TW201627484A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

Provided are: a liquid crystal alignment film which is able to be suppressed in separation of the film or occurrence of foreign substances caused by a physical impact, while enhancing transmittance characteristics of an element and having excellent afterimage characteristics by alternating-current driving; and a liquid crystal aligning agent. A liquid crystal aligning agent which contains a component (A) and a component (B) described below as well as a solvent that dissolves these components. Component (A): a compound represented by formula (1) (In the formula, P has at least one group wherein a carbon atom is substituted by at least two nitrogen atoms, and at least one of the nitrogen atoms is substituted by a monovalent thermally cleavable group having 1-24 carbon atoms, said monovalent thermally cleavable group being substituted by a hydrogen atom by means of heat; X represents a single bond or the like; and Q represents a benzene ring or the like.) Component (B): at least one polymer that is selected from the group consisting of polyimide precursors and polyimides.

Description

Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film, and a liquid crystal display element using the liquid crystal display element used for applying a parallel electric field to a substrate.

Polyimine is a polymer material excellent in heat resistance, mechanical strength, electrical properties, and solvent resistance, and is widely used as an insulating film, a protective film, or a liquid crystal alignment film in a field of electronic materials. When industrially obtaining such a polyimide film, it is generally a method of preparing a coating liquid obtained by dissolving a polyimide or a polyimide precursor in a solvent, and coating and baking the same. .

The polyimine precursor is a polylysine or a polyphthalate. Since the solubility in the solvent is higher than that of the polyimine, the method of using the coating liquid to obtain a polyimide film as described above has a structure and use in which the polyimide can be freely selected. The advantages of the solvent type and the like. The coating film of the polyimide precursor can be fired at 200 to 400 ° C to be imidized to form a polyimide film.

Polylysine can be reacted by reacting a diamine with a tetracarboxylic dianhydride Although it is easy to obtain, since this reaction is a reversible reaction, the reverse reaction with a diamine and an acid dianhydride is performed simultaneously with the hydrazine imidation by the heat of the said baking. As a result, the molecular weight of the obtained polyimine is lower than that of the original polyamine, and there is a possibility that the properties of the polyimide film are adversely affected. On the other hand, polyglycolate does not undergo a reverse reaction such as polyaminic acid, so that the molecular weight does not decrease at the time of firing, but the heat-induced imidization is difficult to perform compared to polyglycine. It is necessary to carry out ruthenium iodization at a higher temperature than polyglycolic acid.

In general, the higher the above-mentioned firing temperature, the higher the imidization ratio of the ruthenium from the polyimide precursor to the polyimide. Depending on the application, it is not necessary to make the ruthenium imidization ratio of the polyimide film to 100%. However, if the target oxime imidization ratio can be achieved at a lower temperature, it is advantageous in terms of energy cost. It is an advantage that a substrate having a low heat resistance can also form a polyimide film.

In order to solve such a problem, a method of mixing various compounds having a ruthenium-improving effect into a polyimide composition precursor composition in the case of heating hydrazine imidization has been proposed. For example, an amino acid compound is disclosed as a polyimide which can be imidized by a low temperature baking (refer to Patent Document 1). Further, an amine compound such as phenethylamine or dodecylamine is disclosed as a temperature at which the ruthenium imidization temperature of the polyalkyl amide is lowered to around 150 °C. (Refer to Non-Patent Document 1).

Further, a thermal base generator which decomposes by heat to produce a 2-stage amine neutral compound is disclosed, and does not form a salt with a carboxyl group of poly-proline when it is not heated, and thus the composition of the polyimide precursor composition Save stability, useful In the case of a ruthenium imidization accelerator which is a poly-proline (see Patent Document 2). It is also described that the thermal base generator can also be used as a thermal hydrazine imidization accelerator of polyglycolate, so that it can be used without selecting a type of polyimide precursor.

At present, the most widely used liquid crystal alignment film in the industry is formed by a film formed of a polyaminic acid derivative and/or a polyimide obtained by imidating it on an electrode substrate. The surface is produced by a so-called rubbing treatment in which a cloth such as cotton, nylon, or polyester is rubbed in one direction.

The rubbing treatment of the film surface during the alignment of the liquid crystal alignment film is an industrially useful method which is simple and has excellent productivity. However, the requirements for high performance, high definition, and large size of the liquid crystal display element are increased, and the surface of the alignment film due to the rubbing treatment is affected by the flaws, dust, mechanical force, or static electricity, and is further aligned in the processing surface. Various problems such as unevenness are becoming apparent.

As a method of replacing the rubbing treatment, a photo-alignment method which imparts a liquid crystal alignment ability by irradiating a polarized radiation is known. In the liquid crystal alignment treatment by the photo-alignment method, a person who uses a photoisomerization reaction, a person who uses a photocrosslinking reaction, or a photodecomposition reactor is used (see Non-Patent Document 2).

On the other hand, the use of a liquid crystal alignment film for light alignment of polyimine has higher heat resistance than the others, and thus its usefulness is expected. Patent Document 3 proposes a polyimine film which is used in a photo-alignment method and has an alicyclic structure having a cyclobutane ring or the like in its main chain.

The above optical alignment method is used as a frictionless alignment treatment method, It not only has industrial advantages but also can be produced by a simple manufacturing process, and is used in an IPS (In-Place-Switching) driving method or a fringe field switching (hereinafter referred to as FFS) driving method. By using the liquid crystal alignment film obtained by the above-described photo-alignment method, it is possible to improve the contrast of the liquid crystal display element or the improvement of the viewing angle characteristics, and the like, compared with the liquid crystal alignment film obtained by the rubbing treatment method. The performance of the display element is therefore attracting attention as a promising liquid crystal alignment processing method.

The liquid crystal alignment film used for the liquid crystal display device of the IPS driving method or the FFS driving method suppresses long-term communication in the liquid crystal display device of the IPS driving method or the FFS driving method, in addition to the basic characteristics such as excellent liquid crystal alignment property and electrical characteristics. The afterimage caused by the drive is necessary.

However, the liquid crystal alignment film obtained by the photo-alignment method has a problem that the anisotropy in the alignment direction of the polymer film is small as compared with the case of the rubbing treatment method. When the anisotropy is small, sufficient liquid crystal alignment property cannot be obtained, and when it is a liquid crystal display element, there is a problem that an afterimage or the like occurs.

Patent Document 4 proposes that a residual image due to AC driving can be suppressed by a liquid crystal alignment treatment agent containing a polyglycine and a compound having a specific structure.

Further, the level of the residual image of the liquid crystal panel is required to be increased, and the alignment control force of the liquid crystal alignment film obtained by the photo-alignment method is required to be equal to or higher than that of the liquid crystal alignment film obtained by the rubbing treatment.

Further, in recent years, the product group of the liquid crystal panel includes various types such as a smart phone or a tablet. In these products, in order to reduce the weight, the step of physically polishing the glass surface of the produced liquid crystal display element is performed. In this step, the liquid crystal alignment film on the column spacer rubs against the liquid crystal alignment film on the substrate on the opposite side to cause peeling of the liquid crystal alignment film. The peeled liquid crystal alignment film becomes a foreign matter, and display defects of the liquid crystal display element are liable to occur. In addition, when a liquid crystal display element is used in a smart phone or a tablet terminal, physical exposure such as finger pressing is applied to the liquid crystal display element. Therefore, similarly to the above, the liquid crystal alignment film is peeled off or foreign matter is generated, and it is easy to be used as a liquid crystal display element. Displaying defects becomes a problem.

In the photo-alignment treatment method which is attracting attention as a new alignment treatment method in place of the rubbing treatment method, when the liquid crystal alignment treatment method is a photo-decomposition reaction, the polishing process or the touch panel application is likely to occur in the glass substrate. The liquid crystal alignment film of the finger press (also referred to as physical punching) is peeled off or foreign matter is generated.

Further, it is not limited to small and medium-sized products, and power saving of liquid crystal panels is progressing, and it is necessary to display images with a small amount of power consumption. Therefore, as one of the characteristics of the liquid crystal alignment film, a liquid crystal alignment treatment agent excellent in film permeability is required.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-291405

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-56196

[Patent Document 3] Japanese Patent Laid-Open Publication No. Hei 9-297313

[Patent Document 4] International Publication WO2013-054858

[Non-patent literature]

[Non-Patent Document 1] W. Volken: Proc. Am. Chem. Soc. Poly m. Mater. Sci. Eng., 1992, Vol. 66, pp. 235-236

[Non-Patent Document 2] "Liquid Crystal Light Alignment Film", Kimura V., Shimura, Functional Materials, November 1997 Vol.17, No.11 13~22

According to the present invention, it is possible to obtain a property which is required from the past, in particular, the afterimage erasing time and the stability of the liquid crystal alignment, and the transmittance is high, and the surface roughness (roughness) is small, and the accompanying liquid crystal can be suppressed. A liquid crystal alignment film that peels off the physical alignment of the liquid crystal alignment film of the element or a foreign matter.

In order to achieve the above object, the inventors of the present invention have found that liquid crystal alignment treatment is carried out by containing at least one polymer selected from the group consisting of a polyimide precursor and a polyimine, and a compound having a specific structure. The above object can be achieved. As such, the present invention is based on the following.

A liquid crystal alignment treatment agent comprising the following components (A), (B), and a solvent for dissolving the same; (A) component: a compound represented by the following formula (1).

[Chemical 1] P-X-Q (1)

(wherein P has a structure in which at least one of the same carbon atoms is substituted with at least two or more nitrogen atoms, and at least one of the nitrogen atoms is substituted with a carbon atom by a heat of 1 to 24; of heat from the substituent group, X is selected from the group consisting of a single bond, -O -, - CONH -, - NHCO -, - CON (CH 3) -, - N (CH 3) CO -, - COO -, - OCO- and -S- at least one bonding group of the group formed, Q represents a benzene ring, or a hydrocarbon group having a carbon number of 6 to 24 having a benzene ring); (B) component: selected from the group consisting of a polyimide precursor and a polyfluorene At least one polymer of the group formed by the imine.

