KR102275486B1 - A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element - Google Patents

Abstract

A liquid crystal aligning agent which can suppress the coating defect of the alignment film generated under the influence of wiring structure or C/H, and the non-uniformity in the display of the liquid crystal display element, and can lower the viscosity while maintaining the resin component and molecular weight; A liquid crystal aligning film and a liquid crystal display element are provided.
The liquid crystal aligning agent containing the at least 1 sort(s) of polymer chosen from the group which consists of a polyimide which is a polyimide precursor and its imidated material, and the solvent containing the following solvent A, solvent B, and solvent C.
Solvent A: selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone and dimethylimidazolidinone.
Solvent B: dipropylene glycol dimethyl ether
Solvent C: It is selected from the group which consists of diethylene glycol diethyl ether and diacetone alcohol.

Description

A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element

This invention is suitable for the inkjet film-forming method, and relates to the liquid crystal aligning agent with high dimensional stability at the time of apply|coating, and the liquid crystal aligning film obtained from this liquid crystal aligning agent.

As a liquid crystal aligning film, the liquid crystal aligning film of so-called polyimide-type liquid crystal aligning film which apply|coated and baked the liquid crystal aligning agent which has as a main component the solution of polyimide precursors, such as a polyamic acid (it is also called polyamic acid), and a soluble polyimide, is used widely.

As a film-forming method of such a liquid crystal aligning film, spin coating, dip coating, flexographic printing, etc. are generally known. Among them, the coating method by flexographic printing has been widely used until now. However, in flexographic printing, various resin plates are required according to the differences in the types of liquid crystal panels, the plate exchange is complicated in the manufacturing process, film formation on a dummy substrate is required to stabilize the film formation process, and plate manufacturing is difficult. There exists a problem, such as becoming one factor of an increase in the manufacturing cost of a liquid crystal display panel.

Therefore, the inkjet method attracts attention as a film-forming method of the liquid crystal aligning film which does not use a printing plate. The inkjet method is a method in which fine droplets are dripped onto a substrate and formed into a film by wet diffusion of the liquid. Not only does not use a printing plate, but since the pattern of printing can be set freely, the manufacturing process of a liquid crystal display element can be simplified. In addition, since film formation on the dummy substrate, which was required in flexographic printing, becomes unnecessary, there is an advantage in that there is little wastage of the coating liquid. By the inkjet method, cost reduction of a liquid crystal panel and the improvement of production efficiency are anticipated.

It is calculated|required that the film-thickness nonuniformity inside an application surface is small, and the film-forming precision of an application|coating peripheral part is high as for the liquid crystal aligning film formed by the inkjet method. Generally, as for the liquid crystal aligning film formed into a film by the inkjet method, the uniformity of the film thickness in an application surface, and the film-forming precision of an application|coating periphery have a trade-off relationship. That is, normally, a material with high in-plane uniformity has low dimensional stability of the application periphery, and the film protrudes from the set dimension. On the other hand, for a material whose application peripheral portion is straight, the uniformity within the application surface becomes low.

In order to improve the film-forming precision of the said application|coating periphery, the method of controlling an alignment film to a predetermined range by a special structure is proposed (refer patent documents 1 - 3). However, these methods have the disadvantage that the use of a special structure is required.

Japanese Laid-Open Patent Publication No. 2004-361623 Japanese Patent Laid-Open No. 2008-145461 Japanese Patent Laid-Open No. 2010-281925

In recent years, with the high definition of a liquid crystal display element, TFT design of multilayer wiring has become mainstream. In TFT design, a contact hole (also referred to as C/H) is formed on the substrate to connect the wiring of the lower layer and the wiring of the upper layer. With this, under the influence of wiring structure or C/H, at the time of liquid crystal aligning agent application|coating, the diffusivity of a liquid becomes easy to be inhibited. As a result, non-uniformity in the thickness of the alignment film, such as dot-like non-uniformity or stripe-like non-uniformity, occurs in the periphery of C/H or other portions, resulting in non-uniform display of the liquid crystal display element.

Moreover, in order for the liquid crystal aligning agent used by the inkjet method to perform aligning agent discharge from an inkjet nozzle stably, it is calculated|required that it is low-viscosity, and it may set the resin component ratio in a liquid crystal aligning agent little by it. . On the other hand, by lowering the resin component ratio, problems such as deterioration of shape stability and film thickness uniformity of the peripheral portion of the coating film, and prolonged application time for obtaining a target film thickness are liable to occur. For this reason, it is desired to reduce a viscosity, maintaining a resin component ratio. On the other hand, although it is possible to reduce the viscosity by lowering the molecular weight of the resin component, since a decrease in the molecular weight of the resin component entails a risk of impairing the physical properties or durability of the alignment film, it is better to lower the viscosity while maintaining the molecular weight of the resin component. is being desired

In view of the above subject, the present invention can suppress the film-forming defect of a liquid crystal aligning film which arises under the influence of a wiring structure or C/H, and the defect which becomes the display of a liquid crystal display element nonuniformity, and also the resin component ratio and It exists in providing the liquid crystal aligning agent which can make low the viscosity of a liquid crystal aligning agent, the liquid crystal aligning film using the same, and a liquid crystal display element, maintaining the molecular weight of a resin component.

As a result of repeating earnest research for the solution of the said subject, this inventor has come to complete this invention.

The summary of this invention contains the solvent containing at least 1 sort(s) of polymer selected from the group which consists of a polyimide precursor and its imidated polyimide, and the following solvent A, solvent B, and solvent C, It is characterized by the above-mentioned It exists in the liquid crystal aligning agent used as

Solvent A: At least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone and dimethylimidazolidinone.

Solvent B: dipropylene glycol dimethyl ether

Solvent C: At least 1 sort(s) selected from the group which consists of diethylene glycol diethyl ether and diacetone alcohol.

ADVANTAGE OF THE INVENTION According to this invention, the film-forming defect of the liquid crystal aligning film which generate|occur|produces under the influence of wiring structure or C/H, and the defect that the display of a liquid crystal display element becomes non-uniform|heterogenous can be suppressed, Furthermore, the resin component ratio and molecular weight of a resin component Since a liquid crystal aligning agent can be made low viscosity, holding|maintaining, the liquid crystal aligning agent of the polyimide type suitable for film-forming by the inkjet method, the liquid crystal aligning film using the same, and a liquid crystal display element are obtained.

