TW202321428A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Provided are a liquid crystal alignment agent and the like, said liquid crystal alignment agent being one that forms a liquid crystal alignment film having high light transmittance and a high voltage holding ratio. This liquid crystal alignment agent contains an (A) component and a (B) component. (A) component: at least one polymer (P) selected from the group consisting of polyimides and polyimide precursors obtained by a polymerization reaction of a diamine component including a diamine represented by formula (1), and a tetracarboxylic acid component including an aromatic tetracarboxylic dianhydride or a derivative thereof. (B) component: a compound having two or more crosslinkable groups. (In the formula, each R1 independently represents a hydrogen atom or a 1-3C monovalent organic group, and at least two of the R1s represent a 1-3C monovalent organic group. Some or all of the hydrogen atoms of the R1s may be substituted. Moreover, some or all of the hydrogen atoms on the benzene rings may be replaced with substituent groups. L represents a single bond or a divalent linking group.).

Description

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

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element equipped with the liquid crystal alignment film.

Liquid crystal display devices are widely used in small applications such as mobile phones and smart phones, as well as larger applications such as TVs and monitors. A liquid crystal display element is generally configured by arranging a pair of electrode substrates to face each other with a predetermined gap (several μm), and sealing liquid crystal between the electrode substrates. In addition, display is performed on the liquid crystal display element by applying a voltage between the transparent conductive films constituting the electrodes of the electrode substrate. These liquid crystal display elements have a liquid crystal alignment film which is indispensable for controlling the alignment state of liquid crystal molecules. For liquid crystal display elements, various driving methods have been developed that differ in electrode structure, physical properties of liquid crystal molecules used, and the like. For example, TN (Twisted Nematic) method, STN (Super Twisted Nematic) method, VA (Vertical Alignment) method, and IPS (In-Plane Switching) method are known. , FFS (Fringe Field Switching, Fringe Field Switching) mode and other modes.

VA (Vertical Alignment) type liquid crystal display element, because of its wide viewing angle, fast response speed, high contrast ratio, and the friction treatment can be omitted in the production process, it is especially used for large-scale TV applications and screen applications. It is widely used (Patent Documents 1 to 2). In terms of polymer materials for forming liquid crystal alignment films, polyimide polymers are generally used. Patent Document 3 discloses a polyimide-based liquid crystal alignment film obtained by using a monomer component containing aromatic tetracarboxylic dianhydride and aromatic diamine in consideration of improving the stability of liquid crystal alignment. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2008-76950 [Patent Document 2] International Publication No. 2008/117615 [Patent Document 3] Japanese Patent Laid-Open No. 57-40227

(Problem to be solved by the invention)

In recent years, ultra-high-definition panels such as 4K and 8K have been developed. In these panels, the share of black matrix (BM) and TFT has increased, and the aperture ratio of the panel has decreased. Therefore, the increase in light transmittance of the display part is affected by Pay attention to.

Also, if the voltage holding ratio (VHR: Voltage Holding Ratio) of the liquid crystal display element is low, it is difficult to apply a sufficient voltage to the liquid crystal molecules even if a voltage is applied. Therefore, due to use under high temperature and high humidity, long-term use, etc., the display contrast may decrease, or flicker may occur, resulting in poor display. Especially in automotive applications such as car navigation systems and instrument panel panels, sometimes they are used or placed in a high-temperature environment for a long time. In this case, the drop in voltage retention rate is more significant, and a liquid crystal alignment film with high voltage retention rate is required. .

On the other hand, the use of so-called wholly aromatic polyimides obtained from monomer components containing aromatic tetracarboxylic dianhydrides and aromatic diamines such as Patent Document 3, due to intramolecular or intermolecular charge transfer ( Hereinafter, the charge transfer migration is also referred to as CT migration), which absorbs in the visible light region and causes the coloring of the polyimide film. The research of the inventors revealed that the coloring of the above-mentioned polyimide film becomes more intense when a cross-linking compound is added.

In view of the foregoing, the object of the present invention is to provide a liquid crystal alignment agent capable of forming a liquid crystal alignment film capable of obtaining a high light transmittance and a high voltage retention even when a crosslinking compound is added, and a liquid crystal alignment obtained by the liquid crystal alignment agent. film, and a liquid crystal display element with the liquid crystal alignment film. (How to solve the problem)

The inventors of the present invention worked hard to achieve the above-mentioned problems, and as a result, found that a liquid crystal alignment agent containing a polymer component obtained using a specific raw material component and a specific cross-linking compound is effective for achieving the above-mentioned object, and completed the present invention.

The present invention is a liquid crystal alignment agent characterized by containing the following components (A) and (B), a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. Component (A): Polymer (P), obtained from the polymerization reaction of a diamine component containing a diamine represented by the following formula (1) and a tetracarboxylic acid component containing an aromatic tetracarboxylic dianhydride or its derivatives At least one of the group consisting of polyimide precursors and polyimides that are imides of the polyimide precursors,

[chemical 1]

In the formula, R ₁ each independently represent a hydrogen atom or a monovalent organic group having 1 to 3 carbons, and at least two of R ₁ represent a monovalent organic group having 1 to 3 carbons. Part or all of the hydrogen atoms possessed by R ₁ may be substituted. In addition, some or all of the hydrogen atoms on the benzene ring may be substituted by substituents. L represents a single bond or a divalent linking group. (B) Component: A compound having two or more crosslinkable groups.

In addition, throughout this specification, a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and * represents an atomic bond. (Effect of Invention)

According to the present invention, it is possible to obtain a liquid crystal alignment agent capable of forming a liquid crystal alignment film having high light transmittance and high voltage retention even when a crosslinking compound is added, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal alignment film having the liquid crystal alignment film. Film liquid crystal display element. The mechanism of the present invention to obtain the above-mentioned effects is not necessarily clear, but it is roughly estimated as follows. By using a specific aromatic diamine whose ortho-position of the amine group involved in polymerization is substituted as a raw material monomer of polyimide, the obtained polyimide will have aromatic acid dianhydride derived from π-conjugation cleavage The skeleton. Thereby, CT migration can be suppressed and the effect of improving the transparency of the polyimide film can be obtained. Also, by using the above-mentioned specific aromatic diamine, intermolecular stacking is hindered, voids appear in the film, electron movement in the film is suppressed, and as a result, the resistance of the polyimide film increases. In this way, the CR time constant represented by the product of C (capacitance) and R (resistance), which is one of the factors determining the voltage retention ratio, can be increased, and the obtained liquid crystal alignment film has a high voltage retention ratio. Furthermore, the cross-linking compound contained in the liquid crystal alignment agent of the present invention has multiple cross-linking groups, so it is easy to undergo a cross-linking reaction with the polymer (P). Therefore, the polar groups such as carboxyl groups possessed by the polymer (P) are reduced, and the obtained liquid crystal alignment film has a higher voltage holding ratio.

The liquid crystal alignment agent of the present invention, as mentioned above, is characterized in that it contains a polymer (P), and the polymer (P) is selected from two diamines (hereinafter also referred to as specific diamines) represented by the above formula (1). Polyimide precursor obtained by polymerization reaction of amine component and tetracarboxylic acid component containing aromatic tetracarboxylic dianhydride or its derivatives and polyimide which is imide of the polyimide precursor At least one of the formed groups. The monovalent organic group of R ₁ in formula (1) having 1 to 3 carbons can include an alkyl group with 1 to 3 carbons (preferably methyl, ethyl, n-propyl or isopropyl.), carbon Alkoxy with 1 to 3 carbons, alkoxyalkyl with 2 to 3 carbons. In view of improving the voltage retention rate, 2 to 4 R _1s are preferably monovalent organic groups with 1 to 3 carbon atoms. Also, from the viewpoint of improving the reactivity with the crosslinkable compound and increasing the voltage retention, it is more preferable that at least two of R ₁ are methyl groups or methoxy groups. Part or all of the hydrogen atoms possessed by R ₁ may be substituted, and examples of such substituents include halogen atoms, hydroxyl groups, and cyano groups. In addition, a part or all of the hydrogen atoms on the benzene ring can also be replaced by a monovalent organic group with 1 to 3 carbons (specific examples can include the example of the monovalent organic group of _R1 above), a halogen atom, a hydroxyl group, a cyano group, etc. Substituents replace.

In the above formula (1), the divalent linking group of L includes -O-, -S-, -SO-, -SO ₂ -, -CO-, -C(=O)-O-, -NR-( R represents a hydrogen atom or an alkyl group with a carbon number of 1 to 6), -CONR- (R represents a hydrogen atom or an alkyl group with a carbon number of 1 to 6.), -CH ₂ -, a straight chain with a carbon number of 2 to 12 or Branched alkylene group, any -CH ₂ -of the aforementioned alkylene group is replaced by -O-, -CO-, -C(=O)-O-, -NR- (R represents a hydrogen atom or a carbon number of 1 to 6 Alkyl), or -CONR- (R represents a hydrogen atom or an alkyl group with 1 to 6 carbons), a divalent organic group substituted by any of them, a cycloalkylene group with 5 to 6 carbons, and a phenylene group , phenylenedioxy, -Si(R ₃ )(R ₄ )-(R ₃ and R ₄ each independently represent an alkyl or alkoxy group with 1 to 6 carbon atoms.), and -(Q) _s -(R ₅ ) _t -(-Si(R ₃ )(R ₄ )-O-) _r -Si(R ₃ )(R ₄ )-(R ₅ ) _t' -(Q) _s' -(R ₃ and R ₄ each independently represent an alkyl or alkoxy group with 1 to 6 carbons. R ₅ each independently represent an alkylene group with 1 to 6 carbons. Q represents -O- or -S-. r is 0 to Integer of 20. s, s', t, t' are integers of 0 or 1, at least one of s, s', t, t' is 1. A plurality of R ₃ , R ₄ , R ₅ and Q can be They may be the same or different.

Among these, in view of ideally obtaining the effects of the present invention, the divalent linking group of L in the above formula (1) is -CH ₂ -, a linear or branched alkylene group having 2 to 12 carbon atoms. ideal. Part or all of the hydrogen atoms possessed by the above-mentioned divalent linking group may be substituted, and examples of such substituents include halogen atoms, hydroxyl groups, and cyano groups.

