TWI513753B - A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device - Google Patents

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 for producing 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, focusing on the ease of formation, insulating properties, and the like. Among them, in a liquid crystal display element which is widely known as a display device, a resin film made of an organic material is used as a liquid crystal alignment film.

A resin film which is industrially used nowadays uses a polyimide-based organic film excellent in durability. In particular, the polyimine-based organic film can also be used as a liquid crystal alignment film of a liquid crystal display element. The polyimine-based organic film is formed of a composition of polyamic acid or polyimine containing a polyimide precursor. In other words, the polyimine-based organic film is formed by applying a composition containing a poly-proline or a polyimide to a substrate and baking it (for example, Patent Document 1).

The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, with the high definition of the liquid crystal display element, and the suppression of the contrast reduction of the liquid crystal display element or the reduction of afterimage development, the liquid crystal alignment film used therein has a high voltage retention rate or a small accumulated charge when a DC voltage is applied or The property of mitigating the charge accumulated by the DC voltage is important. In view of the above, it is known that the time until the residual image due to the DC voltage is high is shortened, and it is known to use a very small amount of the polymer obtained by removing the polyaminic acid or its hydrazine. A liquid crystal alignment treatment agent containing a compound having one carboxylic acid group in the molecule, a compound having one carboxylic acid anhydride group in the molecule, and a compound selected from a compound having one tertiary amino group in the molecule (for example, Patent Document 2 is incorporated by reference). ).

[Previous Technical Literature] [Patent Document]

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

[Patent Document 2] Japanese Patent Publication No. 08-76128

With the high performance of liquid crystal display elements in recent years, liquid crystal display elements can be used in automotive applications such as car navigation systems and instrument panels, and in smart phones or tablet computers. In such a use, in order to improve visibility in the vehicle or outside, there is a case where the amount of light of the backlight is increased or a backlight having a high heat generation is used. Also, on a smart phone or The use of a flat-panel computer is often used outside the house, so that the liquid crystal display element is likely to be exposed to a large amount of external light including ultraviolet rays.

When the liquid crystal display element is irradiated with light such as backlight light or ultraviolet light, there is a possibility that a peripheral member in the liquid crystal display element, for example, a color filter or an organic member such as a Column Spacer is decomposed. As a result, the voltage holding ratio characteristic is lowered, and the line which causes display failure of the liquid crystal display element is burned, and the reliability of the liquid crystal display element is lowered.

Therefore, in the liquid crystal alignment film, even when the light of the liquid crystal display element is irradiated, the peripheral member of the liquid crystal display element is decomposed, and the voltage holding ratio is excellent. In particular, an insulating film composed of an organic member under a liquid crystal alignment film is decomposed by light irradiation, and this property is good.

In addition, the composition of the polyimine-based polymer is generally low in transparency of the resin film, and it is easy to cause decomposition of the resin film by irradiation of light such as ultraviolet rays. Therefore, it is necessary to improve the transparency of the resin film and to suppress decomposition.

Therefore, the present invention has an object of providing a composition having the above characteristics. In other words, the present invention has an object of providing a composition having high transparency of a resin film and suppressing decomposition of a resin film of light such as ultraviolet rays.

Further, in the liquid crystal alignment treatment agent using the above-described composition, the liquid crystal alignment is excellent in voltage maintenance rate even when the light is irradiated in a state in which the insulating film composed of the organic member is provided under the liquid crystal alignment film. The liquid crystal alignment treatment agent for the film is for the purpose.

Further, the present invention provides a liquid crystal having the above requirements The liquid crystal display element of the alignment film is for the purpose.

As a result of intensive studies, the present inventors have found that a polyimine precursor or a polyimine obtained by reacting a cellulose-based polymer having a specific structure and a diamine component with a tetracarboxylic acid component is selected. The composition of at least one polymer 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 containing the following components (A) and (B).

(A) component: a polymer having a structure represented by the following formula [1].

(In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently, and are a group of the structure selected by the following formula [1a] to formula [1m], n is 100. An integer of ~1000000).

(In the formula [1c] to the formula [1m], X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently, and are a benzene ring, a methyl group, an ethyl group, and an n- group. A propyl group, an isopropyl group or a butyl group, in the formula [1h], n is an integer of 0 to 3, and in the formula [1i], m is an integer of 0 to 3).

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

(2) The diamine component in the polymer of the component (B) is a composition described in the above (1), which is characterized by containing a diamine compound having a structure represented by the following formula [2a].

[Chemical 3]-(CH ₂ ) _a -COOH [2a]

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

(3) The composition described in the above (1), wherein the diamine component in the polymer of the component (B) is a diamine compound having a structure represented by the following formula [2a-1].

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

(4) The above-mentioned (1) to the above-mentioned (1) characterized in that the diamine component in the polymer of the component (B) contains at least one selected from the diamine compounds of the structure represented by the following formula [2b] 3) Any of the compositions described.

(In the formula [2b], Y is selected by the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5] The substituent of the structure, m is an integer from 1 to 4).

(In the formula [2b-1], a is an integer of 0 to 4, and in the formula [2b-2], Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O -, -CH ₂ O-, -COO- or -OCO-, Y ² is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, and Y ⁴ is a divalent group selected from a benzene ring, a cyclohexane ring or a hetero ring. a cyclic group or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and 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 a fluorine atom, and Y ⁵ is a divalent ring selected from a benzene ring, a cyclohexane ring or a hetero ring. Any one of the hydrogen atoms on the cyclic 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 carbon number of 1 to 3; 3 is substituted by a fluorine-containing alkoxy group or a fluorine atom, n is an integer of 0 to 4, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 18 carbon atoms. An oxy group or a fluorine-containing alkoxy group having 1 to 18 carbon atoms; in the formula [2b-3], Y ⁷ is -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO -, Y ⁸ An alkyl group having 8 to 22 carbon atoms, the formula [2b-4] in, Y ⁹ and Y ¹⁰ are each independently a hydrocarbon group having 1 to 12 carbon atoms, the formula [2b-5] in, Y ¹¹ is a C number of 1 to 5 alkyl).

(5) The tetracarboxylic acid component in the polymer of the component (B) contains at least one selected from the compounds represented by the following formula [3] The composition according to any one of the above (1) to (4).

(In the formula [3], Z ¹ is a group of the structure selected by the following formula [3a] to formula [3j]).

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

(6) The above (1) to the above (C) containing at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone 5) The composition described in any one of them.

(7) As the component (D), it contains the following formula [D-1] The composition according to any one of the above (1) to (6), wherein at least one solvent selected from the solvent represented by the formula [D-3] is used.

(In the formula [D-1], D ¹ is an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² is an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ is an alkyl group having 1 to 4 carbon atoms).

(8) as component (E), containing 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether The composition according to any one of the above (1) to (7), wherein at least one solvent is selected.

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

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

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

(12) A liquid crystal alignment film obtained by an 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) A liquid crystal composition comprising a polymerizable compound polymerized by at least one of an active energy ray and heat between the pair of substrates, wherein a liquid crystal layer is provided between a pair of substrates having electrodes; A liquid crystal alignment film according to the above (11) or (12), wherein the liquid crystal display element produced by the step of polymerizing the polymerizable compound is applied to the electrode.

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

(16) A liquid crystal alignment film in which a polymerizable group which is 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 provided between a pair of substrates having an electrode. A liquid crystal alignment film according to the above (11) or (12), characterized in that the liquid crystal display element produced by the step of polymerizing the polymerizable group is applied to the electrode.

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

At least one polymer selected from the group consisting of a polyimide-based precursor or a polyimine obtained by reacting a cellulose-based polymer having a specific structure and a diamine component with a tetracarboxylic acid component In the composition, the resin film has high transparency and can suppress decomposition of the resin film accompanying irradiation of light.

Moreover, the liquid crystal alignment treatment by the composition of the present invention Even if the agent has an insulating film composed of an organic member under the liquid crystal alignment film, it is possible to form a liquid crystal alignment film having excellent voltage holding ratio by irradiating light. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained thereby has high reliability.

[Best Practice for Carrying Out the Invention]

As a result of intensive studies, the inventors of the present invention have obtained the following results to complete the present invention.

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

Component (A): a polymer having a structure represented by the following formula [1] (also referred to as a specific cellulose polymer).

(In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently, and are a group of at least one structure selected from the following formulas [1a] to [1m]. , n is an integer from 100 to 1000000).

(In the formula [1c] to the formula [1m], X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently, and are a benzene ring, a methyl group, an ethyl group, and an n- group. A propyl group, an isopropyl group or a butyl group, in the formula [1h], n is an integer of 0 to 3, and in the formula [1i], m is an integer of 0 to 3).

(B) component: a polyimine precursor obtained by reacting a diamine component and a tetracarboxylic acid component, or at least one polymer selected from polyimine (also referred to as a specific polyimine-based polymer) .

The specific cellulose-based polymer of the present invention has higher transparency than a polyimide-based polymer. Therefore, the resin film obtained from the composition of the present invention is less likely to absorb light such as ultraviolet rays than the polymer obtained from a general polyimide-based polymer, and accordingly, decomposition of the resin film is less likely to occur.

Further, the composition of the present invention contains a specific cellulose-based polymer and a specific polyimine-based polymerization excellent in light resistance and heat resistance. The stability of the film against light or heat becomes higher.

The specific cellulose-based polymer of the present invention has a large amount of OH groups (hydroxyl groups) or COOH groups (carboxylic acid groups), and can capture ionic impurities such as metals or low molecular weight organic compounds. Therefore, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention has a state in which the insulating film composed of the organic member is provided under the liquid crystal alignment film, and the irradiation light is a liquid crystal alignment film excellent in voltage retention.

Further, the liquid crystal alignment agent of the present invention contains a specific polyamidene-based polymer, and can form the above-described voltage maintenance ratio characteristics, and has the ability to impart alignment (also referred to as liquid crystal alignment) or impart pretilt angle. Also excellent in liquid crystal alignment film.

From the above, the composition of the present invention can form a resin film having high transparency. Then, the liquid crystal alignment treatment agent obtained by the composition of the present invention has a state in which an insulating film made of an organic member is provided under the liquid crystal alignment film, and the light is irradiated, and the voltage maintenance ratio is excellent, and the liquid crystal alignment property is imparted. And a liquid crystal alignment film excellent in pretilt angle characteristics.

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

<Specific Cellulose Polymer>

The specific cellulose polymer of the component (A) of the present invention is a polymer having the structure represented by the following formula [1].

In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently a group of at least one structure selected from the following formulas [1a] to [1m].

In the formula [1c] to the formula [1m], X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently a benzene ring, a methyl group, an ethyl group or an n-propyl group. , isopropyl or butyl.

In the formula [1h], n is an integer of 0 to 3. Among them, an integer of 0 or 1 is preferred.

In the formula [1i], m is an integer of 0 to 3. Among them, an integer of 0 or 1 is preferred.

In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently a structure selected by the formula [1a] to the formula [1m], but the structures may be 1 A variety or a plurality of types of two or more types. In particular, it is preferable to use a plurality of types of two or more types from the point of solubility of the specific cellulose-based polymer to the solvent, and the coating property of the composition or the liquid crystal alignment treatment agent. It is particularly preferable to use the structure of the formula [1a] and the structure of the formula [1b] to the formula [1m]. More preferably, it is a structure of the formula [1a], a structure of the formula [1c], a structure of the formula [1d], a structure of the formula [1e], a structure of the formula [1h], or a structure of the formula [1i].

