KR20160003204A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

A liquid crystal alignment film, a liquid crystal display element, and a liquid crystal display element which can improve the adhesion between the sealant and the liquid crystal alignment film and suppress the occurrence of display irregularity near the frame of the liquid crystal display element even under high temperature and high humidity conditions, Thereby providing an orientation treatment agent.
A liquid crystal alignment containing an isocyanate group-containing additive, an additive containing an amino group and a hydroxy group, and a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component, and at least one polymer selected from the group consisting of polyimide Treatment agent.

Description

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

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

A film made of an organic material such as a polymer material has attracted attention for ease of formation and insulation performance and is widely used as an interlayer insulating film and a protective film in the field of electronic devices. Among them, in a liquid crystal display element well known as a display device, an organic film made of polyimide is used as a liquid crystal alignment film.

The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. Particularly, as the liquid crystal display element becomes finer and finer, it is required to suppress the display defects accompanying the contrast of the liquid crystal display element and long-term use.

In the case of using polyimide as a liquid crystal alignment film, there has been proposed a liquid crystal alignment process using a liquid crystal alignment treatment agent to which an alkoxysilane compound is added as a method for increasing the liquid crystal alignability and making display defect hardly occur in the periphery of the liquid crystal display screen, (For example, refer to Patent Document 1 or 2).

Japanese Patent Application Laid-Open No. 61-171762 Japanese Patent Application Laid-Open No. 11-119226

2. Description of the Related Art Recently, liquid crystal display devices have been used for mobile applications such as smart phones and cellular phones. In these applications, in order to secure as much display surface as possible, it is necessary to make the width of the sealing agent used for bonding between the substrates of the liquid crystal display element smaller than the conventional one. For the reasons described above, it is also required that the sealing agent is drawn at the position where the sealant is in contact with the end portion of the liquid crystal alignment film having poor adhesiveness to the sealant or the liquid crystal alignment film. In such a case, water is easily mixed between the sealant and the liquid crystal alignment film by use under high temperature and high humidity conditions, and display irregularity occurs near the frame of the liquid crystal display element.

Further, when water is mixed in the liquid crystal display element, the voltage holding ratio, which is one of the electric characteristics of the liquid crystal display element, is significantly lowered, and a burn defect (also called line burn-in), which is one of the display defects of the liquid crystal display element, So that a liquid crystal display element having high reliability can not be obtained.

It is therefore an object of the present invention to provide a liquid crystal display device having the above characteristics and capable of enhancing adhesion between a sealing agent and a liquid crystal alignment film and suppressing occurrence of display unevenness in the vicinity of a frame of a liquid crystal display element under high temperature and high humidity conditions, A liquid crystal alignment treatment agent capable of providing a liquid crystal alignment film capable of inhibiting the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film.

As a result of intensive studies, the present inventors have found that a liquid crystal alignment treatment agent containing a compound having a specific structure and at least one polymer selected from a polyimide precursor or a polyimide is very effective for achieving the above object, And has reached the completion of the invention.

That is, the present invention has the following points.

(1) A liquid crystal alignment treatment agent characterized by comprising the following components (A), (B) and (C).

Component (A): A compound represented by the following formula [1].

Component (B): A compound represented by the following formula [2].

Component (C): at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

[Chemical Formula 1]

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring and X ² represents a group represented by the following formulas [ [1-6].)

(2)

(Wherein A ¹ represents a hydrogen atom or a benzene ring, A ² represents a single bond, or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, A ³ represents 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 fluoro-containing alkoxyl group having 1 to 18 carbon atoms.

(3)

(W ¹ represents an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, W ² represents a single bond, -O-, -NH-, -CO-, -COO-, -OCO-, -NH-, _{N (CH 3) -, -NHCO-} , -N (CH 3) CO-, -CONH-, -CON (CH 3) -, -S- or -SO ₂ - represents, W ³ represents a single bond, a benzene W ⁴ is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N (CH ₃ ) -, -NHCO-, -N (CH ₃ ) CO-, -CONH-, -CON (CH ₃ ) -, -S- or -SO ₂ -, W ⁵ represents an organic group having a single bond, an aliphatic hydrocarbon group or a nonaromatic cyclic hydrocarbon group, n Represents an integer of 1 to 5).

(2) The liquid crystal alignment treating agent according to (1), wherein X ^{1 in} the formula (1) is an alkylene group having 1 to 10 carbon atoms.

(3) The liquid crystal alignment described in (1) or (2), wherein X ² in the formula [1] is a structure selected from the formulas [1-1], [1-2] and [ Treatment agent.

(4) The liquid crystal composition according to any one of (1) to (3) above, wherein W ^{1 in} the formula (2) is a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring or a bicyclohexyl ring. Orientation treatment agent.

(5) The liquid crystal alignment treatment agent according to any one of (1) to (4), wherein W ² in the formula [2] is a single bond, -O- or -OCO-.

(6) The liquid crystal alignment treating agent according to any one of (1) to (5), wherein W ^{3 in} the formula [2] is a single bond or a benzene ring.

(7) The liquid crystal alignment treatment agent according to any one of (1) to (6), wherein W ⁴ in the formula [2] is a single bond, -O-, -NH- or -CONH-.

(8) The liquid crystal alignment described in any one of (1) to (7) above, wherein W ⁵ in the formula [2] is a single bond or a linear or branched alkylene group or a cyclohexane ring having 1 to 10 carbon atoms Treatment agent.

(9) The liquid crystal display according to any one of (1) to (8) above, wherein the diamine component in the polymer of the component (C) comprises at least one diamine compound having a structure represented by the following formula [ Orientation treatment agent.

[Chemical Formula 4]

(Y represents a substituent selected from the following formulas [3-1] to [3-6], and m represents an integer of 1 to 4.)

[Chemical Formula 5]

(a represents an integer of 0 to 4, and b represents an integer of 0 to 4).

Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ² represents a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15), Y ³ is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15) ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 and having a steroid skeleton, The arbitrary 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms, , Y ⁵ represents a divalent cyclic group selected from benzene ring, a cyclohexane ring and a heterocyclic ring, any of the hydrogen atoms on these cyclic group having 1 3 alkyl group, carbon atoms and may be substituted with one to three of an alkoxy group, fluorine-containing alkyl group, fluorine-containing C 1 -C 3 alkoxy group or a fluorine atom of 1 to 3 carbon atoms, n is an integer of 0 ~ 4, Y ⁶ Represents 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.

Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.

Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group of 1 to 12 carbon atoms.

And Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.

(10) The liquid crystal alignment treating agent according to any one of (1) to (9), wherein the tetracarboxylic acid component in the polymer of the component (C) contains a compound represented by the following formula [4].

[Chemical Formula 6]

(Z ¹ is a group of the structure is selected from formula [4a] ~ formula [4j].)

(7)

(Z ² to Z ^{5 each} represent 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 each represent a hydrogen atom or a methyl group,

(11) The liquid crystal alignment treatment agent according to any one of (1) to (10), wherein the polymer of the component (C) is a polyimide obtained by dehydrating and ring-closing a polyamic acid.

(12) The liquid crystal alignment treating agent according to any one of (1) to (11), wherein the amount of the component (A) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (C).

(13) The liquid crystal alignment treating agent according to any one of (1) to (12), wherein the amount of the component (B) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (C).

(14) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of (1) to (13).

(15) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent as described in any one of (1) to (13) above and using an inkjet method.

(16) A liquid crystal display element having the liquid crystal alignment film according to (14) or (15) above.

(17) A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound capable of polymerizing by at least one of active energy rays and heat between the pair of substrates, The liquid crystal alignment film according to (14) or (15), which is used for a liquid crystal display device produced by polymerizing the polymerizable compound while applying a voltage between electrodes.

(18) A liquid crystal display element having the liquid crystal alignment film according to (17) above.

(19) A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, The liquid crystal alignment film according to (14) or (15) above, which is used for a liquid crystal display device produced by polymerizing the polymerizable group while applying a voltage between the liquid crystal alignment layer and the liquid crystal alignment layer.

(20) A liquid crystal display element having the liquid crystal alignment film according to (19) above.

According to the present invention, a liquid crystal alignment treatment agent containing a compound having a specific structure and at least one polymer selected from the group consisting of a polyimide precursor and a polyimide improves the adhesion between the sealant and the liquid crystal alignment film, It is possible to form a liquid crystal alignment film capable of suppressing the occurrence of display irregularities in the vicinity of the frame of the liquid crystal display element and suppressing a decrease in the voltage holding ratio. That is, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be preferably used for a liquid crystal television having a large screen and a high definition.

Hereinafter, the present invention will be described in detail.

The present invention is a liquid crystal alignment treatment agent containing the following components (A), (B) and (C), a liquid crystal alignment film obtained using the liquid crystal alignment treatment agent, and further a liquid crystal display device having the liquid crystal alignment film.

Component (A): A compound represented by the following formula [1] (also referred to as a specific isocyanate compound).

Component (B): A compound represented by the following formula [2] (also referred to as a specific amine compound).

Component (C): at least one polymer (also referred to as a specific polymer) selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

[Chemical Formula 8]

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring and X ² represents a group represented by the following formulas [ [1-6].)

[Chemical Formula 9]

(Wherein A ¹ represents a hydrogen atom or a benzene ring, A ² represents a single bond, or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, A ³ represents 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 fluoro-containing alkoxyl group having 1 to 18 carbon atoms.

[Chemical formula 10]

. (W ¹ represents an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group W ² is a single bond, -O-, -NH-, -CO-, -COO- , -OCO-, -NH-, - _{N (CH 3) -, -NHCO-} , -N (CH 3) CO-, -CONH-, -CON (CH 3) -, -S- or -SO ₂ -. W ³ represents a single bond, a benzene W ⁴ is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N (CH ₃ ) -, -NHCO-, -N (CH _{3) CO-, -CONH-, -CON (} CH 3) -, -S- or -SO ₂ -. W represents a ⁵ denotes an organic group having a single bond, an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon, n Represents an integer of 1 to 5).

In the liquid crystal alignment treatment agent of the present invention, the primary amino group in the specific amine compound is preferably a compound having a carboxyl group or a carboxy ester group in a specific polymer, or a compound having an amide bond Or a bonding reaction involving ring-opening of an imide group to an imide group in a specific polymer is considered to be performed. That is, it is considered that the specific amine compound is salt-formed or chemically bonded to a specific polymer via the primary amino group with respect to the specific polymer.

