KR102544852B1 - The manufacturing method of a liquid crystal aligning agent and a liquid crystal aligning film - Google Patents

Abstract

Provision of a liquid crystal aligning agent for display elements such as monitors requiring high-definition, high-brightness, high-reliability images, and a method for producing a liquid crystal aligning film from the liquid crystal aligning agent since the pretilt angle of the liquid crystal can be made almost 0 degrees. . A polyimide precursor obtained by polymerizing a diamine component containing a diamine represented by Formula [1] and a tetracarboxylic acid component, and at least one polymer selected from the group consisting of a polyimide obtained from the polyimide precursor. The liquid crystal aligning agent and the manufacturing method of the liquid crystal aligning film from this liquid crystal aligning agent. (X: NHCO, CONH, COO- or OCO, m: 1 to 5, n: 0 to 6, R ₁ to R ₄ : each independently a methyl group or an ethyl group)

Description

The manufacturing method of a liquid crystal aligning agent and a liquid crystal aligning film

This invention relates to the manufacturing method of the liquid crystal aligning agent suitably used for the liquid crystal display element which further high luminance, high definition, and a reliable image are requested|required, and a liquid crystal aligning film.

BACKGROUND OF THE INVENTION A liquid crystal display element is currently widely used as a display device that realizes a thin shape and a light weight. Usually, a liquid crystal aligning film is used for this liquid crystal display element in order to determine the orientation state of a liquid crystal. Moreover, most of the liquid crystal aligning films except some vertical alignment type liquid crystal display elements etc. are manufactured by giving some kind of orientation process to the surface of the polymer film formed on the electrode substrate.

As a method for orientation treatment of a polymer film, a method currently generally used is a method in which a so-called rubbing treatment is performed by rubbing the polymer film surface with a cloth made of rayon or the like under pressure. The rubbing treatment can be carried out with simple equipment, produces effective and excellent results, and the difficulty due to the generation of cutting chips of the polymer film accompanying the treatment has been remarkably improved in recent years. Along with the treatment method, it is practiced in a wide field (see Patent Documents 1 and 2).

On the other hand, with the recent high performance of liquid crystal display elements, in addition to applications such as large-screen and high-definition liquid crystal televisions, various applications such as car navigation systems, meter panels, monitors for monitoring cameras and medical cameras for in-vehicle use, etc. A liquid crystal display device is used for a variety of applications. In these applications, while obtaining high luminance, additional high-definition and highly reliable images are required.

As one measure for this, the alignment direction of the liquid crystal in the liquid crystal display element is made from a parallel direction to a direction orthogonal to the rubbing direction, and an alkyl that can make the pretilt angle of the liquid crystal as high as 1 to 10 degrees to almost 0 degrees. The liquid crystal aligning agent and liquid crystal aligning film using the specific polymer obtained from fluorenediamine are proposed (refer patent document 3, 4).

However, in the case of a liquid crystal aligning film using a specific polymer obtained from these alkyl fluorenediamines, stability of the liquid crystal orientation at the time of drive of the liquid crystal display element has a subject further.

Japanese Unexamined Patent Publication No. 9-185065 Japanese Unexamined Patent Publication No. 9-146100 Japanese Unexamined Patent Publication No. 2002-20487 Japanese Unexamined Patent Publication No. 2002-49039

The present invention is a liquid crystal alignment film preferably used for a liquid crystal display element requiring high brightness, high definition and high reliability images, that is, a liquid crystal alignment direction in a liquid crystal display element from a parallel direction to a direction orthogonal to the rubbing direction. It makes it a subject to provide the liquid crystal aligning agent from which the liquid crystal aligning film which can make the pretilt angle of a liquid crystal into substantially 0 degree is obtained, and the manufacturing method of a liquid crystal aligning film.

As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the polymer obtained from the siloxane type diamine which has a specific structure which is not used as a liquid crystal aligning agent conventionally satisfies said subject.

This invention is based on this knowledge, and provides the liquid crystal aligning agent which makes the following a summary, and the manufacturing method of the liquid crystal aligning film from this liquid crystal aligning agent.

At least one selected from the group consisting of a polyimide precursor obtained by polymerizing a diamine component containing a diamine represented by any one of the following formulas [1] to formula [6] and a tetracarboxylic acid component, and a polyimide obtained from the polyimide precursor The liquid crystal aligning agent characterized by containing 1 type of polymer.

[Formula 1]

In addition, in formula [1], R1 _{- R4} is a methyl group or an ethyl group each independently. X is -NHCO-, -CONH-, -O-, -COO- or -OCO-. Hydrogen on the aromatic ring may be substituted with a methyl group, a fluorine group, or a tert-butoxycarbonyl group. m is an integer of 1 to 5; n is an integer of 0-6. In addition, in formula [6], Boc represents a tert-butoxycarbonyl group.

The liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention makes the alignment direction of the liquid crystal from the parallel direction to the orthogonal direction with respect to the rubbing direction, and can make the pretilt angle of the liquid crystal almost 0 degrees, and as a result, very high brightness, A liquid crystal display element capable of providing images with high definition and high reliability is obtained. This liquid crystal display element is suitably used for in-vehicle use, for example, a car navigation system, a meter panel, a monitoring camera, a monitor for a medical camera, and the like.

<Specific Polymer (A)>

The polyimide precursor obtained by making the diamine component and tetracarboxylic-acid component containing the diamine (it is also mentioned specific diamine in this invention) react with the liquid crystal aligning agent of this invention, and its polyimide precursor represented by said Formula [1] At least 1 type of polymer (henceforth also called a specific polymer (A)) chosen from the group which consists of polyimides imidated is contained.

(specific diamine)

Specific diamine is diamine which has a siloxane structure represented by following formula [1].

[Formula 2]

In the formula [1], X, m, R ₁ to R ₄ and n are as defined above. Especially, -CONH- or -COO- of X is preferable. m is preferably 1 or 2, R ₁ to R ₄ are preferably methyl groups, and n is preferably 1 to 4. In addition, in said formula [1], "へ" means " _-CH2- ".

Preferred examples of the specific diamine include the following.

[Formula 3]

[Formula 4]

30-100 mol% is preferable in 100 mol% of all diamine components used in order to obtain a specific polymer, and, as for content of a specific diamine, 50-100 mol% is more preferable.

As a diamine component for obtaining a specific polymer (A), you may contain diamine (henceforth other diamine) other than the specific diamine represented by said Formula [1]. Such diamine is represented by the following general formula (2). In addition, diamine may use together 1 type or 2 or more types.

[Formula 5]

In said Formula [2], _A1 and _A2 are a hydrogen atom, or a C1-C5 alkyl group, a C2-C5 alkenyl group, or a C2-C5 alkynyl group each independently. From the viewpoint of liquid crystal alignment, A ₁ and A ₂ are preferably a hydrogen atom or a methyl group. If the structure of Y ₁ is illustrated, it is as follows formula (Y-1) - formula (Y-171).

[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]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

In the above formula, n is an integer of 1 to 6, and Me represents a methyl group.

[Formula 25]

Boc in the formula above represents a tert-butoxycarbonyl group.

(Tetracarboxylic acid component)

As the tetracarboxylic acid component for obtaining the specific polymer (A), tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester dihalide can be heard In the present invention, these are also collectively referred to as tetracarboxylic acid components.

As the tetracarboxylic acid component, tetracarboxylic dianhydride represented by the following formula [3], tetracarboxylic acid as its derivative, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester Dihalides (these are collectively referred to as the first tetracarboxylic acid component) can also be used.

[Formula 26]

In the formula [3], Z ¹ represents a tetravalent organic group. As the example, at least 1 sort(s) chosen from the group which consists of following formula [3a] - formula [3t] is mentioned.

[Formula 27]

[Formula 28]

In formula [3a], each of Z ¹ to Z ⁴ independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a benzene ring.

In formula [3g], Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group.

Z ¹ in formula [3] is preferably formula [3a], formula [3c] to [3g], formula [3k] to formula [3m] or formula [3p] from the viewpoint of ease of synthesis and ease of polymerization reactivity. , Formula [3a], Formula [3e], Formula [3f], Formula [3l], Formula [3m], or Formula [3p] is more preferable. In particular, the formula [3m], [3n], [3p] or [3t]. In formula [3a], Z ¹ to Z ⁴ have a preferable hydrogen atom.