In the formula [1], n is an integer of 100 to 1,000,000. Among them, the solubility of the specific cellulose-based polymer in the solvent or the operability at the time of adjustment of the composition or the liquid crystal alignment treatment agent is preferably from 100 to 500,000. More preferably 100~100,000.

Specific examples of the specific cellulose-based polymer of the present invention include, for example, the following, but are not limited thereto.

For example, cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, methyl ethyl cellulose, ethyl phthalocyanine, cellulose propionate, hydroxymethyl cellulose, hydroxyl Ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose phthalate, methylamine Cellulose, ethylamino cellulose, propylamino cellulose, benzyl cellulose, benzotriphenyl cellulose, cellulose acetate butyl ester, cellulose acetate propionate, carboxymethyl Cellulose, carboxymethyl B Cellulose or carboxymethylhydroxyethylcellulose. Among them, methyl cellulose, ethyl cellulose, propyl cellulose, ethylene glycol cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, Ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose phthalate, benzyl cellulose, cellulose acetate propionate, carboxymethyl ethyl cellulose or carboxymethyl hydroxy ethyl fiber It is good. More preferred are methyl cellulose, ethyl cellulose, acetyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxy group Cellulose, hydroxypropylmethylcellulose phthalate or carboxymethylethylcellulose. Especially preferred for methyl cellulose, ethyl cellulose, acetyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose or hydroxypropyl methyl Cellulose phthalate.

These particular cellulose derivatives can be obtained in a conventional manner. Further, the method of introducing the structure represented by the formula [1b] to the formula [1m] is not particularly limited, and an existing method can be used.

For example, when the structure of the formula [1b] is introduced, for example, a method in which cellulose and a benzyl chloride are allowed to react in the presence of a base, and a structure in which the formula [1c] is introduced, and a cellulose and a halogen compound having X ^{7 are} mentioned. In the case where the reaction is carried out in the presence of a base, or the structure of the formula [1d] is introduced, a method of reacting cellulose with an acid chloride compound having a structure of X ⁸ in the presence of a base or reacting cellulose with anhydrous acetic acid is carried out. In the case where the structure of the formula [1e] is introduced, a method in which a cellulose is reacted with a halogen compound having a X ⁹ -OH structure in the presence of a base, and a structure of the formula [1f] is introduced, and a cellulose is provided with X. A method of reacting a halogen compound having a ^10- COOH structure in the presence of a base or a structure of the formula [1g], and a method of reacting a cellulose with a halogen compound having a structure of X ¹¹ -NH ₂ in the presence of a base, When introducing the structure of the formula [1h], a method of reacting cellulose with phthalic acid or a structure of the formula [1i], and a halogen compound having a X ¹² and a phthalic acid skeleton in the presence of a base Method of making reaction, introduction method [1k] In the case of the structure, a method of reacting cellulose with anhydrous maleic acid.

The specific cellulose-based polymer represented by the above formula [1] is compatible with the solvent solubility or coating property of the specific cellulose-based polymer of the present invention, and the alignment property of the liquid crystal in the case of forming a liquid crystal alignment film. The characteristics of the voltage maintenance ratio, the accumulated charge, and the like can be used in combination of one type or two types or more.

<Specific Polyimine Polymer>

The specific polyimine-based polymer of the component (B) of the present invention is a polymer selected from a polyimine precursor obtained by reacting a diamine component with a tetracarboxylic acid component or a polyimine.

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, and A ¹ and A ² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, and A ³ And A ⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an ethyl fluorenyl group, which may be the same or different, and n is a positive integer).

The diamine component is a diamine compound having two primary or secondary amine groups in the molecule, and examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, and a tetracarboxylic acid dihalide. A compound, a dialkyl tetracarboxylate compound or a dialkyl tetracarboxylate dihalide compound.

The specific polymer of the present invention can be relatively easily obtained by using the tetracarboxylic dianhydride represented by the following formula [B] and the diamine compound represented by the following formula [C] as a raw material. It is preferable to use a polyperonine composed of a structural formula of a repeating unit represented by the following formula [D] or a polyimine which is imidized with the polyphosphonium amide.

(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 meaning as those defined by the formula [A]).

Further, in the usual synthesis method, the alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A] and the formula [A] can be introduced into the polymer of the formula [D] obtained above. The alkyl group or the ethylidene group having 1 to 5 carbon atoms of A ³ and A ⁴ represented.

<Diamine component>

A conventional diamine compound can be used for the diamine component of the specific polyamidene-based polymer for producing the component (B) of the present invention.

Among them, a diamine compound having a structure represented by the following formula [2a] is preferred.

[Chem. 17]-(CH ₂ ) _a -COOH [2a]

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

In terms of the diamine compound having the structure represented by the formula [2a], Specifically, for example, the diamine compound represented by the following formula [2a-1] can be mentioned.

In the formula [2a-1], a is an integer of 0 to 4. Among them, 0 or 1 is preferable from the point of availability of the raw material or the ease of synthesis.

In the formula [2a-1], n is an integer of 1 to 4. Among them, from the point of difficulty in synthesis, 1 is preferred.

The method for producing the diamine compound represented by the formula [2a] of the present invention is not particularly limited, and preferred embodiments include, for example, the following. For example, a diamine compound represented by the formula [2a-1] can be obtained by synthesizing a dinitro compound represented by the following formula [2a-A], and further reducing the nitro group to an amine group. .

(In the formula [2a-A], a is an integer of 0 to 4, and n is 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 in ethyl acetate, toluene, and tetra. In a solvent such as hydrogen furan, dioxane or an alcohol solvent, palladium-carbon, oxidized platinum, nickel ray, platinum black, lanthanum-alumina or sulfurized platinum carbon is used as a catalyst, and hydrogen gas, hydrazine or A method of carrying out a reaction under hydrogen chloride.

Further, the diamine compound represented by the formula [2a] of the present invention may be, for example, a diamine compound represented by the following formula [2a-2] to the formula [2a-5].

In the formula [2a-2], A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, by the ease of synthesis, a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH- -NHCO-, -COO- or -OCO- is preferred. More preferably, it is a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH- or -N(CH ₃ )-.

In the formula [2a-2], m ¹ and m ² are each an integer of 0 to 4, and m ¹ + m ² is an integer of 1 to 4. Among them, m ¹ + m ² is preferably 1 or 2.

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

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

In the formula [2a-5], A ³ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )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. More preferably -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-.

In the formula [2a-5], m ⁶ is an integer of 1 to 4. Among them, from the point of difficulty in synthesis, 1 is preferred.

The diamine compound represented by the above formula [2a-1] to formula [2a-5] is preferably 20 mol% to 100 mol%, more preferably 30 mol% to 80% of the total diamine component. Moer%.

The diamine compound represented by the above formula [2a-1] to the formula [2a-5] is prepared by liquid crystal alignment in response to solubility in a solvent or coating property of a specific polyamidimide polymer of the present invention. Liquid crystal matching in film applications The characteristics of the directionality, the voltage maintenance ratio, and the accumulated charge can be used in combination of one type or two types or more.

In order to produce the diamine component of the specific polyimine-based polymer of the present invention, it is preferred to use the diamine compound represented by the following formula [2b].

In the formula [2b], Y is at least selected by the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5] A substituent of one structure, m is an integer of 0-4.

In the formula [2b-1], a is an integer of 0 to 4. Among them, an integer of 0 or 1 is preferred from the point of availability of the raw material or the ease of synthesis.

In the formula [2b-2], Y ¹ is 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 point of availability or synthesis difficulty of the raw material, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred. . More preferably, it is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In the formula [2b-2], Y ² is 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 is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, from the point of difficulty in synthesis, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred. More 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 heterocyclic ring, and any hydrogen atom on the cyclic group may be a carbon number of 1~ An alkyl group of 3, 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 a fluorine atom. Further, Y ^{4 may} be a divalent organic group selected from an organic group having 12 to 25 carbon atoms having a steroid skeleton. Among them, from the point of difficulty in synthesis, a benzene ring, a cyclohexane ring or an organic group having a carbon number of 12 to 25 having a steroid skeleton is preferred.

In the formula [2b-2], Y ⁵ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be a carbon number of 1 to 3 The alkyl group, 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 is an integer of 0 to 4. Among them, it is preferable that the availability of the raw material or the ease of synthesis is 0 to 3. More preferably 0 ~2.

In the formula [2b-2], Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an 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. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2b-2] for constituting the substituent Y in the formula [2b] include, for example, The same combination of (2-1) to (2-629) is disclosed in Tables 6 to 47 of 13 items to 34 items of International Publication No. WO2011/132751 (2011.10.27 publication). Further, in the tables of the international publications, Y ¹ to Y ⁶ in the present invention are represented by Y1 to Y6, and Y1 to Y6 are replaceable with Y ¹ to Y ⁶ .

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

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

In the formula [2b-4], Y ⁹ and Y ¹⁰ are each independently a hydrocarbon group having 1 to 12 carbon atoms.

In the formula [2b-5], Y ¹¹ is an alkyl group having 1 to 5 carbon atoms.

The method for producing the diamine compound represented by the formula [2b] of the present invention is not particularly limited, and preferred examples thereof include the following. For example, a diamine compound represented by the formula [2b] can be used, and a dinitro compound represented by the following formula [2b-A] can be synthesized, and the nitro group can be further reduced. It is obtained by conversion to an amine group.

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

The method for reducing the dinitro group of the dinitro compound represented by the formula [2b-A] is not particularly limited, and it is usually used in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent. A method of reacting under hydrogen gas, hydrazine or hydrogen chloride as a catalyst for palladium-carbon, oxidized platinum, Raney nickel, platinum black, lanthanum-alumina or sulfurized platinum carbon.

The specific structure of the diamine compound represented by the formula [2b] of the present invention is as follows, but is not limited to these examples.

That is, in terms of the diamine compound represented by the formula [2b], m-phenylene diamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2 , 4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol Further, for example, a diamine compound having a structure represented by the following formula [2b-6] to [2b-46] can be mentioned.

(In the formula [2b-6] to the formula [2b-9], A ¹ is 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 is -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO-, and R ² is a carbon number of 1 ~22 alkyl, alkoxy, fluoroalkyl or fluoroalkoxy).

(In the formula [2b-37]~Form [2b-39], R ³ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - CH ₂ -, R ⁴ is 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 is an alkyl group having 3 to 12 carbon atoms. Further, the cis-trans isomers of 1,4-cyclohexene are each a trans isomer Better).

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

(In the formula [2b-46], B ⁴ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, B ³ is a 1,4-cyclohexenyl group or a 1,4-phenylene group, and B ² is an oxygen atom or -COO - * (but marked "*" is bonded to B ³ bonded bond), B ¹ is an oxygen atom or -COO - * (but marked "*" is bonded to bond with (CH ₂ ) a ² bond). Further, a ¹ is an integer of 0 or 1, a ² is an integer of 2 to 10, and a ³ is an integer of 0 or 1.