It is also believed that the OCN group (also referred to as isocyanate group) of the specific isocyanate compound contained in the liquid crystal alignment treatment agent is chemically bonded to the terminal OH group (also referred to as hydroxyl group) of a specific amine compound salt-formed or chemically bonded to a specific polymer. That is, although it is a simple method in which the preparation of the liquid crystal alignment treatment agent is mixed in an organic solvent, in the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, the specific isocyanate compound and the specific polymer are efficiently bonded do.

It is also known that the double bond moieties of the formulas [1-1] to [1-6] as X ² in a specific isocyanate compound react by irradiation with heat or ultraviolet rays. These double bond sites are also included in the compounds contained in the sealant.

Therefore, when the liquid crystal alignment treatment agent of the present invention is used, the double bond sites in the liquid crystal alignment film and the compound in the sealant are chemically reacted by the curing step of the sealant when the liquid crystal display element is manufactured, Thus, the sealant and the liquid crystal alignment film are chemically bonded to each other, and the adhesiveness of the sealant and the liquid crystal alignment film can be enhanced.

As described above, the liquid crystal alignment treatment agent containing a specific isocyanate compound, a specific amine compound and a specific polymer of the present invention has high adhesiveness to a sealant, and under the high temperature and high humidity conditions, occurrence of display unevenness near the frame of the liquid crystal display element It is possible to form a liquid crystal alignment film capable of suppressing the deterioration of the voltage holding ratio and suppressing the decrease of the voltage holding ratio.

≪ Specific isocyanate compound >

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

(11)

(Wherein X ¹ and X ² have the same meanings as defined above).

[Chemical Formula 12]

(A ¹ , A ² and A ³ are as defined above.)

In the formula [1], X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring. Among them, an alkylene group having 1 to 10 carbon atoms is preferable, and an alkylene group having 1 to 5 carbon atoms is more preferable.

In the formula [1], X ² is a structure selected from the formulas [1-1] to [1-6].

In the formula [1-3], A ¹ represents a hydrogen atom or a benzene ring. Among them, a hydrogen atom is preferable.

In the formula [1-6], A ² is a single bond or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. Among them, a single bond, a benzene ring, a cyclohexane ring or a biphenyl ring is preferable.

In the formula [1-6], A ³ 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. Among them, an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms is preferable.

In the formula [1], X ² is preferably a structure represented by the formula [1-1], the formula [1-2], the formula [1-4] or the formula [1-6].

More specifically, the structure represented by the following formulas [1a] to [1e] can be mentioned.

[Chemical Formula 13]

(X ³ represents an alkylene group, a benzene ring or a cyclohexane ring of 1 to 5 carbon atoms, and X ⁴ represents an alkylene group, a benzene ring or a cyclohexane ring of 1 to 5 carbon atoms.)

[Chemical Formula 14]

(X ⁵ represents an alkylene group, a benzene ring or a cyclohexane ring having 1 to 5 carbon atoms, X ⁶ represents an alkylene group, a benzene ring or a cyclohexane ring having 1 to 5 carbon atoms, X ⁷ is alkyl of 1 to 5 carbon atoms group, a represents a benzene ring or a cyclohexane ring, X ⁸ is a single bond, represents a benzene ring, a cyclohexane ring or a biphenyl ring, X ⁹ represents an alkyl group or an alkoxy group having a carbon number of 1-9 of the carbon number of 1-9. )

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

≪ Specific amine compound >

The specific amine compound of the present invention is a compound represented by the following formula [2].

[Chemical Formula 15]

In formula [2], W ¹ is an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group in order that the primary amino group contained in the specific amine compound easily undergoes salt formation or binding reaction with a specific polymer.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, a branched alkylene group, and a hydrocarbon group having an unsaturated bond. Among them, a linear or branched alkylene group having 1 to 20 carbon atoms is preferable. More preferably a linear or branched alkylene group having 1 to 15 carbon atoms, and still more preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

Specific examples of the non-aromatic cyclic hydrocarbon group include a cyclopropane ring, a cyclopentane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclooctane ring, A cyclohexadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cyclooctadecane ring, a tricyclohexane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, A tricyclodecanoic acid ring, a bicyclohexyl ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring and the like. Among them, a ring having 3 to 20 carbon atoms is preferable. More preferably a ring of 3 to 15 carbon atoms, more preferably a ring of 6 to 12 carbon atoms, and is a non-aromatic cyclic hydrocarbon group. Specifically, it is a cyclohexane ring or a bicyclohexyl ring, and particularly preferably a cyclohexane ring.

In formula [2], W ² represents a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N (CH ₃ ) -, -NHCO-, -N (CH ₃ ) _{CO-, -CONH-, -CON (CH 3} ) -, -S- or -SO ₂ - a. Among them, a single bond, -O-, -NH-, -COO-, -OCO-, -CONH- or -NHCO- is preferable. More preferably, it is a single bond, -O-, -NH-, -OCO- or -NHCO-, particularly preferably a single bond, -O- or -OCO-.

In the formula [2], W ³ is a single bond, a benzene ring or a cyclohexane ring. More preferably, it is a single bond or a benzene ring.

In formula [2], W ⁴ represents a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N (CH ₃ ) -, -NHCO-, -N (CH ₃ ) _{CO-, -CONH-, -CON (CH 3} ) -, -S- or -SO ₂ - a. Among them, a single bond, -O-, -NH-, -COO-, -OCO-, -CONH- or -NHCO- is preferable. More preferably, it is a single bond, -O-, -NH-, -OCO- or -CONH-, particularly preferably a single bond, -O-, -NH- or -CONH-.

In the formula [2], W ⁵ is an organic group having a single bond, an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Specific examples of the aliphatic hydrocarbon group and the non-aromatic cyclic hydrocarbon group include those described above. Among them, a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, or a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms is preferable. More preferably, it is a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a non-aromatic cyclic hydrocarbon group having 3 to 15 carbon atoms. More preferably, it is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, a cyclohexane ring or a bicyclohexyl ring, particularly preferably a single bond, a linear chain type having 1 to 10 carbon atoms Or branched alkylene group or cyclohexane ring.

In the formula [2], n is an integer of 1 to 5. Among them, an integer of 1 to 4 is preferable. More preferably an integer of 1 to 3.

Preferred combinations of W ¹ , W ² , W ³ , W ⁴ , W ⁵ and n in the formula [2] are as shown in Tables 1 to 14.

The specific amine compound 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.

≪ Specific polymer &

The specific polymer as the component (C) of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

The polyimide precursor has a structure represented by the following formula [A].

[Chemical Formula 16]

(R ¹ is a tetravalent organic group, R ² is a divalent organic group, A ¹ and A ² may be the represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, respectively, be the same or different, A ³ and A ⁴ Each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, which may be the same or different and n is a positive integer.

The diamine component is a diamine compound having two primary or secondary amino groups in the molecule. As the tetracarboxylic acid component, a tetracarboxylic acid compound, a tetracarboxylic acid dianhydride, a tetracarboxylic acid dihalide compound , A tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound.

The specific polymer is preferably a structural unit represented by the structural formula of the repeating unit represented by the following formula [D], because the specific polymer is obtained relatively easily by using the tetracarboxylic acid dianhydride represented by the following formula [B] and the diamine compound represented by the following formula [C] Or a polyimide obtained by imidizing the polyamic acid is preferable.

[Chemical Formula 17]

(In the formulas [B] and [C], R ¹ and R ² are the same as defined in formula [A]).

[Chemical Formula 18]

(Wherein R < ¹ > and R < ² > are as defined in formula [A]

In addition, the polymers of the usual synthesis techniques, equation [D] obtained in the above-mentioned formula [A] represented by A ¹ and A carbon number of alkyl group of 1-8 of Figure ^2, and the equation [A] represented by A ³ and A ⁴ An alkyl group having 1 to 5 carbon atoms or an acetyl group may be introduced.

≪ Diamine component >

As the diamine component for producing a specific polymer which is the component (C), a known diamine compound can be used.

Among them, it is preferable to use at least one kind of diamine compound (also referred to as a specific diamine compound) having a structure represented by the following formula [3].

[Chemical Formula 19]

(Y represents a substituent selected from the following formulas [3-1] to [3-6], and m represents an integer of 1 to 4.)

[Chemical Formula 20]

In the formula [3-1], a represents an integer of 0 to 4. Among them, 0 or 1 is preferable from the viewpoint of availability of raw materials and easiness of synthesis.

In the formula [3-2], b represents an integer of 0 to 4. Of these, an integer of 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.

In formula [3-3], Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -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 in view of availability of raw materials and ease of synthesis. desirable. 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 the formula [3-3], Y ² represents a single bond or - (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 10) is preferable.

In formula [3-3], Y ³ represents 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 15), -O-, -CH ₂ O- or -COO- is preferable from the viewpoint of easiness of synthesis. More preferably, it is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In formula [3-3], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with 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, or a fluorine atom. Y ⁴ may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms and having a steroid skeleton. Among them, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton is preferable from the viewpoint of ease of synthesis.

In formula [3-3], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferable.

In the formula [3-3], n represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials and easiness of synthesis, 0 to 3 is preferable. More preferred is 0 to 2.

In the formula [3-3], Y ⁶ represents 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. 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. And particularly preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [3-3] are described in International Publication WO2011 / 132751 (published on October 27, 2011) (2-1) to (2-629) listed in Table 6 to Table 47 on page 34 are included. In addition, Y1 ~ Y6 in the respective tables of the International Patent Publication, it is assumed that each reading, to change the Y ¹ ~ Y ⁶ of the present invention.

In the formula [3-4], Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-. Among them, -O-, -CH ₂ O-, -COO- or -CONH- is preferable. More preferably -O-, -COO- or -CONH-.

In the formula [3-4], Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.

In the formula [3-5], Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group of 1 to 12 carbon atoms.

In the formula [3-6], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.

The method for producing the specific diamine compound represented by the formula [3] is not particularly limited, but preferred examples include the following.

As an example, the specific diamine compound represented by the formula [3] is obtained by synthesizing a dinitro compound represented by the following formula [3-A], reducing the nitro group and converting it into an amino group.

[Chemical Formula 21]

(Y represents a substituent selected from the above formulas [3-1] to [3-6], and m represents an integer of 1 to 4.)

