WO2021205736A1

WO2021205736A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: WO2021205736A1
Application number: PCT/JP2021/004455
Authority: WO
Inventors: 政太郎大田; 直樹中家
Original assignee: 日産化学株式会社
Priority date: 2020-04-10
Filing date: 2021-02-05
Publication date: 2021-10-14
Also published as: TW202146631A; CN115427876A; JPWO2021205736A1; KR20220166817A

Abstract

The present invention provides: a liquid crystal aligning agent that forms a liquid crystal alignment film that, while having a high refractive index, has high light transmittance because of a lack of coloring properties; and a liquid crystal alignment agent that, in addition to the properties noted above, has high homeotropic alignment.　This liquid crystal alignment agent contains a component (A) and a component (B), described below. Component (A) is a polymer (A) of at least one type chosen from the group consisting of polyimide precursors and polyimides that are imidated forms of such polyimide precursors; and component (B) is a polymer (B) characterized in that the polymer includes a repeated unit structure represented by formula (1) and has at least one triazine ring terminal, at least part of this triazine ring terminal being blocked by an arylamino group that comprises a cross-linking group.

Description

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

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

Conventionally, as a liquid crystal display element, various drive methods having different electrode structures and physical properties of liquid crystal molecules to be used have been developed. For example, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and VA (Vertical Organic) ) Type, IPS (In-Plane Switching) type, FFS (fringe field switching) type and various other display elements are known.
A liquid crystal display element is generally configured by arranging a pair of electrode substrates so as to face each other with a predetermined gap (several μm) and enclosing a liquid crystal crystal between the electrode substrates. Then, by applying a voltage between the transparent conductive films constituting each electrode of the electrode substrate, the display on the liquid crystal display element is performed. Further, these liquid crystal display elements have a liquid crystal alignment film for orienting liquid crystal molecules. As a material for the liquid crystal alignment film, for example, polyamic acid (polyamic acid), polyamic acid ester, polyimide and the like are known (see Patent Document 1 and the like).

International Publication No. 2016-080458

The transparent conductive film described above in a liquid crystal display element is usually formed of a composition (ITO) containing indium oxide as a main component and doped with several% tin oxide, and its refractive index is the refraction of the liquid crystal alignment film. Unlike the rate, it has a high value. Therefore, when the light from the display light source is to be transmitted to the electrode substrate, the light is reflected at the interface between the transparent conductive film and the liquid crystal alignment film in each electrode substrate. As a result, the light transmittance of the electrode substrate cannot be sufficiently obtained, which causes a problem that the display brightness is lowered.
In particular, in recent years, ultra-high-definition panels such as 4K and 8K have been developed, but these panels occupy a large amount of black matrix (BM) and TFT, and the opening ratio of the panel decreases. It is important to improve the transmittance of the display unit.

Therefore, the present inventors have formed the transparent conductive film in order to increase the refractive index of the liquid crystal alignment film from the viewpoint that the above-mentioned problems can be solved by reducing the difference between the refractive index of the transparent conductive film and the refractive index of the liquid crystal alignment film. Various materials were examined. Specifically, in order to increase the refractive index of the liquid crystal alignment film, various types of polymers contained in the liquid crystal alignment agent forming the liquid crystal alignment film were searched for.

As a result, by selecting a specific polymer, a liquid crystal alignment film having a high refractive index close to the refractive index of the transparent conductive film could be obtained, but on the other hand, a liquid crystal alignment film having a high refractive index could be obtained. It has been revealed that the polymer to be formed has a coloring property in many cases. A liquid crystal alignment film formed from a liquid crystal alignment agent containing a colorable polymer results in a decrease in light transmittance and a decrease in display brightness, and as a result, the above object is not achieved. Further, it has become clear that a liquid crystal alignment film having a high vertical orientation cannot easily obtain a high refractive index due to the influence of the side chain structure, and a liquid crystal alignment film having a high refractive index and a vertical orientation has been required.

In view of the above circumstances, an object of the present invention is a liquid crystal alignment agent that forms a liquid crystal alignment film having a high light transmittance because it has a high refractive index but no coloring property, and a liquid crystal alignment obtained from the liquid crystal alignment agent. An object of the present invention is to provide a film and a liquid crystal display element having the liquid crystal alignment film. Further, the present invention provides a liquid crystal alignment agent that forms a liquid crystal alignment film having high vertical orientation in addition to the above characteristics, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. be.

As a result of diligent research to achieve the above object, the present inventor has found that a liquid crystal aligning agent containing a specific polymer is effective for achieving the above object, and completed the present invention. I came to do it.

The present invention includes the following aspects.
[1] A liquid crystal alignment agent containing the following components (A) and (B).
Component (A): At least one polymer (A) selected from the group consisting of a polyimide precursor and polyimide which is an imide of the polyimide precursor.
Component (B): Contains a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a part of the triazine ring terminal is sealed with an arylamino group having a cross-linking group. Polymer (B) characterized by being

(R and R'represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group independently of each other.
Ar represents at least one selected from the group represented by the formulas (2) to (12). )

Any hydrogen atom on the aromatic ring of the formulas (2) to (12) may be substituted.
R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
W ¹ and W ² are independent of each other and single-bonded, -CR ⁹⁵ R ^96- (R ⁹⁵ and R ⁹⁶ are independent of each other and are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms (however, these are They may form a ring together.)), -C (= O)-, -O-, -S-, -S (= O)-, -SO _2- , or-. Represents NR ^97- (R ⁹⁷ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group).
X ¹ and X ² are independent of each other, single bond, alkylene group having 1 to 10 carbon atoms, or -Y ₁ -Ph-Y _2- (Ph represents a phenylene group, and any hydrogen atom on the phenylene group. May be substituted, and Y ₁ and Y ₂ represent a group represented by a single bond or an alkylene group having 1 to 10 carbon atoms independently of each other. )

According to the present invention, a liquid crystal alignment agent that forms a liquid crystal alignment film having a high light transmittance because it has a high refractive index but no coloring property, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and the liquid crystal display. A liquid crystal display element having an alignment film can be provided. Further, it is possible to provide a liquid crystal alignment agent that forms a liquid crystal alignment film having high vertical orientation in addition to the above characteristics, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. can.

It is a graph which shows the measurement result ^{of the 1} H-NMR spectrum of the compound T-1 synthesized in the Example. It is a graph which shows the measurement result ^{of the 1} H-NMR spectrum of the compound T-2 synthesized in the Example.

Hereinafter, the liquid crystal alignment agent of the present invention, the liquid crystal alignment film obtained from the liquid crystal alignment agent, and the liquid crystal display element having the liquid crystal alignment film will be described in detail. It is an example as an embodiment, and is not specified in these contents.

(Liquid crystal alignment agent)
The liquid crystal alignment agent of the present invention contains the following components (A) and (B).
Component (A): At least one polymer (A) selected from the group consisting of a polyimide precursor and polyimide which is an imide of the polyimide precursor.
Component (B): Contains a repeating unit structure represented by the above formula (1), has at least one triazine ring terminal, and at least a part of the triazine ring terminal is sealed with an arylamino group having a cross-linking group. Polymer (B) characterized by being
Each of the polymer (A) which is the component (A) and the polymer (B) which is the component (B) will be described in detail below.

<Polymer (A)>
The liquid crystal aligning agent of the present invention contains at least one polymer (A) selected from the group consisting of a polyimide precursor and polyimide which is an imide of the polyimide precursor. The polymer constituting the component (A) may be composed of one kind or two or more kinds of polymers.
Examples of the polyimide precursor include a polyamic acid, a polyamic acid ester, a polyamic acid-polyamic acid ester copolymer, and the like, and the polyimide precursor preferably has a diamine component and a tetracarboxylic acid component polymerized. Obtained by

<< Diamine component >>
As the diamine component, diamine (a), p-phenylenediamine, m-phenylenediamine, 4- (2- (2-) having at least one selected from the group consisting of the structures represented by the following formulas (S1) to (S3). (Methylamino) ethyl) aniline, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, or represented by the following formulas (3b-1) to (3b-4). Diamine having a carboxyl group such as a diamine compound, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,2-bis (4-) Aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4) 4-Aminophenoxy) benzene, 1,2-bis (4-aminophenoxy) ethane, 1,2-bis (4-amino-2-methylphenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 4- (2- (4-aminophenoxy) ) Ethoxy) -3-fluoroaniline, di (2- (4-aminophenoxy) ethyl) ether, 4-amino-4'-(2- (4-aminophenoxy) ethoxy) biphenyl, 2,2'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- ( 4-Aminophenoxy) phenyl] Hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 1,3-bis (4-aminophenethyl) urea and other diamines with urea bonds, 2-(4-aminophenoxy) methacrylate 2,4-Diaminophenoxy) Diamines having photopolymerizable groups at the ends such as ethyl, 2,4-diamino-N, N-diallylaniline, and diamines having radical initiation functions such as the following formulas (R1) to (R5). , 4,4'-Diaminobenzofe Diamine having a photosensitizing function showing a sensitizing effect by irradiation with light such as non, 3,3'-diaminobenzophenone, 9,9-bis (4-aminophenyl) fluorene, 2,6-diaminopyridine, 3,4 -Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, diamines having a heterocycle such as the following formulas (z-1) to (z-18), Diamines having a diphenylamine skeleton such as the following formulas (Dp-1) to (Dp-9), and groups such as the following formulas (5-1) to (5-10) "-N (D)-" (D is by heating. It represents a protective group that is desorbed and replaced with a hydrogen atom, preferably a tert-butoxycarbonyl group. ), And aromatic diamines such as diamines having an oxazoline structure such as the following formulas (Ox-1) to (Ox-2), but are not limited thereto. The diamine component may be composed of one or two higher types of diamines.