In the diamine compound represented by the above formula [2b], the composition of the diamine compound having the structure represented by the formula [2b-2] in the formula [2b] can be used to improve the hydrophobicity of the resin film. . Further, when a liquid crystal alignment film is formed, the pretilt angle of the liquid crystal can be improved. In this case, for the purpose of improving the effects of the above, the above diamine compound is represented by using the formula [2b-28] to the formula [2b-39] or the formula [2b-42] to the formula [2b-46]. Diamine compounds are preferred. More preferably, it is a diamine compound represented by the formula [2b-24] to the formula [2b-39] or the formula [2b-42] to the formula [2b-46]. Moreover, in order to improve the effect of these, it is preferable that these diamine compounds are 5 mol% or more and 80 mol% or less of the whole diamine component. More preferably, the diamine compound is 5 mol% or more and 60 mol% of the entire diamine component from the viewpoint of the coating property of the composition and the liquid crystal alignment treatment agent or the electrical characteristics of the liquid crystal alignment film.

The diamine compound represented by the above formula [2b] is compatible with the solvent solubility or coating property of the specific polyamidimide polymer of the present invention, the alignment property of the liquid crystal in the case of forming a liquid crystal alignment film, and voltage maintenance. The characteristics of the rate, the accumulated charge, and the like can be used in combination of one type or two types or more.

The diamine compound represented by the formula [2a-1] to the formula [2a-5] and the two represented by the formula [2b] can be used for producing the diamine component of the specific polyamidene-based polymer of the present invention. A diamine compound other than the amine compound (also referred to as another diamine compound) is used as the diamine component. Specific examples of other diamine compounds are listed below, but are not limited thereto.

For example, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamine linkage Benzene, 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'-diaminodiphenylmethane, 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-aminophenyl)decane, double (3- Aminophenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3 '-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2' -diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl (3,3' -diaminodiphenyl)amine, N-methyl (3,4'-di Aminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4' -diaminobenzoacetophenone, 3,3'-diaminobenzoacetophenone, 3,4'-diaminobenzoacetophenone, 1,4-diaminonaphthalene, 2,2 '-Diaminobenzoacetophenone, 2,3'-diaminobenzoacetophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diamino Naphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 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-double ( 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-aminophenoxyl) 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(methylene) Diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3' -[1,3-phenylene bis(methylene)]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)methyl Ketone], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis ( 4-aminobenzoic acid ester), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-amine Phenylphenyl) terephthalate, bis(4-aminophenyl)isophthalate, 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)terephthalamide, N,N'- Bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl) Isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-double [ 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-double ( 4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(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)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)pentane, 1,7-( 3-aminophenoxy)pentane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-double (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, bis(4-amino-3-methyl Cyclohexyl)methane, 1,3-diaminopropane, 1,4- Aminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminopentane, 1,8-diaminooctane, 1,9-di Aminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane.

Further, as for the other diamine compound, for example, the diamine side chain may have an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring, and further have a large cyclic substituent formed thereby. Wait. Specifically, for example, a diamine compound represented by the following formulas [DA1] to [DA13] can be given.

(In the formula [DA1]~form [DA6], A ¹ is -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 is an integer from 1 to 10).

The diamine compound represented by the following formula [DA8] to formula [DA13] can also be used as the other diamine compound without impairing the effects of the present invention.

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

Further, the diamine compound represented by the following formula [DA14] can also be used without impairing the effects of the present invention.

(In the formula [DA14], A ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ ) - or -N(CH ₃ )CO- selected 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 a 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 from 1 to 5), A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4).

Further, as the other diamine compound, a diamine compound represented by the following formula [DA15] and formula [DA16] can also be used.

The other diamine compound in accordance with the solubility of the specific polyamidimide polymer of the present invention, the coating property of the composition, the alignment property of the liquid crystal in the case of forming a liquid crystal alignment film, the voltage retention ratio, and the accumulation. The characteristics of the electric charge or the like may be used in combination of one type or two or more types.

<tetracarboxylic acid component>

The tetracarboxylic acid dianhydride represented by the following formula [3] or the tetracarboxylic acid derivative thereof is used in the tetracarboxylic acid component of the specific polyamidimide-based polymer of the component (B) of the present invention. Preferably, the tetracarboxylic acid, the tetracarboxylic acid dihalide compound, the tetracarboxylic acid dialkyl ester compound or the tetracarboxylic acid dialkyl ester dihalide compound (all also collectively referred to as a specific tetracarboxylic acid component).

In the formula [3], Z ¹ is a group of the structure selected by the following formula [3a] to formula [3j].

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

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

In the structure represented by the formula [3] of the specific tetracarboxylic acid component of the present invention, Z ^{1 is} determined by the ease of synthesis or the degree of difficulty in polymerization reactivity in the production of a polymer, and is represented by the formula [3a] and the formula [3c]. The structure represented by the formula [3d], the formula [3e], the formula [3f] or the formula [3g] is preferable. More preferably, 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 acid component of the present invention is preferably 1 mol% or more of the total tetracarboxylic acid component. More preferably, it is 5 mol% or more, and more preferably 10 mol% or more.

Further, when a specific tetracarboxylic acid component having a structure of the formula [3e], the formula [3f] or the formula [3g] is used, the desired amount can be obtained by using the amount of 20 mol% or more of the entire tetracarboxylic acid component. . It is preferably 30 mol% or more. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure of the formula [3e], the formula [3f] or the formula [3g].

The specific polyamidene-based polymer of the present invention can use other tetracarboxylic acid components other than the specific tetracarboxylic acid component without impairing the effects of the present invention. Examples of the other tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester shown below. Dihalide compound.

That is, other tetracarboxylic acid components include, for example, 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'-benzoacetophenone tetracarboxylic acid, double (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) Diphenyl decane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylanthracene Tetracarboxylic acid, 3,4,9,10-nonanedicarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutyl Alkanetetracarboxylic acid.

The specific tetracarboxylic acid component and the other tetracarboxylic acid component correspond to the solubility in a solvent or the coating property of the specific polyamidene-based polymer of the present invention, and the alignment of the liquid crystal in the case of forming a liquid crystal alignment film. The characteristics of the properties, the voltage maintenance ratio, and the accumulated charge may be used in combination of one type or two or more types.

<Method for Producing Specific Polyimine Polymers>

In the present invention, a method of synthesizing a specific polyimine-based polymer is not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acid and a derivative thereof is reacted with a diamine component of one or more kinds of diamine compounds to obtain a polyamic acid. Specifically, a method of polycondensing a tetracarboxylic dianhydride with a diamine compound of a 1st or 2nd stage to obtain a polyamic acid, and dehydrating polycondensation of a tetracarboxylic acid with a diamine compound of a 1st or 2nd stage can be used. The reaction is carried out to obtain a poly-proline acid or a method in which a tetracarboxylic acid dihalide is polycondensed with a first- or second-order diamine compound to obtain a poly-proline.

In order to obtain a polyalkyl phthalate, a method of polycondensing a carboxylic acid group with a dialkyl esterified tetracarboxylic acid with a 1 or 2 diamine compound may be used, and a carboxylic acid group and a carboxylic acid group may be used. A method of polycondensing an alkyl esterified tetracarboxylic acid dihalide with a grade 1 or 2 diamine compound or a method of converting a carboxyl group of a polyproline to an ester.

When the polyimine is obtained, a method in which the above polyamic acid or polyalkyl amide is ring-closed to form a polyimine can be used.

The reaction of the diamine component with the tetracarboxylic acid component usually involves the diamine component and the tetracarboxylic acid component in an organic solvent. The organic solvent used at this time is not particularly limited as long as it dissolves the produced polyimide precursor. Specific examples of the organic solvent used in the reaction are listed below, but are not limited thereto. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Azulene, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D- 1]~ Solvent represented by the formula [D-3].

(In the formula [D-1], D ¹ is an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² is an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ is an alkyl group having 1 to 4 carbon atoms).

These may be used alone or in combination. Further, even if the solvent which does not dissolve the polyimide precursor is not precipitated in the range in which the produced polyimide precursor is not precipitated, it can be used in combination with the above solvent. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, the organic solvent is preferably dried by dehydration.

For example, the diamine component and the tetracarboxylic acid component are organically dissolved. In the reaction of the agent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid component is directly or dispersed or dissolved in an organic solvent, and then added, or the tetracarboxylic acid component is dispersed or dissolved in the organic solvent. Any method such as a method of adding a diamine component to a solution of a solvent, a method of mutually adding a diamine component and a tetracarboxylic acid component, or the like can be used. Further, when a plurality of kinds of the diamine component or the tetracarboxylic acid component are used for the reaction, the reaction may be carried out in advance, or the individual reaction may be carried out in sequence, or the mixed polymer of the individual reaction may be used as a polymer. The polymerization temperature at this time may be any temperature from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration. However, if 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 is too high and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the polymerization reaction of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimine precursor.

The polyimine of the present invention is a polyimine obtained by ring-closing the above-mentioned polyimine precursor. In the polyimine, the ring closure ratio of the proline group (also referred to as the ruthenium imidation ratio) is not It must be 100% and can be adjusted arbitrarily depending on the purpose or purpose.

The method for imidating the polyimine precursor ruthenium may, for example, be heat-imidized or directly heated in a solution of the polyimide precursor. Catalyst oxime imidization is added to the solution of the polyimide precursor.

The temperature at which the polyimine precursor is thermally imidized in a solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, to discharge water generated by the hydrazine imidization reaction to the system. It is better to do it outside.

The ruthenium imide of the polyimide precursor can be stirred at -20 to 250 ° C, preferably 0 to 180 ° C by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor. get on. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the proline group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it maintains moderate alkalinity during the progress of the reaction. The acid anhydride may, for example, be anhydrous acetic acid, anhydrous trimellitic acid or anhydrous pyromellitic acid. Among them, anhydrous acetic acid is used, and purification after completion of the reaction is easy, which is preferable. The imidization rate of the imidization of the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be introduced into a solvent and then precipitated. The solvent used for the precipitation may, for example, be methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, pentane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water or the like. After the solvent is added and the precipitated polymer is filtered and recovered, it can be dried under normal pressure or reduced pressure at normal temperature or under heating. Further, the polymer recovered by the precipitation is repeatedly dissolved in an organic solvent, and the operation of reprecipitation recovery is repeated 2 to 10 times to reduce impurities in the polymer. The solvent at this time may, for example, be an alcohol It is preferable to use three or more types of solvents selected from the above, such as a ketone or a hydrocarbon, to improve the efficiency of purification.

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

<composition. Liquid crystal alignment agent>

The composition of the present invention or the liquid crystal alignment treatment agent is a coating solution for forming a resin film or a liquid crystal alignment film (also collectively referred to as a resin film), and is formed to contain a specific cellulose-based polymer and a specific polyimine-based polymerization. A coating solution for a resin film of a substance and a solvent.

When the ratio of the specific cellulose-based polymer to the specific polyimine-based polymer in the composition of the present invention or the liquid crystal alignment agent is 1 in the case of the specific polyamidene-based polymer, the cellulose-based polymerization is specified. The ratio of the objects is 0.1~9. Especially good is 0.2~4.

All of the polymer components in the composition of the present invention or the liquid crystal alignment agent may be the specific cellulose polymer of the present invention and the specific polyamidene polymer, or other polymers other than the polymer may be mixed. . 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. In addition to the other polymer, the diamine compound represented by the above formula [2a-1] to the formula [2a-5] and the formula [2b] are not used. A diamine compound and a polyimine-based polymer of a specific tetracarboxylic acid component. Further, examples of the polymer other than the cellulose polymer and the polyimine polymer include an acrylic polymer, a methacryl polymer, polystyrene, polyamine or polyoxyalkylene.

