TWI767870B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent that can obtain a liquid crystal alignment film whose ability to vertically align liquid crystals does not decrease even when exposed to excessive heating, and provides a liquid crystal aligning agent that can vertically align liquid crystals even if some foreign matter contacts the film and causes damage The ability of the liquid crystal alignment agent of the liquid crystal alignment film will not be reduced. The present invention provides a liquid crystal aligning agent containing a diamine represented by the formula [1] (in the formula [1], X represents a single bond or a divalent group such as -O-, and Y represents the formula [1-1]. At least 1 selected from the polyimide precursors of the reaction products of the diamine component and the tetracarboxylic acid component and the polyimide of the imide products thereof. Y ¹ to Y ⁶ represent the specific groups described in the specification a polymer.

Description

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

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element which are excellent in the ability to vertically align liquid crystals.

A liquid crystal display device in which the liquid crystal molecules vertically aligned with respect to the substrate are reacted by an electric field (also referred to as a vertical alignment (VA) method) includes a step of irradiating ultraviolet rays while applying a voltage to the liquid crystal molecules in the manufacturing process. By.

In such a vertical alignment liquid crystal display element, it is known to add a photopolymerizable compound to a liquid crystal composition in advance, and to use a vertical alignment film such as a polyimide type, and to irradiate the liquid crystal cell while applying a voltage. Ultraviolet rays are a technique for increasing the reaction rate of liquid crystal (PSA (Polymer Sustained Alignment) type element, see, for example, Patent Document 1 and Non-Patent Document 1).

As a liquid crystal aligning agent used in this PSA system element. A liquid crystal aligning agent using a side chain having a specific ring structure has been proposed (refer to Patent Document 2). The specific ring structure enables the vertical alignment of liquid crystal to be high, and the liquid crystal display element in the vertical alignment mode using the liquid crystal alignment agent has good display properties. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-307720 [Patent Document 2] WO2006/070819 [Non-patent literature]

[Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, P.1200-1202

[The problem to be solved by the invention]

However, in recent vertical alignment liquid crystal display elements, due to the influence of thinning and increasing the size of the substrate used, a temperature difference occurs between different parts of the same substrate during firing, and the liquid crystal in the part that is overheated The ability of the alignment film to vertically align the liquid crystal will be reduced, and as a result, the resulting liquid crystal display element will cause some problems of poor display. In addition, in the liquid crystal panel manufacturing process, since the liquid crystal alignment film is in contact with the column spacer, the liquid crystal alignment film is damaged, and alignment defects (bright spots) are also generated in this portion.

The present invention is to provide a liquid crystal alignment agent that can obtain a liquid crystal alignment film whose ability to vertically align liquid crystals does not decrease even when exposed to excessive heating. Moreover, even when a certain foreign material contacts a film and causes damage, the liquid crystal aligning agent which can obtain the liquid crystal aligning film whose ability to align a liquid crystal vertically does not fall is provided. [means to solve the problem]

The inventors found that the object can be achieved by a liquid crystal aligning agent having the following constitution, and completed the present invention. That is, the structure of this invention is as follows. 1. A liquid crystal aligning agent comprising a polyimide precursor containing a diamine component and a tetracarboxylic acid component containing a diamine represented by the following formula [1] and a polyimide precursor thereof At least one polymer selected from amines;

In formula [1], X represents a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO _2- , and a divalent organic group formed by any combination of these, and m represents an integer of 1 to 8. Y represents the structure of the following formula [1-1] independently of each other.

In formula [1-1], Y ¹ and Y ³ each independently represent a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, At least one of the group consisting of -CONH-, -NHCO-, -COO- and -OCO-. Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15) (only, when Y ¹ or Y ³ is a single bond, -(CH ₂ ) _a -, Y ² is a single bond, Y ¹ is at least one selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, and/or Y ³ is selected from -O-, When at least one of the group consisting of -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, Y ² is a single bond or -(CH ₂ ) _b -(Only, Y ¹ is -CONH-, Y ² and Y ³ are single bonds)). Y ⁴ represents at least one bivalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a bivalent organic group having 17 to 51 carbon atoms with a steroid skeleton and a tocopherol skeleton, the aforementioned Any hydrogen atom on the cyclic group can be passed through an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a fluorine-containing alkyl group with 1 to 3 carbon atoms, and a fluorine-containing alkyl group with 1 to 3 carbon atoms. Oxygen or fluorine atom substitution. Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these Alkoxy with 1 to 3 carbon atoms, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms, or fluorine atom substitution. Y ⁶ represents selected from a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. At least one of the group consisting of ~18 fluorine-containing alkoxy groups. n represents an integer from 0 to 4. [Effect of invention]

According to the present invention, it is possible to provide a liquid crystal aligning agent capable of obtaining a liquid crystal aligning film in which the ability to vertically align liquid crystals does not decrease even when exposed to excessive heating. Furthermore, the present invention can provide a liquid crystal aligning agent for a liquid crystal aligning film in which the ability to vertically align liquid crystals does not decrease even if some foreign matter contacts the film and causes damage in addition to the above-mentioned effects. Further, according to the present invention, a liquid crystal alignment film obtained from the above-mentioned liquid crystal alignment agent, and a method for obtaining a liquid crystal alignment film using the above-mentioned liquid crystal alignment agent can be provided.

The liquid crystal aligning agent of the present invention contains a diamine component containing a diamine represented by the above formula [1] (hereinafter, "the diamine represented by the above formula [1]" is abbreviated as "specific diamine") and tetramine At least one polymer (hereinafter, abbreviated as "specific polymer") selected from the polyimide precursor of the reaction product of the carboxylic acid component and the polyimide of the imide compound.

The specific polymer contains a specific diamine, but may have diamines other than the specific diamine. The amount of the specific diamine and other diamines, in the specific polymer, can be 5mol%～70mol%, preferably 10mol%～50mol%, more preferably 10mol%～40mol% with the specific diamine, to have specific diamines. Moreover, the liquid crystal aligning agent of this invention may contain "polyimide of a polyimide precursor and/or its imide compound" other than a specific polymer. Hereinafter, the "specific diamine" will be described, and then the diamines other than the "specific diamine" will be described.

<Specific diamine> The specific diamine used for the liquid crystal aligning agent of this invention is represented by following formula [1].

In formula [1], X represents a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -NHCO-, -COO-, -(CH ₂ ) _m -, -SO _2- , and a divalent organic group formed by any combination of these, and m represents an integer of 1 to 8. "Any combination of these" includes -O-(CH ₂ ) _m -O-, -OC(CH ₃ ) ₂ -, -CO-(CH ₂ ) _m -, -NH-(CH ₂ ) _m - , -SO ₂ -(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -, -CONH-(CH ₂ ) _m -NHCO-, -COO-(CH ₂ ) _m -OCO-, etc., but not limited to and so on. X can preferably be a single bond, -O-, -NH-, -O-(CH ₂ ) _m -O-.

In formula [1], the position of Y relative to X may be meta or ortho, preferably ortho. That is, the formula [1] is preferably the following formula [1'].

In the above formula [1], the position of "-NH ₂ " is as shown in the formula [1], and can be any position, preferably the following formulas [1]-a1, [1]-a2, [1]- The position indicated by a3 can be preferably [1]-a1.

From the above formula [1]-a1 to formula [1]-a3 and the above formula [1'], the above formula [1] may be any structure selected from the following formulas, preferably the formula [1]- The structure represented by a1-1.

Y represents the structure of the following formula [1-1] independently of each other.

In formula [1-1], Y ¹ and Y ³ each independently represent a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, At least one of the group consisting of -CONH-, -NHCO-, -COO- and -OCO-. Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15) (only, when Y ¹ or Y ³ is a single bond, -(CH ₂ ) _a -, Y ² is a single bond, Y ¹ is at least one selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, and/or Y ³ is selected from -O-, When at least one of the group consisting of -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO-, Y ² is a single bond or -(CH ₂ ) _b -(Only, Y ¹ is -CONH-, Y ² and Y ³ are single bonds)). Y ⁴ represents at least one bivalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a bivalent organic group having 17 to 51 carbon atoms with a steroid skeleton and a tocopherol skeleton, the aforementioned Any hydrogen atom on the cyclic group can be passed through an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a fluorine-containing alkyl group with 1 to 3 carbon atoms, and a fluorine-containing alkyl group with 1 to 3 carbon atoms. Oxygen or fluorine atom substitution. Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these Alkoxy with 1 to 3 carbon atoms, fluorine-containing alkyl group with 1 to 3 carbon atoms, fluorine-containing alkoxy group with 1 to 3 carbon atoms, or fluorine atom substitution. Y ⁶ represents selected from a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. At least one of the group consisting of ~18 fluorine-containing alkoxy groups. n represents an integer from 0 to 4.

The groups represented by the above formula [1-1] include, but are not limited to, the following groups [1-1]-1 to [1-1]-22. Among these, [1-1]-1 to [1-1]-4, [1-1]-8, and [1-1]-10 are preferable. In addition, * represents the position where it couple|bonds with the phenyl group in the said formula [1], the said formula [1'], the said formula [1]-a1 - the said formula [1]-a3. m represents an integer from 1 to 15, and n represents an integer from 0 to 18.

<Photoreactive side chain> The polymer contained in the liquid crystal aligning agent of the present invention may also have a photoreactive side chain. The "specific polymer" may have the photoreactive side chain, and the "polyimide precursor of a polyimide precursor and/or its imide product" of a polymer other than the "specific polymer" may also have the photoreactive side chain. Photoreactive side chains. <Diamine containing photoreactive side chain> In order to introduce a photoreactive side chain into a "specific polymer" and/or a polymer other than the "specific polymer", a diamine having a photoreactive side chain can be used as a part of the diamine component. Although the diamine which has a side chain represented by a photoreactive side chain is not limited to these, although the diamine which has a side chain represented by formula [VIII] or formula [IX] is mentioned.

The bonding position of the two amine groups (—NH ₂ ) in the formula [VIII] and the formula [IX] is not limited. Specifically, with respect to the bonding group of the side chain, the positions of 2, 3, 2, 4, 2, 5, 2, 6, and 3, 4 on the benzene ring can be exemplified , 3,5 position. From the viewpoint of the reactivity at the time of synthesizing the polyamic acid, the position of 2,4, the position of 2,5, or the position of 3,5 is particularly preferred. When the easiness in synthesizing diamine is also considered, the position of 2,4 or the position of 3,5 is more preferable.

The definitions of R ⁸ , R ⁹ and R ¹⁰ in formula [VIII] are as follows. That is, R ⁸ represents a single bond, -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ ) -, -CON( _CH3 )- or -N( _CH3 )CO-. R ⁸ is particularly preferably a single bond, -O-, -COO-, -NHCO- or -CONH-. R ⁹ represents a single bond, an alkylene group having 1 to 20 carbon atoms that can be substituted by a fluorine atom, and -CH ₂ - of the alkylene group can be optionally substituted by -CF ₂ - or -CH=CH-, any of the following When the groups are not adjacent, they can also be substituted with such groups; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, bivalent carbocyclic or heterocyclic. In addition, the above-mentioned divalent carbocyclic ring or heterocyclic ring can be specifically exemplified by the following, but is not limited to these.

R ⁹ can be formed by an ordinary organic synthesis method, and from the viewpoint of ease of synthesis, it is preferably a single bond or an alkylene group having 1 to 12 carbon atoms. R ¹⁰ represents a photoreactive group selected from the following formula.

From the viewpoint of photoreactivity, R ¹⁰ is preferably a methacrylic group, an acrylic group or a vinyl group.

In addition, the definitions of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ in formula [IX] are as follows. That is, Y ₁ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH- or -CO-. Y ₂ is an alkylene group with 1 to 30 carbon atoms, a bivalent carbocyclic ring or a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, bivalent carbocyclic ring or heterocyclic ring can also be passed through a fluorine atom or Organic substitution. Y ₂ , when the following groups are not adjacent, -CH ₂ - can also be substituted for these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, - NHCONH-, -CO-. Y ₃ represents -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO- or a single bond. Y ₄ represents a cinnamon base. Y ₅ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring, and one or more hydrogen atoms of the alkylene group, the bivalent carbocyclic ring or the heterocyclic ring can also be Fluorine atom or organic group substitution. Y ₅ , when the following groups are not adjacent, -CH ₂ - can also be substituted for these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, - NHCONH-, -CO-. Y ₆ represents an acrylic or methacrylic photopolymerizable group.

Specific examples of the diamine having a photoreactive side chain include, but not limited to, the following. In the following formula, X ⁹ and X ¹⁰ each independently represent a single bond, -O-, -COO-, -NHCO- or -NH- bonding group, and Y represents a carbon number 1~ that can be substituted by a fluorine atom. 20 alkylene.

Moreover, as a diamine which has a photoreactive side chain, the diamine which the side chain represented by the following formula has a group which induces a photodimerization reaction and a group which induces a photopolymerization reaction can also be mentioned.