The method of reducing the dinitro group of the dinitro compound represented by the formula [3-A] is not particularly limited, and it is usually carried out in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, Hydrazine, or hydrogen chloride using platinum oxide, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon or the like as a catalyst.

The specific structure of the specific diamine compound represented by the formula [3] is shown below, but it is not limited to these examples.

Specific diamine compounds include 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,4- Diaminobenzyl alcohol, 4,6-diaminoresorcinol, and the like, as well as the following formulas [3-7] to [3 -47] can be mentioned.

[Chemical Formula 22]

(A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group)

(23)

≪ EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

(34)

(Wherein R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, R ² represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine- Containing alkoxy group.

(35)

(R ³ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ -, and R ⁴ represents an alkyl group having 1 to 22 carbon atoms , An alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

(36)

(R ⁵ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ - or -O-, R ⁶ is a fluorine group, A cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

(37)

(R ⁷ represents an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is preferably a trans isomer.)

(38)

(R ⁸ represents an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is preferably a trans isomer.)

[Chemical Formula 39]

(B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, B ² represents an oxygen atom or -COO- * represents (provided that the combined hand tagged "*" in combination with B ^3), B ¹ is a bond hand attached to an oxygen atom or -COO- * (where, "*" is combined with the (CH ^₂₎ a ₂ A ¹ represents an integer of 0 or 1, a ² represents an integer of 2 to 10, and a ³ represents an integer of 0 or 1.)

Among the specific diamine compounds represented by the above formula [3], when a liquid crystal alignment film is formed using a liquid crystal alignment treatment agent obtained from a specific polymer in which the substituent Y in the formula [3] is a diamine compound having a structure represented by the formula [3-3] , The pretilt angle of the liquid crystal can be increased. In order to increase the pretilt angle, it is preferable to use the diamine compounds represented by the formulas [3-29] to [3-40] or the formulas [3-43] to [3-47] among the above diamine compounds. More preferred are the diamine compounds represented by the formulas [3-25] to [3-40] or the formulas [3-43] to [3-47].

The amount of the diamine compound used for increasing the pretilt angle is preferably from 5 mol% to 80 mol% of the entire diamine component. More preferably, it is from 5 mol% to 60 mol% of the total diamine component in view of coating properties of the liquid crystal alignment treatment agent and electric characteristics as a liquid crystal alignment film.

The specific diamine compound represented by the formula [3] may be one or two kinds (one to two kinds) depending on the solubility of the specific polymer in the solvent, the coating property, the orientation of the liquid crystal in the case of the liquid crystal alignment film, Or more can be mixed and used.

As the diamine component for producing a specific polymer, a diamine compound other than the specific diamine compound represented by the formula [3] (also referred to as another diamine compound) may be used as the diamine component. Specific examples of the other diamine compounds are shown below, but the present invention is not limited to these examples.

m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4 Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-di Fluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl , 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diamino Diphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiamine, 3,3'-sulfonyldiamine, bis Bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl- (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3 , 4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N- (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'- diaminodiphenyl) Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, Diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diamino (4-aminophenyl) ethane, 1,2-diaminonaphthalene, 2,6-diaminonaphthalene, 2,6-diaminonaphthalene, Bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl- (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3 Bis (4-aminophenoxy) benzene, 4,4 '- [1,4-phenylenebis (Methylene)] dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [1,4-phenylenebis 3'- [1, 3-phenylenebis (methylene)] dianiline, 3,3 '- [1,3-phenylenebis (Methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3- (4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis Bis (3-aminobenzoate Aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) Bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ' (1,3-phenylene) bis (4-aminobenzamide), N, N ' Aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) terephthalamide, N, N'- (Aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 '-bis [ - bis (4-aminophenyl) hexafluoro Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'- Bis (4-aminophenoxy) propane, 2,2'-bis (3-aminophenoxy) propane, Propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5- Bis (3-aminophenoxy) pentane, 1,6-bis (3-aminophenoxy) pentane, Heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) heptane, ) Octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) -Aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

As other diamine compounds, those having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the diamine side chain, and those having a cyclic substituent composed of these groups can be given. Specifically, diamine compounds represented by the following formulas [DA1] to [DA7] can be exemplified.

(40)

(41)

(42)

(Wherein A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ² represents a linear chain having 1 to 22 carbon atoms Branched or cyclic alkyl group or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.)

(43)

(p represents an integer of 1 to 10).

As other diamine compounds, diamine compounds represented by the following formulas [DA8] to [DA13] may be used as long as the effects of the present invention are not impaired.

(44)

[Chemical Formula 45]

(m represents an integer of 0 to 3, and n represents an integer of 1 to 5.)

In addition, as long as the effect of the present invention is not impaired, diamine compounds represented by the following formulas [DA14] to [DA17] may be used.

(46)

(A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C (CH ₃ ) ₂ -, -CF ₂ -, -C (CF ₃ ) ₂ -, -O-, _{-NH-, -N (CH 3) -} , -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH 3) - or -N ( CH ₃ ) CO-, m ¹ and m ² each represent an integer of 0 to 4, m ¹ + m ² represents an integer of 1 to 4, m ³ and m ⁴ each represent an integer of 1 to 5 , A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ represents an integer of 1 to 5, A ³ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C (CH ₃ ) ₂ -, -CF ₂ -, -C (CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, _{CH 2 O-, -OCH 2 -,} -COO-, -OCO-, -CON (CH 3) - or -N (CH ₃₎ represents a CO-, m ⁶ is an integer of 1 to 4).

As other diamine compounds, diamine compounds represented by the following formulas [DA18] and [DA19] may also be used.

(47)

Further, as long as the effect of the present invention is not impaired, a diamine compound represented by the following formula [DA20] may be used.

(48)

(A ¹ is -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ ) ₃ ) CO-, A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, A ³ is a single bond, - _{O-, -NH-, -N (CH 3} ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH 3) -, -N (CH 3) CO- , and -O (CH ₂ ) _m - (m is an integer of 1 to 5), A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4.)

The above-mentioned other diamine compound may be used alone or in combination of two or more kinds, depending on the solubility of the specific polymer in a solvent, the application property of the liquid crystal alignment treatment agent, the orientation of liquid crystal when the liquid crystal alignment film is used, the voltage retention rate, May be mixed and used.

≪ Tetracarboxylic acid component >

Examples of the tetracarboxylic acid component for producing the specific polymer as the component (C) of the present invention include a tetracarboxylic acid dianhydride represented by the following formula [4], a tetracarboxylic acid derivative thereof, A tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound (all collectively referred to as a specific tetracarboxylic acid component) is preferably used.

(49)

In the formula [4], Z ¹ is a group of a structure selected from the following formulas [4a] to [4j].

(50)

In the formula [4a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.

In the formula [4g], Z ⁶ and Z ⁷ each represent a hydrogen atom or a methyl group, and may be the same or different.

Among the structures represented by the formula [4], the specific tetracarboxylic acid component, Z ¹ is preferably a tetracarboxylic acid component represented by the formula [4a], the formula [4c], the formula The structure represented by the formula [4d], the formula [4e], the formula [4f] or the formula [4g] is preferable. More preferred is the structure represented by the formula [4a], the formula [4e], the formula [4f] or the formula [4g], and particularly preferable are the formula [4e], the formula [4f] or the formula [4g].

The specific tetracarboxylic acid component is preferably at least 1 mol% of the total tetracarboxylic acid component. More preferably, it is at least 5 mol%, particularly preferably at least 10 mol%. Among them, 15 to 100 mol% is more preferable.

When a specific tetracarboxylic acid component having the structure of the formula [4e], the formula [4f] or the formula [4g] is used, the amount of the tetracarboxylic acid component to be used is preferably 20 mol% or more of the total amount of the tetracarboxylic acid component . More preferably, it is at least 30 mol%. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid component having the structure of the formula [4e], the formula [4f] or the formula [4g].

In the specific polymer, other tetracarboxylic acid components other than the specific tetracarboxylic acid component may be used as long as the effect of the present invention is not impaired.

Examples of the other tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds and tetracarboxylic acid dialkyl ester dihalide compounds shown below .

That is, other tetracarboxylic acid components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8 -Naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid Acid, 2,3,3 ', 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis , 4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2- Bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3, (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4, 9, Perylene tetracarboxylic acid or 1,3-diphenyl- 1,2,3,4-cyclobutane tetracarboxylic acid.

The specific tetracarboxylic acid component and the other tetracarboxylic acid component are preferably selected from the group consisting of solubility of a specific polymer in a solvent, application property of a liquid crystal alignment treatment agent, orientation of liquid crystal in the case of a liquid crystal alignment film, voltage retention rate, , One kind or two or more kinds may be mixed and used.

≪ Process for producing specific polymer &

The method of synthesizing a specific polymer is not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic acid component. Generally, a polyamic acid is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic acid and a derivative thereof and a diamine component composed of one or more kinds of diamine compounds. Specifically, there are a method of polycondensing a tetracarboxylic acid dianhydride and a primary or secondary diamine compound to obtain a polyamic acid, a method of dehydrating polycondensation reaction of a tetracarboxylic acid and a primary or secondary diamine compound, Or a method of polycondensation of a tetracarboxylic acid dihalide and a primary or secondary diamine compound to obtain a polyamic acid is used.

In order to obtain a polyamide acid alkyl ester, a method of polycondensation of a tetracarboxylic acid in which a carboxylic acid group is dialkyl esterified with a primary or secondary diamine compound, a method of polycondensation of a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group A method of polycondensation of a primary or secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.

In order to obtain the polyimide, a method of converting the polyamide acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The reaction between the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent containing a diamine component and a tetracarboxylic acid component. The organic solvent to be used at this time is not particularly limited as long as it dissolves the resulting polyimide precursor. Specific examples of the organic solvent used in the reaction are shown below, but the present invention is not limited to these examples.

Examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyrolactone, N, 1,3-dimethyl-imidazolidinone, and the like. When the solvent solubility of the polyimide precursor is high, it is preferable to use methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formulas [D- -3] can be used.

(51)

(D ¹ is an alkyl group having 1 to 3 carbon atoms, D ² is an alkyl group having 1 to 3 carbon atoms, and D ³ is an alkyl group having 1 to 4 carbon atoms.)

