TW201430055A - Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

A composition containing component (A), component (B), and component (C), described below. Component (A): At least one type of solvent selected from either formula [1a] or formula [1b]. (In formula [1a], X1 indicates a C1-3 alkyl group. In formula [1b], X2 indicates a C1-3 alkyl group.) Component (B): At least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or [gamma]-butyrolactone. Component (C): At least one type of polymer selected from a polyimide precursor or polyimide obtained by reacting: a diamine component including a diamine compound having a carboxyl group; and a tetracarboxylic dianhydride component.

Description

Composition, liquid crystal alignment treatment agent, liquid crystal alignment film, and 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. .

A 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, and is widely used. Among them, among liquid crystal display elements widely known as display devices, a resin film made of an organic material can be used as a liquid crystal alignment film.

The resin film currently used in the industry is an organic film made of a polyimide which is excellent in durability. The polyimine-based organic film is formed of a composition of a polyamidene or a polyimine of a polyimide precursor. That is, the polyimine-based organic film is formed by applying a composition containing polyamic acid or polyimine to a substrate and baking it. In this case, generally, in the composition, a high boiling point solvent such as N-methyl-2-pyrrolidone (also known as NMP) or γ-butyrolactone (also known as γ-BL) is used. It is required to be fired at a high temperature of about 200 to 300 ° C (see, for example, Patent Document 1).

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 09-278724

[Summary of the Invention]

When a liquid crystal alignment film is formed by using a liquid crystal alignment treatment agent containing a polyimine-based polymer, the firing process must be high in the process of producing a liquid crystal display device for the above reasons. This is a liquid crystal alignment treatment agent containing a polyimine-based polymer to dissolve a polyimine-based polymer, and NMP or γ-BL is used in a solvent, so it is necessary to be at a high temperature. However, when a substrate of a liquid crystal display element is used in place of a general glass substrate, a thin and lightweight plastic substrate having low heat resistance is required, and firing at a lower temperature is required. Similarly, in order to suppress the deterioration of the color characteristics of the color filter of the liquid crystal display element caused by the firing at a high temperature, and to reduce the energy cost in the manufacture of the liquid crystal display element, it is necessary to fire at a low temperature.

Further, the liquid crystal alignment film is formed by applying a liquid crystal alignment treatment agent onto a substrate and then baking the coating film. In this case, the coating property (also referred to as coating property) of the liquid crystal alignment film is improved, that is, the occurrence of pinholes caused by cracks or foreign matter is suppressed, and it is required to improve the liquid crystal distribution for the substrate. Wet expandability to the treatment agent.

The present invention provides a composition having the above characteristics. for purpose. In other words, the present invention is a composition containing a polyimine-based polymer to provide a composition for forming a resin film by firing at a low temperature. Further, in order to provide a composition for forming a resin film, the coating property of the substrate is improved.

Moreover, in the liquid crystal alignment treatment agent using the above composition, the present invention provides a liquid crystal alignment treatment agent capable of forming a liquid crystal alignment film by firing at a low temperature. Further, in order to provide a liquid crystal alignment treatment agent which forms a liquid crystal alignment film, the coating property of the substrate is improved.

Further, the present invention has an object of providing a liquid crystal alignment film corresponding to the above requirements. That is, it is intended to provide a liquid crystal alignment film which can be formed by firing at a low temperature and a liquid crystal alignment film which can improve coating properties to a substrate.

Further, the present invention has an object of providing a liquid crystal display element having a liquid crystal alignment film corresponding to the above requirements.

As a result of detailed investigation, the present inventors have found that a polyfluorene imine precursor obtained by reacting a diamine component containing a solvent having a specific structure and a diamine compound having a carboxyl group with a tetracarboxylic dianhydride component or The composition of at least one polymer of polyimine is extremely effective in achieving the above object, and the present invention has been completed.

That is, the present invention has the following gist.

(1) A composition characterized by containing the following (A) Component, (B) component and (C) component.

(A) component: 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 the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone.

Component (C): at least one polymer selected from the group consisting of a polyimine precursor obtained by reacting a diamine component having a diamine compound having a carboxyl group and a tetracarboxylic dianhydride component, or a polyimine.

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

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

[Chemical 2]-(CH ₂ ) _a -COOH [2]

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

(4) The composition as described in the above (1) or (2) above The diamine compound having a carboxyl group as the component (C) is a diamine compound having a structure represented by the following formula [2a].

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

(5) The composition as described in the above (3) or (4) above The above-mentioned diamine compound having a carboxyl group is 20 mol% to 100 mol% of the total diamine used in the above component (C).

(6) As described in any one of the above (1) to (5) In the composition of the diamine component of the component (C), at least one diamine compound selected from the group consisting of the following formula [2b] is contained.

(In the formula [2b], Y represents the following formula [2b-1], formula [2b-2], the formula [2b-3], the formula [2b-4] or the formula [2b-5], m represents an integer of 1 to 4).

(In the formula [2b-1], a represents an integer of 0 to 4, and in the formula [2b-2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O -, -CH ₂ O-, -COO- or -OCO-, Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), and Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, and Y ⁴ represents a divalent ring selected from a benzene ring, a cyclohexane ring or a hetero ring a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon number of 1 a fluorine-containing alkyl group of ~3, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring. Any hydrogen atom on the group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine. Substituted by an atom, n represents an integer of 0 to 4, and Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a carbon number of 1 to 18 the fluorine-containing group, of formula 2b-3 [in], Y ⁷ represents an alkyl group having 8 to 22 carbon atoms, of formula [2b-4] , The Y ⁸ and Y ⁹ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, of formula 2b-5] [In, Y ¹⁰ represents alkyl having 1 to 8).

(7) as described in any one of the above (1) to (6) In the composition, the tetracarboxylic dianhydride component of the component (C) is a compound represented by the following formula [3].

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

(In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different. In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group. , each can be the same or different).

(8) As described in any one of the above (1) to (7) a composition comprising, as component (D), a compound selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, and ethylene glycol At least butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether or diethylene glycol monobutyl ether 1 solvent.

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

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

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

(12) A liquid crystal alignment film which is obtained by the inkjet method using the liquid crystal alignment treatment agent described in the above (10).

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

(14) The liquid crystal alignment film according to the above (11) or (12), which is used in a liquid crystal display element having a liquid crystal layer between one of the electrodes and the substrate A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is input between the electrodes, and a step of polymerizing the polymerizable compound is performed. maker.

(15) A liquid crystal display element characterized by having The liquid crystal alignment film described in (14).

(16) as described in the above (11) or (12) above a liquid crystal alignment element which is used in a liquid crystal display element having a liquid crystal layer between one of the electrodes and a substrate, and is disposed between the pair of substrates by active energy rays and heat A liquid crystal alignment film of a polymerizable group in which at least one of the polymers is polymerized, and a voltage is input between the electrodes, and is produced by a step of polymerizing the polymerizable group.

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

The present invention contains at least one selected from the group consisting of a polyimine precursor or a polyimine which is obtained by reacting a diamine component having a solvent having a specific structure and a diamine compound having a carboxyl group with a tetracarboxylic dianhydride component. The composition of the polymer can be formed by firing at a low temperature to form a resin film. Moreover, the composition of the present invention can improve the wettability to the substrate and suppress the occurrence of pinholes caused by cracks or foreign matter on the resin film.

Further, the liquid crystal alignment treatment agent formed by the composition of the present invention can form a liquid crystal alignment film by firing at a low temperature. The liquid crystal alignment treatment agent can improve the wettability to the substrate, and can also suppress the occurrence of pinholes caused by cracks 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.

[Formation of the Invention]

The inventors have conducted detailed research results and obtained the following findings. The present invention has been completed by the solution.

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

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

(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 the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone.

(C) component: at least one polymer selected from the group consisting of a polyimine precursor obtained by reacting a diamine component having a diamine compound having a carboxyl group and a tetracarboxylic dianhydride component, or a polyimine. For a specific polymer).

The specific alcohol-based solvent of the present invention is in a ratio of NMP or γ-BL to the main solvent generally used in a composition containing a polyimine-based polymer. In comparison, it has a lower boiling point as a solvent and can dissolve the specific polymer of the present invention. Therefore, the amount of introduction of the specific alcohol-based solvent in the entire solvent contained in the composition of the present invention is increased, and the resin film can be formed by firing at a low temperature.

Moreover, the specific alcohol solvent of the present invention is generally used for A solvent having a composition of a polyimine-based polymer such as NMP or γ-BL has a lower surface tension as a solvent. Therefore, the composition using a specific solvent becomes highly wettable to the substrate. Therefore, the occurrence of pinholes caused by cracks on the resin film can be suppressed.

Moreover, the specific polar solvent of the present invention is soluble in a specific poly The effect of the compound is high, and when applied to a substrate, generation of pinholes due to foreign matter on the resin film can be suppressed.

From the above point of view, the composition of the present invention can be The resin film is formed by firing at a low temperature. Further, the composition of the present invention has improved wettability to the substrate, and can suppress generation of pinholes caused by cracks or foreign matter on the resin film. Moreover, the above effects can be obtained for the liquid crystal alignment treatment agent obtained from the composition of the present invention for the same reason.

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

<Specific alcohol solvent>

The specific alcohol solvent of the component (A) of the present invention is 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).

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

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

Among them, the formula [1a-1], the formula [1b-1], the formula [1b-2] or the formula [1b-3] is preferred from the viewpoint of the boiling point of the solvent and the availability.

The specific alcohol-based solvent of the present invention has an effect of improving the wettability of the substrate, and therefore 50 to 99 of the entire solvent contained in the composition. It is better when the mass is %. Among them, 55 to 99% by mass is preferred. It is preferably 55 to 95% by mass.

The specific alcohol of the present invention in the whole solvent in the composition The effect of the present invention is that a resin film or a liquid crystal alignment film can be formed at a low temperature, and the wettability of the coating solution of the substrate is increased, and a resin film excellent in coatability can be obtained. Liquid crystal alignment film.

<Specific polar solvent>

The specific polar solvent of the component (B) of the present invention is at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone.

Among them, N-ethyl-2-pyrrolidone or γ-butyrolactone is good. Preferred is γ-butyrolactone.

The specific polar solvent of the present invention is fired at the above low temperature. When a resin film or a liquid crystal alignment film is formed and a composition or a liquid crystal alignment treatment agent is applied to a substrate, the effect of suppressing the occurrence of pinholes caused by foreign matter on the resin film can be improved, so that the solvent contained in the composition is all. 1 to 40% by mass is preferred. Among them, 1 to 35 mass% is preferred. It is preferably from 1 to 30% by mass, more preferably from 5 to 30% by mass.

<specific polymer>

The specific polymer of the component (C) of the present invention is selected from the group consisting of a polyimine precursor or a polyimine which is obtained by reacting a diamine component having a diamine compound having a carboxyl group with a tetracarboxylic dianhydride component. At least one polymer.

The polyimine precursor is a structure represented by the following formula [A].

(In the formula [A], R ¹ is a tetravalent organic group, R ² is a divalent organic group having a carboxyl group, and A ¹ and A ² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each may be the same or may be the same. Different, n means a positive integer).

The diamine component has two grades 1 in the molecule. Or a diamine compound of a 2-stage amine group, and a tetracarboxylic-acid dianhydride component, a tetracarboxylic-acid dianhydride, a dicarboxylic acid di- Dialkyl ester dihalide compound.

The specific polymer of the present invention has the following formula [B] When a dicarboxylic acid compound having a carboxyl group and a tetracarboxylic dianhydride represented by the following formula [C] are used as a raw material, the structural formula of the repeating unit represented by the following formula [D] can be obtained by a relatively simple method. Preferably, the polyaminic acid or the polyamido acid is amidoximinated polyimine.

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

(In the formula [D], R ¹ and R ² have the same meanings as defined in the formula [A]).

<Diamine compound having a 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.