2. The liquid crystal alignment treatment agent according to the above 1, wherein the thermal release group is an ester group represented by the following formula (2);

(wherein R ² is a hydrocarbon having 1 to 22 carbon atoms).

3. The liquid crystal alignment treatment agent according to 1 or 2 above, wherein P is any one of the following formula (P-1) or (P-2);

(In the formula, S ₁ and S ₂ each independently represent a monovalent organic group having 1 to 6 carbon atoms, and S ₁ and S ₂ may form a ring structure. S ₃ and S ₄ each independently represent a hydrogen atom or carbon. The number 1 to 6 of the monovalent organic group, and S ₃ and S ₄ may form a ring structure. D is a heat-releasing group substituted by a hydrogen atom by heat. * indicates a bonding site with X).

4. The liquid crystal alignment treatment agent according to 3 above, wherein the P is any one of the following formula (PD-1) or (PD-2);

(wherein * represents a bonding site with X, and D is a thermally detachable group substituted with a hydrogen atom by heat).

5. The liquid crystal alignment treatment agent according to the above 4, wherein the component (A) is a compound represented by the following formula (3) wherein X is a single bond in the formula (1), and Q is T-Q'; [Chemical 5] PT -Q' (3)

(wherein P represents a group represented by any one of the above formula (PD-1) or (PD-2), and T represents an alkylene group having 1 to 6 carbon atoms and an alkylene having 2 to 6 carbon atoms. The base or an alkynyl group having 2 to 6 carbon atoms and a hydrogen atom bonded to any of the carbon atoms may be substituted by a halogen-containing alkyl group, a halogen atom or a hydroxyl group (OH group). Q' represents an aromatic hydrocarbon having 6 to 18 carbon atoms.

6. The liquid crystal alignment treatment agent according to any one of the above 1 to 5, wherein the component (A) is represented by the following formula (4-1) or (4-2);

(wherein P and T are the same definitions as above).

7. The liquid crystal alignment treatment agent according to any one of the above 1 to 6, wherein the component (A) is at least one compound selected from the group consisting of the following formulas (A-1) and (A-2).

8. The liquid crystal alignment treatment agent according to any one of the above 1 to 7, wherein the component (B) is contained in an amount of 0.1 to 20% by mass, and the component (A) is contained in an amount of 0.1 to 20% by mass based on the component (B). The solvent is contained in an amount of 76 to 99.5% by mass.

9. The liquid crystal alignment treatment agent according to any one of the above 1 to 8, wherein the polymer of the component (B) is a polyalkylene amide.

10. A liquid crystal alignment film which is as described in the above 1~9 A liquid crystal alignment treatment agent is obtained.

A liquid crystal alignment film obtained by an inkjet method using the liquid crystal alignment treatment agent according to any one of the above 1 to 9.

A liquid crystal alignment film obtained by irradiating a liquid crystal alignment film of the above 10 or 11 with polarized radiation.

A liquid crystal display element comprising the liquid crystal alignment film according to any one of the above 10 to 12.

According to the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal alignment film having a small amount of iridization which is promoted by heating in a small amount, and which has excellent afterimage characteristics due to AC driving, and it is known that the surface of the liquid crystal alignment film is rough. Since the degree of reduction is excellent, the resistance to physical punching is excellent, and since the heat resistance of the added compound is high, a liquid crystal alignment film which suppresses thermal deterioration of the polyimide film at the time of firing and which is less colored can be obtained.

The liquid crystal alignment film formed by the liquid crystal alignment treatment agent of the present invention has a low surface roughness value and has a polyimide film having a high yield of ruthenium iodide, and has excellent afterimage characteristics of AC driving, and can suppress accompanying liquid crystal display elements. The liquid crystal alignment film is peeled off or the foreign matter is generated, the transmittance characteristics of the liquid crystal display element are improved, and the power consumption is reduced. The liquid crystal alignment film is used as a photo-alignment treatment method for irradiating the polarized radiation.

<Compound of (A) component>

The liquid crystal alignment treatment agent of the present invention is characterized by comprising a compound represented by the following formula (1) containing the component (A).

[化8]P-X-Q (1)

In the formula (1), P has at least one group in which the same carbon atom is substituted with at least two or more nitrogen atoms, and at least one of the nitrogen atoms is substituted with a carbon atom of 1 to 24 due to heat. A monovalent heat-releasing group is substituted.

X represents a group selected from the group consisting of a single bond, -O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO-, -OCO-, and -S- At least one binding group of the group. Among them, in terms of ease of synthesis, a single bond, -CONH-, -NHCO-, etc. are preferred.

Q represents a benzene ring or a hydrocarbon group having a carbon number of 6 to 24 having a benzene ring.

Examples of Q include a phenyl group, a biphenyl group, a naphthyl group, a tetrahydronaphthyl group, an anthracenyl group, a fluorenyl group, a phenanthryl group

Among them, a phenyl group, a benzyl group, a naphthyl group, a naphthylmethyl group or the like is preferable from the viewpoint of heat resistance and ease of handling.

The compound of the structure represented by the formula (1) is preferably a compound in which the heat-releasing group is an ester group represented by the following formula (2).

(wherein R ² is a hydrocarbon having 1 to 22 carbon atoms).

R ^{2 is} preferably a hydrocarbon having 1 to 14 carbon atoms, more preferably tert-butyl from the viewpoint of high heat detachment ability.

The above P is preferably any one of the following formula (P-1) or (P-2).

(In the formula, S ₁ and S ₂ each independently represent a monovalent organic group having 1 to 6 carbon atoms, and S ₁ and S ₂ may form a ring structure. S ₃ and S ₄ each independently represent a hydrogen atom or carbon. The number 1 to 6 of the monovalent organic group, and S ₃ and S ₄ may form a ring structure. D is a heat-releasing group substituted by a hydrogen atom by heat. * indicates a bonding site with X).

The above P is preferably any one of the following formula (PD-1) or (PD-2).

(wherein * represents a bonding site with X, and D is a thermally detachable group substituted with a hydrogen atom by heat).

Further, the compound represented by the formula (1) is preferably a compound represented by the following formula (3) wherein X in the formula (1) is a single bond and Q is T-Q'.

[12] P-T-Q’ (3)

(wherein P represents a group represented by any one of the above formula (PD-1) or (PD-2), and T represents an alkylene group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or An alkynyl group having 2 to 6 carbon atoms, a hydrogen atom bonded to any of the carbon atoms, may be substituted by any one of a halogen-containing alkyl group, a halogen atom or a hydroxyl group (OH group). Q' represents carbon Number of 6 to 18 aromatic hydrocarbons).

T is preferably a methylene group, an ethylidene group, a trimethylene group or a tetramethylene group, and is particularly preferably a methylene group from the viewpoint of easiness of obtaining a raw material.

Q' is preferably an aromatic hydrocarbon having 6 to 12 carbon atoms, more preferably a phenyl group, a biphenyl group, a naphthyl group or a tetrahydronaphthyl group.

Among them, a phenyl group, a naphthyl group or the like is preferred from the viewpoint of heat resistance and ease of handling.

The compound represented by the formula (3) is preferably a compound represented by the following formula (4-1) or (4-2).

(wherein P and T are the same definitions as described above).

Specific examples of the compound having a structure represented by the formula (1) or (3) include compounds of the following formula (A-1) or (A-2).

The component (A) is preferably at least one compound selected from the group consisting of the above formulas (A-1) and (A-2). Among them, a compound of (A-1) is more preferable.

The amount of the compound represented by the formula (1) represented by the formula (1) is not particularly limited, but if it is too large, there is a possibility that the alignment property of the liquid crystal is inhibited, and when it is too small, the effects described in the present invention are not obtained. Hey. Therefore, the amount of the compound of the structure represented by the formula (1) is preferably at least one polymer selected from the group consisting of a polyimide precursor and a polyimine. It is 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, still more preferably 1 to 10% by mass.

<Method for Producing Compound of (A) Component>

The compound of the component (A) can be produced, for example, by the following method.

This reaction is to make compound (A-1) with dialkyl dicarbonate, dicarbonic acid The diarylalkyl ester or halide is reacted to produce a reaction of the compound (A).

In the above reaction formula, S ₁ , S ₂ , Q and D are the same as defined above.

The dialkyl dicarbonate which can be used in the present reaction may, for example, be di-t-butyl dicarbonate or di(9-fluorenylmethyl)dicarbonate.

Examples of the halide include t-butoxycarbonyl chloride and 9-fluorenylmethylcarbonyl chloride.

The amount of the dialkyl dicarbonate, the diaralkyl dicarbonate or the halide is from 1.0 to 3.0 mol equivalents, preferably from 1.0 to 2.5 mol, based on 1.0 mol equivalent of the compound (A-1). Ear equivalent.

Further, dialkyl dicarbonate, diaryl dicarbonate or a halide may be used singly or in combination.

In the above reaction, a base may be added as needed. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, and sodium hydride; pyridine, 4-dimethylaminopyridine, and triethyl An organic base such as an amine, tributylamine, N,N-dimethylaniline or 1,8-diazabicyclo[5.4.0]-7-undecene; butyllithium, s-butyllithium Organic lithiums such as lithium diisopropyl decylamine, lithium bis(trimethyldecyl) decylamine; metal alkane such as sodium methoxide, sodium ethoxide or t-butoxide; Oxide and the like. Among them, a base such as 4-dimethylaminopyridine, pyridine or triethylamine is preferred.

The base may be from about 0 to 10 mol equivalents, preferably from 0 to 3 mol equivalents, based on 1.0 molar equivalents of the compound (A-1).