The first tetracarboxylic acid component is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, particularly preferably 100 mol% of all tetracarboxylic acid components for obtaining the specific polymer (A) is 70 to 100 mol%. The 1st tetracarboxylic acid component is solubility to the solvent of a specific polymer (A), the applicability of a liquid crystal aligning agent, the orientation of the liquid crystal in the case of using it as a liquid crystal aligning film, voltage retention, According to characteristics, such as accumulated electric charge, 1 type or 2 or more types can be used.

The tetracarboxylic-acid component for obtaining a specific polymer (A) can use other tetracarboxylic-acid components other than the 1st tetracarboxylic-acid component. Other tetracarboxylic acid components include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl ester dihalide described below.

Specifically, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3' ,4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl) ether, 3,3',4,4 '-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1 ,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane, bis(3,4- Dicarboxyphenyl)diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenyl Sulfontetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid, etc. are mentioned.

Although other tetracarboxylic-acid components may mix and use 1 type or 2 or more types, an aromatic anhydride is preferable from a viewpoint of liquid-crystal orientation.

<Specific Polymer (B)>

The polyimide precursor obtained by making the liquid crystal aligning agent of this invention react with diamine and tetracarboxylic-acid component other than the diamine which has a structure represented by said Formula [1] with a specific polymer (A), and its polyimide precursor At least one type of polymer (also referred to as specific polymer (B) in the present invention) selected from the group consisting of imidized polyimides can be contained.

As for the diamine component for obtaining a specific polymer (B), above-mentioned other diamine which can be used arbitrarily in order to obtain a specific polymer (A) is mentioned. As the specific example, it is the same as the specific example of other diamine illustrated in order to obtain a specific polymer (A). In particular, (Y-68), (Y-72) or (Y-160) is preferable from the viewpoint of the relaxation property of the stored charge.

As a tetracarboxylic-acid component for obtaining a specific polymer (B), the same thing as the said 1st tetracarboxylic-acid component used in order to obtain a specific polymer (A) is mentioned, and the specific example is also the same.

The tetracarboxylic-acid component for obtaining a specific polymer (B) can also use other tetracarboxylic-acid components with a 1st tetracarboxylic-acid component similarly to the case where a specific polymer (B) is obtained. As a specific example of such other tetracarboxylic acid component, what was illustrated as another tetracarboxylic acid component for obtaining a specific polymer (A) is mentioned.

<Method for producing specific polymers (A) and (B)>

In the method for producing these polymers (A) and (B), a polyimide precursor is usually produced by polycondensation of a diamine component and a tetracarboxylic acid component, and the polyimide precursor is imidized to produce a polyimide. When the said polymer polyimide precursor is a polyamic acid (polyamic acid), a polyamic acid is obtained by polycondensing tetracarboxylic dianhydride and the diamine component which consists of 1 type or multiple types of diamine.

When the polymer polyimide precursor is a polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by converting a carboxylic acid group into a dialkyl ester and a primary or secondary diamine, or a tetracarboxylic acid dialkyl obtained by halogenating a carboxylic acid group A method of polycondensing a halide and a primary or secondary diamine or a method of converting a carboxy group of polyamic acid into an ester is used.

Reaction of a diamine component and a tetracarboxylic acid component is normally performed in a solvent. The solvent used in that case is not particularly limited as long as the produced polyimide precursor dissolves therein. Below, although the specific example of the solvent used for reaction is given, it is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, or 1,3-dimethyl-imidazolidinone. Moreover, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or following formula [D-1] - formula [D -3] can be used.

[Formula 29]

(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 an alkyl group having 1 to 4 carbon atoms)

These solvents may be used alone or in combination. In addition, even if it is a solvent that does not dissolve the polyimide precursor, you may mix it with the said solvent and use it within the range in which the produced|generated polyimide precursor does not precipitate. In addition, moisture in the solvent inhibits the polymerization reaction and consequently causes the produced polyimide precursor to be hydrolyzed, so it is preferable to use a solvent obtained by dehydration and drying.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, a solution in which the diamine component is dispersed or dissolved in a solvent is stirred, and the tetracarboxylic acid component is added as it is or after being dispersed or dissolved in a solvent. A method of adding a diamine component to a solution obtained by dispersing or dissolving a carboxylic acid component in a solvent, a method of adding a diamine component and a tetracarboxylic acid component alternately to the reaction system, and the like, using any of these methods can also Moreover, when reacting using multiple types of diamine component or tetracarboxylic acid component, respectively, they may be reacted in a premixed state, may be reacted in sequence individually, or low molecular weight substances reacted individually may be mixed and reacted. It may be made into a polymer.

The temperature at which the diamine component and the tetracarboxylic acid component are polycondensed can be selected from any temperature of -20 to 150°C, but is preferably in the range of -5 to 100°C. The reaction can be carried out at any concentration, but when the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and when the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, the concentration of the polymer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction can be performed at a high concentration, and then a solvent can be added.

In the polymerization reaction for obtaining a polyimide precursor, the ratio of the total number of moles of the tetracarboxylic acid component to the total number of moles of the diamine component is preferably from 0.8 to 1.2. Similar to a typical polycondensation reaction, the closer this molar ratio is to 1.0, the higher the molecular weight of the polyimide precursor produced.

A polyimide is a polyimide obtained by ring-closing a polyimide precursor. In this polyimide, the ring-closing rate (also referred to as the imidization rate) of amic acid groups (amic acid groups) is not necessarily 100%, depending on the use or purpose. can be adjusted arbitrarily.

As a method of imidating the polyimide precursor, thermal imidation in which the solution of the polyimide precursor is heated as it is or catalyst imidation in which a catalyst is added to the solution of the polyimide precursor is exemplified.

The temperature in the case of thermal imidation of the polyimide precursor in the solution is preferably 100 to 400 ° C., more preferably 120 to 250 ° C., and the method of carrying out the imidation reaction while removing the water generated outside the system desirable. Catalytic imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250°C, preferably 0 to 180°C.

The amount of the basic catalyst is preferably 0.5 to 30 mole times, more preferably 2 to 20 mole times the amic acid group, and the amount of the acid anhydride is preferably 1 to 50 mole times, more preferably 3 to 30 mole times the amic acid group. am.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has a suitable basicity for advancing the reaction.

As an acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned. In particular, the use of acetic anhydride is preferable because purification after completion of the reaction becomes easy. The imidation rate by catalyst imidation can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

What is necessary is just to throw in the reaction solution into a solvent and just to precipitate it, when collect|recovering the polyimide precursor or polyimide produced|generated from the reaction solution. Methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water etc. are mentioned as a solvent used for precipitation. The polymer precipitated by pouring into the solvent can be recovered by filtration and then dried at normal temperature or under reduced pressure by heating. In addition, impurities in the polymer can be reduced by re-dissolving the polymer recovered by precipitation in a solvent and repeating the operation of re-precipitation and recovery 2 to 10 times. As a solvent at this time, alcohols, ketones, hydrocarbons, etc. are mentioned, for example. The use of three or more types of solvents selected from among these is preferable because the efficiency of purification is further increased.

In this invention, when a polyimide precursor is a polyamic acid alkylester, the specific method for manufacturing it is shown to following (1)-(3).

(1) Manufacturing method by esterification of polyamic acid

It is a method of manufacturing a polyamic acid alkylester by manufacturing a polyamic acid from a diamine component and a tetracarboxylic acid component, performing a chemical reaction, ie, an esterification reaction, to the carboxy group (COOH group).

In the esterification reaction, the polyamic acid and the esterification agent are reacted in the presence of a solvent, preferably -20 to 150°C, more preferably 0 to 50°C, preferably for 30 minutes to 24 hours, more preferably 1 It is a method of reacting for about 4 hours.

