmol) and NMP (19.2 g) were added and dissolved by stirring at room temperature with nitrogen sparging. After that, CA-1 (2.14 g, 9.53 mmol) and NMP (15.7 g) were added and stirred at 40 ° C. for 24 hours to obtain polyamic acid (PAA-7) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 14,100 and an Mw of 36,500.

(Synthesis Example 8)
DA-3 (0.324 g, 3.00 mmol), DA-4 (0.733 g, 3.00 mmol), DA-5 (0.641 g, 2.00 mmol), DA-6 (0.683 g, 2.00 mmol) and NMP (17.5 g) were added and dissolved by stirring at room temperature with nitrogen sparging. After that, CA-1 (2.16 g, 9.62 mmol) and NMP (15.8 g) were added and stirred at 40 ° C. for 24 hours to obtain polyamic acid (PAA-8) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 12,100 and an Mw of 32,400.

(Synthesis Example 9)
DA-3 (0.324 g, 3.00 mmol), DA-4 (0.733 g, 3.00 mmol), DA-5 (0.641 g, 2.00 mmol), DA-7 (0.797 g, 2.00 mmol) and NMP (18.3 g) were added and dissolved by stirring at room temperature under nitrogen sparging. After that, CA-1 (2.14 g, 9.56 mmol) and NMP (15.7 g) were added and stirred at 40 ° C. for 24 hours to obtain polyamic acid (PAA-9) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 12,100 and an Mw of 32,300.

(Synthesis Example 10)
DA-3 (0.324 g, 3.00 mmol), DA-4 (0.733 g, 3.00 mmol), DA-5 (0.641 g, 2.00 mmol), DA-8 (0.717 g, 2.00 mmol) and NMP (17.7 g) were added and dissolved by stirring at room temperature under nitrogen sparging. After that, CA-1 (2.13 g, 9.49 mmol) and NMP (15.6 g) were added and stirred at 40 ° C. for 24 hours to obtain a polyamic acid (PAA-10) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 12,600 and an Mw of 32,900.

(Synthesis Example 11)
DA-9 (1.59 g, 8.00 mmol), DA-10 (0.304 g, 2.00 mmol) and NMP (13.9 g) were added to a 50 mL four-necked flask equipped with a stirrer and nitrogen inlet tube. was dissolved by stirring at room temperature while blowing nitrogen. After that, CA-2 (2.74 g, 9.30 mmol) and NMP (20.1 g) were added and stirred at 70 ° C. for 12 hours to obtain a polyamic acid (PAA-11) having a solid content concentration of 12% by mass. A solution was obtained. This polyamic acid had an Mn of 9,700 and an Mw of 21,800.

Table 1 shows the specifications of the polyamic acid solution obtained in the above synthesis example. In Table 1, the numbers in parentheses for the tetracarboxylic acid component and the diamine component are the amounts (mol parts) of each tetracarboxylic acid component and each diamine component used with respect to the total amount of 100 mol parts of the diamine component used in each polymerization step. represents

[Preparation of Liquid Crystal Aligning Agent]
(Example 1)
NMP (14.0 g) and BCS (6.00 g) were added to the polyamic acid (PAA-1) solution (10.0 g) obtained in Synthesis Example 1 above, and the mixture was stirred at room temperature for 30 minutes to obtain a liquid crystal. An alignment agent (AL-1) was obtained.

(Example 2, Comparative Examples 1 to 3)
Liquid crystal aligning agent (AL-2), (AL-C1) to (AL-C3) were obtained.

(Example 3)
NMP (6. 80 g) and BCS (7.20 g) were added and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (AL-3).

(Example 4)
NMP (6.0 g) was added to the solution (4.0 g) of polyamic acid (PAA-7) obtained in Synthesis Example 7 and the solution (6.0 g) of polyamic acid (PAA-11) obtained in Synthesis Example 11 above. 80 g) and BCS (7.20 g) were added and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (AL-4).

