KR20150070276A - Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

(식［1a］중, X¹ 은 탄소수 1 ∼ 3 의 알킬기를 나타내고, 식［1b］중, X² 는 탄소수 1 ∼ 3 의 알킬기를 나타낸다). (B) 성분 ： N-메틸-2-피롤리돈, N-에틸-2-피롤리돈 또는 γ-부티로락톤에서 선택되는 적어도 1 개의 용매. (C) 성분 ： 카르복실기를 갖는 디아민 화합물을 함유하는 디아민 성분과 테트라카르복실산 2 무수물 성분을 반응시켜 얻어지는 폴리이미드 전구체 또는 폴리이미드에서 선택되는 적어도 1 종의 중합체.A composition comprising the following components (A), (B) and (C). Component (A): At least one solvent selected from the following formula [1a] or formula [1b].

(In the formula [1a], X ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms. Component (B): at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyrolactone. Component (C): at least one polymer selected from a polyimide precursor or polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic acid dianhydride component.

Description

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

The present invention relates to a composition used for forming a resin film, 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 using the liquid crystal alignment film.

The resin film made of an organic material such as a polymer material is widely used as an interlayer insulating film or a protective film in an electronic device, with attention being paid to ease of formation and insulation performance. Among them, in a liquid crystal display element well known as a display device, a resin film made of an organic material is used as a liquid crystal alignment film.

At present, a polyimide-based organic film having excellent durability is used as a resin film used industrially. This polyimide-based organic film is formed of a composition containing a polyimide precursor polyamide acid or polyimide. That is, the polyimide-based organic film is formed by applying a composition containing polyamic acid or polyimide to the substrate, followed by a firing process. At that time, usually, these compositions use a solvent having a high boiling point such as N-methyl-2-pyrrolidone (also referred to as NMP) or? -Butyrolactone (also referred to as? -BL) It is necessary to sinter at a high temperature of about 300 DEG C (see, for example, Patent Document 1).

Japanese Laid-Open Patent Publication No. 09-278724

When a liquid crystal alignment film containing a polyimide-based polymer is used to form a liquid crystal alignment film, the firing process requires a high temperature in the process for producing a liquid crystal display element for the reasons described above. This is because a liquid crystal alignment treatment agent containing a polyimide-based polymer needs a high temperature in that NMP or? -BL is used as a solvent for dissolving a polyimide-based polymer. However, when a substrate of a liquid crystal display element is replaced by a thin and lightweight plastic substrate having low heat resistance instead of a usual glass substrate, firing at a lower temperature is required. Similarly, in order to suppress deterioration of color characteristics of a color filter of a liquid crystal display element accompanied by firing at a high temperature, and further to reduce the energy cost in the production of a liquid crystal display element, do.

The liquid crystal alignment film is formed by applying a liquid crystal alignment treatment agent to a substrate, and then firing the coating film. At this time, for the purpose of enhancing the film property (also referred to as coatability) of the liquid crystal alignment film, that is, suppressing the occurrence of pinholes accompanying cratering or foreign matter, it is preferable to increase the wettability of the liquid crystal alignment treatment agent .

Accordingly, it is an object of the present invention to provide a composition having the aforementioned characteristics. That is, an object of the present invention is to provide a composition capable of forming a resin coating film by firing at a low temperature in a composition containing a polyimide-based polymer. It is another object of the present invention to provide a composition having improved coatability on a substrate when a resin film is formed.

It is another object of the present invention to provide a liquid crystal alignment treatment agent capable of forming a liquid crystal alignment film by firing at a low temperature in the liquid crystal alignment treatment agent using the above-described composition. It is another object of the present invention to provide a liquid crystal alignment treatment agent which improves the coating property on a substrate when forming a liquid crystal alignment film.

It is another object of the present invention to provide a liquid crystal alignment film corresponding to the above-described requirements. That is, it is an object of the present invention to provide a liquid crystal alignment film which can be formed by firing at a low temperature, and to provide a liquid crystal alignment film in which coating property to a substrate is improved.

Another object of the present invention is to provide a liquid crystal display element provided with a liquid crystal alignment film corresponding to the above-described demand.

As a result of intensive studies, the present inventors have found that a polyimide precursor obtained by reacting a diamine component containing a diamine compound having a specific structure and a diamine compound having a carboxyl group with a tetracarboxylic acid dianhydride component, The present inventors have found that a composition containing a polymer is very effective for achieving the above object, and accomplished the present invention.

That is, the present invention has the following points.

(1) A composition comprising the following components (A), (B) and (C).

Component (A): At least one solvent selected from the following formula [1a] or formula [1b].

[Chemical Formula 1]

(In the formula [1a], X ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms.

Component (B): at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyrolactone.

Component (C): at least one polymer selected from a polyimide precursor or polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic acid dianhydride component.

(2) The composition according to the above (1), wherein the component (A) is 50 to 99 mass% of the total solvent contained in the composition.

(3) The composition according to (1) or (2) above, wherein the diamine compound having a carboxyl group as the component (C) is a diamine compound having a structure represented by the following formula [2].

(2)

(In the formula [2], a represents an integer of 0 to 4).

(4) The composition according to the above (1) or (2), wherein the diamine compound having a carboxyl group as the component (C) is a diamine compound having a structure represented by the following formula (2a).

(3)

(In the formula [2a], a represents an integer of 0 to 4, and n represents an integer of 1 to 4).

(5) The composition according to (3) or (4) above, wherein the diamine compound having a carboxyl group is contained in an amount of 20 mol% to 100 mol% in the total diamine used in the component (C).

(6) The process according to any one of (1) to (5) above, wherein the diamine component of the component (C) contains at least one diamine compound selected from the structures represented by the following formula [2b] ≪ / RTI >

[Chemical Formula 4]

(In the formula [2b], Y represents a structure represented by the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] m represents an integer of 1 to 4).

[Chemical Formula 5]

(Wherein a is an integer of 0 to 4, and Y ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15) in the formula [2b-2] , -O-, -CH ₂ represents an O-, -COO- or -OCO-, Y ² is a single bond or - (CH _{2) b} - represents a (b is an integer of 1 ~ 15), Y ³ is a single _{bond, - (CH 2) c -} (c is an integer from 1 to 15), represents an -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ is a benzene ring, a cyclohexane ring Or a divalent cyclic group selected from a heterocyclic ring or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms , optionally substituted with a fluorine-containing alkyl group, fluorine-containing alkoxy group of 1 to 3 carbon atoms or fluorine atoms of 1 to 3 carbon atoms and, Y ⁵ is a divalent cyclic selected from a benzene ring, a cyclohexane ring or a heterocyclic ring group, And any hydrogen atoms 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 fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom may be, n represents an integer of 0 ~ 4, Y ⁶ is a fluorine-containing alkoxyl group having 1 to 18 alkyl group, having 1 to 18 fluorine-containing alkyl group, having 1 to 18 carbon atoms, an alkoxyl group or a C 1 to 18 of the represents the formula [2b-3] of the, Y ⁷ represents an alkyl group of a carbon number of 8 to 22, formula [2b-4] of, Y ⁸ and Y ⁹ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, formula [ 2b-5], Y ¹⁰ represents an alkyl group having 1 to 8 carbon atoms.

(7) The composition according to any one of (1) to (6) above, wherein the tetracarboxylic acid dianhydride component of the component (C) is a compound represented by the following formula [3].

[Chemical Formula 6]

(In the formula [3], Z ¹ is a group of at least one structure selected from the following formulas [3a] to [3j]).

(7)

(Formula [3a] of, Z ² ~ Z ⁵ represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, may be the same or different in each occurrence, formula [3g] from, Z ⁶ and Z ⁷ is a hydrogen atom or a methyl group And may be the same or different from each other).

(8) The positive resist composition as described in any one of (1) to (8) above, wherein the component (D) is 1-hexanol, (1) to (7) above, wherein the solvent comprises at least one solvent selected from the group consisting of ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether and diethylene glycol monobutyl ether. Lt; RTI ID = 0.0 > 1, < / RTI >

(9) A resin film obtained from the composition according to any one of (1) to (8).

(10) A liquid crystal alignment treatment agent obtained from the composition according to any one of (1) to (8).

(11) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to (10) above.

(12) A liquid crystal alignment film obtained by the ink jet method using the liquid crystal alignment treatment agent according to (10) above.

(13) A liquid crystal display element having the liquid crystal alignment film according to (11) or (12) above.

(14) A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and containing a polymerizable compound polymerized by at least one of an active energy ray and heat between the pair of substrates (11) or (12) above, wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured by a process of polymerizing the polymerizable compound while applying a voltage between the electrodes.

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

(16) A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, and comprising a polymerizable group polymerized by at least one of active energy rays and heat between the pair of substrates The liquid crystal alignment film according to (11) or (12) above, which is used for a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage between the electrodes.

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

A composition containing at least one polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component containing a solvent having a specific structure of the present invention and a diamine compound having a carboxyl group and a tetracarboxylic acid dianhydride component The resin coating can be formed by firing at a low temperature. In addition, the composition of the present invention can improve the wettability to the substrate and suppress the generation of pinholes accompanying cratering or foreign matter on the resin coating.

The liquid crystal alignment treatment agent comprising the composition of the present invention can form a liquid crystal alignment film by firing at a low temperature. This liquid crystal alignment treatment agent can improve the wettability with respect to the substrate and can suppress the generation of pinholes accompanying cratering or foreign matter on the liquid crystal alignment film. Therefore, the liquid crystal display element having the liquid crystal alignment film thus obtained can have high reliability.

As a result of intensive studies, the present inventors have obtained the following findings and have completed the present invention.

The present invention relates to a composition containing the following components (A), (B) and (C), a liquid crystal alignment treatment agent, a resin film obtained by using the composition, a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, , And a liquid crystal display element having the liquid crystal alignment film.

Component (A): At least one solvent (also referred to as a specific alcohol solvent) selected from the following formula [1a] or formula [1b].

[Chemical Formula 8]

(In the formula [1a], X ¹ represents an alkyl group having 1 to 4 carbon atoms, and in the formula [1b], X ² represents an alkyl group having 1 to 4 carbon atoms.

Component (B): at least one solvent (also referred to as a specific polar solvent) selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyrolactone.

Component (C): At least one polymer (also referred to as a specific polymer) selected from a polyimide precursor or polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic acid dianhydride component.

The specific alcoholic solvent of the present invention usually has a lower boiling point than NMP or? -BL used in the main solvent of a composition containing a polyimide-based polymer and is capable of dissolving a specific polymer of the present invention have. Therefore, by increasing the introduction amount of the specific alcohol-based solvent in the entire solvent contained in the composition of the present invention, it is possible to form the resin coating by firing at a low temperature.

The specific alcoholic solvent of the present invention usually has a lower surface tension as a solvent than a solvent such as NMP or? -BL used in a composition having a polyimide-based polymer. Therefore, the composition using a specific solvent has a high wettability to the substrate. Therefore, occurrence of pinholes accompanying cratering on the resin coating can be suppressed.