These may be used alone or in combination. An organic solvent that does not dissolve the polyimide precursor may be used in combination with the organic 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 component are reacted in an organic solvent, a method in which a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred and a tetracarboxylic acid component is added as it is or dispersed or dissolved in an organic solvent , A method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, and the like. May be used. When the diamine component or the tetracarboxylic acid component is reacted using a plurality of kinds, the reaction may be carried out in a preliminarily mixed state. Alternatively, the low molecular weight compounds may be reacted individually or sequentially, . The polymerization temperature at that time may be any temperature of -20 to 150 ° C, preferably -5 to 100 ° C. The reaction can be carried out at an arbitrary concentration. However, if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes excessively high and it becomes difficult to perform uniform stirring. Therefore, the content is preferably 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 total molar number of the diamine component to the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As in the case of the usual 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 ring closure of the polyimide precursor. In this polyimide, the closed rate (also referred to as imidization rate) of the amidic acid group does not necessarily have to be 100% Can be adjusted arbitrarily.

Examples of the method for imidizing the polyimide precursor include thermal imidization for directly heating the solution of the polyimide precursor or catalyst imidization for adding a catalyst to a solution of the polyimide precursor.

The temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C, preferably 120 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 the polyimide precursor solution 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, etc. Among them, pyridine is preferred because it has a basicity suitable for proceeding the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Of these, use of acetic anhydride is preferable since 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 the polyimide is recovered from the polyimide precursor or polyimide reaction solution, the reaction solution may be put into a solvent and precipitated. Examples of the solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene and water. The polymer precipitated by charging into the solvent can be recovered by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. In addition, when the polymer precipitated and recovered is redissolved in an organic solvent and the operation of reprecipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more kinds of solvents selected from these solvents are used, the purification efficiency is further increased, which is preferable.

The molecular weight of the specific polymer is preferably 5,000 to 1,000,000 in terms of the weight average molecular weight measured by gel permeation chromatography (GPC) in consideration of the strength of the liquid crystal alignment film obtained therefrom, the workability at the time of forming the liquid crystal alignment film, And more preferably 10,000 to 150,000.

≪ Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and contains a specific isocyanate compound, a specific amine compound, a specific polymer and a solvent.

The content of the specific isocyanate compound in the liquid crystal alignment treatment agent is 0.1 to 30 parts by mass based on 100 parts by mass of the specific polymer. Among them, the amount is preferably 0.5 to 30 parts by mass, particularly preferably 1 to 20 parts by mass.

The amount of the specific amine compound introduced into the liquid crystal alignment treatment agent is 0.1 to 30 parts by mass based on 100 parts by mass of the specific polymer. Among them, the amount is preferably 0.5 to 30 parts by mass, particularly preferably 1 to 20 parts by mass.

The method of adding the specific isocyanate compound and the specific amine compound to the liquid crystal alignment treatment agent is not particularly limited. Preferably, the following method can be used. That is, a specific amine compound is added to a polymer solution in which a specific polymer is dissolved in a solvent, and a solution of the specific polymer and a specific amine compound is heated and stirred. The temperature at that time is preferably 25 to 100 占 폚, more preferably 25 to 80 占 폚. Then, a specific isocyanate compound is added to this solution, and a solution of the specific polymer, the specific amine compound and the specific isocyanate compound is heated and stirred. The temperature at that time is preferably 25 to 100 占 폚, more preferably 25 to 80 占 폚. The solution thus obtained may be used as it is in the liquid crystal alignment treatment agent as it is, and further the other polymer, solvent, additive, etc. shown below may be added.

All the polymer components in the liquid crystal alignment treatment agent may be all the specific polymers of the present invention, or may be mixed with other polymers. At that time, the content of the other polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the specific polymer. Examples of the other polymer include a polyimide polymer not using the diamine compound represented by the formula [3] and the specific tetracarboxylic acid component. Further, other polymers, specifically cellulose polymers, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, polysiloxanes and the like can be mentioned.

The content of the solvent in the liquid crystal alignment treatment agent is preferably 70 to 99.9 mass%, more preferably 80 to 99 mass%, from the viewpoint that a solvent in the liquid crystal alignment treatment agent forms a uniform liquid crystal alignment film by coating. The content can be appropriately changed according to the thickness of the intended liquid crystal alignment film.

The solvent used in the liquid crystal alignment treatment agent is not particularly limited as long as it is a solvent (also referred to as a good solvent) for dissolving a specific compound and a specific polymer. Specific examples of the two solvents are shown below, but the present invention is not limited to these examples.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone and the like.

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone. Further, when the solubility of the specific compound and the specific polymer in the solvent is high, it is preferable to use the solvent represented by the formula [D-1] to [D-3].

It is preferable that the both solvents in the liquid crystal alignment treatment agent are 10 to 100% by mass of the whole solvent contained in the liquid crystal alignment treatment agent. Among them, 20 to 90% by mass is preferable. More preferred is 30 to 80 mass%.

As the liquid crystal alignment treatment agent, a solvent (also referred to as a poor solvent) which improves the coatability and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied may be used as long as the effect of the present invention is not impaired. Specific examples of the poor solvent include, but are not limited to, the following examples.

Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- (2-ethylhexyl) acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl Propylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- , Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol mono Ethylene glycol monoacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, Diethyleneglycol monomethyl ether, triethyleneglycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid n (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, Propylene glycol monoethyl ether, propyleneglycol monoethyl ether, propyleneglycol monoethyl ether, propyleneglycol monoethyl ether, propyleneglycol monoethyl ether, butylpropyleneglycol monoethylether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, Propyl 3-methoxypropionate, 3-methoxypropyl D-1] to [D-3], and the like can be given, for example, as a solvent, such as methyl ethyl lactate, methyl lactate methyl lactate, ethyl lactate lactate, n-propyl lactate, n-butyl lactate, have.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, It is preferable to use a solvent represented by the formula [D-3].

These poor solvents are preferably 1 to 70% by mass of the total solvent contained in the liquid crystal alignment treatment agent. In particular, it is preferably 1 to 60% by mass. And more preferably 5 to 60% by mass.

The liquid crystal alignment treatment agent may contain at least one kind selected from the group consisting of a compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group A compound having a substituent, and further, a compound having a polymerizable unsaturated bond (collectively referred to as a crosslinkable compound) may also be introduced. These substituent groups and polymerizable unsaturated bonds need to have two or more in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, (Aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate di Glycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4- 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylphenyl) Phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) ) 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 [4A].

(52)

Specific examples thereof include crosslinkable compounds represented by the formulas [4a] to [4k] shown on pages 58 to 59 of International Publication WO2011 / 132751 (published on October 27, 2011).

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A].

(53)

Specific examples thereof include crosslinkable compounds represented by the formulas [5-1] to [5-42] published on pages 76 to 82 of WO2012 / 014898 (published on Feb. 2, 2012).

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include amino resins having a hydroxyl group or alkoxyl group such as melamine resin, urea resin, guanamine Resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethylene urea-formaldehyde resin and the like. Specifically, 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 can be used. The melamine derivative or 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 methoxymethyl groups are substituted in an average of 3.7 methoxymethyl groups per commercially available triazine ring, MWs having an average of 5.8 methoxymethyl groups per triazine ring -30 (manufactured by Sanwa Chemical Co., Ltd.) or methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212, 253 , 254 and the like, butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, and methoxymethylated ethoxymethylated melamines such as Cymel 1123 Methoxymethylated butoxymethylated benzoguanamine such as benzoguanamine, Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl-containing methoxymethylated methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80, And anamine (manufactured by Mitsui Cyanamid Co., Ltd.). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluryl such as Cymel 1172, and methoxymethylolglycoluril such as Powderlink 1174, and the like.

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, examples of the crosslinkable compound represented by the formulas [6-1] to [6-48] listed on pages 62 to 66 of International Patent Publication No. WO2011 / 132751 have.

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) A crosslinkable compound having three polymerizable unsaturated groups such as acryloyloxyethoxy trimethylol propane and glycerin polyglycidyl ether poly (meth) acrylate; Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di Acrylates such as di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (Meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, A crosslinkable compound having two polymerizable unsaturated groups in the molecule; Hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- A crosslinkable compound having one polymerizable unsaturated group such as ester and N-methylol (meth) acrylamide in the molecule; And the like.

Further, a compound represented by the following formula [7A] may also be used.

(54)

(E ₁ has to have a cyclohexane ring, a non-cyclohexane ring, represents a group selected from a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene group consisting of a ring, anthracene ring and phenanthrene ring, E ₂ Represents a group selected from the formulas [7a] and [7b], and n represents an integer of 1 to 4.)

(55)

The compound is an example of a crosslinking compound, but is not limited thereto. The crosslinkable compound used 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 is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. More preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, per 100 parts by mass of all the polymer components.

The liquid crystal alignment treatment agent may be a compound which improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, so long as the effect of the present invention is not impaired.

Examples of the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film 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 and EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals Inc.), Fluorad FC430 and FC431 , Sumitomo 3M), Asahi Guard AG710, Surfron 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, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent.

The liquid crystal alignment treatment agent is a compound which promotes the charge transfer in the liquid crystal alignment film and accelerates charge dropout of the device and is disclosed in International Publication No. WO2011 / 132751 (published on October 27, 2011) A nitrogen-containing heterocyclic amine compound represented by the formula [M1] to formula [M156] may be added. The amine compound may be directly added to the liquid crystal alignment treatment agent, but it is preferable to add the amine compound in an appropriate solvent at a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent to be used is not particularly limited as long as it is an organic solvent for dissolving the above-mentioned specific polymer.

In the liquid crystal alignment treatment agent, in addition to the above-mentioned compounds that improve the uniformity of film thickness or surface smoothness of the poor solvent, the crosslinkable compound, the resinous coating or the liquid crystal alignment film, and the compound which accelerates charge dropout, , A dielectric material or a conductive material may be added for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film.

<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 after being applied and baked on a substrate, subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. In the case of the vertical alignment application, etc., it can be used as a liquid crystal alignment film without alignment treatment. The substrate to be used at this time is not particularly limited as long as it is a substrate having high transparency. A plastic substrate such as an acrylic substrate, a polycarbonate substrate, etc. other than a glass substrate can also be used. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for liquid crystal driving is formed. In a reflection type liquid crystal display element, an opaque substrate such as a silicon wafer can be used only for a substrate on one side, and as the electrode in this case, a material for reflecting light such as aluminum can also be used.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but generally, screen printing, offset printing, flexographic printing, inkjet printing, and the like are common. Examples of other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spraying method, and they may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, it is heated at 30 to 300 占 폚, preferably at 30 to 300 占 폚, depending on the solvent used for the liquid crystal alignment treatment agent, by heating means such as a hot plate, a heat circulation type oven and an IR The liquid crystal alignment layer can be formed by evaporating the solvent at a temperature of 30 to 250 ° C.