The esterifying agent is preferably one that can be easily removed after the esterification reaction, and N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide di Propylacetal, N,N-dimethylformamidedineopentylbutylacetal, N,N-dimethylformamidedi-t-butylacetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p- tolyltriazene, 1-propyl-3-p-tolyltriazene, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, etc. can The amount of the esterifying agent used is preferably 2 to 6 molar equivalents relative to 1 mol of the repeating unit of the polyamic acid. Especially, 2-4 molar equivalents are preferable.

As a solvent used for the said esterification reaction, the solvent used for reaction of the said diamine component and tetracarboxylic acid component is mentioned from the point of solubility to the solvent of a polyamic acid. Especially, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or (gamma)-butyrolactone is preferable. You may use these solvent 1 type or in mixture of 2 or more types.

1-30 mass % is preferable and, as for the density|concentration of the polyamic acid in the solvent in the said esterification reaction, 5-20 mass % is more preferable at the point which precipitation of a polyamic acid does not occur easily.

(2) Method for producing by reaction of diamine component and tetracarboxylic acid diester dichloride

Specifically, the diamine component and the tetracarboxylic acid diester dichloride are mixed in the presence of a base and a solvent, preferably at -20 to 150°C, more preferably at 0 to 50°C, preferably for 30 minutes to 24 time, more preferably a method of reacting for 1 to 4 hours.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used. Among them, pyridine is preferable because the reaction proceeds mildly. The amount of the base used is preferably an amount that can be easily removed after the reaction, and is preferably 2 to 4 times mole, more preferably 2 to 3 times mole relative to tetracarboxylic diester dichloride.

The solvent used for reaction of a diamine component and a tetracarboxylic-acid component is mentioned to a solvent from the point of the solubility with respect to the solvent of the polymer obtained, ie, polyamic-acid alkylester. Especially, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or (gamma)-butyrolactone is preferable. You may use these solvent 1 type or in mixture of 2 or more types.

1-30 mass % is preferable and, as for the density|concentration of the polyamic-acid alkylester in the solvent in reaction, 5-20 mass % is more preferable at the point which precipitation of polyamic acid alkyl ester does not occur easily. Moreover, in order to prevent hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable that the solvent used for manufacture of polyamic-acid alkylester is dehydrated as much as possible. In addition, it is preferable to carry out the reaction in a nitrogen atmosphere to prevent mixing of outside air.

(3) Method for manufacturing by reaction of diamine component and tetracarboxylic acid diester

Specifically, the diamine component and the tetracarboxylic acid diester are mixed in the presence of a condensing agent, a base and a solvent, preferably at 0 to 150°C, more preferably at 0 to 100°C, preferably for 30 minutes to 24 time, more preferably a method of polycondensing from 3 to 15 hours.

Condensing agents 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'-tetramethyluronium tetrafluoroborate, O-(benzotriazole-1 -yl)-N,N,N',N'-tetramethyluronium hexafluorophosphite, (2,3-dihydro-2-thioxo-3-benzooxazolyl)phosphonic acid diphenyl, etc. can The amount of condensing agent used is preferably 2 to 3 moles, more preferably 2 to 2.5 moles, relative to the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base used is preferably an easily removable amount after the polycondensation reaction, preferably 2 to 4 times mole, more preferably 2 to 3 times mole relative to the diamine component.

As for the solvent used for polycondensation reaction, the solvent used for reaction of a diamine component and a tetracarboxylic acid component is mentioned from the point of the solubility with respect to the solvent of polyamic acid alkylester obtained. Especially, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or (gamma)-butyrolactone is preferable. These solvents may be used alone or in combination of two or more.

Moreover, in a polycondensation reaction, reaction advances efficiently by adding a Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. 0.1-10 times mole is preferable with respect to the diamine component, and, as for the usage-amount of Lewis acid, 2.0-3.0 times mole is more preferable.

What is necessary is just to throw in the reaction solution into a solvent and just to precipitate, when collect|recovering polyamic acid alkylester from the solution of the polyamic acid alkylester obtained by the method of said (1)-(3). Water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned as a solvent used for precipitation. The polymer precipitated by being put into a solvent is preferably subjected to a plurality of washing operations with the solvent for the purpose of removing the additives and catalysts used above. After washing and recovering by filtration, the polymer can be dried under normal pressure or reduced pressure at room temperature or by heating. In addition, impurities in the polymer can be reduced by re-dissolving the polymer recovered by precipitation in a solvent and repeating the operation of re-precipitation and recovery 2 to 10 times.

As for polyamic acid alkylester, the manufacturing method of said (2) or (3) is preferable.

<liquid crystal aligning agent>

The liquid crystal aligning agent of this invention is a solution for forming a liquid crystal aligning film, and contains a specific polymer (A) and a specific polymer (B) as needed. 2-10 mass % is preferable in a liquid crystal aligning agent, and, as for content of the specific polymer (A) in a liquid crystal aligning agent, 3-8 mass % is more preferable.

Moreover, as for the ratio, when a liquid crystal aligning agent contains a specific polymer (B), 10-900 mass parts is preferable with respect to 100 mass parts of specific polymers (A), and 25-700 mass parts are more preferable.

As for all the polymer components in the liquid crystal aligning agent of this invention, all may be the specific polymer (A) of this invention and (B), and another polymer other than that may be mixed. Examples of other polymers include cellulose polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamides, and polysiloxanes. The content of the other polymers is preferably from 0.5 to 15 parts by mass, more preferably from 1 to 10 parts by mass, based on a total of 100 parts by mass of the specific polymers (A) and (B).

Moreover, although an organic solvent contains a liquid crystal aligning agent normally, it is preferable that content of an organic solvent is 70-99.9 mass % with respect to a liquid crystal aligning agent. This content can be suitably changed with the film thickness of the liquid crystal aligning film made into the coating method of a liquid crystal aligning agent, or the objective.

The organic solvent used for a liquid crystal aligning agent is preferably a solvent (also referred to as a good solvent) in which a specific polymer (A) and a specific polymer (B) are dissolved. 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, 4-hydroxy-4-methyl-2-pentanone, etc. are mentioned. Especially, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone.

Moreover, when the solubility to the solvent of a specific polymer (A) and a specific polymer (B) is high, it is preferable to use the solvent represented by the said formula [D-1] - formula [D-3].

It is preferable that it is 20-99 mass % of the whole solvent contained in a liquid crystal aligning agent, and, as for the good solvent in the liquid crystal aligning agent of this invention, 20-90 mass % is more preferable, and it is especially preferable that it is 30-80 mass % am.

The liquid crystal aligning agent of this invention can use the solvent (it is also mentioned poor solvent) which improves the coating film property and surface smoothness of the liquid crystal aligning film at the time of apply|coating a liquid crystal aligning agent. A specific example thereof is given below.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 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, 2,6-dimethyl-4-heptanol, 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, diisopropyl ether , 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, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-hep Thanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-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, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2 -(Hexyloxy)ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, diethylene glycol mono Ethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol Acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxymethylpropionate, 3-ethoxyethylpropionate, 3-ethoxymethylethylpropionate, 3-methoxyethylpropionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropylpropionate, 3- butyl methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, solvents represented by the formulas [D-1] to [D-3], etc. can

Among them, preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether, N- Methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyro Lactone, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol diethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and 2,6-dimethyl- 4-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, and the like. 1-80 mass % of the whole solvent contained in a liquid crystal aligning agent is preferable, as for these poor solvents, 10-80 mass % is more preferable, and 20-70 mass % is especially preferable. The type and content of such a solvent are appropriately selected depending on the application device, application conditions, and application environment of the liquid crystal aligning agent.

In the liquid crystal aligning agent of the present invention, polymers other than the polymers described in the present invention, dielectrics for the purpose of changing the electrical properties such as dielectric constant and conductivity of the liquid crystal aligning film, silane coupling agents for the purpose of improving the adhesion between the liquid crystal aligning film and the substrate, liquid crystal A crosslinkable compound for the purpose of increasing the hardness and density of the film when used as an alignment film, and also an imidation accelerator for the purpose of efficiently advancing imidation by heating the polyimide precursor when firing the coating film.

As a compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, a functional silane containing compound and an epoxy group containing compound are mentioned, For example, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureido Propyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-Trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethine Toxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltri Ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis (oxyethylene)-3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N -diglycidylaminomethyl)cyclohexane or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane; and the like.