In addition, since the specific polar solvent of the present invention has a high effect of dissolving a specific polymer, it is possible to suppress the occurrence of pinholes accompanying foreign matters on the resin coating film when the substrate is coated.

In view of the above, the composition of the present invention can form a resin film by firing at a low temperature. Further, the composition of the present invention can improve the wettability to the substrate and suppress the generation of pinholes accompanying cratering or foreign matter on the resin coating. In addition, the liquid crystal alignment treatment agent obtained from the composition of the present invention can also achieve the above-mentioned effects for the same reason.

Hereinafter, embodiments of the present invention will be described in detail.

≪ Specific alcohol solvent >

The specific alcoholic solvent as the component (A) of the present invention is at least one solvent selected from the following formula [1a] or formula [1b].

[Chemical Formula 9]

(In the formula [1a], X ¹ represents an alkyl group having 1 to 3 carbon atoms).

(In the formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms.)

Specifically, the structures represented by the following formulas [1a-1] to [1a-4] and the formulas [1b-1] to [1b-4] can be mentioned.

[Chemical formula 10]

Among them, the formula [1a-1], the formula [1b-1], the formula [1b-2] or the formula [1b-3] are preferable in view of the boiling point and the availability of the solvent.

The specific alcoholic solvent of the present invention is preferably 50 to 99 mass% of the total solvent contained in the composition in order to enhance the effect of increasing the wettability to the above-described substrate. Among these, 55 to 99 mass% is preferable. More preferred is 55 to 95 mass%.

The greater the amount of the specific alcoholic solvent of the present invention in the entire solvent in the composition, the better the effect of the present invention, that is, the resin coating or the liquid crystal alignment film can be formed by firing at a low temperature, It is possible to obtain a resin coating film or a liquid crystal alignment film excellent in coating property.

<Specific polar solvent>

The specific polar solvent as the component (B) of the present invention is at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyrolactone.

Among them, N-ethyl-2-pyrrolidone or? -Butyrolactone is preferable. More preferred is gamma -butyrolactone.

The specific polar solvent of the present invention is characterized in that a resin film or a liquid crystal alignment film is formed by firing at the above-mentioned low temperature and a pinhole accompanying the foreign substance on the resin film film is formed when the composition or the liquid crystal alignment treatment agent is applied to the substrate It is preferably 1 to 40% by mass of the total solvent contained in the composition. Among them, it is preferably 1 to 35% by mass. The content is more preferably from 1 to 30% by mass, and still more preferably from 5 to 30% by mass.

&Lt; Specific polymer &

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

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

(11)

(Wherein [A], R ¹ is a tetravalent organic group, R ² is a divalent organic group having a carboxyl group, A ¹ and A ² is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, it may be each the same or different And n represents a positive integer).

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

The specific polymer of the present invention can be obtained by relatively easily obtaining a diamine compound having a carboxyl group represented by the following formula [B] and a tetracarboxylic acid dianhydride represented by the following formula [C] D] or a polyimide obtained by imidizing the polyamic acid is preferable.

[Chemical Formula 12]

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

[Chemical Formula 13]

(In formula [D], R ¹ and R ² are as defined in formula [A]).

<Diamine Compound Having Carboxyl Group>

The diamine compound having a carboxyl group of the present invention is a diamine compound having a structure represented by the following formula [2] in the molecule.

[Chemical Formula 14]

In the formula [2], a 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.

Specific examples of the diamine compound having a structure represented by the formula [2] include a structure represented by the following formula [2a].

[Chemical Formula 15]

In formula [2a], 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 [2a], n represents an integer of 1 to 4. Among them, 1 is preferable from the viewpoint of easiness of synthesis.

The method for producing the diamine compound represented by the formula [2a] of the present invention is not particularly limited, but preferred examples include the following.

As an example, the diamine compound represented by the formula [2a] can be obtained by synthesizing a dinitro compound represented by the following formula [2a-A], reducing the nitro group and converting it into an amino group.

[Chemical Formula 16]

(In the formula [2a-A], a represents an integer of 0 to 4, and n represents an integer of 1 to 4).

The method for reducing the dinitro group of the dinitro compound represented by the formula [2a-A] is not particularly limited, and typically, a solvent such as palladium (II) acetate, toluene, tetrahydrofuran, dioxane or alcohol- Hydrazine or hydrogen chloride using carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina or platinum sulfide carbon as a catalyst.

Examples of the diamine compound having a carboxyl group of the present invention include structures represented by the following formulas [2a-1] to [2a-4].

[Chemical Formula 17]

In the formula ^[2a-1], A 1 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-. Among them, a single bond, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, -CO-, -NH-, -N (CH ₃ ) -, -CONH- , -NHCO-, -COO- or -OCO-. More preferred is a single bond, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, -CO-, -NH- or -N (CH ₃ ) -.

In the formula [2a-1], m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4. In particular, m ¹ + m ² is 1 or 2 are preferred.

In the formula [2a-2], m ³ and m ⁴ each represent an integer of 1 to 5. Among them, 1 or 2 is preferable from the viewpoint of ease of synthesis.

In the formula [2a-3], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. Among them, a linear alkyl group having 1 to 3 carbon atoms is preferable.

In the formula [2a-3], m ⁵ represents an integer of 1-5. Among them, 1 or 2 is preferable.

In the formula [2a-4], A ³ is a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF 2 -, -C (CF 3) 2 -, - O-, -CO-, -NH-, -N ( CH 3) -, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH ₃₎ - or -N (CH ₃₎ represents a CO-. Among them, a single bond, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ - , -COO-, or -OCO-. More preferred are -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 - is, -COO- or -OCO-.

In the formula [2a-4], m ⁶ represents an integer of 1 to 4. Among them, 1 is preferable from the viewpoint of easiness of synthesis.

The diamine compound having a carboxyl group of the present invention is preferably 20 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, of the total diamine component.

The above-mentioned diamine compound having a carboxyl group can be used in one kind or two or more kinds depending on the solubility of the specific polymer of the present invention in the solvent, the coating property of the composition, the orientation of the liquid crystal when the liquid crystal alignment film is used, Or a mixture of two or more of them may be used.

&Lt; Second diamine compound &gt;

As the diamine component for producing the specific polymer of the present invention, a diamine compound (also referred to as a second diamine compound) represented by the following formula [2b] may be used as the second diamine compound.

[Chemical Formula 18]

(2b-2), (2b-3), (2b-4) Represents an integer of 0 to 4).

[Chemical Formula 19]

In the formula [2b-1], a 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.

Y ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or -OCO- in the formula [2b-2] . 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 preferred is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In the formula [2b-2], 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 [2b-2], 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 a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In formula [2b-2], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, An alkoxyl group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluoro-containing alkoxyl group of 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 [2b-2], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, An alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a 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 [2b-2], 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 [2b-2], 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.

Preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2b-2] for constituting the substituent Y in the formula [2b] (2-1) to (2-629) listed in Tables 6 to 47 of Tables 13 to 34 of International Patent Application No. 132751 (published on October 27, 2011). In each table of the International Publication, Y ¹ to Y ⁶ in the present invention are represented as Y ¹ to Y ⁶ , while Y ¹ to Y ⁶ are read in Y ¹ to Y ⁶ .

In the formula [2b-3], Y ⁷ represents an alkyl group of a carbon number of 8 to 22.

In the formula [2b-4], Y ⁸ and Y ⁹ each independently represent a hydrocarbon group having 1 to 6 carbon atoms.

In the formula [2b-5], Y ¹⁰ represents an alkyl group having 1 to 8 carbon atoms.

The method for producing the diamine compound represented by the formula [2b] of the present invention is not particularly limited, and preferable examples include the following.

As an example, the diamine compound represented by the formula [2b] can be obtained by synthesizing a dinitro compound represented by the following formula [2b-A], reducing the nitro group and converting it into an amino group.

[Chemical Formula 20]

(Wherein Y is at least one selected from the above-mentioned formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5] And m represents an integer of 0 to 4).

The method for reducing the dinitro group of the dinitro compound represented by the formula [2b-A] is not particularly limited, and typically, a solvent such as palladium (II) acetate, toluene, tetrahydrofuran, dioxane or alcohol- Hydrazine or hydrogen chloride using carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina or platinum sulfide carbon as a catalyst.

Specific structures of the second diamine compound represented by the formula [2] of the present invention are shown below, but the present invention is not limited to these examples.

Namely, examples of the second diamine represented by the formula [2] include m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5 Diaminobenzyl alcohol, 2,4,6-diaminobenzyl alcohol, 4,6-diaminoresorcinol, and the like represented by the following formulas [2b-6] to [2b-46] Diamine compound of the structure

[Chemical Formula 21]

(In the formula [2b-6] ~ formula [2b-9], A ¹ represents an alkyl group or a fluorine-containing alkyl group having a carbon number of 1 to 22).

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

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

(34)

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

(35)

(Formula [2b-40] and formula [2b-41] of, R ⁵ is _{-COO-, -OCO-, -COOCH 2 -,} -CH 2 OCO-, -CH 2 O-, -OCH 2 -, - CH ₂ - or -O-, and 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.

(36)

(- trans isomer is preferred trans reason each formula [2b-42] and formula [2b-43] of, R ⁷ is a system having a carbon number of an alkyl group of 3 to 12. In addition, 1,4-cyclohexylene).

(37)

(In the formulas [2b-44] and formula [2b-45], 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.

(38)

(In the formula [2b-46], 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- * (provided that a bonding hand to which &quot; * &quot; is bonded is bonded to B ³ ), B ¹ represents an oxygen atom or -COO- * 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 second diamine compounds of the present invention, a composition using a diamine compound having a structure represented by the formula [2b-2] of the substituent Y in the formula [2b] can increase the hydrophobicity of the resin film. Further, when the liquid crystal alignment film is used, the pretilt angle of the liquid crystal can be increased. Among these diamine compounds, diamine compounds represented by the formulas [2b-28] to [2b-39] or the formulas [2b-42] to [2b-46] are used . More preferred are diamine compounds represented by the formulas [2b-24] to [2b-39] or the formulas [2b-42] to [2b-46]. In order to further improve these effects, it is preferable that these diamine compounds are contained in an amount of not less than 5 mol% and not more than 80 mol% of the total diamine component. More preferably, these diamine compounds are contained in an amount of not less than 5 mol% and not more than 60 mol% of the total diamine component from the viewpoints of coating properties of the composition and the liquid crystal alignment treatment agent and electrical characteristics as a liquid crystal alignment film. Particularly preferably, it is 10 mol% or more and 60 mol% or less of the total diamine component.

The second diamine compound of the present invention may contain one or two or more kinds of monomers selected depending on the solubility or coating properties of the specific polymer of the present invention, the orientation of the liquid crystal when the liquid crystal alignment film is used, the voltage retention rate, Or more.

<Other diamine compounds>

Specific polymers of the present invention may contain a diamine compound having a carboxyl group in the molecule represented by the formula [2a], a formula [2a-1] to a formula [2a-4] ], Other diamine compounds (also referred to as other diamine compounds) can be used as the diamine component.

