JPWO2018190426A1 - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

A liquid crystal aligning agent containing a polymer obtained from a diamine having a structure represented by the following formula (1). R1 represents a hydrogen atom, a linear or branched alkyl or aryl group having 1 to 5 carbon atoms, and two R1s on the same maleimide ring may be the same or different. Two R1s may together form an alkylene having 3 to 6 carbon atoms, W2 represents a divalent organic group, W1 represents a single bond or carbonyl, and L1 represents 1 to 20 carbon atoms. A linear alkylene group, a branched alkylene group having 3 to 20 carbon atoms, a cyclic alkylene group having 3 to 20 carbon atoms, a divalent group selected from a phenylene group and a heterocyclic group, or a plurality of the divalent groups. A phenylene group and a heterocyclic group each independently represent an alkyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, a same or different substituent (s) selected from a halogen group and a cyano group. The bond between the divalent groups may be at least one selected from a single bond, an ester bond, an amide bond, a urea bond, an ether bond, a thioether bond, an amino bond, and a carbonyl. When there are a plurality of groups, the divalent groups may be the same or different, and when the above-mentioned bonds are plural, the bonds may be the same or different, and R is a hydrogen atom or a monovalent group. Wherein two Rs may be different from each other, two Rs may be taken together to form an alkylene having 1 to 6 carbon atoms, or both or any of the two Rs One of them may be bonded to L1.

Description

  The present invention provides a polyamic acid, a polyamic acid ester, a polyimide, a liquid crystal aligning agent, obtained using a novel diamine compound (in the present invention, also simply referred to as diamine), which is useful as a raw material of a polymer used for a liquid crystal alignment film. The present invention relates to a liquid crystal alignment film and a liquid crystal display device.

  2. Description of the Related Art A liquid crystal display device has been widely used as a display unit of a personal computer, a mobile phone, a television receiver, and the like, and its driving method is a vertical electric field method such as a TN method and a VA method, an IPS method, and a fringe method. 2. Description of the Related Art A lateral electric field method such as a field switching (hereinafter, referred to as FFS) method is known.

  In general, the horizontal electric field method in which an electrode is formed only on one side of a substrate and an electric field is applied in a direction parallel to the substrate is wider than the vertical electric field method in which a voltage is applied to electrodes formed on upper and lower substrates to drive a liquid crystal. A liquid crystal display device having viewing angle characteristics and capable of high-quality display is easily obtained. As a method for aligning the liquid crystal in a certain direction, for example, there is a method in which a polymer film such as polyimide is formed on a substrate, and the surface is rubbed with a cloth, so-called rubbing treatment.

  Conventional problems include an improvement in the voltage holding ratio and an improvement in charge accumulation by a DC voltage component applied from the active matrix structure. When the electric charge is accumulated in the liquid crystal display element, the display is adversely affected due to the disorder of the liquid crystal alignment and the occurrence of an afterimage, and the display quality of the liquid crystal display element is remarkably reduced. Alternatively, when driving is performed in a state in which electric charges are accumulated, immediately after driving, liquid crystal molecules are not normally controlled, and flicker occurs.

  Further, as a characteristic required for the liquid crystal alignment film to improve the display quality of the liquid crystal display element, there is an ion density. When the ion density is high, the voltage applied to the liquid crystal decreases, and as a result, the luminance may decrease, which may hinder normal gradation display. Further, even if the initial ion density is low, the ion density after the high-temperature acceleration test may become high. Such a decrease in long-term reliability and occurrence of an afterimage due to residual charges and ionic impurities degrades the display quality of the liquid crystal.

  Various proposals have been made for polyimide-based liquid crystal alignment films in order to meet the above requirements. For example, as one of the liquid crystal alignment films for the purpose of shortening the time until an afterimage generated by a DC voltage disappears, a liquid crystal containing a tertiary amine having a specific structure in addition to a polyamic acid or an imide group-containing polyamic acid. An alignment agent (for example, see Patent Document 1) and a liquid crystal alignment agent containing a soluble polyimide containing a specific diamine compound having a pyridine skeleton or the like as a raw material (for example, see Patent Document 2) Proposed.

JP-A-9-316200 JP-A-10-104633

  Rubbing treatment is widely used industrially as a method for aligning liquid crystals. However, depending on the liquid crystal alignment film used, a phenomenon in which the rubbing direction does not match the alignment direction of the liquid crystal, that is, a so-called twist angle may occur. In other words, the horizontal electric field element displays black when no voltage is applied, but this phenomenon causes a problem that the luminance is increased even when no voltage is applied, and as a result, the display contrast is reduced. there were.

  INDUSTRIAL APPLICABILITY The present invention can suppress ion density in a liquid crystal display element to a low level and rapidly reduce accumulated charges, and can suppress a shift between a rubbing direction and a liquid crystal alignment direction, which is a problem particularly in a lateral electric field driving method. It is an object of the present invention to provide a liquid crystal alignment film that can be used, a liquid crystal alignment agent capable of obtaining such a liquid crystal alignment film, and a liquid crystal display device including such a liquid crystal alignment film.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that various characteristics can be simultaneously improved by introducing a specific structure into a polymer contained in a liquid crystal aligning agent. Completed the invention. The present invention is based on such knowledge, and has the following gist.

  1. A liquid crystal aligning agent containing a polymer obtained from a diamine having a structure represented by the following formula (1).

Ｒ^１は水素原子、炭素数１〜５の直鎖又は分岐してもよいアルキル基又はアリール基を表し、同じマレイミド環上に２つあるＲ^１は互いに同一でも、異なっていてもよく、２つあるＲ^１が一緒になって炭素数３〜６のアルキレンを形成してもよく、Ｗ^２は２価の有機基を表し、Ｗ^１は単結合又はカルボニルを表し、Ｌ^１は炭素数１〜２０の直鎖状アルキレン基、炭素数３〜２０の分岐状アルキレン基、炭素数３〜２０の環状アルキレン基、フェニレン基及び複素環基から選ばれる二価の基、又は当該二価の基が複数結合してなる基であり、フェニレン基及び複素環基はそれぞれ独立にアルキル基、アルコキシ基、ハロアルキル基、ハロアルコキシ基、ハロゲン基及びシアノ基から選ばれる同一又は相異なる１又は複数の置換基で置換されていてもよく、当該二価の基同士の結合は、単結合、エステル結合、アミド結合、ウレア結合、エーテル結合、チオエーテル結合、アミノ結合及びカルボニルから選ばれる少なくとも一種であり、当該二価の基が複数となる場合は、二価の基同士は同一でも異なっていてもよく、上記結合が複数となる場合は、結合同士は同一でも異なっていてもよく、Ｒは水素原子又は一価の有機基を表し、２つあるＲが互いに異なっていてもよく、２つあるＲが一緒になって炭素数１〜６のアルキレンを形成していてもよく、２つあるＲの両方又はいずれか一方がＬ^１に結合していてもよい。

R ¹ represents a hydrogen atom, a linear or branched alkyl group or an aryl group having 1 to 5 carbon atoms, and two R ¹ groups on the same maleimide ring may be the same or different; R ¹ may combine to form an alkylene having 3 to 6 carbon atoms, W ² represents a divalent organic group, W ¹ represents a single bond or carbonyl, and L ¹ represents a carbon atom having 1 to 6 carbon atoms. To 20 linear alkylene groups, branched alkylene groups having 3 to 20 carbon atoms, cyclic alkylene groups having 3 to 20 carbon atoms, divalent groups selected from phenylene groups and heterocyclic groups, or the divalent groups Is a group formed by bonding a plurality of groups, and the phenylene group and the heterocyclic group are each independently one or more substituted groups selected from the same or different alkyl group, alkoxy group, haloalkyl group, haloalkoxy group, halogen group and cyano group Substituted with a group The bond between the divalent groups may be at least one selected from a single bond, an ester bond, an amide bond, a urea bond, an ether bond, a thioether bond, an amino bond and a carbonyl, and the divalent group may be When two or more, the divalent groups may be the same or different, when two or more bonds are plural, the bonds may be the same or different, and R is a hydrogen atom or a monovalent organic group. Wherein two Rs may be different from each other, two Rs may be combined to form an alkylene having 1 to 6 carbon atoms, and both or one of the two Rs may be L may be bonded to ^1.

2. Wherein ^{W 1} represents a single bond, 1. 3. The liquid crystal aligning agent according to 1.

  3. The polymer is at least one selected from a polyimide precursor containing a structural unit represented by the following formula (3) and a polyimide that is an imidized product thereof. Or 2. 3. The liquid crystal aligning agent according to 1.

Ｘ^１はテトラカルボン酸誘導体に由来する４価の有機基を表し、Ｙ^１は式（１）の構造を含むジアミンに由来する２価の有機基を表し、Ｒ^４は水素原子又は炭素数１〜５のアルキル基を表す。

X ¹ represents a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ represents a divalent organic group derived from a diamine having the structure of the formula (1), and R ⁴ represents a hydrogen atom or a carbon atom having 1 structure. To 5 alkyl groups.

4. 2. In the formula (3), the structure of X ¹ represents at least one selected from the following structures. 3. The liquid crystal aligning agent according to 1.

  5. 2. The polymer is at least one selected from a polyimide precursor further containing a structural unit represented by the following formula (4) and a polyimide that is an imidized product thereof. 3. The liquid crystal aligning agent according to 1.

式（４）において、Ｘ^２はテトラカルボン酸誘導体に由来する４価の有機基を表し、Ｙ^２は式（１）の構造を主鎖方向に含まないジアミンに由来する２価の有機基を表し、Ｒ^１４は、それぞれ独立に水素原子又は炭素数１〜５のアルキル基を表し、Ｒ^１５はそれぞれ独立に水素原子又は炭素数１〜４のアルキル基を表す。

In the formula (4), X ² represents a tetravalent organic group derived from a tetracarboxylic acid derivative, and Y ² represents a divalent organic group derived from a diamine not including the structure of the formula (1) in the main chain direction. represents, R ¹⁴ each independently represent a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

6. Wherein ^{Y 2} is represented by the following formula (11), 5. 3. The liquid crystal aligning agent according to 1.

式（１１）中、Ｒ^３２は単結合又は２価の有機基を表し、Ｒ^３３は−（ＣＨ_２）_ｒ−で表される構造を表し、ｒは２〜１０の整数を表し、また、任意の−ＣＨ_２−はそれぞれ隣り合わない条件でエーテル、エステル、アミド、ウレア、カルバメート結合に置き換えられてもよい。Ｒ^３４は単結合又は２価の有機基を表す。ベンゼン環上の任意の水素原子は１価の有機基で置き換えられてもよい。

In Formula (11), R ³² represents a single bond or a divalent organic group, R ³³ represents a structure represented by — (CH ₂ ) _r —, r represents an integer of 2 to 10, any -CH 2 _- ether conditions nonadjacent respectively, esters, amides, ureas, may be replaced by a carbamate linkage. R ³⁴ represents a single bond or a divalent organic group. Any hydrogen atom on the benzene ring may be replaced by a monovalent organic group.