Desirable specific examples of the diamine represented by the above formula (1) include diamines represented by the following formulas (d1-1) to (d1-6), wherein, considering the viewpoint of obtaining the effect of the present invention ideally, (d1-1 )～(d1-3) The diamines represented are more ideal.

[Chem 2]

In the formula, A, B, C, and D each independently represent a hydrogen atom, methyl, ethyl, isopropyl, methoxy, or methoxymethyl, and at least two of A to D are hydrogen atoms foundation. More preferably, A and B each independently represent methyl, ethyl, isopropyl, methoxy, or methoxymethyl, and C and D each independently represent a hydrogen atom or a group as defined above for A and B. A, B, C, and D are more preferably each independently representing a methyl group, an ethyl group, an isopropyl group, a methoxy group, or a methoxymethyl group, and at least two of A to D represent a methyl group or an ethyl group . E represents a single bond, -CH ₂ -, -(CH ₂ ) ₂ -, -O-, -S-, -CO-, -SO-, -SO ₂ -, -C(=O)-O-, - CONH-, -CO-N(CH ₃ )-, -NH-, -N(CH ₃ )-, -Si(CH ₃ ) ₂ -, -Si(OCH ₃ ) ₂ -, -O-Si(CH ₃ ) ₂ -O-, phenylene, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -. In the above formulas (d1-1) ~ (d1-3), the ideal combination of A, B, C, D, E (A, B, C, D, E) can enumerate the following aspects; (methyl, methyl group, hydrogen atom, hydrogen atom, -CH ₂ -), (methyl, ethyl, hydrogen atom, hydrogen atom, -CH ₂ -), (ethyl, ethyl, hydrogen atom, hydrogen atom, -CH ₂ - ), (isopropyl, isopropyl, hydrogen atom, hydrogen atom, -CH ₂ -), (methoxymethyl, methoxymethyl, hydrogen atom, hydrogen atom, -CH ₂ -), (form base, methyl, methyl, hydrogen atom, -CH ₂ -), (ethyl, ethyl, ethyl, hydrogen atom, -CH ₂ -), (isopropyl, isopropyl, methyl, methyl , -CH ₂ -), (methoxymethyl, methoxymethyl, methyl, hydrogen atom, -CH ₂ -), (methyl, ethyl, methyl, hydrogen atom, -CH ₂ -) , (methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, -CH ₂ -), (methyl, methyl, methyl, methyl, -CH ₂ -) , (ethyl, methyl, methyl, ethyl, -CH ₂ -), (ethyl, ethyl, ethyl, ethyl, -CH ₂ -), (methyl, methyl, ethyl, ethyl base, -CH ₂ -), (ethyl, ethyl, isopropyl, isopropyl, -CH ₂ -), (isopropyl, isopropyl, isopropyl, isopropyl, -CH ₂ - ), (isopropyl, isopropyl, methyl, hydrogen atom, -CH ₂ -), (methoxy, methoxy, methyl, methyl, -CH ₂ -); (methyl, methyl , hydrogen atom, hydrogen atom, -O-), (ethyl, ethyl, hydrogen atom, hydrogen atom, -O-), (methyl, methyl, methyl, hydrogen atom, -O-), (form base, methyl, methyl, methyl, -O-), (methyl, methyl, ethyl, ethyl, -O-); (methyl, methyl, hydrogen atom, hydrogen atom, -S- ), (ethyl, ethyl, hydrogen atom, hydrogen atom, -S-), (methyl, methyl, methyl, hydrogen atom, -S-), (methyl, methyl, methyl, methyl , -S-), (ethyl, ethyl, ethyl, ethyl, -S-), (methyl, methyl, ethyl, ethyl, -S-); (methyl, methyl, methyl Base, hydrogen atom, -CO-), (methyl, methyl, hydrogen atom, hydrogen atom, -CO-), (methyl, methyl, methyl, methyl, -CO-); (methyl, Methyl, ethyl, hydrogen atom, -SO ₂ -), (methyl, methyl, hydrogen atom, hydrogen atom, -SO ₂ -), (methyl, methyl, methyl, methyl, -SO ₂ -), (ethyl, ethyl, methyl, methyl, -SO ₂ -); (methyl, methyl, methyl, methyl, -SO-), (methyl, methyl, hydrogen atom, hydrogen atom, -SO-); (methyl, methyl, hydrogen atom, hydrogen atom, -C(=O)-O-), (methyl, methyl, methyl, methyl, -C(=O )-O-); (methyl, methyl, hydrogen atom, hydrogen atom, -CO-N(CH ₃ )-); (methyl, methyl, ethyl, ethyl, -N(CH ₃ )- ), (methyl, methyl, methyl, methyl, -N(CH ₃ )-); (methyl, methyl, hydrogen atom, hydrogen atom, -CO-NH-); (ethyl, methyl , ethyl, methyl, -NH-), (methyl, methyl, methyl, methyl, -NH-); (methyl, methyl, hydrogen atom, hydrogen atom, -Si(CH ₃ ) ₂ -); (ethyl, ethyl, hydrogen atom, hydrogen atom, -Si(OCH ₃ ) ₂ -); (methyl, methyl, methyl, methyl, -O-Si(CH ₃ ) ₂ -O -); (methyl, methyl, hydrogen atom, hydrogen atom, -(CH ₂ ) ₂ -), (methyl, methyl, methyl, methyl, -(CH ₂ ) ₂ -), (ethyl , ethyl, hydrogen atom, hydrogen atom, -(CH ₂ ) ₂ -), (methyl, methyl, ethyl, ethyl, -(CH ₂ ) ₂ -); (methyl, methyl, methyl , methyl, phenylene), (ethyl, ethyl, hydrogen atom, hydrogen atom, phenylene); (methyl, ethyl, methyl, ethyl, -C(CH ₃ ) ₂ -), (methyl, methyl, methyl, methyl, -C(CH ₃ ) ₂ -); (methyl, methyl, methyl, methyl, -C(CF ₃ ) ₂ -); (methyl, methyl group, hydrogen atom, hydrogen atom, single bond), (methyl group, hydrogen atom, methyl group, hydrogen atom, single bond), (trifluoromethyl group, hydrogen atom, trifluoromethyl group, hydrogen atom, single bond) , (methoxy, hydrogen atom, methoxy, hydrogen atom, single bond), (methyl, ethyl, methyl, ethyl, single bond), (methyl, ethyl, methyl, hydrogen atom, single bond), (ethyl, ethyl, ethyl, ethyl, single bond), (methoxy, methoxy, methoxy, methoxy, single bond), (isopropyl, isopropyl , hydrogen atom, hydrogen atom, single bond), (methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, single bond).

(Manufacture of Polymer (P)) The polymer (P) contained in the liquid crystal alignment agent of the present invention is a polyimide precursor obtained by using a diamine component containing a specific diamine, or a polyamide that is an imide of the polyimide precursor imine. Among them, the polyimide precursor is a polyimide polymer obtained by imidizing polyamic acid, polyamic acid ester, and the like.

The polyimide precursor of the above-mentioned polymer (P), that is, polyamic acid (P'), can be obtained by the polymerization reaction of the above-mentioned diamine component containing a specific diamine and a tetracarboxylic acid component. Specific diamines may be used alone or in combination of two or more.

In this case, the usage-amount of a specific diamine is desirably 5 mol% or more with respect to the whole diamine component, More preferably, it is 10 mol% or more, More preferably, it is 20 mol% or more.