Specific examples of other diamine compounds are shown below, but the present invention is not limited to these examples.

Examples of other diamine compounds include 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro- , 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'-diaminodiphenylmethane, Diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- Aminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiamine, 3,3'-sulfonyldiamine, bis Bis (3-aminophenyl) silane, dimethyl-bis (4-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 Naphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2- Bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) Bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3- Phenylene bis (methylene)] dianiline, 3, 4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ 4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, 3,3' - [ Phenylene] methanone], 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [ Bis (4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (3-aminobenzo 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) hexaflue 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- Dodecane, 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and the like.

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 polycyclic substituent composed of these may also be cited. Specifically, the diamine compounds represented by the following formulas [DA1] to [DA13] can be exemplified.

[Chemical Formula 39]

(40)

(41)

(Wherein [DA1] ~ formula [DA6] of, A ¹ is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 - represents, -O-, -CO- or -NH-, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(42)

(In the formula [DA7], 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 they do not impair the effect of the present invention.

(43)

(44)

(In the formula [DA10], m represents an integer of 0 to 3, and in the formula [DA13], n represents an integer of 1 to 5).

In addition, as long as the effect of the present invention is not impaired, a diamine compound represented by the following formula [DA14] may be used.

[Chemical Formula 45]

(Wherein [DA14] of, A ¹ is _{-O-, -NH-, -N (CH 3} ) -, -CONH-, -NHCO-, -CH 2 O-, -OCO-, -CON (CH 3) - or -N (CH ₃₎ is a divalent organic group selected from CO-, a ² is a single bond, C 1 -C 20 aliphatic hydrocarbon group, non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, a ³ is a single -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) -, -N (CH ₃ ) Or -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.

In addition, as other diamine compounds, diamine compounds represented by the following formulas [DA15] and [DA16] may be used.

(46)

The other diamine compounds may be used alone or in combination of two or more kinds, depending on the solubility of the specific polymer of the present invention in the solvent, the coating property of the composition, the orientation of the liquid crystal when the liquid crystal alignment film is used, Two or more kinds may be mixed and used.

&Lt; Tetracarboxylic acid dianhydride component &gt;

As the tetracarboxylic acid dianhydride component for producing a specific polymer of the present invention, a tetracarboxylic acid anhydride or a tetracarboxylic acid derivative (also referred to as a specific tetracarboxylic acid dianhydride component) represented by the following formula [3] .

(47)

In the formula [3], Z ¹ is a group of at least one structure selected from the following formulas [3a] to [3j].

(48)

In the formula [3a], 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.

In the formula [3g], 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 [3], which is a specific tetracarboxylic acid dianhydride component of the present invention, Z ¹ is preferably a tetracarboxylic acid dianhydride represented by the formula [3a], the formula [ 3c], the formula [3d], the formula [3e], the formula [3f] or the formula [3g]. More preferred is a structure represented by Formula [3a], Formula [3e], Formula [3f] or Formula [3g], and particularly preferred is Formula [3e], Formula [3f] or Formula [3g].

The specific tetracarboxylic acid dianhydride component of the present invention is preferably at least 1 mol% of the total tetracarboxylic acid dianhydride component. More preferably, it is 5 mol% or more, particularly preferably 10 mol% or more.

When the specific tetracarboxylic acid dianhydride component having the structure of the formula [3e], the formula [3f] or the formula [3g] is used, the amount of the tetracarboxylic acid dianhydride component to be used is preferably 20 mol% or more of the total amount of the tetracarboxylic acid dianhydride component A desired effect can be obtained. Preferably, it is at least 30 mol%. The tetracarboxylic acid dianhydride component may be a tetracarboxylic acid dianhydride component having the structure of the formula [3e], the formula [3f] or the formula [3g].

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

As other tetracarboxylic acid dianhydride components, tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds or dialkyl ester dihalide compounds shown below may be used. .

That is, other tetracarboxylic acid dianhydride components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5 , 8-naphthalene tetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetra Carboxylic acid, 2,3,3 ', 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis Bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2, (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,5-pyridine tetracarboxylic acid, 2,6- 9,10-perylene tetracarboxylic acid There may be mentioned 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid.

The specific tetracarboxylic acid dianhydride component and the other tetracarboxylic acid dianhydride component can be suitably selected depending on the solubility of the specific polymer of the present invention in the solvent or the coating property of the composition, the orientation of the liquid crystal in the case of a liquid crystal alignment film, One or two or more kinds of them may be mixed and used depending on the characteristics such as charge,

&Lt; Process for producing specific polymer &

In the present invention, a method of synthesizing a specific polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid dianhydride component. Generally, a polyamic acid is reacted with at least one tetracarboxylic acid dianhydride component selected from the group consisting of tetracarboxylic acid and its derivatives and a diamine component composed of one or more kinds of diamine compounds, . Specifically, there are a method of polycondensation of a tetracarboxylic acid dianhydride and a diamine component to obtain a polyamic acid, a method of obtaining a polyamic acid by dehydration polycondensation reaction of a tetracarboxylic acid and a diamine component or a method in which a tetracarboxylic acid dihalide and a diamine A method of polycondensing the components to obtain a polyamic acid is used.

To obtain the polyamide acid alkyl ester, a method of polycondensation of a tetracarboxylic acid having a carboxylic acid group with a dialkyl ester and a diamine component, a method of polycondensation of a diamine component with a tetracarboxylic dihalide obtained by dialkyl esterifying a carboxylic acid group Or a method of converting a carboxyl group of a polyamic acid into an ester is used.

To obtain the polyimide, a method of converting the above polyamic acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The reaction of the diamine component and the tetracarboxylic acid dianhydride component is usually carried out in an organic solvent with a diamine component and a tetracarboxylic acid dianhydride component. The organic solvent to be used at this time is not particularly limited as long as it dissolves the specific alcohol solvent as the component (A), the specific polar solvent as the component (B), and further the resulting polyimide precursor.

Examples of the solvent other than the specific alcoholic solvent and the specific polar solvent of the present invention include the following solvents.

That is, it is preferable to use a solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl- imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy- 4-methyl-2-pentanone, and the like.

These may be used alone or in combination. The solvent may be a solvent that does not dissolve the polyimide precursor, or may be mixed with the solvent to the extent that the resulting polyimide precursor does not precipitate. In addition, water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, and therefore, the organic solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic acid dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred to disperse or dissolve the tetracarboxylic acid dianhydride component intact or in an organic solvent A method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride component and a diamine component, and the like Any of these methods may be used. When a plurality of diamine components or tetracarboxylic acid dianhydride components are used to carry out the reaction, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, or the low molecular weight compounds reacted individually are mixed and reacted It may be a polymer. The polymerization temperature at that time may be any temperature between -20 DEG C and 150 DEG C, preferably between -5 DEG C and 100 DEG C. The reaction can be carried out at an arbitrary concentration, but 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 too high, and uniform stirring becomes difficult. 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 number of moles of the diamine component to the total number of the moles of the tetracarboxylic acid dianhydride 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 above-mentioned polyimide precursor. In this polyimide, the closed rate (also referred to as imidization rate) of the amide acid group does not necessarily have to be 100% Can be adjusted arbitrarily.

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

When the polyimide precursor is thermally imidized in a solution, the temperature is preferably 100 deg. C to 400 deg. C, and more preferably 120 deg. C to 250 deg. C. It is preferable to carry out the removal while removing 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, and the like. Of these, pyridine is preferred because it has a suitable basicity for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. 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 in 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, by repeating the operation of re-dissolving the polymer recovered and precipitated in the organic solvent and re-precipitating and recovering the polymer 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones or hydrocarbons can be exemplified, and when three or more kinds of solvents selected from these solvents are used, the purification efficiency is further improved, which is preferable.

The molecular weight of the specific polymer of the present invention is preferably from 5,000 to 1,000,000, more preferably from 5,000 to 1,000,000, in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography), in consideration of the strength of the resin film or liquid crystal alignment film obtained therefrom, , And more preferably from 10,000 to 150,000.

<Composition / liquid crystal alignment treatment agent>

The composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention is a coating solution for forming a resin coating or a liquid crystal alignment layer (collectively referred to as a resin coating) and forms a resin coating containing a specific alcoholic solvent, a specific polar solvent and a specific polymer .

In the composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention, all the polymer components may be the specific polymer of the present invention, and other polymers may be mixed with the specific polymer of the present invention. At that time, the content of the other polymer is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass of the specific polymer of the present invention. Examples of the other polymer include a polyimide precursor or polyimide which does not use a diamine compound having a carboxyl group, a second diamine compound, or a specific tetracarboxylic acid dianhydride component. Further, polymers other than polyimide precursors and polyimides, specifically, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, and the like can be given.

The organic solvent in the composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention preferably has an organic solvent content of 70 to 99.9 mass% from the viewpoint of forming a uniform resin film by coating. This content can be appropriately changed depending on the thickness of the intended resin film or liquid crystal alignment film.

All of the organic solvents in the organic solvent used in the composition of the present invention or the liquid crystal alignment treatment agent using the same may be the specific alcoholic solvent and the specific polar solvent of the present invention. Organic solvents may be mixed.

At this time, the specific alcoholic solvent of the present invention is preferably 50 to 99% by mass of the total solvent contained in the composition. Among these, 55 to 99 mass% is preferable. More preferred is 55 to 95 mass%.

The specific polar solvent of the present invention is preferably 1 to 40% by mass of the total solvent contained in the composition. Among them, it is preferably 1 to 35% by mass. The content is more preferably from 1 to 30% by mass, and still more preferably from 5 to 30% by mass.

The other organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving a specific polymer. Specific examples thereof are given below.

For example, there may be mentioned N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl- imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-methyl-2-pentanone, and the like.

The composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention may contain an organic solvent which improves the film properties or surface smoothness of the resin film or the liquid crystal alignment film when the composition or the liquid crystal alignment treatment agent using the composition is applied, , That is, a poor solvent can be used.

Specific examples of the poor solvent for improving the coating film property and surface smoothness of the resin coating film or the liquid crystal alignment film are shown below.

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 Diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monohexyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, Propyl ether, diethylene glycol isopropyl ether, or diethylene glycol monobutyl ether, propylene glycol, propylene glycol monobutyl ether, 1- (butoxy Propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate , Triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, But are not limited to, ethyl acetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, , Lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactic acid ester, n-butyl lactic acid ester or lactic acid diisobutyl ester are low organic solvents having a low surface tension.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether or diethylene glycol monobutyl ether (also referred to as component (D)) is preferably used.

These components (D) are preferably contained in an amount of 1 to 50 mass% of the entire organic solvent contained in the composition or the liquid crystal alignment treatment agent using the composition. Among them, 1 to 40% by mass is preferable. The content is more preferably from 5 to 30 mass%, and still more preferably from 10 to 30 mass%.