  7. 3. The structural unit represented by the formula (3) is at least 10 mol% based on all structural units of the polymer. Or 5. 3. The liquid crystal aligning agent according to 1.

  8. 1. ~ 7. A liquid crystal alignment film, comprising the liquid crystal alignment agent according to any one of the above.

  9. 8. A liquid crystal display device comprising the liquid crystal alignment film according to 1.

  10. A diamine having a structure represented by the following formula (1).

Ｒ^１は水素原子、炭素数１〜５の直鎖若しくは分岐してもよいアルキル基又はアリール基を表し、同じマレイミド環上に２つあるＲ^１は互いに同一でも、異なっていてもよく、２つあるＲ^１が一緒になって炭素数３〜６のアルキレンを形成してもよく、Ｗ^２は２価の有機基を表し、Ｗ^１は単結合又はカルボニルを表し、Ｌ^１は炭素数１〜２０の直鎖状アルキレン基、炭素数３〜２０の分岐状アルキレン基、炭素数３〜２０の環状アルキレン基、フェニレン基及び複素環基から選ばれる二価の基、又は当該二価の基が複数結合してなる基を表し、フェニレン基及び複素環基はそれぞれ独立にアルキル基、アルコキシ基、ハロアルキル基、ハロアルコキシ基、ハロゲン基及びシアノ基から選ばれる同一又は相異なる１又は複数の置換基で置換されていてもよく、当該二価の基同士の結合は、単結合、エステル結合、アミド結合、ウレア結合、エーテル結合、チオエーテル結合、アミノ結合及びカルボニルから選ばれる少なくとも一種であり、当該二価の基が複数となる場合は、二価の基同士は同一でも異なっていてもよく、上記結合が複数となる場合は、結合同士は同一でも異なっていてもよく、Ｒは水素原子又は一価の有機基を表し、２つあるＲが互いに異なっていてもよく、２つあるＲが一緒になって炭素数１〜６のアルキレンを形成していてもよく、２つあるＲの両方又はいずれか一方がＬ^１に結合していてもよい。

R ¹ represents a hydrogen atom, a linear or branched alkyl group or an aryl group having 1 to 5 carbon atoms, and two R ¹ groups on the same maleimide ring may be the same or different; R ¹ may combine to form an alkylene having 3 to 6 carbon atoms, W ² represents a divalent organic group, W ¹ represents a single bond or carbonyl, and L ¹ represents a carbon atom having 1 to 6 carbon atoms. To 20 linear alkylene groups, branched alkylene groups having 3 to 20 carbon atoms, cyclic alkylene groups having 3 to 20 carbon atoms, divalent groups selected from phenylene groups and heterocyclic groups, or the divalent groups Represents a group formed by bonding a plurality of groups, wherein the phenylene group and the heterocyclic group are each independently one or more substituents selected from the same or different alkyl group, alkoxy group, haloalkyl group, haloalkoxy group, halogen group and cyano group Substitute with group The bond between the divalent groups may be at least one selected from a single bond, an ester bond, an amide bond, a urea bond, an ether bond, a thioether bond, an amino bond, and a carbonyl. When there are a plurality of groups, the divalent groups may be the same or different, and when the above-mentioned bonds are plural, the bonds may be the same or different, and R is a hydrogen atom or a monovalent group. Represents an organic group, two R's may be different from each other, two R's may be combined to form an alkylene having 1 to 6 carbon atoms, and / or two R's one may be bonded to L ^1.

  11. 10. The polymer which uses the diamine of.

  By using the liquid crystal aligning agent containing the polymer of the present invention, it is possible to suppress the ion density in the liquid crystal display element low and quickly relax the accumulated charges, which is a problem particularly in the horizontal electric field driving method. As a result, a liquid crystal alignment film that can suppress the deviation between the rubbing direction and the alignment direction of the liquid crystal can be obtained. Although it is not clear why the above-mentioned problem can be solved by the present invention, it is generally considered as follows. The structure of the above formula (1) contained in the polymer of the present invention has a nitrogen atom. Thus, for example, in the liquid crystal alignment film, the liquid crystal alignment film has a capability of capturing ionic impurities, can promote the movement of electric charges, and can promote the relaxation of accumulated electric charges.

  The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent containing a polymer (hereinafter, also referred to as a specific polymer) obtained from a diamine having a structure represented by the above formula (1) (hereinafter, also referred to as a specific structure). is there. Hereinafter, each condition will be described in detail.

<Diamine having specific structure>
In the formula (1), R ¹ represents a hydrogen atom, a linear or branched alkyl group or an aryl group having 1 to 5 carbon atoms, and two R ¹ on the same maleimide ring are the same as each other, R ¹ may be different, and two R ¹ may combine to form an alkylene having 3 to 6 carbon atoms, W ² represents a divalent organic group, and L ¹ represents a single bond or 1 carbon atom. Represents an alkylene having from 20 to 20, R represents a hydrogen atom or a monovalent organic group, two Rs may be different from each other, and two Rs may be combined to form an alkylene having 1 to 6 carbon atoms it may also be, both or either of the twofold R may be bonded to L ^1.

R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group, and more preferably a hydrogen atom, a methyl group, or a phenyl group. Further, the alkylene having 3 to 6 carbon atoms which there are two ^{R 1} form together, preferably _{- (CH 2) 3 -,} - (CH 2) 4 -, - (CH 2) 5 - in And more preferably — (CH ₂ ) ₄ —.

The alkylene having 1 to 20 carbon atoms in the definition of L ¹ may be straight-chain or branched, and is a straight-chain represented by-(CH ₂ ) _n- (where n is 1 to 20). Alkylene, 1-methylmethane-1,1-diyl, 1-ethylmethane-1,1-diyl, 1-propylmethane-1,1-diyl, 1-methylethane-1,2-diyl, 1-ethylethane- 1,2-diyl, 1-propylethane-1,2-diyl, 1-methylpropane-1,3-diyl, 1-ethylpropane-1,3-diyl, 1-propylpropane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-ethylpropane-1,3-diyl, 2-propylpropane-1,3-diyl, 1-methylbutane-1,4-diyl, 1-ethylbutane-1,4 -Diyl, 1-propyl Tan-1,4-diyl, 2-methylbutane-1,4-diyl, 2-ethylbutane-1,4-diyl, 2-propylbutane-1,4-diyl, 1-methylpentane-1,5-diyl, 1-ethylpentane-1,5-diyl, 1-propylpentane-1,5-diyl, 2-methylpentane-1,5-diyl, 2-ethylpentane-1,5-diyl, 2-propylpentane-1 , 5-diyl, 3-methylpentane-1,5-diyl, 3-ethylpentane-1,5-diyl, 3-propylpentane-1,5-diyl, 1-methylhexane-1,6-diyl, 1-ethylhexane-1,6-diyl, 2-methylhexane-1,6-diyl, 2-ethylhexane-1,6-diyl, 3-methylhexane-1,6-diyl, 3- Ethyl hexane-1,6- Yl, 1-methylheptane-1,7-diyl, 2-methylheptane-1,7-diyl, 3-methylheptane-1,7-diyl, 4-methylheptane-1,7-diyl, 1-phenylmethane And branched alkylenes such as -1,1-diyl, 1-phenylethane-1,2-diyl, 1-phenylpropane-1,3-diyl. These linear or branched alkylenes may be interrupted by an oxygen atom or a sulfur atom 1 to 5 times, provided that the oxygen atom or the sulfur atom is not adjacent to each other.

Examples of the branched alkylene group having 3 to 20 carbon atoms in the definition of L ¹ include i-propylene group, i-butylene group, s-butylene group, t-butylene group, 1-methyl-n-butylene group, -Methyl-n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1-ethyl-n-propylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl -N-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl- n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1 Other than an -ethyl-1-methyl-n-propylene group and a 1-ethyl-2-methyl-n-propylene group, an alkylene group having a carbon number in the range of up to 20 and branched at an arbitrary position is exemplified. Can be

Examples of the cyclic alkylene group having 3 to 20 carbon atoms in the definition of L ¹ include a monocyclic alkylene group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group. And polycyclic alkylene groups such as a norbornylene group, a tricyclodecylene group, a tetracyclododecylene group, and an adamantylene group.

When the benzene ring in the definition of L ¹ may be substituted with a substituent, examples of the substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group; and a haloalkyl group such as a trifluoromethyl group. Groups; alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as iodine, bromine, chlorine and fluorine; cyano groups and the like.

  R is preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R may be a protective group which causes an elimination reaction by heat and replaces a hydrogen atom. From the viewpoint of storage stability of the liquid crystal aligning agent, R does not desorb at room temperature, and is preferably desorbed by heat at 80 ° C. or higher. It is a protecting group which is released, more preferably a protecting group which is released by heat at 100 ° C. or higher. Examples thereof include a 1,1-dimethyl-2-chloroethoxycarbonyl group, a 1,1-dimethyl-2-cyanoethoxycarbonyl group, and a tert-butoxycarbonyl group, and a tert-butoxycarbonyl group is preferable.

Further, the alkylene having 3 to 6 carbon atoms which there are two R form together, preferably _{-CH 2 -, - (CH 2} ) 2 -, - (CH 2) 3 -, - (CH 2 _{) 4 -, - (CH 2} ) 5 - , more preferably an - _{(CH 2) 2} - or - _{(CH 2) 3} - it is. The divalent organic radical ^{W 2,} is as represented by the following formula ^[W 2 -1] ~ formula ^[W 2 -152].

Among them, W ² -7, W ² -20, W ² -21, W ² -23, W ² ２６26, W ² ３９39, W ² ５１51, W ²と い う 7, W ^{2 、} 20, W ² 、 ^{2 3 , W 2 -52, W 2 -53} , W 2 -54, W 2 -55, W 2 -59, W 2 -60, W 2 -61, W 2 -64, W 2 -65, W 2 -67 ^{, W 2 -68, W 2 -69} , W 2 -70, W 2 -71 is preferred.

<Production method of specific diamine>
Hereinafter, a method for obtaining the above-described diamine will be described. Among the specific diamines represented by the formula (1) of the present invention, a method for synthesizing a diamine wherein W ¹ is a single bond is not particularly limited. For example, a nitromaleimide compound represented by the following formula (A): A method of reacting with a diamino compound represented by the following formula (B1) to obtain an aminonitro compound represented by the following formula (C1) and reducing the same is provided.