In the above formula, Y ₁ to Y ₆ are the same as defined above. The above-mentioned diamine having a photoreactive side chain can be used according to the characteristics of liquid crystal alignment, pretilt angle, voltage retention characteristics, charge storage characteristics, etc. when used as a liquid crystal alignment film, and the reaction speed of liquid crystal when used as a liquid crystal display element. Use 1 type or a mixture of 2 or more types.

In addition, the diamine having a photoreactive side chain is preferably 10 to 70 mol % of the diamine component used in the synthesis using polyamide acid, more preferably 20 to 60 mol %, and particularly preferably 30 mol %. ~50 mol%. Moreover, the diamine which has a side chain which has photoreactivity can also be mentioned the diamine which has a site|part which has a radical generating structure which decomposes by ultraviolet irradiation and generates a radical in a side chain.

In the above formula (1), Ar, R ₁ , R ₂ , T ₁ , T ₂ , S and Q have the following definitions. That is, Ar represents an aromatic hydrocarbon group selected from a phenylene group, a naphthylene group, and a biphenylene group, and an organic group may be substituted thereon, and a hydrogen atom may be substituted with a halogen atom. R ₁ and R ₂ are each independently an alkyl group or an alkoxy group having 1 to 10 carbon atoms. T1 and T2 are each independently a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, - The bonding group of CON(CH ₃ )- and -N(CH ₃ )CO-. S is a single bond or an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms. Only -CH ₂ - or -CF ₂ - of the alkylene group can be arbitrarily substituted by -CH=CH-, and when any of the groups listed below are not adjacent, they can also be substituted with such groups; -O-, - COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbocycle, divalent heterocycle. Q represents a structure selected from the following (in the structural formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents -CH ₂ -, -NR-, -O-, or -S-).

In the above formula (I), Ar to which the carbonyl group is bonded is related to the absorption wavelength of ultraviolet rays. Therefore, when the wavelength is increased, it is preferably a structure with a long conjugation length such as naphthylene or biphenylene. In addition, Ar may be substituted with a substituent, and the substituent is preferably an electron-donating organic group such as an alkyl group, a hydroxyl group, an alkoxy group, and an amine group.

In the formula (I), when Ar has a structure such as a naphthylene group or a biphenylene group, the solubility is deteriorated, and the synthesis difficulty is also increased. As long as the wavelength of the ultraviolet rays is in the range of 250 nm to 380 nm, sufficient properties can be obtained even with the phenyl group, so the phenyl group is the best.

In addition, when R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a benzyl group or a phenethyl group, or an alkyl group or an alkoxy group, R ₁ and R ₂ may also be used. form a ring.

In the formula (I), Q is preferably an electron-donating organic group, preferably the above-mentioned group. When Q is an amine group derivative, the carboxylic acid group and the amine group may form a salt during the polymerization of the polyimide precursor of the polyamide acid, which is more preferable. Hydroxy or alkoxy.

The diaminobenzene in the formula (1) may be any structure of o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, but from the viewpoint of reactivity with acid dianhydride, it is preferably m-phenylenediamine or p-phenylenediamine.

Specifically, from the viewpoints of easiness of synthesis, high versatility, characteristics, and the like, the structure represented by the following formula is optimal. Furthermore, in the formula, n is an integer of 2 to 8.

＜Other diamines＞ Other diamine components for obtaining a specific polymer may contain diamines other than the specific diamine represented by the above formula [1] (hereinafter, also referred to as other diamines). Such a diamine is represented by the following general formula [2]. Other diamines may be used alone or in combination of two or more.

In the above formula [2], 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 the viewpoint of the reactivity of the monomers, A ₁ and A ₂ are preferably a hydrogen atom or a methyl group. When the structure of _Y1 is exemplified, it is as follows.

In the formula, unless otherwise specified, n is an integer of 1 to 6. In the following formula, Boc represents a tert-butoxycarbonyl group.

The other diamine components used in the liquid crystal aligning agent of the present invention are not particularly limited, but are particularly preferably selected from (Y-7) from the viewpoints of coatability, voltage retention characteristics, residual DC voltage characteristics, etc. , (Y-8), (Y-16), (Y-17), (Y-21), (Y-22), (Y-28), (Y-37), (Y-38), ( Diamines selected from Y-60), (Y-67), (Y-68), (Y-71)~(Y-73), (Y-160)~(Y-180) are used in combination.

(tetracarboxylic acid component) The tetracarboxylic acid component used to obtain the specific polymer includes tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester dihalide. In the invention, these are also collectively referred to as a tetracarboxylic acid component. As the tetracarboxylic acid component, tetracarboxylic dianhydride, its derivative tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid dialkyl ester dihalide (these are collectively referred to as is the first tetracarboxylic acid component).

<Tetracarboxylic dianhydride> For example, tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. Specific examples of these include the following groups [1] to [5], etc., respectively.

[1] Aliphatic tetracarboxylic dianhydride, for example, 1,2,3,4-butane tetracarboxylic dianhydride, etc.;

[2] Alicyclic tetracarboxylic dianhydride, for example, acid dianhydrides such as the following formulae (X1-1) to (X1-13);

In formulas (X1-1)~(X1-4), R ₃ to R ₂₃ are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a carbon number An alkynyl group of 2 to 6, a monovalent organic group of 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group may be the same or different. In the above formula, R _M is a hydrogen atom or a methyl group, and Xa is the following A tetravalent organic group represented by formulas (Xa-1) to (Xa-7).

[3] 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 3,5,6-trione Carboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02,6]undecane-3,5,8,10- Tetraketone, etc.;

[4] Aromatic tetracarboxylic dianhydride, for example, pyromellitic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-diphthalic anhydride Phenyl tetracarboxylic dianhydride, acid dianhydrides represented by the following formulae (Xb-1) to (Xb-10), etc., and

[5] Further, acid dianhydrides represented by formulae (X1-44) to (X1-52) and tetracarboxylic dianhydrides described in JP 2010-97188 A can be mentioned.

In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types. The tetracarboxylic dianhydride component used in the liquid crystal aligning agent of the present invention is not particularly limited, but is preferably selected from (X1- 1), (X1-2), (X1-3), (X1-6), (X1-7), (X1-8), (X1-9), (Xa-2), pyromellitic anhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, and tetracarboxylic dianhydride selected from (Xb-6) and (Xb-9) were used.

<Production method of polymer> The method for producing these polymers is usually obtained by reacting a diamine component and a tetracarboxylic acid component. At least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and derivatives of tetracarboxylic acid is reacted with a diamine component consisting of one or more diamines, and The method of obtaining polyamide. Specifically, the method of polycondensing a tetracarboxylic dianhydride and a primary or secondary diamine to obtain a polyamic acid can be used.

In order to obtain a polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterification of a carboxylic acid group and a primary or secondary diamine can be used, and a tetracarboxylic acid obtained by halogenating a carboxylic acid group can be used. A method of polycondensing a carboxylic acid dihalide with a primary or secondary diamine, or a method of converting the carboxyl group of a polyamic acid into an ester. In order to obtain polyimide, the method of ring-closing the above-mentioned polyamic acid or alkyl polyamic acid to obtain polyimide can be used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in a solvent. The solvent used at this time is not particularly limited as long as it dissolves the produced polyimide precursor. Specific examples of the solvent used in the reaction are listed below, but are not limited to these examples. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylethyl amide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D -1] to the solvent represented by the formula [D-3].

In formula [D-1], D ¹ represents an alkyl group with 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group with 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. Furthermore, even if it is a solvent that does not dissolve the polyimide precursor, it can be mixed with the above-mentioned solvent within the range where the polyimide precursor produced will not be precipitated. In addition, the moisture in the solvent inhibits the polymerization reaction and further causes the hydrolysis of the polyimide precursor produced. Therefore, the solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, a solution obtained by stirring and dispersing or dissolving the diamine component in the solvent, and adding the tetracarboxylic acid component as it is, or by dispersing or dissolving it in the solvent, can be used. Method; Conversely, a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in a solvent; a method of alternately adding a diamine component and a tetracarboxylic acid component, etc., any of these methods can be used . In addition, when a plurality of diamine components or tetracarboxylic acid components are respectively used for the reaction, they may be reacted in a premixed state, may be reacted individually sequentially, or the individually reacted low molecular weight bodies may be mixed and reacted to form a polymer.

The temperature at which the diamine component and the tetracarboxylic acid component are polymerized and condensed can be selected at any temperature from -20 to 150°C, 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, and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50 mass %, more preferably 5 to 30 mass %. The initial stage of the reaction is carried out at a high concentration, and a solvent can be added after that. In the polymerization reaction of the polyimide precursor, the ratio of the total molar number of the diamine component and the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As in a general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

Polyimide is a polyimide obtained by closing the ring of the aforementioned polyimide precursor. In the polyimide, the rate of ring closure of the amide group (also called the rate of imidization) is not constant. It needs to be 100% and can be adjusted arbitrarily according to the use or purpose. The method of imidizing the polyimide precursor includes thermal imidization by directly heating the solution of the polyimide precursor, or adding a catalyst to the solution of the polyimide precursor. Mordine imidization.

The temperature when the polyimide precursor is thermally imidized in the solution is 100~400°C, preferably 120~250°C, preferably while removing the water generated by the imidization reaction A method to proceed to the outside of the system. Catalyst imidization of polyimide precursor can be achieved by adding alkaline catalyst and acid anhydride to the solution of polyimide precursor and stirring at -20~250℃, preferably 0~180℃ conduct.

The amount of the alkaline catalyst is 0.5-30 mol times the amide acid group, preferably 2-20 mol times, and the amount of the acid anhydride is 1-50 mol times the amide acid group, preferably 3~30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has an appropriate basicity for the reaction to proceed. The acid anhydride includes acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. In particular, when acetic anhydride is used, purification after completion of the reaction is easy, which is preferable. The imidization rate by catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

When recovering the produced polyimide precursor or polyimide from the polyimide precursor or the polyimide reaction solution, the reaction solution may be poured into a solvent and precipitated. The solvent used for the precipitation includes methanol, ethanol, isopropanol, acetone, hexane, butyl cyloxine, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. The polymer deposited in the solvent can be recovered by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure. In addition, when the polymer recovered by precipitation is re-dissolved in the solvent for 2 to 10 times, and the operation of re-precipitation and recovery is performed, impurities in the polymer can be reduced. The solvent in this case includes, for example, alcohols, ketones, hydrocarbons, and the like. When three or more kinds of solvents selected from these are used, the efficiency of purification is further improved, which is preferable.

A more specific method for producing the polyamic acid alkyl ester of the present invention is shown in the following (1) to (3). (1) Method for producing by esterification of polyamic acid It is a method of producing polyamic acid from a diamine component and a tetracarboxylic acid component, and performing a chemical reaction on its carboxyl group (COOH group), that is, an esterification reaction, to produce a polyamic acid alkyl ester. The esterification reaction is to make the polyamide acid and the esterification agent react at -20~150°C (preferably 0~50°C) for 30 minutes~24 hours (preferably 1~4 hours) in the presence of a solvent. method.

The aforementioned esterification agent is preferably one that can be easily removed after the esterification reaction, and examples thereof include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl Acetal, N,N-Dimethylformamide Dipropyl Acetal, N,N-Dimethylformamide Dineopentyl Butyl Acetal, N,N-Dimethylformamide Di- t-Butyl Acetal, 1-Methyl-3-p-Tolyltriazene, 1-Ethyl-3-p-Tolyltriazene, 1-Propyl-3-p-Tolyltriazene alkene, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, etc. The usage amount of the esterifying agent is preferably 2-6 mol equivalents relative to 1 mol of the repeating unit of the polyamide acid. Among them, 2 to 4 molar equivalents are preferred.

The solvent used for the above-mentioned esterification reaction includes the solvent used for the reaction of the above-mentioned diamine component and tetracarboxylic acid component from the viewpoint of the solubility of the polyamic acid in the solvent. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone are particularly preferred. These solvents may be used alone or in combination of two or more. In the above-mentioned esterification reaction, the concentration of the polyamic acid in the solvent is preferably 1 to 30 mass % from the viewpoint of hardly causing the precipitation of the polyamic acid. Among them, 5 to 20% by mass is particularly preferred.

(2) Method of producing by reaction of diamine component and tetracarboxylic acid diester dichloride Specifically, the diamine component and the tetracarboxylic acid diester dichloride are reacted at -20 to 150° C. (preferably 0 to 50° C.) in the presence of a base and a solvent for 30 minutes to 24 hours ( The method is preferably 1 to 4 hours). As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used. Among them, pyridine is particularly preferred 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 moles relative to the tetracarboxylic acid diester dichloride. Among them, 2 to 3 times molar is particularly preferable.