The reaction solvent is stable under the reaction conditions, and It is not particularly limited as it is inactive without hindering the reaction, and examples thereof include diethyl ether, methyl-t-butyl ether, tetrahydrofuran, diethyl ether, dimethoxymethane, and diethoxymethane. , ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl Ethers such as ether, triethylene glycol dimethyl ether, 1,4-dioxane, anisole, etc.; acetone, methyl ethyl ketone, diethyl ketone, 2-pentanone, methyl isobutyl Ketones such as ketones and cyclohexanone; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, decane; dichloromethane, chloroform, tetrachloride Halogenated hydrocarbons such as carbon, dichloroethane, tetrachloroethylene, etc.; benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, nitrobenzene, tetrahydrogen An aromatic hydrocarbon such as naphthalene; a nitrile such as acetonitrile or propionitrile; an ester of methyl acetate, ethyl acetate, butyl acetate or ethyl propionate; N,N-dimethylformamide, N , phthalamides such as N-dimethylacetamide and N-methylpyrrolidone; 1,3 - Benzyltetrahydroimidazolidone, N, N, N', N'-tetramethylurea, etc.; pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 5-ethyl- Pyridines such as 2-methylpyridine. These can be used singly or in combination. Among them, a halogenated hydrocarbon is preferred, and more preferably dichloromethane.

The reaction (A) produced by (A-1) can be carried out in a wide temperature range. However, a suitable temperature range in consideration of the production economy including the amount of use of the reaction reagent is usually -80 to 100 ° C, particularly preferably -20 to 50 ° C. Moreover, it can also be carried out at room temperature.

The reaction time varies depending on the amount of the reagent to be used, the concentration, the reaction temperature, and the like. However, the reaction time is usually set to be 0.1 to 20 hours, preferably 0.5 to 10 hours.

Further, in the formula (1), a compound having a group (P-2) (S ₃ and S ₄ are hydrogen atoms) can be obtained by the above scheme.

For example, by using, for example, toluene, dichloromethane, chloroform, 1,2-dichloroethane, methanol, ethanol, diethyl ether, t-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran , 1,4-dioxane, ethyl acetate, N,N-dimethylformamide, acetic acid, acetonitrile, water or a mixture of any of these as a solvent, such that formula (A-2) In the above, D represents the same definition as described above, and R _a represents _a compound represented by a lower alkyl group such as _a methyl group or an ethyl group, and an equivalent formula of 1 to 50 equivalents (A-3) [wherein Q represents the above a compound represented by the same meaning] or a salt thereof, if necessary, in the presence of 1 to 20 equivalents of a base such as potassium carbonate, sodium hydrogencarbonate, triethylamine, diisopropylethylamine or pyridine at 0 ° C The reflux temperature range of the solvent is obtained by reacting for 5 minutes to 24 hours.

Further, an additive can be used for the purpose of promoting the reaction rate. Examples of the additive include N-iodosuccinimide and the like.

Some of the compounds represented by the above formulas (A-2) and (A-3) are known compounds, and some of them are commercially available. Further, it may be easily obtained by a general synthesis method of a known first-grade amine.

The reaction in the case of producing the compound of the component (A) can be carried out in a batch form or in a continuous form, and can be selected depending on the substrate concentration, conversion ratio, productivity, and the like required for the reaction.

After the completion of the reaction, the target product may be directly obtained by distilling off the solvent as needed, followed by distillation, or by washing the crude reactant with water and a solvent which is not mixed with water, and then performing distillation and column chromatography from the organic layer. The general method is treated to purify/separate the compound of the target (A).

<(B) Polyimine precursor and polyimine >

The component (B) contained in the liquid crystal alignment agent of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and a quinone imidized polymer.

<Polyimide precursor>

The polyimine precursor of the present invention has a structural unit represented by the following formula (B).

In the formula (B), X ₁ is a tetravalent organic group, and Y ₁ is a divalent organic group. R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and each of A ₁ to A ₂ is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and an alkyl group having 2 to 10 carbon atoms. A base or an alkynyl group having 2 to 10 carbon atoms.

Specific examples of the alkyl group in R ₁ include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, and an n-pentyl group. Wait. From the viewpoint of being easily imidized by heating, R _{1 is} preferably a hydrogen atom or a methyl group.

In the formula (B), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, and the structure thereof is not particularly limited. In the polyimine precursor, X ₁ may be mixed in two or more kinds. In the specific example of X ₁ , the structures of the formulas (X-1) to (X-44) disclosed in pages 11 to 12 of WO (International Publication) 2013/054858 (2013.4.18 publication) are mentioned.

R ₂₁ to R ₂₄ in the above formula (X-1) are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a carbon number of 2 to 6. Alkynyl, or phenyl. When R ₂₁ to R ₂₄ are in a large structure, there is a possibility that the liquid crystal alignment property is lowered, and therefore it is more preferably a hydrogen atom, a methyl group or an ethyl group; particularly preferably a hydrogen atom or a methyl group.

In the formula (B), from the viewpoint of availability of the monomer, X ₁ preferably contains a structure selected from (X-1) to (X-14).

The selected in the (X-1) above ~ (X-14) configured preferred ratio, more lines X ₁ 20 mole% of the whole, more preferably not less than 60 mole%, and more preferably 80 mole% the above.

In the formula (B), A ₁ and A ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, or may have The alkynyl group having 2 to 10 carbon atoms of the substituent.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the alkenyl group include a structure in which one or more CH ₂ -CH ₂ groups present in the above-mentioned alkyl group are substituted with a CH=CH structure, and more specifically, a vinyl group, an allyl group, a 1-propenyl group, and an isopropylene group. A group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group or the like. Examples of the alkynyl group include a structure in which one or more CH ₂ -CH ₂ groups present in the above-mentioned alkyl group are substituted with a C≡C structure, and more specifically, an ethynyl group, a 1-propynyl group, or a 2-propynyl group. Wait.

The above alkyl group, alkenyl group and alkynyl group may have a substituent, and further, a ring structure may be formed by a substituent. Further, the formation of a ring structure by a substituent means that the substituents or the substituents are bonded to one of the parent skeletons to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, and an anthracene group. Amine, alkyl, alkenyl, alkynyl and the like.

The halogen group of the substituent may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The aryl group of the substituent may, for example, be a phenyl group. The above substituent may be further substituted on the aryl group.

The organooxy group of the substituent can be represented by the structure represented by O-R. The R may be exemplified by the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group or the like. The above substituents may be further substituted on the above R. Specific examples of the organic oxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyl group. Oxyl, hexyloxy, heptyloxy, octyloxy and the like.

The organothio group of the substituent can be represented by the structure shown by -S-R. The R may be exemplified by the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group or the like. The above substituents may be further substituted on the above R. Specific examples of the organic sulfur group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, an octylthio group and the like.

The organoalkylene group of the substituent can be represented by a structure represented by -Si-(R) ₃ . The R may be the same or different from the above-mentioned alkyl group, alkenyl group, alkynyl group, aryl group or the like. The above substituents may be further substituted on the above R. Specific examples of the organic decyl group include a trimethyl decyl group, a triethyl decyl group, a tripropyl decyl group, a tributyl decyl group, a tripentyl decyl group, a trihexyl decyl group, and a pentyl dimethyl decane. Base, hexyl dimethyl decyl, and the like.

The thiol group of the substituent can be represented by a structure represented by -C(O)-R. The R may be exemplified by the above-mentioned alkyl group, alkenyl group, aryl group or the like. The above substituents may be further substituted on the above R. Specific examples of the mercapto group include a mercapto group, an ethenyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a benzamidine group, and the like.

The ester group of the substituent can be represented by a structure represented by -C(O)O-R or -OC(O)-R. The respective R may be exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. The above substituents may be further substituted on the above R.

The thioester group of the substituent can be represented by a structure represented by -C(S)O-R or -OC(S)-R. The R can be exemplified by the aforementioned alkyl group, Alkenyl, alkynyl, aryl, and the like. The above substituents may be further substituted on the above R.

The phosphate group of the substituent can be represented by a structure represented by -OP(O)-(OR) ₂ . The respective R, which may be the same or different, are exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. The above substituents may be further substituted on the above R.

The substituent amide group can be -C(O)NH ₂ , or -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , -NRC(O)R The configuration shown is shown. The respective R, which may be the same or different, are exemplified by the aforementioned alkyl group, alkenyl group, alkynyl group, aryl group and the like. The above substituents may be further substituted on the above R.

The aryl group of the substituent may be the same as the aryl group described above. The above substituent may be further substituted on the aryl group.

The alkyl group of the substituent may be the same as the alkyl group described above. The above substituent may be further substituted on the alkyl group.

The alkenyl group of the substituent may be the same as the above-mentioned alkenyl group. The above substituent may be further substituted on the alkenyl group.

The alkynyl group of the substituent may be the same as the alkynyl group described above. The above substituent may be further substituted on the alkynyl group.

In general, when a large structure is introduced, there is a possibility that the reactivity of the amine group or the liquid crystal alignment property is lowered. Therefore, A ₁ and A _{2 are more} preferably a hydrogen atom or a carbon number of 1 to 5 which may have a substituent. An alkyl group; particularly preferably a hydrogen atom, a methyl group or an ethyl group.

In the formula (B), Y ₁ is a divalent organic group derived from a diamine, and the structure thereof is not particularly limited. Specific examples of the Y ₁ structure include (Y-1) to (Y-114) and the following formula (Y-115) disclosed in pages 13 to 18 of WO 2014/010402 (2014.1.16 publication). ~(Y-122).

In (Y-117), j is an integer from 0 to 3. In (Y-120), n2 and n3 are each independently an integer of 1 to 3.

When the liquid crystal alignment property or the pretilt angle of the liquid crystal alignment film to be obtained is further provided, the group having the Y ₁ structure is preferably at least one group selected from the group consisting of the following formulas (5) and (6).