As long as the effect of the present invention is not impaired, the composition of the present invention or the liquid crystal alignment treatment agent using the composition may contain a crosslinkable 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 , Or a crosslinkable compound having at least one kind of substituent selected from the group consisting of a polymerizable unsaturated bond may be introduced. These substituents and polymerizable unsaturated bonds need to have two or more of the crosslinkable compounds.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolak 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) Bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane or 1,3- ) Phenyl) -1- ( 1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol, and the like.

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

(49)

Specifically, it is a crosslinkable compound represented by the following formulas [4-1] to [4-11].

(50)

(In the formula [4-1], n represents an integer of 1 to 3).

(51)

(52)

(53)

(4-7), n represents an integer of 1 to 3, and n in the formula [4-8] represents an integer of 1 to 3, and n in the formula [4-9] Lt; / RTI &gt;

(54)

(In the formula [4-11], n represents an integer of 1 to 10).

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

(55)

Specifically, it is a crosslinkable compound represented by the following formulas [5-1] to [5-37].

(56)

(57)

(58)

[Chemical Formula 59]

(60)

(61)

(62)

(63)

&Lt; EMI ID =

(65)

(66)

(67)

(In the formula [5-24], n represents an integer of 1 to 10, and in the formula [5-25], n represents an integer of 1 to 10).

(68)

(69)

(70)

(71)

(72)

(In the formula [5-36], n represents an integer of 1 to 100, and in the formula [5-37], n represents an integer of 1 to 10).

Also, a polysiloxane having at least one structure represented by the following formulas [5-38] to [5-40] may be used.

(73)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, a carbon number An alkyl group, an alkoxyl group, an aliphatic ring or an aromatic ring of 1 to 10 carbon atoms, and at least one of them represents a structure represented by the formula [5].

More specifically, the compounds of the following formulas [5-41] and [5-42] can be mentioned.

&Lt; EMI ID =

(In the formula [5-42], n represents an integer of 1 to 10).

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group such as a melamine resin, Formaldehyde resin, succinamide-formaldehyde resin or 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 a methoxymethyl group is substituted on average 3.7 per 1 triazine ring of a commercial product, MW- Methomethylated melamines such as Cymel 235, 236, 238, 212, 253, and 309 (manufactured by Sanwa Chemical Co., Ltd.) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 254, methoxymethylated butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, methoxymethylated ethoxymethylated melamine such as Cymel 1123, Guanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl-containing methoxymethylated methoxymethylated ethoxymethylated benzoate such as Cymel 1125-80 Guanamine (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, or 2,6-dihydroxymethyl-p-tert-butylphenol.

More specifically, there are listed crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed on pages 62 to 66 of International Publication 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) Acryloyloxyethoxy trimethylol propane or glycerin polyglycidyl ether poly (meth) acrylate, and also crosslinking compounds having three polymerizable unsaturated groups in the molecule, such as ethylene glycol di (meth) acrylate, diethylene Acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene (Meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (Meth) acrylate such as di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalic acid neopentyl glycol di (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxypropyl Rate, 2 A crosslinkable compound having one polymerizable unsaturated group such as - (meth) acryloyloxyethyl phosphate ester or N-methylol (meth) acrylamide.

In addition, a compound represented by the following formula [7] may be used.

(75)

(Wherein E ₁ represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring) And E ₂ represents a group selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4).

[Formula 76]

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

The content of the crosslinkable compound in the composition of the present invention or the liquid crystal alignment treatment agent using it 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, in order for the crosslinking reaction to proceed and to exhibit the intended effect.

As a compound for promoting charge transfer in the liquid crystal alignment film and promoting charge leakage of the liquid crystal cell using the liquid crystal alignment film when the liquid crystal alignment treatment agent using the composition of the present invention is used as a liquid crystal alignment film, It is preferable to add a nitrogen-containing heterocyclic amine compound represented by the formula [M1] to the formula [M156], which is disclosed on pages 69 to 73 of Published Dec. 27, 2011. The amine compound may be directly added to the composition, but it is preferable to add the amine compound in an appropriate solvent at a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass. This solvent is not particularly limited as long as it is an organic solvent capable of dissolving the above-mentioned polymer.

The composition of the present invention or the liquid crystal alignment treatment agent using the composition can improve the uniformity of the film thickness or the surface smoothness of the resin film or the liquid crystal alignment film when the composition or the liquid crystal alignment treatment agent using the composition is applied, May be used. Further, a compound for improving the adhesion of the resin film or the liquid crystal alignment film to the substrate may be used.

Examples of the compound which improves the uniformity of the film thickness or the surface smoothness of the resin coating film or the liquid crystal alignment film include a fluorinated surfactant, a silicon surfactant and a nonionic surfactant.

More specifically, for example, EF301, EF303 and EF352 (manufactured by Tohchem Products Corporation), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals, Inc.), Florad FC430 and FC431 (Available from Asahi Glass Co., Ltd.), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.). The ratio of these surfactants to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of all the polymer components contained in the composition or the liquid crystal alignment treatment agent.

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

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

When a compound which adheres to these substrates is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the composition or the liquid crystal alignment treatment agent using the same. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the storage stability of the composition or the liquid crystal alignment treatment agent using the composition may be deteriorated.

The composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention may contain, in addition to the compound for improving the uniformity of the film thickness of the poor solvent, the crosslinkable compound, the resin film or the liquid crystal alignment film, If the effect is not hindered, a dielectric material or a conductive material may be added for the purpose of changing electrical characteristics such as dielectric constant and conductivity of the resin film or the liquid crystal alignment film.

&Lt; Resin Coating &gt;

The composition of the present invention can be used as a resin film after being coated and baked on a substrate. As the substrate to be used at this time, a plastic substrate such as a glass substrate, a silicon wafer, an acrylic substrate, or a polycarbonate substrate may be used depending on the intended device. The method of applying the composition is not particularly limited, but the method of industrially is generally carried out by a dipping method, a roll coater method, a slit coater method, a spinner method, a spraying method, a screen printing method, an offset printing method, a flexographic printing method, to be. They may be used according to purpose.

After the composition is applied onto the substrate, it is heated to 50 to 250 DEG C, preferably 80 to 200 DEG C, more preferably 80 to 200 DEG C, by heating means such as a hot plate, a heat circulation type oven or an IR (infrared) The solvent can be evaporated at 150 ° C to form a resin film. The thickness of the resin film after firing can be adjusted to 0.01 to 100 탆, depending on the purpose.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal alignment treatment agent using the composition of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. Further, in the case of 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. In addition to the glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. In a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is a substrate on only one side. As the electrode in this case, a material that reflects light such as aluminum can also be used.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, or inkjet printing are generally used. 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 to 50 to 250 ° C, preferably 80 to 200 ° C, more preferably to 80 to 200 ° C by heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) The liquid crystal alignment layer can be formed by evaporating the solvent at 80 to 150 ° C. When the thickness of the liquid crystal alignment film after firing is too large, the power consumption of the liquid crystal display element is disadvantageously deteriorated. When too thin, the reliability of the liquid crystal display element may deteriorate, so that the thickness is preferably 5 to 300 nm, 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired liquid crystal alignment film is treated by 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, spacers are spread on the liquid crystal alignment film of the substrate of one substrate, the substrates of the other substrate are laminated so that the liquid crystal alignment film surface is inward, Or a method in which liquid crystal is dropped on the surface of the liquid crystal alignment film on which the spacer is spread and the substrate is then subjected to sealing to effect sealing.

Further, the liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound polymerized by at least one of active energy rays and heat between a pair of substrates And then polymerizing the polymerizable compound by at least one of irradiation of an active energy ray and heating while applying a voltage between the electrodes is preferably used for a liquid crystal display device. 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, irradiation with ultraviolet rays and heating may be simultaneously performed.

The liquid crystal display element described above controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound such as a photopolymerizable monomer is mixed in a liquid crystal material, and after a liquid crystal cell is assembled, a predetermined voltage is applied to the liquid crystal layer, And controls the pretilt of the liquid crystal molecules by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is produced is stored even after the voltage is removed, the pretilt 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 vertical alignment type liquid crystal layer which is difficult to control the pretilt by the rubbing treatment.

That is, 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 the liquid crystal alignment treatment agent of the present invention by the above-mentioned technique, preparing a liquid crystal cell, The orientation of the liquid crystal molecules can be controlled.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared. Spacers are sprayed on the liquid crystal alignment film of the substrate of the single chamber to make the liquid crystal alignment film face inward, A method in which liquid crystal is injected under reduced pressure, or a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is spread, and then a substrate is bonded by sealing.

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 or a methacrylate group in the molecule. At that time, the amount of 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, the amount of unreacted polymerizable compound increases, .

After the liquid crystal cell is fabricated, 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.

In addition, 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 polymerized 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 electrodes. 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, irradiation with ultraviolet rays and heating may be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, a method of using a polymer component containing a polymerizable group Method. 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 of ultraviolet rays and heating have.

One example of manufacturing a liquid crystal cell is to prepare a pair of substrates on which a liquid crystal alignment film is formed and spray a spacer on the liquid crystal alignment film of the substrate of the single chamber to make the liquid crystal alignment film face inward, , A method of sealing the liquid crystal by injecting it under a reduced pressure, or a method of dropping liquid crystal on the surface of the liquid crystal alignment film spreading the spacer and then sealing the substrate by bonding.

After the liquid crystal cell is manufactured, the alignment of the liquid crystal molecules can be controlled by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell.

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

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Abbreviations used in Synthesis Examples, Examples and Comparative Examples are as follows.

(Diamine compound having a carboxyl group)

A1: 3,5-diaminobenzoic acid (diamine compound represented by the following formula [A1]):

A2: 2,5-diaminobenzoic acid (diamine compound represented by the following formula [A2]):

[Formula 77]

(Second diamine compound)

B1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene (diamine compound represented by the following formula [B1]

B2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene (diamine compound represented by the following formula [B2]

B3: 1,3-Diamino-4- {trans 4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene (diamine compound represented by the following formula [B3]

B4: diamine compound represented by the following formula [B4]

B5: 1,3-Diamino-4-octadecyloxybenzene (diamine compound represented by the following formula [B5]):

B6: diamine compound represented by the following formula [B6]

(78)

(79)

(80)

(Other diamine compounds)

C1: p-phenylenediamine (diamine compound represented by the following formula [C1]):

C2: m-phenylenediamine (diamine compound represented by the following formula [C2]):

[Formula 81]

(Tetracarboxylic acid component)

D1: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride (tetracarboxylic acid dianhydride represented by the following formula [D1]):

D2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride (tetracarboxylic acid dianhydride represented by the following formula [D2]

D3: tetracarboxylic acid dianhydride represented by the following formula [D3]

D4: tetracarboxylic acid dianhydride represented by the following formula [D4]

(82)

(Component (A) (specific alcohol solvent) of the present invention)

PGME: Propylene glycol monomethyl ether (solvent represented by the formula [1a-1] of the present invention)

MCS: Ethylene glycol monomethyl ether (solvent represented by the formula [1b-1] of the present invention)

ECS: ethylene glycol monoethyl ether (solvent represented by the formula [1b-2] of the present invention)

PCS: ethylene glycol monopropyl ether (solvent represented by the formula [1b-3] of the present invention)

(83)

(Component (B) (specific polar solvent) of the present invention)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

? -BL:? -butyrolactone

(Component (D) of the present invention (other organic solvent))

BCS: ethylene glycol monobutyl ether

(Measurement of molecular weight of polyimide precursor and polyimide)

The molecular weights of the polyimide precursor and the polyimide in the synthesis examples were measured using a gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.), a column (KD-803, KD-805 Manufactured by Mitsui Chemicals, Inc.).