From the viewpoint of the solubility of the obtained polymer, that is, the polyamic acid alkyl ester to the solvent, the solvent used for the reaction of the diamine component and the tetracarboxylic acid component can be mentioned above. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone are particularly preferred. These solvents may be used alone or in combination of two or more. The concentration of the polyamic acid alkyl ester in the solvent during the reaction is preferably 1 to 30 mass % from the viewpoint of hardly causing the precipitation of the polyamic acid alkyl ester. Among them, 5 to 20% by mass is particularly preferred. In addition, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used in the production of the polyamic acid alkyl ester is preferably dehydrated as much as possible. Furthermore, the reaction is preferably carried out in a nitrogen environment to prevent the mixing of external gas.

(3) Method of producing by reaction of diamine component and tetracarboxylic acid diester Specifically, the diamine component and the tetracarboxylic acid diester are subjected to a polycondensation reaction at 0 to 150° C. (preferably 0 to 100° C.) in the presence of a condensing agent, a base and a solvent for 30 minutes to 24 minutes. hours (preferably 3 to 15 hours).

The condensing agent can use triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N' -Carbonyldiimidazole, Dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyl Uidonium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2 -Sulfanyl-3-benzoxazolyl) phosphonic acid diphenyl ester and the like. The amount of the condensing agent used is preferably 2 to 3 moles, particularly 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 amount that can be easily removed after the polycondensation reaction, and relative to the diamine component, it is preferably 2 to 4 moles, more preferably 2 to 3 moles. The solvent used for the polycondensation reaction from the viewpoint of the solubility of the obtained polymer, that is, the polyamide alkyl ester in the solvent, includes the solvent used for the reaction of the diamine component and the tetracarboxylic acid component described above. Among them, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone are particularly preferred. One or more of these solvents can be used.

In addition, in the polycondensation reaction, by adding a Lewis acid as an additive, the reaction proceeds efficiently. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The usage amount of the Lewis acid is preferably 0.1 to 10 times moles relative to the diamine component. Among them, 2.0~3.0 times molar is better.

When recovering the polyamic acid alkyl ester from the solution of the polyamic acid alkyl ester obtained by the methods (1) to (3) above, the reaction solution may be poured into a solvent for precipitation. The solvent used for the precipitation includes water, methanol, ethanol, 2-propanol, hexane, butyl cylosol, acetone, toluene, and the like. The polymer deposited in the solvent is preferably washed several times with the solvent for the purpose of removing the above-mentioned additives and catalysts. After washing, filtration and recovery, the polymer can be dried under normal pressure or reduced pressure, normal temperature or heating. In addition, by repeating the operation of re-dissolving the polymer recovered by precipitation in a solvent for 2 to 10 times, and then re-precipitating and recovering, the impurities in the polymer can be reduced. The production method of the above-mentioned (2) or (3) is preferable for the polyalkylene acid.

<Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention may contain the above-mentioned specific polymer, preferably a solution for forming a liquid crystal alignment film. The content of the polymer in the liquid crystal alignment agent is preferably 2 to 10 mass % in the liquid crystal alignment agent, more preferably 3 to 8 mass %.

All of the polymer components in the liquid crystal aligning agent of the present invention may be all of the specific polymer of the present invention, or may be mixed with other polymers. Other polymers include polyimide and polyimide precursors, cellulose-based polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamide, and polysiloxane. alkane etc. The content of other polymers other than this is preferably 1 to 90 mass %, more preferably 30 to 80 mass % among the resin components contained in the liquid crystal aligning agent.

The good solvent used for the liquid crystal aligning agent of the present invention is not particularly limited as long as it dissolves the specific polymer of the present invention. Specific examples of the solvent used for the liquid crystal aligning agent are listed below, but are not limited to these examples. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylethyl amide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone. In addition, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the above formula [D -1] to the solvent represented by the formula [D-3]. One type of the above-mentioned good solvent may be used, or a more suitable combination and ratio may be used in combination with a coating method or the like. The good solvent in the liquid crystal aligning agent of the present invention is preferably 20 to 99% by mass of the total solvent contained in the liquid crystal aligning agent. Among them, 20 to 90% by mass is particularly preferred. More preferably, it is 30-80 mass %.

The liquid crystal aligning agent of this invention can use the solvent (also called a poor solvent) which improves the film coating property or surface smoothness of the liquid crystal aligning film at the time of coating a liquid crystal aligning agent. Specific examples thereof are listed below. For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1- Butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentanol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol , 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,6-dimethyl-4-heptanol, 1,2-ethylene glycol, 1,2-propanediol , 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl Ethyl-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-heptane ketone, 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 base) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy) ethanol, furanmethanol, diethylene glycol, propylene glycol, propylene glycol monobutyl Ethyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether Ethyl 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 mono Butyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, acetic acid 2- (2-ethoxyethoxy) ethyl ester, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate Ester, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxypropionic acid ethyl ester, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate , butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, represented by the aforementioned formulas [D-1]~[D-3] solvent, etc.

Among them, the preferred combination of solvents can include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether. Butyl ether; N-methyl-2-pyrrolidone, gamma-butyrolactone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether; N-methyl-2 -pyrrolidone, gamma-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether; N-methyl-2-pyrrolidone, gamma-butyrolactone , propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanone; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether; N -Methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanol; N-methyl-2-pyrrolidone, γ-butyrolactone Ester and dipropylene glycol dimethyl ether, etc. These poor solvents are preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass of the total solvent contained in the liquid crystal aligning agent. The type and content of such a solvent are appropriately selected according to the coating apparatus of the liquid crystal alignment agent, coating conditions, coating environment, and the like.

The liquid crystal aligning agent of the present invention may contain, in addition to the above, polymers other than the polymers described in the present invention, dielectrics for the purpose of changing electrical properties such as permittivity and conductivity of the liquid crystal alignment film, and Silane coupling agents for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, crosslinking compounds for the purpose of improving the hardness or density of the film when used as a liquid crystal alignment film, and a polymer for the purpose of baking the coating film. An imidization accelerator or the like for the purpose of efficiently performing imidization by heating of the imide precursor.

Compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds or epoxy-containing compounds, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Ethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2 -aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl -3-Aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane , 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3 -aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3- Aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, Ethyl 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-Hexane Glycol diglycidyl ether, glycerol 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, etc.

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

The above-mentioned additives are preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. When it is less than 0.1 parts by mass, the effect cannot be expected, and when it exceeds 30 parts by mass, the alignment property of the liquid crystal is lowered, so it is more preferably 0.5 to 20 parts by mass.

<Liquid crystal alignment film and liquid crystal display element> The liquid crystal alignment film of the present invention can be formed by applying the liquid crystal alignment agent of the present invention on a substrate and firing. For example, after coating the liquid crystal aligning agent of this invention on a board|substrate, the cured film obtained by drying and baking as needed can also be used directly as a liquid crystal aligning film. Moreover, UV can also be irradiated in the state which rubs this cured film, irradiates polarized light, the light of a specific wavelength, etc., ion beam etc., or as the alignment film for PSA, in the state which applied the voltage to the liquid crystal display element after liquid crystal filling. In particular, it is useful for use as an alignment film for PSA.

In this case, the substrate to be used is not particularly limited as long as it is a substrate with high transparency, and glass plate, polycarbonate, poly(meth)acrylate, polyether, polyarylate, and polyurethane can be used. Ester, polyether, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose , Acetate butyrate cellulose and other plastic substrates. Also, from the viewpoint of process simplification, it is preferable to use a substrate on which ITO electrodes and the like for liquid crystal driving are formed. In addition, in the reflective liquid crystal display element, as long as it is only on one side of the substrate, an opaque material such as a silicon wafer can be used, and a material that reflects light such as aluminum can also be used as the electrode in this case.

The coating method of the liquid crystal alignment agent is not particularly limited, and can include printing methods such as screen printing, offset printing, flexographic printing, etc.; inkjet method, spray method, roll coating method; or dipping, roll coater, narrow Slot coaters, spinners, etc. In terms of productivity, the transfer printing method is widely used industrially, and it can also be suitably used in the present invention.

The coating film formed by apply|coating a liquid crystal aligning agent by the said method can be baked and become a cured film. The drying step after coating the liquid crystal aligning agent is not necessarily necessary, but when the time from coating to firing is not fixed for each substrate, or when not firing immediately after coating, the drying step is preferably performed. The drying should just remove the solvent to such an extent that the shape of the coating film is not deformed by the conveyance of the substrate or the like, and the drying means is not particularly limited. For example, a method of drying for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes on a hot plate at a temperature of 40°C to 150°C, preferably 60°C to 100°C, can be mentioned.

The firing temperature of the coating film formed by applying the liquid crystal aligning agent is not limited, but is, for example, 100 to 350°C, preferably 120 to 350°C, and more preferably 150 to 330°C. The firing time is 5 minutes to 240 minutes, preferably 10 minutes to 90 minutes, and more preferably 10 minutes to 30 minutes. Heating can be performed by a generally known method such as a hot plate, a hot air circulating furnace, an infrared furnace and the like.

Moreover, the thickness of the liquid crystal alignment film obtained by baking is not specifically limited, Preferably it is 5-300 nm, More preferably, it is 20-200 nm.

In the liquid crystal display element, a liquid crystal cell can be produced by a known method after forming a liquid crystal alignment film on a substrate by the above method. A specific example of a liquid crystal display element is a vertical alignment liquid crystal display element, which includes a liquid crystal cell, and the liquid crystal cell has two substrates arranged in opposite directions, a liquid crystal layer disposed between the substrates, and a liquid crystal layer disposed between the substrate and the liquid crystal. The above-mentioned liquid crystal alignment film formed between layers and by a liquid crystal alignment agent. Specifically, it is a vertical alignment liquid crystal display element, which includes a liquid crystal cell, and the liquid crystal cell is formed by coating a liquid crystal alignment agent on two substrates and firing to form a liquid crystal alignment film. Two substrates are arranged so that the alignment films face each other, and a liquid crystal layer composed of liquid crystal is sandwiched between the two substrates.

By using a liquid crystal alignment film formed with a liquid crystal alignment agent containing the specific polymer of the present invention, the polymerizable compound contained in the liquid crystal is reacted by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, resulting in vertical alignment. A PSA-type liquid crystal display element with remarkably excellent capabilities.

The substrate of the liquid crystal display element is not particularly limited as long as it is a substrate with high transparency, and generally, it is a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate. As a specific example, the same thing as the board|substrate described in the said liquid crystal alignment film is mentioned. A substrate provided with a conventional electrode pattern or a projection pattern can also be used, but in a PSA-type liquid crystal display element, since a liquid crystal aligning agent containing the polyimide-based polymer of the present invention is used, one side of the liquid crystal aligning agent is used. The substrate is formed with a line/slit electrode pattern of, for example, 1 to 10 μm, and it can also operate in a structure in which the opposite substrate is not formed with a slit pattern or a protrusion pattern. The liquid crystal display element with this structure can simplify the manufacturing process. process, high transmittance can be obtained.

In addition, as a high-performance element such as a TFT type element, an element such as a transistor formed between an electrode for driving liquid crystal and a substrate is used. In the case of a transmissive liquid crystal display element, the above-mentioned substrate is generally used, but in the case of a reflection type liquid crystal display element, an opaque substrate such as a silicon wafer can also be used as long as it is only a single-sided substrate. At this time, the electrode formed on the substrate may also use a material such as aluminum that reflects light.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element is not particularly limited, and liquid crystal materials used in conventional vertical alignment methods, such as MLC-6608, MLC-6609, MLC-3023 and other negative-type liquid crystals manufactured by Merck & Co. can be used. . Moreover, in the case of a PSA type liquid crystal display element, for example, a liquid crystal containing a polymerizable compound represented by the following formula can be used.

As a method of sandwiching the liquid crystal layer between two substrates, a well-known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer such as beads is spread on the liquid crystal alignment film of one substrate, and the other substrate is bonded so that the surface on the side on which the liquid crystal alignment film is formed becomes the inside. Substrate, a method of injecting and sealing liquid crystal under reduced pressure. In addition, it is also possible to prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers such as beads on the liquid crystal alignment film of one substrate, drop liquid crystal, and then make the surface on which the liquid crystal alignment film is formed the inside. The liquid crystal cell is produced by the method of laminating the other side's substrate for sealing. The thickness of the spacer is preferably 1 to 30 μm, more preferably 2 to 10 μm.

A step of fabricating a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, for example, by applying a voltage between electrodes arranged on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer, A method of irradiating ultraviolet rays under this electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, or preferably 5 to 20 Vp-p. The irradiation dose of ultraviolet rays is, for example, 1 to 60J, preferably 40J or less. The irradiation dose of ultraviolet rays is small, the reliability reduction due to the destruction of the members constituting the liquid crystal display element can be suppressed, and the ultraviolet irradiation time can be shortened. increase, so it is more appropriate.