The diamine component used in the production of the polyamic acid (P') may contain diamines other than the specific diamine (hereinafter also referred to as other diamines). When other diamines are used in combination with the above-mentioned specific diamine, the usage-amount of a specific diamine with respect to a diamine component is desirably 90 mol % or less, More preferably, it is 80 mol % or less. Examples of other diamines are listed below, but the present invention is not limited thereto. The above-mentioned other diamines may be used alone or in combination of two or more. Aromatic diamine (d), 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'-dihydroxy-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4' -diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-bis Aminobiphenyl, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(4-aminophenoxy) ) ethane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-aminophenyl)-2-methyl Phenoxy)butane, 1,4-bis(3-aminophenyl)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-amino Phenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-amine phenoxy)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, 3 -[2-[2-(4-Aminophenoxy)ethoxy]ethoxy]aniline, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4- Aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 4,4'-bis(4-aminophenyl)benzene oxy)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, 4'-[2-(4-aminophenoxy)ethoxy]-[1,1'-biphenyl]-4-amine, 1,4-bis [2-(4-aminophenyl)ethyl]succinate, 1,6-bis[2-(4-aminophenyl)ethyl]adipate, 1,4-phenylene Bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-Phenylbis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate , bis(4-aminophenyl) isophthalate, bis(3-aminophenyl) isophthalate, ; 4,4'-diaminoazobenzene, diaminodi Phenylacetylene (diaminotolan), 4,4-diaminochalcone and other diamines with photoalignment groups; 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4 -Diamine-N,N-diallylaniline and other diamines with photopolymerizable groups at the end; 1-(4-(2-(2,4-diaminophenoxy)ethoxy)benzene base)-2-hydroxy-2-methylacetone, 2-(4-(2-hydroxy-2-methylpropionyl)phenoxy)ethyl-3,5-diaminobenzoate is Representative benzoin or its alkyl ethers, benzyl ketals, acetophenones, acyl phosphine oxides, diphenyl ketones, or amino diphenyl ketones exhibit free radical polymerization Diamines that act as bases for initiators (hereinafter also referred to as diamines with free radicals); 4,4'-diaminobenzoylaniline and other diamines with amide bonds, (4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,3-bis(4-aminophenethyl)urea and other diamines with urea bonds; 4, 4'-sulfonyl diphenylamine, 3,3'-sulfonyl diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4- Aminophenyl)silane, Dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 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 base) 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, 3,3'-diaminodiphenylmethane, 3,4'-diaminobis Phenylmethane, 4,4'-diaminodiphenylmethane, 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-diaminopyridine Pyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperone, 3,6-di Aminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-(3-(1H-imidazol-1-yl)propane Base-3,5-diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl ]-aniline, 1,4-bis(p-aminobenzyl)piperone, 4,4'-[propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, diamines represented by the following formula (z-1) ~ formula (z-5) (formula (z-2 ), each independently has the following definitions), 2,5-bis(4-aminophenyl)pyrrole, 4,4'-(1-methyl-1H-pyrrole-2,5-diyl) Bis[aniline], 1,4-bis-(4-aminophenyl)-piperone, 2-N-(4-aminophenyl)pyridine-2,5-diamine, 2-N-(5 -aminopyridin-2-yl)pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-6- Aminobenzimidazole, 5-(1H-benzimidazol-2-yl)benzene-1,3-diamine and other diamines containing heterocycles, or 4,4'-diaminodiphenylamine, 4,4 '-Diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-1,4-phenylenediamine, N,N'-bis(4-aminophenyl) )-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N Diamines having a diphenylamine structure such as '-dimethyl-1,4-phenylenediamine have at least one compound selected from the group consisting of nitrogen-containing heterocycles, secondary amine groups, and tertiary amine groups. Nitrogen structure (hereinafter also referred to as specific nitrogen-containing structure. ) of diamine (except that there is no amino group in the molecule bonded with a protecting group that is detached by heating and replaced by a hydrogen atom); 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, 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 acid, and 4,4'-bis Aminodiphenyl ether-3,3'-dicarboxylic acid and other diamines with carboxyl groups; 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2 ,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamino-3,3'-dihydroxybiphenyl; 4-(2-(methylamino) Ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-dihydroinden-5-amine, 1- (4-Aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine; N,N'-bis(2-tert-butoxycarbonylamine Base-4-aminophenyl)adipamide, 4-amino-N-(2-tert-butoxycarbonylamino-4-aminophenyl)benzamide, carbamic acid N-[ (2,5-diaminophenyl)methyl]-1,1-dimethylethyl ester, carbamic acid, N-[3-(2,5-diaminophenyl)propyl]-1, 1-Dimethyl ethyl ester, carbamic acid N,N-[(2,5-diamino-1,3-phenylene)di-3,1-propanediyl]bis-C,C-bis( 1,1-Dimethylethyl) ester, N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine, Benzoic acid 4-amino-2-tert-butoxycarbonylamino-1,1'-[(1,1,3,3-tetramethyl-1,3-disiloxanediyl)di- 4,1-Butanediyl]ester, carbamic acid, N-[2-(4-aminophenyl)ethyl]-N-[[[2-(4-aminophenyl)ethyl]amino ]carbonyl]-1,1-dimethylethyl ester, carbamic acid, N-(4-aminophenyl)-N-[[1-(4-aminophenyl)-4-piperidinyl]methanol Group]-1,1-dimethylethyl ester, etc. have the group "-N(D)-" (D represents a protecting group that is detached by heating and replaced by a hydrogen atom, preferably tertiary butoxycarbonyl.) Diamines; 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy-2,4- Diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene, 1-dodecyloxy-2,5 -Diaminobenzene, 1-tetradecyloxy-2,5-diaminobenzene, 1-pentadecyloxy-2,5-diaminobenzene, 1-hexadecyloxy-2, 5-diaminobenzene and 1-octadecyloxy-2,5-diaminobenzene are aromatic diamines represented by long-chain alkyl groups with 12 to 20 carbons; 1,3-bis(3 -aminopropyl)-tetramethyldisiloxane, 1,3-bis[3-(p-aminophenylaminoformyl)propyl]tetramethyldisiloxane, etc. have siloxane bonds Diamines; m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl ) cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), formula (Y-1)～(Y- 167), diamine, etc., in which two amine groups are bonded to the group represented by any one of 167).

[Chem 3]

In the above-mentioned aromatic diamine (d), A represents a monovalent group in which two primary amino groups are bonded to an aromatic group. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, and a biphenyl structure. X represents a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 15.), -CONH-, -NHCO-, -CO-N(CH ₃ )-, -NH-, -O-, - COO-, -CH=CH-COO-(CH ₂ ) _q -(q is an integer from 1 to 18.), or -(A ₁ ) _a0 -((CH ₂ ) _a1 -A ₁ ) _m1 -(a0 is An integer of 0 or 1, a1 is an integer of 1 to 15 _{, A1} represents -O- or -COO-, and when there are multiple A1s, each _A1 independently has the above definition. m1 is an integer of 1 to 2. When m1 is 2, a plurality of a1 each independently have the above-mentioned definition.

J represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an aromatic hydrocarbon group having 6 to 40 carbon atoms. However, at least one of the hydrogen atoms possessed by the above-mentioned alicyclic hydrocarbon groups and aromatic hydrocarbon groups is replaced by a halogen atom, an alkyl group containing a halogen atom, an alkoxy group containing a halogen atom, an alkyl group having 3 to 10 carbon atoms, or an alkyl group having 3 to 10 carbon atoms. Substituted by an alkoxy group with 10 or an alkenyl group with 3 to 10 carbons, and the carbon-carbon bond possessed by any methylene group in these groups can also be interrupted by -O-.

In addition, in addition to the above-mentioned alicyclic hydrocarbon group and aromatic hydrocarbon group, J may further have at least one selected from the group consisting of an alicyclic hydrocarbon group and an aromatic hydrocarbon group that is unsubstituted or substituted with a substituent other than the above-mentioned substituents. 1 base.

An alkyl group containing a halogen atom, for example: an alkyl group containing a halogen atom having 1 to 10 carbon atoms.

An alkoxy group containing a halogen atom, for example: an alkoxy group containing a halogen atom having 1 to 10 carbon atoms.

The alicyclic hydrocarbon group of J includes cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclodecane ring, steroid skeleton (such as cholestanyl group, cholesterol group, lanosteryl group, etc.), etc., aromatic Examples of the hydrocarbon group include a benzene ring, a naphthalene ring, and the like. When J has at least one of a cyclohexane ring and a benzene ring, the group "-X-J" is, for example, the following structure (S1), and more desirable structures include the following formulas (S1-1) to (S1-5).

[chemical 4]

In the above (S1), X ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15.), -CONH-, -CO-N(CH ₃ )-, -NH-, -O -, -COO-, -CH=CH-COO-(CH ₂ ) _q -(q is an integer from 1 to 18.), or -(A ₁ ) _a0 -((CH ₂ ) _a1 -A ₁ ) _m1 - (a0 is an integer of 0 or 1, a1 is an integer of 1 to 15 _{, A1} represents -O- or -COO-, and when there are multiple A1s, each _A1 independently has the above definition. m1 is 1 to 2 An integer of . When m1 is 2, a plurality of a1 each independently have the above definition.

G ¹ represents a divalent cyclic group selected from phenylene and cyclohexylene. Any hydrogen atom on the aforementioned cyclic group can also be replaced by an alkyl group with 1 to 3 carbons, an alkoxy group with 1 to 3 carbons, a fluorine-containing alkyl group with 1 to 3 carbons, or a fluorine-containing group with 1 to 3 carbons. Alkoxy or fluorine atom substitution.

m is an integer of 1-4. When m is 2 or more, a plurality of X ¹ and G ¹ each independently have the above-mentioned definitions.

^R1 represents a fluorine atom, a fluorine-containing alkyl group with 1 to 10 carbons, an alkoxy group with 1 to 10 carbons, an alkyl group with 3 to 10 carbons, and an alkoxy group with 3 to 10 carbons group, or an alkoxyalkyl group with 3 to 10 carbon atoms.

[chemical 5]

X ¹ and R ¹ are synonymous with X ¹ and R ¹ in the above formula (S1). Specific examples of the above-mentioned aromatic diamine (d) include diamines represented by the following formulas (d-1) to (d-2). More ideal specific examples include formulas (d-1) to (d- 2) The diamine represented, and cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4 -diaminobenzene, 3,5-diaminobenzoic acid cholestyl ester, 3,5-diaminobenzoic acid cholestyl ester, 3,5-diaminobenzoic acid lanostyl ester and 3, Diamines having a steroid skeleton such as 6-bis(4-aminobenzoyloxy)cholestane. When X in the above-mentioned group "-XJ" represents "-CH=CH-COO-(CH ₂ ) _q -", more preferable specific examples of the aromatic diamine (d) include [4-[(E)-3 -[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy ) benzoate, or [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4 ,4,4-Trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-propane -1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate.

[chemical 6]

啶、𠰌啉、咪唑、吡唑、吡啶、嘧啶、嗒𠯤、吡𠯤、氮雜吲

、三唑、吲哚、苯并咪唑、咔唑等。 針對其他二胺，考量理想地獲得本發明之效果之觀點，宜為上述芳香族二胺(d)、對苯二胺、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙(3-胺基苯基)六氟丙烷、2,2-雙(3-胺基-4-甲基苯基)六氟丙烷、2,2-雙(4-胺基苯基)丙烷、2,2-雙(3-胺基苯基)丙烷、2,2-雙(3-胺基-4-甲基苯基)丙烷、上述具有羧基之二胺、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基酮、2,2’-二甲基-4,4’-二胺基聯苯、4,4’-二胺基-2,2’-雙(三氟甲基)聯苯、上述具有光配向性基之二胺、具有自由基開始作用之二胺、末端具有光聚合性基之二胺、具有基「-N(D)-」之二胺、上述具有特定之含氮結構之二胺較佳。 X and J are synonymous with X and J of the said aromatic diamine (d) including an ideal form. In the aforementioned formula (d-2), two X and J may be the same as or different from each other. Ideal specific examples of the nitrogen-containing heterocycle in the above-mentioned diamine having a specific nitrogen-containing structure include pyrrole, oxazole, isoxazole, pyrrolidine, imidazolidine, piperidine, piperazole,

Pyridine, 𠰌line, imidazole, pyrazole, pyridine, pyrimidine, pyridine, pyridine, azaind

, triazole, indole, benzimidazole, carbazole, etc. For other diamines, considering the viewpoint of ideally obtaining the effect of the present invention, the above-mentioned aromatic diamine (d), p-phenylenediamine, 2,2-bis[4-(4-aminophenoxy)benzene base]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, the above-mentioned diamines with carboxyl groups, 4,4'-diaminobis Phenylmethane, 4,4'-diaminodiphenylketone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2' -Bis(trifluoromethyl)biphenyl, the above-mentioned diamines having a photoalignment group, diamines having a free radical initiation action, diamines having a photopolymerizable group at the end, and a group "-N(D)-" The diamines and the above-mentioned diamines with specific nitrogen-containing structures are preferred.

When other diamines are used in addition to the above-mentioned specific diamines, the usage-amount of the above-mentioned other diamines is preferably 10-90 mol %, more preferably 20-80 mol % with respect to the whole diamine component.