When the thickness of the liquid crystal alignment layer 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, 10 to 100 nm. When the liquid crystal is horizontally aligned or tilted, the fired liquid crystal alignment film is subjected to rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a substrate on which a liquid crystal alignment film is formed from the liquid crystal alignment treatment agent of the present invention is formed by the above-mentioned technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.

As a manufacturing method of the liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is scattered on the liquid crystal alignment film of the substrate of the one substrate, the liquid crystal alignment film surface is inward, A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is sealed to effect a sealing.

The liquid crystal alignment treatment agent of the present invention comprises a liquid crystal layer between a pair of substrates provided with electrodes and includes a polymerizable compound polymerized by at least one of active energy rays and heat between a pair of substrates And a liquid crystal display device produced by polymerizing a polymerizable compound by irradiation of an active energy ray and heating, while applying a voltage between electrodes. Here, as the active energy ray, ultraviolet ray is preferable. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, ultraviolet rays and heating may be simultaneously performed.

The liquid crystal display element controls a pretilt angle of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is incorporated into a liquid crystal material, and after a liquid crystal cell is assembled, a predetermined voltage is applied to the liquid crystal layer, Ultraviolet light or the like is irradiated, and the pretilt angle of the liquid crystal molecules is controlled by the produced polymer. That is, since the alignment state of the liquid crystal molecules when the polymer is produced is stored even after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed on the liquid crystal layer.

In the PSA method, since the rubbing treatment is not required, it is suitable for forming a vertically aligned liquid crystal layer which is difficult to control the pretilt angle by the rubbing treatment.

The liquid crystal display element of the present invention can be obtained by obtaining a substrate on which a liquid crystal alignment film is formed from a liquid crystal alignment treatment agent by the above-mentioned technique, preparing a liquid crystal cell, and polymerizing the polymerizable compound by at least one of irradiation of ultraviolet rays and heating, The orientation of the molecules can be controlled.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is scattered on the liquid crystal alignment film of the substrate of the single chamber, and the liquid crystal alignment film surface is inward, A method in which a liquid crystal is injected under reduced pressure and sealed, a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed, and then a substrate is bonded and sealed.

The liquid crystal is mixed with a polymerizable compound which 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 and a methacrylate group in the molecule. At this 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, the polymerizable compound is polymerized by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell. Thereby, the orientation of the liquid crystal molecules can be controlled.

The liquid crystal alignment treatment agent of the present invention comprises a liquid crystal layer between a pair of substrates provided with electrodes and includes a polymerizable group polymerizable by at least one of active energy rays and heat between the pair of substrates And a liquid crystal display device manufactured by a process of applying a voltage between the electrodes. Here, as the active energy ray, ultraviolet ray is preferable. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, ultraviolet rays and heating may be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerizing from at least one of active energy ray and heat, a method of adding a compound containing this polymerizable group to a liquid crystal alignment treatment agent, a method of using a polymer component containing a polymerizable group . Since the liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bonding site that reacts by irradiation with heat or ultraviolet rays, the orientation of the liquid crystal molecules can be controlled by at least one of irradiation with ultraviolet rays and heating have.

The liquid crystal cell having the liquid crystal alignment layer containing such a polymerizable group and the alignment of the liquid crystal molecules after production of the liquid crystal cell can be controlled in the same manner as the above-described liquid crystal cell of the PSA type.

The liquid crystal display element having the liquid crystal alignment film produced using the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be suitably used for a liquid crystal television having a large screen and a high definition.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but is not construed as being limited thereto. Abbreviations in Synthesis Examples, Examples and Comparative Examples are as follows.

&Lt; Specific isocyanate compound &gt;

P1: a compound represented by the following formula [P1]

P2: a compound represented by the following formula [P2]

P3: a compound represented by the following formula [P3]

(56)

&Lt; Specific amine compound &gt;

S1: Amino ethanol

S2: 3-amino-1-propanol

(57)

&Lt; Monomer for producing polyimide polymer (specific polymer) &gt;

(Specific diamine compound)

A1: 3,5-diaminobenzoic acid

A2: a diamine compound represented by the following formula [A2]

A3: 1,3-Diamino-4-octadecyloxybenzene

A4: 1,3-Diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

A5: 1,3-Diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl]

A6: 1,3-Diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy}

A7: A diamine compound represented by the following formula [A7]

(58)

[Chemical Formula 59]

(60)

(Other diamine compound)

B1: p-phenylenediamine

B2: m-phenylenediamine

(61)

(Specific tetracarboxylic acid component)

C1: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

C2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

C3: tetracarboxylic acid dianhydride represented by the following formula [C3]

C4: tetracarboxylic acid dianhydride represented by the following formula [C4]

(62)

<Solvent>

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

? -BL:? -butyrolactone

ECS: ethylene glycol monoethyl ether

EC: diethylene glycol monoethyl ether

BCS: ethylene glycol monobutyl ether

PB: Propylene glycol monobutyl ether

&Quot; Method for measuring molecular weight of polyimide polymer &quot;

The molecular weights of the polyimide precursor and the polyimide were measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.), a column (KD-803, KD-805) , And measured by the following method.

Column temperature: 50 ° C

Eluent: 30 mmol / l (liters) of lithium bromide-hydrate (LiBr 占₂ 2O) and 30 mmol / l of phosphoric anhydride crystal (o-phosphoric acid) as an additive , Tetrahydrofuran (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

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

&Quot; Method for measuring imidization rate of polyimide &quot;

(DMSO-d6, 0.05 mass% TMS (tetramethylsilane)) mixture was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, Product) (0.53 ml) was added, and completely dissolved by ultrasonic wave. This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring instrument (JNW-ECA500) (manufactured by Nippon Denshoku Co., Ltd.). The imidization rate is determined as a reference proton derived from a structure that did not change before and after imidization, and the peak integrated value of the proton and the proton peak accumulation value derived from the NH group of the amide acid appearing in the vicinity of 9.5 ppm to 10.0 ppm Value was obtained by the following formula.

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 (imidation rate is 0% The ratio of the number of reference protons to one protopertone.

&Lt; Synthesis Example 1 &

The reaction was carried out at 40 占 폚 for 8 hours to obtain a resin solid content concentration (25 g). The reaction was carried out in the same manner as in Example 1, except that C1 (3.28 g, 16.7 mmol), A2 (0.69 g, 3.41 mmol) To obtain a 25 mass% polyamic acid solution (1). This polyamic acid had a number average molecular weight of 26,800 and a weight average molecular weight of 87,100.

&Lt; Synthesis Example 2 &

C2 (3.64 g, 14.5 mmol), A2 (0.88 g, 4.35 mmol) and B2 (2.67 g, 24.7 mmol) were mixed in NEP (19.9 g) and reacted at 50 ° C for 2 hours. Thereafter, C1 (2.76 g, 14.1 mmol) and NEP (10.0 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25 mass%. This polyamic acid had a number average molecular weight of 23,900 and a weight average molecular weight of 70,900.

&Lt; Synthesis Example 3 &

To polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2, NEP was added and diluted to 6% by mass, acetic anhydride (3.93 g) and pyridine (2.45 g) were added as an imidation catalyst, The reaction was carried out at 70 ° C for 3 hours. The reaction solution was poured into methanol (460 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 (3). The imidization ratio of the polyimide was 69%, the number average molecular weight was 22,500, and the weight average molecular weight was 60,800.

&Lt; Synthesis Example 4 &

C2 (4.25 g, 17.0 mmol), A1 (1.85 g, 12.2 mmol) and A4 (4.61 g, 12.1 mmol) were mixed in NEP (24.1 g) and reacted at 80 ° C for 5 hours. Thereafter, C1 (1.36 g, 6.93 mmol) and NEP (12.1 g) were added and reacted at 40 占 폚 for 8 hours to obtain a polyamic acid solution (4) having a resin solid content concentration of 25 mass%. The polyamic acid had a number average molecular weight of 23,000 and a weight average molecular weight of 68,000.

&Lt; Synthesis Example 5 &

NEP was added to the polyamic acid solution (4) (4) (4) obtained in Synthesis Example 4 to dilute to 6 mass%, acetic anhydride (3.80 g) and pyridine (2.40 g) were added as an imidation catalyst, The reaction was carried out at 70 DEG C for 2 hours. The reaction solution was poured into methanol (460 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 (5). The imidization ratio of the polyimide was 60%, the number average molecular weight was 20,100, and the weight average molecular weight was 58,100.

&Lt; Synthesis Example 6 &

(3.85 g, 9.68 mmol) and A5 (3.82 g, 9.68 mmol) were mixed in NMP (23.8 g) to give 80 Lt; 0 &gt; C for 5 hours. Thereafter, C1 (0.88 g, 4.51 mmol) and NMP (11.9 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the resultant polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.35 g) were added as an imidation catalyst and the reaction was carried out at 80 ° C for 3.5 hours . The reaction solution was poured into methanol (460 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 (6). The imidization ratio of the polyimide was 84%, the number average molecular weight was 16,800, and the weight average molecular weight was 51,300.

&Lt; Synthesis Example 7 &

C2 (2.30 g, 9.19 mmol), A1 (2.45 g, 16.1 mmol) and A6 (2.98 g, 6.89 mmol) were mixed in NEP (20.8 g) and reacted at 80 ° C for 5 hours. Thereafter, C1 (2.65 g, 13.5 mmol) and NEP (10.4 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the resultant polyamic acid solution (30.0 g) to dilute it to 6 mass%, acetic anhydride (4.45 g) and pyridine (3.31 g) were added as imidation catalysts and reacted at 80 ° C for 3 hours . The reaction solution was poured into methanol (460 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 (7). The imidization ratio of the polyimide was 80%, the number average molecular weight was 16,800, and the weight average molecular weight was 50,900.

&Lt; Synthesis Example 8 &

C2 (4.10 g, 16.4 mmol), Al (2.85 g, 18.7 mmol) and A7 (2.31 g, 4.68 mmol) were mixed in NMP (21.1 g) and reacted at 80 ° C for 5 hours. Thereafter, C1 (1.30 g, 6.64 mmol) and NMP (10.6 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NMP was added to the resulting polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (3.88 g) and pyridine (2.53 g) were added as an imidation catalyst and the reaction was carried out at 60 ° C for 3 hours . The reaction solution was poured into methanol (460 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 (8). The imidization ratio of the polyimide was 55%, the number average molecular weight was 17,300, and the weight average molecular weight was 52,100.