(X ¹ and X ² are independent, single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH ₃ ). -, -NH-, -O-, -COO-, -OCO- or-((CH ₂ ) _a1- A ₁ ) _m1- (a1 is an integer from 1 to 15, and A ₁ is an oxygen atom or -COO. -Represents, m ₁ is an integer of 1 to 2. When m ₁ is 2, a plurality of a 1 and A ₁ have the above definitions independently.) G ¹ and G ^{2 represent.} Each independently represents a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen on the cyclic group. The atom is replaced with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom-containing alkyl group having 1 to 3 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. M and n are independently integers of 0 to 3, m + n is an integer of 1 to 6, preferably an integer of 1 to 4. R ¹ has 1 to 20 carbon atoms. Any hydrogen atom representing an alkyl group, an alkoxy group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms ^{and forming R 1} may be substituted with a fluorine atom.)

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

(X ⁴ represents -CONH-, -NHCO-, -O-, -CH ₂ ^{O-, -COO- or -OCO-. R 3} represents a structure having a steroid skeleton.)

(In the formula ^{(3b-1), A} 1 is a single _{_{_{_{bond, -CH 2 -, - C 2}}}} H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, -O-, -CO-, _{-NH-, -N (CH 3} )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CON ( CH ₃₎ -. or -N _(CH 3) CO- represents, m1 and m2 are each independently an integer of 0 to 4, and is m1 + m2 is an integer of 1 to 4. formula (3b-2) Among them, m3 and m4 are independently integers of 1 to 5. In the formula (3b-3), A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 is 1 to 5. of an integer in the formula (3b-4), ^{a 3} and ^{a 4} are each independently a single _{_{_{bond, -CH 2 -., - C}}} 2 H 4 -, - C (CH 3) 2 -, - CF _2- , -C (CF ₃ ) _2- , -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO -, - OCO -, - CON (CH 3) - or -N _(CH 3) CO- represents, m6 is an integer of 1-4).

(In (R3) to (R5), n is an integer of 1 to 6.)

(Boc represents a tert-butoxycarbonyl group.)

The diamine (a) preferably has at least one benzene ring. As a more preferable specific example, a diamine represented by the following formula (d1) or formula (d2) can be mentioned.

(X is a single bond, -O-, -C (CH ₃ ) _2- , -NH-, -CO-,-(CH ₂ ) _m- , -SO _2- , -O- (CH ₂ ) _m- _{_{_{_{O -, - O-C (}}}} CH 3) 2 -, - CO- (CH 2) m -, - NH- (CH 2) m -, - SO 2 - (CH 2) m -, - CONH- (CH ₂ ) represents _m- , -CONH- (CH ₂ ) _m- NHCO-, or -COO- (CH ₂ ) _m- OCO-. M is an integer of 1 to 8. Y is the above formula (S1). Represents any of the structures of (S3). In the formula (d2), the two Ys may be the same as or different from each other).

Preferred examples of the diamine represented by the above formula (d1) include the following formulas (d1-1) to (d1-7). Preferred examples of the diamine represented by the above formula (d2) include the following formulas (d2-1) to (d2-6).

(X ^v1 to X ^v4 and X ^p1 to X ^p8 are independently- (CH ₂ ) _a- (a is an integer of 1 to 15), -CONH-, -NHCO-, and -CON (CH _3). )-, _{-NH-, -O-, -CH 2} O-, -CH _2- OCO-, -COO-, or -OCO-, and X ^V5 to X ^V6 and X ^s1 to X ^s4 are independent of each other. Represents -O-, -CH ₂ O-, -COO- or -OCO-. X ^v7 is -O-, -CH ₂ O-, -CH _2- OCO-, -COO-, or -OCO- X _a to X _f represent a single bond, -O-, -NH-, -O- (CH ₂ ) _m- O- (m is an integer of 1 to 8), and R ^v1 to R. ^v4 and R ^1a to R ^1h independently represent -C _n H _{2n + 1} (n is an integer of 1 to 20) and _{-OC n} H _{2n + 1} (n is an integer of 2 to 20).

The diamine having a radical initiation function or a diamine having a photosensitizing function showing a sensitizing effect by light irradiation enhances the response speed of a liquid crystal display element such as a PSA type liquid crystal display element or a liquid crystal display element for SC-PVA mode. From the point of view, one kind or two or more kinds may be used when producing the polymer (A).

Among the above diamine components, p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, among the above, from the viewpoint of preferably obtaining the effects of the present invention. , 2,2'-dimethyl-4,4'-diaminobiphenyl, 2- (2,4-diaminophenyloxy) ethyl methacrylate, 2,4-diamino-N, N-diallylaniline, the above formulas (R1) to ( The diamine represented by R5), the diamine represented by the above formulas (z-1) to (z-18), the diamine represented by the above formulas (Dp-1) to (Dp-9), and the above formula (Ox). The diamine represented by -1) to (Ox-2) is preferable.

Examples of the diamine component include aliphatic diamines such as m-xylylenediamine, alicyclic diamines such as 4,4-methylenebis (cyclohexylamine), and diamines described in International Publication No. 2016/125870. ..

<< Tetracarboxylic acid component >>
The tetracarboxylic acid component refers to a component containing at least one selected from a tetracarboxylic acid and a tetracarboxylic acid derivative. Examples of the tetracarboxylic acid derivative include tetracarboxylic acid dihalide, tetracarboxylic acid dianhydride, tetracarboxylic acid diester dichloride, and tetracarboxylic acid diester. The tetracarboxylic acid component may be composed of one kind or two or more kinds of tetracarboxylic acids and tetracarboxylic acid derivatives.
Examples of the tetracarboxylic acid component for producing the polymer (A) include aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and derivatives thereof. Be done. Here, the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the aromatic ring. The aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not have to be composed of only a chain hydrocarbon structure, and a part thereof may have an alicyclic structure or an aromatic ring structure. The alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to the alicyclic structure. However, none of these four carboxyl groups are bonded to the aromatic ring. Further, it is not necessary to have only an alicyclic structure, and a chain hydrocarbon structure or an aromatic ring structure may be partially provided.

The tetracarboxylic acid component preferably contains a tetracarboxylic dianhydride represented by the following formula (S4).

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

(R ¹ to R ⁴ independently represent a monovalent organic group having 1 to 6 carbon atoms or a phenyl group containing a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom and a fluorine atom. R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group. J and k are integers of 0 or 1, and A ₁ and A ₂ are independent, single bond, −. Represents an O-, -CO-, -COO-, phenylene, sulfonyl, or amide bond. * 1 is a bond that binds to one acid anhydride group, and * 2 is a bond that binds to the other acid anhydride group. It is a joint hand.)

More preferable specific examples of the above formula (x-1) include the following formulas (X1-1) to (X1-6). In the formula, * represents a bond.

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

As a preferable example of the tetracarboxylic dianhydride represented by the above formula (S4) or a derivative thereof, X is the above formulas (x-1) to (x-7) and (x-11) to (x-13). ), The tetracarboxylic dianhydride represented by the formula (3) or a derivative thereof can be mentioned.

<Method for producing polymer (A)>
The polymer (A) used in the present invention can be synthesized, for example, by a known method as described in WO2013 / 157586.

Polyimide can be obtained by ring-closing (imidizing) the polyimide precursor obtained in the polymer (A). The imidization rate as used herein is the ratio of the imide group to the total amount of the imide group derived from the tetracarboxylic acid dianhydride or its derivative and the carboxyl group (or its derivative).

The molecular weight of the polymer (A) used in the present invention is the weight measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained from the polymer, the workability at the time of film formation, and the coating film property. The average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Polymer (B)>
The liquid crystal aligning agent of the present invention contains a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a part of the triazine ring terminal is an arylamino group having a cross-linking group. It contains a polymer (B) characterized by being sealed with. The polymer constituting the component (B) may be composed of one kind or two or more kinds of polymers.

(R and R'represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group independently of each other.
Ar represents at least one selected from the group represented by the formulas (2) to (12).