The usage-amount of the above-mentioned other diamine is preferably 10-90 mol %, more preferably 20-80 mol % with respect to the whole diamine component used for manufacture of a polymer (P). (tetracarboxylic acid component) When producing the above-mentioned polyamic acid (P'), the tetracarboxylic acid component reacted with the diamine component can use not only tetracarboxylic dianhydride, but also tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic dihalide, and tetracarboxylic acid dihalide. Derivatives of tetracarboxylic dianhydrides such as alkyl esters and tetracarboxylic dialkyl dihalides.

The polymer (P) and polyamic acid (P') of the present invention are obtained by containing aromatic tetracarboxylic dianhydride or derivatives thereof (hereinafter, they are also collectively referred to as aromatic tetracarboxylic acid derivatives.) It is obtained by the polymerization reaction of tetracarboxylic acid component and diamine component. Here, the aromatic tetracarboxylic dianhydride refers to an acid dianhydride obtained by intramolecularly dehydrating four carboxyl groups including at least one carboxyl group bonded to an aromatic ring. Considering the viewpoint of obtaining the effect of the present invention ideally, the above-mentioned aromatic tetracarboxylic dianhydride or its derivatives contain tetracarboxylic dianhydride having at least one substructure selected from the group consisting of benzene ring and naphthalene ring. Or derivatives thereof are more preferable. The tetracarboxylic acid components that can be used in the synthesis of polyamic acid (P') preferably include the following aromatic tetracarboxylic dianhydrides or derivatives thereof (hereinafter also collectively referred to as specific aromatic tetracarboxylic acid derivatives (b )).

Moreover, the said aromatic tetracarboxylic dianhydride or its derivative(s) may be used individually by 1 type, and may use it in combination of 2 or more types.

pyromellitic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 1,4, 5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-Perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetra Carboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, ethylene glycol bis-trimellitic anhydride, 4,4'-(hexafluoroisopropylidene ) diphthalic anhydride, 4,4'-carbonyl diphthalic anhydride, 4,4'-oxybis(1,4-phenylene)bis(phthalic acid)dianhydride, or 4 , 4'-methylene bis(1,4-phenylene) bis(phthalic acid) dianhydride and other aromatic tetracarboxylic dianhydrides; Carboxylic acid dianhydride, etc.

Ideal examples of the above specific aromatic tetracarboxylic acid derivatives (b) include pyromellitic dianhydride, 3,3',4,4'-diphenone tetracarboxylic dianhydride, 3,3' ,4,4'-Biphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3', 4,4'-Diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-Biphenyl tetracarboxylic dianhydride, 2,2',3,3'-Biphenyl tetracarboxylic dianhydride, or derivatives thereof.

The usage ratio of the above-mentioned aromatic tetracarboxylic acid derivatives (more preferably the specific aromatic tetracarboxylic acid derivatives (b)) is more than 10 mol% relative to 1 mol of all the tetracarboxylic acid components used. More preferably 20 mole % or more, more preferably 50 mole % or more. The tetracarboxylic acid component used in the production of the polyamic acid (P') may contain tetracarboxylic acid derivatives other than aromatic tetracarboxylic acid derivatives (hereinafter also referred to as other tetracarboxylic acid derivatives.). When using other tetracarboxylic acid derivatives in addition to the above-mentioned aromatic tetracarboxylic acid derivatives, the amount of aromatic tetracarboxylic acid derivatives relative to the tetracarboxylic acid component is preferably 90 mole % or less, more preferably 80 mole % or less. ideal. Examples of other tetracarboxylic acid derivatives are listed below, but the present invention is not limited thereto. The above-mentioned other tetracarboxylic acid derivatives may be used alone or in combination of two or more.

Examples of the above-mentioned other tetracarboxylic acid derivatives include acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and derivatives thereof. Here, the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecularly dehydrating four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not need to be composed only of a chain hydrocarbon structure, and a part thereof may have an alicyclic structure or an aromatic ring structure. Alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecularly dehydrating four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. But these 4 carboxyl groups are not bonded to the aromatic ring. Moreover, it does not need to consist only of an alicyclic structure, and a part may have a chain hydrocarbon structure and an aromatic ring structure. Alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecularly dehydrating four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. But these 4 carboxyl groups are not bonded to the aromatic ring. Moreover, it does not need to consist only of an alicyclic structure, and a part may have a chain hydrocarbon structure and an aromatic ring structure. The above-mentioned acyclic aliphatic tetracarboxylic dianhydride and alicyclic tetracarboxylic dianhydride may be used alone or in combination of two or more.

Considering the viewpoint of obtaining the effects of the present invention ideally, the above-mentioned alicyclic tetracarboxylic dianhydride or derivatives thereof preferably contain a compound having a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure. Tetracarboxylic dianhydrides of at least one substructure in the group or derivatives thereof are more preferred.

Other tetracarboxylic acid components that can be used in the synthesis of polyamic acid (P') preferably include the following tetracarboxylic dianhydrides or their derivatives (hereinafter also collectively referred to as specific aliphatic tetracarboxylic acids derivative (c)). 1,2,3,4-butanetetracarboxylic dianhydride and other acyclic aliphatic tetracarboxylic dianhydrides; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl -1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic 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 dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid Dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 4-(2,5-dipentoxytetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic 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-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 and other alicyclic tetracarboxylic dianhydrides; anhydride, etc.

Ideal examples of the aforementioned specific aliphatic tetracarboxylic acid derivatives (c) include 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride , 1,2-Dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride , 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutane tetracarboxylic Acid 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-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2, 4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride or derivatives thereof.

(Synthesis of polyamide acid) The synthesis of polyamic acid is carried out by reacting the diamine component containing the above-mentioned specific diamine and the tetracarboxylic acid derivative component containing the above-mentioned aromatic tetracarboxylic dianhydride or its derivatives in an organic solvent. The proportion of tetracarboxylic dianhydride and diamine used in the synthesis reaction of polyamic acid is preferably 0.5-2 equivalents of anhydride groups of tetracarboxylic dianhydride relative to 1 equivalent of amine groups of diamine. , more preferably at a ratio of 0.8 to 1.2 equivalents. Similar to a general polycondensation reaction, the closer the equivalent of the acid anhydride group of the tetracarboxylic dianhydride is to 1 equivalent, the larger the molecular weight of the polyamic acid to be produced becomes.

In the synthesis reaction of polyamic acid, the reaction temperature is preferably -20-150°C, more preferably 0-100°C. Also, the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

The synthesis reaction of polyamic acid can be carried out at any concentration, preferably 1-50% by mass, more preferably 5-30% by mass. The reaction may be carried out at a high concentration in the initial stage, and a solvent may be added thereafter.

Specific examples of the aforementioned organic solvents include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide , N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone. Also, 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, ethyl Glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether.

(Synthesis of polyamide ester) Polyamic acid esters can be obtained, for example, by the following known methods: [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 method of reacting a tetracarboxylic acid diester dihalide with a diamine, etc.

(Synthesis of Polyimide) In addition, the polyimide can be obtained by ring-closing (imidizing) the polyimide precursors such as the above-mentioned polyamic acid or polyamic acid ester. In addition, the imidization rate referred to in this specification refers to the ratio of imide groups to the total amount of imide groups and carboxyl groups (or derivatives thereof) derived from tetracarboxylic dianhydride or its derivatives. . The imidization rate does not necessarily have to be 100%, and can be adjusted arbitrarily according to the application and purpose.

The method of imidizing the polyimide precursor may include thermal imidization by directly heating the solution of the polyimide precursor or adding a catalyst to the solution of the polyimide precursor imidization.

The temperature when the polyimide precursor is thermally imidized in the solution is usually 100-400°C, preferably 120-250°C. It is advisable to discharge the water generated by the imidization reaction to the system It is better to do it outside.

Catalyzed imidization of polyimide precursor can be achieved by adding alkaline catalyst and acid anhydride to the solution of polyimide precursor, preferably at -20 ~ 250 ° C, more preferably at 0 ~ 180 °C for stirring. The amount of alkaline catalyst is preferably 0.5-30 mole times of amide acid group, more preferably 2-20 mole times, and the amount of acid anhydride is preferably 1-50 mole times of amide acid group, more preferably Preferably it is 3-30 mole times. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is more ideal because it has a moderate alkalinity for the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, or pyromellitic anhydride. Among them, acetic anhydride is preferred because it facilitates purification after the reaction. The imidization rate caused by imidization using a catalyst can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be poured into a solvent and precipitated. Solvents used for precipitation include methanol, ethanol, isopropanol, acetone, hexane, butylcytosol, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like. The polymer that has been thrown into a solvent to precipitate can be dried at normal temperature or heated under normal pressure or reduced pressure after being collected by filtration. In addition, the polymer recovered by precipitation is redissolved in an organic solvent and recovered by reprecipitation. If this operation is repeated 2 to 10 times, the impurities in the polymer can be reduced. The solvents at this time are, for example, alcohols, ketones, or hydrocarbons. If three or more solvents selected from these are used, the purification efficiency will be better, so it is ideal.

＜Blocking agent＞ In the present invention, when synthesizing polyimide precursors and polyimides, tetracarboxylic acid components containing tetracarboxylic dianhydride or derivatives thereof, and diamine components containing the above-mentioned specific diamines are used, and appropriate End-capping agent can also be used to synthesize end-sealed polymers. End-sealed polymers have the effect of increasing the film hardness of the liquid crystal alignment film obtained by using the coating film, and improving the adhesion between the sealant and the alignment film.

In the present invention, examples of the terminal of the polyimide precursor and polyimide include an amine group, a carboxyl group, an acid anhydride group, or a group derived from a terminal blocking agent described later. Amino groups, carboxyl groups, and acid anhydride groups can be obtained by a common condensation reaction, or can be obtained by blocking the ends with the following blocking agents.

Capping agents such as acetic anhydride, maleic anhydride, nedylic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-( 3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4 -Acid anhydrides such as ethynyl phthalic anhydride; Dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; Chlorocarbonyl compounds such as acryl chloride, methacryl chloride, and nicotinyl chloride ;Aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminosalicylic acid Benzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and other monoamine compounds; ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or Isocyanates having unsaturated bonds, such as 2-acryloxyethyl isocyanate and 2-methacryloxyethyl isocyanate, etc.

