KR20210082462A - A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element - Google Patents

Abstract

(R_1c, R_2c : 수소 원자 또는 탄소수 1 ∼ 10 의 알킬. Y_c : 단결합 또는 -CO-, Ar¹ : 페닐렌기, 나프틸렌기 또는 비페닐렌기, T_1c, T_2c : 단결합, -O-, -COO- 등, A_c : 단결합, 탄소수 1 ∼ 20 의 알킬렌기 등, n : 1 ∼ 4, * : 결합손)

(Q : 식 (q-1) ∼ (q-4) 등, R_1r, R_2r : 탄소수 1 ∼ 10 의 알킬기 혹은 알콕시기 등, Ar² : 2 가의 방향족 탄화수소기, T_1r, T_2r : 단결합, -O-, -COO- 등, A_r : 단결합, 탄소수 1 ∼ 20 의 알킬렌기 등, * : 결합손)

A viewing angle is wide, a response speed is quick, and the liquid crystal aligning agent which can form the liquid crystal aligning film which provides the large liquid crystal display element of contrast is provided.
The polymer which has a side chain represented by following formula (1), and a side chain represented by following formula (2) is contained, The liquid crystal aligning agent characterized by the above-mentioned.

(R _1c , R _2c : hydrogen atom or alkyl having 1 to 10 carbon atoms. Y _c : single bond or -CO-, Ar ¹ : phenylene group, naphthylene group or biphenylene group, T _1c , T _2c : single bond, -O-, -COO-, etc., A _c : single bond, C1-C20 alkylene group, etc., n: 1-4, *: bond)

(Q: formulas (q-1) to (q-4), etc., R _1r , R _2r : C1-C10 alkyl group or alkoxy group, etc., Ar ² : divalent aromatic hydrocarbon group, T _1r , T _2r : provided a bond, -O-, -COO-, etc., a _r: a single bond, an alkylene group having 1 to 20 carbon atoms such as, *: bonding hand)

Description

A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element

TECHNICAL FIELD This invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element.

BACKGROUND ART Liquid crystal display elements are widely used in televisions, large monitors, personal computers, mobile phones, smart phones, and the like. In recent years, opportunities for liquid crystal display elements to be used under high temperature and high humidity, such as a car navigation system mounted on a vehicle, a meter, and a display unit of an industrial device or a measurement device installed outdoors are increasing.

Especially, since the liquid crystal display element of a vertical alignment system has a wide viewing angle, a response speed is fast, and contrast is large, it is used widely in recent years. In the vertical alignment method, a photopolymerizable compound is added in advance to a liquid crystal composition, used together with a liquid crystal aligning film such as a polyimide-based liquid crystal cell, and a tilt angle is imparted to the film surface by irradiating an ultraviolet ray while applying a voltage to the liquid crystal cell, Techniques for speeding up the response speed are known (see Patent Document 1 and Non-Patent Document 1).

For this reason, conventionally, in order to accelerate the reaction of the said photopolymerizable compound, it is a composition for liquid crystal display elements for forming at least any one of a liquid crystal layer and a liquid crystal alignment layer of a liquid crystal display element, It has a structure which can express a chain transfer function. It is proposed to contain a compound (refer patent document 2).

International publication WO2011/132752 Japanese Patent Laid-Open No. 2014-186301

K. Hanaoka, SID 04 DIGEST, P.1200-1202

However, in Patent Document 2, the sulfide-based compound disclosed as a compound having a structure capable of expressing a chain transfer function contained in the composition for liquid crystal display elements has a strong odor and has a problem in handling, so it is industrially mass-produced. There was a problem that I couldn't. In addition, benzyl isopropenyl ether, which is a vinyl ether disclosed as a compound having a structure capable of expressing a chain transfer function, is a low molecular weight component, and unreacted components remain in the liquid crystal aligning film, resulting in poor display of the liquid crystal display element. there is

In recent years, with the improvement of the quality of the liquid crystal display element, a further increase in the response speed of the liquid crystal display element of the vertical alignment system is required, and the ability of the photopolymerizable compound to react efficiently and to provide a tilt angle is required. is becoming

The present invention responds to such a request, and has the following summary.

The polymer which has a side chain represented by following formula (1), and a side chain represented by following formula (2) is contained, The liquid crystal aligning agent characterized by the above-mentioned.

[Formula 1]

(Wherein, R _1c and R _2c each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Y _c represents a single bond or —CO—. Ar ¹ represents a phenylene group, a naphthylene group, or represents a biphenylene group.T _1c and T _2c are each independently a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO- A _c is a single bond, an alkylene group having 1 to 20 carbon atoms optionally substituted with a fluorine atom, and carbon number A divalent aromatic ring group having 6 to 12 carbon atoms, a divalent alicyclic group having 3 to 8 carbon atoms, or pyrrole, imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, indole, quinoline, carbazole, thiazole, represents a divalent heterocyclic group selected from purine, tetrahydrofuran and thiophene. n represents an integer from 1 to 4. * represents a bonding position to an adjacent atom.)

[Formula 2]

(Q is a group selected from the following formulas (q-1) to (q-4) (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₃ is -CH ₂ -, -NR-, -O represents -, or -S-, and * represents a bond to an adjacent carbon atom.) R _1r and R _2r are each independently an alkyl group or alkoxy group having 1 to 10 carbon atoms, benzyl group, or pe represents a netil. Ar ² is phenylene, naphthylene and biphenyl represents a divalent aromatic hydrocarbon group selected from alkylene, they have been optionally organic group is substituted with a hydrogen atom may be substituted with halogen atoms. T _1r, T _2r is, each independently, a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON (CH ₃₎ -., or -N (CH ₃₎ CO- represents an a _r is a single bond, a fluorine atom is 2 of 1 to 20 carbon atoms alkylene group, having 6 to 12 which may optionally substituted monovalent aromatic group, A divalent alicyclic group having 3 to 8 carbon atoms, or selected from pyrrole, imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, indole, quinoline, carbazole, thiazole, purine, tetrahydrofuran and thiophene represents a divalent heterocyclic group that is used. * represents a bonding position to an adjacent atom.)

[Formula 3]

The liquid crystal display element which has a liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention has a wide viewing angle, a response speed is quick, and contrast is large.

The polymer which has a side chain (henceforth specific side chain 1) and the side chain (henceforth specific side chain 2) shown to the liquid crystal aligning agent of following formula (1) represented by following formula (2) shown to the liquid crystal aligning agent of following formula (1) is contained

[Formula 4]

[Formula 5]

_{The meanings of R 1c} , R _2c , Y _c , Ar ¹ , T _1c , T _2c , A _c and n in the formula (1) are as described above.

Among them, R _1c and R _2c each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among them, R _1c and R _2c each independently represent an alkyl group having 1 to 10 carbon atoms. it is preferable Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2 -Ethylhexyl, t-octyl, nonyl, isononyl, decyl, or isodecyl is preferred.

In addition, Ar ¹ is preferably a phenylene group or a biphenylene group. T _1c and T _2c are each independently preferably a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, or -CH ₂ O-.

A _c is preferably a single bond, a C1-C20 alkylene group optionally substituted with a fluorine atom, a C6-C12 divalent aromatic ring group, or a C3-C8 divalent alicyclic group.

Moreover, as for n, 1-2 are preferable.

^{Preferred structures of -Ar 1} -(Y _c -CHR _1c R _2c ) _n in Formula (1) include the following (ch-1) to (ch-6).

[Formula 6]

(R _1c and R _2c have the same meaning as in Formula (1))

The formula (2) means of, Q, R _{1r, 2r} R, Ar ^2, T _{1r, 2r} T, A _r is in, as described above.

Among them, Ar ² is preferably a phenylene group or a biphenylene group from the viewpoint of high photoreactivity. T _1r and T _2r are each independently preferably a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, or -CH ₂ O-.

A _r is a group is a single bond, a group with a fluorine atom is optionally 2 of 1 to 20 carbon atoms alkylene group, having 6 to 12 of the substituted monovalent aromatic ring, or a divalent cycloaliphatic of 3 to 8 carbon atoms are preferred.

Alkyl group with a carbon number of 1 to 10 constituting the above-mentioned formula (1), R _1c, R _2c, the formula (2) R _{1r, 2r,} and R is a straight-chain, it may be any of the branched to. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and the like.

The formula (1) A _c, the formula (2) alkylene group of 1 to 20 carbon atoms constituting the A _r are linear, and may be either branched or cyclic chain. Specific examples include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, a 1-methyl-cyclopropylene group, a 2-methyl-cyclopropylene group, and a 1,1-dimethyl-n-propylene group. , 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1-ethyl-n-propylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1- Methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1, 2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,3-trimethyl-cyclopropylene group, 1-ethyl-2-methyl-cyclopropylene group, 2-ethyl- 1-methyl-cyclopropylene group, 2-ethyl-2-methyl-cyclopropylene group, 2-ethyl-3-methyl-cyclopropylene group, etc. are mentioned.

Especially, Preferably it is C1-C10, More preferably, it is a 1-3 alkylene group, Specifically, a methylene group, an ethylene group, or n-propylene group is preferable.

The formula (1) A _c, the formula (2) the aromatic ring group having 6 to 12 constituting the A _r, there may be mentioned a benzene ring, a biphenylene ring, a naphthalene ring and the like.

The formula (1) A _c, an alicyclic group of 3 to 8 carbon atoms constituting the A _r of the equation (2) there may be mentioned the cyclopentane ring, a cyclohexane ring.

Preferred structures of -Ar ² -CO-CR _1r R _2r Q in Formula (1) include Formulas (ra-1) to (ra-6). Especially, the viewpoint of the reliability of the liquid crystal display element obtained to (ra-2) or (ra-3) is preferable.

[Formula 7]

In addition to the specific side chain 1 and the specific side chain 2, the polymer contained in the liquid crystal aligning agent of this invention may have the side chain (henceforth specific side chain 3) further represented by following formula (3). .

[Formula 8]

In the formula (3), l, m, and n each independently represent an integer of 0 or 1. R ¹ is -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O -, -CH ₂ OCO-, -COO-, or -OCO-, or -(CH ₂ ) _a1 -A ₁ -(CH ₂ ) _a2 -A ₂ -, A ₁ is an oxygen atom or -COO- * (provided that the hand attached with * bonds to (CH ₂ ) _a2 ), and A ₂ is an oxygen atom or *-COO- (however, the hand attached with * bonds with (CH ₂ ) _a2 ) , a1 is an integer of 0 or 1, and a2 is an integer of 1-10.

In addition, R ² , R ³ , and R ⁴ each independently represent a phenylene group, a fluorine-containing phenylene group, or a cycloalkylene group. R ⁵ represents a C2-C24 linear alkyl group, a C2-C24 fluorine-containing alkyl group, a C2-C24 alkoxy group, a C2-C24 alkoxyalkyl group, or a structure having a steroid skeleton. However, when R ⁵ is a linear alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group having 2 to 24 carbon atoms, l + m + n ≥ 1 is satisfied, and in the case of a structure having a steroid skeleton, l, m , n represents 0, R ¹ is -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O -, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO- is represented.

Specific examples of the structure having a steroid skeleton include a structure having a skeleton represented by the following formula (st).

[Formula 9]

As a preferable structure of the specific side chain 3, following formula (S1-x1) - (S1-x7), a formula (S3-x) are mentioned.

[Formula 10]

In said formula, R<^1> represents a C2-C24 linear alkyl group, a C2-C24 alkoxy group, or a C2-C20 alkoxyalkyl group. X ^p is -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O -, -CH ₂ OCO-, -COO-, or -OCO- is represented. A ₁ is an oxygen atom or -COO-* (however, the bond attached to * bonds to (CH ₂ ) _a2 ), A ₂ is an oxygen atom or *-COO- (provided that the bond attached to * is (CH ₂ ) _{binds to a2} ), a ₁ and a ₃ are each independently an integer of 0 or 1, a ₂ is an integer of 1 to 10, Cy is a 1,4-cyclohexylene group or a 1,4-phenylene group.

[Formula 11]

In the formula, X represents the formula (X1) or (X2). Col represents at least 1 sort(s) selected from the group which consists of said Formula (Col1) - (Col4). G represents the formula (G1) or (G2). * indicates a position binding to another group.

As a more preferable structure of a formula (S3-x), the following formulas (S3-1) - (S3-6) are mentioned.

[Formula 12]

<Specific Polymer>

The specific polymer contained in the liquid crystal aligning agent of this invention may be the polymer (henceforth a specific copolymer) containing the unit which has the unit which has the specific side chain 1, and the unit which has the specific side chain 2, and has the specific side chain 1 The mixture (henceforth a polymer blend) containing a polymer and the polymer which has specific side chain 2 may be sufficient.

A specific copolymer may have the unit which has the specific side chain 3 in addition to the unit which has the specific side chain 1, and the unit which has the specific side chain 2. Moreover, a polymer blend has the polymer which has the specific side chain 1, and the polymer which has the specific side chain 2, and contains the unit which has the specific side chain 3 in any polymer, or the polymer which has the specific side chain 1, and a specific side chain. The mixture containing the polymer which has 2, and the polymer which has specific side chain 3 may be sufficient.

The specific copolymer may be a polymer having a diamine having a specific side chain 1 and a specific side chain 2, but selected from the group consisting of polyamic acids, polyamic acid esters, polyimides, polyorganosiloxanes, and poly(meth)acrylates It is preferable that it is a polymer which has the backbone used. Especially, the polyimide which formed by the polycondensation reaction of the diamine component containing the diamine which has the diamine which has the specific side chain 1, and the specific side chain 2, and a tetracarboxylic-acid component, and/or the polyamic acid imidated. It is preferable to be

The content rate of the unit which has the specific side chain 1 in a specific copolymer, and the unit which has the specific side chain 2 is molar ratio (specific side chain 1/specific side chain 2), Preferably it is 5/95-95/5 , more preferably 10/90 to 90/10. By making such a ratio into said range, the light irradiation amount at the time of providing a tilt is reduced.

When a specific copolymer contains the unit which has specific side chain 3, the content rate is a molar ratio (specific side chain 3/((specific side chain 3/()) with respect to the sum total of the unit which has specific side chain 1, and the unit which has specific side chain 2 As specific side chain 1 + specific side chain 2)), 10/90-90/10 are preferable and 10/90-80/20 are more preferable. By making such a ratio into said range, while a liquid crystal aligning film has high vertical orientation, the light irradiation amount at the time of providing a tilt is reduced.

The said polymer blend is the polyamic acid formed by the polycondensation reaction of the diamine component containing the diamine which has specific side chain 1, and a tetracarboxylic-acid component, and/or the polymer which consists of polyimide which imidated the polyamic acid. It is a mixture of the polymer which consists of the polyimide which imidated the polyamic acid and/or the polyamic acid formed by the polycondensation reaction of the diamine component containing the diamine which has and the specific side chain 2, and a tetracarboxylic-acid component, it is preferable

Preferably the content rate of the polymer which has the specific side chain 1 in a polymer blend, and the polymer which has the specific side chain 2 is 10 by weight ratio (polymer 1/polymer which has specific side chain 2 which has specific side chain 1) /90 to 90/10, more preferably 20/80 to 80/20. By making such a ratio into said range, the light irradiation amount at the time of providing a tilt is reduced.

The specific polymer of this invention, that is, when obtaining the said specific copolymer or the said polymer blend, as a preferable diamine which has the specific side chain 1 used as a part of the raw material, the diamine represented by a following formula (d-1) can be heard

[Formula 13]

In the formula (d-1), _{the meanings of R 1c} , R _2c , Y _c , Ar ¹ , T _1c , T _2c , A _c , and n refer to the case in the above formula (1) and their preferred ones. the same including The _{case where both R 1c} and R _2c are methyl is particularly preferable from the viewpoint of availability of raw materials and the like.

The following formulas (1-a) - (1-j) are mentioned as a preferable specific example of the diamine represented by Formula (d-1).

[Formula 14]

When obtaining the specific polymer of this invention, ie, the said specific copolymer or the said polymer blend, as a preferable diamine which has specific side chain 2 used as a part of the raw material, the diamine represented by a following formula (d-2) is mentioned can

[Formula 15]

In the formula (d-2), _{the meanings of R 1r} , R _2r , Y _r , Ar ² , T _1r , T _2r , and _{Ar r} include those in the formula (2) and their preferred ones. same.

The following formulas (2-a) - (2-d) are mentioned as a preferable specific example of the diamine represented by Formula (d-2).

[Formula 16]

When the specific polymer of this invention is a polymer which has a side chain further represented by following formula (3) in addition to the side chain represented by the said Formula (1) and the side chain represented by said Formula (2), it is a diamine component In addition to the diamine represented by the said Formula (d-1) and the diamine represented by the said Formula (d-2), the diamine represented by a following formula (d-3) is used.

[Formula 17]

In the formula (d-3), ^{the definitions of l, m, n, and R 1} to R ⁵ are the same as in the formula (3), including preferred ones. z represents an integer of 1 to 2, and Y ₃ represents a structure represented by the following formulas (Ar _3-1 ) to (Ar _3-2).

[Formula 18]

In the formula, A _3a represents a single bond or a divalent organic group having an aromatic group. A _3b represents a trivalent group having an aromatic group. *1 represents a bonding position with respect to ^{-R 1} -(R ² ) ₁ -(R ³ ) _m -(R ⁴ ) _n -R ⁵ , and *2 represents a bonding position with respect to _{-NH 2 .}

A divalent organic group having an aromatic group in the A _3a may be, for example, in a structure of the formula (R1).

[Formula 19]

In the above formula, X ₁ is a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO ₂ -, -O-(CH ₂ ) _m -O-, -OC(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-, -COO-(CH ₂ ) _m -OCO-, and the like. Examples of Q ₁ include groups in which two hydrogen atoms have been removed from aromatic hydrocarbons having 6 to 20 carbon atoms, such as a benzene ring and a naphthyl ring. m is an integer of 1-8. *2 _{represents a bonding position with respect to -NH 2} , and *3 represents a bonding position with respect to a benzene ring.

As a trivalent organic group which has an aromatic group in A3b, the structure of a following formula (R2) is mentioned, for example.

[Formula 20]

In the formula, X _{2 has the same meaning as X 1 in the} formula (R1), and Q ₂ is a group obtained by removing three hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms, such as a benzene ring and a naphthyl ring. . *1 ^{represents a bonding position to -R 1} -(R ² ) _l -(R ³ ) _m -(R ⁴ ) _n -R ⁵ , *2 represents a bonding position to -NH ₂ , * 3 represents the bonding position to the benzene ring.

As a preferable specific example of the diamine represented by the said Formula (d-3), the diamine of following formula (V-1) - (V-13) is mentioned.

[Formula 21]

[Formula 22]

In the above formula, X ^v1 to X ^v4 , X ^p1 to X ^p8 are each independently -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON( CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-. X ^V6 to X ^V7 and X ^s1 to X ^s4 each independently represent -O-, -COO- or -OCO-. X _a to X _f represent a single bond, -O-, -NH-, or -O-(CH ₂ ) _m -O-. R ^v1 to R ^v4 and R ^1a to R ^1h each independently represent a linear alkyl group having 2 to 24 carbon atoms, an alkoxy group having 2 to 24 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. m represents the integer of 1-8.

As a diamine component in the case of obtaining a specific polymer, other diamines other than the diamine represented by the diamine represented by the said Formula (d-1), the said Formula (d-2), and the said Formula (d-3) (the following) , other diamines) can also be used in combination.

Specifically, the diamine described in paragraph [0169] of International Publication WO2015/046374, the diamine having a carboxyl group or a hydroxyl group described in paragraphs [0171] to [0172], and the nitrogen-containing heterocyclic ring described in paragraphs [0173] to [0188] A diamine having a diamine having a nitrogen-containing structure described in paragraph [0050] of Japanese Patent Application Laid-Open No. 2016-218149, a diamine having a pyrrole structure described in International Publication WO2017/126627, preferably a structure represented by the following formula (pr) diamine having

[Formula 23]

(R ¹ represents a hydrogen atom, a hydrogen atom, a fluorine atom, a cyano group, a hydroxy group, or a methyl group, R ² each independently represents a single bond or *1-R ³ -Ph-*2, R ³ represents a single bond, a divalent organic group selected from -O-, -COO-, -OCO-, -(CH ₂ )l-, -O(CH ₂ ) _m O-, -CONH-, and -NHCO- (l and m represent an integer of 1 to 5), *1 represents a position bonding to the benzene ring in formula (pr), *2 represents a position bonding to an amino group in formula (pr). Ph is phenyl represents a ren group. n represents 1 to 3.),

A diamine having a pyrrole structure described in International Publication WO2018/062197, preferably a diamine having a structure represented by the following formula (pn)

[Formula 24]

(R ¹ , R ² represents a hydrogen atom or a methyl group, R ³ each independently represents a single bond or *1-R ⁴ -Ph-*2, R ⁴ represents a single bond, -O-, -COO- , -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m represents a divalent organic group selected from O-, -CONH-, and -NHCO- (l, m represents an integer of 1 to 5) ), *1 represents the position to couple with the benzene ring in formula (pn), *2 represents the position to couple with the amino group in formula (pn).Ph represents a phenylene group. n represents 1 to 3 .),

A diamine having a thiophene or furan structure described in International Publication WO2018/092759, preferably a diamine having a structure represented by the following formula (sf);

[Formula 25]

(Y ¹ represents a sulfur atom or an oxygen atom, R ² each independently represents a single bond or *1-R ⁵ -Ph-*2, R ⁵ represents a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _m represents a divalent organic group selected from O-, -CONH-, and -NHCO- (l, m represents an integer of 1 to 5) ), *1 represents the position of bonding with the benzene ring in formula (pn), *2 represents the position of bonding with the amino group of formula (pn).Ph represents a phenylene group. n represents 1 to 3. )

A diamine having a carbazole structure described in International Publication No. WO2018/110354, preferably a diamine having a structure represented by the following formula (cz);

[Formula 26]

(R ¹ represents a hydrogen atom or a methyl group, R ² represents a methyl group),

1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(4-aminobutyl)-1,1,3,3-tetramethyldisiloxane, etc. of organosiloxane-containing diamine, a functional group capable of forming a covalent bond by light irradiation as described in International Publication WO2015/033921 (also referred to as a photoreactive group) for the purpose of increasing the response speed of liquid crystal when used as a liquid crystal display device The diamine which has diamine, the diamine etc. which have a benzophenone frame|skeleton represented by a following formula (z1) or (z2) are mentioned.

[Formula 27]

Specific examples of the diamine having a benzophenone skeleton include 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis[4 -(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone and diamines represented by the following formulas (z-1) to (z-4);

[Formula 28]

Moreover, as said other diamine, what has a structure of following formula (11) is mentioned.

[Formula 29]

In the formula, A is a single bond or a divalent organic group, and R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

In the formula (11), A is a single bond or a divalent organic group. As a divalent organic group, the structure is represented by following formula (12), for example.

[Formula 30]

In the formula, B is a divalent linking group, and R ₅ and R ₆ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of B _{are, -CH 2 -, -CHR 7 -} , -CR 7 R 8 -, -CR 7 = CR 8 -, -C≡C-, -O-, -S-, -NR 9 -, -C(=O)O-, -OC(=O)-, -C(=O)NR ₁₀ -, -NR ₁₀ C(=O)-, -NR ₁₀ C(=O)NR ₁₁ - can, but is not limited to this.

R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Here, the monovalent hydrocarbon group includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, and a decyl group; Cycloalkyl groups, such as a cyclopentyl group and a cyclohexyl group; Bicycloalkyl groups, such as a bicyclohexyl group; alkenyl groups such as a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, and hexenyl group; Aryl groups, such as a phenyl group, a xylyl group, a biphenyl group, and a naphthyl group; Aralkyl groups, such as a benzyl group, a phenylethyl group, and a phenylcyclohexyl group, etc. are mentioned.

In addition, some or all of the hydrogen atoms of these monovalent hydrocarbon groups are halogen atom, hydroxyl group, thiol group, carboxyl group, thioester group, amide group, alkyl group, cycloalkyl group, bicycloalkyl group, alkenyl group, aryl group, aralkyl group and the like may be substituted.

If R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ are bulky structures such as an aromatic ring or an alicyclic structure, the solubility of the polymer may be reduced or the like. Therefore, a methyl group, ethyl group, propyl group, or butyl group An alkyl group, such as group, or a hydrogen atom is preferable, and a hydrogen atom is more preferable.

_{R 1} , R ₂ and R ₃ in the formula (11) are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Examples of the monovalent organic group include a monovalent hydrocarbon group, a hydroxyl group, a thiol group, an ester group, a carboxyl group, a thioester group, an amide group, an organooxy group, an organosilyl group, an organothio group, and an acyl group. The monovalent organic group is preferably a monovalent hydrocarbon group from the viewpoint of high resistance to high temperature and high humidity. Specific examples of the monovalent hydrocarbon group include the monovalent hydrocarbon group, and some or all of the hydrogen atoms of these monovalent hydrocarbon groups are exemplified by _{R 7} , R ₈ , R ₉ , R _{10 above.} Other than the substitutable group, it may be substituted with groups, such as a pyrrole group, an imidazole group, and a pyrazole group.

As R<_1> and R<_2> , from a viewpoint of high temperature, high humidity resistance, alkyl groups, such as a methyl group, an ethyl group, a propyl group, and a butyl group, or a hydrogen atom, a hydrogen atom is more preferable.

R ₃ is preferably an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or a hydrogen atom, more preferably a hydrogen atom, from the viewpoint of high resistance to high temperature and high humidity.

As a specific example of the structure represented by Formula (11), the structure of following formula (H-1) - (H-6) is especially preferable.

[Formula 31]

n1, n2, n3, n4, n5, and n6 each independently represent the integer of 1-10.

It is preferable that diamine which has a structure represented by said Formula (11) is diamine represented by a following formula (M1) from a high temperature, high-humidity tolerance of a liquid crystal aligning film.

[Formula 32]

Z ₁ is a substituent having a structure represented by the formula (11), and n is an integer of 1-4. Y ₁ is a monovalent organic group (n + 2) having a carbon number of 5-40.

Examples _{of the (n + 2) valent organic group having 5 to 40 carbon atoms in Y 1} include a hydrocarbon group such as a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and a carbon-carbon bond in the hydrocarbon group. A functional group such as -O-, -COO-, -OCO-, -CO-, -NHCO-, -S-, -NH-, a divalent heterocyclic ring, or a divalent group containing a steroid skeleton is introduced between and a (n + 2) valent heterocyclic ring. Moreover, each of these groups may have substituents, such as a halogen atom (For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) and an alkoxy group.

Here, the (n + 2) valent chain hydrocarbon group is a group obtained by removing (n + 1) hydrogen atoms from the monovalent alkyl _{group in R 7} , R ₈ , R ₉ , R ₁₀ , and R _{11 ;} and groups obtained by removing (n+1) hydrogen atoms from a monovalent alkenyl group. Examples of the (n + 2) valent alicyclic hydrocarbon group include a group obtained by removing (n + 1) hydrogen atoms from the monovalent cycloalkyl group in _{R 7} , R ₈ , R ₉ , R ₁₀ , and R _{11 ;} and groups in which (n+1) hydrogen atoms have been removed from a valent bicycloalkyl group. Examples of the (n + 2) valent aromatic hydrocarbon group include a group in which (n + 1) hydrogen atoms are removed from the monovalent aryl group in _{R 7} , R ₈ , R ₉ , R ₁₀ , and R _{11 , the monovalent} and groups obtained by removing (n+1) hydrogen atoms from an aralkyl group.

Examples of the divalent heterocyclic ring include a 5-membered heterocyclic ring such as a divalent pyrrole ring, a divalent thiophene ring, a divalent furan ring and a pyrrolidinylene group, a piperidinylene group, a piperazinylene group, and a pyridinylene group. and 6-membered heterocyclic rings such as pyridazinylene group and pyrimidinylene group.

The steroid skeleton has a skeleton represented by the following formula (st) to which three 6-membered rings and one 5-membered ring are bonded.

[Formula 33]

It is preferable that Y<_1> is a C5-C40 (n+2) valence organic group which has an aromatic ring from a high temperature, high-humidity tolerance of a liquid crystal aligning film, Specifically, it is a C5-C40 (n+2) valence Between the carbon-carbon bonds in the aromatic hydrocarbon group, -O-, -COO-, -OCO-, -CO-, -NHCO-, -S-, -NH-, a bivalent heterocyclic ring, or It is preferable that it is a group into which functional groups, such as a divalent group containing a steroid skeleton, are introduce|transduced, and a (n+2) valent group which has an aromatic heterocyclic ring.

In the _{(n+2) valent group having an aromatic heterocycle for Y 1} , the aromatic heterocycle is preferably a nitrogen-containing aromatic heterocycle having a nitrogen atom in the ring moiety. Specifically, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, etc. are mentioned, for example, It is more preferable that they are a pyridine ring, a pyrimidine ring, or a triazine ring.

Y ₁ is preferably an aromatic hydrocarbon group having 5 to 40 (n + 2) valence from the viewpoint of high voltage retention, and having _{a structure represented by the following formula (Ar 1} ), having 5 to 40 (n + 2) It is preferable that it is a group of .

[Formula 34]

A ₁ represents a single bond or a divalent organic group having an aromatic ring.

As a more preferable specific example of the said formula (M1), the following formulas (M1-1) - (M1-13) are mentioned.

[Formula 35]

Z ₁ is a structure represented by the formula (11), c is an integer of 1-4, d and e are integers of 1-2, and n is an integer of 2-6.

It is preferable that it is at least 1 sort(s) chosen from the group which consists of a diamine represented by following formula (M-1) - (M-6) as a diamine which has a structure represented by said formula (11) from a viewpoint of improving vertical orientation.

[Formula 36]

n1, n2, n3, n4, n5, and n6 each independently represent an integer of 1 to 10.

Moreover, as said other diamine, the diamine which has a structure represented by following formula (21) is also mentioned.

[Formula 37]

In said Formula (21), R<^1> represents hydrogen or a monovalent organic group, and * represents the site|part couple|bonded with another group.

As diamine which has oxazoline frame|skeleton represented by said Formula (21), the diamine chosen from the group represented by following formula (21-1) - Formula (21-3) is mentioned.

[Formula 38]

In the formulas (21-1) to (21-3), ^{the definition of R 1} is the same as in the formula (21). R ² is a single bond, -O-, -COO-, -OCO-, -(CH ₂ ) _l -, -O(CH ₂ ) _l O-, -CONR ¹¹ -, -NR ¹¹ CO- and -NR ¹¹ - represents a bond selected from, or a divalent organic group consisting of a combination thereof, W ¹ is a structure selected from the following group (3-1), W ² is a structure selected from the following group (3-2), W ³ represents a structure selected from the following group (3-3), and W ⁴ represents a structure selected from the following group (3-4). Here, R ¹¹ represents hydrogen or a monovalent organic group, l represents an integer of 1 to 12, and a represents an integer of 0 or 1.

[Formula 39]

In said group (3-1), * ₁ represents the site|part couple|bonded with the amino group in Formulas (21-1) - (21-3), and * ₂ represents the site|part couple|bonded with the oxazoline ring. Of the group (3-2), * ₁ denotes an area binding to the amino group in the formula (21-1) to (21-3), * ₃ indicates a portion which combines with R ^2. In group (3-3), * ₃ represents the site|part couple|bonded with R<^2>. In group (3-4), * ₂ represents the site|part couple|bonded with an oxazoline ring. X represents a substituent and is a hydrogen atom; halogen atom; C1-C6 alkyl groups, such as a methyl group, an ethyl group, and a propyl group; halogenated alkyl groups having 1 to 6 carbon atoms such as trifluoromethyl group; Substituted amino groups, such as a dimethylamino group; C1-C6 alkoxy groups, such as a methoxy group and an ethoxy group; It represents an amide group, such as NHCOCH ₃ or NHCOCH ₂ CH _3, NHCOOtBu. tBu represents a tertbutyl group.

The following are illustrated as a specific example of the diamine of said Formula (21-1) - (21-3).

[Formula 40]

In the formula, ^{the definition of R 1} is the same as in the formula (21), and a hydrogen atom, a methyl group (Me), or an ethyl group (Et) is particularly preferable. The definition of R ¹¹ is the same as that in the formula (21), and in particular, a hydrogen atom, Me group, or Et group is preferable. n represents the integer of 1-6, m represents the integer of 1-12.

As a specific example of the diamine component which can be used together as said other diamine, m-phenylenediamine, p-phenylenediamine, 4,4'- diaminobiphenyl, 3,3'- dimethyl-4,4'-dia Minobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,6-diaminonaphthalene, 1, 2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-aminophenoxy)benzene , 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy) C) Benzene, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis( 4-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N ,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 2,2'-bis[ 4-(4-aminophenoxy)phenyl]propane, 2,2'-bis(4-aminophenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-amino Phenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8 -bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,10-(4-aminophenoxy)decane, bis(4-aminocyclohexyl)methane, 1, 3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5- Diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3- Carboxylic acid, 4,4'-diami nobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid Acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-dia Minodiphenylethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylether-3,3'-dicarboxylic acid, 2,6-diaminopyridine, 3,4-diamino Pyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3 ,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N ,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, a compound represented by each of the following formulas (D-2-1) to (D-2-23), furthermore, these amino groups Diamine which is a secondary amino group is mentioned.

[Formula 41]

The said other diamine mixes 1 type or 2 or more types according to characteristics, such as solubility with respect to the solvent of a specific polymer, applicability|paintability of a liquid crystal aligning agent, liquid crystal orientation in the case of setting it as a liquid crystal aligning film, voltage retention, accumulated electric charge, etc. can also be used.

It is preferable to use the tetracarboxylic dianhydride shown by following formula [4] - [6] as a tetracarboxylic-acid component for obtaining the specific polymer of this invention. In that case, tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxyl which are not only the tetracarboxylic dianhydride shown by Formula [4] - [6], but the tetracarboxylic acid derivative. Acid dialkyl ester dihalide can also be used.

[Formula 42]

Z ¹ represents at least one structure selected from the following [4a] to [4k]. In Formula [5] or Formula [6], j and k are each independently the integer of 0 or 1. x and y are each independently a single bond, carbonyl, ester, phenylene, sulfonyl or amide group.

[Formula 43]

Formula [4a] of, Z ¹ ~ Z ⁴ is a hydrogen atom, a methyl group, an ethyl group, a chlorine atom or a benzene ring, may each be the same or different. As a preferable specific example of a formula [4a], the structure of following [4a-1] and [4a-2] is mentioned.

[Formula 44]

In the formula [4g], Z ⁵ and Z ⁶ are may be a hydrogen atom or a methyl group, each may be the same or different.

In Z in Formula [4], from the point of the ease of synthesis|combination and the ease of polymerization reactivity at the time of manufacturing a polymer, the tetra of a structure shown by Formula [4a], Formula [4c] - Formula [4g], or Formula [4k] Carboxylic acid dianhydride and its tetracarboxylic acid derivative are preferable. A more preferable thing is a thing of a structure shown by Formula [4a] or Formula [4e] - Formula [4g]. Especially preferable are tetracarboxylic dianhydride of the structure shown by a formula [4a], a formula [4e], or a formula [4f], and its tetracarboxylic acid derivative. As a more preferable specific example, the tetracarboxylic dianhydride of a structure shown by a formula [4a-1], a formula [4a-2], a formula [4e], and a formula [4f], and its tetracarboxylic acid derivative are mentioned. .

As a preferable specific example of Formula [5] or [6] from a viewpoint of suppressing the accumulation|storage charge of a liquid crystal display element, tetra represented by the following Formulas (5a-1) - (5a-5), (6a-1) and carboxylic acid dianhydride.

[Formula 45]

It is preferable that the tetracarboxylic-acid component shown by Formula [4] is 1-100 mol% in 100 mol% of all the tetracarboxylic-acid components used. Especially, 5-95 mol% is preferable and 20-80 mol% is more preferable.

One type or two types of a tetracarboxylic-acid component according to characteristics, such as the solubility to the solvent of a specific polymer, the applicability|paintability of a liquid crystal aligning agent, the orientation of the liquid crystal in the case where it is set as a liquid crystal aligning film, voltage retention, accumulated electric charge, etc. A mixture of the above can also be used.

Other tetracarboxylic-acid components other than a specific tetracarboxylic-acid component can also be used for the polyimide type polymer of a specific polymer.

As another tetracarboxylic-acid component, the tetracarboxylic acid shown below, tetracarboxylic dianhydride, tetracarboxylic-acid dihalide, tetracarboxylic-acid dialkyl ester, or tetracarboxylic-acid dialkyl ester dihalide is mentioned. .

That is, as the other tetracarboxylic acid component, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-anthracenetetra Carboxylic acid, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4 -dicarboxyphenyl)diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,4,9,10-perylenetetra carboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid;

<Method for producing specific polymer>

The polyimide precursor which is a specific polymer in this invention is obtained by making a diamine component and a tetracarboxylic-acid component react. Specifically, a method of polycondensing tetracarboxylic dianhydride and primary or secondary diamine to obtain a polyamic acid, a method of dehydrating polycondensation reaction of tetracarboxylic acid and primary or secondary diamine to obtain a polyamic acid Alternatively, a method of polycondensing tetracarboxylic acid dihalide and primary or secondary diamine to obtain a polyamic acid is used.

A specific polymer can be obtained by making the above tetracarboxylic-acid component and diamine component react with a molecular weight modifier as needed. Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamines such as aniline, cyclohexylamine and n-butylamine, monoisocyanates such as phenyl isocyanate and naphthyl isocyanate, etc. can be heard 20 mass parts or less are preferable with respect to a total of 100 mass parts of the tetracarboxylic-acid component and diamine component to be used, and, as for the usage ratio of a molecular weight modifier, 10 mass parts or less are more preferable.

In order to obtain polyamic acid alkylester, the method of polycondensing the tetracarboxylic acid which dialkylesterified the carboxylic acid group, and primary or secondary diamine, the tetracarboxylic acid dihalide which dialkylesterified the carboxylic acid group, and 1 A method of polycondensing a primary or secondary diamine or a method of converting a carboxyl group of a polyamic acid into an ester is used.

Reaction of a diamine component and a tetracarboxylic-acid component performs a diamine component and a tetracarboxylic-acid component in a solvent normally. As a solvent used in that case, if the produced|generated polyimide precursor melt|dissolves, it will not specifically limit. Although the specific example of the solvent used for reaction is given below, it is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-2-imidazolidinone is mentioned. Moreover, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a following formula [D-1] - a formula [ D-3] can be used.

[Formula 46]

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

These solvents may be used independently and may be mixed and used. Moreover, even if it is a solvent in which a polyimide precursor is not dissolved, you may use it in the range in which the produced|generated polyimide precursor does not precipitate, mixing with the said solvent. Moreover, since the water|moisture content in a solvent inhibits a polymerization reaction and becomes a cause of hydrolyzing the produced|generated polyimide precursor by extension, it is preferable to use the solvent which carried out dehydration and drying.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, the reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution will decrease. It becomes too high, and uniform stirring becomes difficult. Therefore, Preferably it is 1-50 mass %, More preferably, it is 5-30 mass %. The reaction initial stage can be performed at high concentration, and a solvent can be added after that.

In the polymerization reaction of a polyimide precursor, it is preferable that ratio of the total number of moles of a diamine component and the total number of moles of a tetracarboxylic-acid component is 0.8-1.2. As in a typical polycondensation reaction, the closer this molar ratio to 1.0, the greater the molecular weight of the polyimide precursor produced.

The polyimide of the present invention is a polyimide obtained by ring-closing the polyimide precursor described above, and in this polyimide, the ring-closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%, and is not necessarily 100%. It can be adjusted arbitrarily according to

As for the polyimide which is a specific polymer in this invention, the method of ring-closing the polyamic acid which is a polyimide precursor, or polyamic-acid alkylester is used.

As a method of imidating a polyimide precursor, the thermal imidation which heats the solution of a polyimide precursor as it is, or catalyst imidation which adds a catalyst to the solution of a polyimide precursor is mentioned.

The temperature in the case of thermally imidating a polyimide precursor in a solution is 100-400 degreeC, Preferably it is 120-250 degreeC, It is preferable to carry out, removing the water produced|generated by imidation reaction to the outside of a system.

Catalyst imidation of a polyimide precursor is -20 degreeC - 250 degreeC by adding a basic catalyst and an acid anhydride to the solution of a polyimide precursor, Preferably it can perform by stirring at 0 degreeC - 180 degreeC. The amount of the basic catalyst is 0.5 to 30 mole times of the amic acid group, preferably 2 to 20 mole times, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times of the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, or trioctylamine, and among them, pyridine is preferable because it has suitable basicity to advance the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferably used because purification after completion of the reaction becomes easy. The imidation rate by catalytic imidation can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

When collect|recovering the produced|generated polyimide precursor or polyimide from the reaction solution of a polyimide precursor or a polyimide, what is necessary is just to inject|throw-in a reaction solution to a solvent and just to precipitate. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by putting it in a solvent can be collected by filtration, and then dried under normal pressure or reduced pressure, at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection|recovery is made to dissolve again in a solvent, and operation which carries out reprecipitation collection|recovery is repeated 2 times - 10 times, the impurity in a polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons, and the use of three or more solvents selected from these is preferable because the efficiency of purification further increases.

The weight average molecular weights (Mw) in terms of polyethylene oxide measured by the gel permeation chromatography (GPC) of the polyimide precursor and the polyimide are preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Moreover, the molecular weight distribution (Mw/Mn) shown by ratio of Mw and the number average molecular weight (Mn) in terms of polyethylene oxide measured by GPC becomes like this. Preferably it is 15 or less, More preferably, it is 10 or less. By being in such a molecular weight range, the favorable orientation of a liquid crystal display element can be ensured.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is a coating solution for forming a liquid crystal aligning film, and is a coating solution for forming the liquid crystal aligning film containing a specific polymer and a solvent. Any polyimide-type polymer of a polyamic acid, polyamic-acid alkylester, and a polyimide may be used for a specific polymer.

As for all the polymers in the liquid crystal aligning agent of this invention, all may be a specific polymer, and other polymers other than that may be mixed. As a polymer other than that, the polyimide-type polymer which does not have the specific side chain 1, the specific side chain 2, and the specific side chain 3 is mentioned. Furthermore, a cellulosic polymer, an acrylic polymer, a methacryl polymer, polystyrene, polyamide, or polysiloxane etc. are mentioned. In that case, as content of another polymer other than that, 5-90 mass parts is preferable with respect to 100 mass parts of polymers which put a specific polymer and the said other polymer together, and 10-60 mass parts is more preferable.

Moreover, as for content of the solvent in the liquid crystal aligning agent of this invention, 70-99.9 mass % is preferable. This content can be suitably changed with the coating method of a liquid crystal aligning agent, and the film thickness of the liquid crystal aligning film made into the objective.

The solvent used for the liquid crystal aligning agent of this invention will not be specifically limited if it is a solvent (it is also mentioned a good solvent) in which a polymer is dissolved. Although the specific example of a good solvent is given below, it is not limited to these examples.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, Dimethylsulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N -Dimethyl propanamide, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, etc. are mentioned.

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-butyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, and 1,3-dimethyl Preference is given to -2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, or 3-butoxy-N,N-dimethylpropanamide.

Moreover, when the solubility with respect to the solvent of a polymer is high, it is preferable to use the solvent shown by the said Formula [D-1] - a formula [D-3].

It is preferable that the good solvent in the liquid crystal aligning agent of this invention is 5-99 mass % of the whole solvent contained in a liquid crystal aligning agent. Especially, 10-90 mass % is preferable.

The liquid crystal aligning agent of this invention can use the solvent (it is also mentioned a poor solvent) which improves the coating-film property of a liquid crystal aligning film at the time of apply|coating a liquid crystal aligning agent, and surface smoothness. Although the specific example of a poor solvent is given below, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl Ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl Acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-( Hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, a solvent represented by the formulas [D-1] to [D-3], or propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, Propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl Tyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, Triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3- Methyl methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, and ethyl lactic acid ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester or 4-hydroxy-4-methyl-2-pentanone.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether, diethylene glycol diethyl ether , 4-hydroxy-4-methyl-2-pentanone, propylene glycol diacetate, dipropylene glycol monomethyl ether or propylene carbonate is preferable.

It is preferable that these poor solvents are 1-95 mass % of the whole solvent contained in a liquid crystal aligning agent. Especially, 10-90 mass % is preferable.

The compound which improves the uniformity and surface smoothness of the film thickness of a liquid crystal aligning film when the liquid crystal aligning agent of this invention apply|coats a liquid crystal aligning agent can be used.

As a compound which improves the uniformity of the film thickness of a liquid crystal aligning film, and surface smoothness, a fluorine-type surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. More specifically, for example, EFTOP EF301, EF303, EF352 (above, manufactured by Tochem Products), Megapack F171, F173, R-30 (above, manufactured by Dainippon Ink), Fluorad FC430, FC431 ( As mentioned above, the Sumitomo 3M company make), Asahi Guard AG710, Sufflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, the Asahi Glass company make) etc. are mentioned.

0.01-2 mass parts is preferable with respect to 100 mass parts of all the polymer components contained in a liquid crystal aligning agent, and, as for the usage ratio of these surfactant, 0.01-1 mass part is more preferable.

Moreover, in the liquid crystal aligning agent of this invention, as a compound which accelerates|stimulates the charge transfer in a liquid crystal aligning film, and accelerates|stimulates charge loss of an element, Formula [M1 published in paragraphs [0194] - [0200] of international publication WO2011/132751, ] - a nitrogen-containing heterocyclic amine represented by the formula [M156], more preferably a nitrogen-containing heterocyclic amine represented by the following formulas (B-1) to (B-40). Although you may add this amine directly to a liquid crystal aligning agent, it is 0.1 to 10% of density|concentrations with an appropriate solvent, It is preferable to add, after setting it as the preferably 1 to 7% solution. As this solvent, if it is a solvent in which the above-mentioned polyimide-type polymer is dissolved, it will not specifically limit.

[Formula 47]

Moreover, to the liquid crystal aligning agent of this invention, you may add the close_contact|adherence adjuvant for improving the crosslinkable compound which is a compound which bridge|crosslinks a specific polymer, the adhesiveness of a liquid crystal aligning film and a board|substrate, and the adhesiveness of a liquid crystal aligning film and a sealing material.

(crosslinkable compound)

Examples of the crosslinkable compound include a crosslinkable compound having at least one substituent selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a block isocyanate group, a hydroxyl group and an alkoxyl group, and a crosslinkable compound having a polymerizable unsaturated group. It is preferable to introduce at least one compound selected from the group consisting of compounds.

Moreover, having two or more of these substituents and a polymerizable unsaturated bond in a crosslinkable compound is preferable from a viewpoint of improving crosslinking|crosslinking property. Specific examples of the crosslinkable compound include a compound having an epoxy group or an isocyanate group described in paragraphs [0169] to [0190] of International Publication No. 2011/132751, a compound having an oxetane group, a hydroxyl group, an alkoxyl group or a lower alkoxyalkyl group Benzene or phenolic compound having an amino resin having a hydroxyl group or an alkoxyl group, a compound having a cyclocarbonate group described in paragraphs [0103] to [0112] of International Publication No. 2012/014898, as described in International Publication No. 2015/072554 The compound which has a hydroxyalkyl amide group, the compound etc. which have the blocked isocyanate group of International Publication 2015/141598 are mentioned.

As a preferable specific example of a crosslinkable compound, the compound represented by following formula (CL-1) - (CL-11) is mentioned.

[Formula 48]

It is preferable that content of a crosslinkable compound is 0.1-100 mass parts with respect to 100 mass parts of all the polymer components contained in a liquid crystal aligning agent, From a viewpoint of improving the orientation of a liquid crystal, More preferably, it is 0.1-50 mass parts, More preferably, it is 1-50 mass parts.

(Adhesive Adhesive)

As an adhesion aid, a functional silane compound is mentioned. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonylacetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltri and ethoxysilane. When using these adhesion aids, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of all the polymer components contained in a liquid crystal aligning agent, More preferably, it is 1-20 mass parts. If it is less than 0.1 mass part, the effect of an adhesive improvement cannot be anticipated, and when it increases more than 30 mass parts, the orientation of a liquid crystal may worsen.

In the liquid crystal aligning agent of the present invention, in addition to the above poor solvent, crosslinkable compound, adhesion aid, a compound that improves the uniformity and surface smoothness of the film thickness of the resin film or liquid crystal aligning film, and a compound that promotes charge loss, the liquid crystal aligning film A dielectric material or a conductive material for the purpose of changing electrical properties such as dielectric constant and conductivity may be added.

<Liquid crystal alignment film, liquid crystal display element>

After apply|coating and baking the liquid crystal aligning agent of this invention on a board|substrate, it can orientation-process by a rubbing process, light irradiation, etc., and can be used as a liquid crystal aligning film. Moreover, in the case of a vertical alignment use, etc., it can use as a liquid crystal aligning film without an orientation process.

Although the liquid crystal aligning film of this invention can be used for the liquid crystal aligning film of a horizontal alignment type or a vertical alignment type (VA system, PSA mode, SC-PVA mode, etc.), Especially, vertical alignment types, such as PSA mode and SC-PVA mode, It is a liquid crystal aligning film suitable for a liquid crystal display element, and a pretilt is controllable with a small light irradiation amount.

It will not specifically limit as a board|substrate used at this time, if it is a board|substrate with high transparency, In addition to a glass substrate, plastic substrates, such as an acryl board|substrate and a polycarbonate board|substrate, etc. can be used. From a viewpoint of simplification of a process, it is preferable to use the board|substrate with which the ITO electrode etc. for a liquid crystal drive were formed. In a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is only one substrate, and a light-reflecting material such as aluminum can be used as the electrode in this case.

Although the application method of a liquid crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, an offset printing, a flexographic printing, the inkjet method, etc. is common. As another coating method, there exist a dip method, the roll coater method, the slit coater method, the spinner method, the spray method, etc., You may use these according to the objective.

After apply|coating a liquid crystal aligning agent on a board|substrate, it is 30-300 degreeC depending on the solvent used for a liquid crystal aligning agent by heating means, such as a hot plate, heat circulation type oven, or IR (infrared) type oven, Preferably A solvent can be evaporated at the temperature of 30-250 degreeC, and it can be set as a liquid crystal aligning film. When the thickness of the liquid crystal aligning film after baking is too thick, it becomes disadvantageous from the point of power consumption of a liquid crystal display element, and since the reliability of a liquid crystal display element may fall when too thin, Preferably it is 5-300 nm, More preferably 10 to 100 nm. When a liquid crystal is horizontally orientated or diagonally aligned, the liquid crystal aligning film after baking is processed by rubbing, polarization|polarized-light ultraviolet irradiation, etc.

After the liquid crystal display element of this invention obtained the board|substrate with a liquid crystal aligning film from the liquid crystal aligning agent of this invention by said method, a liquid crystal cell was produced by a well-known method, and it was set as the liquid crystal display element.

As a manufacturing method of a liquid crystal cell, a pair of board|substrates with a liquid crystal aligning film are prepared, a spacer is spread|dispersed on the liquid crystal aligning film of one board|substrate, a liquid crystal aligning film surface is made inside, and the other board|substrate is bonded together, The method of injecting a liquid crystal under reduced pressure and sealing, or the method of bonding a board|substrate together and sealing after dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, etc. can be illustrated.

Moreover, the liquid crystal aligning agent of this invention has a liquid crystal layer between a pair of board|substrates provided with an electrode, and contains a polymeric compound which superposes|polymerizes by at least one of an active energy ray and a heat|fever between a pair of board|substrates It is used suitably also for the liquid crystal display element manufactured through the process of superposing|polymerizing a polymeric compound by at least one of irradiation and heating of an active energy ray, arranging a liquid crystal composition and applying a voltage between electrodes. Here, as an active energy ray, an ultraviolet-ray is preferable. As an ultraviolet-ray, a wavelength is 300-400 nm, Preferably it is 310-360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

Said liquid crystal display element controls the pretilt of a liquid crystal molecule by PSA(Polymer Sustained Alignment) system. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in a liquid crystal material, a liquid crystal cell is assembled, and then ultraviolet rays are applied to the photopolymerizable compound in a state where a predetermined voltage is applied to the liquid crystal layer. and the like, and the pretilt of the liquid crystal molecules is controlled by the resulting polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is memorized even after voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. Moreover, in PSA system, since a rubbing process is not required, it is suitable for formation of the liquid-crystal layer of the vertically-aligned type in which it is difficult to control a pretilt by a rubbing process.

That is, the liquid crystal display element of this invention produces a liquid crystal cell, after obtaining the board|substrate with a liquid crystal aligning film from the liquid crystal aligning agent of this invention by the above-mentioned method, and by at least one of irradiation of an ultraviolet-ray, and a heating, a polymeric compound By superposing|polymerizing, it can be set as controlling the orientation of a liquid crystal molecule.

To give an example of liquid crystal cell preparation of the PSA system, a pair of substrates with a liquid crystal aligning film are prepared, a spacer is dispersed on the liquid crystal aligning film of one substrate, the liquid crystal aligning film surface is inside, the other substrate The method of bonding and sealing a liquid crystal by pressure_reduction|reduced_pressure injection|pouring and sealing, after dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, the method of bonding together and sealing a board|substrate, etc. are mentioned.

A polymeric compound which superposes|polymerizes by heat|fever or ultraviolet irradiation is mixed with a liquid crystal. As a polymeric compound, the compound which has one or more polymerizable unsaturated groups, such as an acrylate group and a methacrylate group, in a molecule|numerator is mentioned. In that case, it is preferable that a polymeric compound is 0.01-10 mass parts with respect to 100 mass parts of a liquid crystal component, More preferably, it is 0.1-5 mass parts. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and it becomes impossible to control the orientation of the liquid crystal, and when it is more than 10 parts by mass, the unreacted polymeric compound increases and the burn-in characteristic of the liquid crystal display element is deteriorated. is lowered

After producing a liquid crystal cell, a heat|fever or an ultraviolet-ray is irradiated and a polymeric compound is superposed|polymerized, applying the voltage of alternating current or direct current to a liquid crystal cell. Thereby, the orientation of liquid crystal molecules can be controlled.

Furthermore, the liquid crystal aligning agent of this invention has a liquid crystal layer between a pair of board|substrates provided with an electrode, and contains the polymeric group which superposes|polymerizes by at least one of an active energy ray and a heat|fever between the pair of board|substrates It is preferable to arrange a liquid crystal aligning film and to use also for the liquid crystal display element manufactured through the process of applying a voltage between electrodes, ie, SC-PVA mode. Here, as an active energy ray, an ultraviolet-ray is preferable. As an ultraviolet-ray, a wavelength is 300-400 nm, Preferably it is 310-360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

In order to obtain the liquid crystal aligning film containing the polymeric group which superposes|polymerizes by at least one of an active energy ray and a heat|fever, the method of adding the compound containing this polymeric group in a liquid crystal aligning agent, The method of using the polymer component containing a polymeric group can be heard It will not specifically limit if it is a polymer which has the said photoreactive group as a specific example of the polymer containing a polymeric group, The polymer obtained using the diamine which has the said photoreactive group is mentioned.

To give an example of liquid crystal cell production in SC-PVA mode, prepare a pair of substrates on which the liquid crystal aligning film of the present invention is formed, and spread the spacers on the liquid crystal aligning film of one substrate, so that the liquid crystal aligning film surface is inside , The method of bonding the other board|substrate together, the method of inject|pouring and sealing a liquid crystal under reduced pressure, or the method of bonding a board|substrate together and sealing after dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, etc. are mentioned.

After producing a liquid crystal cell, the orientation of a liquid crystal molecule can be controlled by irradiating a heat|fever or an ultraviolet-ray, applying the voltage of alternating current or direct current to a liquid crystal cell.

Example

Hereinafter, although it demonstrates concretely based on an Example, this invention is limited to these Examples, and interpretation is not deleted.

The meaning of the abbreviation used below is as follows.

(acid dianhydride)

BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

(diamine)

p-PDA: p-phenylenediamine, DBA: 3,5-diaminobenzoic acid

3AMPDA: 3,5-diamino-N-(pyridin-3-ylmethyl)benzamide

[Formula 49]

[Formula 50]

[Formula 51]

(menstruum)

NMP: N-methyl-2-pyrrolidone, BCS: butyl cellosolve

(additive)

3AMP: 3-picolylamine

<Production of liquid crystal aligning agent>

(Example 1)

Dissolve BODA (1.13 g, 4.5 mmol), DA-1 (0.60 g, 1.8 mmol), DA-3 (0.65 g, 2.7 mmol), and DA-4 (1.71 g, 4.5 mmol) in NMP (16.3 g) After making it react at 60 degreeC for 3 hours, CBDA (0.86 g, 4.5 mmol) and NMP (3.4 g) were added, and it was made to react at 40 degreeC for 12 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (19.3g) and diluting to 6 mass %, acetic anhydride (3.6g) and pyridine (1.1g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was thrown into methanol (220 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (A). The imidation ratio of this polyimide was 77 %.

NMP (25.4g) was added to the obtained polyimide powder (A) (3.2g), and it stirred at 70 degreeC for 12 hours, and made it melt|dissolve. 3AMP (1 wt% NMP solution) 3.2g and BCS (21.2g) were added to this solution, it stirred at room temperature for 5 hours, and the liquid crystal aligning agent (A1) was obtained.

(Example 2)

Dissolve BODA (1.13 g, 4.5 mmol), DA-1 (0.59 g, 1.8 mmol), DA-2 (0.67 g, 2.7 mmol), and DA-4 (1.71 g, 4.5 mmol) in NMP (16.4 g) After making it react at 60 degreeC for 3 hours, CBDA (0.86 g, 4.5 mmol) and NMP (3.4 g) were added, and it was made to react at 40 degreeC for 12 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (16.4g) and diluting to 6 mass %, acetic anhydride (2.9g) and pyridine (0.9g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was thrown into methanol (190 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (B). The imidation ratio of this polyimide was 78 %.

NMP (21.3g) was added to the obtained polyimide powder (B) (2.7g), and it stirred at 70 degreeC for 12 hours, and made it melt|dissolve. 3AMP (1 wt% NMP solution) 2.7g and BCS (17.8g) were added to this solution, it stirred at room temperature for 5 hours, and the liquid crystal aligning agent (B1) was obtained.

(Example 3)

Dissolve BODA (2.25 g, 9.0 mmol), DA-1 (0.60 g, 1.8 mmol), DA-3 (1.74 g, 7.2 mmol), and DA-4 (3.43 g, 9.0 mmol) in NMP (32.1 g) After making it react at 60 degreeC for 3 hours, CBDA (1.76 g, 9.0 mmol) and NMP (6.8 g) were added, and it was made to react at 40 degreeC for 12 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (15.0g) and diluting to 6 mass %, acetic anhydride (2.8g) and pyridine (0.9g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was thrown into methanol (174 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (C). The imidation ratio of this polyimide was 77 %.

NMP (20.3g) was added to the obtained polyimide powder (C) (2.5g), and it stirred at 70 degreeC for 12 hours, and made it melt|dissolve. 2.5g of 3AMP (1 wt% NMP solution) and BCS (16.9g) were added to this solution, it stirred at room temperature for 5 hours, and the liquid crystal aligning agent (C1) was obtained.

(Example 4)

Dissolve BODA (2.25 g, 9.0 mmol), DA-1 (0.60 g, 1.8 mmol), DA-2 (1.79 g, 7.2 mmol), and DA-4 (3.43 g, 9.0 mmol) in NMP (32.3 g) After making it react at 60 degreeC for 3 hours, CBDA (1.76 g, 9.0 mmol) and NMP (6.8 g) were added, and it was made to react at 40 degreeC for 12 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (15.0g) and diluting to 6 mass %, acetic anhydride (2.8g) and pyridine (0.9g) were added as an imidation catalyst, and it was made to react at 75 degreeC for 2.5 hours. This reaction solution was thrown into methanol (174 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (D). The imidation ratio of this polyimide was 69 %.

NMP (19.7g) was added to the obtained polyimide powder (D) (2.5g), and it stirred at 70 degreeC for 12 hours, and made it melt|dissolve. 2.5 g of 3AMP (1 wt% NMP solution) and BCS (16.4g) were added to this solution, and it stirred at room temperature for 5 hours, and obtained the liquid crystal aligning agent (D1).

(Comparative Example 1)

BODA (25.6 g, 102.5 mmol), DA-1 (13.5 g, 41.0 mmol), p-PDA (6.7 g, 61.5 mmol), and DA-4 (39.0 g, 102.5 mmol) were dissolved in NMP (339.4 g) After making it react at 60 degreeC for 3 hours, CBDA (18.9 g, 96.3 mmol) (75.6 g) was added, and it was made to react at 40 degreeC for 12 hours, and the polyamic-acid solution was obtained.

After adding NMP to this polyamic-acid solution (260.0g) and diluting to 6 mass %, acetic anhydride (52.3g) and pyridine (16.2g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was thrown into methanol (3040 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (E). The imidation ratio of this polyimide was 70 %.

NMP (28.6g) was added to the obtained polyimide powder (E) (3.6g), and it stirred at 70 degreeC for 12 hours, and made it melt|dissolve. 3AMP (1 wt% NMP solution) 3.6g and BCS (23.8g) were added to this solution, it stirred at room temperature for 5 hours, and the liquid crystal aligning agent (E1) was obtained.

(Comparative Example 2)

Dissolve BODA (2.50 g, 10.0 mmol), DA-1 (0.66 g, 2.0 mmol), p-PDA (0.87 g, 8.0 mmol), and DA-4 (3.80 g, 8.0 mmol) in NMP (31.3 g) After making it react at 60 degreeC for 3 hours, CBDA (1.88 g, 9.6 mmol) and NMP (7.5 g) were added, and it was made to react at 40 degreeC for 12 hours, and the polyamic acid solution was obtained.

After adding NMP to this polyamic-acid solution (15.0g) and diluting to 6 mass %, acetic anhydride (3.1g) and pyridine (1.0g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was thrown into methanol (175 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 60 degreeC, and obtained polyimide powder (F). The imidation ratio of this polyimide was 69 %.

NMP (21.3g) was added to the obtained polyimide powder (F) (2.7g), and it stirred at 70 degreeC for 12 hours, and was made to melt|dissolve. 3AMP (1 wt% NMP solution) 2.7g and BCS (17.8g) were added to this solution, it stirred at room temperature for 5 hours, and the liquid crystal aligning agent (F1) was obtained.

<Production of liquid crystal cell and measurement of pretilt angle>

(Example 5)

The liquid crystal cell was produced in the procedure as shown below using the liquid crystal aligning agent (A1) obtained in Example 1. The liquid crystal aligning agent (A1) obtained in Example 1 was spin-coated on the ITO surface of the ITO electrode substrate in which the pixel size is 100 micrometers x 300 micrometers and the ITO electrode patterns each 5 micrometers in line/space are formed, 80 degreeC After drying for 90 second on the hotplate of 230 degreeC hot-air circulation type oven, baking was performed for 15 minutes, and the liquid crystal aligning film with a film thickness of 100 nm was formed.

Moreover, after spin-coating the liquid crystal aligning agent (A1) on the ITO surface in which the electrode pattern is not formed and drying it for 90 second on an 80 degreeC hotplate, it bakes in 230 degreeC hot air circulation type oven for 15 minutes, The liquid crystal aligning film with a film thickness of 100 nm was formed.

After spread|dispersing a 4 micrometers bead spacer on the liquid crystal aligning film of one board|substrate with respect to said two board|substrates, the sealing compound (solvent type thermosetting type epoxy resin) was printed on it. Then, after turning inside the surface of the side in which the liquid crystal aligning film of the other board|substrate was formed and bonding together with the previous board|substrate, the sealing compound was hardened and the empty cell was produced. Liquid crystal MLC-3023 (merck company brand name (polymerizable compound containing liquid crystal)) was inject|poured into this empty cell by the reduced pressure injection method, and the liquid crystal cell was produced.

Then, in the state which applied the DC voltage of 15V to this liquid crystal cell, 10 J/cm<2> of UV which let a 365 nm band pass filter pass from the outer side of this liquid crystal cell was irradiated. Thereafter, the pretilt angle of the pixel portion was measured for the cell after UV irradiation. For the measurement, LCD analyzer LCA-LUV42A manufactured by Meiryo Technica was used. A result is shown in Table 1.

(Examples 6 to 12, Comparative Examples 3 to 6)

In Example 5, instead of the liquid crystal aligning agent (A1), what used the liquid crystal aligning agent shown in Table 1 obtained by Examples 1-4 or the comparative example 1 or 2, and what performed UV irradiation on the following conditions Except that, it carried out similarly to Example 5, produced the liquid crystal cell, it carried out similarly to Example 5 about the liquid crystal cell after UV irradiation, and measured the pretilt angle.

In addition, as shown in Table 1, the said UV irradiation was 20 J/cm<2> irradiation in Examples 6, 8, 10, 12, and Comparative Examples 4 and 6.

The measurement result of the pretilt angle is put together in a table and is shown.

As shown in Table 1, in Examples 5-8, compared with Comparative Examples 3-4, and Examples 9-12, compared with Comparative Examples 5-6, the tilt angle of a liquid crystal cell becomes a small value, By using the liquid crystal display element of this invention, it was confirmed that the tilt provision ability improves.

Industrial Applicability

Since the liquid crystal display element which has a liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention has a wide viewing angle, a response speed is quick, and contrast is large, it is a large screen, and it can use suitably for a high-definition television, a large monitor, etc.

In addition, the specification of Japanese Patent Application No. 2018-202179 for which it applied on October 26, 2018, a claim, and the abstract are referred here, and it takes in as an indication of the specification of this invention.

Claims (15)

The polymer which has a side chain represented by following formula (1), and a side chain represented by following formula (2) is contained, The liquid crystal aligning agent characterized by the above-mentioned.

(R _1c and R _2c each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Y _c represents a single bond or —CO—. Ar ¹ represents a phenylene group, a naphthylene group or a biphenylene group. T _1c and T _2c are each independently a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH ₃ )CO- A _c is a single bond, an optionally substituted C1-C20 alkylene group, or a C6-C12 alkylene group A divalent aromatic ring group, a divalent alicyclic group having 3 to 8 carbon atoms, or pyrrole, imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, indole, quinoline, carbazole, thiazole, purine, tetrahydro represents a divalent heterocyclic group selected from furan and thiophene. n represents an integer from 1 to 4. * represents a bonding position to an adjacent atom.)

(Q is a group selected from the following formulas (q-1) to (q-4) (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₃ is -CH ₂ -, -NR-, -O - or -S-.) R _1r and R _2r each independently represent a C1-C10 alkyl group, an alkoxy group, a benzyl group, or a phenethyl group. Ar ² is phenylene, naph represents a divalent aromatic hydrocarbon group selected from tylene and biphenylene, and may be substituted with an organic group, and a hydrogen atom may be substituted with a halogen atom. T _1r and T _2r are each independently a single bond, -O -, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, -CON(CH ₃ )-, or -N(CH _{3 )} ) CO- Ar is a single bond, an alkylene group having 1 to 20 carbon atoms optionally substituted with a fluorine atom, a divalent aromatic ring group having 6 to 12 carbon atoms, a divalent alicyclic group having 3 to 8 carbon atoms, or pyrrole , imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, indole, quinoline, carbazole, thiazole, purine, tetrahydrofuran and a divalent heterocyclic group selected from thiophene. indicates the binding position for .)

The method of claim 1,
In the formula (1), -Ar ¹ -(Y _c -CHR _1c R _2c ) _n represents the following (ch-1) to (ch-6), the liquid crystal aligning agent.

(R _1c and R _2c have the same meaning as in Formula (1)) 3. The method according to claim 1 or 2,
In the formula (2), Ar ² represents a phenylene group or a biphenylene group,
T _1r , T _2r each independently represents a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH- or -CH ₂ O-,
A _r is a single bond, is substituted with a fluorine atom may be a carbon number of 1 to 20 representing an alkylene group, a divalent aromatic ring group having a carbon number of 6-12, or a divalent cycloaliphatic of 3 to 8 carbon atoms, a liquid crystal alignment. 4. The method according to any one of claims 1 to 3,
The liquid crystal aligning agent whose said polymer is an at least 1 sort(s) of polymer chosen from the group which consists of a polyimide which imidated a polyimide precursor and this polyimide precursor. 5. The method according to any one of claims 1 to 4,
The polymer which has a side chain represented by the copolymer and/or the said Formula (1) in which the said polymer contains the unit which has the unit which has a side chain represented by said Formula (1), and the unit which has a side chain represented by said Formula (2). And the liquid crystal aligning agent which is a mixture containing the polymer which has a side chain represented by said Formula (2). 6. The method according to any one of claims 1 to 5,
The liquid crystal aligning agent whose said polymer is a polymer which has a side chain further represented by following formula (3) in addition to the side chain represented by the said Formula (1), and the side chain represented by said Formula (2).

(l, m and n each independently represent an integer of 0 or 1. R ₁ is -(CH ₂ ) _a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-, -(CH ₂ ) _a1 -A ₁ -(CH ₂ ) _a2 -A ₂ -, A ₁ is an oxygen atom or -COO-* (however, the bond attached with * bonds to (CH ₂ ) _a2 ), A ₂ is an oxygen atom or *-COO- (However, the bond attached with * bonds to (CH ₂ ) _a2 ), a1 is an integer of 0 or 1, and a2 is an integer of 1 to 10. R ² , R ³ , and R ⁴ are each Independently represents a phenylene group, a fluorine-containing phenylene group, or a cycloalkylene group.R ⁵ is a linear alkyl group having 2 to 24 carbon atoms, a fluorine-containing alkyl group having 2 to 24 carbon atoms, an alkoxy group having 2 to 24 carbon atoms, or a carbon number A structure having an alkoxyalkyl group of 2 to 20 or a steroid skeleton is shown, provided that when R ⁵ is a linear alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group having 2 to 24 carbon atoms, l + m + n ≥ 1 is satisfied, and in the case of a structure having a steroid skeleton, l, m, and n represent 0. R ¹ is -(CH ₂ )a- (a is an integer of 1 to 15), -CONH-, -NHCO -, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO- is represented.) 7. The method of claim 6,
A copolymer in which the polymer includes a unit having a side chain represented by the formula (1) and a unit having a side chain represented by the formula (2), and a unit having a side chain represented by the formula (3), and Liquid-crystal orientation which is a mixture containing the polymer which has a side chain represented by/or the said Formula (1), the polymer which has a side chain represented by the said Formula (2), and the polymer which has a side chain represented by the said Formula (3) My. 8. The method according to any one of claims 1 to 7,
The liquid crystal aligning agent whose said polymer is a polymer obtained using the diamine represented by a following formula (d-1) for a part of a raw material.

(R _1c , R _2c , Y _c , Ar ¹ , T _1c , T _2c , A _c , n have the same meaning as in Formula (1) above) 9. The method according to any one of claims 1 to 8,
The liquid crystal aligning agent whose said polymer is a polymer obtained using the diamine represented by a following formula (d-2) for a part of a raw material.

(R _1r , R _2r , Y _r , Ar ² , T _1r , T _2r , _{Ar r} have the same meaning as in Formula (2) above) 10. The method according to any one of claims 1 to 9,
The liquid crystal aligning agent whose said polymer is a polymer obtained using the diamine represented by a following formula (d-3) for a part of a raw material.

(l, m, n, and ^{the definitions of R 1} to R ⁵ are the same as in the above formula (3). z represents an integer of 1 to 2, Y ₃ is the following formula (Ar _3-1 ) to ( Ar _3-2 ).)

(A _3a represents a single bond or a divalent organic group having an aromatic group. A _3b represents a trivalent group having an aromatic group. *1 is -R ¹ -(R ² ) ₁ -(R ³ ) _m -(R ⁴ ) _n represents a bond to -R ⁵ , and *2 represents a bond position to _{-NH 2 .)} 11. The method according to any one of claims 1 to 10,
The liquid crystal aligning agent whose said polymer is a polymer obtained using tetracarboxylic dianhydride shown by following formula [4] - [6] for a part of a raw material.

(Z ¹ represents at least one structure selected from the following formulas [4a] to [4k]. In formula [5] or [6], j and k are each independently an integer of 0 or 1. x and y each independently represent a single bond, carbonyl, ester, phenylene, sulfonyl or amide group.)

(Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a benzene ring) It is formed using the liquid crystal aligning agent in any one of Claims 1-11, The liquid crystal aligning film characterized by the above-mentioned. The liquid crystal aligning film of Claim 12 is provided, The liquid crystal display element characterized by the above-mentioned. The process of apply|coating the liquid crystal aligning agent in any one of Claims 1-11 on a board|substrate to form a coating film, The process of baking the said coating film, The liquid-crystal composition is made to contact the obtained baked film, and a liquid crystal layer is formed The manufacturing method of the liquid crystal display element including the process of doing. The liquid crystal composition containing a polymeric compound in the process of apply|coating the liquid crystal aligning agent in any one of Claims 1-11 on a board|substrate to form a coating film, the process of baking the said coating film, and the obtained baked film A method of manufacturing a liquid crystal display device, comprising: a step of forming a liquid crystal layer by contacting it; and a step of irradiating the liquid crystal layer with ultraviolet rays.