Column temperature: 50 ° C

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

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 Toso Co., Ltd.) and polyethylene glycol (molecular weight: about 12,000, 4,000 and 1,000) by Polymer Laboratories.

(Measurement of imidization ratio of polyimide)

The imidization rate of the polyimide in the synthesis example was measured in the following manner. (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) of polyimide powder 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 KK). The proton derived from the structure in which the imidization rate does not change before and after the imidization is defined as the reference proton and the peak integrated value of the proton and the proton peak integrated value derived from the NH group of the amide acid appearing in the vicinity of 9.5 ppm to 10.0 ppm By using the following equation.

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

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

&Quot; Synthesis of specific polymer (polyimide precursor and polyimide) which is component (C) of the present invention &quot;

&Lt; Synthesis Example 1 &

(3.00 g, 15.3 mmol) and A1 (2.33 g, 15.3 mmol) were mixed in PGME (48.0 g) and reacted at 40 ° C for 8 hours to obtain a polyamic acid solution (1) having a resin solid concentration of 10.0 mass% . This polyamic acid had a number average molecular weight of 13,500 and a weight average molecular weight of 32,100.

&Lt; Synthesis Example 2 &

Dl (7.65 g, 30.6 mmol) and A2 (5.82 g, 38.3 mmol) were mixed in NMP (24.7 g) and reacted at 80 ° C for 5 hours. Then, D1 (1.50 g, 7.65 mmol) and NMP And the mixture was allowed to react at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

To the resulting polyamic acid solution (40.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.81 g) and pyridine (3.75 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (2). The imidization ratio of this polyimide was 55%, and the number average molecular weight was 15,800 and the weight average molecular weight was 40,600.

&Lt; Synthesis Example 3 &

D2 (1.91 g, 7.63 mmol), B1 (2.43 g, 6.39 mmol) and A1 (0.97 g, 6.38 mmol) were mixed in PGME (31.2 g) 5.10 mmol) and PGME (25.6 g) were added and reacted at 40 DEG C for 8 hours to obtain a polyamic acid solution (3) having a resin solid content concentration of 10.0 mass%. The polyamic acid had a number average molecular weight of 13,900 and a weight average molecular weight of 36,500.

&Lt; Synthesis Example 4 &

Dl (3.73 g, 14.9 mmol), B1 (4.73 g, 12.4 mmol) and Al (1.89 g, 12.4 mmol) were mixed in NMP (20.3 g) 9.94 mmol) and NMP (16.6 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 25.0 mass%.

To the obtained polyamic acid solution (40.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.80 g) and pyridine (3.75 g) were added as an imidization catalyst and the reaction was carried out at 80 ° C for 4.5 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (4). The imidization ratio of the polyimide was 60%, the number average molecular weight was 14,600, and the weight average molecular weight was 37,200.

&Lt; Synthesis Example 5 &

(5.21 g, 14.0 mmol) and Cl (0.30 g, 2.77 mmol) were mixed in NMP (22.1 g) and heated to 80 &lt; 0 &gt; C for 5 hours After the reaction, D1 (1.10 g, 5.61 mmol) and NMP (18.1 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

To the resulting polyamic acid solution (40.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.80 g) and pyridine (3.75 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (5). The imidization ratio of the polyimide was 57%, and the number average molecular weight was 16,500 and the weight average molecular weight was 39,900.

&Lt; Synthesis Example 6 &

(2.26 g, 14.9 mmol) and B6 (1.21 g, 5.95 mmol) were mixed in NMP (23.0 g), and the mixture was stirred at 80 ° C for 5 hours After the reaction, D1 (1.75 g, 8.92 mmol) and NMP (18.8 g) were added and reacted at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

To the resulting polyamic acid solution (40.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.80 g) and pyridine (3.75 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (6). The imidization ratio of the polyimide was 50%, the number average molecular weight was 18,100, and the weight average molecular weight was 42,500.

&Lt; Synthesis Example 7 &

(3.71 g, 8.58 mmol), A2 (2.61 g, 17.2 mmol) and C2 (0.31 g, 2.87 mmol) were mixed in NMP (21.4 g) After the reaction, D1 (2.80 g, 14.3 mmol) and NMP (17.5 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

To the obtained polyamic acid solution (40.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.80 g) and pyridine (3.75 g) were added as an imidization catalyst and the reaction was carried out at 80 ° C for 4.5 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (7). The imidization ratio of the polyimide was 60%, the number average molecular weight was 19,100, and the weight average molecular weight was 43,000.

&Lt; Synthesis Example 8 &

D2 (6.12 g, 24.5 mmol), B4 (2.26 g, 4.59 mmol) and A2 (3.96 g, 26.0 mmol) were mixed in NMP (22.3 g) 6.12 mmol) and NMP (18.3 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 25.0 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (4.80 g) and pyridine (3.75 g) were added as imidation catalysts and reacted at 80 ° C for 3.5 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (8). The imidization ratio of the polyimide was 48%, the number average molecular weight was 15,800, and the weight average molecular weight was 36,900.

&Lt; Synthesis Example 9 &

(3.0 g, 20.3 mmol) were mixed in NMP (38.7 g) and reacted at 40 占 폚 for 5 hours to obtain a resin solid content concentration of 25.0 mass% (6.50 g, 29.0 mmol) % Polyamic acid solution.

To the resulting polyamic acid solution (40.0 g), NMP was added and diluted to 6 mass%. Acetic anhydride (4.70 g) and pyridine (3.60 g) were added as an imidization catalyst and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (9). The imidization ratio of the polyimide was 54%, the number average molecular weight was 17,500, and the weight average molecular weight was 40,100.

&Lt; Synthesis Example 10 &

(3.25 g, 29.0 mmol), B5 (3.28 g, 8.71 mmol), B6 (1.18 g, 5.80 mmol) and A2 (2.21 g, 14.5 mmol) were mixed in NMP (39.5 g) To obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

To the obtained polyamic acid solution (40.0 g), NMP was added and diluted to 6 mass%. Acetic anhydride (4.81 g) and pyridine (3.70 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (900 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 占 폚 to obtain a polyimide powder (10). The imidization ratio of the polyimide was 55%, and the number average molecular weight was 16,500 and the weight average molecular weight was 38,200.

&Lt; Synthesis Example 11 &

A mixture of D4 (5.05 g, 16.8 mmol), B2 (3.32 g, 8.41 mmol), C2 (0.45 g, 4.16 mmol) and A2 (2.35 g, 15.4 mmol) in NMP (22.1 g) After the reaction, D1 (2.20 g, 11.2 mmol) and NMP (18.1 g) were added and reacted at 40 DEG C for 5.5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

To the resulting polyamic acid solution (40.0 g), NMP was added and diluted to 6 mass%. Acetic anhydride (4.80 g) and pyridine (3.68 g) were added as an imidation catalyst and reacted at 80 ° C for 4.5 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (11). The imidization ratio of the polyimide was 61%, the number average molecular weight was 18,400, and the weight average molecular weight was 39,100.

&Lt; Synthesis Example 12 &

(3.26 g, 8.57 mmol), B6 (1.74 g, 8.56 mmol) and A1 (1.74 g, 11.4 mmol) were mixed in NMP (22.8 g) After the reaction, D1 (2.80 g, 14.3 mmol) and NMP (18.7 g) were added and reacted at 40 DEG C for 5.5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

To the obtained polyamic acid solution (40.0 g), NMP was added and diluted to 6 mass%. Acetic anhydride (4.70 g) and pyridine (3.60 g) were added as an imidation catalyst and reacted at 80 ° C for 3 hours . The reaction solution was poured into methanol (700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (12). The imidization ratio of the polyimide was 55%, the number average molecular weight was 17,500, and the weight average molecular weight was 39,300.

&Lt; Synthesis Example 13 &

(13.50 g, 48.4 mmol) and A1 (7.37 g, 48.4 mmol) were mixed in NMP (50.6 g) and reacted at 40 DEG C for 8 hours to obtain a polyamic acid solution (13) having a resin solid content concentration of 25.0 mass% . The polyamic acid had a number average molecular weight of 17,300 and a weight average molecular weight of 42,900.

&Lt; Synthesis Example 14 &

Dl (7.65 g, 30.6 mmol) and A2 (5.82 g, 38.3 mmol) were mixed in NMP (24.7 g) and reacted at 80 ° C for 5 hours. Then, D1 (1.50 g, 7.65 mmol) and NMP And the mixture was allowed to react at 40 DEG C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

To the resulting polyamic acid solution (40.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.81 g) and pyridine (3.75 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (14). The imidization ratio of this polyimide was 55%, and the number average molecular weight was 15,800 and the weight average molecular weight was 40,600.

&Lt; Synthesis Example 15 &

(3.85 g, 24.5 mmol) was dissolved in NMP (40.1 g) and reacted at 80 ° C for 5 hours. 19.6 mmol) and NMP (32.8 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution (15) having a resin solid content concentration of 25.0 mass%. The polyamic acid had a number average molecular weight of 19,500 and a weight average molecular weight of 46,200.

&Lt; Synthesis Example 16 &

NMP was added to the polyamic acid solution (15) (40.0 g) obtained in Synthesis Example 15 to dilute it to 6 mass%, acetic anhydride (4.80 g) and pyridine (3.75 g) were added as an imidation catalyst, The reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (16). The imidization ratio of the polyimide was 60%, the number average molecular weight was 17,100, and the weight average molecular weight was 40,100.

&Lt; Synthesis Example 17 &

Dl (3.92 g, 15.7 mmol), B1 (4.97 g, 13.1 mmol) and C1 (1.41 g, 13.0 mmol) were mixed in NMP (20.4 g) 10.5 mmol) and NMP (16.7 g) were added and reacted at 40 占 폚 for 5.5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

To the resulting polyamic acid solution (40.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (5.40 g) and pyridine (4.18 g) were added as imidation catalysts and reacted at 80 ° C for 3 hours . The reaction solution was poured into methanol (800 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (17). The imidization ratio of the polyimide was 61%, the number average molecular weight was 16,300, and the weight average molecular weight was 39,100.

Specific polymers of the present invention (polyimide precursor and polyimide) are shown in Table 1.

* 1: Polyamide acid.

&Quot; Composition of the present invention and production of liquid crystal alignment treatment agent &quot;

In the following Examples 1 to 23 and Comparative Examples 1 to 10, production examples of the composition are described. These compositions are also used for evaluation of a liquid crystal alignment treatment agent.