The usage ratio of the end-capping agent is preferably 0.01-20 mole parts, more preferably 0.01-10 mole parts, relative to the total 100 mole parts of the diamine components used.

The polyimide precursor and the polyimide have a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC), preferably from 1,000 to 500,000, more preferably from 2,000 to 300,000. Also, 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 within this molecular weight range, good alignment of liquid crystal display elements can be ensured.

The liquid crystal alignment agent of the present invention contains the above-mentioned compound having two or more crosslinkable groups (hereinafter also referred to as a specific crosslinkable group-containing compound.). The crosslinking group is a group that can form a covalent bond between the same or different molecules by light or heat, and is not particularly limited as long as it is a compound that can react with the polymer (P). Specific examples of crosslinkable groups, such as polymerizable unsaturated bond group, oxirane group, oxetanyl group, oxazoline group, protected isocyanate group, cyclocarbonate group, β-hydroxyalkylamide group, Meldrum's acid group, hydroxymethyl group, or methoxymethyl group, etc. From the viewpoint of obtaining the effects of the present invention ideally, among these, a crosslinkable group having a hydroxyl group is preferable, and a β-hydroxyalkylamide group or a methylol group is preferable. By using a cross-linking group having a hydroxyl group, not only the cross-linking compound and the polymer (P) can be cross-linked, but also the cross-linking compounds can be self-cross-linked, and the obtained liquid crystal alignment film has a high voltage retention rate. The above-mentioned specific cross-linking compound has a molecular weight of 2000 or less, more preferably 200-1800, more preferably 200-1500, from the viewpoint of facilitating the cross-linking reaction. The number of crosslinking groups possessed by the specific crosslinking group-containing compound is preferably 2 to 6, more preferably 4 to 6, in view of obtaining the effect of the present invention. Also, when the cross-linking group is a β-hydroxyalkylamide group, when a specific cross-linking group-containing compound contains one β-hydroxyalkyl group, the number of the cross-linking group is 1, and the β- When 2 to 6 hydroxyalkyl groups are contained in a specific crosslinkable group-containing compound, the number of crosslinkable groups should be 2 to 6. Examples of the polymerizable unsaturated bond group include a (meth)acryl group, a vinylphenyl group, a vinyloxy group (CH ₂ =CH—O—), an allyl group, and a maleimide group. Also, "(meth)acryl" means both acryl and methacryl. Desirable specific examples of the specific crosslinkable group-containing compound include the following compounds. The specific crosslinkable group-containing compound may be used alone or in combination of two or more. Compounds having polymerizable unsaturated bonds include glycerol di(meth)acrylate (1,2-,1,3-body mixture), glycerol ginseng (meth)acrylate, glycerol 1,3-diglycerol di (meth)acrylate, neopentylthritol tri(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate base) acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate; compounds with oxirane groups include N,N,N',N'-tetra Epoxypropyl-1,4-phenylenediamine, N,N,N',N'-tetraepoxypropyl-2,2'-dimethyl-4.4'-diaminobiphenyl, 2,2 -Bis[4-(N,N-diepoxypropyl-4-aminophenoxy)phenyl]propane, N,N,N',N'-tetraepoxypropyl-4,4'- Compounds bonded by tertiary nitrogen atoms and aromatic carbon atoms such as diaminodiphenylmethane; N,N,N',N'-tetraepoxypropyl-1,2-diaminocyclohexane, N ,N,N',N'-tetraepoxypropyl-1,3-diaminocyclohexane, N,N,N',N'-tetraepoxypropyl-1,4-diaminocyclohexane Hexane, Bis(N,N-Diepoxypropyl-4-aminocyclohexyl)methane, Bis(N,N-Diepoxypropyl-2-methyl-4-aminocyclohexyl)methane, Bis(N,N-Diepoxypropyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-Diepoxypropylaminomethyl)cyclohexane, 1, 4-bis(N,N-diecidylaminomethyl)cyclohexane, 1,3-bis(N,N-diecidylaminomethyl)benzene, 1,4-bis(N,N- Diglycidylaminomethyl) benzene, 1,3,5-paraffin (N,N-diepoxypropylaminomethyl)cyclohexane, 1,3,5-paraffin (N,N-diepoxypropylamine Compounds with tertiary nitrogen atoms bonded to aliphatic carbon atoms such as methyl) benzene, isocyanurate compounds such as triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Co., Ltd.); compounds with protected isocyanate groups Examples include CORONATEAP Stable M, CORONATE2503, 2515, 2507, 2513, 2555, MILLIONATEMS-50 (manufactured by Tosoh Corporation), TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B- 870N, B-874N, B-882N (manufactured by Mitsui Chemicals Co., Ltd.), etc.; 1,4-bis{[(3-ethyl-3-oxetane is listed as a compound having an oxetanyl group) base)methoxy]methyl}benzene (ARONE OXETANE OXT-121(XDO)), bis[2-(3-oxetanyl)butyl]ether (ARONE OXETANE OXT-221(DOX)), 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl) )methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), 4,4'-bis[(3- Ethyloxetan-3-yl)methoxy]biphenyl (4,4'-BPOX), 2,2'-bis[(3-ethyl-3-oxetanyl)methoxy Oxy]biphenyl (2,2'-BPOX), 3,3',5,5'-tetramethyl[4,4'-bis(3-ethyloxetan-3-yl)methanol Oxy]biphenyl (TM-BPOX), 2,7-bis[(3-ethyloxetan-3-yl)methoxy]naphthalene (2,7-NpDOX), 1,6-bis [(3-Ethyloxetan-3-yl)methoxy]-2,2,3,3,4,4,5,5-octafluorohexane (OFH-DOX), 2,4 ,6-O-reference [(3-ethyloxetane-3-yl)methyl]cyanuric acid, bisphenol A and 3-ethyl-3-chloromethyloxetane ( OXC) ether compound (BisAOX), bisphenol F and OXC ether compound (BisFOX), phenol novolac and OXC ether compound (PNOX), cresol novolak and OXC ether compound (CNOX), oxygen heterocycle Butyl silsesquioxane (OX-SQ), silane oxide of 3-ethyl-3-hydroxymethyloxetane (OX-SC) (the above brackets are trade names or product names under development, East Asia Compounds having two or more oxetanyl groups as described in paragraphs [0170] to [0175] of WO2011/132751, other than ETARNACOLL OXBP (manufactured by Ube Industries, Ltd.); Compounds having an oxazoline group include 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), 2,2'-bis( 5-methyl-2-oxazoline), 2,2'-bis(5,5-dimethyl-2-oxazoline), 2,2'-bis(4,4-dimethyl-2 -oxazoline), 1,2-bis(2-oxazolin-2-yl)ethane, 1,4-bis(2-oxazolin-2-yl)butane, 1,6-bis( 2-oxazolin-2-yl)hexane, 1,8-bis(2-oxazolin-2-yl)octane, 1,4-bis(2-oxazolin-2-yl)cyclohexyl Alkane, 1,2-bis(2-oxazolin-2-yl)benzene, 1,3-bis(2-oxazolin-2-yl)benzene, 1,4-bis(2-oxazolin- 2-yl)benzene, 1,2-bis(5-methyl-2-oxazolin-2-yl)benzene, 1,3-bis(5-methyl-2-oxazolin-2-yl)benzene , 1,4-bis(5-methyl-2-oxazolin-2-yl)benzene, 2,2'-p-phenylenebis(4,4'-dimethyl-2-oxazolin) , 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 2,3-bis(4 -Isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis(4-benzyl-2-oxazoline), 2,6-bis(4-isopropyl-2 -oxazolin-2-yl)pyridine, 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidene bis(4-benzene base-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), and 2,2'-methylenebis(4-phenyl-2 Compounds such as -oxazoline), 1,2,4-ginseng(2-oxazolin-2-yl)benzene, EPOCROS (trade name, manufactured by Nippon Shokubai Co., Ltd.) Compounds such as polymers and oligomers; compounds with cyclic carbonate groups, such as N,N,N',N'-tetra[(2-side oxy-1,3-dioxolane-4- Base)methyl]-4,4'-diaminodiphenylmethane, N,N'-bis[(2-oxo-1,3-dioxolan-4-yl)methyl]- 1,3-phenylenediamine; Compounds with β-hydroxyalkylamide groups, such as compounds with chain hydrocarbon groups or cyclic groups represented by the following formulas (pL-1) to (pL-7), are more preferred Is N,N,N',N'-tetra(2-hydroxyethyl)adipamide;

[chemical 7]

Q represents a hydrogen atom, an alkyl group with 1 to 3 carbons, or *-C(R) ₂ -C(R') ₂ -OH (R each independently represents a hydrogen atom, an alkyl group with 1 to 3 carbons, or *-CH ₂ -OH. R' each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbons), and at least two of Q represent *-C(R) ₂ -C(R') ₂ -OH. A plurality of Qs may be the same or different from each other. m is an integer of 1-8. L ₃₁ and L ₃₃ each independently represent a single bond, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 6 carbons.), -(CH ₂ ) _n - (n is an integer of 1 to 6.), or *1-(CH ₂ ) _j -NR ₃₁ -(j is an integer of 1 to 6. R ₃₁ represents a hydrogen atom or an alkyl group with 1 to 3 carbons. *1 represents an atomic bond with a carbonyl carbon atom.), L ₃₂ represents a single bond, -NR ₃₂ - (R ₃₂ represents a hydrogen atom or an alkyl group with 1 to 6 carbons.), -(CH ₂ ) _k - (k is an integer of 1 to 6.), -CH=CH -, -CONH-, or -C(=O)-O-. n3 is an integer of 0-1. L ₄₁ , L ₄₂ , L ₄₃ , and L ₅ each independently represent a single bond or -(CH ₂ ) _m - (m is an integer of 1 to 6.). The two _L5s may be the same or different. ) Compounds having a Michaelis acid group can include compounds represented by the following formula ( _ML -1);

[chemical 8]

R ₁ and R ₂ each independently represent a hydrogen atom, or a monovalent organic group with 1 to 5 carbons (preferably an alkyl group with 1 to 5 carbons, an alkenyl group with 2 to 5 carbons, or an alkenyl group with 2 to 5 carbons. alkynyl). G represents a divalent organic group, and a specific example thereof includes a divalent organic group obtained by removing two amine groups from diamine used in the synthesis of the polymer (P). Among them, an aromatic diamine having two amine groups bonded to an aromatic ring such as a benzene ring is preferable. ); Compounds with hydroxymethyl or methoxymethyl groups include 2,2-bis(4-hydroxyl-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxyl-3 ,5-dimethoxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoro Phenolic compounds such as propane, or compounds represented by the following formulas (me-1) to (me-2);

2個R可相同也可不同。 [chemical 9]

Two Rs may be the same or different.