As described above, when the liquid crystal alignment film and the liquid crystal layer are irradiated with ultraviolet rays while applying voltage Displays the response speed of the element. In addition, when irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, from a polyimide precursor having a side chain for vertically aligning the liquid crystal and a side chain for photoreactivity, and the polyimide precursor The photoreactive side chains of at least one polymer selected from the polyimide obtained by imidization, or the photoreactive side chains of the polymer and the polymerizable compound react with each other, so The reaction speed of the obtained liquid crystal display element can be accelerated. [Example]

Examples are given below to describe the present invention in more detail, but the present invention is not to be construed as being limited to these. The abbreviations of the compounds used are shown below. (liquid crystal) MLC-3023 (Merck & Co., liquid crystal containing negative polymerizable compound)

(Specific side chain type diamine component) W-A1: compound represented by formula [W-A1] W-A2: compound represented by formula [W-A2] W-A3: compound represented by formula [W-A3] W-A4: compound represented by formula [W-A4] W-A5: compound represented by formula [W-A5] W-A6: compound represented by formula [W-A6] W-A7: compound represented by formula [W-A7] W-A8: compound represented by formula [W-A8] W-A9: compound represented by formula [W-A9] W-A10: compound represented by formula [W-A10]

(Other side chain diamine compounds) A1: compound represented by formula [A1] A2: compound represented by formula [A2] A3: Compound represented by formula [A3]

(other diamine compounds) C1: compound represented by formula [C1] C2: compound represented by formula [C2] C3: compound represented by formula [C3] C4: compound represented by formula [C4] C5: compound represented by formula [C5] C6: compound represented by formula [C6] C7: compound represented by formula [C7] C8: compound represented by formula [C8] C9: compound represented by formula [C9] C10: compound represented by formula [C10]

(tetracarboxylic acid component) D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride D2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride D3: pyromellitic dianhydride D4: 2,3,5-Tricarboxycyclopentylacetic dianhydride D5: 3,3',4,4'-diphenyltetracarboxylic dianhydride

(solvent) NMP: N-methyl-2-pyrrolidone BCS: Ethylene Glycol Monobutyl Ether NEP: N-ethyl-2-pyrrolidone (crosslinking agent) E1: a crosslinking agent represented by the following formula (E1) (additive) E2: 3-picolylamine

(Molecular weight measurement) The molecular weight of the polyimide precursor and polyimide was measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Co., Ltd.), a column (KD-803, KD -805) (manufactured by Shodex), measured as follows. Column temperature: 50℃ Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr･H ₂ O) 30mmol/L (liter), phosphoric acid･anhydrous crystal (o- Phosphoric acid) 30mmol/L, tetrahydrofuran (THF) 10ml/L) Flow rate: 1.0ml/min SO Co., Ltd.) and polyethylene glycol (molecular weight; about 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratories).

(Measurement of imidization rate of polyimide) 20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sample tube standard, ϕ5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethylsulfite (DMSO-d6, 0.05 mass % TMS) was added. (tetramethylsilane) mixture) (0.53 ml), and ultrasonically applied to dissolve it completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Ltd. Datum). The imidization rate is determined based on the proton derived from the structure that does not change before and after imidization as the reference proton, and the peak integration value of the proton is used to compare the NH group derived from the imidic acid appearing in the vicinity of 9.5~10.0ppm. The proton peak integral value of , is obtained by the following equation. Imidization rate (%)=(1-α･x/y)×100 In the above formula, x is the peak integration value of the proton derived from the NH group of the amide acid, y is the peak integration value of the reference proton, and α is the reference proton when the polyamide acid (imidation rate is 0%) is relative to the The ratio of the number of NH protons of amide acid.

(Viscosity measurement) In the synthesis example or the comparative synthesis example, the viscosity of the polyimide-based polymer was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL, a conical rotor TE-1 (1 °34', R24), and the temperature was measured at 25°C.

W-A1 to W-A3 and W-A4 to W-A10 are novel compounds that have not been disclosed in the literature, and the synthesis methods are described in detail below. The products described in Synthesis Examples 1 to 3 and Synthesis Examples 4 to 10 below were identified by ¹ H-NMR analysis (analysis conditions are as follows). Apparatus: Varian NMR System 400 NB (400 MHz). Measurement solvent: CDCl ₃ , DMSO-d ₆ . Reference material: Tetramethylsilane (TMS) (δ 0.0 ppm for ¹ H).

<<Synthesis Example 1 Synthesis of W-A1>>

<Synthesis of Compound [1] and Compound [2]> In tetrahydrofuran (165.6 g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (41.1 g) was added , 135 mmol) and triethylamine (31.5 g), methanesulfonyl chloride (33.2 g) was dropped under ice-cooling in a nitrogen atmosphere, and reacted for 1 hour to obtain compound [1]. Next, p-(trans-4-heptylcyclohexyl)phenol (77.8 g) dissolved in tetrahydrofuran (246.6 g) was added, and after stirring at 40° C. for 1 hour, a solution of p-(trans-4-heptylcyclohexyl)phenol (233 g) was added at the same temperature. Potassium hydroxide (41.0 g), reacted for 21 hours. After completion of the reaction, a 1.0 M aqueous hydrochloric acid solution (311 ml) and pure water (1050 g) were added to precipitate a crude product, and the crude product was recovered by filtration. The obtained crude product was dissolved in tetrahydrofuran (574 g) by heating at 50° C., methanol (328 g) was added to precipitate crystals, and the compound [2] was obtained by filtration and drying (yield: 97.9 g, yield: 89%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.87-0.90ppm (m, 6H), 0.96-1.05ppm (m, 4H), 1.19-1.39ppm (m, 30H), 1.80-1.85ppm (m, 8H) , 2.33-2.40ppm(m, 2H), 4.77ppm(s, 4H), 6.66-6.70 ppm(m, 4H), 7.02-7.06ppm(m, 4H), 7.40ppm(d, 2H, 8.4), 8.25 ppm(dd, 2H, J =2.4Hz, J =8.4Hz), 8.54ppm(d, 2H, J =2.4Hz).

<Synthesis of W-A1> In tetrahydrofuran (1783 g), compound [2] (74.3 g, 90.9 mmol) and 3% platinum on carbon (5.94 g) were charged and reacted in a hydrogen atmosphere at room temperature. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure so that the total internal weight was 145 g. Next, methanol (297 g) was added to the concentrated solution, followed by stirring under ice-cooling, filtration and drying to obtain W-A1 (yield: 59.2 g, yield: 86%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.87-0.90ppm(m, 6H), 0.96-1.05ppm(m, 4H), 1.19-1.40ppm(m, 30H), 1.81-1.84 ppm(m, 8H) , 2.32-2.38ppm(m, 2H), 3.67ppm(s, 4H), 4.69 ppm(d, 2H, J =12.0Hz), 4.74ppm(d, 2H, J =11.6Hz), 6.62 ppm(dd, 2H, J =2.4Hz, J =8.0Hz), 6.70-6.75ppm(m, 4H), 6.91 ppm(d, 2H, J =2.4Hz), 6.97-7.03ppm(m, 6H).

<<Synthesis Example 2 Synthesis of W-A2>>

<Synthesis of compound [3]> In tetrahydrofuran (327.2 g), 4,4'-dinitro-2,2'-biphenyldicarboxylic acid (40.9 g, 123 mmol) and p-(trans-4- Heptylcyclohexyl)phenol (72.1g), 4-dimethylaminopyridine (1.50g), put into 1-(3-dimethylaminopropyl)-3-ethyl in a nitrogen environment at room temperature Carbodiimide hydrochloride (56.6 g), reacted for 3 hours. After completion of the reaction, the reaction solution was poured into pure water (1226 g) to precipitate a crude product, which was recovered by filtration. Next, the crude product was washed with methanol (245 g) and the slurry was filtered, and the obtained crude product was dissolved in tetrahydrofuran (245 g) by heating at 60°C. After the insoluble matter was removed by filtration, the total internal weight was 232 g by concentration under reduced pressure, methanol (163 g) was added to precipitate crystals, and after stirring under ice-cooling conditions, compound [3] ( Yield: 73.9 g, yield: 71%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.87-0.90ppm(m, 6H), 0.98-1.06ppm(m, 4H), 1.18-1.43ppm(m, 30H), 1.83-1.86 ppm(m, 8H) , 2.41-2.47ppm(m, 2H), 6.89-6.92ppm(m, 4H), 7.17-7.20ppm(m, 4H), 7.48ppm(d, 2H, 8.4), 8.49ppm(dd, 2H, J = 2.4Hz, J =8.4Hz), 9.11ppm(d, 2H, J =2.4Hz).

<Synthesis of W-A2> In tetrahydrofuran (443 g) and methanol (73.9 g), compound [3] (73.9 g, 87.4 mmol) and 5% palladium on carbon (8.80 g) were added, and the mixture was heated to room temperature in a hydrogen atmosphere. reaction. After completion of the reaction, palladium carbon was removed by filtration, and the total internal weight was 171 g by concentration under reduced pressure. Next, methanol (222 g) was added to the concentrated solution to precipitate crystals, which were stirred with ice-cooling, filtered and dried to obtain W-A2 (yield: 66.6 g, yield: 97%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.87-0.90ppm(m, 6H), 0.96-1.05ppm(m, 4H), 1.17-1.42ppm(m, 30H), 1.82-1.85 ppm(m, 8H) , 2.38-2.44ppm(m, 2H), 3.77ppm(s, 4H), 6.80-6.87ppm(m, 6H), 7.08-7.13ppm(m, 6H), 7.41ppm(d, 2H, J =2.4Hz ).

<<Synthesis Example 3 Synthesis of W-A3>>

<Synthesis of Compound [4] and Compound [5]> In toluene (366 g), 4-(trans-4-heptylcyclohexyl)-benzoic acid (73.1 g, 242 mmol) and N,N-dimethylform were added Ethylformamide (0.73 g), and thionyl chloride (35.9 g) was added dropwise in a nitrogen atmosphere at 50°C. After dropping and reacting at the same temperature for 1 hour, compound [4] was obtained by concentrating the reaction solution under reduced pressure. Next, 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (35.0 g, 115 mmol) and triethylamine (26.8 g) were added to tetrahydrofuran (210 g), The compound [4] dissolved in tetrahydrofuran (73.1 g) was dropped under ice-cooling in a nitrogen atmosphere. After completion of the dropping, the reaction temperature was set to room temperature, and the reaction was carried out for 18 hours. After completion of the reaction, triethylamine hydrochloride was removed by filtration, and then concentrated under reduced pressure to obtain an oily compound. The obtained oily compound was added to pure water (1015 g) to precipitate crystals, and the crude product was recovered by filtration. Next, the obtained crude product was washed with methanol (291 g) at room temperature, and the slurry was washed with ethyl acetate (175 g) at room temperature, filtered and dried to obtain compound [5] (yield: 92.7 g) , yield: 92%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.89-0.91ppm(m, 6H), 0.99-1.09ppm(m, 4H), 1.20-1.47ppm(m, 30H), 1.85-1.88 ppm(m, 8H) , 2.46-2.52ppm(m, 2H), 5.14ppm(s, 4H), 7.23-7.26ppm(m, 4H), 7.45ppm(d, 2H, J =8.4Hz), 7.83-7.86 ppm(m, 4H) ), 8.27ppm(dd, 2H, J =2.4Hz, J =8.4Hz), 8.47ppm(d, 2H, J =2.4Hz).

<Synthesis of W-A3> In tetrahydrofuran (484 g) and methanol (161 g), compound [5] (80.5 g, 92.2 mmol) and 3% platinum on carbon (6.44 g) were charged, and the reaction was carried out in a hydrogen atmosphere at room temperature . After completion of the reaction, platinum carbon was removed by filtration, and the solvent was removed by concentration under reduced pressure, so that the total internal weight was 96.6 g. Next, methanol (322 g) was added to the concentrated solution to precipitate crystals, and the mixture was stirred under ice-cooling, and a crude product was obtained by filtration. Next, the obtained crude product was dissolved by heating with ethyl acetate (322 g) at 60° C., methanol (700 g) was added, crystals were precipitated under ice-cooling, filtered and dried to obtain W-A3 (yield: 67.9 g) , yield: 91%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.87-0.91ppm(m, 6H), 0.98-1.08ppm(m, 4H), 1.19-1.47ppm(m, 30H), 1.84-1.87 ppm(m, 8H) , 2.44-2.51ppm(m, 2H), 3.71ppm(s, 4H), 5.02 ppm(d, 2H, J =12.8Hz), 5.09ppm(d, 2H, J =12.4Hz), 6.66 ppm(dd, 2H, J =2.4Hz, J =8.0Hz), 6.84ppm(d, 2H, J =2.4Hz), 7.03ppm(d, 2H, J =8.0Hz), 7.19-7.25ppm(m, 4H), 7.89 -7.92ppm(m,4H).