&Lt; Synthesis Example 9 &

AMP (32.4 g) was added to a mixture of C3 (5.13 g, 22.9 mmol), A1 (2.31 g, 15.2 mmol), A2 (0.48 g, 2.34 mmol) C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

To the obtained polyamic acid solution (30.0 g), NMP was added and diluted to 6 mass%. Acetic anhydride (4.00 g) and pyridine (2.55 g) were added as an imidization catalyst and reacted at 60 ° C for 2 hours . The reaction solution was poured into methanol (460 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 55%, the number average molecular weight was 18,000, and the weight average molecular weight was 51,400.

&Lt; Synthesis Example 10 &

The reaction was carried out at 40 占 폚 for 8 hours to obtain a resin solid content concentration (5.11 g, 22.8 mmol), A1 (2.11 g, 13.9 mmol) and A5 (3.65 g, 9.25 mmol) Of 25% by mass was obtained.

NMP was added to the resultant polyamic acid solution (30.0 g), diluted to 6 mass%, acetic anhydride (4.00 g) and pyridine (2.50 g) were added as imidation catalysts and reacted at 70 ° C for 2 hours . The reaction solution was poured into methanol (460 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 60%, the number average molecular weight was 17,500, and the weight average molecular weight was 52,000.

&Lt; Synthesis Example 11 &

AE (4.19 g, 11.0 mmol) was mixed in NEP (22.9 g) and treated with a solution of C4 (3.31 g, 11.0 mmol), A1 (1.01 g, 6.62 mmol) Lt; 0 &gt; C for 6 hours. Thereafter, C1 (2.09 g, 10.7 mmol) and NEP (11.4 g) were added and reacted at 25 DEG C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

NEP was added to the resulting polyamidic acid solution (30.5 g) to dilute to 6 mass%, acetic anhydride (7.20 g) and pyridine (2.35 g) were added as an imidation catalyst and the reaction was carried out at 40 ° C for 1.5 hours . The reaction solution was poured into methanol (460 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 (11). The imidization ratio of the polyimide was 70%, the number average molecular weight was 18,900, and the weight average molecular weight was 45,300.

Table 15 summarizes the polyimide polymer.

* 1: Polyamide acid.

Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

The liquid crystal alignment treatment agent was pressure-filtered through a membrane filter having a pore diameter of 1 占 퐉 to evaluate the ink-jet applicability. For the ink-jet applicator, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used. The coating was carried out on an ITO (indium tin oxide) -evaporated substrate cleaned with pure water and IPA (isopropyl alcohol) with a coating area of 70 x 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, a coating speed of 40 Mm / sec, the time from application to drying was 60 seconds, and drying was carried out on a hot plate at 70 DEG C for 5 minutes.

The applicability of the obtained substrate on which the liquid crystal alignment film was formed was confirmed. Specifically, the application was carried out by visual observation under a sodium lamp, and the presence or absence of pinholes was confirmed. As a result, even in the liquid crystal alignment film obtained in any of the examples, a pinhole was not observed on the application, and a liquid crystal alignment film excellent in coatability was obtained.

Evaluation of display non-uniformity characteristics in the vicinity of a frame of a liquid crystal cell after high-temperature, high-humidity storage (normal cell) &quot;

The liquid crystal alignment treatment agent was pressure filtered through a membrane filter having a pore diameter of 1 占 퐉 to prepare a liquid crystal cell (ordinary cell). This solution was spin-coated on an ITO surface of a substrate (100 mm long × 100 mm wide, 0.7 mm thick) on which a 100 × 100 mm ITO electrode cleaned with pure water and IPA was formed, and was spin coated on a hot plate at 100 ° C. for 5 minutes An ITO substrate on which a polyimide liquid crystal alignment film having a thickness of 100 nm was formed was obtained by performing heat treatment at 230 deg. C for 30 minutes in a circulating type clean oven. The coated surface of the ITO substrate was rubbed with a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation number of 1000 rpm, a roll advancing speed of 50 mm / sec, and a press amount of 0.1 mm.

Two pieces of the ITO substrates on which the obtained liquid crystal alignment films were formed were prepared, and spacers of 6 mu m were dispersed on the liquid crystal alignment film surface of the substrate on which the one liquid crystal alignment film was formed. Thereafter, an ultraviolet curable sealant was drawn around the substrate, and liquid crystal was injected by an ODF (One Drop Filling) method to obtain a liquid crystal cell. Thereafter, in order to cure the ultraviolet curable sealant, a wavelength of 310 nm or less was cut into the liquid crystal cell using a metal halide lamp having an illuminance of 60 mW, ultraviolet radiation of 5 J / cm 2 in terms of 365 nm was irradiated Respectively. Thereafter, heat treatment was performed in a heat-cycling type clean oven at 120 DEG C for 60 minutes to obtain a liquid crystal cell (ordinary cell).

The liquid crystal cells using the liquid crystal alignment treatment agents (1) to (3) obtained in Examples 1 to 3 and the liquid crystal alignment treatment agents (21) to (26) obtained in Comparative Examples 1 to 6 were each supplied with a nematic liquid crystal (MLC- 2003) (manufactured by Merck Japan) was used.

The liquid crystal alignment treatment agents (4) to (6) obtained in Examples 4 to 6, the liquid crystal alignment treatment agent (8) obtained in Example 8, the liquid crystal alignment treatment agent (9) obtained in Example 9, The obtained liquid crystal alignment treatment agents (11) to (15), the liquid crystal alignment treatment agents (17) to (20) obtained in Examples 17 to 20 and the liquid crystal alignment treatment agents (27) to (32) obtained in Comparative Examples 7 to 12 For the liquid crystal cell, nematic liquid crystal (MLC-6608) (Merck Japan) was used.

The obtained liquid crystal cell (ordinary cell) was evaluated for the liquid crystal alignability near the sealant by visual observation using a polarizing plate and a backlight. As a result, any of the liquid crystal cells obtained in Examples and Comparative Examples exhibited uniform liquid crystal alignability.

Thereafter, the liquid crystal cell was stored in a high-temperature and high-humidity bath having a temperature of 80 캜 and a humidity of 90% RH for 72 hours, and the liquid crystal alignability in the vicinity of the sealing agent was evaluated under the same conditions as described above. Specifically, the fact that no disturbance of the liquid crystal alignment property is not observed in the vicinity of the sealant is considered to be superior to the present evaluation.

In Tables 19 to 21, &quot; No &quot; indicates that the liquid crystal alignment property was not observed, and &quot; Good &quot;

&Quot; Evaluation of voltage holding ratio after storage at high temperature and high humidity (normal cell) &quot;

The liquid crystal alignment treatment agent was pressure filtered through a membrane filter having a pore diameter of 1 占 퐉 to prepare a liquid crystal cell (ordinary cell). This solution was spin-coated on an ITO surface of a substrate (40 mm long × 30 mm wide, 0.7 mm thick) on which a 30 × 40 mm ITO electrode cleaned with pure water and IPA had been formed, and heat-treated on a hot plate at 100 ° C. for 5 minutes An ITO substrate on which a polyimide liquid crystal alignment film having a thickness of 100 nm was formed was obtained by performing heat treatment at 230 deg. C for 30 minutes in a circulating type clean oven. The coated surface of the ITO substrate was subjected to rubbing treatment using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm at a roll rotation speed of 1000 rpm, a roll advancing speed of 50 mm / sec, and an indentation amount of 0.1 mm.

Two sheets of the ITO substrates on which the obtained liquid crystal alignment film was formed were prepared, and the liquid crystal alignment film side was set inside and spacers of 6 占 퐉 were sandwiched therebetween to form an ultraviolet curable sealant. Subsequently, the other substrate and the liquid crystal alignment film surface were faced with each other, and then a process for curing the ultraviolet curable sealant was performed to obtain a public cell. Specifically, a wavelength of 310 nm or less was cut using a metal halide lamp having an illuminance of 60 mW, irradiated with ultraviolet rays of 5 J / cm 2 in terms of 365 nm, and then irradiated in a heat- The heat treatment was performed for 60 minutes to obtain a vacant cell. A liquid crystal was injected into this vacant cell by a low pressure injection method and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).

The liquid crystal used in the production of the liquid crystal cell of each of the examples and the comparative example was made the same as the above-mentioned &quot; evaluation of the display non-uniformity characteristic near the frame of the liquid crystal cell after high temperature and high humidity storage (normal cell) &quot;.

A voltage of 1 V was applied to the obtained liquid crystal cell at a temperature of 80 占 폚 for 60 占 퐏, a voltage after 50 ms was measured, and the degree of voltage maintenance was calculated as a voltage holding ratio (also referred to as VHR). The measurement was performed by setting the voltage: ± 1 V, the pulse width: 60 μs, and the flame period: 50 ms using a voltage sustaining ratio measuring device (VHR-1) (manufactured by Toyotec Corporation).

The liquid crystal cell in which the measurement of the voltage holding ratio was completed was stored for 96 hours in a high-temperature and high-humidity bath having a temperature of 80 캜 and a humidity of 90% RH, and the voltage holding ratio was again measured under the same conditions as above.

The evaluation was made better as the decrease in the value of the voltage holding ratio after storage in the high temperature and high humidity chamber was smaller with respect to the value of the voltage holding ratio immediately after the production of the liquid crystal cell (Tables 19 to 20)

&Quot; Production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) &quot;

The liquid crystal alignment treatment agent was pressure filtered through a membrane filter having a pore diameter of 1 占 퐉 to prepare a liquid crystal cell and evaluate the liquid crystal alignment property (PSA cell). This solution was coated on a substrate (40 mm long × 30 mm wide, 0.7 mm thick) on which ITO electrodes with a pattern interval of 20 μm were formed with 10 × 10 mm in the center, cleaned with pure water and IPA and a 10 × 40 mm ITO electrode (30 mm in length × 30 mm in thickness, 0.7 mm in thickness) was spin-coated on a hot plate at 100 ° C. for 5 minutes and then subjected to heat treatment at 230 ° C. for 30 minutes in a heat- Of 100 nm was obtained.