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

The organic solvent used for the composition of the present invention or the liquid crystal alignment agent is not particularly limited as long as it is an organic solvent (also referred to as a good solvent) in which a specific cellulose polymer and a specific polyamidene polymer are dissolved. Specific examples of the preferred solvent are as follows, but are not limited to these examples.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl hydrazine, γ-butyl Lactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. In addition, examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and the solvent represented by the above formula [D-1] to formula [D-3]. . These may be used alone or in combination.

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone (hereinafter also referred to as component (C)) are preferably used. Further, when the specific cellulose polymer and the specific polyimine-based polymer have high solubility in a solvent, the solvent represented by the above formula [D-1] to formula [D-3] is used (hereinafter also referred to as (D). )))).

The good solvent in the composition of the present invention or the liquid crystal alignment treatment agent is preferably 10 to 100% by mass based on the total amount of the solvent contained in the composition or the liquid crystal alignment treatment agent. Among them, 20 to 90% by mass is preferred. More preferably 30 to 80% by mass.

In the composition of the present invention or the liquid crystal alignment treatment agent, the coating property or surface smoothness of the resin coating film or the liquid crystal alignment film when the coating composition or the liquid crystal alignment treatment agent is improved can be used without impairing the effects of the present invention. Organic solvents (also known as poor solvents). Specific examples of the poor solvent are exemplified below, but are not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1 -butanol, 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-propanediol, 1,3-propane Glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2- Methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl Ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate 1-methylpentyl acetate 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethyl Glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethyl ecarbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoiso Amyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, mercapto alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy)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 Ethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxypropionic acid methyl ester, 3-ethoxypropionic acid Ethyl ethyl ester, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid Butyl ester, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate or the above formula [D-1]~[D-3] The solvent and the like indicated.

Wherein, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether (also referred to as (E) The component) or the solvent represented by the above formula [D-1] to formula [D-3] is preferred.

Such a poor solvent is a composition or a liquid crystal alignment treatment agent. It is preferred that the total amount of the organic solvent contained is from 1 to 70% by mass. Among them, 1 to 60% by mass is preferred. More preferably, it is 5 to 60% by mass.

The composition of the present invention or the liquid crystal alignment treatment agent may further introduce a crosslinkable compound having an epoxy group, an isocyanate group, an oxetanyl group or a cyclic carbonate group, without impairing the effects of the present invention. A crosslinkable compound of at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, or a crosslinkable compound having a polymerizable unsaturated bond. These substituents or polymerizable unsaturated bonds need to be two or more in the crosslinkable compound.

a crosslinkable compound having an epoxy group or an isocyanate group, such as bisphenol acetone epoxy propyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triethoxypropyl isocyanurate, four Epoxypropylaminodiphenylene ester, tetraglycidylpropyl-m-xylenediamine, tetraethoxypropyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl ring Oxypropyl propyl ether, triphenyl epoxypropyl ether ethane, bisphenol hexafluoroacetamethylene diepoxide, 1,3-bis(1-(2,3-epoxypropoxy) 1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triepoxypropyl-p -aminophenol, tetraepoxypropylm-xylenediamine, 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 .

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

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

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

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

(in the formula [4-11], n is 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 represented by the following formula [5-1] to formula [5-37]. Crosslinkable compound.

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

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

Further, for example, a polyoxyalkylene having at least one structure represented by the following formula [5-38] to formula [5-40] may be mentioned.

(In the formula [5-38] to the formula [5-40], R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently, and are a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, and a carbon number. An alkyl group, an alkoxy group, an aliphatic ring or an aromatic ring of 1 to 10, and at least one of the structures represented by the formula [5]).

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

(in the formula [5-42], n is an integer from 1 to 10).

The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, for example, an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, a guanamine resin, and a glycoluril - Formaldehyde resin, amber mercapto amide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycine in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both may be used. Urea. The melamine derivative or the benzoguanamine derivative may also be present as a 2-mer or a 3-mer. It is preferred that each of the triazine rings has an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups.

Examples of such a melamine derivative or a benzoguanamine derivative include, for example, one triazine ring per commercially available product, MX-750 in which methoxymethyl group is substituted by an average of 3.7, and each triazine ring. Methoxymethyl which is substituted by an average of 5.8 MW-30 (manufactured by the above, Sanwa Chemical Co., Ltd.) or Cymel300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methoxylated butoxymethylated melamine such as melamine, Cymel235, 236, 238, 212, 253, 254, etc., butoxymethylated melamine such as Cymel 506 and 508, and carboxylated methoxyl like Cymel1141 Methylated isobutoxymethylated melamine, Cymel1123-like methoxymethylated ethoxymethylated benzoguanamine, Cymel1123-10-like methoxymethylated butoxymethylated benzo Indoleamine, Cymel 1128-like butoxymethylated benzoguanamine, Cymel 1125-80-like carboxylated methoxymethylated ethoxymethylated benzoguanamine (above, manufactured by Mitsui Cyanamid Co., Ltd.). Further, examples of the glycoluril include, for example, Cymel 1170-like butoxymethylated glycoluril, Cymel 1172-like methylolated glycoluril, and Powderlink 1174-like methoxymethylolated glycoluril.

a benzene or phenolic compound having a hydroxyl group or an alkoxy group, such as 1,3,5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1,4 - bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.

More specifically, for example, an international public bulletin The crosslinkable compound represented by the formula [6-1] to the formula [6-48] disclosed on pages 62 to 66 of WO2011/132751 (published on 2011.10.27).

a crosslinkable compound having a polymerizable unsaturated bond, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tris(methyl) a crosslinkable compound having three polymerizable unsaturated groups in the molecule such as propylene methoxy ethoxy trimethylolpropane or glycerol polyepoxy propyl ether poly(meth) acrylate, and further, for example, Such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol II (Meth) acrylate, polypropylene glycol di(meth) acrylate, butene diol di(meth) acrylate, neopentyl diol di(meth) acrylate, ethylene oxide bisphenol A type Di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di Methyl) acrylate, ethylene glycol diepoxypropyl ether di(meth) acrylate, diethylene glycol diepoxy propyl ether di(meth) acrylate, benzene a cross-linking compound having two polymerizable unsaturated groups in the molecule, such as diepoxypropyl dicarboxylate dicarboxylate or hydroxypivalic acid neopentyl glycol di(meth)acrylate; And 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (A) Acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono(meth)acrylic acid Ester, 2-(A) A crosslinkable compound having one polymerizable unsaturated group in the molecule such as acryloxyethyl phosphate or N-methylol (meth) acrylamide.

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

(In the formula [7], E _{1 is selected} from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring or a phenanthrene ring. The base, E _{2 is} a group selected by the following formula [7a] or formula [7b], and n is an integer of 1 to 4).

The above compound is an example of a crosslinkable compound, and is not limited thereto. Moreover, the crosslinkable compound used for the composition of the present invention or the liquid crystal alignment treatment agent may be one type or a combination of two or more types.

The content of the crosslinkable compound in the composition of the present invention or the liquid crystal alignment agent is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. The effect of the crosslinking reaction and the purpose of the performance is preferably from 0.1 to 100 parts by mass, particularly preferably from 1 to 50 parts by mass, per 100 parts by mass of the total polymer component.

When a liquid crystal alignment film is used as the liquid crystal alignment film of the composition of the present invention, the charge movement in the liquid crystal alignment film is promoted, and the compound which uses the liquid crystal cell of the liquid crystal alignment film to remove the charge is removed, and an international publication is added. The nitrogen-containing heterocyclic amine compound represented by the formula [M1] to the formula [M156] disclosed on pages 69 to 73 of WO2011/132751 (2011.10.27) is preferred. The amine compound may be added directly to the composition, but 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 is an organic solvent in which the specific polyimine-based polymer described above is dissolved.

The composition of the present invention or the liquid crystal alignment treatment agent can improve the film thickness uniformity or surface of the resin film or the liquid crystal alignment film when the composition or the liquid crystal alignment treatment agent is applied without impairing the effects of the present invention. Smoothing compound. Further, a compound which lifts the adhesion between the resin film or the liquid crystal alignment film and the substrate can be used.

Examples of the compound which improves the uniformity of the film thickness of the resin film or the liquid crystal alignment film or the surface smoothness include a fluorine-based surfactant, an anthrone-based surfactant, and a nonionic surfactant.

More specifically, for example, EFTOP EF301, EF303, EF352 (above, Thochem Products), MEGAFACE F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (above, Sumitomo 3M), Asahiguard AG710, Surfon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, Asahi Glass Co., Ltd.) Wait. The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the composition or the liquid crystal alignment treatment agent.

Specific examples of the compound which enhances the adhesion between the resin film or the liquid crystal alignment film and the substrate include a functional decane-containing compound or an epoxy group-containing compound shown below.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-( 2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethyl Oxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4,7 - triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9 -triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethyl Oxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(ethylene oxide)-3-aminopropyl Trimethoxy decane, N-bis(ethylene oxide)-3-amine Propyl triethoxy decane, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether, polypropylene glycol Epoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl Ether, glycerol diepoxypropyl ether, 2,2-dibromoneopentyl glycol diepoxypropyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol , N,N,N',N',-tetraepoxypropyl-m-xylylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane or N , N, N', N', - tetraepoxypropyl-4,4'-diaminodiphenylmethane, and the like.

When the compound to be adhered to the substrate is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of all the polymer components contained in the composition or the liquid crystal alignment agent. Share. When the amount is less than 0.1 part by mass, the effect of improving the adhesion is not expected, and when the amount is more than 30 parts by mass, the storage stability of the composition or the liquid crystal alignment treatment agent may be deteriorated.

In the composition of the present invention or the liquid crystal alignment treatment agent, in addition to the above-mentioned poor solvent, a crosslinkable compound, a compound which improves the film thickness uniformity or surface smoothness of the resin film or the liquid crystal alignment film, and a compound which adheres to the substrate In addition, a dielectric or a conductive material for the purpose of 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 without impairing the effect of the present invention.

<Resin film>

The composition of the present invention can be used as a resin film after being coated and fired on a substrate. In the case of 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 depending on the device to be used. The coating method of the composition is not particularly limited, and industrially, a dipping method, a roll coating method, a slit coating method, a spinner method, a spray method, screen printing, Methods such as letterpress printing, flexographic printing or ink jet printing are common. These can be chosen according to the purpose.

After the composition is applied onto a substrate, the solvent used in the composition is heated at 30 to 300 ° C, preferably 30 to 250 by a heating means such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven. The temperature of °C evaporates the solvent to form a resin film. The thickness of the resin film after firing can be adjusted to 0.01 to 100 μm in accordance with the purpose.

<Liquid alignment film. Liquid crystal display element>

The liquid crystal alignment treatment agent using the composition of the present invention is applied to a substrate and fired, and then subjected to an 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, the alignment treatment can also be used as the liquid crystal alignment film. In the substrate to be used at this time, the substrate having high transparency is not particularly limited, 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 process simplification, it is preferred to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. Further, in the reflective liquid crystal display device, an opaque substrate such as a ruthenium wafer can be used as the substrate on one side, and a material for reflecting light such as aluminum can be used as the electrode in this case.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, and industrial methods such as screen printing, letterpress printing, flexographic printing, and ink jet printing are common. Other coating methods include a dipping method, a roll coating method, a slit coating method, a spinner method, or a spray method, and these may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, the solvent used in the liquid crystal alignment treatment agent is preferably 30 to 300 ° C by a heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven. The solvent is evaporated at a temperature of 30 to 250 ° C to form a liquid crystal alignment film. When the thickness of the liquid crystal alignment film after firing is too large, the power consumption surface of the liquid crystal display element becomes unfavorable. If the thickness of the liquid crystal display element is too small, the reliability of the liquid crystal display element is lowered. Therefore, it is preferably 5 to 300 nm, and more preferably 10~100nm. 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.