In the formula (5), R ₁₂ is a single bond or a divalent organic group having 1 to 30 carbon atoms, and R ₁₃ is a hydrogen atom, a halogen atom or a monovalent organic group having 1 to 30 carbon atoms. a is an integer of 1 to 4, and when a is 2 or more, R ₁₂ and R ₁₃ may be the same or different from each other. R ₁₄ in the formula (6) is a single bond, -O-, -S-, -NR ₁₅ -, a guanamine bond, an ester bond, a urea bond, or a divalent organic group having a carbon number of 1 to 40, and R ₁₅ is A hydrogen atom or a methyl group.

The linear structure is high, and when it is used as a liquid crystal alignment film, the alignment of the liquid crystal can be improved. Therefore, Y _{1 is more} preferably Y-7, Y-21~Y-23, Y-25, Y-43~Y-46, Y. -48, Y-63, Y-71~Y-75, Y-98~Y-100 or Y-118.

The ratio of the above structure which can improve the liquid crystal alignment property is preferably 20 mol% or more, more preferably 60 mol% or more, and still more preferably 80 mol% or more of the entire Y ₁ .

When the liquid crystal alignment film is to have a high pretilt angle of the liquid crystal, Y ₁ preferably has a structure in which a side chain has a long-chain alkyl group, an aromatic ring, an aliphatic ring, a steroid skeleton, or a combination thereof. Such Y _{1 is} preferably any of Y-76 to Y-97. Purports pretilt angle of the above-described configuration of the high proportion of all of Y ₁ is preferably 1 to 30 mole%, more preferably from 1 to 20 mole%.

Further, when a polymer having a photo-alignment side chain of a polyimine (precursor) is used as the component (B), it is preferred to use a polyimide (precursor) having a photoreactive side chain. For example, the photoreactive side chain represented by the formula (b) in [0033] to [0041] disclosed in pages 14 to 17 of the International Publication No. WO2014/142168 (published on Sep.

Further, it can also be used in a polyimide intermediate precursor having a photo-alignment group in the main chain. For example, the formula [4] in [0075] to [0080] disclosed in pages 54 to 57 of International Publication WO2013/002345 (2013.1.13 publication) is mentioned.

The polyimine precursor used in the present invention is obtained by a reaction of a diamine component and a tetracarboxylic acid derivative, and examples thereof include polyglycine or polydecylamine.

<Method for Producing Polymer of (B) Component>

The method for producing polylysine is, for example, obtained by the method of [0096] to [0102] disclosed in WO-28/092170 (2014.6.19). The polyglycolate is obtained, for example, by the method [0074] to [0088] disclosed in pages 19 to 22 of WO 2014/010402 (2014.1.16).

The method for producing a polyimine is, for example, obtained by the method of [0103] to [0106] disclosed in 27 to 30 of WO 2014/092170 (2014.6.19).

<Liquid alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film) containing (A) component (hereinafter referred to as a specific compound) and component (B) (hereinafter) There is a coating solution for forming a liquid crystal alignment film, which is called a specific polyimine polymer.

The ratio of the specific compound of the component (A) in the liquid crystal alignment agent of the present invention is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the specific polyamidimide polymer of the component (B). More preferably, it is 0.5 to 15 parts by mass.

All of the polymer components in the liquid crystal alignment agent of the present invention may be all polymers of the component (B) or may be mixed with other polymers. Other examples of the polymer include a cellulose polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamine, polyoxyalkylene, and the like. In this case, the content of the polymer other than the polymer is preferably 0.5 to 15 parts by mass based on 100 parts by mass of the specific polyimine-based polymer of the present invention. Especially preferably 1 to 10 parts by mass.

Further, the content of the solvent in the liquid crystal alignment agent of the present invention is preferably from 76 to 99.5% by mass, more preferably from 80 to 99% by mass. The content of the solvent can be appropriately changed depending on the coating method of the liquid crystal alignment treatment agent or the target liquid crystal alignment film thickness.

The solvent used in the liquid crystal alignment treatment agent of the present invention is a solvent (also referred to as a good solvent) which dissolves the specific compound of the component (A) of the present invention and the specific polyimine polymer of the component (B). There is no special limit. The following series of specific examples of good solvents, but not limited to These examples are limited.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and dimethyl Kea, γ -butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone Wait.

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ -butyrolactone is particularly preferred.

Further, when the specific compound and the specific polyimine-based polymer have high solubility in a solvent, it is preferred to use a solvent represented by the following formula [D-1] to formula [D-3].

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

The good solvent in the liquid crystal alignment treatment agent of the present invention is preferably 20 to 99% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent. Among them, 20 to 90% by mass is preferred. More preferably 30 to 80% by mass.

In the liquid crystal alignment treatment agent of the present invention, a solvent (also referred to as a poor solvent) for improving the coating property or surface smoothness of the liquid crystal alignment film after applying the liquid crystal alignment treatment agent can be used as long as the effect of the present invention is not impaired. Specific examples of the poor solvent include those disclosed in pages 27 to 28 of International Publication WO2014/084362 (published on Apr. 2014). The solvent shown in paragraph [0057]. The amount of the poor solvent is preferably from 1 to 90% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent. Among them, 1 to 80% by mass is preferred. More preferably 5 to 70% by mass.

In the liquid crystal alignment treatment agent of the present invention, an epoxy group, an isocyanate group or an oxetane group may be further selected from the group consisting of a cyclic carbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. A crosslinkable compound having at least one substituent or a crosslinkable compound having a polymerizable unsaturated bond. These substituents or polymerizable unsaturated bonds must have two or more of the crosslinkable compounds. Specific examples include the crosslinking agents shown in paragraphs [0192] to [0232] disclosed in pages 44 to 54 of International Publication No. WO2014/092126 (published on Apr. 2014).

The above compound is an example of a crosslinkable compound, and is not limited thereto. Further, the crosslinkable compound to be used in the liquid crystal alignment agent of the present invention may be one type or two or more types.

In the liquid crystal alignment treatment agent of the present invention, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. In particular, in order to carry out the crosslinking reaction, the effect of exhibiting the object is preferably 0.1 to 100 parts by mass based on 100 parts by mass of all the polymer components. More preferably 1 to 50 parts by mass.

The liquid crystal alignment treatment agent of the present invention can be used as long as it does not impair the effects of the present invention, and can improve the film thickness uniformity or surface smoothness of the liquid crystal alignment film after applying the liquid crystal alignment treatment agent.

Examples of the compound which improves the film thickness uniformity or surface smoothness of the liquid crystal alignment film include a fluorine-based surfactant, a polyfluorene-based surfactant, and a non-ionizing agent. Subsystem surfactants, etc.

More specifically, Eftop EF301, EF303, EF352 (above, Tokem Products Co., Ltd.), Megafac F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (above, Sumitomo 3M Company), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).

The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent.

Further, in the liquid crystal alignment treatment agent of the present invention, the inclusion of the formula [M1] to the formula [M156] disclosed in pages 69 to 73 of International Publication WO2011/132751 (2011.10.27 publication) may be added. The nitrogen heterocyclic amine compound serves as a compound which promotes charge removal in the liquid crystal alignment film and promotes charge removal of the element. The amine compound may be added directly to the liquid crystal alignment agent, but it is preferably added in a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass, in a suitable solvent. The solvent is not particularly limited as long as it dissolves the specific compound and the specific polyimine-based polymer.

In the liquid crystal alignment treatment agent of the present invention, 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 promotes charge removal, The range that impairs the effects of the present invention can also be added to change The dielectric property or electrical conductivity of the liquid crystal alignment film is an intended dielectric or conductive material.

The method for preparing the liquid crystal alignment treatment agent of the present invention is not particularly limited. For example, a method of mixing the component (B) in a solution in a solvent to dissolve the component (B) in a specific ratio to form a homogeneous solution, or further adding the above-mentioned crosslinkable compound as needed at an appropriate stage of the preparation method may be mentioned. A method of increasing the film thickness uniformity or surface smoothness of a resin film or a liquid crystal alignment film, a compound for promoting charge removal, a dielectric or a conductive material, and the like.

In the preparation of the liquid crystal alignment treatment agent of the present invention, a solution of a polymer of the component (B) obtained by polymerization in a solvent can be used as it is. In this case, for example, in the solution of the component (B), the component (A) or the like is added in the same manner as described above to form a homogeneous solution. At this time, it is also possible to further add a solvent for the purpose of concentration adjustment. In this case, the solvent used in the formation of the component (B) and the solvent used for the concentration adjustment of the cured film-forming composition may be the same or different.

Further, the solution of the liquid crystal alignment agent to be prepared is preferably filtered using a filter having a pore size of about 0.2 μm or the like.

<Liquid alignment film/liquid crystal display element>

In the liquid crystal alignment film of the present invention, the liquid crystal alignment treatment agent is applied onto a substrate, dried, and fired. The substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a tantalum nitride substrate, or the like may be used, and an acrylic substrate or a polycarbon may be used. A plastic substrate such as an acid ester substrate. In this case, when a substrate for forming an ITO electrode or the like for driving a liquid crystal is used, it is preferable from the viewpoint of process simplification. Further, in the reflective liquid crystal display device, if only one side substrate is used, an opaque material such as a germanium wafer may be used, and in this case, a material such as aluminum that reflects light may be used.

The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, it is generally a method of performing screen printing, lithography, flexographic printing, inkjet method, or the like. Other coating methods include a dipping method, a roll coating method, a slit coating method, a spinner method, a spray method, and the like, and these can be used according to the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, the solvent can be evaporated by a heating means such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven to obtain a liquid crystal alignment film. The drying and baking steps after applying the liquid crystal alignment agent of the present invention may be selected to any temperature and time. Usually, in order to sufficiently remove the solvent contained, it can be baked at 50 to 120 ° C for 1 to 10 minutes, and then baked at 150 to 300 ° C for 5 to 120 minutes. The thickness of the liquid crystal alignment film after firing is not particularly limited. However, when the thickness is too small, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 200 nm.