The substrate having the liquid crystal alignment film formed thereon was sandwiched between the spacers of 6 占 퐉 with the liquid crystal alignment film surface facing inward and bonded together with a sealant to prepare a vacant cell. A liquid crystal mixture in which 0.3 mass% of the polymerizable compound (1) represented by the following formula was mixed with 100 mass% of a nematic liquid crystal (MLC-6608) was injected into this vacant cell by a reduced pressure injection method, Thereby obtaining a liquid crystal cell.

(63)

A wavelength of 350 nm or less was cut using a metal halide lamp having an illuminance of 60 mW while applying a voltage of 5 V alternating current to the liquid crystal cell obtained and irradiated with ultraviolet rays of 20 J / cm 2 in terms of 365 nm, To obtain a liquid crystal cell (PSA cell) whose alignment direction was controlled. The temperature in the irradiator when the liquid crystal cell was irradiated with ultraviolet rays was 50 占 폚.

The response speeds of the liquid crystal cell before and after ultraviolet irradiation were measured. The response speed was measured from T90 to T10 from a transmittance of 90% to a transmittance of 10%.

It was confirmed that the PSA cell obtained in Examples had a faster response speed after irradiation with ultraviolet rays than before irradiation with ultraviolet rays, so that the alignment direction of the liquid crystal was controlled. It was confirmed that the liquid crystal cell of the example was uniformly aligned by observation with a polarizing microscope (ECLIPSE E600WPOL) (Nikon Corporation).

&Lt; Example 1 &gt;

NMP (20.9 g) and BCS (12.3 g) were added to polyamic acid solution (1) (10.5 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 1 and stirred at 25 占 폚 for 2 hours. Then, S1 (0.132 g) was added to this solution, and the mixture was stirred at 25 占 폚 for 4 hours. Thereafter, P2 (0.263 g) was added and stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) near the frame of the liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 1 .

&Lt; Example 2 &gt;

NEP (9.90 g) and PB (7.50 g) were added to polyamic acid solution (2) (5.50 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 2 and stirred at 25 占 폚 for 2 hours. Then, S1 (0.097 g) was added to this solution, and the mixture was stirred at 25 占 폚 for 4 hours. Thereafter, P2 (0.097 g) was added and the mixture was stirred at 60 占 폚 for 6 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 the solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high-temperature and high-humidity storage and evaluation of the voltage holding ratio after high-temperature and high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 2 .

&Lt; Example 3 &gt;

NEP (14.8 g) and PB (6.30 g) were added to the polyimide powder (3) (1.35 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S2 (0.095 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P2 (0.095 g) was added and the mixture was stirred at 60 占 폚 for 6 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 the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) were performed using the obtained liquid crystal alignment treatment agent 3 .

<Example 4>

NEP (9.90 g) and PB (7.50 g) were added to polyamic acid solution (4) (5.50 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 4 and stirred at 25 占 폚 for 2 hours. Then, S1 (0.097 g) was added to this solution, and the mixture was stirred at 25 占 폚 for 4 hours. Thereafter, P2 (0.097 g) was added and the mixture was stirred at 60 占 폚 for 6 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 the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; .

&Lt; Example 5 &gt;

NEP (9.00 g), EC (2.20 g) and PB (6.60 g) were added to the polyamide acid solution (4) (5.60 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 4, Lt; / RTI &gt; Then, S2 (0.14 g) was added to this solution, and the mixture was stirred at 25 占 폚 for 4 hours. Thereafter, P1 (0.21 g) was added and stirred at 60 占 폚 for 6 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 the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; .

&Lt; Example 6 &gt;

NEP (13.5 g) and PB (7.30 g) were added to the polyimide powder (5) (1.33 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S2 (0.093 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P2 (0.093 g) was added and stirred at 60 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 the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high temperature and high humidity storage "," evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) ", and" (PSA cell) &quot;.

&Lt; Example 7 &gt;

NEP (24.2 g) and PB (13.0 g) were added to the polyimide powder (5) (1.15 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 ° C for 24 hours. Then, S1 (0.081 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P2 (0.115 g) was added and stirred at 60 캜 for 6 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 the solution was a homogeneous solution.

Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot; was performed using the obtained liquid crystal alignment treatment agent (7).

&Lt; Example 8 &gt;

NMP (11.6 g), EC (2.10 g) and BCS (7.40 g) were added to the polyimide powder (5) (1.35 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. Subsequently, S2 (0.135 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P3 (0.203 g) was added, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (8). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high-temperature and high-humidity storage "and" evaluation of the voltage holding ratio after the high temperature and high humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 8 .

&Lt; Example 9 &gt;

NEP (13.2 g) and PB (7.10 g) were added to the polyimide powder (6) (1.30 g) obtained by the synthetic method of Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S1 (0.195 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P1 (0.221 g) was added and stirred at 60 占 폚 for 6 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 the solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high temperature and high humidity storage "," evaluation of the voltage holding ratio after high temperature and high humidity storage (normal cell) ", and" (PSA cell) &quot;.

&Lt; Example 10 &gt;

NEP (23.1 g) and PB (12.4 g) were added to the polyimide powder (6) (1.10 g) obtained by the synthetic method of Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S1 (0.165 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P1 (0.187 g) was added and stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (10). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot; was performed using the obtained liquid crystal alignment treatment agent (10).

&Lt; Example 11 &gt;

NEP (8.30 g),? -BL (4.10 g) and BCS (8.30 g) were added to the polyimide powder (7) (1.32 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S2 (0.026 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P2 (0.066 g) was added and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent (11). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; were performed using the obtained liquid crystal alignment treatment agent 11 .

&Lt; Example 12 &gt;

NMP (12.7 g), ECS (2.10 g) and BCS (6.30 g) were added to the polyimide powder (7) (1.35 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S2 (0.095 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P1 (0.068 g) and P2 (0.135 g) were added and stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (12). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of the display non-uniformity characteristics in the vicinity of the frame of the liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; .

&Lt; Example 13 &gt;

NEP (13.2 g) and PB (7.10 g) were added to the polyimide powder (8) (1.30 g) obtained in Synthesis Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S2 (0.091 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P2 (0.13 g) was added and stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (13). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high temperature and high humidity storage "," evaluation of the voltage holding ratio after high temperature and high humidity storage (normal cell) ", and" (PSA cell) &quot;.

&Lt; Example 14 &gt;

NEP (13.2 g) and PB (7.10 g) were added to the polyimide powder (8) (1.30 g) obtained in Synthesis Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S1 (0.065 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P1 (0.039 g) was added, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (14). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 14 .

&Lt; Example 15 &gt;

NEP (10.6 g),? -BL (2.10 g) and PB (8.50 g) were added to the polyimide powder (9) (1.35 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S1 (0.135 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P3 (0.135 g) was added and stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (15). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of the display non-uniformity characteristics in the vicinity of the frame of the liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; were performed using the obtained liquid crystal alignment treatment agent 15 .

&Lt; Example 16 &gt;

NEP (17.8 g),? -BL (3.60 g) and PB (14.2 g) were added to the polyimide powder (9) (1.10 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S1 (0.077 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P3 (0.11 g) was added and stirred at 60 占 폚 for 6 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 the solution was a homogeneous solution.

Evaluation of ink-jet application property of the liquid crystal alignment treatment agent &quot; was performed using the obtained liquid crystal alignment treatment agent (16).

&Lt; Example 17 &gt;

NMP (13.2 g) and PB (7.10 g) were added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S2 (0.13 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P1 (0.195 g) was added and stirred at 60 캜 for 6 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 the solution was a homogeneous solution.

Evaluation of the display non-uniformity characteristics in the vicinity of the frame of the liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) &quot; were performed using the obtained liquid crystal alignment treatment agent 17 .

&Lt; Example 18 &gt;

NEP (13.2 g) and PB (7.10 g) were added to the polyimide powder (10) (1.30 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S1 (0.091 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P1 (0.091 g) and P2 (0.091 g) were added and stirred at 60 캜 for 6 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 the solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) near the frame of the liquid crystal cell after high temperature and high humidity storage "," evaluation of the voltage holding ratio after high temperature and high humidity storage (normal cell) ", and" (PSA cell) &quot;.

&Lt; Example 19 &gt;

Γ-BL (11.6 g), EC (2.10 g) and BCS (7.40 g) were added to the polyimide powder (11) (1.35 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 ° C. for 24 hours. Subsequently, S2 (0.068 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P3 (0.135 g) was added and stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (19). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio (normal cell) after high temperature and high humidity storage were performed using the obtained liquid crystal alignment treatment agent 19 .

&Lt; Example 20 &gt;

NMP (12.2 g), ECS (2.00 g) and BCS (6.10 g) were added to the polyimide powder (11) (1.30 g) obtained in Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. Then, S1 (0.065 g) was added to this solution, and the mixture was stirred at 50 占 폚 for 6 hours. Thereafter, P1 (0.065 g) and P2 (0.065 g) were added and stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treating agent 20. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio (normal cell) after storage at high temperature and high humidity were performed using the obtained liquid crystal alignment treatment agent 20 .

&Lt; Comparative Example 1 &

NEP (10.1 g) and PB (7.70 g) were added to polyamic acid solution (2) (5.60 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 2 and stirred at 25 占 폚 for 2 hours, A treating agent 21 was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; were performed using the obtained liquid crystal alignment treatment agent 21 .

&Lt; Comparative Example 2 &

NEP (9.90 g) and PB (7.50 g) were added to polyamic acid solution (2) (5.50 g) having a resin solid content concentration of 25 mass% obtained by the synthetic method of Synthesis Example 2 and stirred at 25 캜 for 2 hours . Then, P2 (0.097 g) was added to this solution, and the mixture was stirred at 60 캜 for 6 hours to obtain a liquid crystal alignment treatment agent 22. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 22 .

&Lt; Comparative Example 3 &

NEP (9.90 g) and PB (7.50 g) were added to polyamic acid solution (2) (5.50 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 2 and stirred at 25 占 폚 for 2 hours. Subsequently, S1 (0.097 g) was added to this solution, and the mixture was stirred at 50 캜 for 6 hours to obtain a liquid crystal alignment treatment agent 23. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; were performed using the obtained liquid crystal alignment treatment agent 23 .

&Lt; Comparative Example 4 &

NEP (14.3 g) and PB (6.10 g) were added to the polyimide powder (3) (1.30 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 캜 for 24 hours to obtain a liquid crystal alignment treating agent 24 . No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; were performed using the obtained liquid crystal alignment treatment agent 24 .