Ｒ、Ｒ^１、Ｌ^１、Ｗ¹及びＷ^２の定義は、上記式（１）と同様である。

The definitions of R, R ¹ , L ¹ , W ¹ and W ² are the same as in the above formula (1).

  The amount of the compound represented by the formula (B1) to be used is preferably 0.1 mol to 1 mol, more preferably 0.4 mol to 0.1 mol, per 1 mol of the compound represented by the formula (A). More preferably, it is 5 mol. By making the compound represented by the formula (A) in excess, the reaction can proceed smoothly and by-products can be suppressed.

This reaction is preferably performed in a solvent. The solvent can be used without limitation as long as it does not react with each raw material. For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.); aliphatic hydrocarbons (pentane, Hexane, heptane, petroleum ether, etc.); Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); Halogenous hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane) Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.); These solvents can be appropriately selected in consideration of the easiness of the reaction, and can be used alone or in combination of two or more. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant, and used as a non-aqueous solvent.

  The amount of the solvent used (reaction concentration) is not particularly limited, but is 0.1 to 100 times the mass of the bismaleimide compound. It is preferably from 0.5 to 30 times, more preferably from 1 to 10 times. Although the reaction temperature is not particularly limited, it is in the range from -100C to the boiling point of the solvent used, preferably -50 to 150C. The reaction time is generally 0.05 hours to 350 hours, preferably 0.5 hours to 100 hours.

  This reaction can be carried out, if necessary, in the presence of an inorganic base or an organic base. Examples of the base used in the reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; tert-butoxy Bases such as sodium, potassium tert-butoxy, sodium hydride, potassium hydride; amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, collidine can be used. Among them, triethylamine, pyridine, sodium tert-butoxy, potassium tert-butoxy, sodium hydride, potassium hydride and the like are preferable. The amount of the base used is not particularly limited, but is 0.1 parts by mass to 100 parts by mass with respect to the bismaleimide compound. It is preferably from 0 to 30 times by mass, and more preferably from 0 to 10 times by mass.

One embodiment of the compound (B1) is a compound represented by the following formula (B1-1), wherein L ¹ is a divalent organic group, R is a hydrogen atom, and W ¹ is a single bond. .

R in formula (B1-1) is each independently a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms. ^{L 1} of the compound of formula (B1-1), a structure selected from the above ^{W 2 -1~W} 2 -152 and the like. Preferably, it is selected from the following structures, but is not limited thereto.

In one embodiment of the compound (B1), L ¹ is a divalent organic group, W ¹ is a single bond, Rs together form an alkylene group, or both Rs are L bound to ^1, a compound represented by the following formula (B1-2).

  The compound of the formula (B1-2) is preferably selected from the following structural formulas.

One embodiment of the compound (B1) is a compound represented by the following formula (B1), wherein L ¹ is a divalent organic group, W ¹ is a single bond, and one of Rs is bonded to L ¹ to form a ring. -3).

  R in the formula (B1-3) is independently a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms. The compound of the formula (B1-3) preferably includes the following compounds.

  Next, conditions for producing the specific diamine represented by the formula (1) by reducing the compound represented by the formula (C1) will be described below. As a method of reducing the compound represented by the formula (C1), there is a reduction reaction performed in the coexistence of protons with Fe, Sn, Zn, or a salt thereof. The amount of Fe, Sn, Zn, or a salt thereof to be used is preferably 1 equivalent to 100 equivalents, particularly preferably 3 equivalents to 50 equivalents, to the compound represented by the above formula (1).

  As the reaction solvent, any solvent can be used as long as it does not hinder the desired reaction under the reaction conditions. For example, water; alcohol solvents such as methyl alcohol, ethyl alcohol, and tert-butyl alcohol; aprotic polar organic solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, and N-methylpyrrolidone; diethyl ether, diisopropyl ether, and tert-butyl Ethers such as methyl ether, cyclopentyl methyl ether, tetrahydrofuran and dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane, petroleum ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chloroform, dichloromethane, Halogen-based hydrocarbons such as carbon tetrachloride and dichloroethane; lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; Nitriles such as tonitrile, propionitrile, butyronitrile can be used. These solvents can be appropriately selected in consideration of the easiness of the reaction, and can be used alone or in combination of two or more. In some cases, the solvent can be used as a water-free solvent using a suitable dehydrating agent or desiccant. The use amount (reaction concentration) of the solvent is not particularly limited, but is 0.1 to 100 times by mass the compound represented by the formula (C1). Preferably it is 0.5 times by mass to 50 times by mass, and more preferably 3 times by mass to 30 times by mass.

  Furthermore, in order to make the reaction proceed more effectively, the reaction can be carried out under pressure. In this case, in order to avoid the reduction of the benzene nucleus, the reaction is preferably performed in a pressure range of about 20 atm (kgf), more preferably in a range of up to 10 atm. Further, acids such as hydrochloric acid, sulfuric acid, formic acid, and acetic acid, and salts thereof may coexist. The use amount of these is not particularly limited, but is 0 to 10 times by mass the compound represented by the formula (C1). It is preferably from 0 to 5 times, more preferably 0 to 3 times. The reaction temperature can be preferably selected from a temperature range of -100 ° C or higher to the temperature of the boiling point of the reaction solvent used, more preferably -50 ° C to 150 ° C, particularly preferably 0 ° C to 100 ° C. It is. The reaction time is from 0.1 hour to 1000 hours, more preferably from 1 hour to 200 hours. As a method for reducing the compound represented by the above formula (C1), a hydrogenation reaction using palladium-activated carbon or platinum-activated carbon as a catalyst, a reduction reaction using formic acid as a hydrogen source, and a hydrazine as a hydrogen source Reaction. Further, these reactions can be carried out in combination.

  The catalyst used in the reduction reaction is preferably an activated carbon-supported metal which is commercially available, and examples thereof include palladium-activated carbon, platinum-activated carbon, and rhodium-activated carbon. In addition, it is not always necessary to use an activated carbon-supported metal catalyst such as palladium hydroxide, platinum oxide, and Raney nickel. Palladium-activated carbon and platinum-activated carbon, which are generally widely used, are preferred because good results can be obtained.

  The amount of these catalysts used may be a so-called catalytic amount, preferably 20 mol% or less, particularly preferably 10 mol% or less, based on the compound represented by the above formula (C1).

  As the reaction solvent, any solvent can be used as long as it does not hinder the desired reaction under the reaction conditions. For example, alcohol solvents such as methyl alcohol, ethyl alcohol and tert-butyl alcohol; aprotic polar organic solvents such as dimethylformamide, dimethylsulfoxide, dimethylacetamide and N-methylpyrrolidone; diethyl ether, isopropyl ether and tert-butyl methyl ether Ethers such as cyclopentyl methyl ether, tetrahydrofuran and dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and tetralin; chloroform, dichloromethane and tetrachloride Halogen hydrocarbons such as carbon and dichloroethane; lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, and methyl propionate; acetonito Nitriles such as ril, propionitrile, butyronitrile can be used. These solvents can be appropriately selected in consideration of the easiness of the reaction, and can be used alone or in combination of two or more. In some cases, the solvent can be used as a water-free solvent using a suitable dehydrating agent or desiccant. The use amount (reaction concentration) of the solvent is not particularly limited, but is 0.1 times to 100 times the mass of the compound represented by the formula (C1). Preferably it is 0.5 times by mass to 50 times by mass, and more preferably 3 times by mass to 30 times by mass. The reaction temperature is not particularly limited, but is in the range of -100 ° C to the boiling point of the solvent used, preferably -50 ° C to 150 ° C. The reaction time is generally 0.05 hours to 350 hours, preferably 0.5 hours to 100 hours.

  In order to make the reduction reaction proceed more effectively, the reaction may be carried out in the presence of activated carbon. At this time, the amount of activated carbon used is not particularly limited, but is preferably in the range of 1% by mass to 30% by mass, more preferably 10% by mass to 20% by mass, based on the dinitro compound C1. For similar reasons, the reaction may be carried out under pressure. In this case, in order to avoid reduction of the benzene nucleus, the reaction is performed in a pressure range up to 20 atm. The reaction is preferably carried out in a range up to 10 atmospheres. In consideration of the structure of the compound represented by the formula (C1) and the reactivity of the reduction reaction among the reduction reactions exemplified above, it is preferable to use a hydrogenation reaction.

  When it is desired to introduce a monovalent organic group as R, a compound in which R is a hydrogen atom in the dinitro compound represented by the formula (C1) may be reacted with a compound capable of reacting with amines. Such compounds include, for example, acid halides, acid anhydrides, isocyanates, epoxies, oxetanes, aryl halides, and alkyl halides. Further, the hydroxyl groups of alcohols are OMs, OTf, OTs, etc. Alcohols substituted with a leaving group can be used.

  The method for introducing a monovalent organic group into the NH group is not particularly limited, and includes a method of reacting an acid halide in the presence of a suitable base. Examples of acid halides include acetyl chloride, propionyl chloride, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, i-propyl chloroformate, n-butyl chloroformate, i-butyl chloroformate, and t-chloroformate. Butyl, benzyl chloroformate, and 9-fluorenyl chloroformate. Examples of the base include the above-mentioned bases. The reaction solvent and reaction temperature are as described above.

  A monovalent organic group may be introduced by reacting an acid anhydride with the NH group. Examples of the acid anhydride include acetic anhydride, propionic anhydride, dimethyl dicarbonate, diethyl dicarbonate, and di-tert-butyl dicarbonate. And dibenzyl dicarbonate. A catalyst may be added to promote the reaction, and pyridine, collidine, N, N-dimethyl-4-aminopyridine and the like may be used. The amount of the catalyst is 0.0001 mol to 1 mol with respect to 1 mol of the compound in which R is a hydrogen atom in the dinitro compound represented by the above formula (C1). The reaction solvent and reaction temperature are as described above.

  A monovalent organic group may be introduced by reacting an isocyanate with the NH group. Examples of the isocyanate include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, and phenyl isocyanate. The reaction solvent and reaction temperature are as described above.

  A monovalent organic group may be introduced by reacting an epoxy compound or an oxetane compound with the NH group. Examples of the epoxy or oxetane include ethylene oxide, propylene oxide, 1,2-butylene oxide, trimethylene Oxides and the like. The reaction solvent and reaction temperature are as described above.

  The NH group may be reacted with an aryl halide in the presence of a metal catalyst, a ligand and a base to introduce a monovalent organic group. Examples of the aryl halide include iodobenzene, bromobenzene, chlorobenzene and the like. Is mentioned. Examples of the metal catalyst include palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzo) Nitrile) dichloropalladium, CuCl, CuBr, CuI, CuCN and the like, but are not limited thereto. Examples of the ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, and 1,3-bis (diphenylphosphino) propane. , 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphite, tri-tert-butylphosphine and the like. However, the present invention is not limited to these. Examples of the base include the above-mentioned bases. The reaction solvent and reaction temperature are as described above.

