KR102399376B1 - A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element - Google Patents

Abstract

R₁, R₂ 는 각각 독립적으로, 직사슬 또는 분기의, 탄소수 1 ∼ 8 의 알킬기이다. 단, R₁ 과 R₂ 의 합계 탄소수는 R₂ 는 4 이상이다.The polyimide-type liquid crystal aligning agent suitable for the inkjet method which can form the coating film excellent in the uniformity of the film thickness in a coating surface, the linearity of the application|coating periphery, and dimensional stability, and the liquid crystal aligning film using the same are provided. A polymer and the solvent containing the compound represented by following formula (a) are contained, The liquid crystal aligning agent characterized by the above-mentioned.
[Formula 1]

R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 8 carbon atoms. However, as for the total carbon number of R< ₁ > and R< ₂ >, R< ₂ > is 4 or more.

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 display element provided with the liquid crystal aligning agent with high dimensional stability at the time of apply|coating, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film.

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 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 used a lot until now. However, in flexographic printing, various resin plates are required depending on the type of liquid crystal panel, the plate exchange is complicated in the manufacturing process, the need to form a film on the dummy substrate to stabilize the film formation process, and the production of the plate is difficult. There exists a problem, such as becoming a factor of the increase of 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 the waste of the coating liquid is small. 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 the 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, a material with high in-plane uniformity has low dimensional stability at the application periphery, and the film protrudes from the set dimension. On the other hand, for a material whose application peripheral portion is a straight line, the uniformity within the application surface becomes low.

In order to improve the film-forming precision of the said application|coating peripheral part, the method of controlling an orientation film in a predetermined range by a special structure is proposed (refer patent documents 1 - 3). However, these methods have the disadvantage that the use of additional special structures 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 this design, in order to connect the wiring of the lower layer and the wiring of the upper layer, a contact hole (also referred to as C/H) is formed on the substrate. With this, under the influence of wiring structure and 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, may occur around C/H or other portions, resulting in non-uniform display of the liquid crystal display element.

Liquid crystal aligning agent which this invention can suppress the application defect of the orientation film which generate|occur|produces under the influence of wiring structure or C/H in view of the said subject, and can suppress the defect from which the display of a liquid crystal display element becomes non-uniform|heterogenous , It exists in providing the liquid crystal aligning film using the same, and the liquid crystal display element provided with this liquid crystal aligning film.

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

The gist of the present invention is as described.

1. The polymer which has the ability to orientate a liquid crystal, and the solvent containing the compound represented by following formula (a) are contained, The liquid crystal aligning agent characterized by the above-mentioned.

[Formula 1]

In formula (a), R< ₁ >, R< ₂ > is each independently a linear or branched C1-C8 alkyl group. However, the sum total of carbon number of R< ₁ > and R< ₂ > is 4 or more.

ADVANTAGE OF THE INVENTION According to this invention, the coating defect of the liquid crystal aligning film which generate|occur|produces under the influence of wiring structure or C/H can be suppressed, Furthermore, the liquid crystal orientation of the polyimide system which can suppress the defect used as the display of a liquid crystal display element nonuniformity. i get

It exists in providing the liquid crystal aligning film using the same, and the liquid crystal display element provided with this liquid crystal aligning film.

<Polymer>

The polymer contained in the liquid crystal aligning agent of this invention will not be specifically limited if it has the ability to orientate a liquid crystal. The ability to orientate a liquid crystal can be improved by orientation processing, such as a rubbing process and ultraviolet irradiation, the film obtained from a polymer.

Examples of such a polymer include a polyimide precursor, a polyimide obtained by imidizing the polyimide precursor, an acrylic polymer, a methacryl polymer, an acrylamide polymer, a methacrylamide polymer, polystyrene, polyvinyl, polysiloxane, or polyamide. , polyester, polyurethane, polycarbonate, polyurea, polyphenol (novolak resin), maleimide polymer, and polymers introduced with a compound having an isocyanuric acid skeleton or a triazine skeleton.

The polymer may be in the same form as a branched polymer such as a dendrimer, a hyperbranched polymer, or a star-like polymer, or a non-covalent polymer such as polycatenan or polyrotaxane.