In the liquid crystal display device of the present invention, after the substrate to which the liquid crystal alignment film is attached is obtained from the liquid crystal alignment treatment agent of the present invention, the liquid crystal cell is produced by a conventional method and then a liquid crystal display element is produced.

In the method of producing a liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a spacer is spread on a liquid crystal alignment film of a single-sided substrate, and a liquid crystal alignment film surface is formed inside, and a substrate on the other surface is bonded. A method in which the liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface of a spacer, and a substrate is bonded and then sealed.

Further, the liquid crystal alignment agent of the present invention is preferably used in which a liquid crystal layer is provided between a pair of substrates having electrodes, and polymerization is carried out by disposing at least one of active energy rays and heat between a pair of substrates. A liquid crystal display device produced by the step of polymerizing a polymerizable compound by applying a voltage to the electrodes while applying a voltage between the electrodes, and irradiating and heating the active energy rays. Here, as the active energy ray, ultraviolet rays are preferred. In terms of ultraviolet light, the wavelength is 300~400nm, It is preferably 310 to 360 nm. In the case of heating polymerization, 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 liquid crystal display element is a pre-dipper that controls liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in the liquid crystal material, and after the liquid crystal cell is assembled, a specific voltage state is applied to the liquid crystal layer, and the photopolymerizable compound is irradiated with ultraviolet rays or the like. The pretilt of the liquid crystal molecules is controlled by the generated polymer. Since the alignment state of the liquid crystal molecules at the time of polymer formation is memorized even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. Further, in the PSA method, the rubbing treatment is not required, and therefore it is suitable for the formation of a vertical alignment type liquid crystal layer which is difficult to control the pretilt by the rubbing treatment.

In other words, in the liquid crystal display device of the present invention, the liquid crystal alignment film substrate can be obtained by the liquid crystal alignment treatment agent of the present invention, and the liquid crystal cell can be produced by at least one of ultraviolet irradiation and heating. The polymerizable compound is polymerized to control the alignment of the liquid crystal molecules.

An example of the production of a PSA liquid crystal cell is to prepare a pair of substrates on which a liquid crystal alignment film is formed, and to spread a spacer on a liquid crystal alignment film of a single-sided substrate so that the liquid crystal alignment film surface is inside and the other surface is bonded to the other surface. The substrate is a method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a separator is dispersed, and a substrate is bonded and then sealed.

Polymerization in liquid crystals for polymerization by heat or ultraviolet irradiation A polymeric compound. The polymerizable compound may, for example, 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 not more than 0.01 parts by mass, the polymerizable compound does not polymerize, and the alignment control of the liquid crystal cannot be performed. When the amount is more than 10 parts by mass, the unreacted polymerizable compound increases, and the melting characteristics of the liquid crystal display element are lowered. .

After the liquid crystal cell is produced, an alternating current or a direct current voltage is applied to the liquid crystal cell, and the polymerizable compound is polymerized by heating or irradiating ultraviolet rays. Thereby, the alignment of the liquid crystal molecules can be controlled.

Further, the liquid crystal alignment treatment agent of the present invention is preferably formed by providing a liquid crystal layer between a pair of substrates including electrodes, and arranging and containing at least one of an active energy ray and heat between the pair of substrates. A liquid crystal alignment element produced by a step of applying a voltage between electrodes in a polymerizable group liquid crystal alignment film. Here, as the active energy ray, ultraviolet rays are preferred. In terms of ultraviolet rays, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of heating polymerization, 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.

In order to obtain a liquid crystal alignment film containing a polymerizable group which is polymerized by at least one of an active energy ray and heat, for example, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, or a polymerizable property is used. A method based on a polymer component. The liquid crystal alignment treatment agent of the present invention contains a double bond portion having a reaction by irradiation with heat or ultraviolet rays. For a specific compound, the alignment of the liquid crystal molecules can be controlled by at least one of irradiation and heating of ultraviolet rays.

An example of the liquid crystal cell production is, for example, a pair of substrates on which a liquid crystal alignment film is formed, and a spacer is disposed on a liquid crystal alignment film of a single-sided substrate, and the liquid crystal alignment film surface is inside, and the other surface is bonded to the substrate. A method in which a liquid crystal is injected under reduced pressure and closed, or a method in which a liquid crystal is dropped on a liquid crystal alignment film surface on which a spacer is dispersed, a substrate is bonded, and the like is sealed.

After the liquid crystal cell is produced, the alignment of the liquid crystal molecules can be controlled by applying an alternating current or a direct current voltage to the liquid crystal cell while heating or irradiating the ultraviolet light.

As described above, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be applied to a liquid crystal television or the like having a large screen and high definition.

[Examples]

The present invention will be described in more detail in the following examples, but is not limited thereto.

The abbreviations used in the synthesis examples, examples, and comparative examples are as follows.

(Specific cellulose-based polymer of the component (A) of the present invention)

CE-1: hydroxyethyl cellulose (manufactured by WAKO)

CE-2: hydroxypropylmethylcellulose phthalate (ACROS)

(Diamine compound represented by the formula [2a] of the present invention)

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

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

(Diamine compound represented by the formula [2b] of the present invention)

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 (Formula [B3] below] Derived diamine compound)

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

B5: 1,3-diamino-4-octadecyloxybenzene (described in the following formula [B5] Diamine compound

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]

(Solvent of the component (C) of the present invention)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

(Solvent of the component (D) of the present invention)

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

PCS: ethylene glycol monopropyl ether (solvent represented by the formula [D-2] of the present invention)

DEEE: diethylene glycol monoethyl ether (solvent represented by the formula [D-3] of the present invention)

(Solvent of the component (E) of the present invention)

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

(Measurement of molecular weight of polyimine precursors and polyimine)

The molecular weight of the polyimine precursor and the polyimine in the synthesis example is a normal temperature colloidal soaking chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Co., Ltd.), and a column (KD-803, KD-805). (manufactured by Shodex Co., Ltd.), measured as follows.

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (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 the production of calibration lines: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000, and 30,000) (made by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratories).

(Determination of the imidization ratio of polyimine)

The ruthenium imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR sampling tube stand (NMR sampling tube stand, 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 thereto, and ultrasonic waves were applied to completely dissolve. This solution was measured for 500 MHz proton NMR by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Co., Ltd.). The sulfhydrylation rate is determined by using protons from a structure that has no change before and after imidization as a reference proton, and the peak value of the proton is used and the proton peak of the NH group from the vicinity of 9.5 ppm to 10.0 ppm. The cumulative value is obtained by the following equation.

醯 imidization rate (%) = (1-α.x/y) × 100

In the above formula, x is the proton peak cumulative value of the NH group derived from proline, y is the peak cumulative value of the reference proton, and α is the polyamine (the sulfhydrylation rate is 0%). One base of acid NH proton The proportion of quasi-protons.

"Synthesis of a specific polyimine-based polymer of the component (B) of the present invention" <Synthesis Example 1>

D1 (9.00 g, 45.9 mmol) and A1 (6.98 g, 45.9 mmol) were mixed in NMP (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 concentration of 25% by mass ( 1). The polyamic acid had a number average molecular weight of 26,900 and a weight average molecular weight of 78,100.

<Synthesis Example 2>

D2 (8.17 g, 32.7 mmol) and A2 (6.21 g, 40.8 mmol) were mixed in NMP (26.4 g), and after reacting at 80 ° C for 5 hours, D1 (1.60 g, 8.16 mmol) and NMP (21.6 g) were added. 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% by mass.

After the NMP was diluted to 6 mass% in the obtained polyaminic acid solution (40.0 g), anhydrous acetic acid (4.85 g) and pyridine (3.70 g) were added as a ruthenium catalyzed catalyst, and the mixture was carried out at 80 ° C. Hour response. 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 polyimine had a ruthenium iodide ratio of 54%, a number average molecular weight of 19,800, and a weight average molecular weight of 44,300.

<Synthesis Example 3>

D2 (6.25 g, 25.0 mmol), B1 (6.79 g, 17.8 mmol) and A1 (2.72 g, 17.9 mmol) were mixed in NMP (29.5 g), and after reacting at 80 ° C for 5 hours, D1 (2.10 g) was added. , 10.7 mmol) and NMP (24.1 g) were reacted at 40 ° C for 8 hours to obtain a polyamic acid solution (3) having a resin solid concentration of 25% by mass. The polyamic acid had a number average molecular weight of 23,500 and a weight average molecular weight of 65,600.

<Synthesis Example 4>

In the polyamic acid solution (3) (30.0 g) obtained in Synthesis Example 3, NMP was added and diluted to 6 mass%, and then, as a ruthenium amide catalyst, anhydrous acetic acid (6.75 g) and pyridine (4.90 g) were added. ), the reaction was carried out at 90 ° 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 (4). The polyimine had an oxime imidization ratio of 82%, a number average molecular weight of 17,500, and a weight average molecular weight of 40,100.

<Synthesis Example 5>

D2 (6.63 g, 26.5 mmol), B1 (5.05 g, 13.3 mmol), A1 (2.52 g, 16.6 mmol), and C1 (0.36 g, 3.33 mmol) were mixed in NMP (26.2 g) at 80 ° C hour After the reaction, D1 (1.30 g, 6.63 mmol) and NMP (21.4 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was diluted to 6 mass% in the obtained polyamidic acid solution (40.0 g), anhydrous acetic acid (4.78 g) and pyridine (3.73 g) were added as a ruthenium catalyzed catalyst, and the mixture was carried out at 80 ° C. Hour response. 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 polyimine had a ruthenium iodide ratio of 55%, a number average molecular weight of 17,200, and a weight average molecular weight of 41,600.

<Synthesis Example 6>

D2 (5.17g, 20.7mmol), B2 (4.07g, 10.3mmol), A1 (2.09g, 13.7mmol), and B6 (2.10g, 10.3mmol) were mixed in NMP (26.6g), and it was carried out at 80 °C. After an hour of reaction, D1 (2.70 g, 13.8 mmol) and NMP (21.8 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the NMP was diluted to 6 mass% in the obtained polyaminic acid solution (40.0 g), anhydrous acetic acid (4.80 g) and pyridine (3.75 g) were added as a ruthenium catalyzed catalyst, and the mixture was carried out at 80 ° C. Hour response. 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 polyimine powder (6). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 17,600, and a weight average molecular weight of 41,300.

<Synthesis Example 7>

D2 (4.34 g, 17.3 mmol), B3 (4.50 g, 10.4 mmol), A2 (3.17 g, 20.8 mmol), and C2 (0.37 g, 3.42 mmol) were mixed in NMP (26.0 g) at 80 ° C. After an hour of reaction, D1 (3.40 g, 17.3 mmol) and NMP (21.3 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

The obtained polyaminic acid solution (30.0 g) was diluted with NMP to 6 mass%, and then, as a ruthenium amide catalyst, anhydrous acetic acid (6.74 g) and pyridine (4.90 g) were added, and the mixture was carried out at 90 ° C for 3 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 (7). The polyamidimide had a ruthenium iodide ratio of 78%, a number average molecular weight of 18,500, and a weight average molecular weight of 42,100.