The rubbing treatment method, the optical alignment treatment method, and the like may be mentioned as a method of aligning the obtained liquid crystal alignment film.

Specific examples of the photo-alignment treatment method include radiation that is irradiated in a predetermined direction on the surface of the liquid crystal alignment film, and further heat-treated at a temperature of 150 to 250 ° C, preferably 230 to 250 ° C, depending on the case. A method of imparting liquid crystal alignment (also referred to as liquid crystal alignment ability). The radiation is preferably an ultraviolet ray having a wavelength of 100 to 800 nm, more preferably 100 to 400 nm, particularly preferably 200 to 400 nm.

Further, in order to improve the liquid crystal alignment property, the substrate coated with the liquid crystal alignment film may be heated while being heated at 50 to 250 ° C, preferably 230 to 250 ° C. Further, the irradiation amount of the radiation is preferably from 1 to 10,000 mJ/cm ² , more preferably from 100 to 5,000 mJ/cm ² . The liquid crystal alignment film produced in this manner can stably align liquid crystal molecules in a certain direction.

Further, the liquid crystal alignment film irradiated with the polarized radiation can be subjected to a contact treatment using water or a solvent by the above-described method. The solvent to be used in the contact treatment is not particularly limited as long as it dissolves the decomposition product generated from the liquid crystal alignment film by radiation. Specific examples thereof include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, and butyl. Celluloid, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, and the like. Among them, water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate is preferred from the viewpoint of versatility or solvent safety. More preferably, it is water, 1-methoxy-2-propanol or ethyl lactate. These solvents may be used alone or in combination of two or more.

The contact treatment may be immersion treatment or spray treatment (also referred to as spray treatment). The treatment time is effective in dissolving the decomposition product generated from the liquid crystal alignment film by radiation, and is preferably Immersion treatment is carried out for 10 seconds to 1 hour, more preferably 1 to 30 minutes. Further, the solvent temperature during the contact treatment may be normal temperature or heating, preferably 10 to 80 ° C, more preferably 20 to 50 ° C. Further, from the viewpoint of the solubility of the decomposed product, ultrasonic treatment or the like may be performed as needed.

After the contact treatment, it is preferably subjected to washing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone (also referred to as rinsing) or firing of a liquid crystal alignment film. . At this time, either or both of the rinsing and firing may be performed. The firing temperature is preferably from 150 to 300 °C. Among them, 180 to 250 ° C is preferred, and more preferably 200 to 230 ° C. Further, the firing time is preferably from 10 seconds to 30 minutes, more preferably from 1 to 10 minutes.

The liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film of a liquid crystal display element of a horizontal electric field type such as an IPS (In-Plane Switching) driving method or a fringe electric field switching (also referred to as FFS) method, and is particularly useful as an FFS method. A liquid crystal alignment film of a liquid crystal display element.

In the liquid crystal display device of the present invention, a liquid crystal cell having a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is obtained, and a liquid crystal cell is produced by a known method and obtained by using the liquid crystal cell.

As an example of a method of fabricating a liquid crystal cell, a liquid crystal display device having a passive matrix structure will be described as an example. Further, a liquid crystal display element having an active matrix structure of a switching element such as a TFT (Thin Film Transistor) may be provided in each pixel portion constituting the image display.

Specifically, a transparent glass substrate is prepared, a common electrode is provided on one of the substrates, and a segment electrode is provided on the other substrate. Such electrodes can be, for example, ITO electrodes, patterned to provide the desired image display. Next, an insulating film is provided on each of the substrates so as to cover the common electrode and the segment electrodes. The insulating film may be, for example, a film of SiO ₂ -TiO ₂ formed by a sol-gel method. Next, a liquid crystal alignment film is formed on each of the substrates under the conditions described above, and the other substrate is laminated on one of the substrates so that the liquid crystal alignment film faces of each other face each other, and the periphery is sealed with a sealant. In order to control the substrate gap, a spacer is usually mixed in advance in the sealant system. Further, it is preferable that the inter-substrate portion for controlling the substrate gap is also dispersed in advance in the in-plane portion where the sealant is not provided. In one part of the sealant, an opening portion which can fill the liquid crystal from the outside is provided in advance.

Thereafter, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant by being provided in the opening of the sealant. Thereafter, the opening is sealed with an adhesive. The injection can be performed by a vacuum injection method or a method of utilizing a capillary phenomenon in the atmosphere. As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material can be used. Next, the setting of the polarizing plate is performed. Specifically, a pair of polarizing plates are attached to the surface of the two substrates opposite to the liquid crystal layer.

By using the liquid crystal alignment treatment agent of the present invention, it is possible to obtain a liquid crystal alignment film capable of suppressing peeling of a liquid crystal alignment film or generation of foreign matter accompanying physical etching of a liquid crystal display element. Further, a liquid crystal alignment film capable of improving the transmittance characteristics of the liquid crystal display element and reducing the power consumption of the liquid crystal display element can be obtained. Also, a low surface roughness value can be obtained, and the imine Since the polyimine film having a high rate of conversion has a liquid crystal alignment film excellent in the afterimage characteristics of the AC drive. In particular, it is useful for a liquid crystal alignment film for a photo-alignment treatment method obtained by irradiating a polarized radiation. 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 can be suitably used for a large-screen and high-definition liquid crystal television, a small and medium-sized smart phone, a tablet terminal, or the like. .

[Examples]

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

In addition, the ¹ H-NMR measurement apparatus and measurement conditions are as follows.

Device: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz

Solvent: Hydrogenated chloroform (CDCl3)

Reference material: tetramethyl decane (TMS)

Cumulative number: 8

[Synthesis Example 1] Synthesis of X-1

In a 200 mL four-necked flask equipped with a magnetic stirrer, 73.2 g of methyl chloride, 4.00 g (13.8 mmol) of N,N'-bis(tert-butoxycarbonyl)-S-methylisothiourea, and benzyl group were placed. 1.77 g (1.2 eq) of amine and 2.83 g (2.0 eq) of triethylamine (Et ₃ N). After nitrogen substitution, N-iodosuccinimide (NIS) 3.10 g (1.0 eq) was added to the chamber. Stir in the warm. After 3 hours, 2.22 g (1.5 eq) of benzylamine, 1.54 g (1.0 eq) of N-iodosuccinimide (NIS), and 1.39 g (1.0 eq) of triethylamine (Et ₃ N) were added. Reaction for 40 hours. After completion of the reaction, the methyl chloride layer was washed twice with a 1.0 M aqueous sodium thiosulfate solution (50 ml) and twice with 0.5 M aqueous hydrochloric acid (50 ml). Thereafter, the mixture was washed twice with pure water (100 ml) to recover a methyl chloride layer. The recovered methyl chloride layer was concentrated under reduced pressure to recover yellow crystals, which was dissolved in 28.7 g of methanol at 50 °C. Then, recrystallization was carried out under ice-cooling to obtain (X-1) 3.02 g. (Yield: 63%, trait: white crystal)

¹ H-NMR (400 MHz) in CDCl ₃ : 11.5 ppm (S, 1H), 8.59 ppm (s, 1H), 7.37-7.27 ppm (m, 5H), 4.64 ppm (d, J = 1.2 Hz, 2H), 1.51 Ppm(s,9H), 1.49ppm(s,9H)

[Synthesis Example 2] Synthesis of X-2

In a 100 mL four-necked flask equipped with a magnetic stirrer, 29.4 g of N,N-dimethylformamide, 5.88 g (23.8 mmol) of naphthylpyrazine hydrochloride, and triethylamine (Et ₃ ) were placed. N) 2.65 g (1.1 eq), 1.80 g (1.1 eq) of di-tert-butyl dicarbonate (Boc ₂ O) dissolved in 11.8 g of N,N-dimethylformamide was added dropwise under ice cooling. After dripping, the temperature was raised to room temperature, and the reaction was carried out for 1 hour. After completion of the reaction, the mixture was diluted with 120 g of ethyl acetate, washed once with 120 g of a 0.3 M aqueous hydrochloric acid solution, and washed twice with 120 g of pure water. By concentrating the separated organic phase, a yellow oily compound is obtained. The obtained oily compound was purified by a silica gel column (ethyl acetate / hexane = 1 / 1 vol) to obtain (X-2) 3.57 g (yield: 48%, trait: pale yellow oily compound) ).

¹ H-NMR (400 MHz) in CDCl ₃ : 7.95 ppm (d, J = 8.4 Hz, 1H), 7.85 ppm (d, J = 7.6 Hz, 1H), 7.76 ppm (d, J = 8.0 Hz, 1H), 7.51-7.33 ppm (m, 3H), 7.33 ppm (d, J = 6.8 Hz, 1H), 4.48 ppm (s, 2H), 3.85-3.83 ppm (m, 2H), 3.77-3.75 (m, 2H), 1.37ppm (s, 9H).

[Synthesis Example 3] Synthesis of Z-3

In a 300 mL four-necked flask equipped with a magnetic stirrer, 12.7 g (56.6 mmol) of 2-undecyl imidazoline was suspended in 76.2 g of chloroform, heated to 50 ° C, and di-tert dicarbonate diluted with 12.7 g of chloroform was added dropwise. Butyl ester (Boc ₂ O) 13.1 g (1.05 eq) was stirred at the same temperature. After 3 hours, 2.47 g (0.20 eq) of di-tert-butyl dicarbonate (Boc ₂ O) was added, and the reaction was further carried out for 1 hour. After completion of the reaction, the insoluble matter was removed from the reaction solution by filtration, and chloroform was distilled off under reduced pressure. The residue was diluted with 76.8 g of ethyl acetate and washed three times with 50.9 g of purified water, and the organic phase was dried over sodium sulfate. Then, 0.62 g of activated carbon (special egret dry product, manufactured by Nippon Enviro Chemicals Co., Ltd.) was added to the organic phase, and the mixture was stirred at room temperature for 30 minutes, and filtered and dried to recover a pale yellow oily compound (crude). The obtained crude product was purified by a silica gel column (ethyl acetate / hexane = 1 / 1 vol) to afford (Z-3) 10.8 g (yield: 59%, s.