The liquid crystal aligning agent of this invention is at least 1 sort(s) of polymer (it is also mentioned a specific polymer) chosen from the group which consists of polyimide which is a polyimide precursor and its imidide, and the following solvent A, solvent B, and solvent C A solvent containing (also referred to as a specific solvent) is contained.

<Specific solvent>

The solvent contained in the liquid crystal aligning agent of this invention contains the solvent A, the solvent B, and the solvent C, and the liquid crystal aligning agent of this invention by containing of such combined solvent under the influence of wiring structure and C/H The film-forming defect of the alignment film which generate|occur|produces can be suppressed, and the defect which becomes the display of a liquid crystal display element can be suppressed, Furthermore, the viscosity of a liquid crystal aligning agent, maintaining the content rate of a resin component and the molecular weight of a resin component can be made lower.

<Solvent A>

Solvent A is N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), γ-butyrolactone (GBL), and 1,3-dimethylimidazolidinone ( DMI) at least one solvent selected from the group consisting of. This solvent A dissolves the polymer in a liquid crystal aligning agent.

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone is preferable, and N-methyl-2-pyrrolidone or γ-buty is more preferable. It is Lolactone.

20-80 mass % is preferable with respect to the total mass of a liquid crystal aligning agent, as for content of the solvent A, 30-80 mass % is more preferable, 50-80 mass % is especially preferable.

<Solvent B>

The solvent B is dipropylene glycol dimethyl ether (DME). Solvent B is a solvent which contributes to the improvement of the application|coating uniformity of a liquid crystal aligning agent, and viscosity-lowering.

1-30 mass % is preferable with respect to the total mass of a liquid crystal aligning agent, as for the solvent B, 5-30 mass % is more preferable, and its 10-30 mass % is especially preferable.

<Solvent C>

The solvent C is at least 1 sort(s) selected from the group which consists of diethylene glycol diethyl ether (DGDE) and diacetone alcohol (DAA). Solvent C is a solvent contributing to viscosity-lowering of the liquid crystal aligning agent of this invention.

5-30 mass % is preferable with respect to the total mass of the liquid crystal aligning agent of this invention, as for the solvent C, 10-30 mass % is more preferable, 10-20 mass % is especially preferable.

<Specific Polymer>

It is preferable that the polyimide precursor which is a specific polymer contained in the liquid crystal aligning agent of this invention has a structure shown by following formula (1).

[Formula 1]

In said formula (1), X<_1> is a tetravalent organic group derived from a tetracarboxylic-acid derivative. Y ₁ is a divalent organic group derived from diamine. R ₁ is a hydrogen atom or an alkylene having 1 to 5 carbon atoms. From the point of the easiness of advancing of the imidation reaction at the time of heating, a hydrogen atom, a methyl group, or an ethyl group is preferable and, as for _{R<1>, a hydrogen atom or a methyl group is more preferable.}

A ₁ and A ₂ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. From the point of liquid-crystal orientation, A ₁ and A ₂ have a preferable hydrogen atom or a methyl group.

Each component which is a raw material which manufactures the polyimide precursor which is a specific polymer is demonstrated.

<diamine>

Although the diamine component used for manufacture of a polyimide precursor is not specifically limited, The diamine which is a raw material of the polyimide precursor shown by said Formula (1) is represented by following formula (2).

[Formula 2]

In Formula (2), A ₁ and A ₂ each have the same definitions _{as A 1} and A ₂ in Formula (1), including preferred examples. Examples of the structure of Y ₁ include the following (Y-1) to (Y-170).

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

In said formula, Me represents a methyl group, and n represents the integer of 1-6.

Among them, as Y ₁ , (Y-7), (Y-8), (Y-16), (Y-17), (Y-18), (Y-20), (Y-21), ( Y-22), (Y-28), (Y-35), (Y-38), (Y-43), (Y-48), (Y-64), (Y-66), (Y- 71), (Y-72), (Y-76), (Y-77), (Y-80), (Y-81), (Y-82), (Y-83), (Y-156) , (Y-159), (Y-160), (Y-161), (Y-162), (Y-168), (Y-169), or (Y-170) is preferable. In particular, (Y-7), (Y-8), (Y-16), (Y-17), (Y-18), (Y-21), (Y-22), (Y-28) , (Y-38), (Y-64), (Y-66), (Y-72), (Y-76), (Y-81), (Y-156), (Y-159), ( Y-160), (Y-161), (Y-162), (Y-168), (Y-169), or (Y-170) is preferable.

<Tetracarboxylic acid derivative>

Although the tetracarboxylic acid derivative used for manufacture of a polyimide precursor is not specifically limited, As a tetracarboxylic-acid derivative component which is a raw material of the polyimide precursor represented by said Formula (1), Not only tetracarboxylic dianhydride, The derivatives thereof include tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide.

As tetracarboxylic dianhydride or its derivative(s), especially, what is represented by following formula (3) is preferable.

[Formula 21]

In Formula (3), X<_1> is a tetravalent organic group which has an alicyclic structure, The structure is not specifically limited. Specific examples thereof include the following formulas (X1-1) to (X1-44).

[Formula 22]

In formulas (X1-1) to (X1-4), R ₃ to R ₂₃ 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, or an alkenyl group having 2 to 6 carbon atoms. It is a 6 alkynyl group, a C1-C6 monovalent organic group containing a fluorine atom, or a phenyl group. In terms of liquid crystal alignment, R ₃ ~ R ₂₃ is a hydrogen atom, a halogen atom, a methyl group, or ethyl group is preferable, and is preferably a hydrogen atom, or a methyl group.

Moreover, the following formulas (X1-1-1) - (X1-1-6) are mentioned as a specific example of a formula (X1-1). From the point of the liquid-crystal orientation and the sensitivity of a photoreaction, (X1-1-1) is especially preferable.

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

As tetracarboxylic dianhydride or its derivative(s) which is a raw material of the polyimide precursor of this invention or polyimide, tetracarboxylic acid represented by said Formula (3) with respect to 1 mol of all tetracarboxylic dianhydride or its derivative(s) It is preferable to contain 60-100 mol% of dianhydride or its derivative(s). Since the liquid crystal aligning film which has favorable liquid-crystal orientation is obtained, 80-100 mol% is more preferable, and 90-100 mol% is still more preferable.