(Comparative Example 4)
A liquid crystal aligning agent (AL-C4) was obtained in the same manner as in Example 3 except that the polyamic acid solution used was replaced with (PAA-8) from (PAA-6).

(Comparative Examples 5-6)
Liquid crystal alignment agent (AL-C5) ~ (AL-C6) was obtained.

Table 2 shows the specifications of the liquid crystal aligning agents obtained in the above examples and comparative examples. In the table, the numbers in parentheses for the polyamic acid represent the blending amount (parts by mass) of each polymer with respect to the total of 100 parts by mass of the polymer components.

[Production of liquid crystal cell]
Using the liquid crystal aligning agent obtained above, a liquid crystal cell was produced in the following procedure. After each liquid crystal aligning agent was filtered through a filter with a pore size of 1.0 μm, it was applied to a glass substrate with ITO electrodes (length 40 mm×width 30 mm×thickness 0.7 mm) by a spin coating method and placed on a hot plate at 80° C. for 60 seconds. After drying, it was baked in an infrared heating furnace at 230° C. for 20 minutes to form a liquid crystal alignment film with a film thickness of 100 nm. The coating film surface was subjected to an orientation treatment by irradiating linearly polarized ultraviolet light having a wavelength of 254 nm with an extinction ratio of 26:1 through a polarizing plate at 200 mJ/cm ² , 300 mJ/cm ² or 400 mJ/cm ² . Furthermore, it was baked in an infrared heating furnace at 230° C. for 30 minutes to obtain a substrate with a liquid crystal alignment film (first glass substrate). A substrate with a liquid crystal alignment film (second glass substrate) was obtained in the same manner as described above, except that the alignment treatment was performed so that the alignment direction was orthogonal to that of the first glass substrate. The above two substrates are set as a set, and a bead spacer with a diameter of 4 μm (manufactured by Nikki Shokubai Kasei Co., Ltd., Shinshikyu, SW-D1) is applied on one of the liquid crystal alignment films, leaving a liquid crystal injection port. A sealant (XN-1500T, manufactured by Mitsui Chemicals, Inc.) was printed, and another substrate was attached so that the alignment direction of the liquid crystal alignment film surfaces facing each other was 0°. After that, a heat treatment was performed at 150° C. for 60 minutes to cure the sealant to prepare an empty cell. Liquid crystal MLC-3019 (manufactured by Merck & Co.) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120° C. for 1 hour and then used for evaluation.

[Evaluation of in-plane uniformity of contrast]
Variation in the twist angle of the liquid crystal cell was evaluated using AxoStep manufactured by AXOMETRICS. The liquid crystal cell produced above was placed on a measurement stage, and the distribution of Circular Retardance in the pixel plane was measured with no voltage applied to calculate 3σ, which is three times the standard deviation σ. It can be said that the smaller the 3σ value, the better the in-plane uniformity.

[In-plane uniformity of contrast]
Liquid crystal alignment films (single films) obtained from the liquid crystal alignment agents of Examples 1 and 2 and Comparative Examples 1 and 3 and liquid crystal alignment films obtained from the liquid crystal alignment agents of Examples 3 and 4 and Comparative Examples 4 and 6 ( In the blend film), the in-plane uniformity of the contrast was evaluated. As the evaluation criteria, the case where the value of 3σ was less than 1.65 was evaluated as “◯”, and the case where the value was 1.65 or more was evaluated as “X”. The results are shown in Table 3 (single membrane) and Table 4 (blend membrane).