As a monomer for manufacturing these polymers, the following are mentioned.

When a polymer is a polyimide precursor and polyimide, such as a polyamic acid and polyamic acid ester, the at least 1 sort(s) of tetracarboxylic-acid component and diamine component chosen from tetracarboxylic acid or its derivative(s); When the polymer is an acrylic polymer, acrylic acid or a derivative thereof, acrylic acid ester or a derivative thereof; When a polymer is a methacrylic polymer, methacrylic acid or its derivative(s), methacrylic acid ester or its derivative(s); Polymer In the case of an acrylamide polymer, acrylamide or its derivative(s); When the polymer is a methacrylamide polymer, methacrylamide or its derivative(s); When a polymer is polystyrene, styrene or its derivative(s); When the polymer is polyvinyl, derivatives having a vinyl group; When a polymer is polysiloxane, it is a silane compound which has a methoxy group or an ethoxy group; When the polymer is polyamide, at least one dicarboxylic acid component and a diamine component selected from dicarboxylic acids and derivatives thereof; When a polymer is polyester, the at least 1 sort(s) of dicarboxylic acid component and diol component chosen from dicarboxylic acid and its derivative(s); When a polymer is a polyurethane, the compound which has an isocyanate, a compound, and a hydroxyl group; When a polymer is a polycarbonate, a bisphenol derivative and phosgene, or a phosgene equivalent (for example, trichlorophosgene), or diphenyl carbonate; When the polymer is polyurea, a bisisocyanate derivative and a diamine component; When the polymer is a maleimide polymer, a maleimide derivative alone or copolymerization with styrene; When a polymer is a polymer which introduce|transduced the compound which has an isocyanuric-acid frame|skeleton or a triazine frame|skeleton, the compound which has an isocyanuric-acid frame|skeleton or a triazine frame|skeleton is mentioned.

One type may be sufficient as the monomer for manufacturing the said polymer or a polymer, and 2 or more types may be used together. In addition, a polyimide precursor is a polyimide precursor, and at least 1 polymer selected from the polyimide obtained by imidating this polyimide precursor from a viewpoint of practicality as a liquid crystal aligning agent, and the mechanical and electrical characteristics of a coating film among these (the following) , also referred to as a specific polymer) is preferred.

The polymer which the liquid crystal aligning agent of this invention contains can be manufactured by the method normally implemented. For example, the polyimide precursor which is a specific polymer is obtained by polymerization-reacting the tetracarboxylic-acid derivative component and the diamine component which consist of tetracarboxylic acid or its derivative(s) as mentioned above, and imidating this polyimide precursor A polyimide is obtained.

<Specific solvent>

The solvent containing the solvent (henceforth a specific solvent) which consists of a compound represented by a following formula (a) is contained in the liquid crystal aligning agent of this invention.

[Formula 2]

In formula (a), R< ₁ >, R< ₂ > is respectively independently a C1-C8 linear or branched alkyl group, Preferably it is 3-8, More preferably, it is a 3-6 alkyl group. However, the sum total of carbon number of R< ₁ > and R< ₂ > is 4 or more, Preferably it is 5-12.

Although the following a-1 to a-48 are illustrated as a specific example of a specific solvent, it is not limited to these.

[Formula 3]

[Formula 4]

[Formula 5]

Among them, from the viewpoint of availability and practicality, a-22, a-13 to a-21, a-24, a-26, a-27, a-31, a-34, a-37, or a-38 This is preferable, and a-22 or a-37 is more preferable.

Liquid crystal aligning agent of this invention WHEREIN: 1-50 mass % or less is preferable with respect to the weight of all solvents, as for content of a specific solvent, 1-30 mass % is more preferable, 1-20 mass % is still more preferable Do.

<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 the following formula (1).

[Formula 6]

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 a C1-C5 represents alkylene. From a viewpoint of the easiness of advancing of the imidation reaction at the time of heating, a hydrogen atom, a methyl group, and an ethyl group are 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 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. From a viewpoint of liquid-crystal orientation, A ₁ and A ₂ have a preferable hydrogen atom or a methyl group.

Below, each component used as the raw material which manufactures the said polyimide precursor 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 7]

In the formula (2), A ₁ and A ₂ have the same definitions as A ₁ and A ₂ in the formula (1) including preferred examples. Examples of Y ₁ include the following (Y-1) to (Y-170). It is as follows.

[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]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

In formula, n is an integer of 1-6, and Me is a methyl group.

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 tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester dihalide which are the derivatives are mentioned.

As tetracarboxylic dianhydride or its derivative(s), it is more preferable to use tetracarboxylic dianhydride or its derivative(s) represented by following formula (3).

[Formula 26]

In Formula (3), X ₁ is a tetravalent organic group having an alicyclic structure, and the structure is not particularly limited. Specific examples include the following formulas (X1-1) to (X1-44).

[Formula 27]

In the 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. From a viewpoint of liquid-crystal orientation, a hydrogen atom, a halogen atom, a methyl group, or an ethyl group is preferable, and, as for R3 _{- R23} , a hydrogen atom or a methyl group is more preferable.

Further, specific examples of the formula (X1-1) include the following formulas (X1-1-1) to (X1-1-6). From the viewpoint of the liquid-crystal orientation and the sensitivity of the photoreaction, (X1-1-1) is particularly preferable.

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

As tetracarboxylic dianhydride or its derivative(s) which are the raw material of the polyimide precursor of this invention and a 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 manufactured.

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 polymer concentration in the reaction solution is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint of less likely to cause polymer precipitation and easy to obtain a high molecular weight body.

(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 WHEREIN: 30 minutes - 24 hours, Preferably 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. It is preferable that the usage-amount of a base is a quantity with easy removal, and it is 2-4 times mole 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 a high molecular weight body 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) In case of manufacturing polyamic acid ester from tetracarboxylic acid diester and diamine

Polyamic acid ester can be manufactured by polycondensing tetracarboxylic-acid diester and diamine.

Specifically, in the presence of a condensing agent, a base, and an organic solvent, tetracarboxylic-acid diester and diamine are 0 degreeC - 150 degreeC, 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 easy to remove, 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 synthesis|combining method of said three polyamic acid ester, the synthesis 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 the 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 at -20°C to 150°C in the presence of an organic solvent, 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, after performing precipitation for several times and washing|cleaning with a poor solvent, the powder of the refined polyamic acid can be obtained by normal temperature or heat-drying. Although the poor solvent is not specifically limited, Water, methanol, ethanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned.

<Method for producing 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 be imidated 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 basicity suitable for advancing 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 molar times of an amic acid group, Preferably it is 2-20 molar times, and the quantity of an acid anhydride is 1-50 molar times of an amic-acid group, Preferably it is 3-30 molar 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 solvent containing a specific solvent. As for the molecular weight of the polymer containing a specific polymer, 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 concentration of the polymer containing the specific polymer used in the present invention can be appropriately changed depending on the setting of the thickness of the coating film to be formed, 1 wt% or more is preferable in terms of forming a uniform and defect-free coating film, 10 weight% or less is preferable from the point of storage stability of a solution.

<Other solvents>

The solvent used for the liquid crystal aligning agent of this invention can contain solvents (henceforth another solvent) other than an above-described specific solvent. Other solvents are preferred. It will not specifically limit, if it is a solvent (it is also called a good solvent) in which the polymer of this invention is dissolved. Although the specific example of a good solvent is given below, it is not limited to these examples.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide or 4-hydroxy-4-methyl-2-pentanone, etc. can be heard

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, or 1,3-dimethyl-2 -Imidazolidinone is preferable.

Preferably 20 to 99 weight% of such a good solvent is 20 to 99 weight% of the total solvent amount, More preferably, it contains 30 to 80 weight%.

Moreover, when the solubility with respect to the solvent of the polyimide precursor and polyimide of this invention is high, it is preferable to use the solvent shown by a following formula [D-1] - a formula [D-3].

[Formula 34]

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ represents a C1-C4 alkyl group).

As another solvent, the solvent (it is also mentioned a poor solvent) which improves the coating-film property of a liquid crystal aligning film at the time of apply|coating a liquid crystal aligning agent, and surface smoothness can be contained. As for these poor solvents, 1-80 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable. Especially, 10-80 mass % is preferable. More preferably, it is 20-70 mass %.

Although the specific example of a poor solvent is given below, it is not limited to these examples. For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 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-methyl Cyclohexanol, 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 diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl Ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl Acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy) ethanol, butyl cellosolve, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyl ether) Siloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, 1-butoxy-2-propanol, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol mono Methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, butyl cellosolve acetate, ethylene glycol monoacetate, ethylene glycol Diacetate, diethylene glycol monoethyl ether acetate, diacetone alcohol, propyl Renglycol 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 acetate, methyl pyruvate, ethyl pyruvate, 3-methoxymethyl propionate, methyl ethyl 3-ethoxypropionate, 3 -Ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionate butyl, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl The solvent etc. which are shown by ester, lactic acid isoamyl ester, diisobutyl ketone, ethyl carbitol, or said Formula [D-1] - Formula [D-3] are mentioned.

Among them, butyl cellosolve, 1-butoxy-2-propanol, butyl cellosolve acetate, dipropylene glycol monomethyl ether, diacetone alcohol, diethylene glycol diethyl ether, diisopentyl ether, propylene glycol diacetate , it is preferable to use diisobutyl ketone, ethyl carbitol or dipropylene glycol dimethyl ether.

In the liquid crystal aligning agent of the present invention, a crosslinking 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 having at least one substituent selected from the group consisting of a crosslinking 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 35]

The crosslinking|crosslinked compound specifically, shown by the formula [4a] published on pages 58-59 of international publication WO2011/132751 (2011.10.27 publication) - a formula [4k] 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 36]

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. and a resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin or ethyleneurea-formaldehyde resin. 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. This melamine derivative or benzoguanamine derivative can also exist as a dimer or a trimer. These preferably have an average of 3 to 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 in an average of each triazine ring. MW-30 (above, manufactured by Sanwa Chemical), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 Methoxymethylated melamine, Cymel 235, 236, 238, 212 Methoxymethylated butoxymethylated melamine such as , 253, 254, butoxymethylated melamine such as Cymel 506 and 508, carboxyl 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, methylolation glycoluril, such as Cymel 1170, methylolation glycoluril, such as Cymel 1170, 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 is mentioned.

More specifically, the crosslinking|crosslinked compound of Formula [6-1] - Formula [6-48] which is 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 cross-linkable 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, neopentyl glycol 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 diglycidyl ester di(meth) phthalate or neopentyl glycol di(meth) hydroxypivalate, and 2-hydroxyethyl (meth) acrylate ) 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 37]

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, or a phenanthrene ring , E ₂ represents a group selected from the following formula [7a] or formula [7b], and n represents an integer of 1-4.)

[Formula 38]

In addition, 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 objective 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.

More 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 ( As mentioned above, the Sumitomo 3M company make), Asahi Guard AG710, Sufflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, the Asahi Glass company make) 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 on the 69-73 pages of international publication WO2011/132751 (2011.10.27 publication). ] - the nitrogen-containing heterocyclic amine represented by a 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 this invention, the said poor solvent, a crosslinking|crosslinked compound, the resin film, or the compound which improves the uniformity and surface smoothness of the film thickness of a liquid crystal aligning film, and the compound which accelerates|stimulates charge leakage, besides the liquid crystal aligning film and the adhesiveness of a board|substrate You may add the silane coupling agent for the purpose of improving , the imidation accelerator etc. for the purpose of advancing the imidation by heating of a polyimide precursor efficiently when baking a coating film further.

<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, an opaque material such as a silicon wafer can be used only on one side of the substrate, and a material that reflects light such as aluminum can also be used for the electrode in this case.

As for the film-forming method of a liquid crystal aligning agent, industrially, the method of performing by screen printing, an offset printing, a flexographic printing, the inkjet method, etc. is common. As another film-forming coating method, the dip method, the roll coater method, the slit coater method, the spinner method, the spray method, etc. 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 hot plate, 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 the liquid crystal aligning agent of this invention on a board|substrate, it orientation-processes by a rubbing process, a photo-alignment process, etc., Moreover, in a vertical orientation use etc., it can be used as a liquid crystal aligning film without an orientation process. A known method or apparatus can be used in an orientation process by a rubbing process, a photo-alignment process, etc.

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 the periphery is adhere|attached with a sealing compound. In order to control a board|substrate gap|interval in a sealing compound, it is preferable to mix the spacer normally, and to disperse|distribute the spacer for board|substrate gap|interval control also to the in-plane part which does not form a sealing compound. In a part of 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 into 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 the capillary phenomenon in air|atmosphere may be used. As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material may be used, but a negative liquid crystal material is preferable. Next, a polarizing plate is installed. Specifically, a pair of polarizing plates are affixed to the surface on the opposite side to the liquid crystal layer of two board|substrates.

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

BCS: Butyl Cellosolve, PB: 1-Butoxy-2-propanol

DME: dipropylene glycol dimethyl ether

DPM: dipropylene glycol monomethyl ether

DAA: diacetone alcohol, DEDG: diethylene glycol diethyl ether

DIBC: 2,6-dimethyl-4-heptanol

<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).

<Measuring method of solid content concentration>

After weighing 1.0 g of the solution into an aluminum cup and heat-treating at 200°C for 2 hours, the amount of solid remaining on the cup was measured to measure the solid content concentration of the solution.

[Preparation of polyamic acid A1]

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

[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. 92.2 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 degree|times in nitrogen atmosphere, and polyamic acid (A2 ) (viscosity: 520 mPa·s) was obtained.

[Preparation of polyamic acid solution a1]

264.3 g of NMP and BCS 200.0g were added to 535.7 g of polyamic-acid (A1) solutions, and the density|concentration of A1 obtained the polyamic-acid solution (a1) which is 6.0 weight%.

[Preparation of polyamic acid solution a2]

264.3 g of NMP and PB 200.0g were added to 535.7 g of polyamic-acid (A1) solutions, and the density|concentration of A1 obtained the polyamic-acid solution (a2) which is 6.0 weight%.

[Preparation of polyamic acid solution a3]

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

[Preparation of polyamic acid B1]

87.7 g of DA-3 was put into a 2000 ml four-neck 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 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 (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. Solid content concentration at the time of measuring 1.0 g of this polyamic-acid (B1) solution in an aluminum cup and processing on the conditions of 200 degreeC 2 hours was 9.8 weight%.

[Preparation of polyamic acid B2]

95.6 g of DA-3 was put into a 2000 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube was formed, 18.2 g of DA-4 was put, 967 g of NMP was added, and it was dissolved by stirring while sending nitrogen. 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 become 75.0 g and solid content concentration of 15 weight%, and heating at 50 degreeC in nitrogen atmosphere. This polyamic acid (B2) solution (viscosity: 302 mPa*s) was obtained.

[Example 1]

153.4 g of polyamic acid (B1) solutions are weighed, 38.5 g of GBL solutions which 1.3 g of NMP, 3-glycidoxy propyl triethoxysilane entered 1.3 weight% in the solution, 70.9 g of GBL, PB 78.5g and 50.0 g of DIBC were added, followed by stirring at room temperature for 1 hour. Then, 107.5g of a2 was added, and 500.0g of solutions (C1) of solid content:NMP:GBL:PB:DIBC=4.3:30:35.7:20:10 (weight%) were obtained by stirring for 1 hour further.

[Example 2]

153.4 g of polyamic acid (B1) solutions are weighed, and 1.3 g of NMP and 1.3 weight% of 3-glycidoxypropyl triethoxysilane are contained in the solution for 38.5 g of GBL solutions, GBL 145.9 g, and DIBC 53.5 g was added and stirred at room temperature for 1 hour. Then, 107.5g of a3 was added, and 500.0g of solutions (C2) of solid content:NMP:GBL:DIBC=4.3:30:50.7:15 (weight%) were obtained by stirring for 1 hour further.

[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, 70.9 g of GBL, 78.5 g of BCS and 50.0 g of DIBC were added, followed by stirring at room temperature for 1 hour. Then, 107.5g of a1 was added, and 500.0g of solutions (C3) of solid content:NMP:GBL:BCS:DIBC=4.3:30:35.7:20:10 (weight%) were obtained by stirring for 1 hour further.

[Example 4]

153.4 g of polyamic-acid (B1) solutions are weighed, 38.5 g of GBL solutions which 1.3 g and 3-glycidoxypropyl triethoxysilane entered 1.3 weight% of NMP in the solution, 95.9 g of GBL, DIBC 53.5g and 50.0 g of DAA were added, followed by stirring at room temperature for 1 hour. Then, 107.5g of a3 was added, and 500.0g of solutions (C4) of solid content:NMP:GBL:DIBC:DAA=4.3:30:40.7:15:10 (weight%) were obtained by stirring further for 1 hour.

[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, 120.9 g of GBL, DIBC 53.5g and 25.0 g of DEDG were added, followed by stirring at room temperature for 1 hour. Then, 107.5g of a3 was added, and 500.0g of solutions (C5) of solid content:NMP:GBL:DIBC:DEDG=4.3:30:40.7:15:5 (weight%) were obtained by stirring further for 1 hour.

[Example 6]

After stirring the liquid mixture 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 of NMP and 3-glycidoxy propyl tri with respect to this By adding 20.0 g of NMP solution containing 1.0% by weight of ethoxysilane, 179.0 g of GBL, 75.0 g of DIBC and 75.0 g of BCS, and stirring at room temperature for 3 hours, the polymer solid content ratio of A2 and B2 is 2:8, and the solid content :NMP:GBL:DIBC:BCS=4.2:30:40.8:15:15 (weight%) 500.0g of solutions (C11) were obtained.

[Example 7]

After stirring the liquid mixture 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-glycidoxy propyl tri with respect to this By adding 20.0 g of an NMP solution containing 1.0% by weight of ethoxysilane, adding 6.0 g of an NMP solution containing 10% by weight of AD-1, 179.0 g of GBL, 75.0 g of DIBC and 75.0 g of BCS, and stirring at room temperature for 3 hours , A2 and B2 have a polymer solids ratio of 2:8, and AD-1 is included in 3.0 wt% with respect to the polymer solid content, total solids: NMP: GBL: DIBC: BCS = 4.2: 30: 40.8: 15: 15 (wt%) ) of 500.0 g of a solution (C12) was obtained.

[Example 8]

After stirring the liquid mixture 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 of NMP and 3-glycidoxy propyl tri with respect to this By adding 20.0 g of NMP solution containing 1.0% by weight of ethoxysilane, 179.0 g of GBL, 75.0 g of DIBC and 75.0 g of PB, and stirring at room temperature for 3 hours, the polymer solid ratio of A2 and B2 is 2:8, and the solid content :NMP:GBL:DIBC:PB=4.2:30:40.8:15:15 (weight%) 500.0g of solutions (C13) were 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 in the solution, 145.9 g of GBL, and 53.5 g of BCS was added and stirred at room temperature for 1 hour. Then, 107.5g of a1 was added, and 500.0g of solutions (C6) of solid content:NMP:GBL:BCS=4.3:30:50.7:15 (weight%) were obtained by stirring for 1 hour further.

[Comparative Example 2]

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, BCS 53.5g and 50.0 g of DPM were added, followed by stirring at room temperature for 1 hour. Then, 107.5g of a1 was added, and 500.0g of solutions (C7) of solid content:NMP:GBL:BCS:DPM=4.3:30:40.7:15:10 (weight%) were obtained by stirring for 1 hour further.

[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, 70.9 g of GBL, and BCS 128.5g was added and stirred at room temperature for 1 hour. Then, 107.5g of a1 was added, and 500.0g of solutions (C8) of solid content:NMP:GBL:BCS=4.3:30:35.7:30 (weight%) were obtained by stirring for 1 hour further.

[Comparative Example 4]

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, BCS 53.5g and 50.0 g of DAA were added, followed by stirring at room temperature for 1 hour. Then, 107.5g of a1 was added, and 500.0g of solutions (C9) of solid content:NMP:GBL:BCS:DAA=4.3:30:40.7:15:10 (weight%) were obtained by stirring for 1 hour further.

[Comparative Example 5]

153.4 g of polyamic acid (B1) solutions are weighed, and 1.3 g of NMP and 1.3 weight% of 3-glycidoxypropyl triethoxysilane are 38.5 g of GBL solutions, GBL 120.9 g, PB 78.5 g in the solution. was added and stirred at room temperature for 1 hour. Then, 500.0g of solutions (C10) of solid content:NMP:GBL:PB=4.3:30:45.7:20 (weight%) were obtained by adding 107.5g of a2 and stirring for 1 hour further.

About Examples 1-8 and Comparative Examples 1-5, after filtering with the filter with a pore diameter of 1 micrometer, the viscosity in 25 degreeC was confirmed with the E-type viscometer (made by Toki Industries Co., Ltd.). Then, the following application|coating evaluation was also implemented.

[Evaluation of inkjet applicability]

About the said Examples 1-8 and Comparative Examples 1-5, 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, the film thickness of a coating film apply|coated on the conditions used as 120 nm when baking in IR oven on the conditions of 230 degreeC and 15 minutes.

[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. Lv4 for visually confirming significant non-uniformity on the entire surface, Lv3 for partially visually confirming non-uniformity, Lv2 for non-uniformity visible to the naked eye, and Lv1 for non-uniformity at all even with an optical microscope.

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

In addition, the coating film width was measured and the difference between the measured value and the set value was evaluated as dimensional stability with respect to the set application area|region. In addition, in this evaluation, it becomes a favorable coating film, so that a value is small.

These results are shown in Tables 1 and 2.

In addition, the specification of Japanese Patent Application No. 2016-072568 for which it applied on March 31, 2016, a claim, drawings, and the abstract are referred here, and it takes in as an indication of the specification of this invention.

Claims (12)

A polymer having an ability to align a liquid crystal, and a solvent containing a compound represented by the following formula (a) are contained, the liquid crystal aligning agent comprising:
At least one selected from the group consisting of a polyimide precursor having a structure represented by the following formula (1) obtained by reaction of the polymer with a tetracarboxylic acid derivative component and a diamine component, and a polyimide that is an imidized product thereof A liquid crystal aligning agent that is a polymer of

In formula (a), R< ₁ >, R< ₂ > is each independently a linear or branched C1-C8 alkyl group. However, the sum total of carbon number of R< ₁ > and R< ₂ > is 4 or more.

In 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, and R ₁ is a hydrogen atom or an alkyl having 1 to 5 carbon atoms. and 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. delete The method of claim 1,
The liquid crystal aligning agent in which the said solvent contains 1 to 50 weight% of the total amount of solvents. The method of claim 1,
The liquid crystal aligning agent whose said solvent is at least 1 sort(s) chosen from the group which consists of following a-2 - a-48.

5. The method of claim 4,
The liquid crystal aligning agent whose said solvent is said a-22, a-13 - a-21, a-24, a-26, a-27, a-31, a-34, a-37, or a-38. 5. The method of claim 4,
The liquid crystal aligning agent whose said solvent is said a-22 or a-38. The method of claim 1,
The solvent further comprises N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide and 1,3- The liquid crystal aligning agent containing the at least 1 sort(s) of good solvent chosen from the group which consists of dimethyl-2- imidazolidinone. 8. The method of claim 7,
The liquid crystal aligning agent in which the said good solvent contains 5-30 weight part with respect to 100 weight part of the solvent containing the compound represented by said Formula (a). The method of claim 1,
As a solvent, furthermore, butyl cellosolve, 1-butoxy-2-propanol, butyl cellosolve acetate, dipropylene glycol monomethyl ether, diacetone alcohol, diethylene glycol diethyl ether, diisopentyl ether, propylene The liquid crystal aligning agent containing the at least 1 sort(s) of poor solvent chosen from the group which consists of glycol diacetate, diisobutyl ketone, ethyl carbitol, and dipropylene glycol dimethyl ether. 10. The method of claim 9,
The liquid crystal aligning agent in which the said poor solvent contains 5-40 weight part with respect to 100 weight part of the solvent containing the compound represented by said Formula (a). The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1 and 3-10. A liquid crystal display element provided with the liquid crystal aligning film of Claim 11.