<<Synthesis Example 4 Synthesis of W-A4>>

<Synthesis of Compound [6] and Compound [7]> In toluene (134 g), trans,trans-4'-pentylbiscyclohexyl-4-carboxylic acid (26.7 g, 95.1 mmol) and N,N- Dimethylformamide (0.401 g), and thionyl chloride (13.6 g, 114 mmol) were added dropwise in a nitrogen atmosphere at 50°C. After dripping, after reacting at the same temperature for 1 hour, the reaction solution was concentrated under reduced pressure to obtain compound [6]. Next, 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (12.6 g, 41.4 mmol) and triethylamine (10.9 g) were added to tetrahydrofuran (63.0 g). , 108 mmol), and the compound [6] dissolved in tetrahydrofuran (12.6 g) was added dropwise under ice-cooling in a nitrogen environment. After completion of dropping, the reaction temperature was set to room temperature, and the reaction was carried out for 17 hours. After completion of the reaction, crystals were precipitated by adding the reaction solution to pure water (731 g), and the crude product was recovered after filtration, washing with pure water, and washing with methanol. Next, the obtained crude product was dissolved by heating in toluene (56.0 g), hexane (112 g) was added to precipitate crystals, and after stirring at room temperature, compound [7] was obtained by filtration and drying (yield: 17.0 g, 20.6 mmol, yield: 50%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.82-1.38ppm(m, 44H), 1.67-1.81ppm(m, 12H), 1.90-1.98ppm(m, 4H), 2.19-2.25 ppm(m, 2H) , 4.82ppm(d, 2H, J =13.6Hz), 4.88ppm(d, 2H, J = 13.6Hz), 7.39ppm(d, 2H, J =8.4Hz), 8.26ppm(dd, 2H, J = 2.4 Hz, J =8.4Hz), 8.38ppm(d, 2H, J =2.0Hz)

<Synthesis of W-A4> In tetrahydrofuran (136 g) and methanol (34.0 g), compound [7] (17.0 g, 20.6 mmol) and 3% platinum on carbon (1.36 g) were added, and the mixture was heated in a hydrogen atmosphere at room temperature. The reaction took about 41 hours. After completion of the reaction, the total internal weight was 40 g by filtration and concentration under reduced pressure. Next, methanol (68.0 g) was added to precipitate crystals, which were filtered and dried to obtain W-A4 (yield: 15.2 g, 19.9 mmol, yield: 97%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.81-1.39ppm(m, 44H), 1.67-1.78ppm(m, 12H), 1.90-1.97ppm(m, 4H), 2.14-2.20 ppm(m, 2H) , 3.71ppm(br, 4H), 4.73ppm(d, 2H, J =12.4Hz), 4.78ppm(d, 2H, J =12.4Hz), 6.62ppm(dd, 2H, J =2.4Hz, J =8.0 Hz), 6.73ppm(d, 2H, J =2.8Hz), 6.94ppm(d, 2H, J =8.0Hz)

<<Synthesis Example 5 Synthesis of W-A5>>

<Synthesis of compound [8]> In toluene (227 g), trans-1-bromo-4-(4-heptylcyclohexyl)benzene (45.4 g, 135 mmol) and lithium bis(trimethylsilyl) were added Amide (about 26% tetrahydrofuran solution, about 1.30mol/L, 218mL), tri-tert-butylphosphonium tetrafluoroborate (1.58g, 5.44mmol), bis(dibenzylideneacetone)palladium(0)( 3.14 g, 5.46 mmol), reacted for 17 hours at room temperature in a nitrogen atmosphere. After the reaction, 5.7 mol/L aqueous hydrochloric acid solution (80.0 mL) was added to precipitate crystals, and the hydrochloride of compound [8] was recovered by filtration. The obtained hydrochloride was dispersed in a mixed solution of toluene (300 g), ethyl acetate (200 g), and tetrahydrofuran (100 g), followed by liquid separation with a 3.0 mol/L aqueous sodium hydroxide solution (200 g), and the organic phase was further saturated with water. Wash with salt water. Next, after adding activated carbon (brand: special egret, 2.27 g) to the organic phase and stirring, the activated carbon was removed by filtration. An oily compound was obtained by concentrating the obtained filtrate under reduced pressure. The oily compound was dispersed in hexane (100 g), crystallized under dry ice/ethanol cooling, filtered and dried to obtain compound [8] (yield: 27.5 g, 101 mmol, yield: 75%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.87-1.43ppm(m, 20H), 1.83-1.85ppm(m, 4H), 2.31-2.38ppm(m, 1H), 3.54ppm(br, 2H), 6.62 -6.65ppm(m, 2H), 6.99-7.02ppm(m, 2H)

<Synthesis of compound [9]> In tetrahydrofuran (120 g) and dichloromethane (60.0 g), 4,4'-dinitro-2,2'-biphenyldicarboxylic acid (14.9 g, 45.0 mmol) was added With compound [8] (25.8g, 94.3mmol), 4-dimethylaminopyridine (0.550g, 4.50mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiamide Imine hydrochloride (20.0 g, 104 mmol) was reacted for 14 hours at room temperature in a nitrogen atmosphere. After completion of the reaction, the mixture was diluted with ethyl acetate (375 g), and the organic phase was washed three times with pure water (149 g), and the obtained organic phase was subjected to dehydration treatment with magnesium sulfate. Next, the organic phase was concentrated under reduced pressure to make the total internal weight 112 g, methanol (120 g) was added to precipitate crystals, and the compound [9] was obtained by filtration and drying (yield: 28.0 g, 33.2 mmol, yield: 74 %) ¹ H-NMR (400MHz) in CDCl ₃ : 0.87-1.43ppm(m, 40H), 1.82-1.84ppm(m, 8H), 2.37-2.44ppm(m, 2H), 7.10ppm(d, 4H, J =8.8Hz), 7.26-7.30ppm(m, 4H), 7.40ppm(d, 2H, J =8.4Hz), 8.27ppm(dd, 2H, J =2.4Hz, J =8.4Hz), 8.53ppm( d, 2H, J =2.4Hz), 9.10ppm(s, 2H)

<Synthesis of W-A5> In tetrahydrofuran (140 g) and methanol (56.0 g), compound [9] (28.0 g, 33.2 mmol) and 5% palladium on carbon (2.10 g) were added, and the mixture was heated in a hydrogen atmosphere at room temperature. The reaction is about 3 days. After completion of the reaction, palladium carbon was removed by filtration, and the total internal weight was 122 g by concentration under reduced pressure. Methanol (168 g) was added to the obtained solution to precipitate crystals, which were filtered and dried to obtain W-A5 (yield: 23.8 g, 30.4 mmol, yield: 92%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.87-1.42ppm(m, 40H), 1.81-1.84ppm(m, 8H), 2.36-2.42ppm(m, 2H), 3.73ppm(br, 4H), 6.58 -6.60ppm(m, 2H), 6.88-6.90ppm(m, 4H), 7.07-7.09ppm(m, 4H), 7.34-7.36ppm(m, 4H), 8.85ppm(s, 2H)

<<Synthesis Example 6 Synthesis of W-A6>>

<Synthesis of compound [10]> In tetrahydrofuran (113 g) and dichloromethane (113 g), 4,4'-dinitro-2,2'-biphenyldicarboxylic acid (25.0 g, 75.4 mmol) and Cholesterol (61.7 g, 160 mmol), 4-dimethylaminopyridine (0.919 g, 7.54 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (33.6 g, 175 mmol), and reacted for 18 hours at room temperature in a nitrogen atmosphere. After the completion of the reaction, dichloromethane (375 g) was added to the reaction solution, the organic phase was washed three times with saturated brine (200 g), and then the organic phase was dehydrated with magnesium sulfate. Next, the obtained solution was concentrated under reduced pressure to obtain a brown oily compound, a mixed solution of ethyl acetate (200 g) and isopropanol (200 g) was added to precipitate crystals, and a crude product was obtained by filtration. The obtained crude product was recrystallized from a mixed solution of chloroform (500 g) and methanol (600 g) at 2 degrees, filtered and dried to obtain compound [10] (yield: 41.8 g, 39.1 mmol, yield: 52%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.67-2.21ppm(m, 86H), 4.58-4.63ppm(m, 2H), 5.31-5.33ppm(m, 2H), 7.37-7.39 ppm(m, 2H) , 8.42-8.44ppm(m, 2H), 8.93ppm(m, 2H)

<Synthesis of W-A6> In tetrahydrofuran (320 g) and methanol (80.8 g), compound [10] (40.4 g, 37.8 mmol) and 5% palladium on carbon (3.03 g) were added, and the mixture was heated in a hydrogen atmosphere at room temperature. The reaction is about 3 days. After completion of the reaction, palladium carbon was removed by filtration, and the total internal weight was 112 g by concentration under reduced pressure. Methanol (160 g) was added to the obtained solution to precipitate crystals, which were filtered and dried to obtain W-A6 (yield: 35.0 g, 34.7 mmol, yield: 92%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.66-2.17ppm(m, 86H), 3.74ppm(br, 4H), 4.50-4.56ppm(m, 2H), 5.28ppm(m, 2H), 6.78-6.80 ppm(m, 2H), 6.95-6.97ppm(m, 2H), 7.26-7.28 ppm(m, 2H)

<<Synthesis Example 7 Synthesis of W-A7>>

<Synthesis of Compound [11] and Compound [12]> In tetrahydrofuran (152 g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (40.0 g, 132 mmol) and triethylamine (36.6 g, 362 mmol), and ethanesulfonyl chloride (44.4 g, 345 mmol) was added dropwise under ice-cooling under nitrogen atmosphere. After the dropping was completed, compound [11] was obtained by stirring at a reaction temperature of 40°C for 3 hours. Next, p-(trans-4-propylcyclohexyl)phenol (63.1 g, 289 mmol) dissolved in tetrahydrofuran (240 g) and potassium hydroxide dissolved in pure water (228 g) were added to the reaction solution of compound [11] (85.0% product, 45.1 g, 683 mmol), heated to 50°C and reacted for 39 hours. After completion of the reaction, the reaction solution was poured into pure water (1500 g) to precipitate a crude product, which was filtered and washed with pure water. Next, the slurry was washed with a mixed solution of pure water (378 g) and methanol (378 g), and was filtered again and washed with methanol. The obtained crude crystalline product was dissolved in tetrahydrofuran (600 g) by heating at 60°C, methanol (400 g) was added to precipitate crystals, and after stirring at room temperature, compound [12] was obtained by filtration and drying (yield: 77.7 g, 110 mmol, yield: 83%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.87-0.97ppm(m, 6H), 0.97-1.05ppm(m, 4H), 1.12-1.62ppm(m, 14H), 1.81-1.87 ppm(m, 8H) , 2.34-2.40ppm(m, 2H), 4.77ppm(s, 4H), 6.67-6.69ppm(m, 4H), 7.00-7.05ppm(m, 4H), 7.40ppm(d, 2H, J =8.0Hz ), 8.25ppm(dd, 2H, J =2.0Hz, J =8.4Hz), 8.54ppm(s, 2H).

<Synthesis of W-A7> In tetrahydrofuran (741 g) and methanol (155 g), compound [12] (77.7 g, 110 mmol) and 3% platinum carbon (6.22 g) were charged, and the reaction was carried out at room temperature under hydrogen atmosphere. about 2 days. After completion of the reaction, platinum carbon was removed by filtration, and the filtrate was concentrated under reduced pressure. Tetrahydrofuran (122 g) was added to the obtained concentrated crude product, dissolved by heating at 60°C, acetonitrile (159 g) was added to precipitate crystals, and after stirring at room temperature, W-A7 was obtained by filtration and drying (yield: 58.6 g, 88.1 mmol, yield: 80%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.86-0.91ppm(m, 6H), 0.96-1.06ppm(m, 4H), 1.12-1.44ppm(m, 14H), 1.81-1.84 ppm(m, 8H) , 2.32-2.34ppm(m, 2H), 3.71-3.75ppm(br, 4H), 4.67-4.76ppm(q, 4H, J =10.0Hz), 6.61-6.64ppm(m, 2H), 6.71-6.75ppm (m, 4H), 6.91-6.92ppm(m, 2H), 6.97-7.03 ppm(m, 6H).