<Polyimide precursor>

<The manufacturing method of polyamic acid ester>

The polyamic acid ester which is one of the polyimide precursors used for this invention can be manufactured by the method of (1), (2), or (3) shown below.

(1) In case of manufacturing from polyamic acid

Polyamic acid ester is compoundable by esterifying the polyamic acid obtained from tetracarboxylic dianhydride and diamine. Specifically, a polyamic acid and an esterification agent are -20 degreeC - 150 degreeC in presence of an organic solvent, Preferably in 0 degreeC - 50 degreeC, it is 30 minutes - 24 hours, Preferably by making it react for 1 to 4 hours can be synthesized.

The esterifying agent is preferably one that can be easily removed by purification, and includes N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dineopentylbutyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazine, 1-ethyl-3-p-tolyltriazine , 1-propyl-3-p-tolyltriazine, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, and the like. As for the usage-amount of an esterification agent, 2-6 molar equivalent is preferable with respect to 1 mol of repeating units of a polyamic acid.

The solvent used for the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the viewpoint of polymer solubility, and these are one type or a mixture of two or more types. you can use it. The concentration of the polymer in the reaction solution is preferably 1 to 30 mass%, more preferably 5 to 20 mass%, from the viewpoint that polymer precipitation is less likely to occur and a high molecular weight body is easily obtained.

(2) When produced by reaction of tetracarboxylic acid diester dichloride with diamine

Polyamic acid ester can be manufactured from tetracarboxylic-acid diester dichloride and diamine. Specifically, tetracarboxylic-acid diester dichloride and diamine are -20 degreeC - 150 degreeC in presence of a base and an organic solvent, Preferably it is 0 degreeC - 50 degreeC for 30 minutes - 24 hours, Preferably it is 1 - It can synthesize|combine by making it react for 4 hours.

Although pyridine, triethylamine, 4-dimethylaminopyridine, etc. can be used for the said base, pyridine is preferable since reaction advances mildly. The usage-amount of a base is a quantity with easy removal, and 2-4 times mole is preferable with respect to tetracarboxylic-acid diester dichloride from a viewpoint of being easy to obtain a high molecular weight body.

As for the solvent used for said reaction, N-methyl-2-pyrrolidone or (gamma)-butyrolactone is preferable from the solubility of a monomer and a polymer, and these may be used 1 type or in mixture of 2 or more types. The polymer concentration in the reaction solution is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that polymer precipitation is less likely to occur and high molecular weight is easily obtained. Moreover, in order to prevent hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable that the solvent used for the synthesis|combination of polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent mixing of external air in nitrogen atmosphere.

(3) When producing by reaction of tetracarboxylic acid diester and diamine

Polyamic acid ester can be manufactured by polycondensing tetracarboxylic-acid diester and diamine. Specifically, tetracarboxylic-acid diester and diamine are 0 degreeC - 150 degreeC in presence of a condensing agent, a base, and an organic solvent, Preferably it is 0 degreeC - 100 degreeC WHEREIN: 30 minutes - 24 hours, Preferably 3 It can manufacture by making it react for - 15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1 ,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluroniumtetrafluoroborate, O-(benzotriazole- 1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphite, (2,3-dihydro-2-thioxo-3-benzooxazolyl)phosphonic acid diphenyl, etc. Can be used. As for the addition amount of a condensing agent, 2-3 times mole is preferable with respect to tetracarboxylic-acid diester.

Tertiary amines, such as a pyridine and triethylamine, can be used for the said base. The usage-amount of a base is a quantity with easy removal, and 2-4 times mole is preferable with respect to a diamine component from a viewpoint of being easy to obtain a high molecular weight body.

Moreover, in the said reaction, reaction advances efficiently by adding a Lewis acid as an additive. As a Lewis acid, lithium halides, such as lithium chloride and lithium bromide, are preferable. As for the addition amount of a Lewis acid, 0-1.0 times mole is preferable with respect to a diamine component.

Since high molecular weight polyamic acid ester is obtained among the manufacturing methods of said three polyamic acid ester, the manufacturing method of said (1) or said (2) is especially preferable.

A polymer can be deposited by injecting|pouring into a poor solvent, stirring well the solution of polyamic acid ester obtained by making it above. Precipitation is performed several times, and after washing|cleaning with a poor solvent, the powder of the polyamic acid ester refined by normal temperature or heat-drying can be obtained. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned.

<Method for producing polyamic acid>

The polyamic acid which is a polyimide precursor used for this invention can be manufactured by the method shown below. Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at -20°C to 150°C, preferably at 0°C to 50°C, for 30 minutes to 24 hours, preferably for 1 to 12 hours. It can be synthesized by

The organic solvent used for the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the viewpoint of monomer and polymer solubility, and these are one or two types. You may mix and use the above. From a viewpoint that polymer precipitation does not generate|occur|produce easily and a high molecular weight body is easy to be obtained, 1-30 mass % is preferable, and, as for the density|concentration of a polymer, 5-20 mass % is more preferable.

The polyamic acid obtained as mentioned above can precipitate and collect|recover a polymer by inject|pouring into a poor solvent, stirring a reaction solution well. Moreover, the powder of the refined polyamic acid can be obtained by performing precipitation several times, washing|cleaning with a poor solvent, and drying by normal temperature or heat. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned.

<Manufacturing method of polyimide>

The polyimide used for this invention can be manufactured by imidating the said polyamic acid ester or polyamic acid. When manufacturing a polyimide from polyamic acid ester, chemical imidation which adds a basic catalyst to the polyamic acid solution obtained by dissolving the said polyamic acid ester solution or polyamic acid ester resin powder in an organic solvent is simple. Chemical imidization is preferable because the imidation reaction proceeds at a relatively low temperature, and the molecular weight reduction of the polymer does not easily occur during the imidization process.

Chemical imidation can be performed by stirring polyamic acid ester to imidate in basic catalyst presence in an organic solvent. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, triethylamine is preferable because it has sufficient basicity to advance the reaction.

The temperature at the time of imidation reaction is -20 degreeC - 140 degreeC, Preferably it is 0 degreeC - 100 degreeC, and the reaction time can be carried out for 1 to 100 hours. The quantity of a basic catalyst is 0.5-30 mole times of an amic acid ester group, Preferably it is 2-20 mole times. The imidation rate of the polymer obtained is controllable by adjusting a catalyst amount, temperature, and reaction time. Since the catalyst etc. which added remain in the solution after imidation reaction, it is preferable to collect|recover the obtained imidation polymer, to make it melt|dissolve again in an organic solvent, and to set it as the liquid crystal aligning agent of this invention.