  A monovalent organic group may be introduced by reacting an alcohol in which a hydroxyl group of the alcohol is substituted with a leaving group such as OMs, OTf, or OTs in the presence of an appropriate base to the NH group to introduce a monovalent organic group. , Methanol, ethanol, 1-propanol, and the like. These alcohols are reacted with methanesulfonyl chloride, trifluoromethanesulfonyl chloride, p-toluenesulfonic acid chloride, and the like to remove OMs, OTf, OTs, and the like. An alcohol substituted with a group can be obtained. Examples of the base include the above-mentioned bases. The reaction solvent and reaction temperature are as described above.

  An NH group may be reacted with an alkyl halide in the presence of a suitable base to introduce a monovalent organic group. Examples of the alkyl halides include methyl iodide, ethyl iodide, and n-propyl iodide. , Methyl bromide, ethyl bromide, n-propyl bromide and the like. Examples of the base include, in addition to the above-mentioned bases, metal alkoxides such as potassium-tert-butoxide and sodium-tert-butoxide. The reaction conditions such as the reaction solvent, the reaction temperature and the reaction time are the same as described above.

The amount of the compound capable of reacting with the above amines is 1.0 to 3 molar equivalents with respect to 1.0 molar equivalent of the compound in which R is a hydrogen atom in the dinitro compound represented by the formula (C). It can be about 0.0 molar equivalent. Preferably, the range is from 2.0 molar equivalents to 2.5 molar equivalents. The compounds capable of reacting with the above amines can be used alone or in combination. In the case where the diamine compound represented by the formula (1) has an isomer derived from an asymmetric point, in the present application, each of the isomers and a mixture thereof is converted into a diamine represented by the formula (1). Shall be included. Further, when two R ¹ in the same maleimide ring of the formula (1) are different from each other, the diamine compound represented by the formula (1) has different substitution positions of R ¹ , but in the present application, the isomer also has All of those mixtures are also included in the diamine represented by the formula (1).

[Method of formula (A)]
The method for synthesizing the compound of the formula (A) is not particularly limited, and examples thereof include a method of reacting a commercially available nitroamine represented by the following formula (D) with a maleic anhydride derivative.

The amount of the maleic anhydride derivative to be used is preferably 1 mol to 1.5 mol, more preferably 1 mol to 1.2 mol, per 1 mol of the nitroamine compound represented by the formula (D). More preferred. By making the amount of maleic anhydride excessive, the reaction can proceed smoothly and by-products can be suppressed. This reaction is preferably performed in a solvent. Preferred solvents and reaction conditions are the same as those for the production of compound (1). In addition, among the specific diamines represented by the formula (1) of the present invention, as a method for synthesizing a diamine in which W ¹ is a single bond, an aminomaleimide compound represented by the following formula (E) and a compound represented by the above formula (E) A method of reacting with the diamino compound represented by B1-1) can also be mentioned.

The definitions of R, R ¹ , L ¹ and W ² are the same as in the above formula (1). The amount of the compound represented by the formula (B1-1) to be used is preferably 0.1 mol to 1 mol, more preferably 0.4 mol to 1 mol, per 1 mol of the compound represented by the formula (E). More preferably, it is 0.5 mol. By making the compound represented by the formula (E) in excess, the reaction can proceed smoothly and by-products can be suppressed.

This reaction is preferably performed in a solvent. The solvent can be used without limitation as long as it does not react with each raw material. For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.); ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.); aliphatic hydrocarbons (pentane, Hexane, heptane, petroleum ether, etc.); Aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.); Halogenous hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane) Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.); nitriles (acetonitrile, propionitrile, butyronitrile, etc.); These solvents can be appropriately selected in consideration of the easiness of the reaction, and can be used alone or in combination of two or more. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant, and used as a non-aqueous solvent. The amount of the solvent used (reaction concentration) is not particularly limited, but is 0.1 to 100 times the mass of the bismaleimide compound. It is preferably from 0.5 to 30 times, more preferably from 1 to 10 times. The reaction temperature is not particularly limited, but is in the range of -100 ° C to the boiling point of the solvent used, preferably -50 ° C to 150 ° C. The reaction time is generally 0.05 hours to 350 hours, preferably 0.5 hours to 100 hours.

This reaction can be carried out, if necessary, in the presence of an inorganic base or an organic base.
Examples of the base used in the reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; tert-butoxy Bases such as sodium, potassium tert-butoxy, sodium hydride, potassium hydride; amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, collidine can be used. Among them, triethylamine, pyridine, sodium tert-butoxy, potassium tert-butoxy, sodium hydride, potassium hydride and the like are preferable. The amount of the base to be used is not particularly limited, but is 0.1 to 100 times by mass the bismaleimide compound. It is preferably from 0 to 30 times by mass, and more preferably from 0 to 10 times by mass.

[Method of formula (E)]
The method for synthesizing the compound of the formula (E) is not particularly limited. For example, an anhydrous maleic anhydride may be added to a diamine represented by the following formula (F) under the conditions described in JP-A-2003-321531 or WO2004127735. A method of reacting an acid derivative is exemplified.

  The amount of the maleic anhydride derivative to be used is preferably 0.01 mol to 1 mol, and more preferably 0.1 mol to 1.0 mol, per 1 mol of the diamine compound represented by the formula (F). Is more preferred. By making the amount of the diamine (F) excessive, the reaction can proceed smoothly and by-products can be suppressed. This reaction is preferably performed in a solvent. Preferred solvents and reaction conditions are the same as those for the production of compound (1). In addition, a method of metal-catalyzed reduction of a diamine represented by the following formula (A) is also included.

  This reaction is in accordance with the method of producing the specific diamine represented by the formula (1) by reducing the above compound (C1). Considering the structure of the compound represented by the formula (A) and the reactivity of the reduction reaction among the reduction reactions, a reduction reaction performed in the coexistence of protons with Fe, Sn, Zn, or a salt thereof is preferable.

Among the specific diamines represented by the formula (1) of the present invention, a method for synthesizing a diamine wherein W ¹ is carbonyl is not particularly limited. For example, the following method may be used for the nitromaleimide compound represented by the above formula (A). After reacting an amine represented by the formula (B2) to obtain a compound represented by the following formula (G), this is reacted with a dicarboxylic acid represented by the following formula (H) to react with the following formula (C2) A method of obtaining a dinitro compound represented by the formula (1) and reducing it.

Ｒ、Ｒ^１、Ｌ^１及びＷ^２の定義は、上記式（１）と同様である。

The definitions of R, R ¹ , L ¹ and W ² are the same as in the above formula (1).

Further, preferred ^{L 1} in formula (H) and formula (C2) is the same as the preferable ^{L 1} in the formula (B1-1). The reaction conditions of the compound represented by the formula (B2) and the compound represented by the formula (A) are the same as the reaction conditions of the compound represented by the formula (B1) and the compound represented by the formula (A). Conform.

The compound represented by the above formula (G) and the compound represented by the above formula (H) wherein Z is OH are condensed using a solvent inert to the reaction if necessary and in the presence of a base if necessary. By reacting with the agent, a compound represented by the general formula (C2) can be obtained.
As the amount of the reaction substrate, a compound in which Z is OH in the general formula (H) can be used in an amount of 0.4 equivalent to 0.8 equivalent to 1 equivalent of the compound represented by the formula (G).

  The condensing agent is not particularly limited as long as it is used for ordinary amide synthesis. For example, Mukaiyama reagent (2-chloro-N-methylpyridinium iodide), DCC (1,3-dicyclohexylcarbodiimide), WSC (1 -Ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride), CDI (carbonyldiimidazole), dimethylpropynylsulfonium bromide, propargyltriphenylphosphonium bromide, DEPC (diethyl cyanophosphate), and the like, using the above formula (H) Can be used in an amount of 1 to 4 equivalents to the compound in which Z is OH.

  When a solvent is used, the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction, but, for example, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as hexane and heptane , Alicyclic hydrocarbons such as cyclohexane, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene Such as aliphatic halogenated hydrocarbons, ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate and ethyl propionate; N, N-dimethylformamide; N, N-dimethylacetamide, N-meth Amides such as-2-pyrrolidone, triethylamine, tributylamine, N, N-amines dimethylaniline, pyridine, pyridine picoline, etc., include acetonitrile and dimethyl sulfoxide. These solvents may be used alone or as a mixture of two or more of them.

  Although the addition of a base is not always necessary, when a base is used, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate Alkali metal bicarbonate, such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, etc. An organic base or the like can be used in an amount of 1 to 4 equivalents to the compound in which Z is OH in the above formula (H).

  The reaction temperature can be set at any temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrarily within a range of 5 minutes to 100 hours. Can be set.

  Generally, for example, 0.4 equivalent to 0.8 equivalent of the compound represented by the above formula (H) wherein Z is OH and 1 equivalent to 4 equivalent of the compound represented by the above formula (G) Using a condensing agent such as WSC (1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride) or CDI (carbonyldiimidazole), if necessary, 1-4 equivalents of potassium carbonate, triethylamine, pyridine, In the presence of a base such as-(dimethylamino) pyridine, without solvent or using a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, or 1,4-dioxane, in the range of 0 ° C. to the reflux temperature of these solvents. The reaction is preferably performed for 10 minutes to 24 hours.

  In addition, from a compound in which Z is OH in the above formula (H), a known method described in the literature, for example, a method of reacting with a chlorinating agent such as thionyl chloride, phosphorus pentachloride or oxalyl chloride, pivaloyl chloride or isobutyl chloroformate In the above formula (H), which can be synthesized by a method of reacting with an organic acid halide such as the above in the presence of a base if necessary, or a method of reacting with a carbonyldiimidazole or a sulfonyldiimidazole, etc. Is reacted with a compound represented by the above formula (G) using a solvent inert to the reaction, if necessary, and in the presence of a base, if necessary, to obtain a compound represented by the general formula ( The compound represented by C2) can also be synthesized. As the amount of the reaction substrate, a compound in which Z is Cl in the general formula (H) can be used in an amount of 0.4 equivalent to 0.8 equivalent to 1 equivalent of the compound represented by the formula (G).

  When a solvent is used, the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction, but, for example, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as hexane and heptane , Alicyclic hydrocarbons such as cyclohexane, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene Such as aliphatic halogenated hydrocarbons, ethers such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate and ethyl propionate; N, N-dimethylformamide; N, N-dimethylacetamide, N-meth Amides such as-2-pyrrolidone, triethylamine, tributylamine, N, N-amines dimethylaniline, pyridine, pyridine picoline, etc., and acetonitrile and water and the like. These solvents may be used alone or as a mixture of two or more of them.