<<Synthesis Example 8 Synthesis of W-A8>>

<Synthesis of Compound [11] and Compound [13]> In tetrahydrofuran (156 g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (39.2 g, 129 mmol) and triethylamine (35.0 g, 346 mmol), and ethanesulfonyl chloride (34.8 g, 271 mmol) was added dropwise under ice-cooling under nitrogen atmosphere. After dropping, compound [11] was obtained by stirring at a reaction temperature of 40°C for 3 hours. Next, to the reaction solution of compound [11] were added 4-cyclohexylphenol (50.0 g, 284 mmol) dissolved in tetrahydrofuran (230 g) and potassium hydroxide (85.0% product, 47.1 g, 47.1 g, dissolved in pure water (231 g) 714 mmol), heated to 50 °C and reacted for 39 hours. After the completion of the reaction, the reaction liquid was poured into pure water (660 g), and liquid-separation extraction was performed with chloroform (588 g×4 times). The recovered organic phase was concentrated under reduced pressure, the crude product was dissolved in tetrahydrofuran (118 g) by heating at 60°C, methanol (235 g) was added to precipitate crystals, and the mixture was stirred at room temperature and filtered. The crystal was washed with pure water/methanol=1/1 mixed solvent (118 g) and methanol (118 g x 2 times), and the filter cake was washed and dried to obtain compound [13] (yield: 67.6 g, 120 mmol, yield: 93 %). ¹ H-NMR (400MHz) in CDCl ₃ : 1.18-1.30ppm(m, 2H), 1.31-1.38ppm(m, 8H), 1.71-1.75ppm(m, 2H), 1.80-1.82 ppm(m, 8H) , 2.36-2.44ppm(m, 2H), 4.77ppm(s, 4H), 6.67-6.70ppm(m, 4H), 7.03-7.06ppm(m, 4H), 7.40ppm(d, 2H, J =8.4Hz ), 8.24ppm(d, 1H, J =2.0Hz), 8.26ppm(d, 1H, J =2.0Hz), 8.54ppm(d, 2H, J =2.0Hz).

<Synthesis of W-A8> In tetrahydrofuran (325 g) and methanol (65.0 g), compound [13] (65.0 g, 105 mmol) and 3% platinum carbon (5.20 g) were added, and the mixture was heated to room temperature under hydrogen atmosphere. The response is about 2 days. After completion of the reaction, platinum carbon was removed by filtration, and concentrated under reduced pressure. The crude product was dissolved in tetrahydrofuran (70.4 g) by heating at 60°C, methanol (130 g) was added to precipitate crystals, and the mixture was stirred at room temperature and then filtered. The filter cake was washed with methanol (130 g×2 times) and dried to obtain W-A8 (yield: 54.2 g, 96.7 mmol, yield: 92%). ¹ H-NMR (400 MHz) in CDCl ₃ : 1.19-1.28 ppm(m, 2H), 1.31-1.41 ppm(m, 8H), 1.70-1.73 ppm(m, 2H), 1.79-1.87 ppm(m, 8H) , 1.87-2.39ppm(m, 2H), 3.60-3.79ppm(br, 4H), 4.67-4.76ppm(q, 4H, J =9.6Hz), 6.61-6.64ppm(m, 2H), 6.72-6.75ppm (m, 4H), 6.91-6.92ppm(d, 2H, J =2.4Hz), 6.97-7.03ppm(m, 6H).

<<Synthesis Example 9 Synthesis of W-A9>>

<Synthesis of Compound [11] and Compound [14]> In tetrahydrofuran (83.6 g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (20.9 g) was charged , 68.7 mmol) and triethylamine (15.3 g, 151 mmol), and ethanesulfonyl chloride (18.6 g, 145 mmol) was added dropwise under ice-cooling in a nitrogen environment. After dropping, compound [11] was obtained by stirring at a reaction temperature of 40°C for 3 hours. Next, 4-[(trans,trans)-4'-pentyl[1,1'-biscyclohexyl]-4-yl]phenol (48.6 g) dissolved in tetrahydrofuran (188 g) was added to the reaction solution of compound [11] g, 149 mmol) and potassium hydroxide (85.0% product, 20.9 g, 317 mmol) dissolved in pure water (119.2 g), and reacted for 20 hours. After completion of the reaction, the reaction solution was poured into pure water (800 g) to precipitate a crude product, which was filtered and washed with pure water. Next, the slurry was washed with a mixed solution of pure water (100 g) and methanol (100 g), filtered again, and washed with pure water and methanol. The crude product was dissolved in tetrahydrofuran (400 g) by heating at 60°C, methanol (100 g) was added to precipitate crystals, and after stirring at room temperature, compound [14] was obtained by filtration and drying (yield: 49.7 g, 53.9 mmol). , Yield: 78%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.83-1.34ppm(m, 44H), 1.71-1.85ppm(m, 16H), 2.29-2.36ppm(m, 2H), 4.77ppm(s, 4H), 6.66 -6.68ppm(m, 4H), 7.01-7.03ppm(m, 4H), 7.39ppm(d, 2H, J =8.0Hz), 8.24ppm(dd, 2H, J =2.0Hz, J =8.4Hz), 8.54ppm(d, 2H, J =2.4Hz)

<Synthesis of W-A9> In tetrahydrofuran (361 g) and methanol (90.2 g), compound [14] (45.1 g, 48.7 mmol) and 3% platinum on carbon (3.60 g) were charged, and the mixture was heated to 40°C under 0.4 MPa hydrogen pressure. The reaction was carried out at °C for about 9 hours. After completion of the reaction, the solvent was removed by filtration and concentration under reduced pressure, and methanol (135 g) was added to perform slurry washing. Next, the crude product obtained by filtration was dissolved in tetrahydrofuran (180 g) by heating at 60° C., ethyl acetate (120 g) was added, crystals were precipitated by stirring at room temperature, and W- A9 (yield: 17.8 g, 20.7 mmol, yield: 43%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.88-1.34ppm(m, 44H), 1.71-1.86ppm(m, 16H), 2.29-2.36ppm(m, 2H), 3.69ppm(br, 4H), 4.70 ppm(d, 2H, J =12.4Hz), 4.76ppm(d, 2H, J =12.4Hz), 6.62ppm(dd, 2H, J =2.4Hz, J =8.0Hz), 6.71-6.73ppm(m, 4H), 6.91ppm(d, 2H, J =2.4Hz), 6.96-6.99ppm(m, 6H)

<<Synthesis Example 10 Synthesis of W-A10>>

<Synthesis of compound [15]> In N-methylpyrrolidone (540g), 2-fluoro-5-nitrotoluene (91.0g, 587mmol), 1,3-propanediol (22.3g, 291mmol), potassium hydroxide (85.0% product) were added , 71.6 g, 1.08 mol), and stirred at 80° C. for 20 hours under a nitrogen atmosphere. After the reaction, pure water (1440 g) was added for water dilution and crystallization. After filtration, the crystals were washed with pure water (540 g × 3 times) and methanol (360 g × 2 times), respectively, and the filter cake was washed and dried to obtain a compound. [15] (yield: 57.2 g, 165 mmol, yield: 54%).

<Synthesis of compound [16]> In 1,2-dichloroethane (540 g), compound [15] (40.0 g, 116 mmol), N-bromosuccinimide (45.2 g, 254 mmol), 2,2'-azobis( isobutyronitrile) (3.79 g, 23.1 mmol), after nitrogen substitution, was stirred at 100° C. for about 7 days. The reaction solution was filtered to remove insoluble succinimide, ethyl acetate (250 g) was added to the filtrate, and purified water (250 g × 3 times) was used for liquid separation extraction and washing, and the organic phase was recovered and concentrated. The obtained concentrate was crystallized and filtered from ethyl acetate (346 g) and hexane (395 g), and crystals were recovered. The filtrate was further concentrated, recrystallized with chloroform (223 g) and hexane (434 g) and filtered, respectively, by drying to obtain a crude product of compound [16] (crude yield: 21.3 g, crude yield: 37%).

<Synthesis of compound [17]> In N,N-dimethylacetamide (96.0 g), p-(trans-4-heptylcyclohexyl)phenol (24.0 g, 87.5 mmol) and potassium carbonate were added (12.1 g, 87.5 mmol), and stirred at 100°C. The crude product (20.0 g) of compound [16] dissolved in N,N-dimethylacetamide (54.0 g) was dropped and reacted for 24 hours. The crystals precipitated from the reaction solution were separated by filtration, the slurry was washed with methanol (66.0 g) and pure water (67.0 g), respectively, and then filtered and dried again to obtain compound [17] (yield: 4.23 g, 4.75 mmol, yield: Yield: 4.1% (yield based on the charged compound [15])). ¹ H-NMR (400MHz) in CDCl ₃ : 0.89ppm(t, 6H, J =6.8Hz), 0.99-1.07ppm(m, 4H), 1.19-1.43ppm(m, 30H), 1.84-1.87ppm(m , 8H), 2.36-2.44ppm(m, 4H), 4.29ppm(t, 4H, J =6.0Hz), 5.04ppm(s, 4H), 6.84-6.90ppm(m, 6H), 7.10-7.13 ppm( m, 4H), 8.17ppm(dd, 2H, J =3.2Hz, 9.0Hz), 8.38ppm(d, 2H, J =2.8Hz).

<Synthesis of W-A10> In tetrahydrofuran (28.8 g) and methanol (7.5 g), compound [17] (3.60 g, 4.04 mmol) and 3% platinum on carbon (0.290 g) were added, and the mixture was added in a hydrogen atmosphere at 0.4 MPa. Under pressure conditions, the mixture was stirred at 40°C for 3 hours. After completion of the reaction, platinum carbon was removed by filtration, and concentrated under reduced pressure. The crude product was crystallized by adding ethyl acetate and methanol, stirred at room temperature, filtered, and dried to obtain W-A10 (yield: 2.05 g, 2.47 mmol, yield: 54%). ¹ H-NMR (400MHz) in CDCl ₃ : 0.89ppm(t, 6H, J =6.8Hz), 0.98-1.06ppm(m, 4H), 1.18-1.44ppm(m, 30H), 1.83-1.86 ppm(m , 8H), 2.15-2.21ppm(m, 2H), 2.36-2.42ppm(m, 2H), 3.42ppm(br, 4H), 4.09ppm(t, 4H, J =6.0Hz), 5.00ppm(s, 4H), 6.55-6.57ppm(m, 2H), 6.70ppm(d, 2H, J =8.8Hz), 6.82-6.89ppm(m, 6H), 7.07-7.10ppm(m, 4H).

<Synthesis of polyimide polymer> [Synthesis Example 1] D2 (2.50 g, 10.0 mmol), W-A1 (3.03 g, 4.00 mmol), and C1 (1.73 g, 16.0 mmol) were mixed in NMP (36.2 g), and reacted at 60°C for 3 hours, and then D1 (1.78 g) was added. g, 9.10 mmol), and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 840 mPa･s. NMP was added to the obtained polyamic acid solution (20.0 g), and after diluting to 6.5 mass %, acetic anhydride (4.43 g) and pyridine (1.37 g) as imidization catalysts were added, and the reaction was carried out at 80° C. 3 hours. The reaction solution was poured into methanol (382 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (1). The imidization rate of this polyimide was 76.4%, the number average molecular weight was 16,165, and the weight average molecular weight was 49,988.

[Synthesis Example 2] D2 (2.50 g, 10.0 mmol), W-A2 (3.14 g, 4.00 mmol), and C1 (1.84 g, 16.0 mmol) were mixed in NMP (36.9 g) and reacted at 60°C for 3 hours, and then D1 (1.84 g) was added. g, 9.38 mmol), and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 658 mPa･s. After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5 mass %, acetic anhydride (4.38 g) and pyridine (1.36 g) as imidization catalysts were added and reacted at 80°C 3 hours. The reaction solution was poured into methanol (382 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (2). The imidization rate of this polyimide was 75.8%, the number average molecular weight was 15,430, and the weight average molecular weight was 45,756.

[Synthesis Example 3] D2 (2.50 g, 10.0 mmol), W-A3 (3.25 g, 4.00 mmol), and C1 (1.73 g, 16.0 mmol) were mixed in NMP (37.3 g), and reacted at 60°C for 3 hours, and then D1 (1.84 g, 9.38 mmol), and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 656 mPa･s. After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5% by mass, acetic anhydride (4.32 g) and pyridine (1.34 g) as imidization catalysts were added and reacted at 80°C 3 hours. The reaction solution was poured into methanol (382 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (3). The imidization rate of this polyimide was 74.7%, the number average molecular weight was 13,340, and the weight average molecular weight was 41,948.

[Controlled Synthesis Example 1] Dissolve D2 (1.50 g, 6.0 mmol), C2 (1.83 g, 12.0 mmol), C3 (2.18 g, 9.0 mmol), and A1 (3.43 g, 9.0 mmol) in NMP (41.1 g) and react at 60 °C for 3 After one hour, D3 (1.31 g, 6.0 mmol) was added, followed by D1 (3.47 g, 17.7 mmol) and NMP (13.71 g), and the mixture was reacted at 25° C. for 10 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (50g) and diluting to 6.5 mass %, acetic anhydride (11.1g) and pyridine (3.4g) as an imidization catalyst were added, and it was made to react at 60 degreeC for 3 hours. The reaction solution was poured into methanol (700 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (4). The imidization rate of this polyimide was 79%, the number average molecular weight was 11,000, and the weight average molecular weight was 24,000.