When manufacturing a polyimide from a polyamic acid, chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is simple. Chemical imidization is preferable because the imidation reaction proceeds at a relatively low temperature, and the molecular weight reduction of the polymer does not easily occur during the imidization process.

Chemical imidation can be performed by stirring the polymer to be imidated in presence of a basic catalyst and an acid anhydride in an organic solvent. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has suitable basicity to advance the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, use of acetic anhydride is preferable because purification after completion of the reaction becomes easy.

The temperature at the time of imidation reaction is -20 degreeC - 140 degreeC, Preferably it is 0 degreeC - 100 degreeC, and the reaction time can be carried out for 1 to 100 hours. The quantity of a basic catalyst is 0.5-30 mole times of an amic acid group, Preferably it is 2-20 mole times, and the quantity of an acid anhydride is 1-50 mole times of an amic acid group, Preferably it is 3-30 mole times. The imidation rate of the polymer obtained is controllable by adjusting a catalyst amount, temperature, and reaction time.

Since the catalyst etc. added remain in the solution after imidation reaction of polyamic acid ester or polyamic acid, the obtained imidation polymer is collect|recovered by the means described below, it is made to melt|dissolve again in an organic solvent, and this invention It is preferable to set it as a liquid crystal aligning agent.

A polymer can be deposited by inject|pouring into a poor solvent, stirring well the solution of the polyimide obtained by making it above. Precipitation is performed several times, and after washing|cleaning with a poor solvent, the powder of the polyamic acid ester refined by normal temperature or heat-drying can be obtained.

Although the said poor solvent is not specifically limited, Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this invention has the form of the solution in which the polymer containing a specific polymer melt|dissolved in the organic solvent containing a specific solvent. As for the molecular weight of the polyimide precursor and polyimide of this invention, 2,000-500,000 are preferable at a weight average molecular weight, More preferably, it is 5,000-300,000, More preferably, it is 10,000-100,000. Moreover, the number average molecular weight becomes like this. Preferably it is 1,000-250,000, More preferably, it is 2,500-150,000, More preferably, it is 5,000-50,000.

Although the density|concentration of the polymer of the liquid crystal aligning agent used for this invention can change suitably according to setting of the thickness of the coating film to be formed, 1 weight% or more is preferable at the point which forms a uniform and defect-free coating film, and solution 10 weight% or less is preferable from the point of storage stability of.

<Other solvents>

The solvent in the liquid crystal aligning agent of this invention can contain solvents (henceforth another solvent) other than the solvents A, B, and C which comprise the said specific solvent. As another solvent, the solvent (it is also mentioned a good solvent) which melt|dissolves a polyimide precursor and a polyimide, and the solvent which improves the coating-film property and surface smoothness of the liquid crystal aligning film when a liquid crystal aligning agent is apply|coated (it is also called a poor solvent) may be included. Although the specific example of another solvent is given below, it is not limited to these examples.

Examples of the good solvent include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, methylethylketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N- dimethylpropanamide or 4-hydroxy-4-methyl-2-pentanone; and the like.

Specific examples of the poor solvent include ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2- Ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol , 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether , dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2 -Pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene Glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy)ethanol, butyl cellosolve, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy) Ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, 1-butoxy-2-propanol, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl Ether acetate, propylene glycol diacetate, diisopentyl ether, diethylene glycol Monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, Ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxymethylpropionate, 3-ethoxymethylethylethylpropionate, 3-methoxyethylpropionate, 3-ethoxypropionic acid, 3 -Methoxypropionic acid, 3-methoxypropionate propyl, 3-methoxypropionate butyl, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, diisobutyl ketone, Ethyl carbitol etc. are mentioned.

Moreover, as a poor solvent, when the solubility with respect to the solvent of the polyimide precursor and polyimide contained in a liquid crystal aligning agent is high, the solvent shown by following [D-1] - a formula [D-3] is preferable.

[Formula 29]

Of the formula ^[D-1], D 1 represents an alkyl group having a carbon number of 1 to 3, wherein ^[D-2], D 2 represents an alkyl group having a carbon number of 1 to 3, formula ^[D-3], D 3 represents a C1-C4 alkyl group.

The liquid crystal aligning agent of the present invention is a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group. The crosslinkable compound which has a sex compound or a polymerizable unsaturated bond may be included. It is necessary to have two or more of these substituents and a polymerizable unsaturated bond in a crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene , tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyletherethane, triphenylglycidyletherethane, bisphenolhexafluoroaceto Diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis( 2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2- (4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane or 1,3-bis(4-(1-(4-(2,3-epoxyprop and epoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol.

The crosslinkable compound which has an oxetane group is a compound which has at least two oxetane groups shown by a following formula [4A].

[Formula 30]

Specifically, the crosslinking|crosslinked compound shown by the formula [4a] - a formula [4k] published on pages 58-59 of international publication WO2011/132751 (published on October 27, 2011) is mentioned.

As a crosslinkable compound which has a cyclocarbonate group, it is a crosslinkable compound which has at least two cyclocarbonate groups shown by following formula [5A].

[Formula 31]

The crosslinking|crosslinked compound specifically, shown by Formula [5-1] - Formula [5-42] published on pages 76-82 of International Publication No. WO2012/014898 (published on February 2, 2012) is mentioned.

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group include an amino resin having a hydroxyl group or an alkoxy group, such as a melamine resin, a urea resin, and guanamine. resins, glycoluril-formaldehyde resins, succinylamide-formaldehyde resins or ethyleneurea-formaldehyde resins, and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used. A dimer or a trimer may be sufficient as this melamine derivative or a benzoguanamine derivative. It is preferable that these have an average of 3-6 methylol groups or alkoxymethyl groups per triazine ring.

Examples of the melamine derivative or benzoguanamine derivative include MX-750, in which an average of 3.7 methoxymethyl groups are substituted per triazine ring, and 5.8 methoxymethyl groups are substituted per triazine ring on average. Methoxymethylated melamine such as MW-30 (above, manufactured by Sanwa Chemical) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212 Methoxymethylated butoxymethylated melamine such as , 253 and 254, butoxymethylated melamine such as Cymel 506 and 508, carboxymethyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123, etc. Methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, Butoxymethylated benzoguanamine such as Cymel 1128, and carboxymethyl group-containing methoxymethylated ethoxymethylated such as Cymel 1125-80 Benzoguanamine (above, the Mitsui cyanamide make) is mentioned.