[Evaluation of layer separability]
In Examples 3 to 4 and Comparative Examples 4 to 6 of the preparation example of the liquid crystal aligning agent, a liquid crystal aligning agent was prepared in the same procedure except that (PAA-11) was not used, and a liquid crystal aligning agent (AL-3a) was prepared. ~ (AL-4a) and (AL-C4a) ~ (AL-C6a) were obtained, respectively.
Next, using the liquid crystal aligning agents (AL-3a) to (AL-4a) and (AL-C4a) to (AL-C6a) obtained above, the irradiation amount of ultraviolet rays is set to 300 mJ / cm ² , and the above A liquid crystal cell was produced in the same procedure, and the in-plane uniformity of contrast was evaluated. (Hereinafter, the value obtained by the evaluation is referred to as 3σ (single film).)
Further, using the liquid crystal aligning agents (AL-3) to (AL-4) and (AL-C4) to (AL-C6) obtained in the liquid crystal aligning agent preparation examples, the irradiation amount of ultraviolet rays was 300 mJ / cm. As ² , a liquid crystal cell was produced in the same procedure as above, and the in-plane uniformity of contrast was evaluated. (Hereinafter, the value obtained by the evaluation is referred to as 3σ (blend film).)
Then, the difference between 3σ (single film) and 3σ (blended film) is Δ3σ, and the case where Δ3σ is less than 0.60 is “○” and the case of 0.60 or more is “×”, and the layer separation property is evaluated. gone. Table 5 shows the results.
When the layer separability is low, the value of 3σ (blend film) becomes larger than that of 3σ (single film), and the value of Δ3σ becomes large. On the other hand, when the layer separability is high, the value of Δ3σ becomes small.

As shown in Tables 3 and 4, the liquid crystal alignment film obtained from the liquid crystal alignment agent using the diamine component containing the specific diamine (0) had good in-plane uniformity of contrast. Moreover, as shown in Table 5, high layer separation was exhibited when two or more types of polymers were used.

The liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is widely used in liquid crystal display elements of various operation modes. It can also be used for a film or a liquid crystal alignment film for a transmission scattering type liquid crystal light control device.

The liquid crystal display device of the present invention can be effectively applied to devices having various functions, such as liquid crystal televisions, clocks, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, and digital cameras. , mobile phones, smart phones, various monitors, information displays, etc.

In addition, the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2021-177006 filed on October 28, 2021, and the Japanese Patent Application filed on November 22, 2021 The entire contents of the specification, claims, drawings and abstract of No. 2021-189681 are hereby incorporated by reference and incorporated as disclosure for the present specification.

Claims

At least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component containing a diamine (0) represented by the following formula (D A ) and a polyimide that is an imidized product of the polyimide precursor ( P), a liquid crystal aligning agent characterized by containing.

(Z 1 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms, and the above alkyl group, alkenyl group, or A hydrogen atom of the alkynyl group may be substituted with a monovalent group Any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded may be substituted with a monovalent group.
A represents a divalent organic group (a) in which any carbon-carbon bond in an alkylene group having 4 to 10 carbon atoms satisfies either of the following conditions (1) and (2). In the following conditions (1) and (2), *1 is bonded to a carbon atom possessed by an alkylene group, and the carbon-carbon bond is a carbon-carbon bond forming the main chain of the polymer (P). selected from
(1) "*1-N(Boc)-*1" is inserted between two or more carbon-carbon bonds.
(2) "*1-N(Boc)-C(=O)-N(R)-*1" is inserted between one or more carbon-carbon bonds. R represents a hydrogen atom or a monovalent organic group. Boc represents a tert-butoxycarbonyl group. )
The liquid crystal aligning agent according to claim 1, wherein A in the formula (D A ) is selected from any one of the following.
*-(CH 2 ) n1 -N(Boc)-(CH 2 ) n1′ -N(Boc)-(CH 2 ) n1″ -*, *-(CH 2 ) n2 -N(Boc)-C(= O)-N(R)-( CH2 ) n2' -*, *-( CH2 ) n3 -N(Boc)-C(=O)-N(R)-( CH2 ) n3'- N( R)-C(=O)-N(Boc)-( CH2 ) n3'' -*.
(n1, n1′, n1″, n2, n2′, n3, n3′ and n3″ are each independently an integer of 1 or more, and the sum of n1, n1′ and n1″ is 4 to 10; , n2 and n2′ are 4 to 10, and the sum of n3, n3′ and n3″ is 4 to 10. R and Boc are as defined in claim 1. R is more than one if present, have the above definitions independently of each other.)
3. The liquid crystal aligning agent according to claim 1, wherein the diamine (0) is any diamine selected from the group consisting of the following formulas (d A -1) to (d A -2).