The composition of the present invention and the liquid crystal alignment treatment agent are shown in Tables 2 to 4.

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;, &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent & ), Evaluation of liquid crystal orientation (normal cell), production of liquid crystal cell, evaluation of liquid crystal orientation (PSA cell), and evaluation of voltage holding ratio. The conditions are as follows.

&Quot; Evaluation of applicability of composition and liquid crystal alignment treatment agent &quot;

The compositions obtained in Examples and Comparative Examples of the present invention were subjected to pressure filtration with a membrane filter having a pore diameter of 1 占 퐉 and stored at -15 占 폚 for 48 hours to evaluate the applicability. For application, a spin coater (1H-D7) (manufactured by Mikasa) was used. The coating was performed by spin-coating the 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 (isopropyl alcohol) was formed, And the drying was carried out on a hot plate at 80 DEG C for 5 minutes.

Then, evaluation of the pinhole of the obtained resin coating was carried out. The evaluation of the pinhole of the resin coating was carried out by visually observing the resin coating under a sodium lamp. Specifically, the number of pinholes accompanying crater rings and foreign substances confirmed on the resin film was counted, and the smaller the number of pinholes, the better the evaluation was.

In addition, the compositions obtained in Examples and Comparative Examples of the present invention can be used for a liquid crystal alignment treatment agent. For this reason, the results of the coating properties of the resin coatings obtained in this example and the comparative example were also as a result of the printability of the liquid crystal alignment film.

Tables 5 to 7 show the number of pinholes of the resin coating film (liquid crystal alignment film) obtained in Examples and Comparative Examples.

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

The liquid crystal alignment treatment agent (7) obtained in Example 7 of the present invention and the liquid crystal alignment treatment agent (11) obtained in Example 11 were pressure filtered with a membrane filter having a pore diameter of 1 탆 and stored at -15 캜 for 48 hours , And evaluation of the ink-jet applicability was carried out. 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, 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 / The time from drying to drying was 60 seconds, and drying was carried out on a hot plate at 70 DEG C for 5 minutes.

The evaluation of the pinhole of the obtained liquid crystal alignment film was carried out under the same conditions as &quot; Evaluation of applicability of composition and liquid crystal alignment treatment agent &quot;.

Table 5 shows the number of pinholes of the liquid crystal alignment film obtained in the examples.

&Quot; Fabrication of liquid crystal cell (ordinary cell) &quot;

The liquid crystal alignment treatment agent obtained in Examples and Comparative Examples of the present invention was press-filtered with a membrane filter having a pore diameter of 1 占 퐉 and stored at -15 占 폚 for 48 hours to prepare a liquid crystal cell (ordinary cell) . This solution was spin-coated on the 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 To obtain an ITO substrate on which a polyimide liquid crystal alignment film having a thickness of 100 nm was formed. 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 revolution number of 1000 rpm, a roll progress speed of 50 mm / sec, and an indentation amount of 0.1 mm.

Two pieces of the ITO substrate on which the obtained liquid crystal alignment film was formed were prepared, and a sealing agent (XN-1500T) (manufactured by Mitsui Chemicals) was printed by combining the liquid crystal alignment film face inside with spacers of 6 m in between. Subsequently, the other substrate and the liquid crystal alignment film surface were faced to each other, and the sealant was cured by heat treatment in a thermocycling type clean oven at 120 캜 for 90 minutes to prepare empty cells. A liquid crystal was injected into this empty cell by a low pressure injection method and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).

The liquid crystal alignment treatment agent (1) and the liquid crystal alignment treatment agent (2) obtained in Examples 1 and 2 and the liquid crystal alignment treatment agent (24) to liquid crystal alignment treatment agent (28) obtained in Comparative Examples 1 to 5 were used. For the cell, a nematic liquid crystal (MLC-2003) (manufactured by Merck Japan) was used for the liquid crystal.

The liquid crystal alignment treatment agent (3) to the liquid crystal alignment treatment agent (6) obtained in Examples 3 to 6, the liquid crystal alignment treatment agent (8) to the liquid crystal alignment treatment agent (10) obtained in Examples 8 to 10, The liquid crystal cell using the liquid crystal alignment treatment agent (12) to the liquid crystal alignment treatment agent (23) obtained in Example 12 and the liquid crystal alignment treatment agent (29) to the liquid crystal alignment treatment agent (33) obtained in Comparative Examples 6 to 10, Enematic liquid crystal (MLC-6608) (Merck Japan) was used.

&Quot; Evaluation of liquid crystal alignment property (normal cell) &quot;

The liquid crystal alignability was evaluated using the liquid crystal cell obtained in the above &quot; Fabrication of liquid crystal cell (normal cell) &quot;. The liquid crystal alignability was confirmed by observing the liquid crystal cell with a polarizing microscope (ECLIPSE E600WPOL) (Nikon Corporation) to determine whether there was an alignment defect. Concretely, it was said that the alignment defect was not seen in the evaluation (excellent in Tables 5 to 7).

Tables 5 to 7 show the results of the liquid crystal alignment properties obtained in the examples and comparative examples.

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

The liquid crystal alignment treatment agent (5) obtained in Example 5, the liquid crystal alignment treatment agent (9) obtained in Example 9 and the liquid crystal alignment treatment agent (20) obtained in Example 20 were pressure filtered through a membrane filter having a pore diameter of 1 占 퐉, ° C. for 48 hours to prepare a liquid crystal cell and evaluate the liquid crystal orientation (PSA cell). This solution was applied to a substrate (40 mm long × 30 mm wide × 0.7 mm thick) on which ITO electrodes having a pattern interval of 20 μm were formed in a center of 10 × 10 mm and cleaned with pure water and IPA and a 10 × 40 mm ITO electrode Was spin-coated on an ITO surface of a substrate (40 mm long x 30 mm wide, 0.7 mm thick) formed thereon, and subjected to heat treatment at 100 캜 for 5 minutes on a hot plate to obtain a polyimide coating film having a thickness of 100 nm. After the coated film surface was cleaned with pure water, the substrate was heat-treated at 100 ° C for 15 minutes in a thermocycling type clean oven to obtain a substrate having a liquid crystal alignment film formed thereon.

The substrate on which this liquid crystal alignment film was formed was assembled with spacers of 6 占 퐉 interposed therebetween with the liquid crystal alignment film surface on the inner side, and the periphery was bonded with a sealant to prepare empty cells. The polymerizable compound (1) represented by the following formula was dissolved in 100 mass% of a nematic liquid crystal (MLC-6608) in a nematic liquid crystal (MLC-6608) , And 0.3% by mass of the polymerizable compound (1) were injected into the liquid crystal cell, and the injection port was sealed to obtain a liquid crystal cell.

(84)

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

The response speed of the liquid crystal before the ultraviolet irradiation and after the ultraviolet irradiation of the liquid crystal cell 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 the Example had a higher response speed of the liquid crystal cell after ultraviolet irradiation than in the liquid crystal cell before the ultraviolet irradiation, and thus the alignment direction of the liquid crystal was controlled. It was confirmed that the liquid crystal was uniformly aligned with any liquid crystal cell by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation).

Evaluation of voltage holding ratio &quot;

A voltage of 1 V was applied for 60 占 퐏 at a temperature of 80 占 폚 to the liquid crystal cell obtained in the above-mentioned "production of a liquid crystal cell (normal cell)", and the voltage after 16.67 ms and after 50 ms was measured. Was calculated as a voltage holding ratio (also referred to as VHR). The measurement was carried out by setting the voltage: ± 1 V, the pulse width: 60 μs, the flame period: 16.67 ms, or 50 ms using a voltage sustaining rate measuring apparatus (VHR-1) (manufactured by Toyota Corporation).

Table 8 shows the results of voltage holding ratio obtained in Examples and Comparative Examples.

&Lt; Example 1 &gt;

PGME (11.5 g) and NMP (1.57 g) were added to polyamic acid solution (1) (20.0 g) having a resin solid content concentration of 10.0% by mass obtained by the synthetic method of Synthesis Example 1 and stirred at 25 占 폚 for 2 hours , Thereby obtaining the composition (1). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (1) was also used for evaluation as the liquid crystal alignment treatment agent (1).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (evaluation of liquid crystal alignment property) &quot; were carried out under the conditions described above by using the obtained composition (1) (Normal cell) ".

&Lt; Example 2 &gt;

PGME (21.9 g) and? -BL (2.43 g) were added to polyimide powder (2) (1.55 g) obtained by the synthetic method of Synthesis Example 2 and stirred at 70 占 폚 for 24 hours to obtain Composition (2) . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (2) was also used for evaluation as the liquid crystal alignment treatment agent (2).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, &quot; evaluation of liquid crystal alignment property (Normal cell) &quot; and &quot; evaluation of voltage holding ratio &quot;.

&Lt; Example 3 &gt;

PGME (5.36 g) and NMP (1.65 g) were added to polyamic acid solution (3) (10.5 g) having a resin solid concentration of 10.0% by mass obtained by the synthetic method of Synthesis Example 3 and stirred at 25 占 폚 for 2 hours , Thereby obtaining the composition (3). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (3) was also used for evaluation as the liquid crystal alignment treatment agent (3).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, &quot; evaluation of liquid crystal alignment property (Normal cell) &quot; and &quot; evaluation of voltage holding ratio &quot;.

<Example 4>

PGME (1.97 g),? -BL (1.57 g) and BCS (3.13 g) were added to polyamic acid solution (3) (10.0 g) having a resin solid concentration of 10.0% by mass obtained by the synthetic method of Synthetic Example 3 , And the mixture was stirred at 25 占 폚 for 2 hours to obtain a composition (4). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (4) was also used for evaluation as the liquid crystal alignment treatment agent (4).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (evaluation of liquid crystal alignment property) &quot; were carried out under the conditions described above by using the obtained composition (4) (Normal cell) ".

&Lt; Example 5 &gt;

PGME (22.6 g) and? -BL (2.51 g) were added to the polyimide powder (4) (1.60 g) obtained by the synthetic method of Synthetic Example 4 and stirred at 70 占 폚 for 24 hours to obtain Composition (5) . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (5) was also used for evaluation as the liquid crystal alignment treatment agent (5).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, &quot; evaluation of liquid crystal alignment property (Normal cell) "," production of liquid crystal cell, evaluation of liquid crystal orientation (PSA cell) "and" evaluation of voltage holding ratio ".

&Lt; Example 6 &gt;

PCS (15.0 g),? -BL (2.51 g) and BCS (7.52 g) were added to polyimide powder (4) (1.60 g) obtained by the synthetic method of Synthesis Example 4 and stirred at 70 ° C for 24 hours , Thereby obtaining a composition (6). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (6) was also used for the evaluation as the liquid crystal alignment treatment agent (6).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (evaluation of liquid crystal alignment property) &quot; were carried out under the conditions described above by using the obtained composition (6) (Normal cell) ".