In the above formula (1), R and R'represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group independently of each other, but both are hydrogen atoms from the viewpoint of further increasing the refractive index. It is preferable to have.
In the present invention, the number of carbon atoms of the alkyl groups of R and R'in the above formula (1) is not particularly limited, but 1 to 20 is preferable, and considering that the heat resistance of the polymer is further enhanced, it is considered. The number of carbon atoms is more preferably 1 to 10, and even more preferably 1 to 3. Further, the structure may be chain-shaped, branched or annular.

Specific examples of the alkyl groups of R and R'in the above formula (1) include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1 -Methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl , 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1 , 2-Dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl , 3-Methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2 -Dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl -N-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2 -Methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl -Cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclo Propyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl- Cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl group and the like can be mentioned.

The number of carbon atoms of the alkoxy groups of R and R'in the above formula (1) is not particularly limited, but is preferably 1 to 20, and considering that the heat resistance of the polymer is further enhanced, the number of carbon atoms is 1 to 20. 10 is more preferable, and 1 to 3 is even more preferable. Further, the structure of the alkyl portion may be chain-like, branched or cyclic.

Specific examples of the alkoxy groups of R and R'in the above formula (1) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1 -Methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n -Propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyl Oxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n- Butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n- Examples thereof include propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy group and the like.

The number of carbon atoms of the aryl group of R and R'in the above formula (1) is not particularly limited, but is preferably 6 to 40, and considering that the heat resistance of the polymer is further enhanced, the number of carbon atoms is 6 to 40. 16 is more preferable, and 6 to 13 are even more preferable.
Specific examples of the aryl groups of R and R'in the above formula (1) include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p. -Methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, Examples thereof include 2-phenyl, 3-phenyl, 4-phenyl, 9-phenyl and the like.

The carbon number of the aralkyl group of R and R'in the above formula (1) is not particularly limited, but the carbon number is preferably 7 to 20, and the alkyl portion thereof may be linear, branched or cyclic. good.
Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, Examples thereof include 4-isobutylphenylmethyl and α-naphthylmethyl groups.

Any hydrogen atom on the aromatic ring in the above formulas (2) to (12) is a halogen atom, a carboxy group, a sulfo group, an alkyl group which may have a branched structure having 1 to 10 carbon atoms, and 1 carbon atom. It may be substituted with an alkyl halide group which may have a branched structure of about 10 or an alkoxy group which may have a branched structure of 1 to 10 carbon atoms.

Examples of the halogen atom which is a substituent on the aromatic ring in the above formulas (2) to (12) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group and the alkoxy group, which are substituents on the aromatic ring in the above formulas (2) to (12), are the same as those exemplified in the above formula (1).

The alkyl halide group having 1 to 10 carbon atoms, which is a substituent on the aromatic ring in the above formulas (2) to (12), is one of the alkyl groups having a branched structure having 1 to 10 carbon atoms. At least one of the hydrogen atoms is replaced with a halogen atom, and specific examples thereof include trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 3,3,3-trifluoropropyl, and the like. 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl, perfluoropropyl, 4, 4,4-Trifluorobutyl, 3,3,4,5,4-pentafluorobutyl, 2,2,3,3,4,5,4-heptafluorobutyl, perfluorobutyl, 2,2,3 3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,5,5-octafluoropentyl, perfluoropentyl, 2,2,3,3,4 4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,5,5,6,6-decafluorohexyl, 3,3,4,5,5 , 5,6,6,6-nonafluorohexyl, and perfluorohexyl groups.

^{Examples of the alkylene group having 1 to 10 carbon atoms in X 1} and X ² in the above formula (11) include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene group.

Any hydrogen atom on the phenylene group in the above group "-Y _1- Ph-Y _2- " may have a halogen atom, a carboxyl group, a sulfo group, or an alkyl group having a branched structure of 1 to 10 carbon atoms. , It may be replaced with an alkyl halide group which may have a branched structure having 1 to 10 carbon atoms, or an alkoxy group which may have a branched structure having 1 to 10 carbon atoms.

When any hydrogen atom on the aromatic ring in the above formulas (2) to (12) and an arbitrary hydrogen atom on the phenylene group in the _{group "-Y 1-} Ph-Y _{2-" are substituted, it is exemplified above.} Among them, a halogen atom, a sulfo group, an alkyl group which may have a branched structure having 1 to 5 carbon atoms, an alkyl halide group which may have a branched structure having 1 to 5 carbon atoms, or an alkyl group having 1 carbon atom. An alkoxy group which may have a branched structure of to 5 is preferable.

As the Ar in the above formula (1), at least one type represented by the formulas (2) and (5) to (12) is preferable, and the formulas (2), (5), (7), (8) and (11) are preferable. ) To (12), at least one of them is more preferable. Specific examples of the aryl group represented by the above formulas (2) to (12) include those represented by the following formulas (1-1) to (1-25), but are not limited thereto. No. In the formula, Ph represents a phenyl group.

Among these, since a polymer having a higher refractive index can be obtained, the above formulas (1-1), (1-2), (1-5) to (1-15), (1-18) to (1) The aryl groups represented by -21) and (1-23) to (1-25) are more preferable.

In particular, considering that the solubility of the polymer in an organic solvent is further enhanced, the m-phenylene group represented by the formula (21-a) is preferable as Ar.

Further, the polymer (B) of the present invention has at least one triazine ring terminal, and at least a part of the triazine ring terminal is sealed with an arylamino group having a cross-linking group.
The polymer (B) of the present invention has at least one triazine ring terminal, and the triazine ring at this terminal usually has two halogen atoms that can be substituted with the above-mentioned arylamino group having a cross-linking group. ing. Therefore, the arylamino group having the above-mentioned cross-linking group may be bonded to the same triazine ring terminal, or when there are a plurality of triazine ring terminals, each may be bonded to another triazine ring terminal. ..

Examples of the aryl group of the arylamino group having the above-mentioned cross-linking group include the same as above, but a phenyl group is particularly preferable.

Examples of the cross-linking group include a hydroxy-containing group, a vinyl-containing group, an epoxy-containing group, an oxetane-containing group, a carboxy-containing group, a sulfo-containing group, a thiol-containing group, a (meth) acryloyl-containing group, and the like, and a polymer (B). ) Is considered to be improved, and a hydroxy-containing group and a (meth) acryloyl-containing group are preferable.

Examples of the hydroxy-containing group include a hydroxy group and a hydroxyalkyl group. Both a hydroxy group and a hydroxyalkyl group are preferable, but a hydroxyalkyl group having 1 to 10 carbon atoms is more preferable.
Hydroxyalkyl groups having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, and the like. 9-Hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2-methylpropyl, 3- Hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 4-hydroxy-1-methylbutyl, 4-hydroxy-2-methylbutyl, 4-hydroxy The carbon atom to which the hydroxy group such as -3-methylbutyl group is bonded is a primary carbon atom; 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1 -Hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, 2-hydroxy-2-methylpropyl group and other hydroxy Examples thereof include those in which the carbon atom to which the group is bonded is a secondary or tertiary carbon atom.

In particular, in consideration of improving heat resistance and high-temperature and high-humidity resistance, it is preferable that the carbon atom to which the hydroxy group is bonded is a primary carbon atom, and among them, a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable. Preferably, a hydroxyalkyl group having 1 to 3 carbon atoms is even more preferable, a hydroxymethyl group and a 2-hydroxyethyl group are even more preferable, and a 2-hydroxyethyl group is most preferable.

Examples of the (meth) acryloyl-containing group include a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, and a group represented by the following formula (i), which have an alkyl group having 1 to 10 carbon atoms (meth). Meta) The acryloyloxyalkyl group and the group represented by the following formula (i) are preferable, and the group represented by the following formula (i) is more preferable.

(In the formula, A ¹ represents an alkylene group having 1 to 10 carbon atoms, A ² represents a single bond or a group represented by the following formula (j), and A ³ may be substituted with a hydroxy group. A good divalent or trivalent aliphatic hydrocarbon group is represented, A ⁴ is represented by a hydrogen atom or methyl group, a is represented by 1 or 2, and * is represented by a bond.)

(* Indicates a bond.)

Examples of the alkyl group contained in the (meth) acryloyloxyalkyl group having an alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n. -Pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl group and the like can be mentioned. Considering the improvement of heat resistance and high temperature and high humidity resistance, among these, those having an alkyl group having 1 to 5 carbon atoms are preferable, those having an alkyl group having 1 to 3 carbon atoms are preferable, and those having 1 to 3 carbon atoms are preferable. Alternatively, those having 2 alkyl groups are more preferable.

Specific examples of the above (meth) acryloyloxyalkyl group include, for example, a (meth) acryloyloxymethyl group, a 2- (meth) acryloyloxyethyl group, a 3- (meth) acryloyloxypropyl group, and a 4- (meth) acryloyl group. Oxybutyl group is mentioned.

In the formula (i), A ¹ is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group and an ethylene group. Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene group.

A ² represents a single bond or a group represented by the formula (j), and a group represented by the formula (j) is preferable.