¹ H-NMR (400 MHz) in CDCl ₃ : 3.73 ppm (s, 4H), 2.67 ppm (t, J = 7.6 Hz, 2H), 1.66-1.60 ppm (m, 2H), 1.49 ppm (s, 9H), 1.37-1.25ppm (m, 16H), 0.88ppm (t, J = 7.2Hz, 3H).

The abbreviations of the compounds used are as follows.

<The monomer used to make the polyimine polymer>

(tetracarboxylic acid component)

<specific compound>

<solvent>

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BCS: ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

<Measurement of molecular weight of polyamidene-based polymer>

The molecular weight of the polyimine precursor and the polyimine is a normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD-805). Shodex company, as measured in the following manner.

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (additive is lithium bromide-hydrate (LiBr.H ₂ O) 30 mmol/L (liter), phosphoric acid. anhydrous crystal (o-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) ) 10ml / L)

Flow rate: 1.0ml/min

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

<Measurement of imidization ratio of polythenimine>

20 mg of polyimine powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, 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 thereto to completely dissolve. This solution was measured for proton NMR at 500 MHz by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Ltd.). The ruthenium imidization rate determines the protons from the unaltered structure before and after the imidization as the reference proton, and uses the peak integral value of the proton and the proton peak derived from the NH group of proline in the vicinity of 9.5 to 10.0 ppm. The integral value is obtained by the following formula.

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

In the formula, x is the integral value of the proton peak derived from the NH group of proline, y is the peak integral value of the reference proton, and α is the case of polyproline (the imidization ratio is 0%), and the reference proton is relatively The ratio of the number of NH protons in one proline.

<Production of liquid crystal cell>

A liquid crystal cell was produced in the following manner using each liquid crystal alignment treatment agent.

After the liquid crystal alignment treatment agent was filtered through a 1.0 μm filter, the thickness of the ITO electrode having the film thickness of 50 nm as the electrode of the first layer and the thickness of the second layer as the insulating film were formed on the glass substrate by spin coating. A glass substrate of an FFS driving electrode having 500 nm of tantalum nitride and a third layer of an ITO electrode (electrode width: 3 μm, electrode spacing: 6 μm, electrode height: 50 nm) as an electrode, coated with a liquid crystal alignment treatment agent . It Thereafter, the film was dried on a hot plate at 80 ° C for 5 minutes, and then fired in a hot air circulating oven at 250 ° C for 60 minutes to form a coating film having a film thickness of 100 nm.

The coating film formed by the liquid crystal alignment treatment agents of Production Example 1, Production Examples 3 to 6, Production Examples 9 to 14, and Comparative Production Examples 1 to 5 was irradiated with a polarizing plate at a wavelength of 500 mJ/254 at a wavelength of 254 nm. Cm ² , a substrate with a liquid crystal alignment film was obtained. Further, a coating film was formed in the same manner as the glass substrate having the columnar spacer having a height of 4 μm in which the electrode was not formed as the counter substrate, and the alignment treatment was performed.

Further, the polyimide film formed of the liquid crystal alignment treatment agents of Production Example 2, Production Example 7, and Production Examples 15 to 18 was rubbed with a rubbing cloth (roller diameter: 120 mm, number of revolutions: 1000 rpm, moving speed: 20 mm/sec). After a pushing depth of 0.4 mm, ultrasonic irradiation was performed for 1 minute in pure water, and drying was carried out at 80 ° C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Further, a coating film was formed in the same manner as the glass substrate having the columnar spacer having a height of 4 μm in which the electrode was not formed as the counter substrate, and the alignment treatment was performed.

In the substrate with the ITO transparent electrode with the liquid crystal alignment film subjected to the above-described photoalignment treatment or rubbing alignment treatment, two substrates subjected to the same treatment are prepared, and the two substrates are grouped and printed on the substrate. In the sealant, the other substrate is bonded to each other with the liquid crystal alignment film faces facing each other, and the alignment direction is 0°, and then the sealant is cured to form an empty cell. Liquid crystal cells MLC-2041 (manufactured by Merck Japan Co., Ltd.) were injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain an FFS liquid crystal cell.

<Evaluation of friction treatment tolerance>

The substrate with the ITO transparent electrode with the liquid crystal alignment film subjected to the above-described photoalignment treatment or rubbing treatment is subjected to a rubbing treatment. Specifically, the liquid crystal alignment film surface of the substrate with the ITO transparent electrode subjected to such treatment is used, and the rubbing treatment device having a drum diameter of 120 mm is used, and the number of rotations of the drum is 500 rpm, and the speed of the drum is 20 mm. /sec, pressing distance: 0.6 mm conditions for rubbing treatment.

The surface state of the obtained liquid crystal alignment film was observed using a confocal laser microscope. Specifically, the surface of the liquid crystal alignment film near the center of the substrate was observed at a total of five points by a confocal laser microscope set at a magnification of 100 times, and the friction scar was confirmed from the range of about 6.5 mm square of the observation field. The average value of the amount of friction shavings (attachment) was used to evaluate the friction treatment resistance. Furthermore, the evaluation criteria are as follows.

(assessment basis)

A: 20 or less of scars or shavings

B: 20~40 scars or shavings

C: 40 or more scratches or shavings

Furthermore, the closer the evaluation reference is to A, that is, the less the friction scar or the friction shaving, the more excellent the rubbing treatment resistance. The results are shown in Tables 5-7.

<transmittance rate>

On the quartz substrate, the formation was performed as described above (the liquid crystal cell system) The same alignment treatment of the liquid crystal alignment film. The transmittance of the obtained coating film was measured using an ultraviolet-visible spectrophotometer (UV-3100PC) manufactured by Shimadzu Corporation, and the average value of the transmittance of 360 to 800 nm was calculated. The larger the value, the better (Tables 5-7 show the results of the evaluation).

<surface roughness>

On the ITO substrate, a liquid crystal alignment film which was subjected to the alignment treatment similar to the above (manufacture of a liquid crystal cell) was formed. The surface of the film of the coating film was observed with an atomic force microscope (L-trace probe microscope) manufactured by SII Technologies, and the center line average roughness (Ra) of the film surface was measured to evaluate the flatness of the film surface. The smaller the value, the better (Tables 5-7 show the results of the evaluation).

<Evaluation of residual images of AC drive>

Using the liquid crystal cell of the aforementioned FFS mode, an alternating voltage of ±10 V was applied at a frequency of 60 Hz for 120 hours in a constant temperature environment of 60 °C. Thereafter, the pixel electrode of the liquid crystal cell is short-circuited with the counter electrode, and in this state, it is left at room temperature for one day.

After being placed, the liquid crystal cell is placed between two polarizing plates arranged orthogonally with the polarization axis, and the backlight is preliminarily illuminated without applying a voltage, and the arrangement angle of the liquid crystal cell is adjusted to minimize the luminance of the transmitted light. . Then, the rotation angle at which the liquid crystal cell is rotated from the second region of the first pixel to the darkest angle to the darkest angle of the first region is calculated as the angle Δ (°). Similarly, the second pixel compares the second region with the first For the area, calculate the same angle △ (°). Then, the average value of the angle Δ (°) between the first pixel and the second pixel is calculated as the angle Δ (°) of the liquid crystal cell. In this evaluation, the smaller the value of the angle Δ(°) of the liquid crystal cell is, the better (the evaluation results are shown in Tables 5 to 7).

<Charge relaxation measurement>

The liquid crystal cell of the FFS method was placed on a light source, and the VT characteristic (voltage-transmittance characteristic) at a temperature of 25 ° C was measured, and then the liquid crystal cell was permeated in a state where a rectangular wave of ±3 V/120 Hz was applied. Rate (Ta). Thereafter, a rectangular wave of ±3 V/120 Hz was applied at a temperature of 25 ° C for 10 minutes, and then a DC of 2 V was superposed and driven for 60 minutes. The DC voltage was cut, and the transmittance (Tb) of the liquid crystal cell when driven by AC driving for 60 minutes was measured, and the voltage remaining in the liquid crystal display element was calculated from the difference (ΔT) from the initial transmittance (Ta). The difference in transmittance. In this evaluation, the smaller the difference (ΔT) of the transmittance, the better (the evaluation results are shown in Tables 5 to 7).

<Synthesis of Polyimine Polymers> [Synthesis Example 4]

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, F2 (3.92 g, 20.0 mmol) was weighed, and NMP (55.8 g) was added thereto, and D1 (2.09 g, 19.3 mmol) was added while stirring under a nitrogen atmosphere. Further, NMP was added so that the solid content concentration became 10% by mass, and the mixture was stirred at 25 ° C for 4 hours to obtain a polyaminic acid solution (1). Polyamine The viscosity of the acid solution at a temperature of 25 ° C is 300 mPa. s. Further, the polyamine had a number average molecular weight of 11,000 and a weight average molecular weight of 23,200.

[Synthesis Example 5]

E2 (6.60 g, 31.0 mmol) and NMP (70.7 g) were weighed in a 100 mL four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, and stirred and dissolved while supplying nitrogen. To the above-mentioned diamine solution, F1 (6.94 g, 31.0 mmol) was added, and NMP was added so that the solid content concentration became 10 mass%, and the mixture was stirred at 25 ° C for 4 hours to obtain a polyaminic acid solution (2). The polyamic acid solution has a viscosity of 300 mPa at 25 ° C. s. Further, the polyamine had a number average molecular weight of 12,000 and a weight average molecular weight of 25,200.