Moreover, as an example of glycoluril, butoxymethylation glycoluril, such as Cymel 1170, Methylolation glycoluril, such as Cymel 1172, Methoxymethylolation glycoluril, such as Powder Link 1174, etc. are mentioned.

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

More specifically, the crosslinking|crosslinked compound of Formula [6-1] - Formula [6-48] published on pages 62-66 of International Publication No. WO2011/132751 (published on October 27, 2011) is mentioned.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tri(meth)acrylate. ) A crosslinkable compound having three polymerizable unsaturated groups in the molecule, such as acryloyloxyethoxytrimethylolpropane or glycerin polyglycidyl ether poly(meth)acrylate, furthermore, ethylene glycol di(meth)acrylate, di(meth)acrylate Ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol Di(meth)acrylate, neopentylglycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanediol di(meth) acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, A crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalate neopentyl glycol di (meth) acrylate, in addition to 2-hydroxyethyl (meth) ) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyl oxide Cy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate or N-methylol ( The crosslinkable compound etc. which have one polymerizable unsaturated group, such as meth)acrylamide, are mentioned in a molecule|numerator.

Moreover, the compound shown by a following formula [7A] can also be used.

[Formula 32]

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

[Formula 33]

The number of crosslinkable compounds used for the liquid crystal aligning agent of this invention may be one, and they may combine them two or more types.

As for content of the crosslinkable compound in the liquid crystal aligning agent of this invention, 0.1-150 mass parts is preferable with respect to 100 mass parts of all the polymer components. Especially, in order for a crosslinking reaction to advance and to express the target effect, 0.1-100 mass parts is preferable, More preferably, it is 1-50 mass parts.

The liquid crystal aligning agent of this invention can contain the compound which improves the uniformity of the film thickness of a liquid crystal aligning film at the time of apply|coating a liquid crystal aligning agent, and surface smoothness.

As a compound which improves the uniformity of the film thickness of a liquid crystal aligning film, and surface smoothness, a fluorine-type surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned.

Specifically, for example, FTOP EF301, EF303, EF352 (above, manufactured by Tochem Products), Megapac F171, F173, R-30 (above, manufactured by Dainippon Ink), Fluorad FC430, FC431 (above) , Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Sufflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.), etc. are mentioned.

To [ the usage-amount of surfactant / 100 mass parts of all the polymer components contained in a liquid crystal aligning agent ], Preferably it is 0.01-2 mass parts, More preferably, it is 0.01-1 mass part.

Moreover, in a liquid crystal aligning agent, it is a compound which accelerates|stimulates the charge transfer in a liquid crystal aligning film, and accelerates|stimulates the electric charge leakage of an element, Comprising: Formula [M1 which is published in the 69-73 pages of international publication WO2011/132751 (2011.10.27 publication). ] - the nitrogen-containing heterocyclic amine represented by the formula [M156] can also be added. Although you may add this amine directly to a liquid crystal aligning agent, it is 0.1-10 mass % of density|concentrations, It is preferable to add, after setting it as the solution of preferably 1-7 mass %. This solvent will not be specifically limited if a specific polymer is dissolved.

In the liquid crystal aligning agent of the present invention, in addition to the poor solvent, crosslinkable compound, the compound that improves the uniformity and surface smoothness of the film thickness of the resin film or the liquid crystal aligning film, and the compound that promotes charge leakage, the adhesion between the alignment film and the substrate is When baking a silane coupling agent for the purpose of improving, and a coating film, you may contain the imidation promoter etc. for the purpose of advancing the imidation by heating of a polyimide precursor efficiently.

<Liquid crystal alignment film, liquid crystal display element>

The liquid crystal aligning film of this invention is a film|membrane obtained by apply|coating said liquid crystal aligning agent to a board|substrate, drying and baking. It will not specifically limit if it is a board|substrate with high transparency as a board|substrate which apply|coats the liquid crystal aligning agent of this invention, Plastic substrates, such as a glass substrate, a silicon nitride board|substrate, an acryl board|substrate, and a polycarbonate board|substrate, etc. can also be used. In that case, it is preferable from the point of simplification of a process to use the board|substrate with which the ITO electrode etc. for driving a liquid crystal were formed. In the reflective liquid crystal display element, a silicon wafer or the like can be used even if it is opaque as long as it is only a one-side substrate, and a material that reflects light such as aluminum can also be used for the electrode in this case.

Industrially, as for the coating method of a liquid crystal aligning agent, the method of performing by screen printing, an offset printing, a flexographic printing, an inkjet method, etc. is common, As another application|coating method, the dip method, the roll coater method, the slit coater method , a spinner method, a spray method, and the like are known.

Especially, since the liquid crystal aligning agent of this invention can make a liquid crystal aligning agent low viscosity, maintaining high the content component ratio of a polymer, and molecular weight of a polymer as above-mentioned, application|coating by an inkjet method, and the film-forming method are preferable. can be used

After apply|coating a liquid crystal aligning agent on a board|substrate, a solvent can be evaporated by heating means, such as a hotplate, heat circulation type oven, or IR (infrared) type|mold oven, and it can be set as a liquid crystal aligning film. Drying after apply|coating a liquid crystal aligning agent, and a baking process can select arbitrary temperature and time. Usually, in order to fully remove the solvent to contain, it bakes at 50-120 degreeC for 1 to 10 minutes, and the conditions which bake at 150-300 degreeC after that for 5 to 120 minutes are mentioned. When the thickness of the liquid crystal aligning film after baking is too thin, since reliability of a liquid crystal display element may fall, 5-300 nm is preferable and 10-200 nm is more preferable.

After apply|coating and baking on a board|substrate, the liquid crystal aligning agent of this invention orientates by a rubbing process, a photo-alignment process, etc., and can use it as a liquid crystal aligning film without an orientation process in a vertical alignment use etc. In orientation processing, such as a rubbing process and a photo-alignment process, a well-known method and apparatus can be used.