A ³ is a divalent or trivalent aliphatic hydrocarbon group which may be substituted with a hydroxy group. Specific examples thereof include an alkylene group having 1 to 5 carbon atoms and the following formula (k-1). ) To (k-3), an alkylene group having 1 to 5 carbon atoms is preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, and a methylene group and an ethylene group are even more preferable. Examples of the alkylene group of A ³ include alkylene groups having 1 to 5 carbon atoms among the alkylene groups exemplified in ^{A 1.}

(In the formula, * is the same as above.)

In formula (i), a represents 1 or 2, but 1 is preferable.

Preferable embodiments of the group represented by the formula (i) include those represented by the following formula (i-1).

(In the formula, A ¹ , A ³ , A ⁴ and * are the same as above.)

More preferable aspects of the group represented by the formula (i) include those represented by the following formulas (i-2) to (i-3).

(In the formula, * is the same as above.)

Examples of the vinyl-containing group include an alkenyl group having a vinyl group at the terminal and having 2 to 10 carbon atoms. Specific examples include ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 2-pentenyl group and the like.

Examples of the epoxy-containing group include an epoxy group, a glycidyl group, a glycidyl alkyl group, and a glycidyl oxy group. Specific examples include glycidylmethyl, 2-glycidylethyl, 3-glycidylpropyl, 4-glycidylbutyl group and the like.

Examples of the oxetane-containing group include oxetane-3-yl, (oxetane-3-yl) methyl, 2- (oxetane-3-yl) ethyl, 3- (oxetane-3-yl) propyl, and 4- (oxetane-3-yl). Il) Butyl group and the like can be mentioned.

Examples of the carboxy-containing group include a carboxy group and a carboxyalkyl group having 1 to 10 carbon atoms. As the carboxyalkyl group having 1 to 10 carbon atoms, the carbon atom to which the carboxy group is bonded is preferably a primary carbon atom, and specific examples thereof include carboxymethyl, 2-carboxyethyl, 3-carboxypropyl and 4-. Examples include a carboxybutyl group.

Examples of the sulfo-containing group include a sulfo group and a sulfoalkyl group having 1 to 10 carbon atoms. As the sulfoalkyl group having 1 to 10 carbon atoms, the carbon atom to which the sulfo group is bonded is preferably a primary carbon atom, and specific examples thereof include sulfomethyl, 2-sulfoethyl, 3-sulfopropyl and 4-sulfobutyl groups. And so on.

Examples of the thiol-containing group include a thiol group and a mercaptoalkyl group having 1 to 10 carbon atoms. As the mercaptoalkyl group having 1 to 10 carbon atoms, the carbon atom to which the thiol group is bonded is preferably a primary carbon atom, and specific examples thereof include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl and 4-. Examples thereof include a mercaptobutyl group.

The number of cross-linking groups is not particularly limited and may be any number that can be substituted on the aryl group, but 1 to 4 is preferable, 1 to 2 is more preferable, and 1 is even more preferable. preferable.

Examples of the arylamino group having a suitable cross-linking group include those represented by the formula (15), and in particular, those represented by the formula (16) having a cross-linking group at the para position with respect to the amino group are preferable.

(Wherein, R ¹⁵ represents a bridging group. * Represents a bond.)

(Wherein, R ¹⁵ represents the same meaning as above. * Represents a bond.)

Specific examples of the arylamino group having a cross-linking group include those represented by the following formulas (16-1) to (16-13), but are not limited thereto. In the formula, * represents a bond.

An arylamino group having a hydroxyalkyl group can be introduced by using a corresponding hydroxyalkyl group-substituted arylamino compound in the production method described later.
Specific examples of the hydroxyalkyl group-substituted arylamino compound include (4-aminophenyl) methanol and 2- (4-aminophenyl) ethanol.

The arylamino group having a (meth) acryloyloxyalkyl group can be prepared by a method using the corresponding (meth) acryloyloxyalkyl group-substituted arylamino compound or after introducing an arylamino group having a hydroxyalkyl group into the polymer (B). Further, it can be introduced by a method in which (meth) acrylate halide or glycidyl (meth) acrylate is allowed to act on the hydroxy group contained in the hydroxyalkyl group.

The arylamino group having a group represented by the formula (i) can be prepared by a method using an arylamino compound having a desired cross-linking group or by introducing an arylamino group having a hydroxyalkyl group into the polymer (B). Further, it can be introduced by a method in which a (meth) acrylic acid ester compound having an isocyanate group represented by the following formula (i') is allowed to act on the hydroxy group contained in the hydroxyalkyl group.

(In the formula, A ³ , A ⁴ and a are the same as above.)

As a specific example of the (meth) acryloyloxyalkyl group-substituted arylamino compound, for example, it is obtained by allowing (meth) acrylic acid halide or glycidyl (meth) acrylate to act on the hydroxy group of the above-mentioned hydroxyalkyl group-substituted arylamino compound. The ester compound is mentioned.
Examples of the (meth) acrylic acid halide include (meth) acrylic acid chloride, (meth) acrylic acid bromide, and (meth) acrylic acid iodide.
Specific examples of the (meth) acrylic acid ester compound having an isocyanate group represented by the above formula (i') include 2-isocyanatoethylacryllate, 2-isocyanatoethyl methacrylate and 1,1- (bis). Acryloyloxymethyl) ethyl isocyanate can be mentioned.

In the present invention, particularly suitable polymer (B) includes those containing repeating units represented by the formulas (18) to (21).

(In the formula, R, R', and R ¹⁵ have the same meanings as described above. R ¹ to R ⁴ have a branched structure of a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, and 1 to 10 carbon atoms. It represents an alkyl group which may have an alkyl group, an alkyl halide group which may have a branched structure having 1 to 10 carbon atoms, or an alkoxy group which may have a branched structure having 1 to 10 carbon atoms. , R, R'are hydrogen atoms at the same time.)

(In the formula, R ¹⁵ has the same meaning as above. R ¹ to R ⁴ have the same meaning as the above formula (18), except when all of ^{R 1} to R ^{4 are hydrogen atoms.)}

(In the formula, R ¹⁵ has the same meaning as above.)

(In the formula, R ¹⁵ has the same meaning as above.)

The weight average molecular weight of the polymer (B) in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000, further improving heat resistance and shrinkage rate. From the viewpoint of lowering the amount, 2,000 or more is preferable, and from the viewpoint of further increasing the solubility and lowering the viscosity of the obtained solution, 50,000 or less is preferable, and 30,000 or less is more preferable. It is more preferably 000 or less, and particularly preferably 10,000 or less.
The weight average molecular weight in the present invention is the average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (hereinafter referred to as GPC) analysis.

The polymer (B) (hyperbranched polymer) of the present invention can be produced according to the method disclosed in International Publication No. 2010/128661 described above.
That is, after reacting the trihalogenated triazine compound with the aryldiamino compound in an organic solvent, for example, an arylamino compound having a hydroxyalkyl group (hydroxy-containing group), which is a terminal encapsulant, or an acryloyloxyalkyl group (acryloyloxyalkyl group). The polymer of the present invention (acryloyl-containing group) by reacting with at least one arylamino compound selected from an arylamino compound having a group (acryloyl-containing group) and an arylamino compound having a group represented by the formula (i) (acryloyl-containing group). B) can be obtained.

For example, as shown in Scheme 1 below, the polymer (B) (20') is a terminal encapsulant after reacting the triazine compound (22) and the aryldiamino compound (23) in a suitable organic solvent. It can be obtained by reacting with at least one arylamino compound (24) selected from the arylamino compound having a hydroxyalkyl group and the arylamino compound having a group represented by the formula (i).

(In the formula, X represents a halogen atom independently of each other, and Ra represents ^a hydroxyalkyl group or a group represented by the formula (i).)

In the above reaction, the charging ratio of the aryldiamino compound (23) is arbitrary as long as the desired polymer can be obtained, but the aryldiamino compound (23) is 0.01 to 10 per 1 equivalent of the triazine compound (22). Equivalents are preferred, more preferably 1-5 equivalents.
The aryldiamino compound (23) may be added in a neat manner or in a solution dissolved in an organic solvent, but the latter method is preferable in consideration of ease of operation and ease of control of the reaction. ..
The reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, and is particularly preferably about −30 to 150 ° C., more preferably −10 to 100 ° C.

As another embodiment, the method shown in the following scheme 2 can be mentioned. In this procedure, the polymers (B) (20') have a hydroxyalkyl group, which is an end-capping agent, after reacting the triazine compound (22) and the aryldiamino compound (23) in a suitable organic solvent. It is reacted with an arylamino compound (24') to obtain a polymer (B) (20 ″) (first step), and then a hydroxyalkyl further contained in the polymer (B) (20 ″). It can be obtained by allowing a (meth) acrylic acid ester compound having an isocyanate group represented by the formula (i') to act on the hydroxy group of the group (second step).
When the polymer (B) (20 ″) is used as the target product, the reaction in the second step may not be carried out and may be completed in the first step.