  Although the addition of a base is not always necessary, when a base is used, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate Alkali metal bicarbonate such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene and the like An organic base or the like can be used in an amount of 1 to 4 equivalents to the compound in which Z is Cl in the above formula (H). The reaction temperature can be set at any temperature from −60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrarily within a range of 5 minutes to 100 hours. Can be set.

  Generally, for example, 0.4 equivalent to 0.8 equivalent of the compound represented by general formula (H) in which Z is Cl relative to 1 equivalent of the compound represented by formula (G), and if necessary, 1 equivalent to In the presence of 2 equivalents of a base such as potassium carbonate, triethylamine, pyridine and 4- (dimethylamino) pyridine, no solvent or a solvent such as dichloromethane, chloroform, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethyl acetate, acetonitrile, etc. It is preferable to carry out the reaction at 0 ° C. to the reflux temperature of these solvents for 10 minutes to 48 hours. The reaction conditions for reducing the dinitro compound represented by the formula (C2) to obtain the diamine represented by the formula (1) are the same as those described above.

  The target product in each step obtained by each of the above reactions may be purified by distillation, recrystallization, column chromatography such as silica gel, or the like, or may be subjected to the next step as it is without purification. Can also.

<Polymer>
The polymer of the present invention is a polymer obtained using the above diamine. Specific examples include polyamic acid, polyamic acid ester, polyimide, polyurea, and polyamide. From the viewpoint of use as a liquid crystal aligning agent, a polyimide precursor containing a structural unit represented by the following formula (3): More preferably, it is at least one selected from polyimides, and imidates thereof.

In the above formula (3), X ¹ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ is a divalent organic group derived from a diamine having the structure of the formula (1), and R ⁴ Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ⁴ is preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoint of imidization by heating.

<Tetracarboxylic dianhydride>
X ¹ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. Further, X ¹ of the polyimide precursor is applied of solubility and liquid crystal aligning agent to the solvent of the polymer liquid crystal orientation in the case where the liquid crystal alignment film, the voltage holding ratio, such as the accumulated charge, is required One kind may be appropriately selected according to the degree of the characteristic, and one kind may be used in the same polymer, or two or more kinds may be mixed.
If dare Specific examples of X ^1, is published in the 13 pages to 14 pages of WO 2015/119168, such as the structure of formula (X-1) ~ (X -46) are mentioned. Below, shows the structure of a preferred X ^1, the present invention is not limited thereto.

  Of the above structures, (A-1) and (A-2) are particularly preferable from the viewpoint of further improving rubbing resistance, and (A-4) is particularly preferable from the viewpoint of further improving the relaxation rate of accumulated charge. , (A-15) to (A-17) are particularly preferable from the viewpoint of further improving the liquid crystal orientation and the relaxation rate of accumulated charge.

<Polymer (other structural units)>
The polyimide precursor containing the structural unit represented by the formula (3) is at least selected from the structural unit represented by the following formula (4) and a polyimide that is an imidized product thereof, as long as the effects of the present invention are not impaired. One type may be included.

In the formula (4), X ² is a tetravalent organic group derived from a tetracarboxylic acid derivative, and Y ² is a divalent organic group derived from a diamine not including the structure of the formula (1) in the main chain direction. R ¹⁴ is the same as defined for R ^{4 in} the formula (3), and R ¹⁵ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Specific examples of X ^2, may include the same structure as that illustrated preferred embodiment be included in X ¹ of the formula (3). Further, Y ² in the polyimide precursor is a divalent organic group derived from a diamine that does not include the structure of the formula (1) in the main chain direction, and the structure is not particularly limited. Y ² depends on the degree of required properties such as solubility of the polymer in a solvent, applicability of a liquid crystal aligning agent, liquid crystal alignment when forming a liquid crystal alignment film, voltage holding ratio, and accumulated charge. One kind may be selected as appropriate, and two or more kinds may be mixed in the same polymer.

If dare Specific examples of Y ^2, include groups represented by the formula ^[W 2 -1] ~ formula ^[W 2 -152]. Further, the structure of formula (2) described on page 4 of International Publication WO 2015/119168, and the formulas (Y-1) to (Y-97) and (Y-97) described on pages 8 to 12 are described. 101) to (Y-118); a divalent organic group obtained by removing two amino groups from the formula (2) described on page 6 of WO2013 / 008906; and 8 of WO2015 / 122413. Divalent organic group obtained by removing two amino groups from formula (1) published on page; structure of formula (3) published on page 8 of International Publication WO 2015/060360; A divalent organic group obtained by removing two amino groups from the formula (1) described on page 8 of 173514; an amino group derived from the formulas (A) to (F) described on page 9 of International Publication No. 2010/050523; And a divalent organic group excluding two.

Preferred examples of the structure of Y ² include a structure represented by the following formula (11).

In the formula (11), R ³² is a single bond or a divalent organic group, and a single bond is preferable. R ³³ is a structure represented by — (CH ₂ ) _r —. r is an integer of 2 to 10, and preferably 3 to 7. Also, any -CH 2 _- ether conditions nonadjacent respectively, esters, amides, ureas, may be replaced by a carbamate linkage. R ³⁴ is a single bond or a divalent organic group. Any hydrogen atom on the benzene ring may be replaced by a monovalent organic group, and is preferably a fluorine atom or a methyl group. Examples of the structure represented by the formula (11) include, but are not limited to, the following structures.

When the polyimide precursor containing the structural unit represented by the formula (3) simultaneously contains the structural unit represented by the formula (4), the accumulated charge is rapidly relaxed, and the difference between the rubbing direction and the alignment direction of the liquid crystal is reduced. In view of controlling the structural unit, the amount of the structural unit represented by the formula (3) is preferably 1 mol% to 80 mol%, more preferably 5 mol%, based on the total of the formulas (3) and (4). Mol% to 60 mol%, particularly preferably 10 mol% to 40 mol%. Preferred examples of the structure of Y ² include a structure having at least one selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring.

Such a structure of Y ² has at least one kind of structure selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, or a thermally labile group is substituted on a nitrogen atom. The structure is not particularly limited as long as it has at least one kind of structure selected from an amino group, an imino group, and a nitrogen-containing heterocyclic ring. If specific examples are given, at least one kind selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocycle represented by the following formulas (YD-1) to (YD-5). And a divalent organic group having a structure.

In the formula (YD-1), A ₁ is a nitrogen-containing heterocyclic ring having 3 to 15 carbon atoms, and Z ₁ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. is there. In the formula (YD-2), V ₁ is a hydrocarbon group having 1 to 10 carbon atoms, and A ₂ is a monovalent organic group having 3 to 15 carbon atoms having a nitrogen-containing heterocyclic ring, or 1 carbon atom. And 6 is a disubstituted amino group substituted with an aliphatic group. In the formula (YD-3), V ₂ is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and V ₃ is alkylene or biphenylene having 2 to 5 carbon atoms; Z ₂ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring, or a thermally desorbable group, and a is an integer of 0 to 1. In the formula (YD-4), A ₃ is a nitrogen-containing heterocyclic ring having ₃ to 15 carbon atoms. In the formula (YD-5), A ₄ is a nitrogen-containing heterocycle having 3 to 15 carbon atoms, and V ₅ is an alkylene having 2 to ₅ carbon atoms. )

A ₁ , A ₂ , A ₃ , and A _{4 in} the formulas (YD-1), (YD-2), (YD-4), and (YD-5), a nitrogen-containing heterocyclic ring having 3 to 15 carbon atoms. Is not particularly limited as long as it has a known structure. Among them, pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyrazine, indole, benzimidazole, quinoline, isoquinoline, and piperazine, piperidine, indole, benzimidazole, imidazole, carbazole, and pyridine. More preferred. The thermally desorbable group may be any substituent that does not desorb at room temperature but is desorbed and replaced by a hydrogen atom when the alignment film is fired. Specifically, a tert-butoxycarbonyl group and 9-fluoro group may be used. Oleynylmethoxycarbonyl group is exemplified.

Specific examples of such Y ² include a divalent organic group having a nitrogen atom represented by the following formulas (YD-6) to (YD-52), which can suppress charge accumulation by AC driving. Therefore, the formulas (YD-14) to (YD-21) are more preferable, and (YD-14) and (YD-18) are particularly preferable.

式（ＹＤ−１４）及び（ＹＤ−２１）中、ｊは０〜３の整数である。

In the formulas (YD-14) and (YD-21), j is an integer of 0 to 3.

式（ＹＤ−２４）、（ＹＤ−２５）、（ＹＤ−２８）及び（ＹＤ−２９）中、ｊは０〜３の整数である。

In the formulas (YD-24), (YD-25), (YD-28) and (YD-29), j is an integer of 0 to 3.

（式（ＹＤ−５０）中、ｍ、ｎはそれぞれ１〜１１の整数であり、ｍ＋ｎは２〜１２の整数である。）

(In the formula (YD-50), m and n are each an integer of 1 to 11, and m + n is an integer of 2 to 12.)

<Production method of polyamic acid>
Polyamic acid which is a polyimide precursor used in the present invention can be synthesized by the following method. Specifically, tetracarboxylic dianhydride and diamine are mixed at -20 ° C to 150 ° C, preferably 0 ° C to 70 ° C, in the presence of an organic solvent, for 30 minutes to 24 hours, preferably 1 hour to 12 hours. It can be synthesized by reacting. The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc., from the solubility of the monomer and the polymer. These may be used alone or in combination of two or more. May be used.

  The concentration of the polymer is preferably from 1% by mass to 30% by mass, more preferably from 5% by mass to 20% by mass, from the viewpoint that the precipitation of the polymer hardly occurs and a high molecular weight product is easily obtained. The polyamic acid obtained as described above can be recovered by precipitating a polymer by injecting it into a poor solvent while stirring the reaction solution well. The polyamic acid powder can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating. The poor solvent is not particularly limited, but includes water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like, and water, methanol, ethanol, 2-propanol and the like are preferable.

<Production method of polyimide>
The polyimide used in the present invention can be produced by imidizing the polyamic acid. In the case of producing a polyimide from a polyamic acid, chemical imidization in which a catalyst is added to a solution of the polyamic acid obtained by reacting a diamine component with a tetracarboxylic dianhydride is simple. Chemical imidization is preferred because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer hardly decreases during the imidization process. Chemical imidization can be performed by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, the solvent used in the polymerization reaction described above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for causing the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferred because purification after the reaction is facilitated.

  The temperature at which the imidization reaction is performed is -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time can be 1 hour to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles of the polyamic acid group, and the amount of the acid anhydride is 1 to 50 moles of the polyamic acid group. Preferably it is 3 to 30 moles. The imidation ratio of the obtained polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. In the solution after the polyamic acid imidization reaction, the added catalyst and the like remain, so that the obtained imidized polymer is recovered and redissolved in an organic solvent according to the present invention, by the means described below. It is preferable to use a liquid crystal aligning agent.