&Lt; Comparative Example 5 &

NEP (14.3 g) and PB (6.10 g) were added to the polyimide powder (3) (1.30 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. Thereafter, P2 (0.091 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (25). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) near the frame of the liquid crystal cell after high temperature and high humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high temperature and high humidity storage (normal cell) &quot; .

&Lt; Comparative Example 6 &gt;

NEP (14.3 g) and PB (6.10 g) were added to the polyimide powder (3) (1.30 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 24 hours. Subsequently, S2 (0.091 g) was added to this solution, and the mixture was stirred at 50 캜 for 6 hours to obtain a liquid crystal alignment treatment agent 26. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display non-uniformity characteristics (near-frame) of the liquid crystal cell after high-temperature and high-humidity storage (normal cell) &quot; and evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) &quot; were performed using the obtained liquid crystal alignment treatment agent 26 .

&Lt; Comparative Example 7 &

NEP (10.1 g) and PB (7.70 g) were added to polyamic acid solution (4) (5.60 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 4 and stirred at 25 캜 for 2 hours, A treating agent 27 was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 27 .

&Lt; Comparative Example 8 &gt;

NEP (10.1 g) and PB (7.70 g) were added to polyamic acid solution (4) (5.60 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 4 and stirred at 25 占 폚 for 2 hours. Then, P2 (0.098 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (28).

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 28 .

&Lt; Comparative Example 9 &

NEP (10.1 g) and PB (7.70 g) were added to polyamic acid solution (4) (5.60 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 4 and stirred at 25 占 폚 for 2 hours. Subsequently, S1 (0.098 g) was added to this solution and stirred at 50 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (29).

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 29 .

&Lt; Comparative Example 10 &

NEP (13.7 g) and PB (7.40 g) were added to the polyimide powder (5) (1.35 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 캜 for 24 hours to obtain a liquid crystal alignment treating agent 30 . No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio (normal cell) after storage at high temperature and high humidity "were performed using the obtained liquid crystal alignment treatment agent 30 .

&Lt; Comparative Example 11 &

NEP (13.7 g) and PB (7.40 g) were added to the polyimide powder (5) (1.35 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. Then, P2 (0.095 g) was added to this solution, and the mixture was stirred at 60 占 폚 for 6 hours to obtain a liquid crystal alignment treatment agent (31). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of the display unevenness characteristics (normal cell) in the vicinity of the frame of the liquid crystal cell after high-temperature and high-humidity storage "and" evaluation of the voltage holding ratio after the high temperature and high humidity storage (normal cell) "were carried out using the obtained liquid crystal alignment treatment agent 31 .

&Lt; Comparative Example 12 &gt;

NEP (13.7 g) and PB (7.40 g) were added to the polyimide powder (5) (1.35 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. Subsequently, S2 (0.095 g) was added to this solution, and the mixture was stirred at 50 캜 for 6 hours to obtain a liquid crystal alignment treatment agent 32. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

Evaluation of display unevenness characteristics (normal cell) in the vicinity of a frame of a liquid crystal cell after high-temperature and high-humidity storage "and" Evaluation of voltage holding ratio after high-temperature and high-humidity storage (normal cell) "were performed using the obtained liquid crystal alignment treatment agent 32 .

* 1: Disordering of the liquid crystal alignment property was observed in the vicinity of the sealant and the central portion of the cell.

* 2: Disturbance of liquid crystal orientation was observed near the sealant.

As can be seen from the above results, the liquid crystal alignment treatment agent of the examples is superior to the liquid crystal alignment treatment agent of the comparative example in that the liquid crystal alignment treatment agent in the liquid crystal alignment treatment agent of the liquid crystal cell, An orientation film was obtained. Further, even when the liquid crystal cell was stored for a long period of time in a high-temperature and high-humidity bath, a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio was obtained. That is, the liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment film capable of suppressing occurrence of display irregularities near the frame of the liquid crystal display element and lowering of the voltage holding ratio under high temperature and high humidity conditions.

Specifically, it is a comparison of Example 2 and Comparative Example 1, Example 3 and Comparative Example 4, Example 4 and Comparative Example 7, and Example 6 and Comparative Example 10, Comparison of a comparative example in which a specific isocyanate compound as the component (A) is not contained and a specific amine compound as the component (B) is not introduced. When the liquid crystal alignment treatment agent of the comparative example was used, when the liquid crystal cell was stored for a long period of time in a high-temperature and high-humidity bath, disturbance of liquid crystal alignability occurred in the central part of the cell along with the sealant of the liquid crystal cell,

Next, the comparison between Example 2 and Comparative Example 2, Example 3 and Comparative Example 5, Example 4 and Comparative Example 8, and Example 6 with Comparative Example 11, And Comparative Example in which a specific isocyanate compound as the component (A) is used and a specific amine compound as the component (B) is not introduced. In the case of using the liquid crystal alignment treatment agent of the comparative example, when the liquid crystal cell was stored for a long period of time in a high-temperature and high-humidity bath, the liquid crystal alignability in the liquid crystal cell and the voltage holding ratio were lowered, but the characteristics were significantly inferior to those in Examples.

Industrial availability

The liquid crystal display device having a liquid crystal alignment film formed using the liquid crystal alignment treatment agent of the present invention is preferably used for a liquid crystal display device which is excellent in reliability, And is useful as a vertically aligned liquid crystal display element.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-096469 filed on May 1, 2013 are incorporated herein by reference and are hereby incorporated by reference.

Claims (20)

A liquid crystal alignment treatment agent characterized by containing the following components (A), (B) and (C).
Component (A): A compound represented by the following formula [1].
Component (B): A compound represented by the following formula [2].
Component (C): at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.
[Chemical Formula 1]

(X ¹ represents a divalent organic group having an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent organic group having 6 to 24 carbon atoms having a benzene ring or a cyclohexane ring and X ² represents a group represented by the following formulas [ [1-6].)
(2)

(Wherein A ¹ represents a hydrogen atom or a benzene ring, A ² represents a single bond, or a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, A ³ represents 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 fluoro-containing alkoxyl group having 1 to 18 carbon atoms.
(3)

(W ¹ represents an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, W ² represents a single bond, -O-, -NH-, -CO-, -COO-, -OCO-, -NH-, _{N (CH 3) -, -NHCO-} , -N (CH 3) CO-, -CONH-, -CON (CH 3) -, -S- or -SO ₂ - represents, W ³ represents a single bond, a benzene W ⁴ is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N (CH ₃ ) -, -NHCO-, -N (CH ₃ ) CO-, -CONH-, -CON (CH ₃ ) -, -S- or -SO ₂ -, W ⁵ represents an organic group having a single bond, an aliphatic hydrocarbon group or a nonaromatic cyclic hydrocarbon group, n Represents an integer of 1 to 5). The method according to claim 1,
Wherein X ^{1 in} the formula [1] is an alkylene group having 1 to 10 carbon atoms. 3. The method according to claim 1 or 2,
Wherein the liquid crystal alignment treatment agent has a structure in which X ² in the formula [1] is selected from the formulas [1-1], [1-2] and [1-4]. 4. The method according to any one of claims 1 to 3,
A liquid crystal alignment treatment agent wherein W ^{1 in} the formula [2] is a linear or branched alkylene group, a cyclohexane ring or a bicyclohexyl ring having 1 to 10 carbon atoms. 5. The method according to any one of claims 1 to 4,
W ² in the formula [2] is a single bond, -O- or -OCO-. 6. The method according to any one of claims 1 to 5,
Wherein W ^{3 in} the formula [2] is a single bond or a benzene ring. 7. The method according to any one of claims 1 to 6,
Wherein W ⁴ in the formula [2] is a single bond, -O-, -NH- or -CONH-. 8. The method according to any one of claims 1 to 7,
Wherein W ⁵ in the formula [2] is a single bond, a linear or branched alkylene group or a cyclohexane ring having 1 to 10 carbon atoms. 9. The method according to any one of claims 1 to 8,
A liquid crystal alignment treatment agent comprising at least one diamine compound having a structure represented by the following formula [3], wherein the diamine component in the polymer of the component (C) comprises at least one diamine compound.
[Chemical Formula 4]

(Y represents a substituent selected from the following formulas [3-1] to [3-6], and m represents an integer of 1-4)
[Chemical Formula 5]

(a represents an integer of 0 to 4, and b represents an integer of 0 to 4).
Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ² represents a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15), Y ³ is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15) ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 and having a steroid skeleton, The arbitrary 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 fluoro-containing alkoxyl group having 1 to 3 carbon atoms, , Y ⁵ represents a divalent cyclic group selected from benzene ring, a cyclohexane ring and a heterocyclic ring, any of the hydrogen atoms on these cyclic group having 1 3 alkyl group, carbon atoms and may be substituted with one to three of an alkoxy group, fluorine-containing alkyl group, fluorine-containing C 1 -C 3 alkoxy group or a fluorine atom of 1 to 3 carbon atoms, n is an integer of 0 ~ 4, Y ⁶ Represents 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.
Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-, and Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.
Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group of 1 to 12 carbon atoms.
And Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms. 10. The method according to any one of claims 1 to 9,
A liquid crystal alignment treatment agent comprising a tetracarboxylic acid component in the polymer of the component (C) represented by the following formula [4].
[Chemical Formula 6]

(Z ¹ is a group of the structure is selected from formula [4a] ~ formula [4j].)
(7)

(Z ² to Z ^{5 each} represent 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 each represent a hydrogen atom or a methyl group, 11. The method according to any one of claims 1 to 10,
Wherein the polymer of component (C) is a polyimide obtained by dehydrating and ring-closure of polyamic acid. 12. The method according to any one of claims 1 to 11,
Wherein the component (A) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (C). 13. The method according to any one of claims 1 to 12,
Wherein the component (B) is 0.1 to 30 parts by mass based on 100 parts by mass of the component (C). A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 13. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 13 and using an ink jet method. A liquid crystal display element having the liquid crystal alignment film according to claim 14 or 15. 16. The method according to claim 14 or 15,
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and a polymerizable compound capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, A liquid crystal alignment film used in a liquid crystal display device produced by polymerizing the polymerizable compound while applying a voltage. A liquid crystal display element having the liquid crystal alignment film according to claim 17. 16. The method according to claim 14 or 15,
A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable group capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, And then polymerizing the polymerizable group while applying the polymerizable group to the liquid crystal alignment layer. A liquid crystal display element having the liquid crystal alignment film according to claim 19.