<Synthesis Example 8>

D2 (6.12 g, 24.5 mmol), B4 (2.26 g, 4.59 mmol) and A2 (3.96 g, 26.0 mmol) were mixed in NMP (22.3 g), 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. A polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

After the NMP was added to the obtained polyamidamine solution (40.0 g) and diluted to 6 mass%, anhydrous acetic acid (4.82 g) and pyridine (3.75 g) were added as a ruthenium catalyzed catalyst, and 3.5 at 80 ° C was carried out. Hour response. 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 polyimine had a hydrazide conversion ratio of 50%, a number average molecular weight of 16,200, and a weight average molecular weight of 38,100.

<Synthesis Example 9>

D3 (7.70 g, 34.3 mmol), B1 (3.92 g, 10.3 mmol) and A1 (3.66 g, 24.1 mmol) were mixed in NMP (45.8 g), and reacted at 40 ° C for 5 hours to obtain a resin solid content concentration of 25 mass% polyamine solution.

After the obtained polyaminic acid solution (40.0 g) was added to NMP and diluted to 6 mass%, anhydrous acetonitrile (4.70 g) and pyridine (3.60 g) were added as a ruthenium catalyzed catalyst, and the mixture was allowed to stand at 80 ° C for 4 hours. reaction. 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 (9). The polyimine had a ruthenium iodide ratio of 54%, a number average molecular weight of 17,300, and a weight average molecular weight of 41,000.

<Synthesis Example 10>

D3 (7.50 g, 33.5 mmol), B5 (3.78 g, 10.0 mmol), B6 (1.36 g, 6.69 mmol) and A1 (2.55 g, 16.8 mmol) were mixed in NMP (45.6 g) at 5 ° C After an hour of reaction, a polyamic acid solution having a resin solid concentration of 25% by mass was obtained.

After the obtained polyaminic acid solution (40.0 g) was added to NMP and diluted to 6 mass%, anhydrous acetonitrile (4.80 g) and pyridine (3.75 g) were added as a ruthenium catalyzed catalyst, and the mixture was subjected to an hour at 80 ° C for 4 hours. reaction. 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 (10). The polyimine had a quinone imidization ratio of 55%, a number average molecular weight of 18,100, and a weight average molecular weight of 39,900.

<Synthesis Example 11>

D4 (5.51 g, 18.4 mmol), B2 (3.62 g, 9.17 mmol), C2 (0.66 g, 6.10 mmol), and A1 (2.33 g, 15.3 mmol) were mixed in NMP (24.0 g) at 80 ° C After an hour of reaction, D1 (2.40 g, 12.2 mmol) and NMP (19.6 g) were added, and the reaction was carried out at 40 ° C for 5 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

After the obtained polyaminic acid solution (40.0 g) was added to NMP and diluted to 6% by mass, anhydrous acetonitrile (4.80 g) and pyridine (3.70 g) were added as a ruthenium catalyzed catalyst, and the mixture was allowed to stand at 80 ° C for 4.5 hours. reaction. The reaction solution was poured into methanol (800 ml), and the precipitate obtained by filtration was filtered. Things. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (11). The polyimine had a hydrazide conversion ratio of 60%, a number average molecular weight of 16,800, and a weight average molecular weight of 37,500.

<Synthesis Example 12>

D4 (5.66 g, 18.9 mmol), B1 (4.31 g, 11.3 mmol), B6 (2.30 g, 11.3 mmol), and A1 (2.30 g, 15.1 mmol) were mixed in NMP (30.2 g), and carried out at 80 ° C. After an hour of reaction, D1 (3.70 g, 18.9 mmol) and NMP (24.7 g) were added, and the reaction was carried out at 40 ° C for 5 hours to obtain a polyamic acid solution (12) having a resin solid concentration of 25% by mass. The polyamic acid had a number average molecular weight of 23,500 and a weight average molecular weight of 66,900.

<Synthesis Example 13>

In the polyaminic acid solution (12) (30.0 g) obtained in Synthesis Example 12, NMP was added and diluted to 6 mass%, and then, as a ruthenium amide catalyst, anhydrous acetic acid (6.70 g) and pyridine (4.80 g) were added. ), the reaction was carried out at 90 ° C for 3.5 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 (13). The polyimine had an oxime imidization ratio of 81%, a number average molecular weight of 15,800, and a weight average molecular weight of 37,500.

The specific polyamidene-based polymer of the present invention is as shown in Table 1. Show.

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

In the following Example 1 to Example 19 and Comparative Example 1 to Comparative Example 5, production examples of the composition were described. Moreover, these compositions can also be 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 by the examples and the comparative examples of the present invention or the liquid crystal alignment treatment agent, "evaluation of transparency of the resin film", "evaluation of inkjet coating property of the liquid crystal alignment agent", and "liquid crystal" were performed. Production of cell and evaluation of liquid crystal alignment (general cell), "production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" and "evaluation of voltage holding ratio of insulating film coated substrate" . The conditions are as follows.

"Evaluation of transparency of resin film"

The composition obtained in the examples and the comparative examples of the present invention was filtered under pressure with a membrane filter having a pore diameter of 1 μm to evaluate the transparency of the resin film. This solution was spin-coated on a 40×50 mm quartz substrate, and heat-treated at 100° C. for 5 minutes on a hot plate to obtain a quartz substrate having an agglomerated yttrium imide resin film having a thickness of 100 nm.

Using the obtained resin-coated quartz substrate, an ultraviolet-visible absorption spectrum at a wavelength of 300 to 750 nm was measured by an ultraviolet-visible spectrophotometer (UV-2550) (manufactured by Shimadzu Corporation). Among them, the higher the transmittance at the wavelengths of 310 nm and 340 nm, the better the transparency of the resin film.

Tables 5 to 7 are the results of the transparency of the resin films obtained in the examples and the comparative examples.

"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 (13) obtained in Example 13 were subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm to carry out inkjet coating properties. evaluation of. For the inkjet coater, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used. Coated with pure water and IPA (isopropyl alcohol) ITO (indium tin oxide) was evaporated on the substrate to have a coating area of 70×70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, a coating speed of 40 mm/sec, and a time from coating to temporary drying. The drying was carried out for 60 seconds at 70 ° C for 5 minutes on a hot plate.

"Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (General 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 to prepare a liquid crystal cell. The solution was spin-coated on an ITO surface of a 30×40 mm ITO electrode substrate (length 40 mm×width 30 mm, thickness 0.7 mm) washed with pure water and IPA, and heat-treated on a hot plate at 100° C. for 5 minutes. An ITO substrate of an agglomerated iridium imine liquid crystal alignment film having a film thickness of 100 nm was obtained. The coating surface of the ITO substrate was rubbed by a rubbing device having a roll diameter of 120 mm, using a rayon cloth, a number of rolls of 1000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.1 mm.

Two ITO substrates with a liquid crystal alignment film were prepared, and the liquid crystal alignment film surface was placed inside, and a 6 μm spacer was interposed therebetween, and a sealant (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was printed. Next, the other substrate was opposed to the liquid crystal alignment film surface, and after bonding, the sealing agent was heat-treated at 120 ° C for 90 minutes in a heat cycle type dust-free oven to be hardened to form an empty cell. The liquid crystal cell is injected into the liquid crystal by a vacuum injection method, and the injection port is closed to obtain a liquid crystal cell (general unit cell).

Further, the liquid crystal alignment treatment agent (1), the liquid crystal alignment treatment agent (2), and the comparative example 1 obtained in Example 1 and Example 2 were used. The liquid crystal alignment treatment agent (20) obtained in Comparative Example 2, the liquid crystal alignment treatment agent (21), and the liquid crystal cell of the liquid crystal alignment treatment agent (24) obtained in Comparative Example 5 were used, and the nematic liquid crystal (MLC- was used for the liquid crystal). 2003) (Minuku. Japanese company system).

Further, the liquid crystal alignment treatment agent (3) to liquid crystal alignment treatment agent (6) obtained in Examples 3 to 6 and the liquid crystal alignment treatment agent (8) to liquid crystal alignment obtained in Examples 8 to 12 were used. The treatment agent (12), the liquid crystal alignment treatment agent (14) to liquid crystal alignment treatment agent (19) obtained in Examples 14 to 19, and the liquid crystal alignment treatment agent (22) obtained in Comparative Example 3 and Comparative Example 4 and The liquid crystal cell of the liquid crystal alignment agent (23) was used as a liquid crystal, and a nematic liquid crystal (MLC-6608) (manufactured by Meinu Co., Ltd.) was used for the liquid crystal.

The liquid crystal alignment property was evaluated using the liquid crystal cell obtained above. The alignment of the liquid crystal 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 8 to 10).

Tables 8 to 10 are the results of the liquid crystal alignment properties obtained in the examples and comparative examples.

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

The liquid crystal alignment treatment agent (6) obtained in Example 6, the liquid crystal alignment treatment agent (9) obtained in Example 9, and the liquid crystal alignment treatment agent (16) obtained in Example 16 were filtered through a membrane having a pore diameter of 1 μm. Carry out The solution was stored under pressure filtration at -15 ° C for 48 hours to prepare a liquid crystal cell and evaluate the liquid crystal alignment. The ITO electrode substrate (length 40 mm × width 30 mm, thickness 0.7 mm) and the center 10×40 mm ITO electrode substrate (length 40 mm) of the solution were placed at a center of 10×10 mm in the center of pure water and IPA. The ITO surface of ×30 mm in width and 0.7 mm in thickness was spin-coated, and heat-treated on a hot plate at 100 ° C for 5 minutes to obtain a polyimide film having a film thickness of 100 nm. After the coating film surface was washed with pure water, the film was heat-treated at 100 ° C for 15 minutes in a heat cycle type dust-free oven to obtain a liquid crystal alignment film substrate.

The liquid crystal alignment film substrate was placed so that the liquid crystal alignment film surface was inside, and a spacer of 6 μm was sandwiched, and a hollow cell was formed by a sealant. The polymerizable compound (1) represented by the following formula is used as a nematic liquid crystal in a nematic liquid crystal (MLC-6608) (manufactured by Meinu Co., Ltd.) in a vacuum cell. 100% by mass of (MLC-6608), 0.3% by mass of liquid crystal of the mixed polymerizable compound (1) was injected, and the injection port was closed to obtain a liquid crystal cell.

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

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

In the PSA unit cell obtained in the example, the response speed of the liquid crystal cell after the ultraviolet irradiation was faster than that of the liquid crystal cell before the ultraviolet irradiation, and it was confirmed that the alignment direction of the liquid crystal was controlled. Further, any liquid crystal cell was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by NIKON Co., Ltd.), and it was confirmed that the liquid crystal was uniformly aligned.