  By pouring the polyimide solution obtained as described above into a poor solvent while stirring well, a polymer can be precipitated. Precipitation is performed several times, and the polymer is washed with a poor solvent and then dried at room temperature or under heat to obtain a purified polymer powder. The poor solvent is not particularly limited, but includes methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and the like, and methanol, ethanol, 2-propanol, Acetone and the like are preferred.

<Manufacture of polyimide precursor-polyamic acid ester>
The polyamic acid ester which is a polyimide precursor used in the present invention can be produced by the following method (1), (2) or (3).

(1) When Producing from Polyamic Acid The polyamic acid ester can be produced by esterifying the polyamic acid produced as described above. Specifically, reacting the polyamic acid and the esterifying agent in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 hour to 4 hours. Can be manufactured by As the esterifying agent, those which can be easily removed by purification are preferable, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like. The addition amount of the esterifying agent is preferably 2 molar equivalents to 6 molar equivalents per 1 mol of the repeating unit of the polyamic acid.

  Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and 1,3-dimethyl- And imidazolidinone. When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or formulas [D-1] to [D-3] described later. Can be used. These solvents may be used alone or as a mixture. Furthermore, even if the solvent does not dissolve the polyimide precursor, the solvent may be mixed with the solvent as long as the generated polyimide precursor does not precipitate. Further, since water in the solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, it is preferable to use a solvent that has been dehydrated and dried.

  The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the viewpoint of solubility of the polymer. These solvents may be used alone or in combination of two or more. Good. The concentration at the time of production is preferably from 1% by mass to 30% by mass, more preferably from 5% by mass to 20% by mass, from the viewpoint that polymer precipitation hardly occurs and a high molecular weight product is easily obtained.

(2) When Producing by Reaction of Tetracarboxylic Diester Dichloride and Diamine Polyamic acid ester can be produced from tetracarboxylic diester dichloride and diamine. Specifically, a tetracarboxylic diester dichloride and a diamine are prepared in the presence of a base and an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 hour to 4 hours. It can be produced by reacting for a time. As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds gently. The amount of the base to be added is preferably 2 to 4 times the mol of the tetracarboxylic diester dichloride from the viewpoint of easy removal and easy production of a high molecular weight compound.

  The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the monomer and the polymer, and these may be used alone or in combination of two or more. The polymer concentration at the time of production is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 20% by mass, since precipitation of the polymer hardly occurs and a high molecular weight product is easily obtained. In order to prevent hydrolysis of the tetracarboxylic diester dichloride, the solvent used for producing the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent outside air from being mixed in a nitrogen atmosphere.

(3) When producing from tetracarboxylic acid diester and diamine The polyamic acid ester can be produced by polycondensing tetracarboxylic acid diester and diamine. Specifically, tetracarboxylic diester and diamine are condensed with a condensing agent, a base, and an organic solvent at 0 ° C to 150 ° C, preferably at 0 ° C to 100 ° C, for 30 minutes to 24 hours, preferably 3 hours to It can be produced by reacting for 15 hours.

  Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triadiazole. Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ', N'-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate and the like can be used. The amount of the condensing agent to be added is preferably 2 to 3 times the mol of the tetracarboxylic diester.

  Tertiary amines such as pyridine and triethylamine can be used as the base. The amount of the base to be added is preferably 2 to 4 times the mol of the diamine component from the viewpoint of easy removal and easy production of a high molecular weight compound. In the above reaction, the reaction proceeds efficiently by adding a Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0 to 1.0 times the molar amount of the diamine component. Among the above three methods for producing a polyamic acid ester, the method (1) or (2) is particularly preferable because a high molecular weight polyamic acid ester is obtained. The solution of the polyamic acid ester obtained as described above can be poured into a poor solvent with good stirring to precipitate a polymer. After performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating, a purified polyamic acid ester powder can be obtained. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

  In order to produce the polymer of the present invention, a diamine represented by the formula (1) may be used as the diamine in the above production method. The molecular weight of the polyimide precursor or polyimide, which is a polymer included in the liquid crystal alignment agent of the present invention, is determined when a liquid crystal alignment film is obtained from the liquid crystal alignment agent containing the polymer. In consideration of strength, workability in forming a coating film, and uniformity of the coating film, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) is preferably 2,000 to 500,000, It is more preferably from 000 to 300,000, and still more preferably from 10,000 to 100,000.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of the present invention contains a polymer (specific polymer) obtained from a diamine having a structure represented by the formula (1), but is different as long as the effects described in the present invention are exhibited. Two or more specific polymers having a structure may be contained. Further, in addition to the specific polymer, another polymer, that is, a polymer having no divalent group represented by the formula (1) may be contained. Other types of polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or its derivative, poly (styrene-phenylmaleimide) derivative, poly (meta ) Acrylates and the like. When the liquid crystal aligning agent of the present invention contains another polymer, the ratio of the specific polymer to all polymer components is preferably 5% by mass or more, and an example thereof is 5% by mass to 95% by mass. .

  The liquid crystal aligning agent is used for producing a liquid crystal alignment film, and generally takes a form of a coating liquid from the viewpoint of forming a uniform thin film. The liquid crystal aligning agent of the present invention is also preferably a coating liquid containing the polymer component described above and an organic solvent that dissolves the polymer component. At that time, the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed by setting the thickness of the coating film to be formed. The amount is preferably 1% by mass or more from the viewpoint of forming a uniform and defect-free coating film, and is preferably 10% by mass or less from the viewpoint of storage stability of the solution. A particularly preferred concentration of the polymer is 2% by mass to 8% by mass.

  The organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, and 1,3-dimethyl. -Imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone and the like. Especially, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone.

  In addition, the organic solvent contained in the liquid crystal aligning agent uses a mixed solvent that is used in combination with a solvent that improves the applicability and the surface smoothness of the coating film when applying the liquid crystal aligning agent in addition to the above-described solvents. In general, such a mixed solvent is suitably used in the liquid crystal aligning agent of the present invention. Specific examples of the organic solvent used in combination are shown below, but the present invention is not limited to these examples. For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol , 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etangi Diol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane Diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pe Tanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate , Ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, Diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl Ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Butyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol Ethylene glycol monomethyl ether, Polyethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ethyl, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, Examples thereof include n-butyl lactate, isoamyl lactate, and solvents represented by the following formulas [D-1] to [D-3].

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

  Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether or It is preferred to use dipropylene glycol dimethyl ether.

  The type and content of such a solvent are appropriately selected according to the application device, application conditions, application environment, and the like of the liquid crystal aligning agent.

  The liquid crystal aligning agent of the present invention may further contain components other than the polymer component and the organic solvent as long as the effects of the present invention are not impaired. Such additional components include an adhesion aid for improving the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealing material, a crosslinking agent for increasing the strength of the liquid crystal alignment film, and a liquid crystal alignment. Examples include a dielectric and a conductive substance for adjusting the dielectric constant and electric resistance of the film. Specific examples of these additional components are variously disclosed in publicly known documents relating to liquid crystal aligning agents, and if one example is shown, an international publication 2015/060357 pamphlet, page 53 [0105] -55. And the components disclosed on page [0116].

<Liquid crystal alignment film>
The liquid crystal alignment film of the present invention is obtained from the liquid crystal alignment agent. As an example of a method for obtaining a liquid crystal alignment film from a liquid crystal alignment agent, a liquid crystal alignment agent in the form of a coating liquid is applied to a substrate, dried, and baked. And a method of performing an orientation treatment. The substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with a glass substrate and a silicon nitride substrate. At that time, it is preferable to use a substrate on which an ITO electrode or the like for driving the liquid crystal is formed in terms of simplification of the process. In a reflection type liquid crystal display device, an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as aluminum can be used for the electrode.

  The method for applying the liquid crystal aligning agent is not particularly limited, but industrially, screen printing, offset printing, flexographic printing, an inkjet method and the like are generally used. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, a spray method and the like, and these may be used according to the purpose. After the liquid crystal aligning agent is applied on the substrate, the solvent is evaporated and baked by a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven. In the drying and baking steps after the application of the liquid crystal aligning agent, any temperature and time can be selected. Usually, in order to sufficiently remove the contained solvent, the conditions include firing at 50 ° C. to 120 ° C. for 1 minute to 10 minutes, and then firing at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes. The thickness of the liquid crystal alignment film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, the thickness is preferably 5 nm to 300 nm, and more preferably 10 nm to 200 nm. INDUSTRIAL APPLICABILITY The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film of a liquid crystal display element of an in-plane switching method such as an IPS method or an FFS method, and is particularly useful as a liquid crystal alignment film of an FFS liquid crystal display element.

<Liquid crystal display device>
The liquid crystal display element of the present invention is obtained by obtaining a substrate with a liquid crystal alignment film obtained from the above liquid crystal alignment agent, then manufacturing a liquid crystal cell by a known method, and using the liquid crystal cell as an element. As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. Note that an active matrix liquid crystal display element in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion forming an image display may be used. Specifically, a transparent glass substrate is prepared, and a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. These electrodes can be, for example, ITO electrodes, and are patterned so that a desired image can be displayed. Next, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrodes. The insulating film can be, for example, a film made of SiO ₂ —TiO ₂ formed by a sol-gel method. Next, a liquid crystal alignment film is formed on each substrate under the above conditions.

  Next, for example, an ultraviolet-curable sealing material was disposed at a predetermined position on one of the two substrates on which the liquid crystal alignment film was formed, and liquid crystal was disposed at predetermined predetermined positions on the liquid crystal alignment film surface. Then, the other substrate is bonded and pressed so that the liquid crystal alignment film faces the liquid crystal, and the liquid crystal is pushed out to the front surface of the liquid crystal alignment film. Then, the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealing material. Get the cell. In addition, as a step after forming the liquid crystal alignment film on the substrate, when a sealing material is arranged at a predetermined place on one substrate, an opening capable of filling the liquid crystal from the outside is provided, and the liquid crystal is formed. After bonding the substrates without disposing them, a liquid crystal material is injected into the liquid crystal cell through an opening provided in the sealant, and then the opening is sealed with an adhesive to obtain a liquid crystal cell. The liquid crystal material may be injected by a vacuum injection method or a method utilizing capillary action in the air.

  In any of the above methods, in order to secure a space where the liquid crystal material is filled in the liquid crystal cell, a columnar projection is provided on one substrate, a spacer is scattered on one substrate, or a sealing material is used. It is preferable to take measures such as mixing a spacer into the mixture or combining them.

  Examples of the liquid crystal material include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and any of a positive liquid crystal material and a negative liquid crystal material may be used. Next, a polarizing plate is installed. Specifically, it is preferable that a pair of polarizing plates be attached to surfaces of the two substrates opposite to the liquid crystal layer.

  Note that the liquid crystal alignment film and the liquid crystal display element of the present invention are not limited to the above description as long as the liquid crystal alignment agent of the present invention is used, and may be formed by other known methods. Good. Processes for obtaining a liquid crystal display element from a liquid crystal aligning agent are disclosed in, for example, page 17 [0074] to page 19 [0081] of JP-A-2015-135393 (Japanese Patent Laid-Open Publication) and many other documents. I have.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
The abbreviations of the compounds used in the examples and comparative examples and the methods for evaluating the characteristics are as follows.
NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve GBL: γ-butyl lactone NMP: N-methyl-2-pyrrolidone DA-1-1: Compound represented by the following formula DA-1-1 DA-2: Following Compound of Formula DA-2 DA-3: Compound of Formula DA-3 CA-1: Compound of Formula CA-1 CA-2: Formula CA-2 Compound

Example 1A
Synthesis of (DA-1-1)

15.00 g (68.8 mmol) of N- (4-nitrophenyl) maleimide and 300 g of terahydrofuran (hereinafter, THF) were added to the flask, and the mixture was ice-cooled. 3.37 g (33.0 mmol) of N, N'-dimethyl-1,3-propanediamine was added to the mixture. Then, after gradually returning to room temperature, the mixture was stirred at room temperature for 1 day. After confirming that the reaction was completed, 200 g of ethyl acetate was added to the reaction mixture, followed by stirring. The obtained crystals were filtered and then dried at 50 ° C. to obtain 11.1 g of the target nitro intermediate (DA-1-1-1) (yield: 62%).
1H-NMR (D6-DMSO, δ ppm): 8.37 (d, 4H), 7.62 (d, 4H), 4.15-4.21 (m, 1H), 2.93-3.03 ( m, 2H), 2.80-2.89 (m, 2H), 2.53-2.70 (m, 4H), 2.32 (s, 6H), 1.57-1.67 (m, 2H)

In a flask purged with nitrogen, 11.1 g (20.6 mmol) of DA-1-1-1 and 1 g of 5% Pd-C (STD type, wet product, manufactured by NE Chemcat Corporation) and N, N- After 300 g of dimethylformamide (hereinafter, DMF) was charged, the inside of the flask was replaced with hydrogen. The reaction mixture was stirred at room temperature under hydrogen pressure and normal pressure for 3 days. After confirming that the reaction was completed, Pd-C was removed from the reaction mixture by filtration, and the filtrate was distilled off under reduced pressure. Chloroform was added to the obtained residue and stirred. The insoluble material was removed by filtration, and the obtained filtrate was distilled off under reduced pressure to obtain 8.93 g (yield: 90%) of the target DA-1-1 as a viscous liquid.
1H-NMR (D6-DMSO, δ ppm): 6.79 (d, 4H), 6.55 (d, 4H), 5.274 (brs, 4H), 3.99-4.04 (m, 2H). , 2.79-2.89 (m, 2H), 2.44-2.71 (m, 6H), 3.23 (s, 6H), 1.51-1.61 (m, 2H)

Example 2A
Synthesis of (DA-1-2)

After 0.1246 g (0.662 mmol) of N- (4-aminophenyl) maleimide and 3 g of THF were added to the flask, the mixture was ice-cooled. 0.0285 g (0.331 mmol) of piperazine was added into the mixture. Then, after gradually returning to room temperature, the mixture was stirred at room temperature for 3 days. After confirming that the reaction was completed, the precipitated crystals were filtered and washed with diisopropyl ether (hereinafter, IPA). The obtained crystals were dried at 50 ° C. to obtain 0.067 g of the target DA-1-2 (47% yield).
1H-NMR (D6-DMSO, δ ppm): 6.82 (d, 4H), 6.59 (d, 4H), 5.30 (brs, 4H), 3.92-3.98 (m, 2H) , 2.70-2.95 (m, 8H), 2.40-55 (m, 2H)

Example 3A
Synthesis of (DA-1-3)

2.90 g (15.4 mmol) of N- (4-aminophenyl) maleimide and 30 g of terahydrohydrofuran (hereinafter, THF) were added to the flask, and the mixture was ice-cooled. 1.00 g (7.34 mmol) of 4- (aminomethyl) benzylamine was added to the mixture. Then, after gradually returning to room temperature, the mixture was stirred at room temperature for 3 hours. After confirming that the reaction was completed, the reaction mixture was cooled again, and the precipitated crystals were filtered. The obtained crystals were dried at 45 ° C. under reduced pressure to obtain 1.59 g of the desired compound (DA-1-3) as yellow crystals (42% yield).
1H-NMR (D6-DMSO, δ ppm): 7.32 (s, 4H), 6.84 (d, 4H), 6.59 (d, 4H), 5.31 (brs, 4H), 3.82. -3.95 (m, 4H), 3.74-3.82 (m, 2H), 2.91-3.01 (m, 2H), 2.94 (brs, 2H), 2.53-2 .56 (m, 1H), 2.48-2.51 (m, 1H)

[Viscosity measurement]
The viscosity of the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample amount of 1.1 mL and a cone rotor TE-1 (1 ° 34 ′, R24).

[Example 1]
After DA-1-1 (3.34 g, 7 mmol) was added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 31.5 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution, CA-1 (1.43 g, 6.58 mmol) was added, 3.5 g of NMP was added, and the mixture was further stirred at 50 ° C. for 12 hours to obtain a polyamic acid solution (PAA- 1) was obtained. The viscosity at 25 ° C. of this polyamic acid solution was 270 mPa · s.

[Example 2]
After DA-1-1 (3.34 g, 7 mmol) was added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 31.1 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution, CA-1 (0.61 g, 2.8 mmol) and CA-2 (0.75 g, 3.9 mmol) were added, and 3.5 g of NMP were added. And stirred for 12 hours to obtain a polyamic acid solution (PAA-2). The viscosity at 25 ° C. of this polyamic acid solution was 280 mPa · s.

[Comparative Example 1]
DA-2 (5.73 g, 20 mmol) was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, NMP (65.1 g) was added, and the mixture was stirred and dissolved while sending nitrogen. After adding CA-1 (4.14 g, 19 mmol) while stirring this diamine solution, adding 7.2 g of NMP, and further stirring at room temperature for 18 hours, the polyamic acid solution (PAA-3) was added. ) Got. The viscosity at 25 ° C. of this polyamic acid solution was 500 mPa · s.

[Comparative Example 2]
After DA-3 (1.98 g, 10 mmol) was added to a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 26.0 g of NMP was added, and the mixture was stirred and dissolved while sending nitrogen. While stirring this diamine solution, CA-1 (0.87 g, 4.0 mmol) and CA-2 (1.08 g, 5.5 mmol) were added, and 2.9 g of NMP was added. And stirred for 12 hours to obtain a polyamic acid solution (PAA-4). The viscosity at 25 ° C. of this polyamic acid solution was 300 mPa · s.

[Example 3]
7.5 g of the polyamic acid solution (PAA-1) obtained in Example 1 was dispensed, and containing 5.6 g of NMP, 6.0 g of BCS, and 1% by weight of 3-aminopropyltriethoxysilane while stirring. 0.9 g of NMP solution was added, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (Q-1).

[Example 4]
7.5 g of the polyamic acid solution (PAA-2) obtained in Example 2 was taken, and 5.6 g of NMP, 6.0 g of BCS, and 1% by weight of 3-aminopropyltriethoxysilane were contained with stirring. 0.9 g of NMP solution was added, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (Q-2).

[Comparative Example 3]
7.5 g of the polyamic acid solution (PAA-3) obtained in Comparative Example 1 was taken, and 5.6 g of NMP, 6.0 g of BCS, and 1% by weight of 3-aminopropyltriethoxysilane were contained with stirring. 0.9 g of NMP solution was added, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (Q-3).

[Comparative Example 4]
7.5 g of the polyamic acid solution (PAA-4) obtained in Comparative Example 2 was collected and, while stirring, contained 5.6 g of NMP, 6.0 g of BCS, and 1% by weight of 3-aminopropyltriethoxysilane. 0.9 g of NMP solution was added, and the mixture was further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (Q-4).

[Production of liquid crystal cell for measuring ion density]
After filtering the liquid crystal aligning agent with a filter of 1.0 μm, a substrate with electrodes (a glass substrate of 30 mm in width × 40 mm in length and 1.1 mm in thickness. The electrode is a rectangle of 10 mm in width × 40 mm in length, (ITO electrode having a thickness of 35 nm) by spin coating. After drying on a hot plate at 50 ° C. for 5 minutes, baking was performed in an IR oven at 230 ° C. for 20 minutes to form a 100-nm-thick coating film, thereby obtaining a substrate with a liquid crystal alignment film. This liquid crystal alignment film was rubbed with a rayon cloth (YA-20R manufactured by Yoshikawa Kako) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm), and then into pure water. The substrate was washed by irradiating ultrasonic waves for 1 minute to remove water droplets by air blow, and then dried at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.

  After preparing two substrates with the above liquid crystal alignment film, spraying a 4 μm spacer on one of the liquid crystal alignment film surfaces, printing a sealing material thereon, and rubbing the other substrate in the opposite direction. After laminating so that the directions and the film surfaces face each other, the sealing material was cured to produce an empty cell. MLC-3019 (manufactured by Merck) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour and left at 23 ° C. overnight to obtain a liquid crystal cell for ion density measurement.

[Ion density measurement]
The ion density of the liquid crystal cell manufactured by the method described in [Production of Liquid Crystal Cell for Ion Density Measurement] was measured. In the ion density measurement, the ion density was measured when a triangular wave having a voltage of ± 10 V and a frequency of 0.01 Hz was applied to the liquid crystal cell. The measurement was performed at a temperature of 60 ° C. As a measuring device, a 6256 type liquid crystal physical property evaluation device manufactured by Toyo Technica was used. The measurement of the ion density was performed after the cell was manufactured and after the manufactured cell was aged at 60 ° C. and 90% high temperature and high humidity for 120 hours.

[Production of liquid crystal display element]
First, a substrate with electrodes was prepared. The substrate is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. As a first layer, an IZO electrode having a solid pattern and constituting a counter electrode is formed on the substrate. On the counter electrode of the first layer, an SiN (silicon nitride) film formed by a CVD method is formed as a second layer. The thickness of the second-layer SiN film is 500 nm, and functions as an interlayer insulating film. A comb-shaped pixel electrode formed by patterning an IZO film as a third layer is disposed on the second-layer SiN film, and two pixels, a first pixel and a second pixel, are formed. ing. The size of each pixel is about 10 mm long and about 5 mm wide. At this time, the first layer counter electrode and the third layer pixel electrode are electrically insulated by the action of the second layer SiN film.