&Lt; Example 7 &gt;

PCS (21.5 g),? -BL (7.17 g) and BCS (10.8 g) were added to the polyimide powder (4) (1.30 g) obtained by the synthetic method of Synthetic Example 4 and stirred at 70 ° C for 24 hours , Thereby obtaining a composition (7). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (7) was also used for evaluation as the liquid crystal alignment treatment agent (7).

Using the obtained liquid crystal alignment treatment agent (7), &quot; evaluation of inkjet application property of liquid crystal alignment treatment agent &quot;

&Lt; Example 8 &gt;

MCS (14.6 g), NEP (3.64 g) and BCS (6.07 g) were added to polyimide powder (5) (1.55 g) obtained by the synthetic method of Synthesis Example 5 and stirred at 70 占 폚 for 24 hours, (8). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (8) was also used for evaluation as the liquid crystal alignment treatment agent (8).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (evaluation of liquid crystal alignment property) &quot; were carried out under the above- (Normal cell) ".

&Lt; Example 9 &gt;

PGME (15.0 g),? -BL (7.52 g) and BCS (2.51 g) were added to the polyimide powder (5) (1.60 g) obtained by the synthetic method of Synthesis Example 5 and stirred at 70 ° C for 24 hours , Thereby obtaining a composition (9). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (9) was also used for evaluation as the liquid crystal alignment treatment agent (9).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, &quot; evaluation of liquid crystal alignment property (Normal cell) &quot; and &quot; production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) &quot;.

&Lt; Example 10 &gt;

PGME (22.6 g) and? -BL (2.51 g) were added to polyimide powder (6) (1.60 g) obtained by the synthetic method of Synthetic Example 6 and stirred at 70 占 폚 for 24 hours to obtain Composition 10 . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (10) was also used for evaluation as the liquid crystal alignment treatment agent (10).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Example 11 &gt;

PGME (32.3 g) and? -BL (3.58 g) were added to polyimide powder (6) (1.30 g) obtained by the synthetic method of Synthesis Example 6 and stirred at 70 占 폚 for 24 hours to obtain Composition 11 . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (11) was also used for the evaluation as the liquid crystal alignment treatment agent (11).

Using the obtained liquid crystal alignment treatment agent 11, &quot; Evaluation of inkjet application property of liquid crystal alignment treatment agent &quot; under the conditions described above was performed.

&Lt; Example 12 &gt;

PCS (17.6 g), NEP (5.01 g) and BCS (2.51 g) were added to the polyimide powder (6) (1.60 g) obtained by the synthetic method of Synthetic Example 6 and stirred at 70 캜 for 24 hours, (12). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (12) was also used for evaluation as the liquid crystal alignment treatment agent (12).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Example 13 &gt;

ECS (15.0 g), NMP (5.01 g) and BCS (5.01 g) were added to the polyimide powder (7) (1.60 g) obtained by the synthetic method of Synthetic Example 7 and stirred at 70 캜 for 24 hours, (13). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (13) was also used for evaluation as the liquid crystal alignment treatment agent (13).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (evaluation of liquid crystal alignment property) &quot; were carried out under the above- (Normal cell) ".

&Lt; Example 14 &gt;

PGME (21.9 g) and? -BL (2.43 g) were added to polyimide powder (8) (1.55 g) obtained by the synthetic method of Synthetic Example 8 and stirred at 70 占 폚 for 24 hours to obtain Composition 14 . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (14) was also used for evaluation as the liquid crystal alignment treatment agent (14).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Example 15 &gt;

MCS (21.3 g),? -BL (1.25 g) and BCS (2.51 g) were added to polyimide powder (8) (1.60 g) obtained by the synthetic method of Synthesis Example 8 and stirred at 70 ° C for 24 hours , Thereby obtaining a composition (15). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (15) was also used for evaluation as the liquid crystal alignment treatment agent (15).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Example 16 &gt;

PGME (22.6 g) and? -BL (2.51 g) were added to polyimide powder (9) (1.60 g) obtained by the synthetic method of Synthesis Example 9 and stirred at 70 占 폚 for 24 hours to obtain Composition 16 . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (16) was also used for evaluation as the liquid crystal alignment treatment agent (16).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Example 17 &gt;

PCS (22.6 g),? -BL (5.01 g) and BCS (2.51 g) were added to polyimide powder (9) (1.60 g) obtained by the synthetic method of Synthesis Example 9 and stirred at 70 ° C for 24 hours , Thereby obtaining a composition (17). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (17) was also used for the evaluation as the liquid crystal alignment treatment agent (17).

Evaluation of composition and coating property of liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property &quot;, under the conditions described above, using the obtained composition (17) (Normal cell) ".

&Lt; Example 18 &gt;

PCS (17.6 g) and NMP (5.88 g) were added to the polyimide powder (10) (1.50 g) obtained by the synthetic method of Synthesis Example 10 and stirred at 70 占 폚 for 24 hours to obtain Composition (18). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (18) was also used for the evaluation as the liquid crystal alignment treatment agent (18).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property &quot;, under the above-described conditions, using composition 18 and liquid crystal alignment treatment agent 18. [ (Normal cell) ".

&Lt; Example 19 &gt;

PGME (23.3 g) and? -BL (2.59 g) were added to polyimide powder (11) (1.65 g) obtained by the synthetic method of Synthesis Example 11 and stirred at 70 占 폚 for 24 hours to obtain Composition 19 . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (19) was also used for evaluation as the liquid crystal alignment treatment agent (19).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (evaluation of liquid crystal alignment property) &quot; were carried out under the above- (Normal cell) ".

&Lt; Example 20 &gt;

PGME (20.1 g),? -BL (2.51 g) and BCS (2.51 g) were added to the polyimide powder (11) (1.60 g) obtained by the synthetic method of Synthesis Example 11 and stirred at 70 ° C for 24 hours , Thereby obtaining a composition (20). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (20) was also used for the evaluation as the liquid crystal alignment treatment agent (20).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, &quot; evaluation of liquid crystal orientation property &quot;, and evaluation of liquid crystal alignment property were carried out under the above- (Normal cell) &quot; and &quot; production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) &quot;.

&Lt; Example 21 &gt;

PCS (17.6 g),? -BL (2.51 g) and BCS (5.01 g) were added to the polyimide powder (11) (1.60 g) obtained by the synthetic method of Synthesis Example 11 and stirred at 70 ° C for 24 hours , Thereby obtaining a composition (21). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (21) was also used for evaluation as the liquid crystal alignment treatment agent (21).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Example 22 &gt;

PGME (22.6 g) and? -BL (2.51 g) were added to polyimide powder (12) (1.60 g) obtained by the synthetic method of Synthesis Example 12 and stirred at 70 占 폚 for 24 hours to obtain Composition 22 . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (22) was also used for evaluation as the liquid crystal alignment treatment agent (22).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (evaluation of liquid crystal alignment property) &quot; were carried out under the conditions described above by using the obtained composition (22) (Normal cell) ".

&Lt; Example 23 &gt;

MCS (17.0 g),? -BL (1.21 g) and BCS (6.07 g) were added to polyimide powder (12) (1.55 g) obtained by the synthetic method of Synthesis Example 12 and stirred at 70 ° C for 24 hours , Thereby obtaining a composition (23). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (23) was also used for the evaluation as the liquid crystal alignment treatment agent (23).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Comparative Example 1 &

NMP (17.4 g) was added to polyamic acid solution 13 (5.50 g) having a resin solid content concentration of 25.0% by mass obtained by the synthetic method of Synthesis Example 13 and stirred at 25 占 폚 for 2 hours to obtain Composition 24 . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (24) was also used for evaluation as the liquid crystal alignment treatment agent (24).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Comparative Example 2 &

NMP (13.1 g) and BCS (4.31 g) were added to polyamic acid solution 13 (5.50 g) having a resin solid content concentration of 25.0% by mass obtained by the synthetic method of Synthetic Example 13 and stirred at 25 占 폚 for 2 hours , Thereby obtaining the composition (25). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (25) was also used for the evaluation as the liquid crystal alignment treatment agent (25).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Comparative Example 3 &

? -BL (19.6 g) was added to polyimide powder (14) (1.25 g) obtained by the synthetic method of Synthesis Example 14 and stirred at 70 占 폚 for 24 hours to obtain Composition (26). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (26) was also used for evaluation as the liquid crystal alignment treatment agent (26).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, &quot; evaluation of liquid crystal alignment property &quot;, and evaluation of liquid crystal alignment property were carried out under the above- (Normal cell) &quot; and &quot; evaluation of voltage holding ratio &quot;.

&Lt; Comparative Example 4 &

(19.6 g) and BCS (4.07 g) were added to polyimide powder (14) (1.30 g) obtained by the synthetic method of Synthesis Example 14 and stirred at 70 占 폚 for 24 hours to obtain Composition 27 . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (27) was also used for evaluation as the liquid crystal alignment treatment agent (27).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Comparative Example 5 &

PGME (20.4 g) was added to polyimide powder (14) (1.30 g) obtained by the synthetic method of Synthesis Example 14 and stirred at 70 占 폚 for 24 hours to obtain Composition (28). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (28) was also used for evaluation as the liquid crystal alignment treatment agent (28).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (evaluation of liquid crystal alignment property) &quot; were carried out under the conditions described above by using the obtained composition (28) (Normal cell) ".

&Lt; Comparative Example 6 &gt;

NMP (17.4 g) was added to polyamic acid solution 15 (5.50 g) having a resin solid content concentration of 25.0% by mass obtained by the synthetic method of Synthesis Example 15 and stirred at 25 占 폚 for 2 hours to obtain Composition 29 . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (29) was also used for the evaluation as the liquid crystal alignment treatment agent (29).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, &quot; evaluation of liquid crystal alignment property &quot;, and evaluation of liquid crystal alignment property were carried out under the above- (Normal cell) &quot; and &quot; evaluation of voltage holding ratio &quot;.

&Lt; Comparative Example 7 &

? -BL (20.4 g) was added to polyimide powder 16 (1.30 g) obtained by the synthetic method of Synthesis Example 16 and stirred at 70 占 폚 for 24 hours to obtain Composition (30). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (30) was also used for evaluation as the liquid crystal alignment treatment agent (30).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; production of liquid crystal cell (normal cell) &quot;, &quot; evaluation of liquid crystal alignment property &quot;, and evaluation of liquid crystal alignment property were carried out under the above- (Normal cell) &quot; and &quot; evaluation of voltage holding ratio &quot;.

&Lt; Comparative Example 8 &gt;

(16.3 g) and BCS (4.07 g) were added to the polyimide powder 16 (1.30 g) obtained by the synthetic method of Synthesis Example 16 and stirred at 70 占 폚 for 24 hours to obtain a composition 31 . No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (31) was also used for the evaluation as the liquid crystal alignment treatment agent (31).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Comparative Example 9 &

PGME (19.6 g) was added to polyimide powder (16) (1.25 g) obtained by the synthetic method of Synthesis Example 16 and stirred at 70 占 폚 for 24 hours to obtain Composition (32). No abnormality such as turbidity or generation of precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (32) was also used for the evaluation as the liquid crystal alignment treatment agent (32).