"Evaluation of Voltage Maintenance Rate of Insulating Film-Coated Substrate" (Adjustment of composition for insulating film)

In a 100 ml eggplant type flask, an acrylic resin ((meth)acrylic acid/hydroxyethyl (meth) acrylate/methyl (meth) acrylate = 9/25.5/65.5 propylene glycol monomethyl ether acetate) was added. Solution, solid content concentration: 22.0% by weight, weight average molecular weight 6000 (in terms of polystyrene) (7.07 g), propylene glycol monomethyl ether acetate (25.1 g), KAYARADDPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) 3.30 g), I-369 (manufactured by Ciba Specialty Chemicals Inc.) (0.30 g), ITX (manufactured by First Chemical Corporation), and MEGAFACE R-30 (0.015 g) were stirred at 25 ° C for 3 hours to obtain an insulating film composition. Things. No insoluble matter was observed in the composition for the insulating film, and a uniform solution was obtained.

(Production of insulating film coated substrate)

The composition for an insulating film obtained above was filtered through a 0.2 μm filter. Thereafter, the composition was placed on an ITO electrode substrate (length 40 mm × width 30 mm, thickness 0.7 mm) and a center 10×40 mm ITO electrode substrate separated by 20 μm in a center of 10×10 mm in a center washed with pure water and IPA. The ITO surface (length 40 mm × width 30 mm, thickness 0.7 mm) was spin-coated, and the hot plate was heat-treated at 110 ° C for 5 minutes. The coating film was irradiated with ultraviolet rays having an irradiation amount of 500 mJ/cm ² at 365 nm by an ultraviolet irradiation apparatus PLA-501 (F) (manufactured by Canon Inc.), and heat-treated at 120 ° C for 1 minute on a hot plate. Thereafter, the film was further heated at 200 ° C for 60 minutes on a hot plate to obtain a substrate coated with an insulating film having a film thickness of 1.12 μm.

(Production of liquid crystal cell)

The liquid crystal alignment treatment agent obtained by 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 stored at -15 ° C for 48 hours to prepare a liquid crystal cell. This solution was spin-coated on the insulating film-coated surface of the insulating film-coated substrate obtained above, and heat-treated at 100 ° C for 5 minutes on a hot plate to obtain an agglomerated imipenem liquid crystal alignment having a film thickness of 100 nm. The ITO substrate of the film. The coating surface of the ITO substrate was rubbed by a rubbing device having a roll diameter of 120 mm, using a rayon cloth, a number of rolls of 1000 rpm, a roll speed of 50 mm/sec, and a press-in amount of 0.1 mm.

Two ITO substrates with a liquid crystal alignment film were prepared, and the liquid crystal alignment film surface was placed inside, and a 6 μm spacer was interposed therebetween, and a sealant (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was printed. Next, the other substrate was opposed to the liquid crystal alignment film surface, and after bonding, the sealing agent was heat-treated at 120 ° C for 90 minutes in a heat cycle type dust-free oven, and hardened to prepare an empty cell. The liquid crystal cell was injected into the liquid crystal by a reduced pressure injection method, and the injection port was closed to obtain a liquid crystal cell.

(evaluation of voltage maintenance rate)

The liquid crystal cell obtained above was applied with a voltage of 1 V for 60 μs at a temperature of 70 ° C, and the voltage after 16.67 ms and 50 ms was measured, and the voltage maintenance rate (also referred to as VHR) was calculated. In addition, the measurement using the voltage maintenance rate measuring device (VHR-1) (manufactured by TOYO Corporation) was carried out with a setting of Voltage: ±1 V, Pulse Width: 60 μs, Flame Period: 16.67 ms, or 50 ms.

The liquid crystal cell in which the measurement of the voltage maintenance rate was completed was irradiated with ultraviolet rays of 10 J/cm ² in terms of 365 nm, and then VHR was measured under the same conditions. Further, ultraviolet irradiation was carried out using a desktop type UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT CORPORATION).

Tables 8 to 10 are the results of evaluation of the voltage maintenance ratio of the insulating film-coated substrate obtained in the examples and the comparative examples.

<Example 1>

The polyamic acid solution (1) (11.5 g) and CE-2 (0.72 g) obtained by the synthetic method of Synthesis Example 1 were added to a solid concentration of 25% by mass, and NMP (27.0 g) and BCS (26.2 g) were added. The mixture was stirred at 50 ° C for 6 hours to obtain a composition (1). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (1) was also used for evaluation as a liquid crystal alignment treatment agent (1).

Using the obtained composition (1) and the liquid crystal alignment treatment agent (1), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 2>

In the polyimine powder (2) (2.33 g) and CE-1 (1.00 g) obtained by the synthetic method of Synthesis Example 2, NEP (32.7 g), PCS (5.70 g) and BCS (21.2 g) were added. The mixture was stirred at 70 ° C for 24 hours to obtain a composition (2). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (2) was also used as a liquid crystal alignment treatment agent (2) for evaluation.

Using the obtained composition (2) and the liquid crystal alignment treatment agent (2), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 3>

NMP (15.7 g), BCS (15.9 g) and PB were added to a polyamic acid solution (3) (12.6 g) and CE-1 obtained by a synthetic method of Synthesis Example 3 in a solid concentration of 25% by mass. (19.1 g) was stirred at 50 ° C for 6 hours to obtain a composition (3). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (3) was also used as a liquid crystal alignment treatment agent (3) for evaluation.

Using the obtained composition (3) and the liquid crystal alignment treatment agent (3), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 4>

NMP (26.7 g), PCS (5.61 g) and BCS were added to the polyamic acid solution (3) (7.80 g) and CE-2 obtained by the synthetic method of Synthesis Example 3 in a solid concentration of 25% by mass. (17.7 g) was stirred at 50 ° C for 6 hours to obtain a composition (4). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, this composition (4) was also used as a liquid crystal alignment treatment agent (4) for evaluation.

Using the obtained composition (4) and the liquid crystal alignment treatment agent (4), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 5>

Polyimide powder (4) (2.45 g) and CE-2 (1.05 g) obtained by the synthetic method of Synthesis Example 4 were added with NMP (9.27 g), NEP (24.7 g) and PB (28.6 g). The mixture was stirred at 70 ° C for 24 hours to obtain a composition (5). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, this composition (5) was also used as a liquid crystal alignment treatment agent (5) for evaluation.

Using the obtained composition (5) and the liquid crystal alignment treatment agent (5), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 6>

Polyimide powder (5) (2.00 g) and CE-2 (1.33 g) obtained by the synthetic method of Synthesis Example 5 were added with NMP (11.6 g), NEP (17.3 g) and PB (30.2 g). The mixture was stirred at 70 ° C for 24 hours to obtain a composition (6). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, this composition (6) was also used as a liquid crystal alignment treatment agent (6) for evaluation.

Using the obtained composition (6) and the liquid crystal alignment treatment agent (6), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. "Evaluation of Liquid Crystal Cell Production and Evaluation of Liquid Crystal Alignment (PSA Cell)" and "Evaluation of Voltage Holding Rate of Insulating Film-Coated Substrate".

<Example 7>

To the polyimine powder (5) (1.08 g) and CE-2 (0.72 g) obtained by the synthesis method of Synthesis Example 5, NMP (11.7 g), NEP (17.6 g) and PB (30.0 g) were added. The mixture was stirred at 70 ° C for 24 hours to obtain a composition (7). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, this composition (7) was also used as a liquid crystal alignment treatment agent (7) for evaluation.

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

<Example 8>

The polyimine powder (5) (2.15 g) and CE-2 (0.92 g) obtained by the synthetic method of Synthesis Example 5 were added with γ-BL (24.2 g), DEEE (11.7 g) and BCS (24.5). g), stirring at 70 ° C for 24 hours to obtain a composition (8). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, this 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), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 9>

NEP (35.9 g) and BCS (24.2 g) were added to the polyimine powder (6) (2.83 g) and CE-1 (0.50 g) obtained by the synthetic method of Synthesis Example 6, and carried out at 70 ° C. Stirring was carried out for 24 hours to obtain a composition (9). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, this composition (9) was also used as a liquid crystal alignment treatment agent (9) for evaluation.

Using the obtained composition (9) and the liquid crystal alignment treatment agent (9), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. "Evaluation of Liquid Crystal Cell Production and Evaluation of Liquid Crystal Alignment (PSA Cell)" and "Evaluation of Voltage Holding Rate of Insulating Film-Coated Substrate".

<Example 10>

In the polyimine powder (7) (1.89 g) and CE-2 (1.55 g) obtained by the synthetic method of Synthesis Example 7, NEP (26.6 g), BCS (12.5 g) and PB (21.9 g) were added. The mixture was stirred at 70 ° C for 24 hours to obtain a composition (10). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (10) was also used as a liquid crystal alignment treatment agent (10) for evaluation.

Using the obtained composition (10) and the liquid crystal alignment treatment agent (10), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 11>

Polyimide powder (8) (1.53 g) and CE-2 (1.87 g) obtained by the synthetic method of Synthesis Example 8 were added with NMP (14.5 g), NEP (14.5 g) and PB (30.9 g). The mixture was stirred at 70 ° C for 24 hours to obtain a composition (11). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (11) was also used as a liquid crystal alignment treatment agent (11) for evaluation.

Using the obtained composition (11) and the liquid crystal alignment treatment agent (11), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 12> Polyimine powder (8) (1.88 g) and CE-2 (1.25 g) obtained by the synthesis method of Synthesis Example 8 were added with γ-BL (24.7 g), PGME (17.8 g) and PB (18.8). g), stirring at 70 ° C for 24 hours to obtain a composition (12). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform 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), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 13>

The polyimine powder (8) (1.08 g) and CE-2 (0.75 g) obtained by the synthetic method of Synthesis Example 8 were added with γ-BL (22.3 g) and PGME (39.4 g) at 70 ° C. The mixture was stirred for 24 hours to obtain a composition (13). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (13) was also used as a liquid crystal alignment treatment agent (13) for evaluation.

Using the obtained liquid crystal alignment treatment agent (13), "evaluation of inkjet coating property of liquid crystal alignment treatment agent" was carried out under the above conditions.

<Example 14>

Polyimine powder (9) (2.80 g) and CE-1 (0.70 g) obtained by the synthetic method of Synthesis Example 9 were added with NMP (35.0 g), DEEE (12.0 g) and BCS (15.9 g). The mixture was stirred at 70 ° C for 24 hours to obtain a composition (14). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform 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), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 15>

Polyimine powder obtained by the synthetic method of Synthesis Example 10 (10) (2.38 g) and CE-2 (1.02 g), NEP (26.8 g), BCS (24.7 g), and PB (9.27 g) were added, and the mixture was stirred at 70 ° C for 24 hours to obtain a composition (15). . When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform 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), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 16>

In the polyimine powder (11) (2.45 g) and CE-2 (1.05 g) obtained by the synthetic method of Synthesis Example 11, NEP (37.5 g), DEEE (6.02 g) and BCS (19.1 g) were added. The mixture was stirred at 70 ° C for 24 hours to obtain a composition (16). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform 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), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. "Evaluation of Liquid Crystal Cell Production and Evaluation of Liquid Crystal Alignment (PSA Cell)" and "Evaluation of Voltage Holding Rate of Insulating Film-Coated Substrate".

<Example 17>

NMP (26.3 g), BCS (12.8 g) and PB were added to a polyamic acid solution (12) (11.2 g) and CE-2 obtained by a synthetic method of Synthesis Example 12 in a solid concentration of 25% by mass. (12.8 g) was stirred at 50 ° C for 6 hours to obtain a composition (17). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform 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), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 18>

Polyimine powder (13) (2.23 g) and CE-2 (1.20 g) obtained by the synthesis method of Synthesis Example 13 were added with NMP (30.8 g), PCS (14.7 g) and BCS (15.6 g). The mixture was stirred at 70 ° C for 24 hours to obtain a composition (18). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (18) was also used as a liquid crystal alignment treatment agent (18) for evaluation.