As an example of the manufacturing method of a liquid crystal cell, the liquid crystal display element of a passive matrix structure is given and demonstrated. Moreover, the liquid crystal display element of the active matrix structure in which switching elements, such as TFT (Thin Film Transistor), were formed in each pixel part which comprises an image display may be sufficient.

Specifically, a transparent glass substrate is prepared, a common electrode is formed on one substrate, and a segment electrode is formed on the other substrate. These electrodes can be set as, for example, an ITO electrode, and are patterned so that a desired image display can be performed. Next, an insulating film is formed on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a SiO ₂ -TiO ₂ film formed by a sol-gel method.

Next, a liquid crystal aligning film is formed on each board|substrate, the other board|substrate is superposed|polymerized so that a mutual liquid crystal aligning film surface may oppose to one board|substrate, and periphery is adhere|attached with a sealing compound. In order to control a board|substrate clearance gap in a sealing compound, it is preferable to mix the spacer normally, and to disperse|distribute the spacer for board|substrate clearance gap control also to the in-plane part which does not form a sealing compound. In a part of a sealing compound, the opening part which can be filled with a liquid crystal from the outside is provided. Next, a liquid crystal material is inject|poured in the space surrounded by the board|substrate of 2 sheets and sealing agent through the opening part formed in the sealing compound, and this opening part is sealed with an adhesive agent after that. A vacuum injection method may be used for injection|pouring, and the method which utilized capillary phenomenon in air|atmosphere may be used. The liquid crystal material may be either a positive liquid crystal material or a negative liquid crystal material, but is preferably a negative liquid crystal material. Next, a polarizing plate is installed. A pair of polarizing plates are affixed to the surface on the opposite side to the liquid-crystal layer of two board|substrates specifically,.

Example

Next, the present invention will be described in more detail by way of Examples. However, the present invention should not be construed as being limited to these examples. The meaning and measurement method of the abbreviation used below are as follows.

DA-1: 1,5-bis(4-aminophenoxy)pentane

DA-2: 4,4'-diaminodiphenylmethane

DA-3: 4,4'-diaminodiphenylamine,

CA-1: pyromellitic dianhydride

CA-2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

CA-3: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride

NMP: N-methyl-2-pyrrolidone, GBL: γ butyllactone

DME: dipropylene glycol dimethyl ether

DPM: dipropylene glycol monomethyl ether

DAA: diacetone alcohol

DEDG: Diethylene glycol diethyl ether

NEP: N-ethyl-2-pyrrolidone

<Measurement of viscosity>

Viscosity, such as a polyamic acid and a liquid crystal aligning agent, was measured at the temperature of 25 degreeC with the E-type viscometer (made by the Toki Sangyo company).

<Method for measuring solid content concentration>

The solid content concentration in solutions, such as a polyamic-acid solution, was measured. After weighing 1.0 g of the solution in an aluminum cup and heat-treating it at 200°C for 2 hours, the amount of solid remaining in the cup was measured to measure the solid content concentration of the solution.

[Preparation of polyamic acid A1]

171.8 g of DA-1 was put into a 2000 ml flask equipped with a stirring device and provided with a nitrogen inlet tube, NMP 1676 g was added, and it was dissolved by stirring while sending nitrogen. 113.8 g of CA-1 is added, stirring this diamine solution under water cooling, NMP is further added so that solid content concentration may be 12 weight%, and it stirs for 20 hours, heating at 50 degreeC in nitrogen atmosphere, and polyamic acid (A1) ) (viscosity: 90 mPa·s, solid content concentration: 11.2 wt%) was obtained.

[Preparation of polyamic acid solution a1]

With respect to 535.7 g of polyamic-acid (A1) solutions, 264.3 g of NMP and DME 200.0g were added, and solid content concentration obtained the polyamic-acid solution (a1) whose solid content concentration is 6.0 weight%.

[Preparation of polyamic acid a2]

With respect to 535.7 g of polyamic-acid (A1) solutions, 264.3 g and DAA 200.0g added NMP, and solid content concentration obtained the polyamic-acid solution (a2) solution whose solid content concentration is 6.0 weight%.

[Preparation of polyamic acid solution a3]

With respect to 535.7 g of polyamic-acid (A1) solutions, 264.3 g and DPM 200.0g addition of NMP were added, and the density|concentration of solid content obtained the polyamic-acid solution (a3) which is 6.0 weight%.

[Preparation of polyamic acid A2]

100.8 g of DA-1 and 34.9 g of DA-5 were put into a 2000 ml flask equipped with a stirring device and provided with a nitrogen inlet tube, NMP 1337 g was added, and it was dissolved by stirring while sending nitrogen. 92.2g of CA-1 is added, stirring this diamine solution under water cooling, NMP is further added so that solid content concentration may be 12 weight%, and it stirs for 20 hours, heating at 50 degree|times in nitrogen atmosphere, and polyamic acid (A2 ) (viscosity: 520 mPa·s) was obtained.

[Preparation of polyamic acid B1]

87.7 g of DA-3 was put into a 2000 ml four-necked flask equipped with a stirring device and a nitrogen inlet tube was formed, and 1052.5 g of a solvent in which NMP and GBL were blended in a ratio of 50% by weight (hereinafter solvent 1) was added, It was dissolved by stirring while sending nitrogen. 70.1 g of CA-2 and 382.7g of solvent 1 were added, stirring this diamine solution under water cooling, and it stirred under water cooling under nitrogen atmosphere for 3 hours.

Then, 21.8 g of DA-2 and 191.3 g of solvent 1 were added, and it stirred. After DA-2 melt|dissolves, 33.0g of CA-3 and 287.0g of solvent 1 are added, and the solution of the polyamic acid (B1) whose solid content concentration is 9.8 weight% by adding and stirring under nitrogen atmosphere and water cooling for 3 hours again ( Viscosity: 65 mPa·s) was obtained.

[Preparation of polyamic acid B2]

95.6 g of DA-3 and 18.2 g of DA-4 were put into a 2000 ml four-necked flask equipped with a stirring device and a nitrogen inlet tube, and 967 g of NMP was added thereto, followed by stirring while sending nitrogen to dissolve. 54.8 g of CA-2 and 276 g of NMP were added, stirring this diamine solution under water cooling, and it stirred under water cooling under nitrogen atmosphere for 3 hours. Then, it stirred for 12 hours, adding NMP so that CA-4 might be set to 75.0 g and solid content concentration of 15 weight%, and heating at 50 degreeC in nitrogen atmosphere. It was this polyamic-acid (B2) solution (viscosity: 302 mPa*s).