The content of the specific crosslinkable group-containing compound contained in the liquid crystal alignment agent of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, with respect to the total of 100 parts by mass of component (A), and More preferably, it is 1-10 mass parts. (Liquid Crystal Alignment Agent) The liquid crystal alignment agent of the present invention is preferably a liquid composition obtained by dispersing or dissolving component (A), component (B) and other components used as necessary in an appropriate solvent. The total content of the polymers contained in the liquid crystal alignment agent of the present invention can be appropriately changed according to the setting of the thickness of the coating film to be formed. In consideration of the viewpoint of forming a uniform and defect-free coating film, 1% by mass or more is ideal. Considering the thickness of the solution From the viewpoint of storage stability, 10% by mass or less is preferable. A particularly preferable total content of the polymers is 2 to 8% by mass.

The liquid crystal alignment agent of the present invention may also contain other polymers other than component (A) (except component (B)). Specific examples of other polymers include polymers selected from the group consisting of: using a diamine component selected from (1) not using the above-mentioned specific diamine, or (2) not using a diamine containing A polyimide precursor obtained from the monomer component of either or both of the tetracarboxylic acid components of aromatic tetracarboxylic dianhydride or its derivatives and the imide that is the polyimide precursor At least one polymer (U) from the group consisting of polyimide, polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal , polystyrene derivatives, poly(styrene-maleic anhydride) copolymers, poly(isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleic anhydride) copolymers, poly(styrene-phenylmaleic anhydride) copolymers imide) derivatives, poly(meth)acrylates. With respect to the aforementioned polymer (U), considering the viewpoint of improving the vertical alignment, examples include polyimide precursors obtained by using the diamine components containing the aromatic diamine (d) and the polyimide precursors. At least one polymer of the group consisting of imides. 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 specific examples of poly(isobutylene-maleic anhydride) copolymers. Examples include ISOBAM-600 (manufactured by Kuraray Co., Ltd.), and specific examples of poly(vinyl ether-maleic anhydride) copolymers include Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by ASHLAND).

The other polymers may be used alone or in combination of two or more. The content ratio of other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, based on the total of 100 parts by mass of the polymers contained in the liquid crystal alignment agent.

The liquid crystal alignment agent of the present invention may further contain components other than those mentioned above as required. Such components, for example: functional silane compounds, metal chelate compounds, hardening accelerators, surfactants, antioxidants, sensitizers, preservatives, compounds used to adjust the dielectric constant and resistance of liquid crystal alignment films, etc.

The compound used to adjust the dielectric constant and resistance includes monoamines having nitrogen-containing aromatic heterocycles such as 3-picolylamine. When using the monoamine which has a nitrogen-containing aromatic heterocycle, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polymer components contained in a liquid crystal alignment agent, and it is more preferable that it is 0.1-20 mass parts.

Ideal specific examples of functional silane compounds include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, Aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-amino Ethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methoxysilane Acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- Methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, ginseng[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercapto Propylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. When using a functional silane compound, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of polymer components contained in a liquid crystal alignment agent, and it is more preferable that it is 0.1-20 mass parts.

Organic solvents used in the liquid crystal alignment agent of the present invention, such as γ-valerolactone, γ-butyrolactone and other lactone solvents; γ-butyrolactam, N-methyl-2-pyrrolidone, N-ethyl-2 -pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N- Lactamide solvents such as cyclohexyl-2-pyrrolidone; N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-di Methacrylamide, N,N-diethylacrylamide, N,N-dimethyllactamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy -N,N-dimethylpropaneamide, tetramethylurea and other amide solvents; 1,3-dimethyl-2-imidazolidinone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methanone -2-pentanone, butyl lactate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxy Propyl propionate, 3-methoxybutyl propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl Cellosu), ethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether , diisobutylmethanol (2,6-dimethyl-4-heptanol), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethyl carbonate, Propylene carbonate, etc. These can be used in mixture of 2 or more types.

The ideal combination of solvents can include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2- 2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 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 Base-2-pyrrolidone and N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and 2,6-di Methyl-4-heptanone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and dipropylene glycol monomethyl ether Ether and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and N-methyl -2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, γ-butyrolactone and 4-hydroxy-4 -Methyl-2-pentanone and 2,6-dimethyl-4-heptanone, 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 and 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether With diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether with 2,6-dimethyl-4-heptanol, 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 dimethyl ether, γ-butyrolactone and ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether, cyclohexanone and ethylene glycol monobutyl ether, cyclohexanone and propylene glycol monobutyl ether, cyclohexanone and propylene glycol monomethyl ether, cyclopentyl Ketone and Propylene Glycol Monobutyl Ether, Cyclopentanone and Propylene Glycol Monomethyl Ether, Cyclohexanone and Diethylene Glycol Monoethyl Ether, Cyclopentanone and Diethylene Glycol Monoethyl Ether, Cyclohexanone and Diisobutyl Ketone, Cyclopentanone Ketone and diisobutyl ketone, methyl isobutyl ketone and propylene glycol monobutyl ether, methyl ethyl ketone and propylene glycol monobutyl ether, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone, cyclopentanone and 4 -Hydroxy-4-methyl-2-pentanone, cyclohexanone and diethylene glycol diethyl ether, cyclopentanone and diethylene glycol diethyl ether, tetramethylurea and propylene glycol diacetate, N,N- Dimethylacrylamide and propylene glycol monobutyl ether, tetramethylurea and propylene glycol monobutyl ether, tetramethylurea and cyclohexanone and propylene glycol monomethyl ether, N,N-dimethylacrylamide and propylene glycol monomethyl ether Ether, N,N-dimethylacrylamide and ethylene glycol monobutyl ether acetate, N,N-dimethylacrylamide and ethylene glycol monobutyl ether, N,N-diethylacrylamide Amine and propylene glycol monomethyl ether, tetramethylurea and propylene glycol monomethyl ether, N,N-dimethylacrylamide and cyclohexanone and diethylene glycol diethyl ether, N,N-diethylformamide and Propylene glycol monomethyl ether, N,N-diethylformamide and 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and n-butyl acetate, cyclopentanone and n-butyl acetate, 4- Hydroxy-4-methyl-2-pentanone and ethylene glycol monobutyl ether, cyclohexanone and propylene glycol diacetate, cyclopentanone and propylene glycol diacetate, etc. The type and content of such a solvent can be appropriately selected according to the coating device, coating conditions, and coating environment of the liquid crystal alignment agent.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., preferably 1 to 10 mass % range. From the viewpoint of forming a uniform and defect-free coating film, 1% by mass or more is preferable, and from the viewpoint of storage stability of the solution, 10% by mass or less is preferable. A particularly desirable concentration of the polymer is 2 to 8% by mass. ＜Liquid crystal alignment film＞ The liquid crystal alignment film of the present invention is obtained from the above-mentioned liquid crystal alignment agent. The liquid crystal alignment film of the present invention can be used in horizontal alignment type or vertical alignment type liquid crystal alignment film. Among the vertical alignment type liquid crystal alignment films, the liquid crystal alignment film used in vertical alignment type liquid crystal display elements such as VA method or PSA (Polymer Sustained Alignment) method is preferable. ＜Liquid crystal display elements＞ The liquid crystal alignment agent of the present invention has the above-mentioned liquid crystal alignment film. The liquid crystal alignment agent of the present invention also preferably has a liquid crystal layer between a pair of substrates with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and passes through the edge It is used in a liquid crystal display device manufactured in a step of polymerizing a polymerizable compound by at least one of irradiating an active energy ray and heating while applying a voltage between electrodes.

The liquid crystal display element of the present invention can be manufactured, for example, by a method of sequentially performing the following steps (1) to (3) or steps (1) to (4). (1) Coating a liquid crystal alignment agent on at least one of a pair of substrates having a conductive film to form a coating film On one side of at least one substrate of a pair of substrates provided with a patterned transparent conductive film, use an appropriate coating method such as roll coating method, spin coating method, printing method, inkjet method, etc. to coat the liquid crystal of the present invention Alignment agent to make coating film. Here, the substrate is not particularly limited as long as it is highly transparent, and a plastic substrate such as a glass substrate, a silicon nitride substrate, an acrylic substrate, or a polycarbonate substrate may be used together. In addition, if the reflective liquid crystal display element has only one side substrate, opaque objects such as silicon wafers can also be used, and the electrodes at this time can also use materials that reflect light such as aluminum. (2) Calcining the coating film After coating the liquid crystal alignment agent, in order to prevent the dripping of the coated liquid crystal alignment agent, the above-mentioned coating film is calcined. Preliminary heating (prebaking) is preferably carried out in advance. The pre-baking temperature is preferably 30-200°C, more preferably 40-150°C, especially preferably 40-100°C. The pre-baking time is preferably from 0.25 to 10 minutes, more preferably from 0.5 to 5 minutes. And it is better to implement a heating (post-baking) step. The subsequent baking temperature is preferably 80-300°C, more preferably 120-250°C. The post-baking time is preferably from 5 to 200 minutes, more preferably from 10 to 100 minutes. The thickness of the film formed in this way is preferably 5 to 300 nm, more preferably 10 to 200 nm.

The coating film formed in the above steps (1) and (2) can be directly used as a liquid crystal alignment film, but the coating film can also be subjected to an alignment ability imparting treatment. Alignment-imparting treatment includes rubbing treatment in which the coated film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and photo-alignment treatment in which the coated film is irradiated with polarized or non-polarized radiation. wait.