(Z 1 has the same definition as formula (D A ). n1, n1′, n1″, n2 and n2′ are each independently an integer of 1 or more, and the sum of n1, n1′ and n1″ is 4 to 10. The sum of n2 and n2' is 4 to 10. Any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded may be substituted with a monovalent group. and Boc are as defined in claim 1.)
The polymer (P) is a polymer having at least one repeating unit selected from the group consisting of repeating units (p1) represented by the following formula (1) and imidized structural units of the repeating units (p1). The liquid crystal aligning agent according to any one of claims 1 to 3.

(In the formula (1), X 1 represents a tetravalent organic group. Y 1 is a divalent organic group obtained by removing two amino groups from the diamine (0) represented by the formula (D A ). (R and Z each independently represent a hydrogen atom or a monovalent organic group.)
The polymer (P) contains the diamine component, an acyclic aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or a derivative thereof. The liquid crystal aligning agent according to any one of claims 1 to 4, obtained by a polycondensation reaction with a tetracarboxylic acid component.
The liquid crystal aligning agent according to any one of claims 1 to 5, wherein the diamine (0) is used in an amount of 5 mol% or more with respect to the diamine component.
Furthermore, at least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component that does not contain the diamine (0) and a polyimide that is an imidized product of the polyimide precursor (B). The liquid crystal aligning agent according to any one of claims 1 to 6.
A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1 to 7.
A liquid crystal display element comprising the liquid crystal alignment film according to claim 8.
A method for manufacturing a liquid crystal display device, comprising the following steps (1) to (3).
Step (1): A step of applying the liquid crystal aligning agent according to any one of claims 1 to 7 onto a substrate Step (2): A step of baking the applied liquid crystal aligning agent to obtain a film Step (3) ): a step of subjecting the film obtained in step (2) to orientation treatment
The method for manufacturing a liquid crystal display element according to claim 10, wherein the alignment treatment is a photo-alignment treatment.
Diamines represented by the following formulas (d A -1) to (d A -2).

(Z 1 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms, and the above alkyl group, alkenyl group, or A hydrogen atom of the alkynyl group may be substituted with a monovalent group. n1, n1′, n1″, n2 and n2′ are each independently an integer of 1 or more, and n1, n1′ and The sum of n1″ is 4 to 10. The sum of n2 and n2′ is 4 to 10. Boc represents a tert-butoxycarbonyl group.
Any hydrogen atom on the benzene ring to which the amino groups at both ends are bound may be substituted with a monovalent group. )
A polymer obtained from a diamine component containing the diamine according to claim 12.
A polyimide that is a polyimide precursor or an imidized product thereof obtained by a polycondensation reaction of a diamine component containing the diamine according to claim 12 and a tetracarboxylic acid component.
At least one polymer selected from the group consisting of a polyimide precursor obtained using a diamine component containing a diamine (0) represented by the following formula (D A ) and a polyimide that is an imidized product of the polyimide precursor.

(Z 1 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms, and the above alkyl group, alkenyl group, or A hydrogen atom of the alkynyl group may be substituted with a monovalent group Any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded may be substituted with a monovalent group.
A represents a divalent organic group (a) in which any carbon-carbon bond in an alkylene group having 4 to 10 carbon atoms satisfies either of the following conditions (1) and (2). In the following conditions (1) and (2), *1 is bonded to a carbon atom possessed by an alkylene group, and the carbon-carbon bond is a carbon-carbon bond forming the main chain of the polymer (P). selected from
(1) "*1-N(Boc)-*1" is inserted between two or more carbon-carbon bonds.
(2) "*1-N(Boc)-C(=O)-N(R)-*1" is inserted between one or more carbon-carbon bonds. R represents a hydrogen atom or a monovalent organic group. Boc represents a tert-butoxycarbonyl group. )
The diamine according to claim 12, wherein the formulas (d A -1) to (d A -2) are the following formulas DA-1 or DA-2.