Moreover, in order to raise the mechanical strength of a liquid crystal aligning film, you may add the following additives to the liquid crystal aligning agent of this invention.

[Formula 30]

It is preferable that said additive is 0.1-30 mass parts with respect to 100 mass parts of the polymer components contained in a liquid crystal aligning agent. If it is less than 0.1 part by mass, no effect can be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal will be reduced. Therefore, it is more preferably 0.5 to 20 parts by mass.

<Method for Manufacturing Liquid Crystal Alignment Film>

The liquid crystal aligning film is obtained by forming a film of the liquid crystal aligning agent on a substrate by application or the like, preferably drying it, and then baking it. As the substrate, a highly transparent substrate is preferable, and ceramics such as glass and silicon nitride, plastics such as acryl and polycarbonate, and the like can be used as the material. As the substrate, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving the liquid crystal is formed, in view of simplifying the process. Further, in the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used for the substrate on one side, and a material that reflects light such as aluminum can be used for the electrode.

As a method of forming a film on a substrate from a liquid crystal aligning agent, screen printing, offset printing, flexographic printing, an inkjet method, etc. can be used industrially, and also a dip method, a roll coater method, a slit coater method, a spinner method, spray method, etc. can also be used depending on the purpose.

After forming the film of the liquid crystal aligning agent on the substrate, the film is preferably heated to 30 to 120 ° C., more preferably 50 ° C. It is preferable to evaporate the solvent by carrying out a drying treatment at 120°C, preferably for 1 minute to 10 minutes, and more preferably for 1 minute to 5 minutes.

Next, the coating film obtained from the liquid crystal aligning agent is subjected to a baking treatment at preferably 120 to 250°C and more preferably at 150 to 230°C by the same heating means as the above drying treatment. The temperature of this firing treatment is preferably 90 to 130°C higher than the temperature of the drying treatment, and more preferably 100 to 110°C higher. The firing treatment time varies depending on the firing temperature, but is preferably 5 minutes to 1 hour, more preferably 5 minutes to 40 minutes.

By such baking treatment, the polyimide precursor constituting the polymer contained in the film obtained from the liquid crystal aligning agent is imidized by dehydration ring closure, but in the present invention, the imidation rate of the polyimide precursor contained in the film obtained after baking is , 20 to 100% is preferable, and 30 to 100% or more is more preferable. When the imidation ratio is within the above range, the pretilt angle can be made low, and the effect of the present invention is sufficiently achieved.

The thickness of the film after the baking treatment is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may decrease, and if it is too thick, the electrical resistance of the obtained liquid crystal aligning film increases, so 5 to 300 nm is preferable, 10-200 nm is more preferable.

After the firing treatment, the obtained film is subjected to orientation treatment. Although a rubbing treatment method, a photo-alignment treatment method, etc. are mentioned as a method of orientation treatment, the rubbing treatment method is especially preferable.

As the rubbing treatment method, an existing rubbing method or apparatus can be used. Examples of the material of the rubbing cloth include cotton, rayon, nylon, and polyester. For example, as shown in Japanese Unexamined Patent Publication No. 55-143525, as a liquid crystal alignment substrate, an alignment film applied on a transparent electrode substrate is used, and a rubbing cloth is applied to a roller on the alignment film surface. A method of obtaining uniform liquid crystal orientation by rubbing with a rubbing machine is widely used as a rubbing method.

Rubbing intensity|strength is an index at the time of a rubbing process, and has substantially the same meaning as a rubbing density. As shown in Unexamined-Japanese-Patent No. 2011-140161, the formula of rubbing strength is shown below, and it is known that a desired strength can be processed by adjusting related values.

Rubbing strength (mm) = N × L × (1 ± 2π × r × n/60/v)

In the above formula, N is the number of times of the rubbing treatment, and L is the amount (mm) of pressing the rubbing roll around the rubbing cloth. r is the rubbing roll radius (mm). n is the rotational speed of the rubbing roll (rpm: 1/60 s ^-1 ). v is the moving speed of the film strip (mm/s). Further, the + side of ± in the equation means reverse rotation with respect to the film band moving direction, and the - side means forward rotation with respect to the film band moving direction.

If the rubbing strength is too weak or too strong, it is difficult to obtain uniform orientation, so it is preferably 20 to 130 mm, and more preferably 30 to 100 mm from the viewpoint of liquid crystal orientation.

Moreover, in this invention, as a method of orientation treatment, a photo-alignment treatment method can also be used together. As a specific example of the photo-alignment treatment, the surface of the film is irradiated with radiation deflected in a certain direction. As radiation, ultraviolet rays or visible rays having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferred, and ultraviolet rays having a wavelength of 200 to 400 nm are more preferred.

In this invention, after orientation-processing the film obtained from the said liquid crystal aligning agent, it is preferable to heat-process a film further.

The heat treatment after the orientation treatment can be performed by the same heating means as the above drying treatment or firing treatment, and is preferably carried out at 180 to 250°C, more preferably 180 to 230°C. The temperature of the heat treatment here is different depending on the heating time, but it is preferably carried out at a temperature that is preferably 0 to 130 ° C., more preferably 0 to 50 ° C. higher than the above-mentioned baking treatment of the film. When the temperature of heat processing is performed in said range, the pretilt angle obtained by the liquid crystal aligning film obtained can be made small enough.

The heat treatment time varies depending on the heating temperature, but is preferably 5 minutes to 1 hour, more preferably 5 to 40 minutes.

It is preferable that the liquid crystal aligning film in this invention expresses liquid-crystal orientation after the said baking process or heat processing from an orientation point, and it is more preferable that imidation does not advance by the said heat process.

Although the liquid crystal aligning film obtained by the said heat processing can be used as it is, it can also be wash|cleaned by contact processing using water or a solvent as needed. It will not specifically limit, if it is a solvent which dissolves the impurity etc. which adhered to the liquid crystal aligning film as a solvent to be used.

Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate , diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, and the like. Among them, water, 2-propanol, 1-methoxy-2-propanol or ethyl lactate is preferable from the viewpoint of versatility and safety of the solvent. More preferred are water, 1-methoxy-2-propanol or ethyl lactate. One type or two or more types may be sufficient as these solvent.

Examples of the contact treatment include immersion treatment and spray treatment (also referred to as spray treatment). As for the treatment time in these treatments, 10 seconds - 1 hour are preferable, and it is preferable to carry out immersion treatment for 1 to 30 minutes especially. Further, the temperature at the time of the contact treatment may be normal temperature or heated, but is preferably 10 to 80°C, preferably 20 to 50°C. During the contact treatment, ultrasonic treatment or the like may be further performed as needed.

After the contact treatment, rinsing with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone (also referred to as rinsing) or drying is preferably performed. In that case, either one of rinsing and drying may be performed, and both may be performed. The drying temperature is preferably 50 to 150°C, and preferably 80 to 120°C. Moreover, 10 second - 30 minutes are preferable and, as for drying time, 1 to 10 minutes are preferable.

<liquid crystal display element>

The liquid crystal aligning film of the present invention is suitable as a liquid crystal aligning film of a liquid crystal display element of a horizontal electric field system such as an IPS system or a FFS system, and is particularly useful for a liquid crystal display element of an FFS system. After the liquid crystal display element of this invention obtained the board|substrate with a liquid crystal aligning film obtained from the said liquid crystal aligning agent, it manufactured a liquid crystal cell by a known method, and used the liquid crystal cell as an element.

As an example of a method for manufacturing a liquid crystal cell, a liquid crystal display element having a passive matrix structure will be described as an example. Alternatively, a liquid crystal display element having an active matrix structure in which switching elements such as TFTs are formed in each pixel portion constituting an image display may be used.

Specifically, a transparent glass substrate is prepared, and a common electrode is formed on one substrate and a segment electrode is formed on the other substrate. These electrodes can be, for example, ITO electrodes, 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 film made of SiO ₂ -TiO ₂ formed by a sol-gel method. Next, on conditions similar to the above, a liquid crystal alignment film is formed on each substrate, and the other substrate is overlaid on one substrate so that the liquid crystal alignment film surfaces face each other, and the periphery is bonded with a sealant. In order to control the substrate gap, it is usually preferable to mix a spacer into the sealant. Further, it is preferable to spread spacers for controlling the gap between the substrates also in the in-plane portion where the sealant is not formed. It is preferable to form an opening that can be filled with liquid crystal from the outside in a part of the sealing agent.

After that, the liquid crystal material is injected into the space surrounded by the two substrates and the sealant through an opening formed in the sealant. Next, this opening is sealed with an adhesive. For the injection, a vacuum injection method or a method using capillarity in the air may be exemplified, and a One Drop Fill (ODF) method may be used. As the liquid crystal material, any of positive and negative dielectric anisotropy may be used. In the present invention, a liquid crystal having negative dielectric anisotropy is preferable from the viewpoint of liquid crystal orientation, but it can be used properly depending on the application.

After the liquid crystal material is injected into the liquid crystal cell, the polarizing plate is installed. Specifically, it is preferable to attach a pair of polarizing plates to the surfaces of the two substrates opposite to the liquid crystal layer.

Example

Below, the present invention will be specifically described by giving examples and the like, but the present invention is not limited to these examples. In addition, the symbol of a compound and a solvent is as follows.

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

[Formula 31]

[Formula 32]

<Viscosity>

The viscosity of the polymer solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) at a sample amount of 1.1 ml, a cone rotor TE-1 (1° 34', R24), and a temperature of 25°C.

<Identification of the compound>

The structure of the compound was confirmed by obtaining the following spectral data by ¹ H-NMR analysis.

NMR measurement conditions;

Device: Varian NMR System 400NB (400 MHz)

Reference substance: tetramethylsilane (TMS) (δ = 0.0 ppm)

(Synthesis Example 1)

4.86g (9.98mmol) of DA-1 was weighed out in a 100ml four-necked flask equipped with a stirrer and a nitrogen inlet pipe, 17.2g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. Stirring this diamine solution under water cooling, 0.509g (2.40 mmol) of CA-2 was added, 8.73g of NMP was added, and it stirred at 40 degreeC by nitrogen atmosphere for 2 hours. Further, 2.11 g (7.18 mmol) of CA-1 was added, and 15.4 g of NMP was further added, and stirred at 40°C for 24 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (PAA-1, viscosity: 100 mPa·s). ) was obtained.

9.00 g of this polyamic acid solution (PAA-1) was aliquoted into a 100 ml Erlenmeyer flask equipped with a stirrer, and a NMP solution containing 12.1 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane was added. 7.50g of 1.35g and BCS were added, and it stirred with the magnetic stirrer for 2 hours, and obtained the liquid crystal aligning agent (A-1).

(Synthesis Example 2)

4.86g (9.98mmol) of DA-1 was weighed out in a 100ml four-necked flask equipped with a stirrer and a nitrogen inlet pipe, 17.2g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this diamine solution under water cooling, 2.93 g (9.96 mmol) of CA-1 was added, and 26.3 g of NMP was further added, followed by stirring under a nitrogen atmosphere at 40°C for 24 hours to obtain a solution of polyamic acid (viscosity: 180 mPa·s) was obtained.

9.00 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask equipped with a stirrer bar, 1.35 g of NMP solution containing 12.1 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane, and BCS 7.50g of was added, and it stirred for 2 hours with a magnetic stirrer, and obtained the liquid crystal aligning agent (A-2).

(Synthesis Example 3)

4.86g (9.98mmol) of DA-1 was weighed out in a 100ml four-necked flask equipped with a stirrer and a nitrogen inlet pipe, 17.2g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. Stirring this diamine solution under water cooling, 0.495g (2.50 mmol) of CA-3 was added, 8.92g of NMP was added, and it stirred at 40 degreeC by nitrogen atmosphere for 2 hours. Furthermore, 2.20 g (7.47 mmol) of CA-1 was added, 16.6 g of NMP was further added, and the mixture was stirred under a nitrogen atmosphere at 40°C for 24 hours to obtain a polyamic acid solution (viscosity: 70 mPa·s).

9.00 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask equipped with a stirrer bar, 1.35 g of NMP solution containing 12.1 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane, and BCS 7.50g of was added, and it stirred for 2 hours with a magnetic stirrer, and obtained the liquid crystal aligning agent (A-3).

(Synthesis Example 4)

3.02 g (15.0 mmol) of DA-2 and 0.753 g (3.80 mmol) of DA-3 were weighed into a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 43.5 g of NMP was added. , and dissolved by stirring while sending nitrogen. While stirring this diamine solution under water cooling, 3.42 g (17.4 mmol) of CA-4 was added, 21.4 NMP was added, and stirred at 23°C for 2 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (viscosity: 160 mPa·s). ) was obtained.

50.0 g of this polyamic acid solution was aliquoted into a 200 ml Erlenmeyer flask equipped with a stirrer, and 5.00 g of a NMP solution containing 28.3 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane and BCS 27.7 g of was added, and the mixture was stirred for 2 hours with a magnetic stirrer to obtain a polyamic acid solution (PAA-2).

(Synthesis Example 5)

2.04 g of the liquid crystal aligning agent (A-1) obtained in Synthesis Example 1 and 4.76 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 4 were weighed and taken in a 50 ml Erlenmeyer flask containing a stirrer, and taken with a magnetic stirrer. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-4).

(Synthesis Example 6)

2.03 g of the liquid crystal aligning agent (A-2) obtained in Synthesis Example 2 and 4.73 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 4 were weighed and taken in a 50 ml Erlenmeyer flask equipped with a stirrer, and taken with a magnetic stirrer. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-5).

(Synthesis Example 7)

Into a 100 ml Erlenmeyer flask equipped with a stirring bar, 9.00 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1 was aliquoted, and 11.7 g of NMP and 1 mass% of 3-glycidoxypropyltriethoxysilane were contained. 7.50g of 0.400g and BCS were added for the NMP solution containing 1.35g and 10 mass % of AD-1 for the NMP solution to do, and it stirred with the magnetic stirrer for 2 hours, and obtained the liquid crystal aligning agent (A-6).

(Synthesis Example 8)

4.87 g (10.0 mmol) of DA-1 was weighed and taken into a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet pipe, 17.3 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this diamine solution under water cooling, 2.66 g (9.92 mmol) of CA-5 was added, and 25.4 g of NMP was further added, followed by stirring under a nitrogen atmosphere at 40°C for 24 hours to obtain a solution of polyamic acid (viscosity: 170 mPa·s) was obtained.

8.50 g of this polyamic acid solution was dispensed into a 100 ml Erlenmeyer flask with a stirrer bar, 1.27 g of NMP solution containing 11.5 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane, and BCS 7.08g of was added, and it stirred for 2 hours with a magnetic stirrer, and obtained the liquid crystal aligning agent (A-7).

(Synthesis Example 9)

4.87 g (10.0 mmol) of DA-1 was weighed and taken into a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet pipe, 17.3 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. Stirring this diamine solution under water cooling, 1.25g (4.99 mmol) of CA-6 was added, 17.4g of NMP was added, and it stirred at 50 degreeC by nitrogen atmosphere for 2 hours. Furthermore, 1.46g (4.96 mmol) of CA-1 was added, 8.30g of NMP was further added, and it stirred at 40 degreeC for 24 hours by nitrogen atmosphere, and obtained the solution of a polyamic acid (viscosity: 200 mPa*s).

8.52 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask equipped with a stirrer bar, 1.27 g of NMP solution containing 11.6 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane, and BCS 7.10g of was added, and it stirred for 2 hours with a magnetic stirrer, and obtained the liquid crystal aligning agent (A-8).

(Synthesis Example 10)

4.60g (9.98 mmol) of DA-5 was weighed out in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 18.4 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this diamine solution under water cooling, 2.91 g (9.89 mmol) of CA-1 was added, and 11.7 g of NMP was further added, followed by stirring under a nitrogen atmosphere at 40°C for 24 hours to obtain a solution of polyamic acid (viscosity: 350 mPa·s) was obtained.

10.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer bar, 2.00 g of NMP solution containing 18.0 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane, and BCS 10.0g of was added, and it stirred for 2 hours with a magnetic stirrer, and obtained the liquid crystal aligning agent (A-9).

(Synthesis Example 11)

[Formula 33]

Synthesis of compound [1]

In tetrahydrofuran (540 g), 3-nitrobenzoylchloride (42.0 g) was charged, and at 5°C, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane (30.0 g, 108 mmol) and triethylamine (24.0 g) in tetrahydrofuran (60 g) were added dropwise, and then reacted at room temperature for 1 hour. After filtering the salt from the reaction solution, the filtrate was concentrated to dryness. After diluting the resulting suspension with ethyl acetate (360 g), the organic layer was washed with 1 N aqueous sodium hydroxide solution (400 g), pure water (400 g) and saturated brine (300 g) in this order, and dehydrated with sodium sulfate. Subsequently, this was concentrated, and the obtained residue was isolated by silica gel column chromatography (ethyl acetate:hexane = 9:1 → 8:2 volume ratio) to obtain compound [1] (5.4 g, yield 89%, light yellow color). Liquid).

Synthesis of DA-6

Compound [1] (54.0 g, 93.6 mmol) and 5% palladium carbon (5.4 g) were prepared in tetrahydrofuran (432 g), and the mixture was stirred under a hydrogen atmosphere at 40°C for 128 hours. The catalyst was filtered and the filtrate was concentrated to obtain DA-6 (48.3 g, 99% yield, pale yellow liquid).

(Synthesis Example 12)

In a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 6.72 g (13.0 mmol) of DA-6 obtained in Synthesis Example 11 was weighed and taken, 29.4 g of NMP was added, and stirring was performed while blowing nitrogen. dissolved While stirring this diamine solution under water cooling, 3.78 g (12.8 mmol) of CA-1 was added, and 12.6 g of NMP was further added, followed by stirring under a nitrogen atmosphere at 40°C for 24 hours to obtain a solution of polyamic acid (viscosity: 340 mPa·s) was obtained.

10.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer bar, 2.00 g of NMP solution containing 18.0 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane, and BCS 10.0g of was added, and it stirred for 2 hours with a magnetic stirrer, and obtained the liquid crystal aligning agent (A-10).

(Synthesis Example 13)

[Formula 34]

Synthesis of Compound [2]

In toluene (75 g) and tetrahydrofuran (30 g), add 2-fluoro-5-nitrobenzoic acid (15.0 g, 81.0 mmol), dimethylformamide (0.075 g), thionyl chloride (11.6 g) and stirred at 70°C for 4 hours. An acid chloride was obtained by concentrating the reaction solution under reduced pressure.

In tetrahydrofuran (180 g), an acid chloride (17.0 g) was injected, and under ice-cooling, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane (10.3 g, 36.8 mmol) and triethylamine ( 8.94 g) in tetrahydrofuran (20 g) was added dropwise, and then reacted overnight at room temperature. After filtering the salt from the reaction solution, the filtrate was concentrated to dryness. After diluting the resulting suspension with ethyl acetate (150 g), the organic layer was washed with 2 N aqueous sodium hydroxide solution (100 g), pure water (100 g) and saturated brine (100 g) in this order, and dehydrated with sodium sulfate. Then, by concentrating this and isolating the obtained residue by silica gel column chromatography (ethyl acetate:hexane = 9:1 volume ratio), compound [2] was obtained (20.9 g, yield 93%, pale yellow liquid).

Synthesis of DA-7

In tetrahydrofuran (168 g), compound [2] (20.9 g, 34.2 mmol) and 5% palladium carbon (2.1 g) were charged, and stirred in an autoclave under a 0.4 MPa hydrogen atmosphere at 40°C for 16 hours. did The catalyst was filtered, the filtrate was concentrated, and the obtained residue was isolated by silica gel column chromatography (ethyl acetate:hexane = 6:4 volume ratio) to obtain DA-7 (14.3 g, yield 76%, orange crystals). .

(Synthesis Example 14)

Into a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.98 g (7.20 mmol) of DA-7 obtained in Synthesis Example 13 was weighed and taken, 17.0 g of NMP was added, and stirring was performed while blowing nitrogen. dissolved While stirring this diamine solution under water cooling, 2.09 g (7.10 mmol) of CA-1 was added, and 7.29 g of NMP was further added, and stirred under a nitrogen atmosphere at 40°C for 24 hours to obtain a solution of polyamic acid (viscosity: 1050 mPa·s) was obtained.

10.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer bar, 2.00 g of NMP solution containing 18.0 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane, and BCS 10.0g was added, and it stirred for 2 hours with a magnetic stirrer, and obtained the liquid crystal aligning agent (A-11).

(Synthesis Example 15)

[Formula 35]

Synthesis of compound [3]

3-bromobenzoic acid (25.0 g, 124 mmol), 4-nitrophenylboronic acid (22.8 g), potassium carbonate (51.4 g) in toluene (500 mL), ethanol (500 mL) and pure water (62 mL) was added, and after nitrogen substitution, tetrakistriphenylphosphine palladium (1.0 g) was added, and it stirred at 80 degreeC for 5 hours. After cooling to room temperature, ethyl acetate (500 ml) and pure water (600 ml) were added, and liquid separation operation was performed. The organic layer was subjected to liquid separation again with pure water (200 ml), and the combined aqueous layers were separated and washed twice with dichloroethane (250 ml). The aqueous layer was recovered, 2 normal hydrochloric acid (300 ml) was added little by little, and after confirming that the pH had become 3 or less, it was filtered. The obtained filtrate was filtered after slurry washing with toluene (150 ml), and a crude body was obtained by drying the filtrate. After dissolving the crude body in dimethylformamide (50 g) at 100°C, the mixture was filtered while hot, toluene (200 g) was added to the filtrate, and the mixture was ice-cooled to precipitate crystals. The residue obtained by filtration was dried to obtain compound [3] (15.5 g, yield 52%, light brown crystals).

Synthesis of compound [4]

Compound [3] (15.5 g, 64.0 mmol), dimethylformamide (0.08 g), and thionyl chloride (9.14 g) were added to toluene (311 g), and the mixture was stirred at 110°C for 3 hours. An acid chloride was obtained by concentrating the reaction solution under reduced pressure.

In tetrahydrofuran (250 g), an acid chloride (14.0 g) was injected, and under ice-cooling, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane (6.77 g, 24.3 mmol) and triethylamine ( 5.90 g) in tetrahydrofuran (28 g) was added dropwise, and then reacted overnight at 40°C. After filtering the salt from the reaction solution, the filtrate was concentrated to dryness. Ethyl acetate (54 g) was added to the obtained suspension, and after stirring at 60°C, hexane (108 g) was added, cooled, filtered, and the filtrate was concentrated to obtain a crude product. The crude product was isolated by silica gel column chromatography (ethyl acetate : hexane = 85 : 15 volume ratio) to obtain compound [4] (11.1 g, yield 63%, pale orange crystals).

Synthesis of DA-8

In tetrahydrofuran (89 g), compound [4] (11.1 g, 15.3 mmol) and 5% palladium carbon (1.1 g) were charged, and stirred in an autoclave under a 0.4 MPa hydrogen atmosphere at 40°C for 14 hours. did The catalyst was filtered, the filtrate was concentrated, and hexane (80 g) was added to the residue, which was stirred at room temperature overnight to precipitate crystals. By filtering and drying the filtrate, DA-8 was obtained (9.4 g, yield 93%, white crystals).

(Synthesis Example 16)

4.21 g (6.29 mmol) of DA-8 was weighed out in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 16.9 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. While stirring this diamine solution under water cooling, 1.83 g (6.22 mmol) of CA-1 was added, and 7.26 g of NMP was further added, followed by stirring under a nitrogen atmosphere at 40°C for 24 hours to obtain a solution of polyamic acid (viscosity: 1740 mPa·s) was obtained.

10.0 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask containing a stirrer bar, 2.00 g of NMP solution containing 18.0 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane, and BCS 10.0g of was added, and it stirred for 2 hours with a magnetic stirrer, and obtained the liquid crystal aligning agent (A-12).

(Synthesis Example 17)

15.9 g (79.7 mmol) of DA-2 and 3.97 g (20.0 mmol) of DA-3 were weighed in a 300 ml flask equipped with a stirrer and a nitrogen inlet tube, 170 g of NMP was added, and nitrogen While sending, it was stirred and dissolved. 4.31g (21.9 mmol) of CA-4 was added, stirring this diamine solution under water cooling, and also 48g of NMP was added, and it stirred at 23 degreeC by nitrogen atmosphere for 1 hour. After that, 18.7 g (74.7 mmol) of CA-6 was added, and 25.6 g of NMP was further added, followed by stirring under a nitrogen atmosphere at 50°C for 20 hours to obtain a solution of polyamic acid (viscosity: 1370 mPa·s). .

50.0 g of this polyamic acid solution was aliquoted into a 200 ml Erlenmeyer flask containing a stirrer bar, and 7.50 g of NMP solution containing 66.9 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane and BCS 41.6 g of was added, and the mixture was stirred for 2 hours with a magnetic stirrer to obtain a polyamic acid solution (PAA-3).

(Synthesis Example 18)

3.23 g of the liquid crystal aligning agent (A-10) obtained in Synthesis Example 12 and 7.53 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 17 were weighed in a 50 ml conical flask containing a stirrer, and taken with a magnetic stirrer. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-13).

(Synthesis Example 19)

3.13 g of the liquid crystal aligning agent (A-11) obtained in Synthesis Example 14 and 7.30 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 17 were weighed and taken in a 50 ml Erlenmeyer flask containing a stirrer, and taken with a magnetic stirrer. It stirred for 2 hours and obtained the liquid crystal aligning agent (A-14).

(Synthesis Example 20)

4.72 g (19.0 mmol) of DA-4 was weighed and taken into a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 14.1 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. Stirring this diamine solution under water cooling, 1.00g (4.71 mmol) of CA-2 was added, 8.75g of NMP was added, and it stirred at 40 degreeC by nitrogen atmosphere for 2 hours. Furthermore, 4.13 g (14.0 mmol) of CA-1 was added, 16.5 g of NMP was further added, and the mixture was stirred under a nitrogen atmosphere at 40°C for 24 hours to obtain a polyamic acid solution (viscosity: 80 mPa·s).

10.2 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask equipped with a stirrer, 1.89 g of NMP solution containing 11.5 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane, and BCS 7.87g of was added, and it stirred for 2 hours with a magnetic stirrer, and obtained the liquid crystal aligning agent (B-1).

(Synthesis Example 21)

2.77 g (13.9 mmol) of DA-3 was weighed out in a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet pipe, 17.0 g of NMP was added, and the mixture was stirred and dissolved while blowing nitrogen. Stirring this diamine solution under water cooling, 0.742g (3.49 mmol) of CA-2 was added, 8.75g of NMP was added, and it stirred at 40 degreeC by nitrogen atmosphere for 2 hours. Further, 2.76 g (9.38 mmol) of CA-1 was added, and 20.2 g of NMP was further added, and the mixture was stirred under a nitrogen atmosphere at 40°C for 24 hours to obtain a solution of a polyamic acid (viscosity: 180 mPa·s).

12.2 g of this polyamic acid solution was aliquoted into a 100 ml Erlenmeyer flask equipped with a stirrer, and 1.43 g of NMP solution containing 7.88 g of NMP and 1% by mass of 3-glycidoxypropyltriethoxysilane and BCS 7.18g of was added, and it stirred for 2 hours with a magnetic stirrer, and obtained the liquid crystal aligning agent (B-2).

(Example 1)

Below, the manufacturing method of the liquid crystal cell for evaluating a pretilt angle and liquid-crystal orientation is shown.

At the very beginning, a substrate with attached electrodes was prepared. The substrate is a glass substrate having a length of 30 mm, a width of 35 mm, and a thickness of 0.7 mm. On the substrate, as a first layer, an IZO electrode constituting a counter electrode is formed over the entire surface. On the counter electrode of the first layer, as a second layer, a SiN (silicon nitride) film formed by the CVD method is formed. The film thickness of the SiN film of the 2nd layer is 500 nm, and it functions as an interlayer insulating film. On the SiN film of the 2nd layer, as a 3rd layer, the comb-shaped pixel electrode formed by patterning the IZO film is arrange|positioned, and two pixels, a 1st pixel and a 2nd pixel, are formed. The size of each pixel is 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the third layer has a comb-like shape formed by arranging a plurality of "K"-shaped electrode elements with bent central portions. The width of each electrode element in the short direction is 3 μm, and the interval between the electrode elements is 6 μm. Since the pixel electrodes constituting each pixel are constituted by arranging a plurality of z-shaped electrode elements with curved central portions, the shape of each pixel is not rectangular, but is curved in the central portion similarly to the electrode element. It has a shape similar to the "く character" in . Then, each pixel is divided up and down with the central bending part as a boundary, and has a first region above the bending part and a second region below the bending part.

Comparing the 1st area and the 2nd area|region of each pixel, the formation direction of the electrode element of the pixel electrode which comprises them differs. That is, when the rubbing direction of the liquid crystal alignment film described later is taken as a standard, in the first area of the pixel, the electrode element of the pixel electrode is formed so as to form an angle of +10 ° (clockwise direction), and in the second area of the pixel, the pixel The electrode elements of the electrode are formed to form an angle of -10° (clockwise). That is, in the first area and the second area of each pixel, the rotational motion (in-plane switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the opposite electrode within the substrate surface is in the opposite direction to each other. It is composed so that

Next, after filtering the liquid crystal aligning agent (A-1) obtained in Synthesis Example 1 with a filter having a hole diameter of 1.0 μm, it was applied to the prepared substrate with electrodes by spin coating. After drying for 2 minutes on an 80 degreeC hot plate, it baked in 180 degreeC IR type oven for 1000 second, and obtained the polyimide film with a film thickness of 60 nm. After rubbing this polyimide film with a ray hot spring (roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm/sec, pressing amount: 0.3 mm), post-heating for 1000 seconds in an IR oven at 230 ° C. was carried out. Further, ultrasonic irradiation was performed for 1 minute in pure water to perform cleaning, and water droplets were removed by air blowing. Then, it was made to dry at 80 degreeC for 10 minute(s), and the board|substrate with a liquid crystal aligning film was obtained. Further, as a counter substrate, a polyimide film was formed in the same manner as above on a glass substrate having a columnar spacer having a height of 4 μm and having an ITO electrode formed on the back surface, followed by orientation treatment in the same procedure as above The board|substrate with a liquid crystal aligning film on which was performed was obtained. These two substrates with a liquid crystal alignment film are set as one set, a sealant is printed in a form leaving a liquid crystal inlet on the substrate, and the other substrate is bonded so that the liquid crystal alignment film surfaces face each other and the rubbing direction is antiparallel. did After that, the sealing compound was cured to prepare an empty cell having a cell gap of 4 μm. Liquid crystal MLC-3019 (manufactured by Merck & Co., Ltd.) exhibiting positive dielectric anisotropy was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell of an FFS system. Then, after heating the obtained liquid crystal cell at 120 degreeC for 1 hour and leaving it to stand at 23 degreeC overnight, it used for evaluation of a pretilt angle and liquid-crystal orientation.

<Pretilt angle>

The measurement of the pretilt angle of the liquid crystal cell was measured by the Muller matrix method using "AxoScan" by Axometrics. A result is shown in Table 1.

<Evaluation of liquid crystal orientation>

With respect to said liquid crystal cell, the alternating voltage from which brightness|luminance becomes the maximum was applied on the frequency of 30 Hz in a 60 degreeC constant temperature environment for 140 hours. Then, it was set as the state which short-circuited between the pixel electrode of a liquid crystal cell and a counter electrode, and it was left to stand at room temperature for one day as it was.

After standing, the liquid crystal cell was installed between two polarizing plates arranged so that the polarization axes were orthogonal, the backlight was turned on with no voltage applied, and the angle of arrangement of the liquid crystal cell was adjusted so that the luminance of the transmitted light was minimized. And the rotation angle at the time of rotating the liquid crystal cell from the angle at which the 2nd area|region of the 1st pixel becomes the darkest to the angle at which the 1st area|region becomes the darkest was computed as angle (DELTA). Similarly, also in the second pixel, the second area and the first area were compared, and the same angle Δ was calculated. And the average value of the angle Δ value of the 1st pixel and the 2nd pixel was computed as angle Δ of a liquid crystal cell. That is, the smaller the angle Δ, the better the liquid-crystal orientation. A result is shown in Table 1.

(Examples 2 to 5)

In Synthesis Example 2, 3, 5, 6, Example 1 except having used the obtained liquid crystal aligning agent (A-2), (A-3), (A-4), (A-5), respectively A liquid crystal cell was produced in the same way, and the angle Δ of the pretilt angle and the liquid crystal cell was measured. A result is shown in Table 1.

(Example 6)

A liquid crystal cell was prepared in the same manner as in Example 1, except that the liquid crystal was changed to liquid crystal MLC-7026 (manufactured by Merck) exhibiting negative dielectric anisotropy, and the pretilt angle and the angle Δ of the liquid crystal cell were measured. . A result is shown in Table 1.

(Examples 7 to 10)

In Synthesis Example 2, 5, 6, 7, Example 6 except having used the obtained liquid crystal aligning agent (A-2), (A-4), (A-5), (A-6), respectively A liquid crystal cell was produced in the same way, and the angle Δ of the pretilt angle and the liquid crystal cell was measured. A result is shown in Table 1.

(Example 11)

Except having changed the temperature of postheating to 180 degreeC, the liquid crystal cell was manufactured similarly to Example 6, and the pretilt angle in this liquid crystal cell and angle (DELTA) of the liquid crystal cell were measured. A result is shown in Table 1.

(Examples 12 to 19)

In Synthesis Examples 8, 9, 10, 12, 14, 16, 18, 19, respectively obtained liquid crystal aligning agents (A-7), (A-8), (A-9), (A-10), Except for using (A-11), (A-12), (A-13) and (A-14), a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle and the angle Δ of the liquid crystal cell were measured. A result is shown in Table 1.

(Comparative Example 1)

Except not performing post-heating, the liquid crystal cell was manufactured similarly to Example 6, and the pretilt angle in this liquid crystal cell was measured. A result is shown in Table 1.

(Comparative Example 2)

Except having changed the temperature of baking to 230 degreeC, the liquid crystal cell was manufactured similarly to the comparative example 1, and the pretilt angle in this liquid crystal cell was measured. A result is shown in Table 1.

(Comparative Example 3)

Except having changed the temperature of baking to 230 degreeC, the liquid crystal cell was manufactured similarly to Example 6, and the pretilt angle in this liquid crystal cell was measured. A result is shown in Table 1.

(Comparative Examples 4 and 5)

In Synthesis Examples 20 and 21, as a result of manufacturing a liquid crystal cell similarly to Example 6 except having used the obtained liquid crystal aligning agents (B-1) and (B-2), respectively, uniform liquid crystal orientation was not obtained. .

<Measurement of phase transition temperature>

After filtering the liquid crystal aligning agent obtained by each synthesis example with a 1.0 micrometer filter, it applied to the board|substrate with an ITO electrode by spin coating application|coating. After drying for 2 minutes on an 80 degreeC hot plate, it baked in 180 degreeC IR type oven for 1000 second, and obtained the polyimide film of 100 nm thickness. This polyimide film was peeled off with a cutter, and the rate of temperature increase and temperature decrease was measured twice at 10°C/min each using a differential scanning calorimetry (DSC) DSC3100SR (manufactured by Mac Science Co., Ltd.), and the phase transition temperature was determined. measured.

(Example 20)

As a result of measurement using (A-2) obtained in Synthesis Example, an endothermic peak derived from a phase transition was observed around 200°C during the first temperature increase. At the time of the 1st temperature fall, in the 2nd time, a specific peak was not seen.

(Examples 21 to 23)

As a result of measurement using (A-10) (A-11) and (A-12) in the same manner as in Example 20, an endothermic peak and an exothermic peak were observed at the time of temperature increase and temperature decrease, respectively.

The result of the obtained phase transition temperature is shown in Table 2.

A liquid crystal display element having a liquid crystal aligning film formed from the liquid crystal aligning agent of the present invention is particularly suitable for in-vehicle use of car navigation systems and meter panels and surveillance cameras, for example, in which images with extremely high brightness, high definition and high reliability are required. , which is preferably used for monitors of medical cameras.

In addition, the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2017-9759 and Japanese Patent Application No. 2017-9760 filed on January 23, 2017 are cited here, and the specification of the present invention is to be accepted as the initiation of

Claims (16)

A polyimide precursor obtained by polymerizing a diamine component containing a diamine represented by any one of the following formulas [I] to formula [VI] and a tetracarboxylic acid component, and a polyimide obtained from the polyimide precursor, selected from the group consisting of The liquid crystal aligning agent characterized by containing at least 1 type of polymer.

(In formula [I], R ₁ , R ₂ , R ₃ , R ₄ are each independently a methyl group or an ethyl group, and X is -NHCO-, -CONH-, -COO- or -OCO-. Direction Hydrogen on the ring may be substituted with a methyl group, a fluorine group, or a tert-butoxycarbonyl group, n is an integer of 0 to 6, m is an integer of 1 to 5. In formula [VI], Boc is tert- Represents a butoxycarbonyl group.) According to claim 1,
The liquid crystal aligning agent in which the said polyimide precursor is a polyamic acid According to claim 1,
The liquid crystal aligning agent in which the said diamine component contains 50-100 mol% of diamines represented by any of said formula [I] - formula [VI]. According to claim 1,
The liquid crystal aligning agent in which the said tetracarboxylic-acid component contains tetracarboxylic dianhydride represented by following formula [3].

(In Formula [3], Z ¹ represents a tetravalent organic group) According to claim 4,
The liquid crystal aligning agent which is at least 1 sort(s) chosen from the group which Z ^<1> consists of following formula [3a] - formula [3t] in said formula [3].

According to claim 5,
The liquid crystal aligning agent whose said Z ^<1> is formula [3m], formula [3n], formula [3p], formula [3q], formula [3r], or formula [3t]. According to claim 1,
A liquid crystal aligning agent in which the diamine represented by the formula [I] is represented by the following formula.

According to claim 1,
The liquid crystal aligning agent containing 2-10 mass % of said at least 1 sort(s) of polymer. The liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-8. The liquid crystal display element which has the liquid crystal aligning film of Claim 9. The group consisting of a polyimide precursor obtained by polymerizing a diamine component containing a diamine represented by any one of the following formulas [I] to formula [VI] and a tetracarboxylic acid component, and a polyimide obtained by imidizing the polyimide precursor. A film formed from a liquid crystal aligning agent containing at least one type of polymer selected from The manufacturing method of a liquid crystal alignment film.

(In formula [I], R ₁ , R ₂ , R ₃ , R ₄ are each independently a methyl group or an ethyl group, and X is -NHCO-, -CONH-, -O-, -COO- or -OCO Hydrogen on the aromatic ring may be substituted with a methyl group, a fluorine group, or a tert-butoxycarbonyl group, n is an integer of 0 to 6, and m is an integer of 1 to 5. In the formula [VI], Boc represents a tert-butoxycarbonyl group.) According to claim 11,
The manufacturing method of the liquid crystal aligning film whose temperature in the said heat treatment is 0-130 degreeC higher than the temperature of the said baking treatment. According to claim 11,
The manufacturing method of the liquid crystal aligning film characterized by having liquid crystallinity after baking processing or heat processing. According to any one of claims 11 to 13,
The manufacturing method of the liquid crystal aligning film whose thickness of the film after the said heat processing is 5-300 nm. According to any one of claims 11 to 13,
The manufacturing method of the liquid crystal aligning film whose said orientation process is a rubbing process independent or a rubbing process and a photo-alignment process. According to any one of claims 11 to 13,
The manufacturing method of the liquid crystal aligning film which performs the immersion process or spray process by water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate after the said heat process.