[Comparative Synthesis Example 1] D2 (2.88 g, 11.5 mmol), A1 (3.50 g, 9.20 mmol), and C1 (1.49 g, 13.8 mmol) were mixed in NMP (40.2 g), and reacted at 60 °C for 3 hours, and then D1 (2.19 g, 13.8 mmol) was added. 11.2 mmol) and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 680 mPa･s. After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6.5% by mass, acetic anhydride (4.64 g) and pyridine (1.44 g) as imidization catalysts were added and reacted at 80°C 3 hours. The reaction solution was poured into methanol (382 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (R1). The imidization rate of this polyimide was 75.1%, the number average molecular weight was 15,322, and the weight average molecular weight was 45,800.

[Synthesis Example 5] D2 (2.50 g, 10.0 mmol), W-A4 (4.62 g, 6.00 mmol), and C1 (1.51 g, 14.0 mmol) were mixed in NMP (24.5 g), and reacted at 60°C for 3 hours, and then D1 (1.92 g, 9.80 mmol), and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 783 mPa･s. NMP was added to the obtained polyamic acid solution (20.0 g), and after diluting to 6.5% by mass, acetic anhydride (3.86 g) and pyridine (1.20 g) as imidization catalysts were added, and the reaction was carried out at 80° C. 3 hours. The reaction solution was poured into methanol (233 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (5). The imidization rate of this polyimide was 76.7%, the number average molecular weight was 14,399, and the weight average molecular weight was 38,573.

[Synthesis Example 6] D2 (2.50 g, 10.0 mmol), W-A5 (4.70 g, 6.00 mmol), and C1 (1.51 g, 14.0 mmol) were mixed in NMP (24.9 g), and reacted at 60°C for 3 hours, then D1 (1.92 g, 9.80 mmol), and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 769 mPa･s. NMP was added to the obtained polyamic acid solution (20.0 g), and after diluting to 6.5% by mass, acetic anhydride (3.83 g) and pyridine (1.19 g) as imidization catalysts were added, and the reaction was carried out at 80° C. 3 hours. The reaction solution was poured into methanol (232 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (6). The imidization rate of this polyimide was 73.4%, the number average molecular weight was 13,841, and the weight average molecular weight was 37,284.

[Synthesis Example 7] D2 (6.26 g, 25.0 mmol), W-A6 (5.05 g, 5.00 mmol), and C1 (4.87 g, 45.0 mmol) were mixed in NMP (62.0 g), and reacted at 60°C for 3 hours, then D1 (4.51 g) was added. g, 23.0 mmol), and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 658 mPa･s. NMP was added to the obtained polyamic acid solution (75.0 g), and after diluting to 6.5 mass %, acetic anhydride (18.2 g) and pyridine (5.6 g) as imidization catalysts were added, and the reaction was carried out at 80° C. 3 hours. The reaction solution was poured into methanol (1000 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (7). The imidization rate of this polyimide was 72.9%, the number average molecular weight was 13,362, and the weight average molecular weight was 38,725.

[Synthesis Example 8] D2 (6.26 g, 25.0 mmol), W-A7 (8.06 g, 12.5 mmol), and C1 (4.06 g, 37.5 mmol) were mixed in NMP (69.2 g) and reacted at 60°C for 3 hours, and then D1 (4.71 g) was added. g, 24.0 mmol), and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 725 mPa･s. NMP was added to the obtained polyamic acid solution (75.0 g), and after diluting to 6.5% by mass, acetic anhydride (16.5 g) and pyridine (5.1 g) as imidization catalysts were added, and the reaction was carried out at 80° C. 3 hours. The reaction solution was poured into methanol (1000 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (8). The imidization rate of this polyimide was 73.1%, the number average molecular weight was 13,628, and the weight average molecular weight was 39,937.

[Synthesis Example 9] D2 (6.26 g, 25.0 mmol), W-A8 (7.01 g, 12.5 mmol), and C1 (4.06 g, 37.5 mmol) were mixed in NMP (66.1 g) and reacted at 60°C for 3 hours, and then D1 (4.71 g) was added. g, 24.0 mmol), and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 674 mPa･s. NMP was added to the obtained polyamic acid solution (75.0 g), and after diluting to 6.5% by mass, acetic anhydride (17.2 g) and pyridine (5.3 g) as imidization catalysts were added, and the reaction was carried out at 80° C. 3 hours. The reaction solution was poured into methanol (1000 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (9). The imidization rate of this polyimide was 73.2%, the number average molecular weight was 10,425, and the weight average molecular weight was 37,759.

[Synthesis Example 10] D2 (6.26 g, 25.0 mmol), W-A9 (2.16 g, 2.5 mmol), and C1 (5.14 g, 47.5 mmol) were mixed in NMP (54.8 g), and reacted at 60°C for 3 hours, and then D1 (4.71 g) was added. g, 24.0 mmol), and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 823 mPa･s. NMP was added to the obtained polyamic acid solution (75.0 g), and after diluting to 6.5 mass %, acetic anhydride (20.7 g) and pyridine (6.4 g) as imidization catalysts were added, and the reaction was carried out at 80° C. 3 hours. The reaction solution was poured into methanol (1000 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (10). The imidization rate of this polyimide was 71.5%, the number average molecular weight was 13,732, and the weight average molecular weight was 38,921.

[Synthesis Example 11] D2 (2.50 g, 10.0 mmol), W-A10 (3.31 g, 4.00 mmol), and C1 (1.73 g, 16.0 mmol) were mixed in NMP (30.2 g) and reacted at 60°C for 3 hours, and then D1 (1.84 g) was added. g, 9.40 mmol), and reacted at 40° C. for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 695 mPa･s. NMP was added to the obtained polyamic acid solution (20.0 g), and after diluting to 6.5% by mass, acetic anhydride (4.35 g) and pyridine (1.35 g) as imidization catalysts were added, and the reaction was carried out at 80° C. 3 hours. The reaction solution was poured into methanol (235 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (11). The imidization rate of this polyimide was 76.1%, the number average molecular weight was 12,913, and the weight average molecular weight was 39,182.

[Synthesis Example 12] D2 (25.0 g, 100 mmol), W-A1 (37.9 g, 50.0 mmol), C3 (12.1 g, 50.0 mmol), and C8 (33.0 g, 100 mmol) were mixed in NMP (432 g) and reacted at 60 °C for 3 hours Then, D1 (18.8 g, 96.0 mmol) was added, and it was made to react at 40 degreeC for 3 hours, and the polyamic acid solution of resin solid content concentration 20 mass % was obtained. After measuring the viscosity of the polyamide solution, it was 721 mPa･s. NMP was added to the obtained polyamic acid solution (100 g), and after diluting to 6.5 mass %, acetic anhydride (16.0 g) and pyridine (4.96 g) as imidization catalysts were added, and the reaction was carried out at 80° C. for 3 Hour. The reaction solution was poured into methanol (1150 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (12). The imidization rate of this polyimide was 75.1%, the number average molecular weight was 14,736, and the weight average molecular weight was 39,645.

[Synthesis Example 13] D2 (25.0 g, 100 mmol), W-A1 (37.9 g, 50.0 mmol), C6 (20.5 g, 60.0 mmol), C8 (6.61 g, 20,0 mmol), C7 (27.9 g, 70,0 mmol) were dissolved in NMP (471 g) and reacted at 60°C for 3 hours, then D1 (18.8 g, 96.0 mmol) was added, and the mixture was reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 771 mPa･s. NMP was added to the obtained polyamic acid solution (100 g), and after diluting to 6.5% by mass, acetic anhydride (14.9 g) and pyridine (4.63 g) as imidization catalysts were added, and the reaction was carried out at 80° C. for 3 Hour. The reaction solution was poured into methanol (1150 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (13). The imidization rate of this polyimide was 76.2%, the number average molecular weight was 15,835, and the weight average molecular weight was 39,145.

[Synthesis Example 14] Combine D2 (25.0 g, 100 mmol), W-A1 (37.9 g, 50.0 mmol), C6 (17.0 g, 50.0 mmol), C8 (16.5 g, 50.0 mmol), C3 (12.1 g, 50.0 mmol) in NMP (434 g) ) and reacted at 60°C for 3 hours, D1 (18.8 g, 96.0 mmol) was added, and the mixture was reacted at 40°C for 3 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 701 mPa･s. NMP was added to the obtained polyamic acid solution (100 g), and after diluting to 6.5% by mass, acetic anhydride (16.0 g) and pyridine (4.97 g) as imidization catalysts were added, and the reaction was carried out at 80° C. for 3 Hour. The reaction solution was poured into methanol (1150 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (14). The imidization rate of this polyimide was 74.8%, the number average molecular weight was 17,635, and the weight average molecular weight was 41,647.

[Synthesis Example 15] Combine D4 (43.9 g, 196 mmol), W-A1 (30.3 g, 40.0 mmol), C4 (13.9 g, 70.0 mmol), C8 (16.5 g, 50.0 mmol), C5 (7.59 g, 40.0 mmol) in NMP (455 g) ), and reacted at 60° C. for 15 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 662 mPa･s. NMP was added to the obtained polyamic acid solution (100 g), and after diluting to 6.5 mass %, acetic anhydride (17.9 g) and pyridine (5.55 g) as imidization catalysts were added, and the reaction was carried out at 100° C. for 3 Hour. The reaction solution was poured into methanol (1160 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (15). The imidization rate of this polyimide was 71.7%, the number average molecular weight was 13,329, and the weight average molecular weight was 40,527.

[Synthesis Example 16] D2 (25.0 g, 100 mmol), C2 (21.3 g, 140 mmol), and C10 (24.6 g, 60.0 mmol) were dissolved in NMP (284 g), and after reacting at 60° C. for 3 hours, D5 (14.3 g, 40.0 mmol) was added and then D1 (11.0 g, 56.0 mmol) and NMP (100 g) were reacted at 25° C. for 10 hours to obtain a polyamic acid solution. NMP was added to this polyamic acid solution (100 g), and after diluting to 6.5 mass %, acetic anhydride (21.0 g) and pyridine (6.52 g) as imidization catalysts were added, and it was made to react at 80 degreeC for 3 hours. The reaction solution was poured into methanol (1170 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (16). The imidization rate of this polyimide was 75.8%, the number average molecular weight was 14679, and the weight average molecular weight was 35747.

[Synthesis Example 17] Dissolve D2 (25.0 g, 100 mmol), C6 (50.0 g, 120 mmol), C9 (15.1 g, 60.0 mmol), and W-A1 (15.1 g, 20.0 mmol) in NMP (385 g), and react at 60°C for 3 hours Then, D1 (18.8 g, 96.0 mmol) and NMP (75.3 g) were added, and it was made to react at 40 degreeC for 3 hours, and the polyamic acid solution of resin solid content concentration 20 mass % was obtained. After measuring the viscosity of the polyamide solution, it was 753 mPa･s. After adding NMP to this polyamic acid solution (100g) and diluting to 6.5 mass %, acetic anhydride (17.6g) and pyridine (5.47g) as an imidization catalyst were added, and it was made to react at 80 degreeC for 3 hours. The reaction solution was poured into methanol (1160 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain polyimide powder (17). The imidization rate of this polyimide was 71.1%, the number average molecular weight was 17635, and the weight average molecular weight was 38427.

[Comparative Synthesis Example 2] D2 (6.26 g, 25.0 mmol), A2 (12.23 g, 30.0 mmol), and C1 (2.16 g, 20.0 mmol) were mixed in NMP (76.7 g) and reacted at 80 °C for 5 hours, and then D1 (4.90 g, 25.0 mmol) and reacted at 40° C. for 12 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 338 mPa･s. After adding NMP to the obtained polyamic acid solution (75.0 g) and diluting to 6.5 mass %, acetic anhydride (15.0 g) and pyridine (4.6 g) as imidization catalysts were added and reacted at 80°C 3 hours. The reaction solution was poured into methanol (1000 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (R2). The imidization rate of this polyimide was 73.0%, the number average molecular weight was 10,175, and the weight average molecular weight was 23,642.

[Comparative Synthesis Example 3] D2 (6.26 g, 25.0 mmol), A3 (7.06 g, 25.0 mmol), and C1 (2.70 g, 25.0 mmol) were mixed in NMP (62.8 g), and reacted at 80 °C for 5 hours, then D1 (4.90 g, 25.0 mmol) was added. 25.0 mmol) and reacted at 40° C. for 12 hours to obtain a polyamic acid solution with a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamide solution, it was 446 mPa･s. NMP was added to the obtained polyamic acid solution (75.0 g), and after diluting to 6.5 mass %, acetic anhydride (18.3 g) and pyridine (5.7 g) as imidization catalysts were added, and the reaction was carried out at 80° C. 3 hours. The reaction solution was poured into methanol (1000 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder (R3). The imidization rate of this polyimide was 72.2%, the number average molecular weight was 11,636, and the weight average molecular weight was 24,624. The compositions of the polyimide powders obtained in the synthesis examples and comparative synthesis examples are summarized in Table 1.