(In the formula, R ^a1 represents a hydroxyalkyl group, and X, A ³ , A ⁴ , ^Ra and a represent the same meanings as described above.)

In the above reaction, the charging ratio and addition method of the aryldiamino compound (23) in the first step, and the reaction temperature in the reaction until the polymer (B) (20 ″) is obtained are the same as those described in Scheme 1. Can be.
Further, in the second step, the charging ratio of the (meth) acrylic acid ester compound having an isocyanate group represented by the formula (i') to the polymer (B) (20 ″) is the hydroxyalkyl group and the formula (i). ) Can be arbitrarily set according to the ratio with the group represented by), and is preferably 0.1 to 10 equivalents, more preferably 0, with respect to 1 equivalent of the arylamino compound having a hydroxyalkyl group used. It is .5 to 5 equivalents, more preferably 0.7 to 3 equivalents, and even more preferably 0.9 to 1.5 equivalents. For example, when all the hydroxyalkyl groups contained in the polymers (B) (20 ″) are groups represented by the formula (i), the charging ratio is 1 of the arylamino compounds having the hydroxyalkyl groups used. With respect to the equivalent, the above (meth) acrylic acid ester compound is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, even more preferably 1.0 to 3 equivalents, still more preferably 1.0. ~ 1.5 equivalents.
The reaction temperature in the reaction is the same as the reaction temperature in the reaction for obtaining the polymer (B) (20 ″), but in consideration of preventing the (meth) acryloyl group from polymerizing during the reaction. 30 to 80 ° C. is preferable, 40 to 70 ° C. is more preferable, and 50 to 60 ° C. is even more preferable.

As the organic solvent, various solvents usually used in this kind of reaction can be used, for example, tetrahydrofuran (THF), 1,4-dioxane, dimethylsulfoxide; N, N-dimethylformamide, N-methyl-2. -Pyrrolidone, tetramethylurea, hexamethylphosphoramide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylethyleneurea, N, N, N', N'-tetramethylmalonic acid Amide, N-methyl-ε-caprolactam, N-acetylpyrrolidin, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N-dimethylpropionic acid amide, N, N-dimethylisobutylamide, N-methyl Examples thereof include amide-based solvents such as formamide and N, N'-dimethylpropyleneurea, and mixed solvents thereof.
Of these, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and a mixture thereof are preferable, and N, N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferable. Is preferable.

Further, in the first step reaction of the above scheme 1, various bases usually used at the time of polymerization or after polymerization may be added.
Specific examples of this base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxydo, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, and oxidation. Calcium, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, Examples thereof include 2,2,6,6-tetramethyl-N-methylpiperidin, pyridine, 4-dimethylaminopyridine, N-methylmorpholin and the like.
The amount of the base added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, relative to 1 equivalent of the triazine compound (22). In addition, these bases may be used as an aqueous solution.
It is preferable that no raw material component remains in the obtained polymer, but some raw materials may remain as long as the effects of the present invention are not impaired.
After completion of the reaction, the product can be easily purified by a reprecipitation method or the like.

As a terminal sealing method using an arylamino compound having a cross-linking group, a known method may be adopted.
In this case, the amount of the end-capping agent used is preferably about 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, relative to 1 equivalent of a halogen atom derived from a surplus triazine compound that was not used in the polymerization reaction. Preferably, 0.5 to 2 equivalents are even more preferred.
As the reaction solvent and the reaction temperature, the same conditions as those described in the first step reaction of the above scheme 1 can be mentioned, and the terminal encapsulant may be charged at the same time as the aryldiamino compound (23).
An unsubstituted arylamino compound having no cross-linking group may be used, and terminal encapsulation may be performed with two or more kinds of groups. Examples of the aryl group of this unsubstituted arylamino compound include the same as above.

Specific examples of the unsubstituted arylamino group include those represented by the following formula (26), but the present invention is not limited thereto.

The unsubstituted arylamino group can be introduced by using the corresponding unsubstituted arylamino compound in the production method described later.
Specific examples of the unsubstituted arylamino compound include aniline and the like.

When an unsubstituted arylamino group is introduced, the ratio of the arylamino compound having a crosslinking group and the unsubstituted arylamino compound is such that the crosslinkable group is used from the viewpoint of achieving a good balance between solubility in an organic solvent and yellowing resistance. With respect to 1 mol of the arylamino compound having, 0.1 to 1.0 mol of the unsubstituted arylamino compound is preferable, 0.1 to 0.5 mol is more preferable, and 0.1 to 0.3 mol is even more preferable.

(Liquid crystal alignment agent)
The liquid crystal alignment agent is used for producing a liquid crystal alignment film, and takes the form of a coating liquid from the viewpoint of forming a uniform thin film. The liquid crystal alignment agent of the present invention is also preferably a coating liquid containing the above-mentioned polymer component and an organic solvent. At that time, the concentration of the polymer component in the liquid crystal alignment agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, 0.5% by mass or more is preferable, and from the viewpoint of storage stability of the solution, 15% by mass or less is preferable. A particularly preferable concentration of the polymer component is 1 to 10% by mass.

From the viewpoint of enhancing the liquid crystal orientation, the content ratio of the component (A) and the component (B) contained in the liquid crystal alignment agent of the present invention is 10 in terms of the mass ratio of [component (A)] / [component (B)]. It may be / 90 to 90/10, 20/80 to 90/10, or 20/80 to 80/20.

Further, in the liquid crystal alignment agent used for producing the liquid crystal alignment film, the polymer component may be a mixture of the polymer (A), the polymer (B), and other polymers. At that time, the content of the other polymer is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass, based on the total amount of the polymer components. Other polymers include acrylic polymers, methacrylic polymers, polystyrene, polyamides and polysiloxanes.

The solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can dissolve the polymer (A) and the polymer (B), and for example, lactones such as γ-valerolactone and γ-butyrolactone. Solvents: γ-butylolactam, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-butyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-ethyl Lactam solvents such as -2-pyrrolidone and N-methyl-2-pyrrolidone; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyllactoamide, 3-butoxy-N, N-dimethylpropanamide , 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and other amide solvents 4-Hydroxy-4-methyl-2-pentanone, 2,6-dimethyl-4-heptanone (diisobutylketone), methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, n-butyl acetate , Ethylene propylene glycol monoethyl ether, methyl pyrrolidone, ethyl pyrrolidone, methyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, Ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Butyl ether, propylene glycol diacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, isoamyl propionate, isoamyl isobutyrate, diisopropyl ether, diiso Pentyl ether; carbonate solvents such as ethylene carbonate and propylene carbonate, 1-hexanol, cyclohexanol, 1,2-ethanediol, 2,6-dimethyl-4-heptanol (diisobutylcarbinol), propylene carbonate and the like can be mentioned. .. These can be used alone or in admixture of two or more.

Preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene. Glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2 -Pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and diisobutylketone, N-methyl- 2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl -2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diisobutylketone, γ-butyrolactone and 4-hydroxy-4. -Methyl-2-pentanone and propylene glycol diacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl Ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol Monobutyl ether and diisobutylcarbinol, N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol Examples thereof include monobutyl ether and dipropylene glycol dimethyl ether. The type and content of such a solvent are appropriately selected according to the coating apparatus for the liquid crystal alignment agent, coating conditions, coating environment, and the like.

<Other ingredients>
If necessary, the liquid crystal alignment agent of the present invention may contain other components other than the above, such as a crosslinkable compound, a functional silane compound, a surfactant, and a compound having a photopolymerizable group.

The crosslinkable compound can be used for the purpose of increasing the strength of the liquid crystal alignment film. The crosslinkable compound is at least selected from the group consisting of a compound having an isocyanate group or a cyclocarbonate group, or a lower alkoxyalkyl group described in paragraphs [0109] to [0113] of WO2016 / 047771. In addition to the compound having one kind of group, the compound having a blocked isocyanate group and the like can be mentioned.

Blocked isocyanate compounds are available as commercial products, for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Tosoh Corporation), Takenate B-830, B. -815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.) and the like can be preferably used.

Specific examples of preferable crosslinkable compounds include compounds represented by the following formulas (CL-1) to (CL-11).

The above is an example of a crosslinkable compound, and the present invention is not limited to these. Further, the crosslinkable compound used in the liquid crystal alignment agent of the present invention may be one kind or a combination of two or more kinds.

The content of the other crosslinkable compound in the liquid crystal aligning agent of the present invention is 0.1 to 150 parts by mass, 0.1 to 100 parts by mass, or 1 to 1 to 100 parts by mass with respect to 100 parts by mass of all the polymer components. It is 50 parts by mass.

The functional silane compound can be used for the purpose of improving the adhesion between the liquid crystal alignment film and the underlying substrate. As a specific example, the silane compound described in paragraph [0019] of International Publication 2014/119682 can be mentioned. The content of the functional silane compound is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of all the polymer components.

The surfactant can be used for the purpose of improving the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a nonion-based surfactant. Specific examples of these include the surfactants described in paragraph [0117] of WO2016 / 047771. The amount of the surfactant used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.