[Preparation of polyamic acid B3]

87.7 g of DA-3 was put into a 2000 ml four-necked flask equipped with a stirring device and a nitrogen inlet tube was formed, and 1052.5 g of a solvent in which NMP and NEP were blended in a ratio of 50 wt% (hereinafter solvent 1) were added, It was dissolved by stirring while sending nitrogen. 70.1 g of CA-2 and 382.7g of solvent 1 were added, stirring this diamine solution under water cooling, and it stirred under water cooling under nitrogen atmosphere for 3 hours. Then, 21.8 g of DA-2 and 191.3 g of solvent 1 were added, and it stirred. After DA-2 melt|dissolves, 33.0g of CA-3 and 287.0g of solvent 1 are added, and the solution of the polyamic acid (B3) whose solid content concentration is 9.8 weight% by adding and stirring under nitrogen atmosphere and water cooling for 3 hours again ( Viscosity: 65 mPa·s) was obtained.

[Example 1]

153.4 g of polyamic-acid (B1) solutions are measured, 38.5 g of GBL solutions which 1.3 g of NMP and 3-glycidoxy propyl triethoxysilane entered in the solution are 95.9 g, DME 53.5g for 38.5g, GBL and 50.0 g of DAA were added, followed by stirring at room temperature for 1 hour. Next, 107.5g of the said polyamic-acid solution (a1) is added, and by stirring for 1 hour further, it is a weight% ratio, and solid content:NMP:GBL:DME:DAA=4.3:30:40.7:15:10 solution ( 500.0 g of liquid crystal aligning agents which consist of C1) were obtained.

[Example 2]

With respect to 153.4 g of polyamic acid (B1) solutions, 1.3 g of NMP and 3-glycidoxypropyl triethoxysilane are 38.5 g of GBL solutions containing 1.3 weight%, 95.9 g of GBL, 53.5 g of DME, and 50.0 g of DEDG was added and stirred at room temperature for 1 hour. Next, 107.5g of the said polyamic-acid solution (a1) is added, and by stirring for 1 hour, it is a weight% ratio, and solid content:NMP:GBL:DME:DEDG=4.3:30:40.7:15:10 solution ( 500.0 g of liquid crystal aligning agents which consist of C2) were obtained.

[Example 3]

After stirring the mixed solution of 33.3 g of a 12 weight% polyamic-acid (A2) solution and 106.6 g of a 15 weight% polyamic-acid (B2) solution for 30 minutes, 11.1 g and 3-glycidoxypropyl for NMP with respect to this By adding 20.0 g of an NMP solution containing 1.0% by weight of triethoxysilane, 204.0 g of GBL, 75.0 g of DME and 50.0 g of DAA, and stirring at room temperature for 3 hours, the polymer solid ratio of A2 and B2 is 2:8, 500.0g of liquid crystal aligning agents which consist of a solution (C7) which are solid content:NMP:GBL:DME:DAA=4.2:30:40.8:15:10 in the ratio of weight% were obtained.

[Example 4]

After stirring the mixed solution of 33.3 g of a 12 weight% polyamic-acid (A2) solution and 106.6 g of a 15 weight% polyamic-acid (B2) solution for 30 minutes, 11.1 g and 3-glycidoxypropyl for NMP with respect to this By adding 20.0 g of an NMP solution containing 1.0% by weight of triethoxysilane, 204.0 g of GBL, 75.0 g of DME and 50.0 g of DEDG, and stirring at room temperature for 3 hours, the polymer solid content ratio of A2 and B2 is 2:8, 500.0 g of liquid crystal aligning agents which consist of a solution (C8) of solid content:NMP:GBL:DME:DEDG=4.2:30:40.8:15:10 in the ratio of weight% were obtained.

[Example 5]

After stirring the mixed solution of 33.3 g of a 12 weight% polyamic acid (A2) solution and 106.6 g of a 15 weight% polyamic acid (B2) solution for 30 minutes, NMP is 5.1g and 3-glycidoxypropyl with respect to this 20.0 g of an NMP solution containing 1.0% by weight of triethoxysilane, 6.0 g of an NMP solution containing 10% by weight of AD-1, 204.0 g of GBL, 75.0 g of DME and 50.0 g of DAA are added, followed by stirring at room temperature for 3 hours By doing so, the polymer solid content ratio of A2 and B2 is 2:8, and AD-1 is contained in a weight % ratio of 3.0 wt% with respect to the polymer solid content, total solid content: NMP: GBL: DME: DAA = 4.2: 30: 40.8 : 500.0g of liquid crystal aligning agents which consist of a solution (C9) of 15:10 (weight%) were obtained.

[Example 6]

153.4 g of polyamic-acid (B3) solutions are weighed, 38.5 g of NEP solutions which 1.3 g of NMP and 3-glycidoxy propyl triethoxysilane entered 1.3 weight% in the solution, 95.9 g of NEP, and DME 53.5g and 50.0 g of DAA were added, followed by stirring at room temperature for 1 hour. Then, 107.5 g of a1 is added, and the liquid crystal which consists of a solution (C10) of solid content:NMP:NEP:DME:DAA=4.3:30:40.7:15:10 in the ratio of weight% by adding a1 and stirring for 1 hour further. 500.0 g of an aligning agent was obtained.

[Comparative Example 1]

153.4 g of polyamic-acid (B1) solutions are weighed, 38.5 g of GBL solutions which 1.3 g of NMP and 3-glycidoxy propyl triethoxysilane entered 1.3 weight% in the solution, 145.9 g of GBL, and 53.5 g of DME was added and stirred at room temperature for 1 hour. Next, 107.5g of said polyamic-acid solution (a1) is added, and by stirring for 1 hour further, it consists of a solution (C3) of solid content:NMP:GBL:DME=4.3:30:50.7:15 in a weight% ratio. 500.0 g of liquid crystal aligning agents were obtained.

[Comparative Example 2]

153.4 g of polyamic-acid (B1) solutions are measured, 38.5 g of GBL solutions which 1.3 g of NMP and 3-glycidoxy propyl triethoxysilane entered in the solution are 95.9 g, DME 53.5g for 38.5g, GBL and 50.0 g of DPM, followed by stirring at room temperature for 1 hour. Next, 107.5g of the said polyamic-acid solution (a1) is added, and by stirring for 1 hour, it is a weight% ratio, and the solution which has solid content:NMP:GBL:DME:DPM=4.3:30:40.7:15:10 500.0g of liquid crystal aligning agents which consist of (C4) were obtained.