Using the obtained composition (18) and the liquid crystal alignment treatment agent (18), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Example 19>

Polyimine powder (13) (1.89 g) and CE-2 (1.26 g) obtained by the synthesis method of Synthesis Example 13 were added with γ-BL (24.9 g), PCS (18.0 g) and PB (18.9). g), stirring at 70 ° C for 24 hours to obtain a composition (19). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (19) was also used as a liquid crystal alignment treatment agent (19) for evaluation.

Using the obtained composition (19) and the liquid crystal alignment treatment agent (19), "Evaluation of transparency of resin film", "Production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Comparative Example 1>

The polyamic acid solution (1) (12.5 g) having a solid concentration of 25% by mass of the resin obtained by the synthetic method of Synthesis Example 1 was added to NMP (21.6 g) and BCS (22.7 g) for 3 hours at 25 ° C. Stirring to obtain a composition (20). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (20) was also used as a liquid crystal alignment treatment agent (20) for evaluation.

Using the obtained composition (20) and the liquid crystal alignment treatment agent (20), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Comparative Example 2>

In the polyimine powder (2) (3.12 g) obtained by the synthetic method of Synthesis Example 2, NEP (31.5 g), PCS (5.41 g), and BCS (19.9 g) were added, and the mixture was subjected to a reaction at 70 ° C for 24 hours. Stirring to obtain a composition (21). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (21) was also used as a liquid crystal alignment treatment agent (21) for evaluation.

Using the obtained composition (21) and the liquid crystal alignment treatment agent (21), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Comparative Example 3>

To a polyamic acid solution (3) (12.0 g) having a solid content of 25% by mass of a resin obtained by the synthesis method of Synthesis Example 3, NMP (12.5 g), BCS (13.6 g), and PB (16.4 g) were added. The mixture was stirred at 25 ° C for 3 hours to obtain a composition (22). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (22) was also used as a liquid crystal alignment treatment agent (22) for evaluation.

Using the obtained composition (22) and the liquid crystal alignment treatment agent (22), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Comparative Example 4>

The polyimine powder (5) (3.20 g) obtained by the synthetic method of Synthesis Example 5 was added with NMP (11.6 g), NEP (17.5 g) and PB (29.1 g), and stirred at 70 ° C for 24 hours. , the composition (23) was obtained. When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (23) was also used as a liquid crystal alignment treatment agent (23) for evaluation.

Using the obtained composition (23) and the liquid crystal alignment treatment agent (23), "Evaluation of transparency of resin film", "Production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

<Comparative Example 5>

To CE-2 (2.02 g), NMP (9.28 g), NEP (13.9 g) and PB (25.3 g) were added, and the mixture was stirred at 70 ° C for 24 hours to obtain a composition (24). When the composition was confirmed, no abnormality such as turbidity or precipitation was observed, and it was a uniform solution. Further, the composition (24) was also used as a liquid crystal alignment treatment agent (24) for evaluation.

Using the obtained composition (24) and the liquid crystal alignment treatment agent (24), "evaluation of transparency of the resin film", "production of liquid crystal cell, and evaluation of liquid crystal alignment (general cell)" were carried out under the above conditions. And "Evaluation of voltage maintenance rate of the substrate coated with an insulating film".

From the above results, it is understood that the composition of the examples of the present invention can obtain a resin film having high transparency as compared with the composition of the comparative example. Specifically, it is a composition of a specific polyimine-based polymer using the same component (B) of the present invention and a specific cellulose-based polymer using the component (A) of the present invention, and a specific cellulose system is not used. Comparison of the composition of the polymer, that is, the comparison between Example 1 and Comparative Example 1, the comparison between Example 2 and Comparative Example 2, the comparison between Example 3 and Comparative Example 3, and the comparison between Example 6 and Comparative Example 4. .

In the evaluation of the voltage maintenance ratio of the insulating film-coated substrate, the liquid crystal alignment treatment agent obtained from the composition of the present invention is in the liquid crystal alignment film as compared with the liquid crystal alignment treatment agent obtained from the composition of the comparative example. In the state in which the insulating film made of the organic member is provided, even when the light is irradiated, the voltage maintenance ratio is excellent (the evaluation of the voltage holding ratio of the insulating film-coated substrate in the examples and the comparative examples). Specifically, it is a group of a specific polyimine-based polymer using the same component (B) of the present invention and a specific cellulose-based polymer using the component (A) of the present invention. Comparison of the composition with the composition without the specific cellulose polymer, that is, the comparison between Example 1 and Comparative Example 1, the comparison between Example 2 and Comparative Example 2, and the comparison between Example 3 and Comparative Example 3. And a comparison between Example 6 and Comparative Example 4. Further, in Comparative Example 5 containing no specific polyamidene-based polymer, the above-mentioned voltage maintenance ratio was excellent.

[industrial use]

In the composition of the present invention, the resin film has high transparency and can suppress decomposition of the resin film by light such as ultraviolet rays.

In addition, the liquid crystal alignment treatment agent of the present invention has a state in which an insulating film made of an organic member is provided under the liquid crystal alignment film, and is a liquid crystal alignment film excellent in voltage retention ratio even when irradiated with light.

Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and is preferably used for a large-screen, high-definition liquid crystal television, etc., in a TN element, an STN element, a TFT liquid crystal element, In particular, a vertical alignment type liquid crystal display element is useful.

Further, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is useful for a liquid crystal display element which is required to be irradiated with ultraviolet rays when producing a liquid crystal display element. In other words, it is preferable to use a liquid crystal composition in which a liquid crystal layer is provided between a pair of substrates including an electrode, and a polymerizable compound containing at least one of an active energy ray and heat is disposed between the pair of substrates. a liquid crystal display element produced by the step of polymerizing the polymerizable compound while applying a voltage between the electrodes, and further a liquid crystal layer having a liquid crystal layer between a pair of substrates having an electrode, and a polymerizable group-containing liquid crystal alignment film which is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates A liquid crystal display element produced by a step of polymerizing the polymerizable group while applying a voltage.

Claims (21)

A composition comprising the component (A) and the component (B) described below, wherein the component (A) is a polymer having a structure represented by the following formula [1]. (In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently, and are a group of the structure selected by the following formula [1a] to formula [1m], n is 100. An integer of ~1000000], (In the formula [1c] to the formula [1m], X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently, and are a benzene ring, a methyl group, an ethyl group, and an n- group. a propyl group, an isopropyl group or a butyl group, wherein n is an integer of 0 to 3 in the formula [1h], m is an integer of 0 to 3 in the formula [1i], and the component (B) is composed of the following: [. 2A] at least one polymeric structure of the diamine component diamine compound represented by reaction with a tetracarboxylic acid component obtained polyimide precursor and the polyimide of the selected formula, [Chemical formula 3] - (CH ₂ ) _a -COOH [2a] (in the formula [2a], a is an integer of 0 to 4). The composition of the present invention, wherein the diamine component represented by the formula [2a] is a diamine compound having the structure represented by the following formula [2a-1], (In the formula [2a-1], a is an integer of 0 to 4, and n is an integer of 1 to 4). The composition according to claim 1, wherein the diamine component in the polymer of the component (B) contains at least one selected from the diamine compounds having the structure represented by the following formula [2b]. (In the formula [2b], Y is selected by the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5] a substituent of the structure, m is an integer from 1 to 4], (In the formula [2b-1], a is an integer of 0 to 4, and in the formula [2b-2], Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O -, -CH ₂ O-, -COO- or -OCO-, Y ² is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, and Y ⁴ is a divalent group selected from a benzene ring, a cyclohexane ring or a hetero ring. a cyclic group or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and 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 a fluorine atom, and Y ⁵ is a divalent ring selected from a benzene ring, a cyclohexane ring or a hetero ring. Any one of the hydrogen atoms on the cyclic 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 carbon number of 1 to 3; 3 is substituted by a fluorine-containing alkoxy group or a fluorine atom, n is an integer of 0 to 4, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 18 carbon atoms. An oxy group or a fluorine-containing alkoxy group having 1 to 18 carbon atoms; in the formula [2b-3], Y ⁷ is -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO -, Y ⁸ An alkyl group having 8 to 22 carbon atoms, the formula [2b-4] in, Y ⁹ and Y ¹⁰ are each independently a hydrocarbon group having 1 to 12 carbon atoms, the formula [2b-5] in, Y ¹¹ is a C number of 1 to 5 alkyl). The composition according to claim 1, wherein the tetracarboxylic acid component in the polymer of the component (B) contains at least one selected from the compounds represented by the following formula [3]. (In the formula [3], Z ¹ is a base of a structure selected by the following formula [3a] to formula [3j]], (In the formula [3a], Z ² to Z ⁵ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z ⁶ and Z ⁷ are a hydrogen atom or a methyl group. Can be the same or different). The composition according to claim 1, wherein the component (C) contains at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone. . The composition according to claim 1, wherein the component (D) contains at least one solvent selected from the solvents represented by the following formula [D-1] to formula [D-3], (In the formula [D-1], D ¹ is an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² is an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ is an alkyl group having 1 to 4 carbon atoms). The composition according to claim 1, wherein the component (E) contains 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, and propylene glycol monobutyl ether. Or at least one solvent selected from ethylene glycol monobutyl ether. A resin film obtained by the composition according to any one of claims 1 to 7. A liquid crystal alignment treatment agent obtained by the composition according to any one of claims 1 to 7. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent described in claim 9. A liquid crystal alignment film which is obtained by an inkjet method using the liquid crystal alignment treatment agent described in claim 9. A liquid crystal display element characterized by comprising the liquid crystal alignment film of claim 10. A liquid crystal display element characterized by comprising the liquid crystal alignment film of claim 11. The liquid crystal alignment film according to claim 11, wherein the liquid crystal alignment layer is provided between the pair of substrates including the electrodes, and the polymerization is performed by at least one of an active energy ray and heat disposed between the pair of substrates. A liquid crystal display device produced by the step of polymerizing the polymerizable compound while applying a voltage to the electrode between the electrodes. The liquid crystal alignment film according to claim 12, wherein the liquid crystal alignment layer is provided between the pair of substrates including the electrodes, and the polymerization is performed by at least one of an active energy ray and heat disposed between the pair of substrates. A liquid crystal display device produced by the step of polymerizing the polymerizable compound while applying a voltage to the electrode between the electrodes. A liquid crystal display element comprising the liquid crystal alignment film of claim 14. A liquid crystal display element comprising the liquid crystal alignment film of claim 15. The liquid crystal alignment film according to claim 10, wherein the liquid crystal alignment layer is provided between the pair of substrates including the electrodes, and the polymerization is performed by at least one of an active energy ray and heat disposed between the pair of substrates. A liquid crystal display element produced by the step of polymerizing the polymerizable group while applying a voltage to the liquid crystal alignment film of the polymerizable group. The liquid crystal alignment film according to claim 11, which is used in a liquid crystal layer is formed between a pair of substrates of the backup electrode, 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 the electrode inter-electrode is interposed between the pair of substrates. A liquid crystal display element produced by a step of polymerizing the polymerizable group while applying a voltage. A liquid crystal display element comprising the liquid crystal alignment film of claim 18. A liquid crystal display element comprising the liquid crystal alignment film of claim 19.