The compound having a photopolymerizable group is a compound having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in the molecule, for example, as represented by the following formulas (M-1) to (M-7). Compounds can be mentioned.

Further, the liquid crystal aligning agent of the present invention is a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge loss of the device, as described in Paragraph of International Publication No. WO2011 / 132751 (Published 2011.10.27) [ The nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed in 0194] to [0200], more preferably 3-picorylamine and 4-picorylamine can be added. This amine compound may be added directly to the liquid crystal alignment agent, but it is preferably added after making a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. This solvent is not particularly limited as long as it dissolves the polymer component.

The liquid crystal alignment agent of the present invention may be added with an imidization accelerator or the like for the purpose of efficiently advancing imidization by heating when firing the coating film.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferable. It is in the range of 0.5 to 15% by mass, more preferably 1 to 10% by mass.
The range of particularly preferable solid content concentration depends on the method used when applying the liquid crystal alignment agent to the substrate. For example, in the case of the spin coating method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by mass, and the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by mass and the solution viscosity is in the range of 3 to 15 mPa · s.

(Liquid crystal alignment film / liquid crystal display element)
The liquid crystal alignment film of the present invention is obtained from the above liquid crystal alignment agent. The liquid crystal alignment film of the present invention can be used for a horizontally oriented type or a vertically oriented type liquid crystal alignment film, and is particularly suitable for a vertically oriented type liquid crystal display element such as a VA type liquid crystal display element or a PSA type liquid crystal display element. It is a liquid crystal alignment film. The liquid crystal display element of the present invention includes the liquid crystal alignment film. The liquid crystal display element of the present invention can be manufactured, for example, by a method including the following steps (1) to (3) or steps (1) to (4). Further, the liquid crystal alignment film of the present invention is applied onto a pair of substrates having a conductive film to form a coating film, and the liquid crystal cells are arranged so as to face each other via a layer of liquid crystal molecules so that the liquid crystal cells are arranged. It can be preferably used for a liquid crystal display element obtained by a method for manufacturing a liquid crystal display element which is formed and irradiates the liquid crystal cell with light in a state where a voltage is applied between the conductive films of the pair of substrates. More specifically, it is a PSA type liquid crystal display element or a liquid crystal display element for SC-PVA mode, which will be described later.

(1) Step of Applying Liquid Crystal Alignment Agent on Substrate The liquid crystal alignment agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film, for example, by a roll coater method, a spin coating method, a printing method, or an inkjet. Apply by an appropriate coating method such as the method. Here, the substrate is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with the glass substrate and the silicon nitride substrate. Further, in the reflective liquid crystal display element, if only one side of the substrate is used, an opaque object such as a silicon wafer can be used, and in this case, a material that reflects light such as aluminum can also be used for the electrode.

(2) Step of firing the coating film After the liquid crystal alignment agent is applied, preheating is preferably performed first for the purpose of preventing the applied alignment agent from dripping. The pre-baking temperature is preferably 30 to 200 ° C., more preferably 40 to 150 ° C., particularly preferably 40 to 100 ° C., and the pre-baking time is preferably 0.25 to 10 minutes, more preferably 0. .5-5 minutes. Then, in order to completely remove the solvent, it is preferable that a heating (post-baking) step is further carried out.
The post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 5 to 300 nm, more preferably 10 to 200 nm.

The coating film formed in the above step (1) can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment. The alignment ability-imparting treatment includes a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, and cotton, and photoalignment in which the coating film is irradiated with polarized or unpolarized radiation. Processing etc. can be mentioned.

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

(3) Step of forming a liquid crystal layer (3-1) In the case of a VA type liquid crystal display element Two substrates on which a liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is formed between the two substrates arranged opposite to each other. To place. Specifically, the following two methods can be mentioned. The first method is a conventionally known method. First, two substrates are arranged facing each other through a gap (cell gap) so that the liquid crystal alignment films face each other. Next, the peripheral portions of the two substrates are bonded together using a sealant, and the liquid crystal composition is injected and filled into the surface of the substrate and the cell gap partitioned by the sealant to contact the film surface, and then the injection holes are sealed. Stop.

The second method is a method called the ODF (One Drop Fill) method. For example, an ultraviolet light-curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is further applied to a predetermined number of places on the liquid crystal alignment film surface. Is dropped. After that, the other substrate is attached so that the liquid crystal alignment films face each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant. In any case, it is desirable to remove the flow orientation at the time of filling the liquid crystal by further heating the liquid crystal composition used to a temperature at which it takes an isotropic phase and then slowly cooling it to room temperature.

(3-2) When manufacturing a PSA type liquid crystal display element The same procedure as in (3-1) above is applied except that a liquid crystal composition containing a polymerizable compound is injected or dropped. Examples of the polymerizable compound include polymerizable compounds represented by the above formulas (M-1) to (M-7).

(3-3) When a coating film is formed on a substrate using a liquid crystal alignment agent containing a compound having a polymerizable group (liquid crystal display element for SC-PVA mode).
After the same as the above (3-1), a method of manufacturing a liquid crystal display element may be adopted through a step of irradiating ultraviolet rays, which will be described later. According to this method, a liquid crystal display element having an excellent response speed can be obtained with a small amount of light irradiation, as in the case of manufacturing the PSA type liquid crystal display element. The compound having a polymerizable group is a compound having one or more polymerizable unsaturated groups in the molecule such as an acrylate group and a methacrylate group as represented by the above formulas (M-1) to (M-7). The content thereof is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of all the polymer components. Further, the above-mentioned polymerizable group may be contained in the polymer used as the liquid crystal aligning agent, and as such a polymer, for example, a diamine component containing a diamine having the above-mentioned photopolymerizable group at the terminal is used in the reaction. Examples thereof include the obtained polymer.

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

Then, a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. As the polarizing plate attached to the outer surface of the liquid crystal cell, a polarizing plate called "H film" in which polyvinyl alcohol is stretch-oriented and iodine is absorbed is sandwiched between cellulose acetate protective films or the H film itself. A polarizing plate made of the above can be mentioned.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a cam coder, a PDA, a digital camera, a mobile phone, a smartphone, and the like. It can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.

Examples will be given below to explain the present invention in more detail, but the present invention is not limited thereto. The meanings of the abbreviations of the compounds used in the examples are shown below.

(Specific diamine)
DA-1 to DA-5: Compounds represented by the following formulas [DA-1] to [DA-5], respectively.

(Tetracarboxylic acid component)
D1: 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride D2: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride D3: benzene-1,2 , 4,5-Tetracarboxylic acid anhydride

(Additive component)
A-1: Compound represented by the following formula [A-1]

(Triazine ring-containing polymer)
T-1: Compound having a repeating unit structure represented by the following formula [T-1] T-2: Compound having a repeating unit structure represented by the following formula [T-2]

(solvent)
NMP: N-methyl-2-pyrrolidone BCS: Ethylene glycol monobutyl ether THF: Tetrahydrofuran DMAc: N, N-dimethylacetamide

(Measurement of molecular weight of polymer (A))
The molecular weight of the polymer (A) in the synthetic example was as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Kagaku Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex. Was measured.
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr · H2O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphate) is 30 mmol / L, tetrahydrofuran (THF) ) Is 10 ml / L)
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratory (molecular weight: about 900,000, 150,000, 100,000, 30,000). Molecular weight of about 12,000, 4,000, 1,000).

(Synthesis of polymer (A))
<Synthesis example 1>
D2 (15.01 g), which is a tetracarboxylic acid dianhydride, DA-1 (15.65 g, a molar ratio to the total diamine component, 0.3) and DA-2 (8.33 g, total diamine), which are diamine components. Molar ratio to component 0.35), DA-3 (5.95 g, molar ratio to total diamine component 0.2), and DA-4 (5.81 g, molar ratio to total diamine component 0) .15) was mixed in an NMP solvent (203.00 g), reacted at 60 ° C. for 3 hours, and then the tetracarboxylic acid dianhydrides D1 (11.30 g) and NMP (44.24 g) were added. -Mixed and reacted at 40 ° C. for 12 hours to obtain a polyamic acid solution (A). The polyamic acid polymer had a number average molecular weight of 9,600 and a weight average molecular weight of 22,900.

<Synthesis example 2>
D1 (14.43 g), which is a tetracarboxylic acid dianhydride, DA-2 (9.12 g, molar ratio to total diamine component 0.4), which is a diamine component, DA-3 (8.36 g, total diamine). A molar ratio of 0.3) to a component and DA-5 (14.16 g, a molar ratio of 0.3 to a total diamine component) were mixed in an NMP solvent (221.94 g) and at room temperature for 1 hour. After the reaction, D3 (7.52 g), which is a tetracarboxylic acid dianhydride, and NMP (81.79 g) were added and mixed, and the mixture was reacted at room temperature for 12 hours to obtain a polyamic acid solution (B). The polyamic acid polymer had a number average molecular weight of 10,800 and a weight average molecular weight of 32,500.