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

(3) Forming a liquid crystal layer between the above-mentioned pair of substrates to produce a liquid crystal cell (3-1) When manufacturing VA liquid crystal display elements Prepare two substrates on which the liquid crystal alignment film of the present invention is formed on at least one of the two substrates as described above, and arrange liquid crystals between the two facing substrates. Specifically, the following two methods can be mentioned. The first method is a method known from the past. First, two substrates are arranged facing each other with a gap (cell gap) therebetween so that the respective liquid crystal alignment films face each other. Then, the peripheral parts of the two substrates are bonded together using a sealant, and the liquid crystal composition is injected into the cell gap partitioned by the substrate surface and the sealant to make contact with the film surface, and then the injection hole is sealed. The above-mentioned 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. Hereinafter, a liquid crystal composition having a positive dielectric anisotropy is also referred to as a positive type liquid crystal, and a liquid crystal composition having a negative dielectric anisotropy is also referred to as a negative type liquid crystal. The above liquid crystal composition may also contain a fluorine atom, a hydroxyl group, an amino group, a group containing a fluorine atom (for example: trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, Liquid crystal compounds of heterocycles, cycloalkanes, cycloalkenes, steroid skeletons, benzene rings, or naphthalene rings may also contain compounds with two or more rigid sites (mesogen skeletons) exhibiting liquid crystallinity in the molecule (for example: rigid Two biphenyl structures, or a double mesogen compound formed by linking two terphenyl structures with an alkyl group, etc.). The liquid crystal composition may be a liquid crystal composition in a nematic phase, a liquid crystal composition in a smectic phase, or a liquid crystal composition in a cholesteric phase. In addition, from the viewpoint of improving the alignment of liquid crystals, additives may be further added to the above-mentioned liquid crystal composition. Such additives are, for example: photopolymerizable monomers such as compounds having the following polymerizable groups; optically active compounds (for example: S-811 manufactured by Merck Co., Ltd.); antioxidants; ultraviolet absorbers; pigments; defoaming agent; polymerization initiator; or polymerization inhibitor, etc. Examples of positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081 manufactured by Merck & Co., Ltd. Negative liquid crystal, such as MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, or MLC-7029 manufactured by Merck wait. In addition, in the PSA mode, MLC-3023 manufactured by Merck is exemplified as a liquid crystal containing a compound having a polymerizable group.

Also, the second method is a method called ODF (One Drop Fill) method. Coat, for example, a UV-curable sealant on predetermined positions on one of the two substrates on which the liquid crystal alignment film has been formed, and then drop liquid crystal composition on predetermined positions on the surface of the liquid crystal alignment film. Then attach another substrate with the liquid crystal alignment film facing it, and push the liquid crystal composition onto the entire surface of the substrate so that it contacts the film surface. Then, the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant.

In the case of using either method, heat it up until the liquid crystal composition used takes the temperature of the isotropic phase, and then cool slowly to room temperature to remove the flow alignment when the liquid crystal is filled. (3-2) The liquid crystal composition containing a polymerizable compound is injected or dripped at the time of manufacture of the liquid crystal display element of a PSA system, and it carries out similarly to said (3-1). A compound having a polymerizable group, for example, a compound having a mesogen structure and two or more photopolymerizable groups or thermal polymerizable groups. Compounds with polymeric groups, for example: in terms of mesogen structure, structures formed by linking two or more aromatic groups or aliphatic groups, such as biphenyl structure, terphenyl structure, naphthalene ring, bisphenol A A fluorine atom-containing structure in which two hydroxyl groups are removed, or a part or all of the hydrogen atoms possessed by such structures are replaced by fluorine atoms. Specific compounds include 4,4'-dimethacryloxybiphenyl and 3-fluoro-1,1'-biphenyl-4,4'-diyl dimethacrylate. (3-3) When using a liquid crystal alignment agent containing a compound having a polymerizable group to form a coating film on the substrate, it is also possible to use the method of manufacturing a liquid crystal display element through the step of irradiating ultraviolet rays described later in the same manner as in (3-1) above. . According to this method, a liquid crystal display element excellent in response speed can be obtained with a small amount of light irradiation, as in the case of manufacturing the above-mentioned PSA type liquid crystal display element. The compound having a polymerizable group may be the above-mentioned compound having a polymerizable group, and its content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the entire polymer component. In addition, the above-mentioned polymerizable group may be possessed by the polymer used in the liquid crystal alignment agent. Such a polymer is, for example, a polymer obtained by reacting a diamine component containing a diamine having the above-mentioned photopolymerizable group at the end. (4) Irradiation of the liquid crystal cell The liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates obtained in the above (3-2) or (3-3). The voltage to be applied here can be, for example, a direct current or alternating current of 5 to 50V. Also, as the light to be irradiated, for example, ultraviolet rays and visible rays including light with a wavelength of 150 to 800 nm can be used, but ultraviolet light with a wavelength of 300 to 400 nm is preferably used. Light sources for irradiating light, such as low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, etc. The amount of light irradiation is preferably from 1,000 to 200,000 J/m ² , more preferably from 1,000 to 100,000 J/m ² .

Furthermore, a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. The polarizing plate attached to the outer surface of the liquid crystal cell includes: Polarizing film made of polarizing film called "H film" obtained by sandwiching cellulose acetate protective film while stretching and aligning polyvinyl alcohol to absorb iodine Polarizing plate composed of plate or H film itself.

The liquid crystal display device of the present invention can be effectively applied to various devices, such as: clocks, portable game machines, word processors, notebook personal computers, navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones Various display devices such as mobile phones, various monitors, LCD TVs, and information displays. In addition, the above-mentioned liquid crystal alignment agent can also be used in the liquid crystal alignment film for the phase difference film, the liquid crystal alignment film for the scanning antenna, the liquid crystal array antenna, or the liquid crystal alignment film for the transmission and scattering type liquid crystal dimming element, or other than these Applications, such as protective films for color filters, gate insulating films for flexible displays, and substrate materials. [Example]

The following examples are given to describe the present invention in more detail, but the present invention is not limited thereto. The abbreviations of the compounds used and the measurement methods of the respective physical properties are as follows. (Organic solvents) NMP: N-methyl-2-pyrrolidone BCS: butyl cellosu (ethylene glycol monobutyl ether) (tetracarboxylic dianhydride)

[chemical 10]

(diamine)

[chemical 11]

(additive)

[chemical 12]

＜Measurement of Viscosity＞ Using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), using a sample volume of 1.1 mL (milliliters) and a conical rotor TE-1 (1°34', R24), it was measured at a temperature of 25°C. ＜Determination of Molecular Weight＞ Mn and Mw were calculated using the following room temperature GPC (Gel Permeation Chromatography) apparatus, and calculated values in terms of polyethylene glycol and polyethylene oxide.

GPC device: GPC-101 (manufactured by Showa Denko Co., Ltd.), column: GPC KD-803, GPC KD-805 (manufactured by Showa Denko Co., Ltd.) in series, column temperature: 50°C, eluent: N,N-Dimethicone Methyl formamide (additives are lithium bromide monohydrate (LiBr･H2O) 30mmol/L, phosphoric acid anhydrous crystal (orthophosphoric acid) 30mmol/L, tetrahydrofuran (THF) 10mL/L), flow rate: 1.0mL/min Standard samples for calibration line production: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000, and 1,000) (Polymer Laboratory Corporation). [Synthesis of polyamide acid] <Synthesis Example 1> Add DA-1 (2.26g, 8.00mmol), DA-4 (1.45g, 6.00mmol), DA-5 (2.46g, 6.00mmol) and NMP ( 24.7 g), and was dissolved by stirring at room temperature while feeding nitrogen gas. Then, CA-1 (2.63 g, 13.4 mmol) and NMP (10.0 g) were added, and it stirred at room temperature for 2 hours. Then add CA-2 (1.31g, 6.00mmol) and NMP (5.20g), and stir at room temperature for 20 hours to obtain a solution of polyamic acid (PAA-1) with a solid content concentration of 20% by mass (viscosity: 714mPa・s). The Mn of this polyamide acid is 11,329, and the Mw is 27,338. <Synthesis Example 2> Add DA-2 (2.48g, 8.00mmol), DA-4 (1.45g, 6.00mmol), DA-5 (2.46g, 6.00mmol) and NMP ( 25.6 g), and was dissolved by stirring at room temperature while feeding nitrogen gas. Then, CA-1 (2.51 g, 12.8 mmol) and NMP (10.0 g) were added, and it stirred at room temperature for 2 hours. Then add CA-2 (1.31g, 6.00mmol) and NMP (5.20g), and stir at room temperature for 20 hours to obtain a solution of polyamic acid (PAA-2) with a solid content concentration of 20% by mass (viscosity: 839mPa· s). The Mn of this polyamide acid is 14,348, and the Mw is 37,799. <Synthesis Example 3> Add DA-3 (1.98g, 10.0mmol), DA-4 (1.82g, 7.50mmol), DA-5 (3.08g, 7.50mmol) and NMP ( 27.5 g), and was dissolved by stirring at room temperature while feeding nitrogen gas. Then, CA-1 (3.14 g, 16.0 mmol) and NMP (12.6 g) were added, and it stirred at room temperature for 2 hours. Then add CA-2 (1.64g, 7.50mmol) and NMP (6.50g), and stir at room temperature for 20 hours to obtain a solution of polyamic acid (PAA-3) with a solid content concentration of 20% by mass (viscosity: 750mPa· s). The Mn of this polyamide acid was 9,793, and the Mw was 22,690.

Table 1 shows the kinds and amounts of tetracarboxylic acid components and diamine components used in Synthesis Examples 1 to 3 above. In the table, the numerical value of each component is the mole part of each component relative to the total amount of 100 mole parts of the diamine component.

[Table 1] Synthesis example Polyamide Tetracarboxylic acid component Diamine component specific diamine Other diamines CA-1 CA-2 DA-1 DA-2 DA-3 DA-4 DA-5 1 PAA-1 67 30 40 - - 30 30 2 PAA-2 64 30 - 40 - 30 30 3 PAA-3 64 30 - - 40 30 30

[Preparation of liquid crystal alignment agent] <Example 1> Add NMP (4.80g) and BCS (8.00g) to the polymer solution (6.00g) obtained in Synthesis Example 1, then add AD-1 (10% by mass NMP solution, 1.20g), and stir at room temperature for 2 hours to obtain liquid crystal alignment agent AL-1. Abnormalities such as turbidity and precipitation were not observed in the above-mentioned liquid crystal alignment agent AL-1, and it was confirmed that the resin component was uniformly dissolved. <Example 2, Comparative Example 1> The polyamic acid solution used was changed as shown in Table 2, except that it was carried out in the same manner as in Example 1 to obtain the liquid crystal alignment agent AL-2 of Example 2 and the liquid crystal alignment agent AL-C1 of Comparative Example 1. Abnormalities such as turbidity and precipitation were not observed in the above-mentioned liquid crystal alignment agents AL-2 and AL-C1, and it was confirmed that the resin components were uniformly dissolved.