[Synthesis Example 6]

D1 (2.92 g, 27.0 mmol) and A1 (0.71 g, 2.99 mmol) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and NMP (81.8 g) was added thereto, and the mixture was stirred while being fed with nitrogen. It dissolves. F1 (6.46 g, 28.8 mmol) was added to the diamine solution, and NMP was added so that the solid content concentration became 10 mass%, and the mixture was stirred at 25 ° C for 4 hours to obtain a polyaminic acid solution (3). ). The polyamic acid solution has a viscosity of 230 mPa at a temperature of 25 ° C. s. Further, the polyamine has a number average molecular weight of 11,100 and a weight average molecular weight of 30,000.

[Synthesis Example 7]

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, C1 (7.68 g, 36.0 mmol) and E1 (0.61 g, 4.01 mmol) were weighed, and NMP (24.0 g) and γ- BL (6.00 g) were added. The mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, F5 (6.34 g, 32.0 mmol) and γ- BL (12.0 g) were added, and the mixture was stirred at 25 ° C for 2 hours. Thereafter, F6 (1.74 g, 7.98 mmol) was added, and γ- BL was added so that the solid content concentration became 10% by mass, and the mixture was stirred at 25 ° C for 4 hours to obtain a polyaminic acid solution (4). The polyamic acid solution has a viscosity of 460 mPa at a temperature of 25 ° C. s. Further, the polyamine had a number average molecular weight of 12,000 and a weight average molecular weight of 24,000.

[Synthesis Example 8]

B1 (5.97 g, 20.0 mmol) was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and NMP (75.9 g) was added thereto, and the mixture was stirred and dissolved while supplying nitrogen. F3 (5.53 g, 18.8 mmol) was added to the diamine solution, and NMP was added so that the solid content concentration became 10 mass%, and the mixture was stirred at 25 ° C for 4 hours to obtain a polyaminic acid solution (5). ). The polyamic acid solution has a viscosity of 400 mPa at a temperature of 25 ° C. s. Further, the polyamine had a number average molecular weight of 11,500 and a weight average molecular weight of 24,400.

[Synthesis Example 9]

The 500 mL four-necked flask equipped with a stirring device was made into a nitrogen atmosphere. D1 (2.80 g, 25.9 mmol) was added, A1 (1.45 g, 6.11 mmol) was added, and NMP (111 g) and pyridine (6.18 g) were added, and the mixture was stirred and dissolved. Next, this diamine solution was stirred, and F4 (9.89 g, 30.4 mmol) was added, and it reacted at 15 degreeC for 15 hours. Thereafter, propylene chloride (0.38 g) was added and reacted at 15 ° C for 4 hours. The obtained solution of the polyalkyl amide was dropped on water (1230 g) while stirring. Then, the precipitated white precipitate was collected by filtration, and then washed five times with IPA (isopropyl alcohol) (1230 g), and dried to obtain white polyalkyl phthalate powder (10.2 g). The polyalkyl amide had a number average molecular weight of 20,800 and a weight average molecular weight of 41,000. The obtained polyalkyl amide powder (0.80 g) was weighed into a 100 mL Erlenmeyer flask, and γ-BL (7.18 g) was added thereto, and the mixture was stirred at 25 ° C for 24 hours to be dissolved to obtain a polythene having a solid concentration of 10% by mass. Alkylamine solution (6).

[Synthesis Example 10]

A1 (0.47 g, 1.98 mmol) and D2 (4.40 g, 18.0 mmol) were weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and NMP (59.5 g) was added thereto, and the mixture was stirred while being fed with nitrogen. It dissolves. Further, F1 (4.15 g, 18.5 mmol) was added to the diamine solution, and NMP was added so that the solid content concentration became 10% by mass, and the mixture was stirred at 25 ° C for 4 hours to obtain a polyaminic acid solution.

After adding NEP to the obtained polyaminic acid solution (66.0 g), the mixture was diluted to 9 mass%, and acetic anhydride (5.38 g) and pyridine (1.39 g) as a ruthenium catalyst were added, and reacted at 60 ° C for 3 hours. . Put the reaction solution into A In the alcohol (360 ml), the resulting precipitate was filtered off. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (7). The polyimine had a hydrazine imidation ratio of 75%, a number average molecular weight of 10,100, and a weight average molecular weight of 20,500.

[Synthesis Example 11]

D1 (2.16 g, 20.0 mmol) was weighed in a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and NMP (31.6 g) was added thereto, and the mixture was stirred and dissolved while supplying nitrogen. F1 (4.21 g, 18.8 mmol) was added to the diamine solution, and NMP was added so that the solid content concentration became 10 mass%, and the mixture was stirred at 25 ° C for 4 hours to obtain a polyaminic acid solution (8). ). The polyamic acid solution has a viscosity of 250 mPa at a temperature of 25 ° C. s. Further, the polyamine had a number average molecular weight of 11,500 and a weight average molecular weight of 24,400.

[Synthesis Example 12]

E2 (2.78 g, 14.0 mmol) was weighed in a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and NMP (17.4 g) was added thereto, and the mixture was stirred and dissolved while supplying nitrogen. The diamine solution was stirred, and F7 (2.10 g, 6.99 mmol) was added, and the mixture was stirred at 25 ° C for 2 hours. Then, F2 (1.26 g, 6.42 mmol) was added, and NMP was added so that the solid content concentration became 10 mass%, and the mixture was stirred at 25 ° C for 4 hours to obtain a polyaminic acid solution (9). The polyamic acid had a number average molecular weight of 15,200 and a weight average molecular weight of 47,500.

[Synthesis Example 13]

B1 (1.49 g, 5.00 mmol) and D3 (1.43 g, 5.00 mmol) were weighed in a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and NMP (12.0 g) was added thereto, and the mixture was stirred while being fed with nitrogen. It dissolves. This diamine solution was stirred, and F8 (1.25 g, 5.00 mmol) was added, and the mixture was stirred at 25 ° C for 2 hours. Then, F2 (0.98 g, 5.00 mmol) was added, and NMP was added so that the solid content concentration became 10 mass%, and the mixture was stirred at 25 ° C for 4 hours to obtain a polyaminic acid solution (10). The polyamic acid had a number average molecular weight of 12,200 and a weight average molecular weight of 36,100.

After adding NMP to the obtained polyamic acid solution (10.0 g), and diluting it to 5 mass%, acetic anhydride (2.24g) and pyridine (0.87g) which are a ruthenium catalyzing catalyst were added, and it reacted at 50 degreeC for 2 hours. . The reaction solution was poured into methanol (150 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 hydrazine imidation ratio of 50%, a number average molecular weight of 24,800, and a weight average molecular weight of 88,000.

[Synthesis Example 14]

B1 (1.49 g, 5.00 mmol) and D3 (1.43 g, 5.00 mmol) were weighed in a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and NMP (12.0 g) was added thereto, and the mixture was stirred while being fed with nitrogen. It dissolves. F9 (1.12 g, 5.00 mmol) was added to the diamine solution while stirring, and the mixture was stirred at 25 ° C for 2 hours. Next, add F2 (0.98g, 5.00mmol) and NMP was added so that the solid content concentration might become 10 mass%, and it stirred at 25 degreeC for 4 hours, and the poly amide acid solution (11) was obtained. The polyamine had a number average molecular weight of 13,200 and a weight average molecular weight of 39,000.

[Synthesis Example 15]

B1 (1.79 g, 5.00 mmol) and D4 (0.60 g, 4.00 mmol) were weighed in a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, and NMP (12.0 g) was added thereto, and the mixture was stirred while being fed with nitrogen. It dissolves. While stirring this diamine solution, F11 (1.12 g, 5.00 mmol) was added, and the mixture was stirred at 25 ° C for 2 hours. Then, F10 (1.53 g, 5.00 mmol) was added, and NMP was added so that the solid content concentration became 10 mass%, and the mixture was stirred at 25 ° C for 4 hours to obtain a polyaminic acid solution (12). The polyamic acid had a number average molecular weight of 9,800 and a weight average molecular weight of 21,000.

(Manufacturing Examples 1 to 18 and Comparative Manufacturing Examples 1 to 6)

In addition, the physical properties (characteristics) of the respective liquid crystal alignment treatment agents obtained in the production examples and the comparative production examples are shown in Tables 2 to 4.

[Manufacturing Example 1]

NMP (4.75 g), BCS (3.44 g), and X-1 (0.05 g) were added to the polyamic acid solution (1) (10.0 g) obtained in Synthesis Example 4 to obtain a liquid crystal having a solid concentration of 5.5% by mass. Orientation treatment agent (1). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 2]

NMP (4.75 g), BCS (3.44 g), and X-1 (0.025 g) were added to the polyamic acid solution (1) (10.0 g) obtained in Synthesis Example 4 to obtain a liquid crystal having a solid concentration of 5.5% by mass. Orientation treatment agent (2). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 3]

NMP (1.20 g), γ- was added to the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7 and the polyalkyl amide solution (6) (3.30 g) obtained in Synthesis Example 9. BL (12.7 g), PB (5.34 g), and X-1 (0.042 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (3) having a solid concentration of 3.0% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 4]

NMP (3.35 g) and γ-BL (NMP) were added to the polyamic acid solution (3) (3.30 g) obtained in Synthesis Example 6 and the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7. 0.56 g), BCS (2.84 g) and X-1 (0.042 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (4) having a solid concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 5]

NMP (3.35 g) and γ-BL (NMP) were added to the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7 and the polyamic acid solution (8) (3.30 g) obtained in Synthesis Example 11. 0.56 g), BCS (2.84 g) and X-1 (0.042 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (5) having a solid concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 6]

NMP (3.35 g) and γ-BL (NMP) were added to the polyamic acid solution (2) (3.30 g) obtained in Synthesis Example 5 and the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7. 0.56 g), BCS (2.84 g) and X-1 (0.042 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (6) having a solid concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 7]

NMP (3.90 g), γ-BL (0.87 g), BCS (3.44 g), and X-1 (0.05 g) were added to the polyamic acid solution (4) (10.0 g) obtained in Synthesis Example 7 The mixture was stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (7) having a solid concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 8]