Evaluation of coating property of composition and liquid crystal alignment treatment agent &quot;, &quot; preparation of liquid crystal cell (normal cell) &quot;, and &quot; evaluation of liquid crystal alignment property (Normal cell) ".

&Lt; Comparative Example 10 &

To polyimide powder (17) (1.30 g) obtained by the synthetic method of Synthesis Example 17, PGME (20.4 g) was added and the mixture was stirred at 70 占 폚 for 24 hours. Since the polyimide powder remained dissolved in the solution, the polyimide powder was stirred at 70 DEG C for 12 hours, but the polyimide powder could not be completely dissolved.

Therefore, the composition (33) and the liquid crystal alignment treatment agent (33) could not be produced.

* 2: Represents the proportion of the polymer in the composition (liquid crystal alignment treatment agent).

* 3: Represents the ratio of the polymer in the composition (liquid crystal alignment treatment agent).

* 4: Represents the proportion of the polymer in the composition (liquid crystal alignment treatment agent).

* 5: The pinhole accompanying the foreign object was seen.

* 6: Since the polyimide powder was not completely dissolved, the composition and the liquid crystal alignment treatment agent could not be adjusted.

* 7: 25 or more alignment defects were identified.

* 8: 11 to 24 alignment defects were confirmed.

* 9: Five to ten alignment defects were identified.

As can be seen from the above results, the compositions of the examples of the present invention exhibited uniform film-like properties that did not cause pinholes accompanied by cratering or foreign matter when applied to a substrate, as compared with the composition of the comparative example. Concretely, the comparison in the composition using the same polyimide precursor or the solvent-soluble polyimide, that is, the comparison between Example 1 and Comparative Example 1 or Comparative Example 2, the comparison between Example 2 and Comparative Example 3 or Comparative Example 4 , A comparison between Example 3 and Comparative Example 6, and a comparison between Example 5 and Comparative Example 7 or Comparative Example 8. Further, in the example using the specific polar solvent as the component (B) of the present invention, generation of pinholes accompanying foreign matters could be suppressed. Specifically, the comparison between Example 2 and Comparative Example 5 and the comparison between Example 5 and Comparative Example 9 are made.

The liquid crystal alignment film obtained from the liquid crystal alignment treatment agent using the composition of the present invention was also able to obtain the same results. Concretely, the comparison in the composition using the same polyimide precursor or the solvent-soluble polyimide, that is, the comparison between Example 1 and Comparative Example 1 or Comparative Example 2, the comparison between Example 2 and Comparative Example 3 or Comparative Example 4 , A comparison between Example 3 and Comparative Example 6, and a comparison between Example 5 and Comparative Example 7 or Comparative Example 8. Further, a comparison between Example 2 and Comparative Example 5 and a comparison between Example 5 and Comparative Example 9 are shown. Particularly, even when a liquid crystal alignment treatment agent using a polyimide precursor or a solvent-soluble polyimide obtained by using a diamine compound having a side chain as a diamine component exhibits uniform film properties free from pinholes as described above.

Further, in the evaluation of the liquid crystal alignability of the liquid crystal cell, the liquid crystal cell obtained from the liquid crystal alignment treatment agent using the composition of the present invention showed no alignment defects due to pinholes as compared with the liquid crystal cell obtained from the liquid crystal alignment treatment agent using the composition of the comparative example , Uniform liquid crystal alignability was obtained. Concretely, the comparison between the liquid crystal alignment treatment agent using the same polyimide precursor or the solvent-soluble polyimide, that is, the comparison between Example 1 and Comparative Example 1 or Comparative Example 2, the comparison between Example 2 and Comparative Example 3 or Comparative Example 4 A comparison of Example 3 and Comparative Example 6, and a comparison of Example 5 and Comparative Example 7 or Comparative Example 8. Further, a comparison between Example 2 and Comparative Example 5 and a comparison between Example 5 and Comparative Example 9 are shown.

In addition, in evaluating the voltage holding ratio, the liquid crystal cell obtained from the liquid crystal alignment treatment agent using the composition of the present invention showed a higher value than the liquid crystal cell obtained from the liquid crystal alignment treatment agent using the composition of the comparative example. Concretely, the comparison in the liquid crystal alignment treatment agent using the same polyimide precursor or the solvent-soluble polyimide, that is, the comparison between Example 2 and Comparative Example 3, the comparison between Example 3 and Comparative Example 6, Comparison of Comparative Example 7.

Industrial availability

The composition of the present invention can provide a resin coating exhibiting a uniform coating film property free from pinholes accompanied by cratering or foreign matter when applied to a substrate. In the liquid crystal alignment treatment agent using the composition of the present invention, the same result can be obtained.

In addition, the liquid crystal alignment treatment agent of the present invention can obtain a liquid crystal cell in which alignment defects due to pinholes accompanied by cratering or foreign matter do not occur. Particularly, the same result can be obtained even with a liquid crystal alignment treatment agent using a polyimide precursor obtained by using a diamine compound having a side chain as a diamine component or a solvent-soluble polyimide.

In addition, the liquid crystal alignment treatment agent of the present invention can exhibit a high voltage holding ratio even at a low temperature.

The liquid crystal alignment treatment agent of the present invention is a liquid crystal display element that performs switching between the transmissive state of liquid crystal (also referred to as a transparent state) and the scattered state, that is, a polymer dispersed liquid crystal (PDLC) And is also useful for a liquid crystal display element using a network liquid crystal (PNLC (Polymer Network Liquid Crystal)).

Particularly, it is useful for a reverse type device which becomes transparent when no voltage is applied and is in a scattering state when voltage is applied. This reverse type device is a liquid crystal display for the purpose of display using a glass substrate, or a plastic substrate such as PET (polyethylene terephthalate) or an acrylic substrate, and further, a dimmer window for controlling the transmission and blocking of light, It becomes useful for a dimmer window of a transportation agency such as an element, a car, and a plate of a transparent display.

Therefore, 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 with a high precision on a large screen, and can be suitably used for TN devices, STN devices, TFT liquid crystal devices, Type liquid crystal display device.

Further, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is also useful for a liquid crystal display element which needs to irradiate ultraviolet rays when a liquid crystal display element is manufactured. That is, a liquid crystal composition containing a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates And a liquid crystal display element manufactured through a process of polymerizing the polymerizable compound while applying a voltage between the electrodes and further comprising a liquid crystal layer between a pair of substrates provided with electrodes, It is also applicable to a liquid crystal display device manufactured by arranging a liquid crystal alignment film containing a polymerizable group polymerized in at least one of active energy ray and heat between substrates and polymerizing the polymerizable group while applying a voltage between the electrodes Do.

Claims (17)

A composition comprising the following components (A), (B) and (C).
Component (A): At least one solvent selected from the following formula [1a] or formula [1b].
[Chemical Formula 1]

(In the formula [1a], X ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms.
Component (B): at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyrolactone.
Component (C): at least one polymer selected from a polyimide precursor or polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic acid dianhydride component. The method according to claim 1,
Wherein the component (A) is from 50 to 99 mass% of the total solvent contained in the composition. 3. The method according to claim 1 or 2,
Wherein the diamine compound having a carboxyl group as the component (C) is a diamine compound having a structure represented by the following formula [2].
(2)

(In the formula [2], a represents an integer of 0 to 4). 3. The method according to claim 1 or 2,
Wherein the diamine compound having a carboxyl group as the component (C) is a diamine compound having a structure represented by the following formula [2a].
(3)

(In the formula [2a], a represents an integer of 0 to 4, and n represents an integer of 1 to 4). The method according to claim 3 or 4,
Wherein the diamine compound having a carboxyl group is 20 mol% to 100 mol% of the total diamine used in the component (C). 6. The method according to any one of claims 1 to 5,
Wherein the diamine component of the component (C) contains at least one diamine compound selected from the structures represented by the following formula [2b].
[Chemical Formula 4]

(In the formula [2b], Y represents a structure represented by the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] m represents an integer of 1 to 4).
[Chemical Formula 5]

(Wherein a is an integer of 0 to 4, and Y ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15) in the formula [2b-2] , -O-, -CH ₂ represents an O-, -COO- or -OCO-, Y ² is a single bond or - (CH _{2) b} - represents a (b is an integer of 1 ~ 15), Y ³ is a single _{bond, - (CH 2) c -} (c is an integer from 1 to 15), represents an -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ is a benzene ring, a cyclohexane ring Or a divalent cyclic group selected from a heterocyclic ring or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms , optionally substituted with a fluorine-containing alkyl group, fluorine-containing alkoxy group of 1 to 3 carbon atoms or fluorine atoms of 1 to 3 carbon atoms and, Y ⁵ is a divalent cyclic selected from a benzene ring, a cyclohexane ring or a heterocyclic ring group, And any hydrogen atoms 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 fluorinated alkyl group having 1 to 3 carbon atoms, a fluorinated alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom may be, n represents an integer of 0 ~ 4, Y ⁶ is a fluorine-containing alkoxyl group having 1 to 18 alkyl group, having 1 to 18 fluorine-containing alkyl group, having 1 to 18 carbon atoms, an alkoxyl group or a C 1 to 18 of the represents the formula [2b-3] of the, Y ⁷ represents an alkyl group of a carbon number of 8 to 22, formula [2b-4] of, Y ⁸ and Y ⁹ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, formula [ 2b-5], Y ¹⁰ represents an alkyl group having 1 to 8 carbon atoms. 7. The method according to any one of claims 1 to 6,
Wherein the tetracarboxylic acid dianhydride component of the component (C) is a compound represented by the following formula [3].
[Chemical Formula 6]

(In the formula [3], Z ¹ is a group of at least one structure selected from the following formulas [3a] to [3j]).
(7)

(Formula [3a] of, Z ² ~ Z ⁵ represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, may be the same or different in each occurrence, formula [3g] from, Z ⁶ and Z ⁷ is a hydrogen atom or a methyl group And may be the same or different from each other). 8. The method according to any one of claims 1 to 7,
As the component (D), there may be mentioned, for example, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, At least one solvent selected from glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether or diethylene glycol monobutyl ether. A resin film obtained from the composition according to any one of claims 1 to 8. A liquid crystal alignment treatment agent characterized by being obtained from the composition according to any one of claims 1 to 8. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to claim 10. A liquid crystal alignment film obtained by an inkjet method using the liquid crystal alignment treatment agent according to claim 10. A liquid crystal display element having the liquid crystal alignment film according to claim 11 or 12. 13. The method according to claim 11 or 12,
A liquid crystal composition containing a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, Wherein the polymerizable compound is used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable compound while applying a voltage between the electrodes. A liquid crystal display element having the liquid crystal alignment film according to claim 14. 13. The method according to claim 11 or 12,
A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group polymerized by at least one of active energy rays and heat between the pair of substrates is disposed, Wherein the liquid crystal alignment layer is used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage between the electrodes. A liquid crystal display element having the liquid crystal alignment film according to claim 16.