[Table 2] Liquid crystal alignment agent Polyamide additive solvent Example 1 AL-1 PAA-1 AD-1 NMP,BCS Example 2 AL-2 PAA-2 AD-1 NMP,BCS Comparative example 1 AL-C1 PAA-3 AD-1 NMP,BCS

[Measurement of transmittance] Spin-coat the liquid crystal alignment agents AL-1-AL-2 and AL-C1 obtained in the above-mentioned Examples 1-2 and Comparative Example 1 on a quartz substrate, and calcinate on a hot plate at 70°C for 90 seconds, then use infrared rays at 230°C Calcined in a heating furnace for 20 minutes to produce a quartz substrate with a film thickness of 100 nm and a liquid crystal alignment agent. This substrate with a liquid crystal alignment film was placed inside, and another quartz substrate was used to sandwich a contact liquid (manufactured by Shimadzu Device Manufacturing Co., Ltd.) in order to prevent light interference. This was measured with UV-3600 manufactured by Shimadzu Corporation at a temperature of 25° C. and a scanning wavelength of 380 to 800 nm. At this time, the contact solution was sandwiched between two quartz substrates without coating as a control. The evaluation uses the transmittance at a wavelength of 380nm. The results are shown in Table 3.

[table 3] Liquid crystal alignment agent Transmittance (%) (380nm) Example 1 AL-1 97.4 Example 2 AL-2 97.6 Comparative example 1 AL-C1 96.1

As shown in Table 1, the liquid crystal alignment films of Examples 1 to 2 obtained from liquid crystal alignment agents using diamine components containing specific diamines DA-1 to DA-2 are compared to those obtained from liquid crystal alignment films that do not contain specific diamines. The liquid crystal alignment film of Comparative Example 1 obtained from the liquid crystal alignment agent composed of diamine exhibited higher transmittance. Also, a difference of 1% in transmittance is a significant difference in this technical field. [Preparation of liquid crystal cells for evaluation of voltage retention] Using the liquid crystal alignment agents AL-1 to AL-2 and AL-C1 obtained in Examples 1 to 2 and Comparative Example 1 above, the liquid crystal cells were prepared according to the procedure shown below. make. The liquid crystal alignment agent was spin-coated on the glass substrate with ITO electrodes, dried on a hot plate at 70°C for 90 seconds, and then calcined in an infrared heating furnace at 230°C for 20 minutes to form a liquid crystal alignment film with a film thickness of 100nm. Prepare 2 substrates with the liquid crystal alignment film, and coat a bead spacer with a diameter of 4 μm (manufactured by Nikki Catalyst Chemicals Co., Ltd., silk ball, SW-D1) on the liquid crystal alignment film of one of the substrates, and keep the liquid crystal injection port. A thermosetting sealant (manufactured by Mitsui Chemicals, Inc., XN-1500T) was printed on the periphery. Then, the surface of the other substrate on which the liquid crystal alignment film has been formed is set as the inner side, and after being bonded to the previous substrate, the sealant is hardened to form void cells. Liquid crystal MLC-3023 (manufactured by Merck & Co.) was injected into the ghost cell by a reduced-pressure injection method to produce a liquid crystal cell. Then, with a DC voltage of 15V applied to the liquid crystal cell, 10J/cm ₂ of ultraviolet light that has passed through a cut-off filter with a wavelength of 325nm or less is irradiated from the outside of the liquid crystal cell. In addition, the illuminance of ultraviolet rays was measured using UV-MO3A manufactured by ORC Corporation. Afterwards, in order to inactivate the unreacted polymerizable compound remaining in the liquid crystal cell, ultraviolet light (UV lamp: FLR40SUV32/A-1) was irradiated for 30 minutes using a UV-FL irradiation device manufactured by TOSHBA LIGHTECH Co., Ltd. without applying voltage. [Evaluation of Voltage Holding Rate] The voltage holding rate was measured using a liquid crystal cell for evaluating the voltage holding rate after ultraviolet irradiation. Apply a voltage of 1V for 60μsec in a hot air circulation oven at 60°C, then measure the voltage after 1667msec, calculate how much voltage can be maintained and define it as the voltage retention rate. The measurement of the voltage retention ratio used VHR-1 manufactured by TOYO TECHNICA. Higher values are better. The results are shown in Table 4.

[Table 4] Liquid crystal alignment agent VHR(%) Example 1 AL-1 91.6 Example 2 AL-2 90.7 Comparative example 1 AL-C1 90.8

As shown in Table 4, the liquid crystal alignment films using the liquid crystal alignment agents of Examples 1-2 maintained good voltage retention.

In addition, the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2021-129553 filed on August 6, 2021 are cited here, and are cited as the disclosure content of the specification of the present invention.

Claims (17)

A liquid crystal alignment agent, characterized by containing the following (A) component and (B) component, (A) component: polymer (P), is selected from the diamine component containing the diamine represented by the following formula (1) and containing Polyimide precursor obtained by polymerization reaction of tetracarboxylic acid component of aromatic tetracarboxylic dianhydride or its derivatives and group consisting of polyimide which is imide of the polyimide precursor At least one of them, (B) component: a compound having two or more crosslinkable groups,

In the formula, R ₁ each independently represent a hydrogen atom or a monovalent organic group with 1 to 3 carbons, at least two of R ₁ represent a monovalent organic group with 1 to 3 carbons, and one of the hydrogen atoms possessed by R ₁ A part or all may be substituted, and a part or all of the hydrogen atoms on the benzene ring may be substituted by a substituent, and L represents a single bond or a divalent linking group. The liquid crystal alignment agent according to Claim 1, wherein the divalent linking group in L of the formula (1) is selected from -O-, -S-, -SO-, -SO ₂ -, -CO-, -C (=O)-O-, -NR-(R represents a hydrogen atom or an alkyl group with 1 to 6 carbons), -CONR-(R represents a hydrogen atom or an alkyl group with 1 to 6 carbons), -CH ₂ - , a straight chain or branched alkylene group with 2 to 12 carbon atoms, any -CH ₂ - contained in the alkylene group is replaced by -O-, -CO-, -C(=O)-O-, -NR- (R represents a hydrogen atom or an alkyl group with 1 to 6 carbons), or -CONR- (R represents a hydrogen atom or an alkyl group with 1 to 6 carbons), a divalent organic group with 5 carbons ~6 cycloalkylene, phenylene, phenylenedioxy, -Si(R ₃ )(R ₄ )-(R ₃ and R ₄ each independently represent an alkyl or alkane group with 1 to 6 carbon atoms Oxygen), and -(Q) _s -(R ₅ ) _t -(-Si(R ₃ )(R ₄ )-O-) _r - Si(R ₃ )(R ₄ )-(R ₅ ) _t' -(Q) _s' -(R ₃ and R ₄ each independently represent an alkyl or alkoxy group with 1 to 6 carbons, each R ₅ independently represents an alkylene group with 1 to 6 carbons, Q represents -O -or-S-, r is an integer from 0 to 20, s, s', t, t' is an integer of 0 or 1, at least one of s, s', t, t' is 1, multiple R _3. R ₄ , R ₅ and Q may be the same or different. The liquid crystal alignment agent according to Claim 1, wherein the diamine represented by the formula (1) is the diamine represented by the following formulas (d1-1) to (d1-6),

In the formula, A, B, C, and D each independently represent a hydrogen atom, methyl, ethyl, isopropyl, methoxy, or methoxymethyl, and at least two of A to D are hydrogen atoms E represents a single bond, -CH ₂ -, -(CH ₂ ) ₂ -, -O-, -S-, -CO-, -SO-, -SO ₂ -, -C(=O)-O -, -CONH-, -CO-N(CH ₃ )-, -NH-, -N(CH ₃ )-, -Si(CH ₃ ) ₂ -, -Si(OCH ₃ ) ₂ -, -O-Si (CH ₃ ) ₂ -O-, phenylene, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -. The liquid crystal alignment agent according to claim 3, wherein, in the formulas (d1-1) to (d1-3), A and B each independently represent methyl, ethyl, isopropyl, methoxy, or methoxy C and D each independently represent a hydrogen atom or a group defined by A and B. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the aromatic tetracarboxylic dianhydride or its derivative has at least one substructure selected from the group consisting of benzene ring and naphthalene ring. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the aromatic tetracarboxylic dianhydride or its derivatives are pyromellitic dianhydride, 3,3',4,4'-diphenyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3, 3'-biphenyltetracarboxylic dianhydride, or a derivative thereof. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the crosslinking group is selected from polymerizable unsaturated bond groups, oxirane groups, oxetane groups, oxazoline groups, Protect isocyanate group, cyclocarbonate group, β-hydroxyalkylamide group, Meldrum's acid group, hydroxymethyl group, and methoxymethyl group. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the crosslinking group is selected from β-hydroxyalkylamide group, hydroxymethyl group, and methoxymethyl group. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the crosslinkable group has a hydroxyl group. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the tetracarboxylic acid component further contains acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, or derivatives thereof . The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the amount of the diamine represented by the formula (1) used to obtain the polymer (P) is 5 mol% or more relative to the total diamine components . The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the diamine component further contains diamines other than the diamine represented by formula (1). The liquid crystal alignment agent in any one of Claims 1-4 whose content of this (B) component is 0.1-30 mass parts with respect to the total 100 mass parts of this (A) component. A liquid crystal alignment film obtained from the liquid crystal alignment agent according to any one of claims 1 to 13. A liquid crystal display element comprising the liquid crystal alignment film according to claim 14. A method for manufacturing a liquid crystal display element, comprising the following steps (1) to (3) in sequence, Step (1): Coating the liquid crystal alignment agent according to any one of Claims 1 to 13 on at least one of a pair of substrates having a conductive film to form a coating film, Step (2): calcining the coating film, Step (3): Forming a liquid crystal layer between the pair of substrates to produce a liquid crystal cell. The method for manufacturing a liquid crystal display element as claimed in item 16 further includes performing the following step (4) after steps (1) to (3), Step (4): Illuminate the liquid crystal cell.