[Comparative Example 3]

153.4 g of polyamic acid (B1) solutions are weighed, 38.5 g of GBL solutions which 1.3 g of NMP and 3-glycidoxy propyl triethoxysilane entered 1.3 weight% in the solution, 20.9 g of GBL, 83.5 g of DAA and 95.0 g of DEDG were added, followed by stirring at room temperature for 1 hour. Next, 107.5g of the said polyamic-acid solution (a2) is added, and by stirring for 1 hour, it is a weight% ratio, and the solution which has solid content:NMP:GBL:DAA:DEDG=4.3:30:25.7:21:19 500.0g of liquid crystal aligning agents which consist of (C5) were obtained.

[Comparative Example 4]

153.4 g of polyamic-acid (B1) solutions are weighed, 38.5 g of GBL solutions containing 1.3 weight% of NMP and 3-glycidoxy propyl triethoxysilane in the solution, 145.9 g of GBL, and 53.5 g of DAA was added and stirred at room temperature for 1 hour. Then, the liquid crystal aligning agent which consists of a solution (C6) which has solid content:NMP:GBL:DAA=4.3:30:50.7:15 in the ratio of weight% by adding 107.5g of a2 and stirring for 1 hour further 500.0 g were obtained.

[Comparative Example 5]

153.4 g of polyamic-acid (B1) solutions are weighed, 38.5 g of GBL solutions which 1.3 g of NMP and 3-glycidoxy propyl triethoxysilane entered 1.3 weight% in the solution, 95.9 g of GBL, DPM 53.5g and 50.0 g of DAA were added, followed by stirring at room temperature for 1 hour. Then, 107.5 g of a3 is added and stirred for an additional 1 hour, in a weight% ratio, solid content:NMP:GBL:DPM:DAA=4.3:30:40.7:15:10 (weight%) solution (C11) 500.0g of liquid crystal aligning agents which consist of ) were obtained.

About the liquid crystal aligning agent of said Examples 1-6 and Comparative Examples 1-5, after filtering with the filter with a hole diameter of 1 micrometer, the viscosity was measured and it was shown in Table 2. When a viscosity is low, it can be said that it is a more favorable liquid crystal aligning agent. Moreover, the following application|coating evaluation was also implemented.

[Evaluation of applicability by inkjet method]

About Examples 1 and 2 and Comparative Examples 1-4 prepared above, it apply|coated on the TFT board|substrate using the inkjet coating apparatus (made by Ishii Corporation). The application|coating conditions were implemented by 127 micrometers in pitch between nozzles, 250 mm/sec of application|coating speed|rate, 70 pL of dispensing amounts, and 36 x 36 mm of application areas. After temporary drying for 1 minute on a 110 degreeC hotplate, when the coating film was baked with IR oven on the conditions of 230 degreeC for 15 minutes, it apply|coated on the conditions used as 120 nm in thickness.

[Evaluation method of coating film]

The degree of non-uniformity in dots or stripes generated under the influence of contact holes or wiring with respect to the coating film temporarily dried at 110 DEG C on the applied substrate was evaluated in four stages. What can confirm the remarkable nonuniformity on the whole surface was Lv4, the thing which can confirm the nonuniformity partially was Lv3, what the nonuniformity was not visible with the naked eye, Lv2, and the thing which the nonuniformity was not seen at all even with an optical microscope was made into Lv1.

Moreover, it apply|coated also on the glass substrate on which chromium was vapor-deposited on the surface, the width|variety of the part with the color tone change (film thickness nonuniformity) of the coating-film edge part was measured with a nogise, and it evaluated as Halo size. In addition, the Halo size is a better coating film, so that a value is small.

These results are shown in Tables 1 and 2.

As an indication of the specification of this invention, the specification of the Japanese Patent Application No. 2016-072566 for which it applied on March 31, 2016, a claim, drawing, and the abstract are all cited here, and it takes in.

Claims (12)

The at least 1 sort(s) of polymer chosen from the group which consists of a polyimide which is a polyimide precursor and its imidate, and the solvent containing the following solvent A, solvent B, and solvent C are contained, The liquid crystal aligning agent characterized by the above-mentioned.
Solvent A: At least one selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone and dimethylimidazolidinone.
Solvent B: dipropylene glycol dimethyl ether
Solvent C: At least 1 sort(s) selected from the group which consists of diethylene glycol diethyl ether and diacetone alcohol. The method of claim 1,
The liquid crystal aligning agent whose solvent A is N-methyl- 2-pyrrolidone or (gamma)-butyrolactone. The method of claim 1,
The liquid crystal aligning agent in which a polyimide precursor has a structure represented by following formula (1).

(X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative. Y ₁ is a divalent organic group derived from diamine. R ₁ is a hydrogen atom or an alkylene having 1 to 5 carbon atoms. A ₁ and A ₂ is each independently a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms.) The method of claim 1,
The liquid crystal aligning agent in which the solvent A contains 20-80 mass % with respect to the total mass of a liquid crystal aligning agent. The method of claim 1,
The liquid crystal aligning agent in which the solvent B contains 1-30 mass % with respect to the total mass of a liquid crystal aligning agent. The method of claim 1,
The liquid crystal aligning agent in which the solvent C contains 1-30 mass % with respect to the total mass of a liquid crystal aligning agent. The method of claim 1,
The liquid crystal aligning agent in which the sum total of the solvent A is 50-80 mass %, the solvent B is 10-30 mass %, and the solvent C contains 1-20 mass % with respect to total mass % of a liquid crystal aligning agent. The method of claim 1,
The liquid crystal aligning agent in which the sum total of the solvent B and the solvent C contains 10-60 mass % with respect to the total mass of a liquid crystal aligning agent, and the solvent B contains more than the solvent C. 9. The method of claim 8,
The liquid crystal aligning agent in which the solvent B contains 1-20 mass % more than the solvent C. The method of claim 1,
The liquid crystal aligning agent for film-forming by the inkjet method. The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-10. A liquid crystal display element provided with the liquid crystal aligning film of Claim 11.