(Synthesis of polymer (B))
<Preparation of triazine ring-containing polymer solution>
<Synthesis example 3>

To a 1,000 mL four-necked flask, add 1,3-phenylenediamine [2] (42.22 g, 0.390 mol, manufactured by Amino-Chem) and DMAc (672.62 g, manufactured by Kanto Chemical Co., Inc.) and replace with nitrogen. Then, the mixture was stirred to dissolve 1,3-phenylenediamine [2] in DMAc. Then, cool to -10 ° C in an ethanol-dry ice bath, and add 2,4,6-trichloro-1,3,5-triazine [1] (60.00 g, 0.325 mol, manufactured by Tokyo Chemical Industry Co., Ltd.). It was added while confirming that the temperature did not exceed 0 ° C. After stirring for 30 minutes, the reaction solution was heated in an oil bath at 90 to 100 ° C. so that the internal temperature was 85 ± 5 ° C. After stirring at an internal temperature of 85 ° C. for 1 hour, aniline [6] (18.18 g, 0.195 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 2- (4-aminophenyl) ethanol [3] (26.78 g, 0. 195 mol (manufactured by Oakwood) was previously dissolved in DMAc (42.93 g), added dropwise, and the mixture was stirred for 3 hours. Then, 2-aminoethanol (59.62 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, the temperature was lowered to room temperature, the mixture was stirred for 30 minutes, and then the stirring was stopped. THF (369 g), ammonium acetate (415 g) and ion-exchanged water (415 g) were added to the reaction solution, and the mixture was stirred for 30 minutes. After stopping stirring, the solution was transferred to a separating funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was added dropwise to a mixed solution of methanol (461 g) and ion-exchanged water (1,845 g) for reprecipitation. The obtained precipitate was filtered off and dried at 120 ° C. for 8 hours using a vacuum dryer to obtain 89.3 g of the target polymer compound [10] (hereinafter referred to as T-1). ^{The measurement results of the 1} H-NMR spectrum of compound T-1 are shown in FIG.
The weight average molecular weight Mw of compound T-1 measured by GPC in terms of polystyrene was 23,350, and the polydispersity Mw / Mn was 6.5.
The triazine ring-containing polymer (T-1) (5.00 g) and the NMP solvent (20.0 g) were dissolved by stirring at 40 ° C. for 12 hours to obtain a triazine ring-containing polymer solution (C).

To a 1,000 mL four-necked flask, 1,3-phenylenediamine [2] (45.15 g, 0.418 mol) and DMAc (685.16 g) were added, replaced with nitrogen, and then stirred to stir 1,3-phenylene. Diamine [2] was dissolved in DMAc. Then, the mixture is cooled to -10 ° C by an ethanol-dry ice bath, and the internal temperature of 2,4,6-trichloro-1,3,5-triazine [1] (70.00 g, 0.380 mol) is raised to 0 ° C or higher. I put it in while checking that it did not become. After stirring for 30 minutes, the whole reaction vessel was transferred to an oil bath set at 90 to 110 ° C., and the temperature of the reaction solution was raised until the internal temperature reached 85 ± 5 ° C. After stirring for 1 hour, 3-aminophenol [3] (49.71 g, 0.456 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in DMAc (120.91 g) was added dropwise, and the mixture was stirred for 3 hours. Then, 2-aminoethanol (69.56 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was stirred for 30 minutes and then the stirring was stopped. THF (416 g), ammonium acetate (468.2 g) and ion-exchanged water (468.2 g) were added to the reaction solution, and the mixture was stirred for 30 minutes. After stopping stirring, the solution was transferred to a separating funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was added dropwise to a mixed solution of methanol (1,040 g) and ion-exchanged water (1,561 g) for reprecipitation. The obtained precipitate was filtered off and dried at 120 ° C. for 8 hours using a vacuum dryer to obtain 95.1 g of the target polymer compound [5] (hereinafter referred to as T-2).
The weight average molecular weight Mw of compound T-2 measured by GPC in terms of polystyrene was 12,384, and the polydispersity Mw / Mn was 3.3. ^{The measurement results of the 1} H-NMR spectrum of compound T-2 are shown in FIG.
The triazine ring-containing polymer (T-2) (5.00 g) and the NMP solvent (20.0 g) were dissolved by stirring at 40 ° C. for 12 hours to obtain a triazine ring-containing polymer solution (D).

<Preparation of liquid crystal alignment agent>
<Example 1>
The polyamic acid solution (A) (1.8 g) obtained in Synthesis Example 1, the triazine ring-containing polymer solution (C) (4.2 g) obtained in Synthesis Example 3, and the additive [A-1] (0. NMP (3.88 g) and BCS (10.0 g) were added to 12 g), and the mixture was stirred for 5 hours to obtain the liquid crystal aligning agent [1] of Example 1. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment agent, and it was confirmed that the resin component was uniformly dissolved.

<Examples 2 to 6, Comparative Examples 1 and 2>
In Example 1, the liquid crystal alignment agents [2] to [6] of Examples 2 to 6 and Comparative Examples 1 and 2 were followed in accordance with the method of Example 1 except that the blending amounts were changed to those shown in Table 1 below. Liquid crystal alignment agents [7] and [8] were obtained. No abnormalities such as turbidity or precipitation were observed in these liquid crystal alignment agents, and it was confirmed that the resin components were uniformly dissolved.

(Measurement of refractive index)
The liquid crystal alignment agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above are spin-coated on a silicon substrate, fired on a hot plate at 70 ° C. for 90 seconds, and then fired in an infrared heating furnace at 230 ° C. for 20 minutes. Firing was performed to prepare a liquid crystal aligning agent-coated Si substrate having a film thickness of 100 nm.

Next, the refractive index was measured with M-2000 manufactured by JA Woolam Japan, and the refractive index at 550 nm was compared.
The measurement results of the refractive index in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 2 below.

(Measurement of transmittance)
The liquid crystal alignment agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above are spin-coated on a quartz substrate, fired on a hot plate at 70 ° C. for 90 seconds, and then fired in an infrared heating furnace at 230 ° C. for 20 minutes. Firing was performed to prepare a quartz substrate coated with a liquid crystal alignment agent having a film thickness of 100 nm.

Next, the transmittance in the visible light region (380 nm to 780 nm) was measured using a quartz substrate before coating with a liquid crystal alignment agent as a reference with UV-2600 manufactured by Shimadzu Corporation. Then, the average transmittance Y in the XYZ color system determined by CIE was calculated and used as the visual average transmittance.
The measurement results of the transmittance in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 2 below.

As shown in Table 2, it was confirmed that the refractive index of Comparative Examples 1 and 2 was 1.64 or less, whereas that of Examples 1 to 6 was as high as 1.66 or more. Further, in Examples 1 to 6, it was confirmed that the visual average transmittance was as high as 95% or more while ensuring a high refractive index.

(Evaluation of voltage retention rate)
<Manufacturing of liquid crystal cell for voltage retention evaluation>
A glass substrate with ITO (length 30 mm, width 40 mm, thickness 0.7 mm) obtained by washing the liquid crystal alignment agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above with pure water and IPA (isopropyl alcohol), respectively. The ITO surface was spin-coated and fired on a hot plate at 70 ° C. for 90 seconds, and then fired in an infrared heating furnace at 230 ° C. for 20 minutes to prepare a polyimide-coated substrate having a film thickness of 100 nm.

Two liquid crystal alignment agent-coated substrates are prepared by the above method, a 4 μm bead spacer is sprayed on the liquid crystal alignment film surface of one substrate, and then a thermosetting sealant (XN-manufactured by Kyoritsu Kagaku Sangyo Co., Ltd.) is sprayed on the beads spacer. 1500T) was printed. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was turned inside, and after bonding with the previous substrate, the sealant was cured to prepare an empty cell. A liquid crystal cell containing a polymerizable compound for PSA MLC-3023 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell. The voltage retention rate of this liquid crystal cell was measured.

Next, with a DC voltage of 15 V applied to the liquid crystal cell, UV was irradiated from the outside of the liquid crystal cell through a 325 nm cut filter at 10 J / cm ² (also referred to as primary PSA treatment). The illuminance of UV was measured using UV-MO3A manufactured by ORC.

After that, for the purpose of inactivating the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32 /) was used using a UV-FL irradiation device manufactured by Toshiba Lighting & Technology Corporation in a state where no voltage was applied. A-1) was irradiated for 30 minutes (referred to as secondary PSA treatment). After that, the voltage holding ratio was measured.

<Measurement of voltage retention rate>
Using the liquid crystal cell produced above, a voltage of 1 V is applied for 60 μs in a hot air circulation oven at 60 ° C., and then the voltage after 1667 msec is measured, and how much the voltage can be maintained is defined as the voltage retention rate (VHR). Calculated. VHR-1 manufactured by Toyo Corporation was used for measuring the voltage holding ratio.
The measurement results of the voltage holding ratios in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 3 below.