[化14]-(CH ₂ ) _a -COOH [2]

In the formula [2], a represents an integer of 0 to 4. Among them, an integer of 0 or 1 is preferred from the viewpoint of availability of raw materials or ease of synthesis.

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

In the formula [2a], a represents an integer of 0 to 4. Among them, 0 or 1 is preferred from the viewpoint of availability of raw materials or ease of synthesis.

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

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

As an example, the diamine compound represented by the formula [2a] is obtained by synthesizing a dinitro compound represented by the following formula [2a-A], and further reducing the nitro group to convert it into an amine group.

(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 is usually a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent. A method in which palladium-carbon, platinum oxide, Raney nickel, platinum black, ruthenium-alumina or platinum sulfide carbon is used as a catalyst, and is reacted under hydrogen, helium or hydrogen chloride.

The diamine compound having a carboxyl group of the present invention may have a structure represented by the following formula [2a-1] to formula [2a-4].

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 )CO-. Among them, a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH- are considered from the viewpoint of ease of synthesis. -NHCO-, -COO- or -OCO- is preferred. 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. Wherein m ¹ + m ² is preferably 1 or 2.

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

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

In the formula [2a-4], A ³ represents a single bond, -CH ₂ -, -C ₂ H ₄ - , -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-'-N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Wherein a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO- is preferred. Preferred are -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -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 ease of synthesis.

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

The diamine compound having a carboxyl group may be used in combination with the solubility of a specific polymer of the present invention in a solvent or the coating property of a composition, and may be used as a liquid crystal alignment property, a voltage retention ratio, and an accumulated charge when used as a liquid crystal alignment film. 1 type or a mixture of 2 or more types.

<2nd diamine compound>

In the diamine component in the production of the specific polymer of the present invention, as the second diamine compound, a diamine compound (also referred to as a second diamine compound) represented by the following formula [2b] can be used.

(In the formula [2b], Y represents the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5], m represents an integer of 0 to 4).

In the formula [2b-1], a represents an integer of 0 to 4. Among them From the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is preferred.

In the formula [2b-2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, from the viewpoint of availability of raw materials or ease of synthesis, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is good. It is preferably 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 preferred.

In the 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 preferred from the viewpoint of ease of synthesis. It is preferably a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In the formula [2b-2], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group may be an alkyl group having 1 to 3 carbon atoms or carbon. The alkoxy group having 1 to 3 atoms, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom are substituted. Further, Y ⁴ may be selected from a divalent organic group having an organic group having a carbon number of 12 to 25 of a steroid skeleton. Among them, an organic group having a benzene ring, a cyclohexane ring or a carbon number of 12 to 25 having a steroid skeleton is preferred from the viewpoint of ease of synthesis.

In the 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 an alkyl group having 1 to 3 carbon atoms. The alkoxy group having 1 to 3 carbon atoms, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted. Among them, a benzene ring or a cyclohexane ring is preferred.

In the formula [2b-2], n represents an integer of 0 to 4. Which is taken from the raw materials From the standpoint of availability or ease of synthesis, 0 to 3 is preferred. It is preferably 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 alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkane having 1 to 18 carbon atoms. Oxygen. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

A preferred combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2b-2] to form the substituent Y in the formula [2b] is exemplified by international disclosure. The same combination of (2-1) to (2-629) disclosed in Tables 6 to 47 of 13 items to 34 items of the publication WO2011/132751 (2011.10.27). Further, in the tables of the International Publications, Y ¹ to Y ⁶ in the present invention may be represented by Y1 to Y6, but Y1 to Y6 may be read as Y ¹ to Y ⁶ .

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

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 of the formula [2b] of the present invention is not particularly limited, and preferred examples thereof include the following.

As an example, the diamine compound represented by the formula [2b] is obtained by synthesizing a dinitro compound represented by the following formula [2b-A], and further reducing the nitro group to convert it into an amine group.

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

As a dinitro compound represented by the reduced formula [2b-A] The method of dinitro is not particularly limited, and is generally used in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent, palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina. Or platinum sulphide carbon or the like is used as a catalyst, which is a method of carrying out a reaction under hydrogen, helium or hydrogen chloride.

The specific structure of the second diamine compound represented by the formula [2] of the present invention is exemplified below, but the examples are not limited thereto.

In other words, examples of the second diamine represented by the formula [2] include m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, and 2,6-diaminotoluene. 2,4-Diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diamine In addition to the benzenediol, a diamine compound having the structure represented by the following formula [2b-6] to [2b-46] can also be mentioned.

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

(In the formula [2b-34]~Form [2b-36], R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO-, and R ² represents a carbon number of 1 ~22 alkyl, alkoxy, fluoroalkyl or fluoroalkoxy).

(In the formula [2b-37] to the formula [2b-39], R ³ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - CH ₂ -, R ⁴ represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(In the formula [2b-40] and the formula [2b-41], R ⁵ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, - CH ₂ - or -O-, R ⁶ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group).

(In the formula [2b-42] and the formula [2b-43], R ⁷ represents an alkyl group having 3 to 12 carbon atoms; and the cis-trans isomerism of the 1,4-cyclohexyl group is each a trans isomer Better).

(In the formula [2b-44] and the formula [2b-45], R ⁸ represents an alkyl group having 3 to 12 carbon atoms. Further, the cis-trans isomerism of the 1,4-cyclohexyl group is each trans isomer Things are better).

(In the formula [2b-46], B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, B ³ represents a 1,4-cyclohexyl group or a 1,4-phenylene group, and B ² represents an oxygen group. Atom or -COO-* (however, the bond with "*" is bonded to B ³ ), and B ¹ represents an oxygen atom or -COO-* (however, the bond with "*" is combined with (CH ₂ a ^{2 is} combined.) Further, 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.

In the second diamine compound of the present invention, in the formula [2b] The substituent Y is a composition of a diamine compound having a structure represented by the formula [2b-2], and the hydrophobicity of the resin film can be improved. Further, when used as a liquid crystal alignment film, the pretilt angle of the liquid crystal can be increased. In this case, for the purpose of improving these effects, in the above diamine compound, the formula [2b-28] to the formula [2b-39] or the formula [2b-42] to the formula [2b-46] is also used. Amine compounds are preferred. The diamine compound represented by the formula [2b-24] to the formula [2b-39] or the formula [2b-42] to the formula [2b-46] is preferred. Further, in order to further improve these effects, it is preferred that these diamine compounds are 5 mol% or more and 80 mol% or less of the entire diamine component. More preferably, these diamine compounds are 5 mol% or more and 60 mol% or less of the entire diamine component from the viewpoints of the coating property of the composition and the liquid crystal alignment agent or the electrical properties of the liquid crystal alignment film. It is particularly preferably 10 mol% or more and 60 mol% or less of the entire diamine component.

The second diamine compound of the present invention is formulated in accordance with the present invention. The solubility of the specific polymer in the solvent, the coating property, the alignment property of the liquid crystal when the liquid crystal alignment film is used, the voltage holding ratio, and the accumulated electric charge can be used in one type or in a mixture of two or more types.

<Other diamine compounds>

In the specific polymer of the present invention, a diamine compound or a formula having a carboxyl group in the molecule represented by the formula [2a], the formula [2a-1] to the formula [2a-4] can be used without impairing the effects of the present invention. In addition to the second diamine compound represented by [2b], other diamine compounds (also referred to as other diamine compounds) may also be used. Used as a diamine component.

Specific examples of other diamine compounds are listed below, but are not limited thereto.

That is, as other diamine compounds, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'- Methoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-di Aminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- Diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diamine Diphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'- Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2 '-Diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-amine Phenyl) decane, bis(3-aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4 '-Thiodiphenylamine, 3,3'-thio Diphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diamino Diphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl (3,3'-diamino Diphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2 , 3'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminodiphenyl Ketone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-Diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-di Amino naphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl) Ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene , 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4 - bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylene bis(methyl)] Aniline, 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3, 4'-[1,3-phenylenebis(methyl)diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'-[ 1,3-phenylene bis(methyl)diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3- Aminophenyl)methanone], 1,3-phenylene bis[(4- Aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylphenylbis(4-aminobenzoate), 1 , 4-phenylphenyl bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-amine Benzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl) Phthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N, N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3- Aminobenzamide, N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)-p-benzene Dimethylamine, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)m-xylyleneamine, N,N '-bis(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenyl Base, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane , 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4 -methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis (3 -Amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-double (4-Aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5- Bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)-n-hexane, 1,6-bis(3-aminophenoxy)-hexane, 1,7 - bis(4-aminophenoxyl) Heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy) Octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy) ) decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy) Undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, double (4-Amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamine Base hexane, 1,7-Diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane Or 1,12-diaminododecane and the like.

Further, as another diamine compound, a diamine side may be mentioned. The chain has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring, and examples thereof include those having a large cyclic substituent. Specific examples thereof include diamine compounds represented by the following formulas [DA1] to [DA13].

(In the formula [DA1]~[DA6], A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ² It is 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.

(In the formula [DA7], p represents an integer of 1 to 10).

Other diamines as well without impairing the effects of the present invention As the compound, a diamine compound represented by the following formula [DA8] to formula [DA13] can be used.

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

And without impairing the effects of the present invention, the following formula may be used A diamine compound represented by [DA14].

(In the formula [DA14], A ¹ represents a group selected from -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH) ₃ )- or -N(CH ₃ )CO-divalent organic group, A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, and A ³ is selected from the group consisting of Single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO -or-O(CH ₂ ) _m - (m is an integer of 1 to 5), A ⁴ is an aromatic heterocyclic ring containing nitrogen, and n is an integer of 1 to 4).

In addition, as another diamine compound, the following formula can be used [DA15] and a diamine compound represented by the formula [DA16].

The above other diamine compounds are specific to the present invention The properties of the polymer to the solvent, the coating property of the composition, the alignment property of the liquid crystal when the liquid crystal alignment film is used, the voltage holding ratio, and the accumulated electric charge can be used in one type or in a mixture of two or more types.

<tetracarboxylic dianhydride component>

The tetracarboxylic dianhydride component which produces the specific polymer of the present invention includes a tetracarboxylic acid anhydride represented by the following formula [3] or the tetracarboxylic acid derivative (also referred to as a specific tetracarboxylic dianhydride component).

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

In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different.

In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and each may be the same or different.

In the structure represented by the formula [3] of the specific tetracarboxylic dianhydride component of the present invention, Z ^{1 is} represented by the formula [3a] from the viewpoint of easiness of production synthesis or ease of polymerization reactivity in the case of a polymer. The structure represented by [3c], formula [3d], formula [3e], formula [3f] or formula [3g] is preferred. The structure represented by the formula [3a], the formula [3e], the formula [3f] or the formula [3g] is preferably a formula [3e], a formula [3f] or a formula [3g].

The specific tetracarboxylic dianhydride component of the present invention is tetracarboxylic acid II It is preferred that one part or more of the anhydride component is 1 mol% or more. It is preferably 5 mol% or more, and particularly preferably 10 mol% or more.

Also, the knot of the formula [3e], the formula [3f] or the formula [3g] is used. In the case of the specific tetracarboxylic dianhydride component, the amount used is 20 mol% or more of the entire tetracarboxylic dianhydride component, and thus the desired effect can be obtained. It is preferably 30 mol% or more. Further, the tetracarboxylic dianhydride component may be a tetracarboxylic dianhydride component having a structure of the formula [3e], the formula [3f] or the formula [3g].

In the specific polymer of the present invention, other tetracarboxylic dianhydride components other than the specific tetracarboxylic dianhydride component can be used without impairing the effects of the present invention.

Examples of the other tetracarboxylic dianhydride component include the following tetracarboxylic acid compound, tetracarboxylic dianhydride, dicarboxylic acid dihalide compound, dicarboxylic acid dialkyl ester compound or dialkyl ester dihalide. Compound.

That is, examples of the other tetracarboxylic dianhydride component include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5. , 8-naphthalenetetracarboxylic acid, 2,3,6,7-nonanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid , 2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis( 3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3 ,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylnonane, bis(3,4-dicarboxyphenyl) Diphenyldecane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylfluorene Carboxylic acid, 3,4,9,10-苝 Tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

Specific tetracarboxylic dianhydride components and other tetracarboxylic dianhydride components In combination with the solubility of the solvent of the specific polymer of the present invention, the coating property of the composition, the alignment property of the liquid crystal when the liquid crystal alignment film is used, the voltage holding ratio, and the accumulated electric charge, one type or a mixture of two or more types can be used. use.

<Method of Manufacturing Specific Polymer>

For the present invention, the method of synthesizing a specific polymer is not particularly limited. It is generally obtained by reacting a diamine component with a tetracarboxylic dianhydride component. Generally, at least one tetracarboxylic dianhydride component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component of one or a plurality of diamine compounds to obtain a polyamic acid. Specifically, a method of polycondensing a tetracarboxylic dianhydride with a diamine component to obtain a poly-proline, a method of dehydrating polycondensation of a tetracarboxylic acid and a diamine component to obtain a poly-proline, or a tetracarboxylic acid A method in which a dihalide and a diamine component are polycondensed to obtain a poly-proline.

When a polyalkyl amide is desired, a carboxylic acid group can be used. a method of polycondensing a dialkyl esterified tetracarboxylic acid and a diamine component, a method of polycondensing a dialkyl esterified tetracarboxylic acid dihalide with a diamine component, or a polyfluorene A method of converting a carboxyl group of an amine acid into an ester.

In order to obtain a polyimine, a method of subjecting the aforementioned polyamic acid or polyalkyl amide to ring closure as a polyimine can be used.

The reaction of the diamine component with the tetracarboxylic dianhydride component generally involves the diamine component and the tetracarboxylic dianhydride component in an organic solvent. As this time The organic solvent to be used is only the specific alcohol solvent of the component (A) of the present invention, the specific polar solvent of the component (B), and the polyimine precursor which is further soluble, and there is no particular limited.

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

Namely N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone , cyclopentanone or 4-hydroxy-4-methyl-2-pentanone and the like.

These can be used alone or in combination. And that is The solvent which is incapable of dissolving the polyimide precursor can be used in the above solvent only in the range in which the produced polyimide precursor is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and further causes the polyimine precursor formed by the hydrolysis, the organic solvent is preferably dried by dehydration.

The diamine component and the tetracarboxylic dianhydride component are organic When the reaction is carried out in a solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride component is directly dispersed or dissolved in an organic solvent, and the tetracarboxylic dianhydride is instead added. Any of these methods may be used in a method in which a component is dispersed or dissolved in an organic solvent, a method of adding a diamine component, a method of adding a tetracarboxylic dianhydride component and a diamine component in an interactive manner, and the like. Further, when the diamine component or the tetracarboxylic dianhydride component is reacted with each of a plurality of kinds, the reaction can be carried out in a state of being mixed in advance, or the respective reactions can be carried out in order, and the respective reactions can be further lowered. A polymer in which a molecular weight body is subjected to a mixing reaction. The polymerization temperature at this time is optional Any temperature from -20 ° C to 150 ° C is selected, preferably in the range of -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid becomes too high, and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter an organic solvent can be added.

For the polymerization of polyimine precursors, diamine components The ratio of the total number of moles to the total number of moles of the tetracarboxylic dianhydride component is preferably from 0.8 to 1.2. As in the case of the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyimide intermediate precursor.

The polyimine of the present invention will be the aforementioned polyimine precursor The polyimine obtained by ring closure is not required to have a ring closure ratio (also referred to as a sulfhydrylation ratio) of the phthalic acid group of 100%, and can be arbitrarily adjusted for use or purpose.

As a method for the imidization of a polyimide precursor The method may be a solution of a thermal amidoxime or a polyimide precursor which directly heats a solution of a polyimide precursor, and a catalyst is added to the amidoxime.

Thermally amidizing a polybendimimine precursor in solution The temperature at which the temperature is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, is preferably carried out by removing the water formed by the imidization reaction to the outside of the system.

The catalyst of the polyamidiamine precursor is amidated to The solution of the imine precursor is added with a basic catalyst and an acid anhydride, and is stirred at -20 to 250 ° C, preferably at 0 to 180 ° C. Alkaline catalyst The amount is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the prolyl group. . The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is also preferred because it has moderate alkalinity in the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, purification after completion of the reaction can be easily carried out, which is preferable. The amidoximination rate by the catalyst amidation can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

a reaction solution of a polyimine precursor or a polyimine, When the produced polyimine precursor or polyimine is recovered, the reaction solution may be added to a solvent to precipitate. Examples of the solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. The polymer which has been introduced into the solvent and precipitated is recovered by filtration, and dried under normal pressure or reduced pressure at normal temperature or under heating. Further, after the precipitated polymer is redissolved in an organic solvent, the operation of reprecipitation and recovery is repeated 2 to 10 times to reduce impurities in the polymer. The solvent in this case is preferably an alcohol, a ketone or a hydrocarbon. When it is used in three or more types of solvents selected from the group, the purification efficiency can be further improved, which is preferable.

The molecular weight of the specific polymer of the present invention, if considered When the strength of the obtained resin film or liquid crystal alignment film, the workability at the time of film formation, and the film coating property, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000. It is preferably 10,000 to 150,000.

<composition. Liquid crystal alignment agent>

The composition of the present invention or the liquid crystal alignment treatment agent using the same is a coating solution for forming a resin film or a liquid crystal alignment film (also referred to as a resin film), and is formed to contain a specific alcohol solvent, a specific polar solvent, and a specific polymer. A coating solution of the resin film.

For the composition of the present invention or the liquid crystal alignment thereof using the same In the physicochemical agent, all of the polymer components may be specific polymers of the present invention, and other polymers other than the polymer may be mixed in the specific polymer of the present invention. In this case, the content of the other polymer other than the above is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass based on the specific polymer of the present invention. Examples of the other polymer other than the above include a polyimine precursor or a polyimine which does not use the above-described diamine compound having a carboxyl group, a second diamine compound or a specific tetracarboxylic dianhydride component. Further, examples of the polyimine precursor and the polymer other than the polyimine may, for example, be an acrylic polymer, a methacrylic polymer, polystyrene or polyamine.

Composition of the present invention or liquid crystal alignment treatment agent using the same In the organic solvent, the content of the organic solvent is preferably from 70 to 99.9% by mass from the viewpoint of forming a uniform resin film during coating. The content can be appropriately changed in accordance with the film thickness of the intended resin film or liquid crystal alignment film.

In the organic solvent used in the composition of the present invention or the liquid crystal alignment treatment agent using the same, all the organic solvents may be the specific alcohol solvent and the specific polar solvent of the present invention, and may be mixed with the organic solvent of the present invention. Other organic solvents.

In this case, the specific alcohol solvent of the present invention is preferably 50 to 99% by mass based on the total amount of the solvent contained in the composition. Among them, 55 to 99% by mass is preferred. It is preferably 55 to 95% by mass.

Further, the specific polar solvent of the present invention is preferably from 1 to 40% by mass based on the total of the solvent contained in the composition. Among them, 1 to 35 mass% is preferred. It is preferably from 1 to 30% by mass, more preferably from 5 to 30% by mass.

As other organic solvents other than this, only specific ones can be dissolved The organic solvent of the polymer is not particularly limited. The following specific examples are mentioned.

For example, N,N-dimethylformamide, N,N-dimethylacetamidine Amine, dimethyl hydrazine, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.

Composition of the present invention or liquid crystal alignment treatment agent using the same A solvent which can improve the coating property or the surface smoothness of the resin film or the liquid crystal alignment film when the coating composition or the liquid crystal alignment treatment agent is used can be used without using the effect of the present invention, and a weak solvent can be used.

Specific examples of the weak solvent which can improve the coating property or surface smoothness of a resin film or a liquid crystal alignment film are mentioned below.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl 1-butanol, isoamyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2- Methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2 - propane diol, 1,3-propane diol, 1,2-butane diol, 1,3-butane diol, 1,4-butane diol, 2,3-butane diol, 1 , 5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, Dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene Alcohol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene Alcohol diacetate, propyl carbonate, ethyl ethyl carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol Monohexyl ether, 2-(hexyloxy)ethanol, mercapto alcohol, diethylene glycol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether or diethylene glycol monobutyl ether, propylene glycol, propylene glycol monobutyl ether, 1-(butoxy B Oxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate Base, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate Ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, methyl lactate, ethyl lactate, lactate n An organic solvent having a low surface tension of a solvent such as a propyl ester, n-butyl lactate or isoamyl lactate.

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, two Ethylene glycol isopropyl ether or diethylene glycol monobutyl ether (which may also be referred to as component (D)) is preferred.

These (D) components are used in the composition or the liquid crystal used It is preferable that it is 1 to 50% by mass of the entire organic solvent contained in the treatment agent. It is also preferably 1 to 40% by mass. It is preferably 5 to 30% by mass, more preferably 10 to 30% by mass.

Composition of the present invention or liquid crystal alignment treatment agent using the same A crosslinkable compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclic carbonate group, having a hydroxyl group, a hydroxyalkyl group and a lower alkane, may be introduced without impairing the effects of the present invention. A crosslinkable compound having at least one substituent grouped in the group of oxyalkyl groups or a crosslinkable compound having a polymerizable unsaturated bond. These substituents or polymerizable unsaturated bonds must have two or more of the crosslinkable compounds.

As a crosslinkable compound having an epoxy group or an isocyanate group For example, bisphenol acetone glycidyl ether, phenol novolac epoxy Resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylamine diphenyl, tetraglycidyl-m-xylylenediamine, tetraglycidyl ester-1, 3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether ether, triphenyl glycidyl ether ether, bisphenol hexafluoroacetic acid diglycidyl ether, 1,3-double ( 1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxyoxypropoxy) Octafluorobiphenyl, triglycidyl ester-p-aminophenol, tetraglycidyl di-toluenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)- 2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane or 1,3-bis(4-(1-(4) -(2,3-epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl Phenyl)ethyl)phenoxy)-2-propanol and the like.

a crosslinkable compound having an oxetane group having Two less crosslinkable compounds of the oxetanyl group represented by the following formula [4].

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

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

(In the formula [4-7], n represents an integer of 1 to 3, and in the formula [4-8], n represents an integer of 1 to 3, and in the formula [4-9], n represents 1 to 100. Integer).

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

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

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

(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).

(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).

Further, polyfluorene oxide having at least one structure represented by the following formula [5-38] to formula [5-40] can be given.

(In the formula [5-38] to the formula [5-40], 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, and a carbon number of 1~. At least one of the alkyl group, the alkoxy group, the aliphatic ring or the aromatic ring of 10 represents a structure represented by the formula [5].

More specifically, a compound of the following formula [5-41] and formula [5-42] can be mentioned.

(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 alkoxy group include an amine-based resin having a hydroxyl group or an alkoxy group, and examples thereof include a melamine resin, a urea resin, and the like. Polycyanamide resin, glycol urea-formaldehyde resin, amber mercapto amide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanaline derivative, or a glycolic urea which can use a hydrogen atom of an amine group from a methylol group or an alkoxymethyl group or both. The melamine derivative or the benzocyanamide derivative may be present as a 2- or 3-dimer form. It is preferred that these have an average of three or more and six or less hydroxymethyl groups or alkoxymethyl groups per one triazine ring.

As an example of such a melamine derivative or a benzocyanamide derivative, each of the triazine rings of the sold product may be exemplified by a methoxy group. MX-30, which is substituted by an average of 3.7, MW-30 (manufactured by Sanwa Chemical Co., Ltd.) or CYMEL300, 301, 303, 350, which is replaced by an average of 5.8 methoxymethyl groups per one. Methoxylized melamine, CYMEL235, 236, 238, 212, 253, 254, etc. such as methoxylized melamine, CYMEL 506, 508, etc. such as 370, 771, 325, 327, 703, and 712 Butoxymethylated melamine, carboxymethylated methoxymethylated isobutoxymethylated melamine such as CYMEL1141, methoxymethylated ethoxymethylated benzotrimethane CYMEL1123 Amine, such as methoxymethylated butoxymethylated benzoguanamine, such as CYMEL 1123-10, such as CYMEL 1128, butoxymethylated benzoguanamine, such as CYMEL 1125-80 Methoxymethylated ethoxymethylated benzodiacyanamide of a carboxyl group (manufactured by Mitsui Cyanamide Co., Ltd.). Further, examples of the glycol urea include butyloxymethylated glycol urea such as CYMEL 1170, methylolated glycol urea such as CYMEL 1172, and methoxymethylolated glycol urea such as Powder link 1174. Wait.

As a benzene or phenolic compound having a hydroxyl group or an alkoxy group, For example, 1,3,5-glycol (methoxymethyl)benzene, 1,2,4-para(isopropoxymethyl)benzene, 1,4-bis(sec-butoxymethyl) Benzene or 2,6-dihydroxymethyl-p-tert-butylphenol and the like.

More specifically, the international publication WO2011/132751 (26.

As a crosslinkable compound having a polymerizable unsaturated bond, For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) propylene decyl ethoxy ethoxy III a crosslinkable compound having three polymerizable unsaturated groups in a molecule such as methylolpropane or glycerol polyglycidyl ether poly(meth)acrylate, and further, ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(a) Acrylate, butanediol di(meth)acrylate, neopentyl di(meth)acrylate, ethylene oxide bisphenol A di(meth)acrylate, propylene oxide bisphenol type II (Meth) acrylate, 1,6-n-hexanediol di(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(meth) acrylate, ethylene glycol diglycidyl ether II ( Methyl) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, diglycidyl phthalate di(meth) acrylate a crosslinkable compound having two polymerizable unsaturated groups in a molecule such as hydroxypivalic acid neopentyl alcohol di(meth)acrylate, and 2-hydroxyethyl (meth) acrylate and 2-hydroxyl group Propyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene decyloxy 2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono(meth) acrylate, 2-(methyl) propylene decyloxy B A crosslinkable compound having one polymerizable unsaturated group in a molecule such as a phosphatidyl ester or N-methylol (meth) acrylamide.

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

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

The above compound is an example of a crosslinkable compound, but it is not Limited to this. In addition, the cross-linkable compound to be used in the composition of the present invention or the liquid crystal alignment agent to be used may be one type or two or more types.

Composition of the present invention or liquid crystal alignment treatment agent using the same The content of the crosslinkable compound is preferably 0.1 to 150 parts by mass based on 100 parts by mass of all the polymer components. The effect of the crosslinking reaction is preferably 0.1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass, based on 100 parts by mass of all the polymer components.

As a liquid crystal alignment film using a liquid crystal alignment treatment agent using the composition of the present invention, as a charge transfer in the liquid crystal alignment film is promoted The compound [M1]~[M156] disclosed in pages 69-73 of International Publication WO2011/132751 (2011.10.27 publication) is added to promote the detachment of the charge of the unit cell using the liquid crystal alignment film. The nitrogen-containing heterocyclic amine compound shown is preferred. Although the amine compound may be directly added to the composition, it is preferably added in a suitable solvent to a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass. The solvent is not particularly limited as long as it dissolves only the organic solvent of the above polymer.

Composition of the present invention or liquid crystal alignment treatment agent using the same A compound which improves the uniformity of the film thickness or the surface smoothness of the resin film or the liquid crystal alignment film when the coating composition or the liquid crystal alignment treatment agent is used can be used only in order not to impair the effect of the present invention. Further, a compound which can improve the adhesion between the resin film or the liquid crystal alignment film and the substrate can be used.

As the film thickness of the resin film or the liquid crystal alignment film is increased Examples of the compound which is mono- or surface-smooth include a fluorine-based surfactant, a silicone resin-based surfactant, and a nonionic surfactant.

More specifically, for example, EftopEF301, EF303, EF352 (above is made by Tohkem Products), Megafac F171, F173, R-30 (above is manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (above is Sumitomo 3M), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103 , SC104, SC105, SC106 (above is manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is 0.01 to 2 by mass for 100 parts by mass of all the polymer components contained in the composition or the liquid crystal alignment treatment agent. The amount is preferably from 0.01 to 1 part by mass.

As a result of increasing the density of the resin film or the liquid crystal alignment film and the substrate Specific examples of the compound to be used include a compound having a functional decane or an epoxy group-containing compound.

For example, 3-aminopropyltrimethoxydecane, 3-amine Propyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethyl Oxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxy Decane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltri Ethyltriamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl -1,4,7-triazanonane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-triethoxydecyl-3,6-diaza Mercaptoacetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-amine Propyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxirane)-3-aminopropyltrimethoxydecane, N-double (ring Oxyethane)-3-aminopropyltriethoxydecane, ethylene glycol Glycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl diglycidyl ether, 1,6-hexanediol Glycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N, N', N', - four Glycidyl ester-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane or N,N,N',N',-tetraglycidyl ester-4 , 4'-diaminodiphenylmethane, and the like.

When using a compound that is dense with these substrates, for the composition The content of 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass. When the amount is less than 0.1 part by mass, the effect of improving the adhesion is not expected. When 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.

Composition of the present invention or liquid crystal alignment treatment agent using the same In addition to the weak solvent, the crosslinkable compound, the compound which improves the uniformity of the film thickness of the resin film or the liquid crystal alignment film, or the surface smoothness, and the compound which adheres to the substrate, the range of the effect of the present invention is not impaired. A dielectric or a conductive material for changing the electrical properties such as the dielectric constant or the conductivity of the resin film or the liquid crystal alignment film may be added.

<Resin film>

The composition of the present invention can be applied to a substrate and fired, and then used as a resin film. As the substrate to be used at this time, a plastic substrate such as a glass substrate, a tantalum wafer, an acrylic substrate, or a polycarbonate substrate can be used as the intended device. The coating method of the composition is not particularly limited, and industrially, a dipping method, a roll coater method, a slit coater method, a rotor method, a spray method, a screen printing, an offset printing, a flexographic printing, or an inkjet method. The method performed by the method is general. These can be used for the purpose.

After the composition is coated on the substrate, the hot plate and the heat are used. A resin film such as a ring oven or an IR (infrared) type oven is used to evaporate the solvent at 50 to 250 ° C, preferably 80 to 200 ° C, more preferably 80 to 150 ° C. The thickness of the resin film after firing is adjusted to 0.01 to 100 μm.

<Liquid alignment film. Liquid crystal display element>

The liquid crystal alignment treatment agent using the composition of the present invention is applied onto a substrate, and after firing, it is subjected to alignment treatment by rubbing treatment or light irradiation, and can be used as a liquid crystal alignment film. Further, in the case of vertical alignment use or the like, it can be used as a liquid crystal alignment film even without alignment treatment. The substrate to be used in this case is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to the glass substrate. From the viewpoint of simplification of the process, it is preferred to use a substrate on which an ITO electrode or the like to be driven by a liquid crystal is formed. Further, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the single-sided substrate, and a material that reflects light such as aluminum can be used as the electrode at this time.

The coating method of the liquid crystal alignment treatment agent is not particularly limited. The method of industrial screen printing, offset printing, flexographic printing or ink jet printing is generally used. As another coating method, there are a dipping method, a roll coater method, a slit coater method, a rotor method, a spray method, and the like, and they can be used for the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, the heat is applied A heating means such as a plate, a heat cycle type oven or an IR (infrared) type oven is used to form a liquid crystal alignment film at 5o to 250 ° C, preferably 80 to 200 ° C, more preferably 80 to 150 ° C. When the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of the power consumption of the liquid crystal display element. When the thickness is too thin, the reliability of the liquid crystal display element is lowered. Therefore, it is preferably 5 to 300 nm. Preferably, it is 10 to 100 nm. When the liquid crystal is aligned horizontally or obliquely, the liquid crystal alignment film after firing is treated by rubbing or polarized ultraviolet irradiation or the like.

The liquid crystal display element of the present invention is obtained by the above method In the liquid crystal alignment treatment agent of the present invention, a substrate having a liquid crystal alignment film is obtained, and a unit cell is produced by a known method and used as a liquid crystal display element.

As a method of fabricating a unit cell, preparing a liquid crystal alignment film One of the pair of substrates is disposed on the liquid crystal alignment film of the single substrate, and the liquid crystal alignment film surface is formed inside, and the other single substrate is bonded, and the liquid crystal is injected under reduced pressure to be sealed, or the liquid crystal alignment is dispersed. A method in which a liquid crystal is dropped on a film surface, and a substrate is bonded and sealed is exemplified.

Moreover, the liquid crystal alignment treatment agent of the present invention is provided with an electrode A liquid crystal layer is provided between a pair of substrates, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between a pair of substrates, and a voltage is input between the electrodes. A liquid crystal display device produced by a step of polymerizing a polymerizable compound by at least one of irradiation and heating of an active energy ray is also applicable. Among them, ultraviolet rays are preferred as the active energy ray. As the ultraviolet light, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. When the polymerization is carried out by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, the irradiation and heating of the ultraviolet rays can be simultaneously performed.

The above liquid crystal display element is available by PSA (Polymer) Sustained Alignment), which controls the pretilt angle of liquid crystal molecules. In the PSA system, when a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in a liquid crystal material, after the unit cell is combined, a photopolymerizable compound is irradiated with ultraviolet rays or the like while a predetermined voltage is applied to the liquid crystal layer. The pretilt angle of the liquid crystal molecules is controlled by the generated polymer. The alignment state of the liquid crystal molecules when the polymer is formed is still memorized after the voltage is removed. Therefore, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed by the liquid crystal layer or the like. Further, in the PSA method, since the rubbing treatment is unnecessary, it is suitable for the formation of a vertical alignment type liquid crystal layer which is difficult to control the pretilt angle by the rubbing treatment.

That is, the liquid crystal display element of the present invention is In the liquid crystal alignment treatment agent of the present invention, a substrate having a liquid crystal alignment film is obtained, and a unit cell is produced, and the alignment of the liquid crystal molecules can be controlled by polymerizing the polymerizable compound by at least one of irradiation and heating of ultraviolet rays.

To give an example of the cell fabrication of the PSA method, A method of forming a pair of substrates of a liquid crystal alignment film, dispersing a space on a liquid crystal alignment film of a single-sided substrate, forming a liquid crystal alignment film surface inside, bonding another single-sided substrate, and sealing the liquid crystal under reduced pressure Or a method in which a liquid crystal is dropped onto a liquid crystal alignment film surface which is interspersed, and a substrate is bonded and sealed.

Polymerization by liquid crystal mixing by heat or ultraviolet irradiation Synthetic compound. The polymerizable compound may be a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. In this case, 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 parts by mass, the polymerizable compound cannot be subjected to the alignment control of the liquid crystal without polymerization. When the amount is more than 10 parts by mass, the amount of the unreacted polymerizable compound increases, and the printing characteristics of the liquid crystal display element are lowered. .

After making the unit cell, input AC or DC on the side of the unit cell. The polymerizable compound is polymerized under pressure, irradiation heat or ultraviolet light. Thereby, the alignment of the liquid crystal molecules can be controlled.

In addition, the liquid crystal alignment treatment agent of the present invention is provided with electricity A liquid crystal layer is provided between the pair of substrates, and a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is input between the electrodes. The liquid crystal display element produced in the step is also preferred. Ultraviolet light is preferred as the active energy ray. As the ultraviolet light, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. When the polymerization is carried out by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, the irradiation and heating of the ultraviolet rays can be simultaneously performed.

Want to get at least one of the active energy lines and heat The liquid crystal alignment film of the polymerizable group to be polymerized may be a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, or a method of using a polymer component containing a polymerizable group. Liquid crystal alignment treatment of the present invention Since the agent contains a specific compound having a reactive bonding site by irradiation with heat or ultraviolet rays, the alignment of the liquid crystal molecules can be controlled by at least one of irradiation and heating of ultraviolet rays.

To give an example of cell fabrication, it is ready to form One of the liquid crystal alignment films is disposed on the liquid crystal alignment film of the single-sided substrate, and the liquid crystal alignment film surface is formed inside, and the other surface substrate is bonded to each other, and the liquid crystal is injected under reduced pressure and sealed, or at intervals of dispersion. After the liquid crystal is dropped onto the liquid crystal alignment film surface, the substrate is bonded and sealed.

After the unit cell is produced, the AC or DC voltage is input to the cell, and the alignment of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays.

As described above, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be suitably used for a high-definition liquid crystal television or the like in a large screen.

[Examples]

The present invention will be described in more detail below by way of examples, but not limited thereto.

The abbreviations used in the 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])

(2nd 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-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene (shown in the following formula [B3]) Amine compound)

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

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

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

(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])

(tetracarboxylic acid component)

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

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

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

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

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

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

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

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

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

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

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

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

BCS: ethylene glycol monobutyl ether

(Measurement of molecular weight of polyimine precursor and polyimine)

The molecular weight of the polyimine precursor and the polyimine in the synthesis example is a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD). -805) (manufactured by Shodex Co., Ltd.), the measurement was carried out as follows.

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (as an additive, using lithium bromide-water and water (LiBr.H ₂ O) is 30 mmol / L (liter), phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol /L, tetrahydrofuran (THF) is 10ml / L)

Flow rate: 1.0ml/min

Standard sample for calibration line preparation: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000, and 1,000) (polymer Laboratory company system).

(Measurement of the amidoximation rate of polyimine)

The imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR standard sampling tube, 5 (manufactured by Kusano Scientific Co., Ltd.), a solution of dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane)) (0.53 ml) was added, and it was completely dissolved by ultrasonic waves. This solution was measured for proton NMR at 500 MHz by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Ltd.). The imidization ratio is determined by using a proton derived from a structure which does not change before and after amidation as a reference proton, and an absorption peak value of the proton is used and an NH group derived from proline which appears in the vicinity of 9.5 ppm to 10.0 ppm. The proton absorption peak product value is obtained by the following formula.

Amidoxime rate (%) = (1-α.x/y) × 100

In the above formula, x is the proton absorption peak integrated value of the NH group derived from proline, y is the absorption peak integrated value of the reference proton, and α is the polyamine (the amidoxime rate is 0%). The ratio of the number of acids to the reference proton of one NH matrix.

"Synthesis of a specific polymer (polyimine precursor and polyimine) of the component (C) of the present invention"

<Synthesis Example 1>

D1 (3.00 g, 15.3 mmol) and A1 (2.33 g, 15.3 mmol) were mixed in PGME (48.0 g), and the reaction was carried out at 40 ° C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 10.0% by mass. 1). The polyamic acid had a number average molecular weight of 13,500 and a weight average molecular weight of 32,100.

<Synthesis Example 2>

D2 (7.65 g, 30.6 mmol) and A2 (5.82 g, 38.3 mmol) were mixed in NMP (24.7 g), and after reacting at 80 ° C for 5 hours, D1 (1.50 g, 7.65 mmol) and NMP (20.2) were added. g) The reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

In the obtained polyaminic acid solution (40.0 g), added After NMP was diluted to 6% by mass, acetic anhydride (4.81 g) and pyridine (3.75 g) were added as a berylation catalyst, and the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (2). The polyamidimide had a mercapto amination ratio of 55%, a number average molecular weight of 15,800, and a weight average molecular weight of 40,600.

<Synthesis Example 3>

D2 (1.91 g, 7.63 mmol), B1 (2.43 g, 6.39 mmol) ), A1 (0.97 g, 6.38 mmol) was mixed in PGME (31.2 g), and after reacting at 80 ° C for 5 hours, D1 (1.00 g, 5.10 mmol) and PGME (25.6 g) were added, and the reaction was carried out at 40 ° C. The reaction was carried out for an hour to obtain a polyamic acid solution (3) having a resin solid content concentration of 10.0% by mass. The polyamic acid had a number average molecular weight of 13,900 and a weight average molecular weight of 36,500.

<Synthesis Example 4>

D2 (3.73 g, 14.9 mmol), B1 (4.73 g, 12.4 mmol), A1 (1.89 g, 12.4 mmol) were mixed in NMP (20.3 g), and reacted at 80 ° C for 5 hours, then D1 (1.95) was added. g, 9.94 mmol) and NMP (16.6 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass.

After the obtained polyaminic acid solution (40.0 g) was diluted with NMP to 6 mass%, acetic anhydride (4.80 g) and pyridine (3.75 g) were added as a ruthenium 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 obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). The polyamidimide had a mercapto amination ratio of 60%, a number average molecular weight of 14,600, and a weight average molecular weight of 37,200.

<Synthesis Example 5>

D2 (5.61 g, 22.4 mmol), B1 (4.27 g, 11.2 mmol), A1 (2.13 g, 14.0 mmol), C1 (0.30 g, 2.77 mmol) After mixing in NMP (22.1 g) and reacting at 80 ° C for 5 hours, D1 (1.10 g, 5.61 mmol) and NMP (18.1 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a resin solid concentration of 25.0. Mass% polyamine solution.

Add NMP to the obtained polyaminic acid solution (40.0g) After diluting to 6% by mass, acetic anhydride (4.80 g) and pyridine (3.75 g) were added as a ruthenium catalyst, and the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyamidimide had a mercapto amination rate of 57%, a number average molecular weight of 16,500, and a weight average molecular weight of 39,900.

<Synthesis Example 6>

D2 (5.21 g, 20.8 mmol), B2 (3.52 g, 8.92 mmol), A1 (2.26 g, 14.9 mmol), B6 (1.21 g, 5.95 mmol) were mixed in NMP (23.0 g) at 80 ° C After 5 hours of reaction, D1 (1.75 g, 8.92 mmol) and NMP (18.8 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

Add NMP to the obtained polyaminic acid solution (40.0g) After diluting to 6% by mass, acetic anhydride (4.80 g) and pyridine (3.75 g) were added as a ruthenium catalyst, and the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol and dried at 100 ° C under reduced pressure. Polyimine powder (6). The polyamidimide had a mercapto amination rate of 50%, a number average molecular weight of 18,100, and a weight average molecular weight of 42,500.

<Synthesis Example 7>

D2 (3.57 g, 14.3 mmol), B3 (3.71 g, 8.58 mmol), A2 (2.61 g, 17.2 mmol), C2 (0.31 g, 2.87 mmol) were mixed in NMP (21.4 g) at 80 ° C After 5 hours of reaction, D1 (2.80 g, 14.3 mmol) and NMP (17.5 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

After the NMP was added to the obtained polyamidamine solution (40.0 g) and diluted to 6 mass%, acetic anhydride (4.80 g) and pyridine (3.75 g) were added as a ruthenium 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 obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyamidimide had a mercapto amination ratio of 60%, a number average molecular weight of 19,100, and a weight average molecular weight of 43,000.

<Synthesis Example 8>

D2 (6.12 g, 24.5 mmol), B4 (2.26 g, 4.59 mmol), A2 (3.96 g, 26.0 mmol) were mixed in NMP (22.3 g), and after reacting at 80 ° C for 6 hours, D1 (1.20 g) was added. 6.12 mmol) and NMP (18.3 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

After the NMP was added to the obtained polyamidamine solution (40.0 g) and diluted to 6 mass%, acetic anhydride (4.80 g) and pyridine (3.75 g) were added as a mercaptoamide catalyst, and the reaction was carried out at 80 ° C for 3.5 hours. . The reaction solution was poured into methanol (800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyamidimide had a mercapto amination rate of 48%, a number average molecular weight of 15,800, and a weight average molecular weight of 36,900.

<Synthesis Example 9>

D3 (6.50 g, 29.0 mmol), B1 (3.31 g, 8.70 mmol), and A1 (3.09 g, 20.3 mmol) were mixed in NMP (38.7 g), and reacted at 40 ° C for 5 hours to obtain a resin solid content concentration of 25.0% by mass of a polyaminic acid solution.

NMP was added to the obtained polyamic acid solution (40.0 g), and after diluting to 6% by mass, acetic anhydride (4.70 g) and pyridine (3.60 g) were added as a ruthenium catalyst, and it was carried out at 80 ° C for 4 hours. reaction. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The polyamidimide had a mercapto amination rate of 54%, a number average molecular weight of 17,500, and a weight average molecular weight of 40,100.

<Synthesis Example 10>

D3 (6.50 g, 29.0 mmol), B5 (3.28 g, 8.71 mmol), B6 (1.18 g, 5.80 mmol), A2 (2.21 g, 14.5 mmol) The mixture was mixed in NMP (39.5 g), and reacted at 40 ° C for 5 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

Adding NMP to the obtained polyaminic acid solution (40.0 g), After diluting to 6% by mass, acetic anhydride (4.81 g) and pyridine (3.70 g) were added as a ruthenium catalyst, and the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (900 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (10). The polyamidimide had a mercapto amination ratio of 55%, a number average molecular weight of 16,500, and a weight average molecular weight of 38,200.

<Synthesis Example 11>

D4 (5.05 g, 16.8 mmol), B2 (3.32 g, 8.41 mmol), C2 (0.45 g, 4.16 mmol), A2 (2.35 g, 15.4 mmol) were mixed in NMP (22.1 g) at 80 ° C After 5 hours of reaction, D1 (2.20 g, 11.2 mmol) and NMP (18.1 g) were added, and the mixture was reacted at 40 ° C for 5.5 hours to obtain a polyamine acid solution having a resin solid concentration of 25.0% by mass.

Adding NMP to the obtained polyaminic acid solution (40.0 g), After diluting to 6% by mass, acetic anhydride (4.80 g) and pyridine (3.68 g) were added as a ruthenium 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 obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (11). The polyamidimide had a mercapto amination rate of 61%, a number average molecular weight of 18,400, and a weight average molecular weight of 39,100.

<Synthesis Example 12>

D4 (4.29 g, 14.3 mmol), B1 (3.26 g, 8.57 mmol), B6 (1.74 g, 8.56 mmol), A1 (1.74 g, 11.4 mmol) were mixed in NMP (22.8 g) at 80 ° C After 5 hours of reaction, D1 (2.80 g, 14.3 mmol) and NMP (18.7 g) were added, and the mixture was reacted at 40 ° C for 5.5 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

Add to the obtained polyaminic acid solution (40.0g) After diluting to 6 mass% of NMP, acetic anhydride (4.70 g) and pyridine (3.60 g) were added as a methylene chloride catalyst, and the reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (12). The polyamidimide had a mercapto amination ratio of 55%, a number average molecular weight of 17,500, and a weight average molecular weight of 39,300.

<Synthesis Example 13>

D1 (9.50 g, 48.4 mmol) and A1 (7.37 g, 48.4 mmol) were mixed in NMP (50.6 g), and the reaction was carried out at 40 ° C for 8 hours to obtain a polyamine acid solution having a resin solid concentration of 25.0% by mass. 13). The polyamic acid had a number average molecular weight of 17,300 and a weight average molecular weight of 42,900.

<Synthesis Example 14>

D2 (7.65 g, 30.6 mmol) and A2 (5.82 g, 38.3 mmol) were mixed in NMP (24.7 g), and after reacting at 80 ° C for 5 hours, D1 (1.50 g, 7.65 mmol) and NMP (20.2) were added. g) The reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

Add NMP to the obtained polyaminic acid solution (40.0g) After diluting to 6% by mass, acetic anhydride (4.81 g) and pyridine (3.75 g) were added as a ruthenium catalyst, and the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (14). The polyamidimide had a mercapto amination ratio of 55%, a number average molecular weight of 15,800, and a weight average molecular weight of 40,600.

<Synthesis Example 15>

D2 (7.37 g, 29.5 mmol), B1 (9.34 g, 24.5 mmol), A1 (3.73 g, 24.5 mmol) were mixed in NMP (40.1 g), and after reacting at 80 ° C for 5 hours, D1 (3.85) was added. g, 19.6 mmol) and NMP (32.8 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution (15) having a resin solid content concentration of 25.0% by mass. The polyamic acid had a number average molecular weight of 19,500 and a weight average molecular weight of 46,200.

<Synthesis Example 16>

The polyaminic acid solution (15) obtained in Synthesis Example 15 (40.0 g) After the NMP was added and diluted to 6 mass%, acetic anhydride (4.80 g) and pyridine (3.75 g) were added as a berylation catalyst, and the reaction was carried out at 80 ° C for 4 hours. The reaction solution was poured into methanol (800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (16). The polyamidimide had a mercapto amination ratio of 60%, a number average molecular weight of 17,100, and a weight average molecular weight of 40,100.

<Synthesis Example 17>

D2 (3.92 g, 15.7 mmol), B1 (4.97 g, 13.1 mmol), C1 (1.41 g, 13.0 mmol) were mixed in NMP (20.4 g), and reacted at 80 ° C for 5 hours, then D1 (2.05) was added. g, 10.5 mmol) and NMP (16.7 g) were reacted at 40 ° C for 5.5 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

Add NMP to the obtained polyaminic acid solution (40.0g) After diluting to 6% by mass, acetic anhydride (5.40 g) and pyridine (4.18 g) were added as a ruthenium catalyst, and the reaction was carried out at 80 ° C for 3 hours. The reaction solution was poured into methanol (800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (17). The polyamidimide had a mercapto amination rate of 61%, a number average molecular weight of 16,300, and a weight average molecular weight of 39,100.

Specific polymers of the invention (polyimine precursors and poly 醯imine) is shown in Table 1.

*1: Polylysine.

"Manufacture of the composition of the present invention and liquid crystal alignment treatment agent"

The production examples of the compositions are described in the following Examples 1 to 23 and Comparative Examples 1 to 10. Moreover, these compositions are also used for the evaluation of liquid crystal alignment treatment agents.

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

Using the composition obtained in the examples and the comparative examples of the present invention or the liquid crystal alignment treatment agent, "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and the "evaluation of the inkjet coating property of the liquid crystal alignment treatment agent" and " Production of unit cell (general unit cell), "evaluation of liquid crystal alignment (general unit cell)", "production of cell and evaluation of liquid crystal alignment" (PSA unit cell) and "evaluation of voltage retention rate". This condition is as follows.

"Evaluation of the coating properties of the composition and the liquid crystal alignment agent"

The composition obtained in the examples and the comparative examples of the present invention was subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and a solution which was stored at -15 ° C for 48 hours was used to evaluate the coatability. For the coating system, a spin coater (1H-D7) (manufactured by Mikasa Co., Ltd.) was used. The ITO surface coated with a 30×40 mm ITO electrode (length 40 mm × horizontal 30 mm, thickness 0.7 mm) coated with pure water and IPA (isopropyl alcohol) was spin-coated, and applied to the pseudo-drying. The time was 30 seconds, and the dummy drying was carried out on a hot plate at 80 ° C for 5 minutes.

Evaluation of the pinhole of the obtained resin film was performed. The pinhole of the resin film was evaluated by visually observing the resin film under a sodium lamp. Specifically, the number of pinholes caused by cracks and foreign matter confirmed on the resin film was counted, and the number of pinholes was small, indicating that the evaluation was excellent.

Further, the compositions obtained in the examples and comparative examples of the present invention can be used for a liquid crystal alignment treatment agent. Therefore, the results of the applicability of the resin film obtained in the examples and the comparative examples were also the results of the printability of the liquid crystal alignment film.

The number of pinholes of the resin film (liquid crystal alignment film) obtained in the examples and the comparative examples is shown in Tables 5 to 7.

"Evaluation of inkjet coating properties of liquid crystal alignment agents"

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 subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and carried out at -15 ° C for 48 hours. The stored solution was evaluated for inkjet coating properties. In the inkjet coater, HIS-200 (manufactured by Hitachi Industrial Equipment Technology Co., Ltd.) was used. The coating was applied to an ITO (Indium Tin Ionate) vapor-deposited substrate which was washed with pure water and IPA, and had a coating area of 70×70 mm, a nozzle pitch of 0.423 mm, a scanning pitch of 0.5 mm, a coating speed of 40 mm/sec, and self-coating. The time until the dummy drying was 60 seconds, and the dummy drying was carried out on a hot plate at 70 ° C for 5 minutes.

Evaluation and "composition of pinholes of the obtained liquid crystal alignment film" The evaluation was carried out under the same conditions as in the evaluation of the applicability of the material and the liquid crystal alignment agent.

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

"The production of unit cell (general unit cell)"

The liquid crystal alignment treatment agent obtained in the examples and the comparative examples of the present invention was subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and the solution was stored at -15 ° C for 48 hours to prepare a unit cell (general unit cell). . The solution was washed with pure water and IPA, and the ITO surface of a substrate (length 40 mm × width 30 mm, thickness 0.7 mm) with a 30×40 mm ITO electrode was spin-coated, and heated on a hot plate at 100° C. for 5 minutes. After treatment, an ITO substrate with a polyimide film alignment film having a film thickness of 100 nm was obtained. The coating surface of the ITO substrate is a friction device having a roll diameter of 120 mm, and is used by a user. The wire-making cloth was subjected to a rubbing treatment under the conditions of a roller rotation number of 1000 rpm, a roll speed of 50 mm/sec, and a pushing amount of 0.1 mm.

Prepare 2 pieces of ITO base with liquid crystal alignment film In the panel, the liquid crystal alignment film surface was placed inside, and the sealing agent (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was applied by being combined with a space of 6 μm. Next, after bonding the other substrate and the liquid crystal alignment film surface in the front direction, the sealing agent was heat-treated at 120 ° C for 90 minutes in a heat cycle type dust-free oven, and then hardened to produce a hollow cell. A liquid crystal (general unit cell) is obtained by injecting a liquid crystal into the cell by a vacuum injection method and sealing the injection port.

Moreover, the liquid crystals obtained in Example 1 and Example 2 were used. In the unit cell of the alignment treatment agent (1), the liquid crystal alignment treatment agent (2), the liquid crystal alignment treatment agent (24) to the liquid crystal alignment treatment agent (28) obtained in Comparative Examples 1 to 5, and the nematic liquid crystal in the liquid crystal. (MLC-2003) (made by Merck & Co., Japan).

Further, the liquid crystal alignments obtained in Examples 3 to 6 were used. Liquid crystal alignment agent (3) to liquid crystal alignment treatment agent (6), liquid crystal alignment treatment agent (8) to liquid crystal alignment treatment agent (10) obtained in Examples 8 to 10, and liquid crystal alignment obtained in Examples 12 to 23. In the liquid crystal alignment treatment agent (29) to the liquid crystal alignment treatment agent (33) obtained from the treatment agent (12) to the liquid crystal alignment treatment agent (23) and the liquid crystal alignment treatment agent (23) to the comparative example 10, a nematic liquid crystal is used for the liquid crystal ( MLC-6608) (made by Merck & Co., Japan).

"Evaluation of Liquid Crystal Alignment (General Cell)"

The liquid crystal alignment property was evaluated by using the unit cell obtained by the above-mentioned "cell fabrication (general unit cell)". The liquid crystal alignment property was observed by a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Co., Ltd.) to confirm the presence or absence of alignment defects. Specifically, those who did not see the alignment defect were excellent in this evaluation (good in Tables 5 to 7).

Tables 5 to 7 show the liquid crystal distributions obtained in the examples and comparative examples. The result of sexuality.

"Production of Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)"

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 added in a membrane filter having a pore diameter of 1 μm. The solution was stored under pressure at -15 ° C for 48 hours to prepare a unit cell and evaluate the liquid crystal alignment (PSA unit cell). The solution was washed with pure water and IPA, and a 10×10 mm pattern was placed at a distance of 20 μm from the substrate with the ITO electrode (40 mm in length × 30 mm in width, 0.7 mm in thickness) and 10×40 mm in the center. The ITO surface of the substrate having an ITO electrode (40 mm in length × 30 mm in width and 0.7 mm in thickness) was spin-coated, and heat-treated at 100 ° C for 5 minutes on a hot plate to obtain a polyimide film having a film thickness of 100 nm. The surface of the coating film was washed with pure water, and then heat-treated at 100 ° C for 15 minutes in a heat cycle type dust-free oven to obtain a substrate with a liquid crystal alignment film.

The liquid crystal alignment film is attached to the substrate with the liquid crystal alignment film As the inner side, the space of 6μm is sandwiched and combined, and the sealant is adhered to the circumference. Create a hollow cell. In the nematic liquid crystal (MLC-6608) (manufactured by Merck & Co., Inc.), the polymerizable compound (1) represented by the following formula was used for the nematic liquid crystal (MLC-6608). 100% by mass, 0.3% by mass of the polymerizable compound (1) was mixed, and liquid crystal was injected, and the injection port was sealed to obtain a unit cell.

A voltage of 5 V was input to the obtained unit cell, and a metal halide lamp having an illuminance of 60 mW was used to block a wavelength of 350 nm or less, and ultraviolet irradiation of 20 J/cm ² in terms of 365 nm was performed to obtain a crystal in which the alignment direction of the liquid crystal was controlled. Cell (PSA unit cell). The temperature in the irradiation apparatus when the cells were irradiated with ultraviolet rays was 50 °C.

Measuring the unit cell before ultraviolet irradiation and after ultraviolet irradiation The response speed of the liquid crystal. The response speed is T90→T10 which measures the transmittance from 90% to the transmittance of 10%.

PSA unit cells obtained in the examples and crystals before ultraviolet irradiation The cell response speed after ultraviolet irradiation was faster than that of the cells, and it was confirmed that the alignment direction of the liquid crystal was controlled. Further, any cell was observed by a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Co., Ltd.) to confirm that the liquid crystal was uniformly aligned.

"Evaluation of Voltage Retention Rate"

The unit cell obtained in the above "production of a unit cell (general unit cell)". The voltage of 1 V was input to 60 μs at a temperature of 80 ° C, and the voltage after 16.67 ms and after 50 ms was measured, and the degree of voltage retention was calculated as a voltage holding ratio (also referred to as VHR). Further, the measurement was carried out using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Technica Co., Ltd.) with a setting of Voltage: ±1 V, Pulse Width: 60 μs, Flame Period: 16.67 ms, or 50 ms.

Table 8 shows the voltage holding ratios obtained in the examples and comparative examples. the result of.

<Example 1>

PGME (11.5 g) and NMP (1.57 g) were added to a polyamic acid solution (1) (20.0 g) having a resin solid content concentration of 10.0% by mass obtained by the synthesis method of Synthesis Example 1, and 2 hours at 25 ° C. The composition (1) was obtained by stirring. No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (1) was used for evaluation as a liquid crystal alignment treatment agent (1).

Use of the obtained composition (1) and liquid crystal alignment treatment agent (1) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Example 2>

PGME (21.9 g) and γ-BL (2.43 g) were added to the polyimine powder (2) (1.55 g) obtained by the synthetic method of Synthesis Example 2, and the mixture was stirred at 70 ° C for 24 hours to obtain a composition ( 2). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (2) was also used as a liquid crystal alignment treatment agent (2) for evaluation.

Use of the obtained composition (2) and liquid crystal alignment treatment agent (2) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", "Evaluation of the liquid crystal alignment property (general unit cell)", and "Evaluation of Voltage Retention Rate".

<Example 3>

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

Use of the obtained composition (3) and liquid crystal alignment treatment agent (3) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", "Evaluation of the liquid crystal alignment property (general unit cell)", and "Evaluation of Voltage Retention Rate".

<Example 4>

The polyamic acid solution (3) (10.0 g) obtained by the synthetic method of Synthesis Example 3 and having a resin solid content concentration of 10.0% by mass was added with PGME (1.97 g), γ-BL (1.57 g), and BCS (3.13 g). After stirring at 25 ° C for 2 hours, the composition (4) was obtained. No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (4) was also used as a liquid crystal alignment treatment agent (4) for evaluation.

Use of the obtained composition (4) and liquid crystal alignment treatment agent (4) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Example 5>

PGME (22.6 g) and γ-BL (2.51 g) were added to the polyimine powder (4) (1.60 g) obtained by the synthetic method of Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to obtain a composition ( 5). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (5) was also used as a liquid crystal alignment treatment agent (5) for evaluation.

Use of the obtained composition (5) and liquid crystal alignment treatment agent (5) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", "Evaluation of the liquid crystal alignment property (general unit cell)", "Evaluation of Cell Production and Evaluation of Liquid Crystal Alignment (PSA Cell)" and "Evaluation of Voltage Retention Rate".

<Example 6>

The polyimine powder (4) (1.60 g) obtained by the synthetic method of Synthesis Example 4 was added with PCS (15.0 g), γ-BL (2.51 g), BCS (7.52 g), and stirred at 70 ° C for 24 hours. , the composition (6) was obtained. No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (6) was also used for evaluation as a liquid crystal alignment treatment agent (6).

Use of the obtained composition (6) and liquid crystal alignment treatment agent (6) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Example 7>

PCS (21.5 g), γ-BL (7.17 g), BCS (10.8 g) were added to the polyimine powder (4) (1.30 g) obtained by the synthetic method of Synthesis Example 4, and stirred at 70 ° C for 24 hours. , the composition (7) was obtained. No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (7) was also used as a liquid crystal alignment treatment agent (7) for evaluation.

Using the obtained liquid crystal alignment treatment agent (7), "evaluation of inkjet coating property of liquid crystal alignment treatment agent" was carried out under the above conditions.

<Example 8>

MCS (14.6 g), NEP (3.64 g), and BCS (6.07 g) were added to the polyimine powder (5) (1.55 g) obtained by the synthetic method of Synthesis Example 5, and stirred at 70 ° C for 24 hours to obtain Composition (8). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (8) was also used as a liquid crystal alignment treatment agent (8) for evaluation.

Using the obtained composition (8) and the liquid crystal alignment treatment agent (8), under the above conditions, "evaluation of the coating properties of the composition and the liquid crystal alignment treatment agent", "production of a unit cell (general unit cell)", and "Evaluation of liquid crystal alignment (general unit cell)".

<Example 9>

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

Use of the obtained composition (9) and liquid crystal alignment treatment agent (9) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", "Evaluation of the liquid crystal alignment property (general unit cell)", and "Evaluation of cell production and evaluation of liquid crystal alignment (PSA unit cell)".

<Example 10>

PGME (22.6 g) and γ-BL (2.51 g) were added to the polyimine powder (6) (1.60 g) obtained by the synthetic method of Synthesis Example 6, and stirred at 70 ° C for 24 hours to obtain a composition (10). ). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (10) was also used as a liquid crystal alignment treatment agent (10) for evaluation.

Using the obtained composition (10) and liquid crystal alignment treatment agent (10) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Example 11>

PGME (32.3 g) and γ-BL (3.58 g) were added to the polyimine powder (6) (1.30 g) obtained by the synthetic method of Synthesis Example 6, and stirred at 70 ° C for 24 hours to obtain a composition (11). ). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (11) was also used as a liquid crystal alignment treatment agent (11) for evaluation.

Using the obtained liquid crystal alignment treatment agent (11), "evaluation of inkjet coating property of liquid crystal alignment treatment agent" was carried out under the above conditions.

<Example 12>

Polyimine powder obtained by the synthetic method of Synthesis Example 6 (6) (1.60 g), PCS (17.6 g), NEP (5.01 g), and BCS (2.51 g) were added, and the mixture was stirred at 70 ° C for 24 hours to obtain a composition (12). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (12) was also used as a liquid crystal alignment treatment agent (12) for evaluation.

Using the obtained composition (12) and the liquid crystal alignment treatment agent (12), under the above conditions, "evaluation of the coating properties of the composition and the liquid crystal alignment treatment agent", "production of the unit cell (general unit cell)", and "Evaluation of liquid crystal alignment (general unit cell)".

<Example 13>

ECS (15.0 g), NMP (5.01 g), and BCS (5.01 g) were added to the polyimine powder (7) (1.60 g) obtained by the synthetic method of Synthesis Example 7, and stirred at 70 ° C for 24 hours to obtain Composition (13). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (13) was also used as a liquid crystal alignment treatment agent (13) for evaluation.

Use of the obtained composition (13) and liquid crystal alignment treatment agent (13) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Example 14>

Polyimine powder obtained by the synthetic method of Synthesis Example 8 (8) PGME (21.9 g) and γ-BL (2.43 g) were added to (1.55 g), and the mixture was stirred at 70 ° C for 24 hours to obtain a composition (14). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (14) was also used as a liquid crystal alignment treatment agent (14) for evaluation.

Using the obtained composition (14) and the liquid crystal alignment treatment agent (14), under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of liquid crystal alignment (general unit cell)".

<Example 15>

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

Using the obtained composition (15) and the liquid crystal alignment treatment agent (15), under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of liquid crystal alignment (general unit cell)".

<Example 16>

Polyimine powder obtained by the synthetic method of Synthesis Example 9 (9) PGME (22.6 g) and γ-BL (2.51 g) were added to (1.60 g), and the mixture was stirred at 70 ° C for 24 hours to obtain a composition (16). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (16) was also used as a liquid crystal alignment treatment agent (16) for evaluation.

Using the obtained composition (16) and the liquid crystal alignment treatment agent (16), under the above conditions, "evaluation of the coating properties of the composition and the liquid crystal alignment treatment agent", "production of a unit cell (general unit cell)", and "Evaluation of liquid crystal alignment (general unit cell)".

<Example 17>

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

Using the obtained composition (17) and the liquid crystal alignment treatment agent (17), under the above conditions, "evaluation of the coating properties of the composition and the liquid crystal alignment treatment agent", "production of a unit cell (general unit cell)", and "Evaluation of liquid crystal alignment (general unit cell)".

<Example 18>

Polyimine powder obtained by the synthetic method of Synthesis Example 10 (10) (1.50g) was added PCS (17.6g), NMP (5.88g) at 70 ° C Stirring was carried out for 24 hours to obtain a composition (18). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (18) was also used as a liquid crystal alignment treatment agent (18) for evaluation.

Use of the obtained composition (18) and liquid crystal alignment treatment agent (18) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Example 19>

PGME (23.3 g) and γ-BL (2.59 g) were added to the polyimine powder (11) (1.65 g) obtained by the synthetic method of Synthesis Example 11, and stirred at 70 ° C for 24 hours to obtain a composition (19). ). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (19) was also used as a liquid crystal alignment treatment agent (19) for evaluation.

Use of the obtained composition (19) and liquid crystal alignment treatment agent (19) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Example 20>

PGME (20.1 g), γ-BL (2.51 g), BCS were added to the polyimine powder (11) (1.60 g) obtained by the synthetic method of Synthesis Example 11. (2.51 g), stirring at 70 ° C for 24 hours to obtain a composition (20). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (20) was also used as a liquid crystal alignment treatment agent (20) for evaluation.

Using the obtained composition (20) and liquid crystal alignment treatment agent (20) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", "Evaluation of the liquid crystal alignment property (general unit cell)", and "Evaluation of cell production and evaluation of liquid crystal alignment (PSA unit cell)".

<Example 21>

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

Use of the obtained composition (21) and liquid crystal alignment treatment agent (21) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Example 22>

Polyimine powder obtained by the synthetic method of Synthesis Example 12 (12) PGME (22.6 g) and γ-BL (2.51 g) were added to (1.60 g), and the mixture was stirred at 70 ° C for 24 hours to obtain a composition (22). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (22) was also used as a liquid crystal alignment treatment agent (22) for evaluation.

Using the obtained composition (22) and liquid crystal alignment treatment agent (22) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Example 23>

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

Use of the obtained composition (23) and liquid crystal alignment treatment agent (23) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Comparative Example 1>

The solid content of the resin obtained by the synthetic method of Synthesis Example 13 NMP (17.4 g) was added to a 25.0% by mass polyamine acid solution (13) (5.50 g), and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (24). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (24) was also used as a liquid crystal alignment treatment agent (24) for evaluation.

Using the obtained composition (24) and liquid crystal alignment treatment agent (24) Under the above conditions, carry out "composition and liquid crystal alignment treatment agent" "Evaluation of coating properties", "Production of cell (general cell)" and "Evaluation of liquid crystal alignment (general cell)".

<Comparative Example 2>

NMP (13.1 g) and BCS (4.31 g) were added to a polyamic acid solution (13) (5.50 g) having a resin solid content concentration of 25.0% by mass in the synthetic method of Synthesis Example 13, and stirred at 25 ° C for 2 hours. The composition (25) is obtained afterwards. No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (25) was also used as a liquid crystal alignment treatment agent (25) for evaluation.

Use of the obtained composition (25) and liquid crystal alignment treatment agent (25) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Comparative Example 3>

Polyimine powder obtained by the synthetic method of Synthesis Example 14 (14) γ-BL (19.6 g) was added to (1.25 g) and stirred at 70 ° C for 24 hours. Mix to obtain the composition (26). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (26) was also used as a liquid crystal alignment treatment agent (26) for evaluation.

Use of the obtained composition (26) and liquid crystal alignment treatment agent (26) Under the above conditions, carry out "composition and liquid crystal alignment treatment agent" "Evaluation of coating properties", "Production of cell (general cell)", "Evaluation of liquid crystal alignment (general cell)" and "Evaluation of voltage retention".

<Comparative Example 4>

γ-BL (19.6 g) and BCS (4.07 g) were added to the polyimine powder (14) (1.30 g) obtained by the synthetic method of Synthesis Example 14, and stirred at 70 ° C for 24 hours to obtain a composition (27). ). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (27) was also used as a liquid crystal alignment treatment agent (27) for evaluation.

Use of the obtained composition (27) and liquid crystal alignment treatment agent (27) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Comparative Example 5>

Polyimine powder obtained by the synthetic method of Synthesis Example 14 (14) PGME (20.4 g) was added to (1.30 g) and allowed to stand at 70 ° C for 24 hours. Stirring to obtain a composition (28). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (28) was also used as a liquid crystal alignment treatment agent (28) for evaluation.

Use of the obtained composition (28) and liquid crystal alignment treatment agent (28) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Comparative Example 6>

NMP (17.4 g) was added to the polyamic acid solution (15) (5.50 g) of the resin solid content concentration of 25.0% by mass of the synthetic method of Synthesis Example 15, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (29). ). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (29) was also used as a liquid crystal alignment treatment agent (29) for evaluation.

Use of the obtained composition (29) and liquid crystal alignment treatment agent (29) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", "Evaluation of the liquid crystal alignment property (general unit cell)", and "Evaluation of Voltage Retention Rate".

<Comparative Example 7>

Polyimine powder obtained by the synthetic method of Synthesis Example 16 (16) γ-BL (20.4 g) was added to (1.30 g) and stirred at 70 ° C for 24 hours. The mixture was mixed to obtain a composition (30). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (30) was also used as a liquid crystal alignment treatment agent (30) for evaluation.

Using the obtained composition (30) and liquid crystal alignment treatment agent (30) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", "Evaluation of the liquid crystal alignment property (general unit cell)", and "Evaluation of Voltage Retention Rate".

<Comparative Example 8>

γ-BL (16.3 g) and BCS (4.07 g) were added to the polyimine powder (16) (1.30 g) obtained by the synthetic method of Synthesis Example 16 and stirred at 70 ° C for 24 hours to obtain a composition (31). ). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (31) was also used as a liquid crystal alignment treatment agent (31) for evaluation.

Using the obtained composition (31) and liquid crystal alignment treatment agent (31) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Comparative Example 9>

Polyimine powder obtained by the synthetic method of Synthesis Example 16 (16) PGME (19.6 g) was added to (1.25 g) and allowed to stand at 70 ° C for 24 hours. Stirring to obtain a composition (32). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (32) was also used as a liquid crystal alignment treatment agent (32) for evaluation.

Use of the obtained composition (32) and liquid crystal alignment treatment agent (32) Under the above conditions, "Evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "Production of the unit cell (general unit cell)", and "Evaluation of the liquid crystal alignment property (general unit cell)" were carried out.

<Comparative Example 10>

PGME (20.4 g) was added to the polyimine powder (17) (1.30 g) obtained by the synthetic method of Synthesis Example 17, and stirred at 70 ° C for 24 hours. The dissolution residue of the polyimide pigment was observed in the solution, and further stirred at 70 ° C for 12 hours, but the polyimine powder was not completely dissolved.

Therefore, the composition (33) and the liquid crystal alignment cannot be produced. Treatment agent (33).

*2: Polymer in the composition (liquid crystal alignment treatment agent) The ratio.

*3: Polymer in the composition (liquid crystal alignment treatment agent) The ratio.

*4: Polymer in the composition (liquid crystal alignment treatment agent) The ratio.

*5: No pinholes caused by foreign matter were observed.

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

*7: More than 25 alignment defects were confirmed.

*8: 11 to 24 alignment defects were confirmed.

*9: 5 to 10 alignment defects were confirmed.

From the above results, the composition of the embodiment of the present invention is known Compared with the composition of the comparative example, it was shown that uniform coating property of pinholes due to cracks or foreign matter did not occur at the time of substrate coating. Specifically, a comparison of compositions of the same polyimine precursor or solvent-soluble polyimine, that is, comparison of Example 1 with Comparative Example 1 or Comparative Example 2, Example 2 and Comparative Example 3 or Comparison of Comparative Example 4, Comparison of Example 3 with Comparative Example 6, and Comparison of Example 5 with Comparative Example 7 or Comparative Example 8. Further, in the case of using the specific polar solvent of the component (B) of the present invention, generation of pinholes due to foreign matter can be suppressed. Specifically, it is a comparison between Example 2 and Comparative Example 5 and a comparison between Example 5 and Comparative Example 9.

Further, liquid crystal alignment treatment using the composition of the present invention The liquid crystal alignment film obtained by the agent also gave the same result. Specifically, a comparison using a composition of the same polyimine precursor or a solvent-soluble polyimine, that is, a comparison between Example 1 and Comparative Example 1 or Comparative Example 2, Example 2 and Comparative Example 3 or Comparative Example Comparison of 4, comparison of Example 3 with Comparative Example 6, and comparison of Example 5 with 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. Especially for making A liquid crystal alignment treatment agent obtained by using a diamine compound having a side chain to use a diamine component or a solvent-soluble polyimine is also uniform in the same manner as described above. Film coating properties.

And, for the evaluation of the liquid crystal alignment of the unit cell, by use The unit cell obtained by the liquid crystal alignment treatment agent of the composition of the present invention is compared with the unit cell obtained by using the liquid crystal alignment treatment agent of the composition of the comparative example, and a uniform liquid crystal alignment in which no alignment defect due to pinhole is observed is obtained. Sex. Specifically, it is a comparison with a liquid crystal alignment treatment agent using the same polyimide intermediate or solvent-soluble polyimide, that is, comparison between Example 1 and Comparative Example 1 or Comparative Example 2, and Example 2 and Comparative Example 3 Or a comparison of 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 made.

In addition to the evaluation of the voltage holding ratio, the use of the present invention The unit cell obtained by the liquid crystal alignment treatment agent of the composition showed a high value as compared with the unit cell obtained by using the liquid crystal alignment treatment agent of the composition of the comparative example. Specifically, a comparison of liquid crystal alignment treatment agents using the same polyimide intermediate or solvent-soluble polyimide, that is, comparison between Example 2 and Comparative Example 3, comparison between Example 3 and Comparative Example 6, and implementation Example 5 is compared with Comparative Example 7.

[Industrial availability]

When the composition of the present invention is a coated substrate, a resin which exhibits uniform coating property without pinholes due to cracks or foreign matter can be obtained. membrane. Further, the same results were obtained with the liquid crystal alignment treatment agent of the composition of the present invention.

In addition, the liquid crystal alignment treatment agent of the present invention can be obtained without cause A unit cell resulting from an alignment defect caused by pinholes caused by cracks or foreign matter. The same results can be obtained by using a liquid crystal alignment treatment agent which is a polyimine precursor obtained by using a diamine compound having a side chain and a solvent-soluble polyimide.

Moreover, the liquid crystal alignment treatment agent of the present invention is even at a low temperature When fired, it can also exhibit high voltage retention.

Moreover, the liquid crystal alignment treatment agent of the present invention is transparent in liquid crystal A liquid crystal display element that switches between an over-state (also referred to as a transparent state) and a disordered state, that is, a polymer dispersed liquid crystal (PDLC) or a polymer network liquid crystal (PNLC (Polymer Network Liquid) Liquid crystal display elements of Crystal)) are also useful.

Especially for voltage without input, it becomes transparent, for electricity It is useful to have an inverted type element that exhibits a disordered state when pressed. The reverse type element is a liquid crystal display for display purposes using a glass substrate or a plastic substrate such as PET (polyethylene terephthalate) or an acrylic substrate, and further controls light transmission. It is useful for a dimming window, a light shutter element, a dimming window of a vehicle such as a vehicle, and a back plate of a transparent display.

Therefore, the composition obtained by the liquid crystal alignment treatment agent of the present invention A liquid crystal display element having a liquid crystal alignment film is excellent in reliability, and It can be suitably used for a liquid crystal television or the like having a large screen and high definition, and is useful for a TN element, an STN element, a TFT liquid crystal element, and particularly a vertical alignment type liquid crystal display element.

Moreover, the liquid crystal obtained by the liquid crystal alignment treatment agent of the present invention The alignment film is also useful for a liquid crystal display element which is required to emit ultraviolet light when producing a liquid crystal display element. In other words, a liquid crystal layer containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a liquid crystal layer is formed between the pair of substrates. The liquid crystal display element produced by the step of polymerizing the polymerizable compound is further provided with a liquid crystal layer between the pair of substrates, and the active layer is disposed between the pair of substrates. A liquid crystal alignment film in which a polymerizable group in which at least one of an energy ray and a heat is polymerized is used, and a liquid crystal display element produced by a step of polymerizing the polymerizable group is also useful while inputting a voltage between the electrodes.

Claims (23)

a composition comprising: (A) component, (B) component, and (C) component; (A) component: 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, in the formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms); and (B) component: is selected from N-methyl group- At least one solvent of 2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone; (C) component: selected from a diamine component and a tetracarboxylic dianhydride component which contain a diamine compound having a carboxyl group At least one polymer of the polyimine precursor or polyimine obtained by the reaction is carried out. The composition of claim 1, wherein the component (A) is 50 to 99% by mass based on the total amount of the solvent contained in the composition. The composition of claim 1, wherein the diamine compound having a carboxyl group of the component (C) is a diamine compound having a structure represented by the following formula [2]; (In the formula [2], a represents an integer of 0 to 4). The composition of claim 1, wherein the diamine compound having a carboxyl group of the component (C) is a diamine compound having a structure represented by the following formula [2a]; (In the formula [2a], a represents an integer of 0 to 4, and n represents an integer of 1 to 4). The composition of claim 3, wherein the diamine compound having a carboxyl group is 20 mol% to 100 mol% of the total diamine used in the component (C). The composition of claim 4, wherein the diamine compound having a carboxyl group is 20 mol% to 100 mol% of the total diamine used in the component (C). The composition of claim 1, wherein the diamine component of the component (C) is at least one diamine compound having a structure selected from the group consisting of the following formula [2b]; (In the formula [2b], Y represents a structure of the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5], and m represents An integer from 1 to 4); (In the formula [2b-1], a represents an integer of 0 to 4, and in the formula [2b-2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O -, -CH ₂ O-, -COO- or -OCO-, Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), and Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, and Y ⁴ represents a divalent ring selected from a benzene ring, a cyclohexane ring or a hetero ring a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon number of 1 a fluorine-containing alkyl group of ~3, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring. Any hydrogen atom on the group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms or Substituted by a fluorine atom, n represents an integer of 0 to 4, and Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a carbon number of 1 to fluoroalkoxy containing 18, of formula 2b-3 [in], Y ⁷ represents an alkyl group having 8 to 22 carbon atoms, of formula [2b-4 In, the Y ⁸ and Y ⁹ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, of formula 2b-5] [In, Y ¹⁰ represents alkyl having 1 to 8). The composition of claim 1, wherein the tetracarboxylic dianhydride component of the component (C) is a compound represented by the following formula [3]; (In the formula [3], Z ¹ is a group selected from at least one of the following formulas [3a] to [3j]); (In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different. In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group. , each can be the same or different). The composition of claim 1, wherein the component (D) contains a selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, and B. Glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl At least one solvent of diol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether or diethylene glycol monobutyl ether. A resin film obtained by the composition according to any one of claims 1 to 9. A liquid crystal alignment treatment agent obtained by the composition according to any one of claims 1 to 9. A liquid crystal alignment film characterized by using the liquid crystal alignment treatment agent of claim 11. A liquid crystal alignment film which is obtained by an inkjet method using the liquid crystal alignment treatment agent of claim 11. A liquid crystal display element characterized by having a liquid crystal alignment film as claimed in claim 12. A liquid crystal display element characterized by having a liquid crystal alignment film as claimed in claim 13. The liquid crystal alignment element according to claim 12, which is used in a liquid crystal display device having a liquid crystal layer between one of the electrodes and disposed between the pair of substrates A liquid crystal composition of a polymerizable compound obtained by polymerizing at least one of an energy ray and a heat is produced by a step of polymerizing the polymerizable compound while inputting a voltage between the electrodes. The liquid crystal alignment film according to claim 13, which is used in a liquid crystal display device having a liquid crystal layer between one of the electrodes and disposed between the pair of substrates a polymerizable compound polymerized by at least one of an active energy ray and heat The liquid crystal composition is produced by a step of polymerizing the polymerizable compound while inputting a voltage between the electrodes. A liquid crystal display element characterized by having a liquid crystal alignment film of claim 16. A liquid crystal display element characterized by having a liquid crystal alignment film as claimed in claim 17. The liquid crystal alignment element according to claim 12, which is used in a liquid crystal display device comprising: a liquid crystal layer formed between one of the electrodes; and an active layer disposed between the pair of substrates A liquid crystal alignment film of a polymerizable group in which at least one of an energy ray and a heat is polymerized, and a voltage is input between the electrodes, and is produced by a step of polymerizing the polymerizable group. The liquid crystal alignment film according to claim 13, which is used in a liquid crystal display device having a liquid crystal layer between the substrates having one pair of electrodes, and disposed between the pair of substrates A liquid crystal alignment film in which at least one of an active energy ray and heat is polymerized, and a voltage is input between the electrodes, and the polymerizable group is polymerized. A liquid crystal display element characterized by having a liquid crystal alignment film as claimed in claim 20. A liquid crystal display element characterized by having a liquid crystal alignment film as claimed in claim 21.