To the polyamic acid solution (5) (10.0 g) obtained in Synthesis Example 8, NMP (4.75 g), BCS (3.44 g) and X-1 (0.05 g) were added, and the mixture was stirred at 25 ° C for 1 hour to obtain a solid. A liquid crystal alignment treatment agent (8) having a component concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 9]

NMP (5.00 g), γ-BL (2.74 g), and NEP (5.15 g) were added to the polyimine powder (7) (0.60 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to dissolve. . Then, the polyamic acid solution (4) (4.00 g) obtained in Synthesis Example 7, BCS (4.12 g), and X-1 (0.12 g) were added to the solution, and the mixture was stirred at 25 ° C for 1 hour to obtain a solid component. Liquid crystal alignment treatment agent (9) having a concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 10]

NMP (1.20 g), γ- was added to the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7 and the polyalkyl amide solution (6) (3.30 g) obtained in Synthesis Example 9. BL (12.7 g), PB (5.34 g), and X-2 (0.042 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (10) having a solid concentration of 3.0% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 11]

NMP (3.35 g) and γ-BL (NMP) were added to the polyamic acid solution (3) (3.30 g) obtained in Synthesis Example 6 and the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7. 0.56 g), BCS (2.84 g) and X-1 (0.021 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (11) having a solid concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 12]

NMP (3.35 g) and γ-BL (NMP) were added to the polyamic acid solution (3) (3.30 g) obtained in Synthesis Example 6 and the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7. 0.56 g), BCS (2.84 g) and X-1 (0.082 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (12) having a solid concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 13]

NMP (3.35 g) and γ-BL (NMP) were added to the polyamic acid solution (3) (3.30 g) obtained in Synthesis Example 6 and the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7. 0.56 g), BCS (2.84 g) and X-2 (0.021 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (13) having a solid concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 14]

NMP (3.35 g) and γ-BL (NMP) were added to the polyamic acid solution (3) (3.30 g) obtained in Synthesis Example 6 and the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7. 0.56 g), BCS (2.84 g) and X-2 (0.082 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (14) having a solid concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 15]

NMP (4.75 g), BCS (3.44 g), and X-1 (0.05 g) were added to the polyamic acid solution (9) (10.0 g) obtained in Synthesis Example 12, and stirred at 25 ° C for 1 hour to obtain a solid. A liquid crystal alignment treatment agent (15) having a component concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 16]

NMP (13.90 g) was added to the polyimine powder (10) (0.82 g) obtained in Synthesis Example 13, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, BCS (3.44 g) and X-1 (0.042 g) were added, and the mixture was stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (16) having a solid concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 17]

NMP (4.75 g), BCS (3.44 g), and X-1 (0.05 g) were added to the polyamic acid solution (11) (10.0 g) obtained in Synthesis Example 14, and stirred at 25 ° C for 1 hour to obtain a solid. A liquid crystal alignment treatment agent (17) having a component concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Manufacturing Example 18]

NMP (4.75 g), BCS (3.44 g), and X-1 (0.05 g) were added to the polyamic acid solution (12) (10.0 g) obtained in Synthesis Example 15, and stirred at 25 ° C for 1 hour to obtain a solid. A liquid crystal alignment treatment agent (18) having a component concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Comparative Manufacturing Example 1]

NMP (4.75 g) and BCS (3.44 g) were added to the polyamic acid solution (1) (10.0 g) obtained in Synthesis Example 4 to obtain a liquid crystal alignment treatment agent (19) having a solid concentration of 5.5% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Comparative Manufacturing Example 2]

NMP (4.75 g), BCS (3.44 g), and Z-1 (0.05 g) were added to the polyamic acid solution (1) (10.0 g) obtained in Synthesis Example 4 to obtain a liquid crystal having a solid concentration of 5.5% by mass. Orienting treatment agent (20). to In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Comparative Manufacturing Example 3]

NMP (1.20 g), γ- was added to the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7 and the polyalkyl amide solution (6) (3.30 g) obtained in Synthesis Example 9. BL (12.7 g) and PB (5.34 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (21) having a solid concentration of 3.0% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Comparative Manufacturing Example 4]

NMP (1.20 g), γ- was added to the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7 and the polyalkyl amide solution (6) (3.30 g) obtained in Synthesis Example 9. BL (12.7 g), PB (5.34 g) and Z-1 (0.042 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (22) having a solid concentration of 3.0% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Comparative Manufacturing Example 5]

NMP (1.20 g), γ- was added to the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7 and the polyalkyl amide solution (6) (3.30 g) obtained in Synthesis Example 9. BL (12.7 g), PB (5.34 g) and Z-2 (0.042 g) were stirred at 25 ° C for 1 hour to give a solid concentration of 3.0. % by mass of liquid crystal alignment treatment agent (22). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

[Comparative Manufacturing Example 6]

NMP (1.20 g), γ- was added to the polyamic acid solution (4) (4.95 g) obtained in Synthesis Example 7 and the polyalkyl amide solution (6) (3.30 g) obtained in Synthesis Example 9. BL (12.7 g), PB (5.34 g), and Z-3 (0.042 g) were stirred at 25 ° C for 1 hour to obtain a liquid crystal alignment treatment agent (23) having a solid concentration of 3.0% by mass. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

The polyimide-based polymer of the present invention is shown in Table 1.

*2: Polyalkylene amide

From the comparison between Example 1 and Comparative Example 1, and Example 3 and Comparative Examples 3 to 6, it is understood that the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is more resistant to rubbing treatment than the comparative example. The rate, the surface roughness value, and the hydrazine imidization ratio and the afterimage characteristics of the AC drive were excellent results.

[Industrial Applicability]

The liquid crystal alignment film formed by the liquid crystal alignment treatment agent of the present invention is a liquid crystal display element which is used as a liquid crystal alignment film for a photo-alignment treatment method, and has a liquid crystal display element of the liquid crystal alignment film of the present invention, and is suitable for a large-screen and high-definition liquid crystal television. Small and medium-sized smart phones or tablet terminals.

In addition, the entire contents of the specification of the Japanese Patent Application No. 2014-197380, filed on Sep

Claims (13)

A liquid crystal alignment treatment agent comprising the following (A) component, (B) component, and a solvent for dissolving the same; (A) component: a compound represented by the following formula (1), [Chem. 1] P ^- XQ (1) (wherein P has at least one group in which the same carbon atom is substituted with at least two or more nitrogen atoms, and at least one of the nitrogen atoms is replaced by a hydrogen atom by heat 1~ a valence of 24 to 12, which is selected from the group consisting of a single bond, -O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO-, - at least one of the groups of OCO- and -S-, Q represents a benzene ring, or a hydrocarbon group having a carbon number of 6 to 24 having a benzene ring), and (B) component: selected from the group consisting of polyimine precursors And at least one polymer of the group formed by the polyimine. The liquid crystal alignment treatment agent of claim 1, wherein the thermal release group is an ester group represented by the following formula (2), (wherein R ² is a hydrocarbon having 1 to 22 carbon atoms). The liquid crystal alignment treatment agent according to claim 1 or 2, wherein the P is any one of the following formula (P-1) or (P-2), (In the formula, S ₁ and S ₂ each independently represent a monovalent organic group having 1 to 6 carbon atoms, and S ₁ and S ₂ may form a ring structure; and S ₃ and S ₄ each independently represent a hydrogen atom or carbon. The number 1 to 6 of the monovalent organic group, S ₃ and S ₄ may also form a ring structure; D is a thermally detachable group substituted with a hydrogen atom by heat; * indicates a bonding site with X). The liquid crystal alignment treatment agent of claim 3, wherein the P is any one of the following formula (PD-1) or (PD-2), (wherein * represents a bonding site with X, and D is a thermally detachable group substituted with a hydrogen atom by heat). The liquid crystal alignment treatment agent of claim 4, wherein the component (A) is a compound represented by the following formula (3) wherein X is a single bond in the formula (1), and Q is T-Q', [Chem. 5] PT- Q' (3) (wherein P represents a group represented by any one of the above formula (PD-1) or (PD-2), and T represents an alkylene group having a carbon number of 1 to 6, and a carbon number of 2 to 6 An alkenyl group or an alkynyl group having 2 to 6 carbon atoms, a hydrogen atom bonded to any of the carbon atoms, may be substituted by a halogen-containing alkyl group, a halogen atom or a hydroxyl group (OH group); Q' represents Aromatic hydrocarbons with a carbon number of 6 to 18). The liquid crystal alignment treatment agent according to any one of claims 1 to 5, wherein the component (A) is represented by the following formula (4-1) or (4-2), (wherein P represents a group represented by any one of the above formulae (PD-1) and (PD-2), and T represents an alkylene group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms; Or an alkynyl group having 2 to 6 carbon atoms, and a hydrogen atom bonded to any of the carbon atoms may be substituted by a halogen-containing alkyl group, a halogen atom or a hydroxyl group (OH group). The liquid crystal alignment treatment agent according to any one of claims 1 to 6, wherein the component (A) is at least one compound selected from the group consisting of the following formulas (A-1) and (A-2). The liquid crystal alignment treatment agent according to any one of claims 1 to 7, wherein the component (B) is contained in an amount of 0.1 to 20% by mass, and the component (A) is contained in an amount of 0.1 to 20% by mass based on the component (B). Solvent contains 76~99.5 quality%. The liquid crystal alignment treatment agent according to any one of claims 1 to 8, wherein the polymer of the component (B) is a polyalkylene amide. A liquid crystal alignment film obtained by the liquid crystal alignment treatment agent according to any one of claims 1 to 9. A liquid crystal alignment film obtained by an inkjet method using the liquid crystal alignment treatment agent according to any one of claims 1 to 9. A liquid crystal alignment film obtained by irradiating a liquid crystal alignment film of claim 10 or 11 with polarized radiation. A liquid crystal display element having the liquid crystal alignment film according to any one of claims 10 to 12.