As shown in Table 3, in Examples 1 to 6, the VHR after the secondary PSA treatment was all around 90%, which was confirmed to be equivalent to that of the comparative example.
It was confirmed that the liquid crystal elements of Examples 1 to 6 exhibited a practically good voltage holding ratio.

(Evaluation of pre-tilt angle)
<Manufacturing of liquid crystal cell for pre-tilt angle evaluation>
The liquid crystal alignment agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above were washed with pure water and IPA (isopropyl alcohol), and an ITO electrode pattern having a pixel size of 200 μm × 600 μm and a line / space of 3 μm, respectively. The ITO electrode substrate (length 35 mm, width 30 mm, thickness 0.5 mm) on which the is formed and the glass substrate with ITO electrode (length 35 mm, width 30 mm, thickness 0.5 mm) in which a photospacer having a height of 3.2 μm is patterned (length 35 mm, width 30 mm, thickness). 0.7 mm) spin-coated on each ITO surface, fired on a hot plate at 70 ° C. for 90 seconds, and then fired in an infrared heating furnace at 230 ° C. for 20 minutes or 60 minutes to obtain a polyimide-coated substrate having a film thickness of 100 nm. Was produced.
The ITO electrode substrate on which this ITO electrode pattern is formed is divided into four parts in a cross checker (checkerboard) pattern so that each of the four areas can be driven separately.

Two polyimide-coated substrates were prepared by the above method, and a thermosetting sealant (XN-1500T manufactured by Kyoritsu Kagaku Sangyo Co., Ltd.) was printed on the two polyimide-coated substrates. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was turned inside, and after bonding with the previous substrate, the sealant was cured to prepare an empty cell. A liquid crystal cell containing a polymerizable compound for PSA MLC-3023 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell. The voltage retention rate of this liquid crystal cell was measured.

After that, for the purpose of inactivating the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32 /) was used using a UV-FL irradiation device manufactured by Toshiba Lighting & Technology Corporation in a state where no voltage was applied. A-1) was irradiated for 30 minutes (referred to as secondary PSA treatment). After that, the pre-tilt angle was measured.

<Measurement of pre-tilt angle>
Using an LCD analyzer (LCA-LUV42A manufactured by Meiryo Technica Co., Ltd.), the pre-tilt angle of the liquid crystal cell for pre-tilt angle evaluation produced above was measured. The value obtained by subtracting the pretilt angle measured using the polyimide-coated substrate baked for 60 minutes from the pre-tilt angle measured using the polyimide-coated substrate fired in an infrared heating furnace at 230 ° C. for 20 minutes was defined as the pretilt angle difference.
The measurement results of the pretilt angles in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 4 below.

As shown in Table 4, it was confirmed that Examples 1 to 6 showed the same tilt angle characteristics as Comparative Examples 1 and 2, and showed good vertical orientation.

Claims

A liquid crystal alignment agent containing the following components (A) and (B).
Component (A): At least one polymer (A) selected from the group consisting of a polyimide precursor and polyimide which is an imide of the polyimide precursor.
Component (B): Contains a repeating unit structure represented by the following formula (1), has at least one triazine ring terminal, and at least a part of the triazine ring terminal is sealed with an arylamino group having a cross-linking group. Polymer (B) characterized by being

(R and R'represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group independently of each other.
Ar represents at least one selected from the group represented by the formulas (2) to (12). )

Any hydrogen atom on the aromatic ring of the formulas (2) to (12) may be substituted.
R 12 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
W 1 and W 2 are independent of each other and single-bonded, -CR 95 R 96- (R 95 and R 96 are independent of each other and are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms (however, these are They may form a ring together.)), -C (= O)-, -O-, -S-, -S (= O)-, -SO 2- , or-. Represents NR 97- (R 97 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group).
X 1 and X 2 are independent of each other, single bond, alkylene group having 1 to 10 carbon atoms, or -Y 1 -Ph-Y 2- (Ph represents a phenylene group, and any hydrogen atom on the phenylene group. May be substituted, and Y 1 and Y 2 represent a group represented by a single bond or an alkylene group having 1 to 10 carbon atoms independently of each other. )
The liquid crystal alignment agent according to claim 1, wherein the arylamino group having a cross-linking group of the polymer (B) is represented by the formula (15).

(In the formula, R 15 represents a cross-linking group.)
The liquid crystal alignment agent according to any one of claims 1 to 2, wherein the cross-linking group of the polymer (B) is a hydroxy-containing group or a (meth) acryloyl-containing group.
The cross-linking group of the polymer (B) is a hydroxy group, a hydroxymethyl group, a 2-hydroxyethyl group, a (meth) acryloyloxymethyl group, a (meth) acryloyloxyethyl group, and the following formulas (i-2) to formulas (i-2). The liquid crystal aligning agent according to any one of claims 1 to 3, which is one or more selected from the groups represented by (i-3).
The liquid crystal alignment agent according to any one of claims 1 to 4, wherein a part of the triazine ring terminal of the polymer (B) is sealed with an unsubstituted arylamino group.
The claim that the polymer (A) is obtained by using a diamine component containing a diamine (a) having at least one selected from the group consisting of the structures represented by the following formulas (S1) to (S3). The liquid crystal alignment agent according to any one of 1 to 5.

(X 1 and X 2 are independent, single bond,-(CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON (CH 3 ). -, -NH-, -O-, -COO-, -OCO- or-((CH 2 ) a1- A 1 ) m1- (a1 is an integer from 1 to 15, and A 1 is an oxygen atom or -COO. -Represents, m 1 is an integer of 1 to 2. When m 1 is 2, a plurality of a 1 and A 1 have the above definitions independently.) G 1 and G 2 represent. Each independently represents a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen on the cyclic group. The atom is replaced with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom-containing alkyl group having 1 to 3 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. M and n are independently integers of 0 to 3, and m + n is an integer of 1 to 6. R 1 is an alkyl group having 1 to 20 carbon atoms and 1 to 20 carbon atoms. Any hydrogen atom representing an alkoxy group or an alkoxyalkyl group having 2 to 20 carbon atoms and forming R 1 may be substituted with a fluorine atom.)

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

(X 4 represents -CONH-, -NHCO-, -O-, -CH 2 O-, -COO- or -OCO-. R 3 represents a structure having a steroid skeleton.)
The liquid crystal alignment agent according to any one of claims 1 to 6, wherein the diamine (a) is a diamine represented by the following formula (d1) or formula (d2).

(X is a single bond, -O-, -C (CH 3 ) 2- , -NH-, -CO-,-(CH 2 ) m- , -SO 2- , -O- (CH 2 ) m- O -, - O-C ( CH 3) 2 -, - CO- (CH 2) m -, - NH- (CH 2) m -, - SO 2 - (CH 2) m -, - CONH- (CH 2) m -, - CONH- ( CH 2) m -NHCO-, or -COO- (CH 2) .m representing a divalent organic group m -OCO- is an integer of 1 ~ 8 .Y is , Represents the structure of any of the above formulas (S1) to (S3). In the formula (d2), the two Ys may be the same or different from each other.)
According to any one of claims 1 to 7, the polymer (A) can be obtained by using a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (S4) or a derivative thereof. The liquid crystal alignment agent described.

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

(R 1 to R 4 independently represent a monovalent organic group having 1 to 6 carbon atoms or a phenyl group containing a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom and a fluorine atom. R 5 and R 6 represent a hydrogen atom or a methyl group. J and k are integers of 0 or 1, and A 1 and A 2 are independently single-bonded, -O-, -CO, respectively. Represents a-, -COO-, phenylene, sulfonyl, or amide bond. * 1 is a bond that binds to one acid anhydride group, and * 2 is a bond that binds to the other acid anhydride group. )
In the tetracarboxylic dianhydride represented by the formula (S4) or a derivative thereof, X is a tetra having the formulas (x-1) to (x-7) and (x-11) to (x-13). The liquid crystal aligning agent according to claim 8, which is a carboxylic acid dianhydride or a derivative thereof.
Any of claims 1 to 9, wherein the content ratio of the component (A) and the component (B) is 10/90 to 90/10 in terms of the mass ratio of [component (A)] / [component (B)]. The liquid crystal alignment agent according to item 1.
A liquid crystal alignment film formed by using the liquid crystal alignment agent according to any one of claims 1 to 10.
A liquid crystal display element including the liquid crystal alignment film according to claim 11.
A method for manufacturing a liquid crystal display element, which comprises a step of applying the liquid crystal alignment agent according to any one of claims 1 to 10 onto a substrate.
The liquid crystal aligning agent according to any one of claims 1 to 10 is applied onto a pair of substrates having a conductive film to form a coating film, so that the coating films face each other via a layer of liquid crystal molecules. The method for manufacturing a liquid crystal display element according to claim 13, wherein the liquid crystal cells are formed so as to face each other, and the liquid crystal cells are irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates.