KR101775181B1 - Liquid-crystal alignment agent, liquid-crystal alignment film, and liquid-crystal display element - Google Patents

Abstract

A liquid crystal alignment treatment agent comprising a polymer obtained by reacting a diamine component containing a diamine compound of the formula [1] and a formula [2] with a tetracarboxylic dianhydride. X ₁ Is a divalent organic group selected from -NHCO- and the like. X ₂ Is a divalent organic group selected from a single bond, a benzene ring, and a cyclohexyl ring. X ₃ , X ₄ Is a divalent organic group selected from a benzene ring and a cyclohexyl ring. X ₅ Is an alkyl group having 1 to 18 carbon atoms and the like, and n is an integer of 1 to 4. Y ₁ , Y ₃ Is a divalent organic group selected from _a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, or -OCO-. Y ₂ Is a single bond or a divalent organic group selected from - (CH ₂ ) _b - (b is an integer of 1 to 10). Y ₄ Represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton. Y ₅ Represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring, and n is an integer of 0 to 4. Y ₆ Is an alkyl group having 1 to 18 carbon atoms or the like or a hydrogen atom, and m is an integer of 1 to 4.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display element,

The present invention relates to a liquid crystal alignment treatment agent used in producing a liquid crystal alignment film and a liquid crystal display element using the same.

At present, a polyimide film is usually used for a liquid crystal alignment film used in a liquid crystal display device. This polyimide film is a film obtained by applying a solution of polyamic acid, which is a precursor of polyimide, or a solution of solvent- soluble polyimide, The method is being taken. The polyamic acid or solvent-soluble polyimide is generally synthesized by the reaction of a tetracarboxylic acid derivative such as a tetracarboxylic acid dianhydride with a diamine.

One of the characteristics required for a liquid crystal alignment film is so-called liquid crystal pretilt angle control in which the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained at an arbitrary value. It is known that the size of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film.

Among techniques for controlling the pretilt angle by the structure of polyimide, a method of using a diamine having a side chain as a part of a polyimide raw material can control the pretilt angle according to the use ratio of the diamine, It is relatively easy to make the pretilt angle, which is useful as means for increasing the pretilt angle. As a side chain structure of a diamine which increases the pretilt angle of a liquid crystal, a long chain alkyl group or a fluoroalkyl group (see, for example, Patent Document 1), a cyclic group or a combination of a cyclic group and an alkyl group ), A steroid skeleton (for example, see Patent Document 3), and the like.

Japanese Patent Application Laid-Open No. 2-282726 Japanese Unexamined Patent Application Publication No. 3-179323 Japanese Patent Application Laid-Open No. 4-281427

Recently, a multi-domain vertical alignment (MVA) mode in which a wide viewing angle can be obtained is widely used as a liquid crystal display device having a better viewing angle characteristic than a conventional TN (twisted nematic) mode liquid crystal display device. In this MVA mode, it is necessary to vertically align the liquid crystal molecules with respect to the substrate (to set the pre-tilt angle to 90 DEG), and a liquid crystal alignment film using the above-mentioned diamine component having many side chains is required. However, this liquid crystal alignment film lowers the affinity with the liquid crystal, and the liquid crystal on the liquid crystal alignment film lowers the extended wettability. Specifically, when the injection of the liquid crystal is performed by the vacuum injection method, the injection rate of the liquid crystal is lowered, so that the production efficiency at the time of manufacturing the liquid crystal display element is deteriorated. In the case of the ODF (One Drop Filling) Alignment irregularity tends to occur in liquid crystal drop portions or fusion portions of liquid crystals, resulting in display defects of liquid crystal display elements.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid crystal alignment treatment agent, a liquid crystal alignment treatment agent, and a liquid crystal alignment treatment agent, which can enhance liquid crystal widening wettability on a liquid crystal alignment film, An orientation film and a liquid crystal display element.

As a result of intensive studies, the present inventors have found that a liquid crystal alignment treatment agent comprising a polyimide precursor having a specific side chain structure and a polyimide obtained by dehydrating and cyclizing the polyimide precursor is very effective for achieving the above object , Thereby completing the present invention.

That is, the present invention has the following points.

(One)

A liquid crystal alignment treatment agent comprising a polymer obtained by reacting a diamine compound represented by the following formula [1] and a diamine compound containing a diamine compound represented by the following formula [2] with a tetracarboxylic acid dianhydride.

[Chemical Formula 1]

(In the formula [1], X ₁ Is _{-NHCO-, -N (CH 3) CO-} , -CONH-, -CON (CH 3) - is a divalent organic group selected from, X ₂ Is a divalent organic group selected from a single bond, a benzene ring, or a cyclohexyl ring, X ₃ Is a divalent organic group selected from a benzene ring or a cyclohexyl ring, and X ₄ Is a divalent organic group selected from a cyclohexyl ring or a benzene ring and X ₅ Is selected from an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, and n is an integer of 1 to 4).

(2)

(In the formula [2], Y ₁ Is a divalent organic group selected from -O-, -CH ₂ O-, - (CH ₂ ) _a - (a is an integer of 1 to 10), -COO-, -OCO-, ₂ Is a single bond or a divalent organic group selected from - (CH ₂ ) _b - (b is an integer of 1 to 10), and Y ₃ Is a divalent organic group selected from a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, or -OCO- and Y ₄ Represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and a steroid skeleton, and any hydrogen atom on the cyclic group may have 1 to 3 carbon atoms alkyl group, is optionally substituted by is selected from a fluorine-containing alkoxy group, a fluorine atom, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms of a, Y ₅ Represents a divalent cyclic group selected from a cyclohexyl ring, a benzene ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, and a fluorine atom, n is an integer of 0 to 4, Y ₆ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a fluoro-containing alkoxyl group having 1 to 18 carbon atoms, or a hydrogen atom;

(2)

In the formula [1], X ₁ Is -NHCO-. ≪ / RTI >

(3)

The liquid crystal alignment treatment agent according to (1) or (2), wherein the tetracarboxylic acid dianhydride is a tetracarboxylic acid dianhydride represented by the following formula [3].

(3)

(In the formula [3], Z ₁ Is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.

(4)

Z ₁ Is a structure represented by the following formulas [3a] to [3j].

[Chemical Formula 4]

(In the formula [3a], Z ₂ to Z ₅ Is a group selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring and may be the same or different, and Z ₆ and Z _{7 in the} formula [3g] Are each a hydrogen atom or a methyl group, and may be the same or different.

(5)

A liquid crystal aligning treatment agent containing a crosslinkable compound having at least one substituent selected from the group consisting of an epoxy group, an oxetane group, an isocyanate group and a cyclocarbonate group, a group consisting of a hydroxyl group, a hydroxyalkyl group, an alkoxyl group and a lower alkoxyalkyl group (1) to (4), wherein the crosslinking compound has at least one kind of substituent selected from the group consisting of a halogen atom, a hydroxyl group,

(6)

A liquid crystal alignment treatment agent according to any one of (1) to (5), wherein the polymer in the liquid crystal alignment treatment agent is a polyimide obtained by dehydrating and ring-closing a polyamic acid.

(7)

The liquid crystal alignment treatment agent according to any one of (1) to (6), wherein the liquid crystal alignment treatment agent contains 5 to 60 mass% of a poor solvent.

(8)

A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of (1) to (7).

(9)

A liquid crystal display element having the liquid crystal alignment layer described in (8).

(10)

A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent described in any one of (1) to (7), wherein a liquid crystal material in which a polymerizable compound polymerized by irradiation with heat or ultraviolet light is mixed is used as a liquid crystal alignment film, And a polymer obtained by polymerizing the polymerizable compound while controlling the alignment direction of the liquid crystal at the time of driving the liquid crystal alignment film.

(11)

(10), a liquid crystal material obtained by mixing a liquid crystal with a polymerizable compound polymerized by irradiation with heat or ultraviolet light is used to polymerize the polymerizable compound while applying a voltage to the liquid crystal layer A liquid crystal display element obtained by a method of controlling the alignment direction of liquid crystal during driving.

By using the liquid crystal alignment treatment agent of the present invention, it is possible to provide a liquid crystal display element which has high expansion wettability of liquid crystal on a liquid crystal alignment film, high production efficiency in production of liquid crystal display element, and display defect of orientation irregularity does not occur have.

Hereinafter, the present invention will be described in detail.

The present invention relates to a diamine compound containing a diamine compound (also referred to as a specific diamine compound) represented by the following formula [1] and a diamine compound (also referred to as a specific side chain type diamine compound) represented by the following formula [2] A liquid crystal alignment treatment agent containing a polymer obtained by reacting a carboxylic acid dianhydride and a carboxylic acid dianhydride, a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and further, a liquid crystal display device having the liquid crystal alignment film.

[Chemical Formula 5]

(In the formula [1], X ₁ Is _{-NHCO-, -N (CH 3) CO-} , -CONH-, -CON (CH 3) - is a divalent organic group selected from, X ₂ Is a divalent organic group selected from a single bond, a benzene ring, or a cyclohexyl ring, X ₃ Is a divalent organic group selected from a benzene ring or a cyclohexyl ring, and X ₄ Is a divalent organic group selected from a cyclohexyl ring or a benzene ring and X ₅ Is selected from an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, and n is an integer of 1 to 4).

[Chemical Formula 6]

(In the formula [2], Y ₁ Is a divalent organic group selected from -O-, -CH ₂ O-, - (CH ₂ ) _a - (a is an integer of 1 to 10), -COO-, -OCO-, ₂ Is a single bond or a divalent organic group selected from - (CH ₂ ) _b - (b is an integer of 1 to 10), and Y ₃ Is a divalent organic group selected from a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, or -OCO- and Y ₄ Represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and a steroid skeleton, and any hydrogen atom on the cyclic group may have 1 to 3 carbon atoms alkyl group, is optionally substituted by is selected from a fluorine-containing alkoxy group, a fluorine atom, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms of a, Y ₅ Represents a divalent cyclic group selected from a cyclohexyl ring, a benzene ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, and a fluorine atom, n is an integer of 0 to 4, Y ₆ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a fluoro-containing alkoxyl group having 1 to 18 carbon atoms, or a hydrogen atom;

Since the liquid crystal alignment film obtained from the specific diamine compound of the present invention and the liquid crystal alignment treatment agent using the specific side chain diamine compound has high pretilt angle, even when a large amount of the diamine component having side chain is used, The liquid crystal has high expansion wettability. Thereby, by using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention, it is possible to provide a liquid crystal display device which has high production efficiency at the time of manufacturing liquid crystal display elements and does not cause display defects of orientation irregularities.

≪ Specific diamine compound &

The specific diamine compound of the present invention is a diamine compound represented by the following formula [1].

(7)

In the formula [1], X ₁ Is _{-NHCO -, - N (CH 3} ) CO-, -CONH-, -CON (CH 3) - is a divalent organic group selected from, among them preferably a -NHCO-, -CONH-. More preferably -NHCO-.

In the formula [1], X ₂ Is a divalent organic group selected from a single bond, a benzene ring or a cyclohexyl ring, that is, a phenylene group or a cyclohexylene group, and among these, a single bond or a benzene ring is preferable.

In the formula [1], X ₃ Is a divalent organic group selected from a benzene ring or a cyclohexyl ring.

In the formula [1], X ₄ Is a divalent organic group selected from a benzene ring or a cyclohexyl ring.

In the formula [1], X ₅ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, A fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

In the formula [1], n is an integer of 1 to 4, preferably 1 or 2.

The preferable combination of X ₁ , X ₂ , X ₃ , X ₄ and n in the formula [1] is the same as 1-1 to 1-64 shown in Tables 1 to 5.

≪ Specific side chain type diamine compound >

The specific side chain type diamine compound of the present invention is a diamine compound represented by the following formula [2].

[Chemical Formula 8]

In the formula [2], Y ₁ Is a divalent organic group selected from _a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, or -OCO-. Among them, a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- is preferable because it facilitates synthesis of a side chain structure. More preferably, it is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O-, or -COO-.

In formula [2], Y ₂ Is a single bond or a divalent organic group selected from - (CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 0) is preferable.

In the formula [2], Y ₃ Is a divalent organic group selected from a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or -OCO-. Among them, a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, or -OCO- is preferable because it is easy to synthesize. More preferably, it is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, or -OCO-.

In formula [2], Y ₄ Represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group may have 1 to 3 carbon atoms , An alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxyl group having 1 to 3 carbon atoms, and a fluorine atom. Among them, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexyl ring or a steroid skeleton is preferable.

In formula [2], Y ₅ Represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, and a fluorine atom. Among them, a benzene ring or a cyclohexyl ring is preferable.

In the formula [2], Y ₆ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, a fluoro-containing alkoxyl group having 1 to 18 carbon atoms, or a hydrogen atom. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

In the formula [2], n is an integer of 0 to 4. Preferably, it is an integer of 0 to 2.

Preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in the formula [2] are the same as 2-1 to 2-629 shown in Tables 6 to 47.

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, a is an integer of 1 to 10)

(In the table, a is an integer of 1 to 10)

(In the table, a is an integer of 1 to 10)

(In the table, a is an integer of 1 to 10)

(In the table, a is an integer of 1 to 10)

(Wherein, a and c are each independently an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, c is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

(In the table, b is an integer of 1 to 10)

In the formula [2], m is an integer of 1 to 4. Preferably an integer of 1 to 2.

Specifically, it is a structure represented by the following formulas [2-1] to [2-32], for example.

[Chemical Formula 9]

(Of the formulas [2-1] and [2-2], R ₁ Is _{-O-, -OCH 2 -, -CH 2} O-, -COOCH 2 -, represents a -CH ₂ OCO-, R ₂ Is an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

[Chemical formula 10]

(Of the formulas [2-3] to [2-5], R ₃ Is _{-COO-, -OCO-, -COOCH 2 -,} -CH 2 OCO-, -CH 2 O-, -OCH 2 -, or -CH ₂ - represents a, R ₄ Is an alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

(11)

(Of the formulas [2-6] and [2-7], R ₅ Represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, or -O-, and R ₆ Is a fluorine, cyano, trifluoromethane, nitro, azo, formyl, acetyl, acetoxy or hydroxyl group.

[Chemical Formula 12]

(Of the formulas [2-8] and [2-9], R ₇ Is an alkyl group having 3 to 12 carbon atoms and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer.

[Chemical Formula 13]

(Of the formulas [2-10] and [2-11], R ₈ Is an alkyl group having 3 to 12 carbon atoms and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer.

[Chemical Formula 14]

(Formula [2-12] of, A ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₃ is a 1,4-cyclohexylene group, or a 1,4-phenylene group, A ₂ is An oxygen atom, or -COO- * (provided that a bonding hand to which " * " is bonded is bonded to A ₃ ), A ₁ represents an oxygen atom or -COO- * CH ₂ ) a ₂ Lt; / RTI > A ₁ is an integer of 0 or 1, and a ₂ Is an integer of 2 to 10, a ₃ Is an integer of 0 or 1).

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

≪ Other diamine compounds >

In the present invention, other diamine compounds other than the specific diamine compound and the specific side chain diamine compound may be used in combination as a diamine component as long as the effect of the present invention is not impaired. Specific examples thereof are given below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- Diaminodiphenol, 3,5-diaminophenol, 3,5-diaminobenzyl, 2,4-diaminophenol, 3,5-diaminophenol, Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- diaminobiphenyl, Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Methane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diamino Phenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, Bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl- bis (3-aminophenyl) silane, Aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,3-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, (2,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 ' - diaminobenzophenone, 2,3'-diaminobenzophenone, Diaminonaphthalene, 1,6-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,6-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) ) Propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3- Phenylene bis (methylene)] dianiline, 3, 4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ 4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, Phenylenebis [(3-amino)] phenanthrene [(4-aminophenyl) methanone] Phenylenemethanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [ Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate) Bis (3-aminophenyl) isophthalate, bis (4-aminophenyl) isophthalate, N, N ' Bis (4-aminobenzamide), N, N '- (1,4-phenylene) bis (3-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide), N, N'- Bis (3-aminophenyl) terephthalamide, N, N'-bis (4- ) Isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'- , 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, Bis (3-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, , 2,5-diaminobenzoic acid, 1,3-bis (4-aminophenoxy) propane, 1,3-bis Bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) pentane, -Aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7 Bis (4-aminophenoxy) heptane, 1,7-bis (4-aminophenoxy) heptane, Octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) (4-aminophenoxy) undecane, 1,12- (4-aminophenoxy) undecane, 1,11- Alicyclic diamines such as bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane; aromatic diamines such as 1,3- Aminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- And aliphatic diamines such as 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

In addition, diamines having an alkyl group or a fluorine-containing alkyl group in the diamine side chain may be used as long as the effect of the present invention is not impaired.

Specifically, diamines represented by the following formulas [DA1] to [DA12] can be exemplified.

(25)

(Wherein [DA1] ~ formula [DA5] of, A ₁ is an alkyl group, or fluorine-containing alkyl group having a carbon number of less than 122).

(26)

(Wherein [DA6] ~ formula [DA11] of, A ₂ is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, represents a -CO-, or -NH- , A ₃ represents an alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkyl group).

(27)

(In the formula [DA12], p is an integer of 1 to 10).

The other diamine compounds may be used alone or in combination of two or more thereof, depending on the properties such as liquid crystal alignment property, voltage holding ratio, and accumulated charge when the liquid crystal alignment film is used.

≪ Tetracarboxylic acid dianhydride >

In order to obtain the polymer of the present invention, it is preferable to use a tetracarboxylic acid dianhydride (also referred to as a specific tetracarboxylic acid dianhydride) represented by the following formula [3] as a part of the starting material.

(28)

In the formula [3], Z ₁ Is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.

Z ₁ Specifically, it is, for example, a tetravalent group represented by the following formulas [3a] to [3j].

[Chemical Formula 29]

In the formula [3a], Z ₂ to Z ₅ Is a group selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring and may be the same or different, and Z ₆ and Z _{7 in the} formula [3g] Is a hydrogen atom or a methyl group, and may be the same or different.

Especially preferred structures of Z _{1 in} the formula [3] are those of the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] 3g].

≪ Other tetracarboxylic acid dianhydrides >

In the present invention, other tetracarboxylic acid dianhydrides other than the specific tetracarboxylic acid dianhydrides may be used in combination as long as the effect of the present invention is not impaired. Specific examples thereof are dianhydrides of the following compounds.

Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, Anthracene tetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4- Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4- Dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- Dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid, 2 , 6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid.

The other tetracarboxylic acid dianhydrides may be used alone or in combination of two or more thereof, depending on the properties such as liquid crystal alignability, voltage retention rate, and accumulated charge when the liquid crystal alignment film is used.

<Polymer>

As described above, the polymer used in the present invention is a polymer in which the diamine component containing the specific diamine compound represented by the formula [1] and the specific side chain diamine compound represented by the formula [2] and the diamine component containing the tetracarboxylic acid 2 Polyamide acid obtained by reaction of anhydride or polyimide obtained by dehydration ring closure of the polyamide acid. Both of these polyamic acids and polyimides are useful as polymers for obtaining liquid crystal alignment films.

The method for synthesizing the polymer of the present invention is not particularly limited, but a method of reacting a diamine component with a tetracarboxylic acid dianhydride is carried out in the same manner as in the synthesis of a general polyimide precursor (for example, polyamic acid) or polyimide Can be used. At this time, a tetracarboxylic acid derivative such as a tetracarboxylic acid or a tetracarboxylic acid dihalide may be used.

The liquid crystal alignment film obtained by using the polymer of the present invention has an effect of increasing the liquid crystal expansion wettability on the liquid crystal alignment film as the content ratio of the specific diamine compound in the diamine component increases, Can be provided and a display defect of orientation irregularity does not occur. Further, as the content ratio of the specific side chain type diamine compound increases, the pretilt angle of the liquid crystal can be increased.

For the purpose of enhancing the above-mentioned characteristics, the content of the specific side chain type diamine compound in the diamine component is preferably 0.01 to 99 mol based on 1 mol of the specific diamine compound. More preferably 0.1 to 50 moles, still more preferably 0.5 to 20 moles, and most preferably 0.5 to 10 moles.

In order to obtain the polymer of the present invention, it is preferable to use the specific tetracarboxylic acid dianhydride represented by the above formula [3] as the tetracarboxylic acid dianhydride. At this time, it is preferable that at least 1 mol% of the tetracarboxylic acid dianhydride is a specific tetracarboxylic acid dianhydride. Further, it is preferable that 5 mol% or more of the tetracarboxylic acid dianhydride is a specific tetracarboxylic acid dianhydride, more preferably 10 mol% or more. In addition, 100 mol% of the tetracarboxylic acid dianhydride may be a specific tetracarboxylic acid dianhydride.

In order to obtain the polyimide precursor of the present invention by the reaction of the diamine component and the tetracarboxylic acid dianhydride, a known synthesis technique can be used. Generally, this is a method of reacting a diamine component and a tetracarboxylic acid dianhydride in an organic solvent. The reaction between the diamine component and the tetracarboxylic acid dianhydride is advantageous in that it proceeds comparatively easily in an organic solvent and does not generate by-products.

The organic solvent used for the reaction of the diamine component and the tetracarboxylic acid dianhydride is not particularly limited as long as it dissolves the resulting polyimide precursor. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoric triamide methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, methyl cellosolve, methyl cellosolve, methyl cellosolve, methyl cellosolve, ethyl cellosolve, ethyl cellosolve, Propyleneglycol monobutylether, propyleneglycol monobutylether, propyleneglycol monobutylether, propyleneglycol monoacetate, ethyleneglycol monobutylether, propyleneglycol monobutylether, propyleneglycol monobutylether, propyleneglycol monobutylether, Acetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, di Ethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monoethyl ether, Propyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, N-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, propylene carbonate, propylene carbonate, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate Methoxypropionate, 3-methoxypropionate, 3-methoxypropionate, propyl 3-methoxypropionate, propyl 3-methoxypropionate, propyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination. In addition, a solvent that does not dissolve the polyimide precursor may be used in combination with the solvent insofar as the resulting polyimide precursor does not precipitate. In addition, water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, and therefore, the organic solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic acid dianhydride are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid dianhydride is dispersed or dissolved in the organic solvent A method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride and a diamine component, and the like, Either method may be used. When the diamine component or the tetracarboxylic acid dianhydride is composed of a plurality of compounds, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, or the low molecular weight compounds reacted individually may be mixed and reacted, .

The polymerization temperature at that time may be any temperature between -20 ° C and 150 ° C, preferably between -5 ° C and 100 ° C. If the concentration is too low, it becomes difficult to obtain a copolymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high and it becomes difficult to perform uniform stirring. Therefore, Is 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the number of moles of the diamine component to the total number of moles of the tetracarboxylic acid dianhydride is preferably 0.8 to 1.2. As in the case of a typical polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by dehydrocondylating a polyamic acid which is the above polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.

In the polyimide of the present invention, the dehydration / removal rate (imidization rate) of the amidic acid group does not necessarily have to be 100%, and can be arbitrarily adjusted depending on the application and purpose.

Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, and catalyst imidization in which the catalyst is added to the solution of the polyimide precursor.

The temperature at which the polyimide precursor is thermally imidized in a solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and it is preferable to carry out the removal while removing the water generated by the imidization reaction out of the system.

The catalyst imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferred because it has a suitable basicity for promoting the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

When the polyimide precursor or polyimide is recovered from the reaction solution of the polyimide precursor or polyimide, the reaction solution may be put into a poor solvent and precipitated. Examples of the poor solvent used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried at room temperature or under reduced pressure or by heating. In addition, by repeating the operation of re-dissolving the precipitated and recovered polymer in an organic solvent and repeating the precipitation and recovering 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more poor solvents selected from these are used, the purification efficiency is further increased, which is preferable.

The molecular weight of the polyimide precursor or polyimide contained in the liquid crystal alignment treatment agent of the present invention can be suitably selected according to the method of GPC (Gel Permeation Chromatography) (GPC) in consideration of the strength of the coating film obtained therefrom, the workability in forming the coating film, Is preferably from 5,000 to 1,000,000, and more preferably from 10,000 to 150,000.

&Lt; Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film, in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the above-mentioned resin component can be obtained by reacting the polymer of the present invention, that is, the specific diamine compound represented by the formula [1] and the diamine component containing the specific side chain type diamine compound represented by the formula [2] And at least one polymer selected from polymers obtained by reacting an acid dianhydride. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the present invention, all of the above-mentioned resin components may be the polymer of the present invention, and other polymers may be mixed with the polymer of the present invention. At that time, the content of the polymer other than the polymer of the present invention in the resin component is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.

Examples of such another polymer include a specific diamine compound and a polyimide precursor or polyimide not containing a specific side chain-type diamine compound as a raw material.

The liquid crystal alignment treatment agent of the present invention is preferably a crosslinkable compound which is a compound for crosslinking a polymer, specifically, an epoxy group, an isocyanate group, an oxetane group or an oxetane group for the purpose of obtaining a liquid crystal alignment film, , And a cyclocarbonate group, a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, an alkoxyl group and a lower alkoxyalkyl group, and a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, , It is preferable to introduce a crosslinkable compound having a polymerizable unsaturated bond. In addition, these substituents and polymerizable unsaturated bonds need to have two or more of the crosslinkable compounds.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl aminodiphenylene, tetra Glycidyl-m-xylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenylglycidyl ether ethane, bisphenol hexafluoroacetate diglyme Bis (2, 3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4- 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methoxyphenyl) oxypropoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl methaxylenediamine, 2- - (1- (4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane, 1,3- Phenyl) -1- (4- (1- (4 - (2,3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

(30)

Specifically, it is a crosslinkable compound represented by the following formulas [4a] to [4k], for example.

(31)

(32)

(33)

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxyl group and a lower alkoxyalkyl group include amino resins having a hydroxyl group, an alkoxyl group or a lower alkoxyalkyl group, for example, Melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethylene urea-formaldehyde resin and the like. The lower alkoxyalkyl group is, for example, an alkoxyalkyl group having 1 to 4 carbon atoms.

The crosslinkable compound may be, for example, a melamine derivative in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group, or a benzoguanamine derivative or glycoluril. The melamine derivative and the benzoguanamine derivative may be present as a dimer or trimer. These groups preferably have 3 to 6 on average of methylol groups or alkoxymethyl groups per one triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750 in which a methoxymethyl group is substituted on average 3.7 per 1 triazine ring of a commercial product, MW- (Meth) acrylates such as methoxymethylated melamine, Cymel 235, 236, 238, 212, 253, and 309 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 254, methoxymethylated butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, methoxymethylated ethoxymethylated melamine such as Cymel 1123, Guanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl-containing methoxymethylated methoxymethylated ethoxymethylated benzoate such as Cymel 1125-80 Ana min can be given (or more, produced by Mitsui mid between Ana). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluril such as Cymel 1172, and methoxymethylolglycoluril such as Powderlink 1174.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 4-bis (sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.

More specifically, it is a crosslinkable compound represented by the following formulas [6-1] to [6-48].

(34)

(35)

(36)

(37)

(38)

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxy A crosslinkable compound having three polymerizable unsaturated groups such as methoxyethyl (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, Acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bis Acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di A polymerizable unsaturated group such as acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy- Hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy- , 2- (meth) acryloyloxy It can be given a cross-linking compound having one polymerizable unsaturated group in the molecule, such as phosphoric acid ethyl ester, N- methylol (meth) acrylamide.

In addition, a compound represented by the following formula [5] may be used.

[Chemical Formula 39]

(Wherein A ₁ represents an n-valent group selected from a cyclohexyl ring, a bicyclohexyl ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, or a phenanthrene ring A ₂ is a group selected from the following formula [5a] or formula [5b], and n is an integer of 1 to 4.

(40)

The above compound is an example of a crosslinkable compound, but is not limited thereto. The crosslinkable compound contained in the liquid crystal alignment treatment agent of the present invention may be one kind or two or more kinds.

The content of the crosslinkable compound in the liquid crystal alignment treatment agent of the present invention is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the polymer of the present invention comprising the polyimide precursor or polyimide, More preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, in order to exhibit the effect of improving the alignment properties of the liquid crystal and not deteriorating the orientation properties of the liquid crystal.

It is preferable to add a nitrogen-containing heterocyclic amine compound represented by the following formulas [M1] to [M156] as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge leakage of the liquid crystal cell using the liquid crystal alignment film . The nitrogen-containing heterocyclic amine compound may be directly added to the solution of the polymer, but it is preferable to add the nitrogen-containing heterocyclic amine compound in an appropriate solvent at a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% . This solvent is not particularly limited as long as it is an organic solvent for dissolving the resin component described above.

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

(47)

The organic solvent used in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the above-mentioned resin component. For example, N-methyl-2-pyrrolidone or butyl cellosolve can be given.

The liquid crystal alignment treatment agent of the present invention preferably contains a poor solvent. The poor solvent refers to a solvent that improves film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied. Specific examples of the poor solvent include the following.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, lactic acid, methyl lactate, isobutylene, amyl acetate, butyl butylate, butyl ether, diisobutyl ketone, methylcyclohexene, Ethyl acetate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy- , 1-phenoxy Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether- Ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, and lactic acid diisobutyl ester.

These solvents may be used alone or in combination. When such a poor solvent is used, it is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, still more preferably 20 to 60% by mass, of the entire solvent contained in the liquid crystal alignment treatment agent, to be.

The liquid crystal alignment treatment agent of the present invention may contain components other than those described above. A solvent compound that improves film thickness uniformity and surface smoothness, and a compound that improves adhesion between a liquid crystal alignment film and a substrate.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, it is possible to use, for example, EF Top EF301, EF303, EF352 (manufactured by TOKEM PRODUCTS), Megafac F171, F173, R-30 (manufactured by Dainippon Ink), FLORAD FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Sapron S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass based on 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment layer and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When a compound which adheres to these substrates is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected, and if it is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

The liquid crystal alignment treatment agent of the present invention may contain a dielectric material or a conductive material for the purpose of changing electric characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effect of the present invention is not impaired.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without rubbing treatment, light irradiation or the like, or without orientation treatment in a vertical alignment application, after being applied and baked on a substrate. At this time, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. It is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed from the viewpoint of simplifying the process. In a reflection type liquid crystal display element, if it is only a substrate on one side, it can be used as opaque silicon wafer or the like. In this case, a material that reflects light such as aluminum can also be used.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but is generally industrially carried out by screen printing, offset printing, flexographic printing, inkjet or the like. As other coating methods, there are dip, roll coater, slit coater and spinner, and they may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, the solvent can be evaporated by heating means such as a hot plate at 50 to 300 DEG C, preferably 80 to 250 DEG C to form a coating film. When the thickness of the coated film after firing is too large, the power consumption of the liquid crystal display element is disadvantageously deteriorated. When the thickness is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, the thickness is preferably 5 to 300 nm, more preferably 10 to 100 Nm. When the liquid crystal is horizontally oriented or tilted, the coated film after firing is treated by rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a substrate having a liquid crystal alignment film attached thereto from the liquid crystal alignment treatment agent of the present invention is obtained by the aforementioned technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is sprayed on the liquid crystal alignment film of one substrate, and the other substrate is bonded A method in which a liquid crystal is injected under reduced pressure and a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is spread and a substrate is bonded and sealed is exemplified. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉. Further, since the liquid crystal alignment agent on the liquid crystal alignment film of the present invention has high expansion wettability, the liquid crystal can be rapidly injected without decompression.

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent of the present invention which uses a liquid crystal material in which orientation irregularities at the time of liquid crystal injection tend to occur, that is, a liquid crystal material in which a polymerizable compound polymerized by heat or ultraviolet ray irradiation is mixed, Which is obtained by polymerizing a polymerizable compound while applying a voltage to a liquid crystal display device obtained by a method of controlling the alignment direction of the liquid crystal upon driving.

This liquid crystal display element is obtained by obtaining a substrate having a liquid crystal alignment film attached thereto from the liquid crystal alignment treatment agent of the present invention by the above-mentioned technique, preparing a liquid crystal cell, and polymerizing the polymerizable compound by irradiation with heat or ultraviolet rays, And the liquid crystal display element.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is spread on the liquid crystal alignment film of one substrate, and the other substrate is bonded so that the liquid crystal alignment film surface is inward, A method in which a liquid crystal is injected under reduced pressure and a method in which liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is spread and a substrate is bonded and sealed. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉.

The liquid crystal used at this time is mixed with a polymerizable compound that is polymerized by irradiation with heat or ultraviolet rays. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. At that time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal can not be controlled. When the amount is larger than 10 parts by mass, unreacted polymerizable compound increases, .

After the liquid crystal cell is manufactured, alignment of the liquid crystal can be controlled by irradiating heat or ultraviolet rays while polymerizing alternating current or direct current to the liquid crystal cell to polymerize the polymerizable compound.

As described above, the liquid crystal display element manufactured by using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be preferably used for a liquid crystal television of high precision on a large screen.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

&Quot; Synthesis of polyimide precursor and polyimide of the present invention &quot;

(Tetracarboxylic acid dianhydride)

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

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

TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4: 2,3-2 anhydride

TDA: 3,4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride

(48)

(Specific diamine compound)

DA-1: 4- (trans-4-heptylcyclohexyl) benzamide-2 ', 4'-phenylenediamine

(49)

(Specific side chain type diamine compound)

PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

PBCH5DAB: 1,3-Diamino-4- {4- [trans- 4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy}

m-PBCH5DABz: 1,3-diamino-5- {4- [4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxymethyl}

ColDAB-1: Specific side chain type diamine compound represented by the following formula

(50)

(Other diamine compounds)

p-PDA: p-phenylenediamine

m-PDA: m-Phenylenediamine

DBA: 3,5-diaminobenzoic acid

AP18: 1,3-Diamino-4-octadecyloxybenzene

(51)

(Crosslinkable compound)

Crosslinkable compound (1): YH-434L (manufactured by Tohto Kasei Co., Ltd.) (epoxy-based crosslinkable compound)

Crosslinking compound (2): OXT-221 (manufactured by TOA Corporation) (oxetane-based crosslinking compound)

Crosslinkable compound (3): A crosslinkable compound represented by the following formula (hydroxylated phenol-based crosslinkable compound)

(52)

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(Measurement of molecular weight of polyimide precursor and polyimide)

The molecular weight of the polyimide in Synthesis Example was measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.), a column (KD-803, KD-805) Was measured as follows.

Column temperature: 50 ° C

Eluent: 30 mmol / l of lithium bromide · hydrate (LiBr · H ₂ O), 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid) as an additive, N, N'-dimethylformamide Furan (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

Standard samples for preparing calibration curves: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) (Tosoh) and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) (Polymer Laboratories).

(Measurement of imidization rate)

The imidization rate of the polyimide in the synthesis example was measured in the following manner. 20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ5 (manufactured by Kusano Kagaku)) and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) , And completely dissolved by applying ultrasonic waves. This solution was subjected to proton NMR measurement at 500 MHz using an NMR meter (JNW-ECA500) (manufactured by Nippon Denshoku). A proton derived from a structure which does not change before and after imidization is defined as a reference proton and the proton peak integrated value derived from the NH group of the amide acid which appears in the vicinity of 9.5 to 10.0 ppm and the peak integrated value of this proton is used And was obtained by the following equation.

Imidization ratio (%) = (1 -? X / y) x 100

In the above formula, x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? Is the NH of the amide acid in the case of the polyamic acid (the imidization rate is 0% The ratio of the number of reference protons to one protopertone.

&Lt; Synthesis Example 1 &

A solution of BODA (7.50 g, 30.0 mmol), DA-1 (1.53 g, 3.75 mmol), PCH7DAB (5.71 g, 15.0 mmol), p-PDA (2.03 g, 18.8 mmol) (1.47 g, 7.50 mmol) and NMP (24.8 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid having a resin solid content concentration of 24.9% by mass To obtain a solution (1). This polyamic acid had a number average molecular weight of 25,400 and a weight average molecular weight of 73,300.

&Lt; Synthesis Example 2 &

NMP was added to the polyamide acid solution (1) (20.2 g) having a resin solid content concentration of 24.9% by mass obtained in Synthesis Example 1 and diluted to 6% by mass, acetic anhydride (2.47 g) and pyridine (1.88 g), and the mixture was reacted at 80 DEG C for 4 hours. The reaction solution was poured into methanol (320 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (2). The imidization ratio of the polyimide was 55%, the number average molecular weight was 21,200, and the weight average molecular weight was 54,400.

&Lt; Synthesis Example 3 &

BODA (6.89 g, 27.5 mmol), DA-1 (1.40 g, 3.43 mmol), PBCH5DAB (4.47 g, 10.3 mmol), DBA (3.14 g, 20.6 mmol) were mixed in NMP (28.6 g) , CBDA (1.35 g, 6.88 mmol) and NMP (23.4 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 24.9% by mass .

To the obtained polyamic acid solution (20.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.53 g) and pyridine (3.31 g) were added as imidation catalysts and reacted at 90 캜 for 3 hours . This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (3). The polyimide had an imidization rate of 80%, a number average molecular weight of 19,600 and a weight average molecular weight of 49,700.

&Lt; Synthesis Example 4 &

To a solution of BODA (3.99 g, 15.9 mmol), DA-1 (1.86 g, 4.56 mmol), m-PBCH5 DAABz (2.54 g, 5.69 mmol), DBA (1.91 g, 12.6 mmol) (1.34 g, 6.83 mmol) and NMP (15.7 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass &Lt; / RTI &gt;

To the resulting polyamic acid solution (20.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.51 g) and pyridine (3.30 g) were added as an imidation catalyst and reacted at 90 deg. C for 3 hours . The reaction solution was poured into methanol (320 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (4). The imidization ratio of the polyimide was 81%, the number average molecular weight was 20,100, and the weight average molecular weight was 50,200.

&Lt; Synthesis Example 5 &

PDA (2.49 g, 23.0 mmol) was reacted with NMP (27.9 g, 23.3 mmol), BODA (7.09 g, 28.3 mmol), DA- 1 (2.89 g, 7.09 mmol), ColDAB- ) And reacted at 80 DEG C for 4 hours. Then, CBDA (1.39 g, 7.09 mmol) and NMP (22.5 g) were added and reacted at 40 DEG C for 5 hours to obtain a polyamide having a resin solid content concentration of 24.6% To obtain an acid solution.

To the resulting polyamic acid solution (20.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (2.50 g) and pyridine (1.93 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 占 폚 to obtain a polyimide powder (5). The imidization ratio of the polyimide was 55%, the number average molecular weight was 21,200, and the weight average molecular weight was 54,200.

&Lt; Synthesis Example 6 &

PCA7DAB (2.33 g, 6.12 mmol), p-PDA (0.83 g, 7.68 mmol) was added to a solution of TCA (3.43 g, 15.3 mmol), DA-1 (0.62 g, 1.52 mmol) And the mixture was reacted at 40 DEG C for 7 hours to obtain a polyamic acid solution (6) having a resin solid content concentration of 25.0 mass%. This amic acid had a number average molecular weight of 25,900 and a weight average molecular weight of 69,900.

&Lt; Synthesis Example 7 &

(1.80 g, 4.16 mmol), m-PDA (0.90 g, 8.32 mmol) was added to NMP (19.2 g) And the mixture was reacted at 40 DEG C for 7 hours to obtain a polyamic acid solution having a resin solid content concentration of 24.9 mass%.

NMP was added to the resultant polyamic acid solution (20.5 g) to dilute it to 6 mass%, acetic anhydride (2.52 g) and pyridine (1.95 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (7). The imidization ratio of the polyimide was 52%, the number average molecular weight was 18,800, and the weight average molecular weight was 48,300.

&Lt; Synthesis Example 8 &

BODA (1.21 g, 4.84 mmol), DA-1 (1.31 g, 3.21 mmol), PBCH5DAB (2.09 g, 4.83 mmol) DBA (1.23 g, 8.08 mmol) were mixed in NMP (13.8 g) (2.53 g, 11.3 mmol) and NMP (11.3 g) were added and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass .

NMP was added to the obtained polyamic acid solution (20.0 g) to dilute to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.32 g) were added as imidation catalysts and reacted at 90 ° C for 3 hours . The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (8). The imidization ratio of the polyimide was 82%, the number average molecular weight was 21,300, and the weight average molecular weight was 49,900.

&Lt; Synthesis Example 9 &

(1.22 g, 4.88 mmol), DA-1 (0.66 g, 1.62 mmol), ColDAB-1 (1.60 g, 3.25 mmol), m-PDA (1.23 g, 11.4 mmol) ) And reacted at 80 DEG C for 1.5 hours. Then, TCA (2.55 g, 11.4 mmol) and NMP (10.0 g) were added and reacted at 40 DEG C for 7 hours to obtain a polyamide having a resin solid content concentration of 24.4% by mass To obtain an acid solution.

NMP was added to the obtained polyamic acid solution (20.5 g) to dilute to 6 mass%, acetic anhydride (2.52 g) and pyridine (1.91 g) were added as an imidization catalyst and reacted at 80 ° C for 3.5 hours. The reaction solution was poured into methanol (310 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (9). The imidization ratio of the polyimide was 53%, the number average molecular weight was 22,800, and the weight average molecular weight was 56,100.

&Lt; Synthesis Example 10 &

(1.49 g, 4.96 mmol), DA-1 (1.35 g, 3.31 mmol), PCH7DAB (2.52 g, 6.62 mmol), DBA (1.01 g, 6.64 mmol) were mixed in NMP (14.2 g) , CBDA (2.27 g, 11.6 mmol) and NMP (11.7 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass% .

NMP was added to the resultant polyamic acid solution (20.1 g) to dilute to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.33 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (310 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 占 폚 to obtain a polyimide powder (10). The polyimide had an imidization rate of 76%, a number average molecular weight of 18,200 and a weight average molecular weight of 47,800.

&Lt; Synthesis Example 11 &

PDA (2.20 g, 20.3 mmol) was mixed in NMP (25.0 g), and the mixture was reacted at 80 ° C for 4 hours. Then, CBDA (1.33 g, 6.78 mmol) and NMP (20.5 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution (11) having a resin solid content concentration of 25.4 mass%. This polyamic acid had a number average molecular weight of 24,400 and a weight average molecular weight of 69,400.

&Lt; Synthesis Example 12 &

NMP was added to the polyamic acid solution (11) (20.0 g) having a resin solid content concentration of 25.4% by mass obtained in Synthesis Example 11 and diluted to 6% by mass, acetic anhydride (2.45 g) and pyridine (1.86 g), and the mixture was reacted at 80 DEG C for 4 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (12). The imidization ratio of the polyimide was 56%, and the number average molecular weight was 19,800 and the weight average molecular weight was 51,900.

&Lt; Synthesis Example 13 &

P-PDA (1.82 g, 16.8 mmol) was added to a solution of BODA (6.74 g, 26.9 mmol), DA-1 (1.37 g, 3.36 mmol), AP18 (5.07 g, 13.5 mmol) (1.32 g, 6.73 mmol) and NMP (22.8 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 24.7% by mass &Lt; / RTI &gt;

To the resulting polyamic acid solution (20.2 g) was added NMP and diluted to 6 mass%. Acetic anhydride (2.51 g) and pyridine (1.92 g) were added as an imidization catalyst and reacted at 80 ° C for 3.5 hours. The reaction solution was poured into methanol (310 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (13). The imidization ratio of the polyimide was 55%, the number average molecular weight was 20,800, and the weight average molecular weight was 50,100.

&Lt; Synthesis Example 14 &

PDA (2.02 g, 18.7 mmol) was mixed in NMP (24.0 g), and the mixture was reacted at 80 ° C for 4 hours to obtain a mixture of BODA (6.23 g, 24.9 mmol), DA-1 (5.07 g, 12.4 mmol) , CBDA (1.22 g, 6.22 mmol) and NMP (19.6 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

To the resulting polyamic acid solution (20.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (2.48 g) and pyridine (1.90 g) were added as an imidation catalyst and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (14). The imidization ratio of the polyimide was 55%, and the number average molecular weight was 25,300 and the weight average molecular weight was 62,100.

&Lt; Synthesis Example 15 &

BODA (1.12 g, 4.48 mmol), ColDAB-1 (1.47 g, 2.98 mmol) and m-PDA (1.29 g, 11.9 mmol) were mixed in NMP (10.8 g) and reacted at 80 ° C for 2 hours , TCA (2.34 g, 10.4 mmol) and NMP (8.42 g) were added and reacted at 40 ° C for 8 hours to obtain a polyamic acid solution having a resin solid concentration of 24.4% by mass.

NMP was added to the obtained polyamic acid solution (20.0 g) to dilute to 6 mass%, acetic anhydride (2.43 g) and pyridine (1.85 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (15). The imidization ratio of the polyimide was 52%, the number average molecular weight was 19,200, and the weight average molecular weight was 51,900.

Table 48 shows the polyamic acid and polyimide of the present invention.

&Quot; Production of liquid crystal alignment treatment agent of the present invention &quot;

In the following Examples 1 to 13 and Comparative Examples 1 to 5, a production example of a liquid crystal alignment treatment agent is described. The liquid crystal alignment treatment agent of the present invention used for evaluation of each liquid crystal alignment treatment agent is shown in Tables 49 and Lt; tb &gt;

Production of Liquid Crystal Alignment Film, Evaluation of Expanding Wettability of Liquid Crystal, Production of Liquid Crystal Cell, and Evaluation of Liquid Crystal Orientation and Pretilt Angle are as follows. Table 51 to Table 54 show the properties of the respective liquid crystal alignment treatment agents obtained in Examples 1 to 13 and Comparative Examples 1 to 5.

&Lt; Production of liquid crystal alignment film &

The liquid crystal alignment treatment agent was spin-coated on the ITO surface of the substrate having the 3 × 4 cm ITO electrode attached thereto and heat-treated on a hot plate at 80 ° C. for 5 minutes and at 220 ° C. for 30 minutes in a thermocycling type clean oven, A substrate with a polyimide liquid crystal alignment film was obtained.

&Quot; Evaluation of expansion wettability of liquid crystal &quot;

Using liquid crystal alignment film obtained in the above-mentioned &quot; Production of Liquid Crystal Orientation Film &quot;, using liquid crystal MLC-6608 (Merck Japan) and fully automatic contact angle CA-W (manufactured by Kyowa Interface Science Co., Ltd.) Wettability was evaluated. In the evaluation, the contact angle of the liquid crystal after 10 seconds after the liquid crystal was immersed in the liquid crystal alignment film was measured, and the lower the contact angle of the liquid crystal was, the higher the liquid crystal expansion wettability on the liquid crystal alignment film was.

&Quot; Production of liquid crystal cell &quot;

The coated film surface of the substrate with the liquid crystal alignment film attached thereto obtained in the above-mentioned &quot; Production of Liquid Crystal Alignment Film &quot; was coated with a roll diameter of 120 mm, a rubbing apparatus of rayon cloth at 300 rpm, a moving speed of 20 mm / sec, . Two substrates on which the liquid crystal alignment film was adhered were prepared, the liquid crystal alignment film surface was set inward, and the spacers having a size of 6 mu m were interposed therebetween so that the rubbing directions were opposite to each other. did. MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a nematic liquid crystal cell having an anti-ferroleol orientation.

&Quot; Evaluation of liquid crystal orientation and pretilt angle &quot;

The liquid crystal cell obtained in the above-mentioned &quot; Production of Liquid Crystal Cell &quot; was measured at room temperature using the pretilt angle measuring device PAS-301 (manufactured by ELSICON) after the initial injection of the liquid crystal and after the heating treatment at 95 DEG C for 5 minutes. The alignment uniformity of the liquid crystal was confirmed by observing a polarizing microscope for each condition of the liquid crystal cell. No liquid crystal cell was shaved or defective in orientation due to the rubbing treatment, and the liquid crystal was uniformly oriented.

&Lt; Example 1 &gt;

Polyamic acid solution (1) (10.5 g), NMP (8.50 g) and BCS (24.6 g) having a resin solid content concentration of 24.9% by mass obtained in Synthesis Example 1 were mixed at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent ). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 2 &gt;

The polyimide powder (2) (2.52 g) obtained in Synthesis Example 2, NMP (22.3 g) and BCS (19.7 g) were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treating agent (2). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 3 &gt;

The polyimide powder (3) (2.50 g), NMP (24.0 g) and BCS (17.6 g) obtained in Synthesis Example 3 were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treating agent (3). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

<Example 4>

The polyimide powder (4) (2.51 g) obtained in Synthesis Example 4, NMP (26.1 g) and BCS (15.7 g) were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treating agent (4). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 5 &gt;

The polyimide powder (5) (2.50 g) obtained in Synthesis Example 5, NMP (29.9 g) and BCS (11.8 g) were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 6 &gt;

(11.0 g), NMP (11.1 g) and BCS (23.7 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 6 were mixed at 25 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent 6 . No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 7 &gt;

The polyimide powder (7) (2.51 g) obtained in Synthesis Example 7, NMP (30.0 g) and BCS (11.8 g) were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 8 &gt;

The polyimide powder (8) (2.50 g) obtained in Synthesis Example 8, NMP (26.0 g) and BCS (15.7 g) were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (8). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 9 &gt;

The polyimide powder (9) (2.50 g) obtained in Synthesis Example 9, NMP (31.9 g) and BCS (9.80 g) were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (9). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 10 &gt;

The polyimide powder (10) (2.53 g) obtained in Synthesis Example 10, NMP (30.3 g) and BCS (11.9 g) were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (10). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 11 &gt;

The polyimide powder (2) (2.50 g), NMP (22.1 g), BCS (19.6 g) and the crosslinkable compound (1) (0.25 g) obtained in Synthesis Example 2 were mixed at 25 占 폚 for 12 hours, (11). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 12 &gt;

The polyimide powder (3) (2.50 g), NMP (24.0 g), BCS (17.6 g) and the crosslinkable compound (2) (0.50 g) obtained in Synthesis Example 3 were mixed at 25 占 폚 for 12 hours, (12). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Example 13 &gt;

The polyimide powder (3) (2.51 g), NMP (24.1 g), BCS (17.7 g) and the crosslinkable compound (3) (0.25 g) obtained in Synthesis Example 3 were mixed at 25 占 폚 for 12 hours, (13). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Comparative Example 1 &

The polyamic acid solution 11 (10.0 g), NMP (8.50 g) and BCS (23.9 g) having a resin solid content concentration of 25.4% by mass obtained in Synthesis Example 11 were mixed at 25 占 폚 for 6 hours, . No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Comparative Example 2 &

The polyimide powder (12) (2.50 g), NMP (22.1 g) and BCS (19.6 g) obtained in Synthesis Example 12 were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treating agent (15). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Comparative Example 3 &

The polyimide powder (13) (2.51 g) obtained in Synthesis Example 13, NMP (24.1 g) and BCS (17.7 g) were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent 16. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Comparative Example 4 &

The polyimide powder (14) (2.50 g) obtained in Synthesis Example 14, NMP (22.1 g) and BCS (19.6 g) were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent (17). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

&Lt; Comparative Example 5 &

The polyimide powder (15) (2.50 g), NMP (29.9 g) and BCS (11.8 g) obtained in Synthesis Example 15 were mixed at 25 占 폚 for 8 hours to obtain a liquid crystal alignment treatment agent 18. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that it was a homogeneous solution.

As can be seen from the above results, in the liquid crystal alignment layers obtained from the liquid crystal alignment treatment agents of Examples 1 to 13, the pretilt angle of the liquid crystal was high, and the liquid crystal expansion wettability on the liquid crystal alignment layer was high.

In Comparative Example 1, Comparative Example 2 and Comparative Example 5 using only a specific side chain diamine compound, the pretilt angle of the liquid crystal was high, but the liquid crystal expansion wettability on the liquid crystal alignment film was low. In Comparative Example 3, in which a specific diamine compound and a side chain type diamine compound other than the specific side chain type diamine compound were used, the pretilt angle of the liquid crystal was high, but the result of low expansion wettability of the liquid crystal on the liquid crystal alignment film was . In addition, in Comparative Example 4 using only a specific diamine compound, the liquid crystal extended wettability on the liquid crystal alignment film was high, but the pretilt angle of the liquid crystal was low.

Industrial availability

The liquid crystal alignment treatment agent of the present invention can obtain a liquid crystal alignment film having a high expansion wettability of liquid crystal on the liquid crystal alignment film. In particular, in order to obtain a high pretilt angle, the effect is obtained even when a large amount of diamine components having side chains is used. Therefore, by using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal display device which has high production efficiency in production of a liquid crystal display element and does not cause defective display in orientation irregularity. As a result, it can be preferably used for a high-definition liquid crystal television with a large screen, and is useful for a TN device, an STN device, and a TFT liquid crystal device, particularly a vertically aligned liquid crystal display device.

Further, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal display element in which alignment unevenness at the time of liquid crystal injection tends to occur, that is, a liquid crystal material in which a polymerizable compound polymerized by heat or ultraviolet ray irradiation is mixed And is also useful for a liquid crystal display element obtained by a method of controlling the alignment direction of liquid crystal during driving with a polymer obtained by polymerizing a liquid crystal layer while applying a voltage thereto.

Claims (11)

A liquid crystal alignment treatment agent comprising a polymer obtained by reacting a diamine compound represented by the following formula [1] and a diamine compound containing a diamine compound represented by the following formula [2] with a tetracarboxylic acid dianhydride.

(Wherein X ₁ is a divalent organic group selected from -NHCO-, -N (CH ₃ ) CO-, -CONH- and -CON (CH ₃ ) -, X ₂ is a single bond, benzene Or a cyclohexyl ring, X ₃ is a divalent organic group selected from a benzene ring or a cyclohexyl ring, X ₄ is a divalent organic group selected from a cyclohexyl ring or a benzene ring X ₅ is selected from an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms, and n is an integer of 1 to 4 Integer).

(Formula [2], Y ₁ is _{-O-, -CH 2 O-, - (} CH 2) a - (a is an integer of 1 ~ 10), -COO-, -OCO- , or a single bond in Y ₂ is a single bond or a divalent organic group selected from - (CH ₂ ) _b - (b is an integer of 1 to 10), Y ₃ is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, or -OCO-, Y ₄ is a benzene ring, cyclohexyl Or a divalent cyclic group selected from a heterocyclic ring or a divalent cyclic group having 12 to 25 carbon atoms and having a steroid skeleton, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, and a fluorine atom, and Y ₅ is a cyclohexyl ring, a benzene ring, And any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a divalent cyclic group having 1 to 3 carbon atoms A fluorine-containing alkoxyl group having 1 to 18 carbon atoms, and n is an integer of 0 to 4, Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, An alkoxyl group, a fluorine-containing alkoxyl group having 1 to 18 carbon atoms or a hydrogen atom, and m is an integer of 1 to 4). The method according to claim 1,
In the formula [1], X ₁ Is -NHCO-. The method according to claim 1,
Wherein the tetracarboxylic acid dianhydride is a tetracarboxylic acid dianhydride represented by the following formula [3].

(In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.) The method of claim 3,
The following equation is Z ₁ [3a] ~ formula [3j] The liquid crystal alignment treating agent represented by the structure.

(Formula [3a] of, Z ₂ ~ Z ₅ is a group, and the same or different and each is selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, the formula [3g], Z ₆ and Z ₇ are Hydrogen An atom, or a methyl group, which may be the same or different). The method according to claim 1,
A liquid crystal aligning treatment agent containing a crosslinkable compound having at least one substituent selected from the group consisting of an epoxy group, an oxetane group, an isocyanate group and a cyclocarbonate group, a group comprising a hydroxyl group, a hydroxyalkyl group, an alkoxyl group and a lower alkoxyalkyl group , Or a crosslinkable compound having a polymerizable unsaturated bond. The method according to claim 1,
Wherein the polymer in the liquid crystal alignment treatment agent is a polyimide obtained by dehydrating and ring-closure of polyamic acid. The method according to claim 1,
A liquid crystal alignment treatment agent containing 5 to 60 mass% of a poor solvent in the liquid crystal alignment treatment agent. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 7. 9. A liquid crystal display element having the liquid crystal alignment film according to claim 8. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 7 as a liquid crystal alignment film in which a liquid crystal material in which a polymerizable compound polymerized by irradiation with heat or ultraviolet light is mixed is used, And a polymer obtained by polymerizing the polymerizable compound while controlling the alignment direction of the liquid crystal at the time of driving the liquid crystal alignment film. A liquid crystal display device comprising the liquid crystal alignment film according to claim 10, wherein a liquid crystal material in which a liquid crystal polymerizable compound polymerized by heat or ultraviolet light irradiation is mixed is used to polymerize the polymerizable compound while applying a voltage to the liquid crystal layer A liquid crystal display element obtained by a method of controlling the alignment direction of liquid crystal during driving.