  The pixel electrode of the third layer has a comb-like shape formed by arranging a plurality of square-shaped electrode elements whose central portion is bent, similarly to the diagram described in JP-A-2014-77845. . The width in the lateral direction of each electrode element is 3 μm, and the interval between the electrode elements is 6 μm. Since the pixel electrode forming each pixel is configured by arranging a plurality of bent-shaped electrode elements at the center portion, the shape of each pixel is not rectangular but is similar to the electrode element at the center portion. Bends have a shape resembling a bold letter. Each pixel is vertically divided by a center bent portion, and has a first region above the bent portion and a second region below the bent portion.

  When the first region and the second region of each pixel are compared, the formation directions of the electrode elements of the pixel electrodes constituting the first region and the second region are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed so as to form an angle of + 10 ° (clockwise) in the first region of the pixel, and is formed in the second region of the pixel. The electrode element of the electrode is formed so as to form an angle of -10 ° (clockwise). That is, in the first region and the second region of each pixel, the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the application of the voltage between the pixel electrode and the counter electrode in the substrate plane are mutually different. It is configured to be in the opposite direction.

  Next, after filtering the obtained liquid crystal aligning agent through a 1.0 μm filter, an ITO film is formed on the back surface of the prepared substrate with electrodes and a counter substrate, and a columnar spacer having a height of 4 μm. Was spin-coated on each of the glass substrates having. Next, after drying on a hot plate at 80 ° C. for 5 minutes, it was baked at 230 ° C. for 20 minutes to obtain a polyimide film on each substrate as a 60-nm thick coating film. The polyimide film is rubbed with a rayon cloth (roll diameter 120 mm, rotation number 500 rpm, moving speed 30 mm / sec, pushing amount 0.3 mm) in a predetermined rubbing direction, and then irradiated with ultrasonic waves in pure water for 1 minute. And dried at 80 ° C. for 10 minutes.

  After that, using the two types of substrates with the liquid crystal alignment film, the rubbing directions are combined so as to be antiparallel, and the periphery is sealed except for the liquid crystal injection port. Produced. After vacuum injection of liquid crystal (MLC-3019, manufactured by Merck) into this empty cell at room temperature, the injection port was sealed to obtain an anti-parallel liquid crystal cell. The obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour, left overnight, and then used for each evaluation.

[Evaluation of stability of liquid crystal alignment]
Using this liquid crystal cell, an AC voltage of 10 VPP was applied for 168 hours at a frequency of 30 Hz under a constant temperature environment of 60 ° C. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited and left at room temperature for one day. After standing, the liquid crystal cell is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the backlight is turned on in a state where no voltage is applied so that the luminance of transmitted light is minimized. The arrangement angle of the liquid crystal cell was adjusted. Then, the rotation angle when the liquid crystal cell was rotated from the angle at which the second area of the first pixel was darkest to the angle at which the first area was darkest was calculated as the angle Δ. Similarly, the second pixel was compared with the second region and the first region, and the same angle Δ was calculated. Then, the average value of the angle Δ values of the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell. A liquid crystal cell having an angle Δ of 0.15 ° or less was evaluated as good, and a liquid crystal cell having an angle Δ higher than 0.15 ° was evaluated as poor.

[Relaxation characteristics of accumulated charge]
The above liquid crystal cell is placed between two polarizing plates arranged so that the polarizing axes are orthogonal to each other, and the pixel electrode and the counter electrode are short-circuited to have the same potential. The backlight was irradiated, and the angle of the liquid crystal cell was adjusted such that the luminance of the transmitted light of the LED backlight measured on the two polarizing plates was minimized. Next, a VT characteristic (voltage-transmittance characteristic) at a temperature of 23 ° C. was measured while applying a rectangular wave having a frequency of 30 Hz to the liquid crystal cell, and an AC voltage having a relative transmittance of 23% was measured. Calculated. Since this AC voltage corresponds to a region where the change in luminance with respect to the voltage is large, it is convenient to evaluate the accumulated charge through the luminance.

  Next, a rectangular wave having a relative transmittance of 23% and a frequency of 30 Hz was applied for 5 minutes, and then a DC voltage of +1.0 V was superimposed and driven for 30 minutes. Thereafter, the DC voltage was cut off, and only an AC voltage having a relative transmittance of 23% and a rectangular wave having a frequency of 30 Hz was applied again for 30 minutes. The faster the relaxation of the accumulated charge, the faster the charge accumulation in the liquid crystal cell when the DC voltage is superimposed. Therefore, the relaxation characteristic of the accumulated charge is such that the relative transmittance immediately after the superposition of the DC voltage is 30% or more. It was evaluated by the time required until the temperature decreased from 23% to 23%. The shorter this time is, the better the relaxation characteristics of the accumulated charges are.

<Examples 5 to 6 and Comparative Examples 5 to 6>
Using the liquid crystal aligning agents Q-1 to Q-2 obtained in Examples 3 to 4 and the liquid crystal aligning agents Q3 to Q4 obtained in Comparative Examples 3 to 4, ion density measurement, stability evaluation of liquid crystal alignment, and The relaxation characteristics of the stored charge were evaluated. Table 1 shows the results.

  The liquid crystal alignment film of the present invention can reduce the ion density in the liquid crystal display element and reduce the accumulated charge quickly, particularly in the liquid crystal display element of the IPS drive system or the FFS drive system that requires a rubbing treatment. In addition, since the deviation between the rubbing direction and the alignment direction of the liquid crystal can be suppressed, display performance with excellent afterimage characteristics and contrast can be obtained. Therefore, it is particularly useful as a liquid crystal alignment film used for a liquid crystal display element of an IPS drive system or an FFS drive system, a multifunctional mobile phone (smartphone), a tablet personal computer, a liquid crystal television, and the like.

Claims (11)

A liquid crystal aligning agent containing a polymer obtained from a diamine having a structure represented by the following formula (1).

R ¹ represents a hydrogen atom, a linear or branched alkyl group or an aryl group having 1 to 5 carbon atoms, and two R ¹ groups on the same maleimide ring may be the same or different; R ¹ may combine to form an alkylene having 3 to 6 carbon atoms, W ² represents a divalent organic group, W ¹ represents a single bond or carbonyl, and L ¹ represents a carbon atom having 1 to 6 carbon atoms. To 20 linear alkylene groups, branched alkylene groups having 3 to 20 carbon atoms, cyclic alkylene groups having 3 to 20 carbon atoms, divalent groups selected from phenylene groups and heterocyclic groups, or the divalent groups Represents a group formed by bonding a plurality of groups, wherein the phenylene group and the heterocyclic group are each independently one or more substituents selected from the same or different alkyl group, alkoxy group, haloalkyl group, haloalkoxy group, halogen group and cyano group Substitute with group The bond between the divalent groups may be at least one selected from a single bond, an ester bond, an amide bond, a urea bond, an ether bond, a thioether bond, an amino bond, and a carbonyl. When there are a plurality of groups, the divalent groups may be the same or different, and when the above-mentioned bonds are plural, the bonds may be the same or different, and R is a hydrogen atom or a monovalent group. Represents an organic group, two R's may be different from each other, two R's may be combined to form an alkylene having 1 to 6 carbon atoms, and / or two R's one may be bonded to L ^1. The liquid crystal aligning agent according to claim 1, wherein W ¹ represents a single bond. The liquid crystal aligning agent according to claim 1, wherein the polymer is at least one selected from a polyimide precursor containing a structural unit represented by the following formula (3) and a polyimide that is an imidized product thereof. 4.

X ¹ represents a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ¹ represents a divalent organic group derived from a diamine having the structure of the formula (1), and R ⁴ represents a hydrogen atom or a carbon atom having 1 structure. To 5 alkyl groups. Formula (3), the structure of X ¹ represents at least one selected from the following structures, the liquid crystal aligning agent of claim 3.

The liquid crystal aligning agent according to claim 3, wherein the polymer is at least one selected from a polyimide precursor further containing a structural unit represented by the following formula (4) and a polyimide that is an imidized product thereof.

In the formula (4), X ² represents a tetravalent organic group derived from a tetracarboxylic acid derivative, and Y ² represents a divalent organic group derived from a diamine not including the structure of the formula (1) in the main chain direction. represents, R ¹⁴ each independently represent a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Wherein Y ² is represented by the following formula (11), a liquid crystal aligning agent of claim 5.

In Formula (11), R ³² represents a single bond or a divalent organic group, R ³³ represents a structure represented by — (CH ₂ ) _r —, r represents an integer of 2 to 10, any -CH 2 _- ether conditions nonadjacent respectively, esters, amides, ureas, may be replaced by a carbamate linkage. R ³⁴ represents a single bond or a divalent organic group. Any hydrogen atom on the benzene ring may be replaced by a monovalent organic group.   The liquid crystal aligning agent according to claim 3, wherein the structural unit represented by the formula (3) is at least 10 mol% based on all structural units of the polymer.   A liquid crystal alignment film comprising the liquid crystal alignment agent according to claim 1.   A liquid crystal display device comprising the liquid crystal alignment film according to claim 8. A diamine having a structure represented by the following formula (1).

R ¹ represents a hydrogen atom, a linear or branched alkyl group or an aryl group having 1 to 5 carbon atoms, and two R ¹ groups on the same maleimide ring may be the same or different; R ¹ may combine to form an alkylene having 3 to 6 carbon atoms, W ² represents a divalent organic group, W ¹ represents a single bond or carbonyl, and L ¹ represents a carbon atom having 1 to 6 carbon atoms. To 20 linear alkylene groups, branched alkylene groups having 3 to 20 carbon atoms, cyclic alkylene groups having 3 to 20 carbon atoms, divalent groups selected from phenylene groups and heterocyclic groups, or the divalent groups Represents a group formed by bonding a plurality of groups, wherein the phenylene group and the heterocyclic group are each independently one or more substituents selected from the same or different alkyl group, alkoxy group, haloalkyl group, haloalkoxy group, halogen group and cyano group Substituted with a group The bond between the divalent groups may be at least one selected from a single bond, an ester bond, an amide bond, a urea bond, an ether bond, a thioether bond, an amino bond and a carbonyl, and the divalent group may be When two or more, the divalent groups may be the same or different, when two or more bonds are plural, the bonds may be the same or different, and R is a hydrogen atom or a monovalent organic group. Wherein two Rs may be different from each other, two Rs may be combined to form an alkylene having 1 to 6 carbon atoms, and both or one of the two Rs may be L may be bonded to ^1.   A polymer comprising the diamine according to claim 10.