<Preparation of liquid crystal alignment treatment agent> In the Example and the comparative example, the preparation example of a liquid crystal aligning agent is described. Using the liquid crystal alignment treatment agents obtained in Examples and Comparative Examples, production of liquid crystal display elements and various evaluations were performed.

<Example 1> NMP (28.2 g) was added to the polyimide powder (1) (3.00 g) obtained in Synthesis Example 1, and the mixture was stirred and dissolved at 70°C for 24 hours. NMP (g) and BCS (18.8g) were added to this solution, and it stirred at room temperature for 5 hours, and obtained the liquid crystal aligning agent (V-1). Abnormalities, such as turbidity and precipitation, were not seen in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 2> and <Example 3> In Example 1, the polyimide powders (2) and (3) were used in place of the polyimide powder (1), and the liquid crystal aligning agents (V-2) and (V-2) were obtained by the same procedure as in Example 1. V-3). Abnormalities, such as turbidity and precipitation, were not seen in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Control 1> In Example 1, the polyimide powder (4) obtained in Controlled Synthesis Example 1 was used to replace the polyimide powder (1), and a liquid crystal aligning agent (V-4) was obtained by the same procedure as in Example 1. ). Abnormalities, such as turbidity and precipitation, were not seen in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 4> The liquid crystal aligning agent (V-1) obtained in Example 1 was mixed with 3.0 g as the first component, and the liquid crystal aligning agent (V-4) obtained in Control 1 was mixed with 7.0 g as the second component. A liquid crystal aligning agent (V-5) was obtained in 1 hour.

<Example 5> to <Example 6> In Example 4, the liquid crystal alignment treatment agent (V-2) or (V-3) was used to replace the liquid crystal alignment treatment agent (V-1), as the first component, by the same procedure as in Example 4, respectively, to obtain Liquid crystal alignment treatment agents (V-6) and (V-7).

<Comparative Example 1> NMP (28.2 g) and BCS (18.8 g) were added to the polyimide powder (R1) (3.00 g) obtained in Comparative Synthesis Example 1, followed by stirring at 70° C. for 24 hours to obtain a liquid crystal aligning agent (R-V1). ). Abnormalities, such as turbidity and precipitation, were not seen in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution. Using the obtained liquid crystal alignment treatment agent (R-V1), production of a liquid crystal display element, evaluation of vertical alignment, evaluation of pretilt angle, evaluation of voltage retention, and evaluation of afterimage characteristics were performed.

<Example 7> NMP (22.0 g) was added to the polyimide powder (5) (3.00 g) obtained in Synthesis Example 5, and the mixture was stirred at 70° C. for 24 hours to dissolve. To this solution, 3.0 g of E2 (1 wt % NMP solution) and BCS (20.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (V-8). Abnormalities, such as turbidity and precipitation, were not seen in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Examples 8 to 13, 15 to 17, 19, 20, and Comparative Examples 2 to 4> In the same operation as in Example 7, the polyimide powders (6) to (11), ( 13)~(15), (17), (R1~R3), (4) to prepare liquid crystal alignment treatment agents (V-9~V-21), (R-V2~R-V4).

<Example 14> NEP (22.0 g) was added to the polyimide powder (12) (3.00 g) obtained in Synthesis Example 12, and the mixture was stirred at 70° C. for 24 hours to dissolve. NEP (3.0 g) and BCS (20.0 g) were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (V-15). Abnormalities, such as turbidity and precipitation, were not seen in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 18> The same operations as in Example 14 were also performed for the polyimide powder (16) obtained in Synthesis Example 16 to obtain a liquid crystal alignment film treating agent (V-19).

<Example 21> As the first component, 3.0 g of the liquid crystal alignment agent (V-15) obtained in Example 14 and 7.0 g of the liquid crystal alignment agent (V-19) obtained in Example 18 as the second component were mixed. The resin component in the liquid crystal alignment film agent was 5 wt % of the crosslinking agent E1, and the liquid crystal alignment treatment agent (W-2) was obtained by stirring for 1 hour.

<Examples 22 to 24> For the liquid crystal alignment treatment agents (V-16) to (V-21) obtained in Examples 15 to 20, the same operations as in Example 21 were used to obtain the liquid crystal alignment treatment agents (W-3) to (W-5) .

Using the liquid crystal alignment treatment agents obtained in the examples and the liquid crystal alignment treatment agents obtained in the comparative examples, the production of liquid crystal display elements, evaluation of vertical alignment, scratch test, evaluation of pretilt angle, evaluation of voltage retention, residual like evaluation of characteristics.

<Preparation of a liquid crystal display element for voltage holding ratio measurement> The liquid crystal alignment treatment agent obtained in the example and the liquid crystal alignment treatment agent obtained in the comparative example were filtered under pressure with a membrane filter having a pore size of 1 μm. The obtained solution was spin-coated on the ITO surface of a glass substrate (length: 40 mm, width: 30 mm, thickness: 1.1 mm) with ITO electrodes of 40 mm×30 mm washed with pure water and IPA (isopropyl alcohol). Then, heat treatment at 70° C. on a hot plate for 90 seconds, and heat treatment at 230° C. for 30 minutes in a thermal cycle type clean oven to obtain an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm. Two obtained ITO substrates with a liquid crystal alignment film were prepared, and the liquid crystal alignment film surface of one of the substrates was coated with a bead spacer of 4 μm in diameter (manufactured by Nippon Kasei Co., Ltd., silk ball, SW-D1) . Next, the periphery was coated with a sealant (XN-1500T manufactured by Mitsui Chemicals). Next, the surface of the other substrate on the side where the liquid crystal alignment film is formed is used as the inner side, and after bonding with the previous substrate, the sealing material is cured to obtain an empty cell. Liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell. Then, in the state of applying a DC voltage of 15V to the obtained liquid crystal cell, using an ultraviolet irradiation device using a high-pressure mercury lamp as a light source, irradiating ultraviolet rays of 15J/cm ² through a bandpass filter with a wavelength of 365nm to obtain a vertical alignment type liquid crystal display element. In addition, the measurement of the ultraviolet irradiation amount was used with the UV-M03A made by ORC Co., Ltd. connected with the light receiver of UV-35.

<Preparation of liquid crystal display element for pretilt angle and afterimage evaluation> The liquid crystal alignment treatment agent obtained in the Example was filtered under pressure with a membrane filter having a pore size of 1 μm. The obtained solution was spin-coated on an ITO electrode substrate (length: 35 mm) with a pixel size of 200 μm×600 μm and an ITO electrode pattern with a line/space of 3 μm, washed with pure water and IPA (isopropyl alcohol), respectively. , horizontal: 30mm, thickness: 0.7mm), and the ITO surface of the glass substrate (vertical: 35mm, horizontal: 30mm, thickness: 0.7mm) with a patterned optical spacer with a height of 3.2 μm with ITO electrodes, Heat treatment at 70° C. on a hot plate for 90 seconds, and heat treatment at 230° C. for 30 minutes in a thermal cycle type clean oven to obtain an ITO substrate with a liquid crystal alignment film with a thickness of 100 nm. Furthermore, the ITO electrode substrate on which the ITO electrode pattern is formed is divided into four checkerboard (checkered) patterns, and the four regions can be driven individually. Next, the periphery was coated with a sealant (XN-1500T manufactured by Mitsui Chemicals). Next, the surface of the other substrate on the side on which the liquid crystal alignment film was formed was used as the inner side, and after bonding with the previous substrate, the sealing material was cured to form an empty cell. Liquid crystal MLC-3023 (trade name, manufactured by Merck & Co., Ltd.) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell. After that, a DC voltage of 15V was applied to the obtained liquid crystal cell, and while the entire pixel area was driven, an ultraviolet irradiation device using a high-pressure mercury lamp as a light source was used to irradiate ultraviolet rays 10J/ cm ² to obtain a vertical alignment type liquid crystal display element. The ultraviolet radiation dose was measured using the UV-M03A made by ORC Corporation and the light receiver connected to UV-35. Further, in Examples 1 to 3 and Comparative Example 1, in addition to the above standard conditions, the heat treatment was set to 230° C. for 120 minutes as severe conditions to form a liquid crystal alignment film. A vertical alignment type liquid crystal display element was fabricated under the same conditions.

＜Assessment＞ (Vertical alignment) The liquid crystal alignment of the liquid crystal display element was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to confirm whether or not the liquid crystal was vertically aligned. Specifically, those who did not see a defect due to liquid crystal flow or a bright spot due to an alignment defect were rated as good. The evaluation results are shown in Table 2.

(voltage holding ratio) After applying a voltage of 1V to the liquid crystal display element for evaluating the voltage holding ratio prepared above at an application time of 60 microseconds and an interval of 1667 milliseconds, the voltage holding ratio (%) after 1667 milliseconds after the application was released was measured. . As the measuring apparatus, VHR-1 manufactured by Toyo Technica was used. The evaluation results are shown in Table 2.

(pre-tilt angle) Using an LCD analyzer (LCA-LUV42A, manufactured by Meiling Technica), among the liquid crystal display elements for pretilt angle evaluation prepared above, the liquid crystal display elements in which defects due to liquid crystal flow were not observed were measured. The evaluation results are shown in Table 2.

(Afterimage feature) Using the liquid crystal display element for afterimage evaluation produced above, an AC voltage of 60 Hz, 20 Vp-p was applied to two diagonal regions among the four pixel regions, and the device was driven at a temperature of 23° C. for 168 hours. After that, all the four pixel regions were driven with an AC voltage of 5Vp-p, and the luminance difference between the pixels was visually observed. A state in which the difference in luminance was hardly recognized was considered good. The evaluation results are shown in Table 3.

(scratch test) The scratch test was carried out using UMT-2 (manufactured by Bruker AXS Co., Ltd.) on the alignment film surface of the polyimide coating film-attached substrate obtained in the Example. The sensor of UMT-2 is FVL, and a 1.6mm sapphire ball is installed at the front end of the scratching part. The scratch test was performed by changing the load from 1 mN to 20 mN in the range of 0.5 mm in width and 2.0 mm in length for 100 seconds in a state where the tip of the scratch portion was in contact with the surface of the liquid crystal alignment film with a load of 1 mN. At this time, the moving direction of the front end of the scraping part was back and forth in the lateral direction, and the moving speed was performed at 5.0 mm/sec. The movement of the scratch area in the vertical direction was performed by moving the substrate with the liquid crystal alignment film in the vertical direction at 20 μm/sec. After the scratch test, MLC-3022 (negative liquid crystal manufactured by Merck & Co.) was dropped on the surface of the liquid crystal alignment film subjected to the scratch test. For this, another substrate with a liquid crystal alignment film obtained in Example 1 was superimposed so that the surfaces of the liquid crystal alignment films were facing each other, and spacers of 4 μm were scattered, and the dropped MLC-3022 was sandwiched. Using a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation), the polarization axes of the upper and lower polarizing plates are at 90° (crossed polarizers), and the portion subjected to the scratch test was observed to observe whether light was transmitted. For the parts subjected to the scratch test, the state where no bright spot or light leakage is seen at all is ○, the state where a few bright spots or light leakage are seen is △, and the state where the entire scratched part has light leakage is x, as shown in Table 6.

[Table 4] No. Liquid crystal alignment agent Specified polyimide polymer Vertical alignment (standard/strict) Pre-tilt [°] (standard/critical) Voltage holding ratio [%] (standard) Example 1 V-1 Polyimide Powder (1) good/good 87.7/87.9 28.6 Example 2 V-2 Polyimide Powder (2) good/good 87.6/87.5 47.7 Example 3 V-3 Polyimide Powder (3) good/good 87.2/87.4 63.0 Comparative Example 1 R-V1 Polyimide Powder (R1) good/bad 87.3/Vertical none 45.2

[table 5] No. Liquid crystal alignment agent Afterimage characteristics (4 pixel evaluation) Example 4 V-5 good Example 5 V-6 good Example 6 V-7 good

The above results, specifically, from the comparison of Examples 1 to 3 shown in Table 4 and Comparative Example 1, it can be seen that the liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention can be used even under severe conditions. Under the same conditions, the pretilt angle did not change, and the liquid crystal alignment was good. Moreover, as shown in Table 5, in Example 4 - Example 6 which mixed the liquid crystal aligning agent (V-4), it turned out that the afterimage characteristic was favorable. Further, from this example, it can be seen that the liquid crystal alignment film obtained by using the specific side chain type diamine is excellent in the stability of the pretilt angle even if it is fired under severe conditions. In addition, it was also confirmed that even when the liquid crystal alignment film was physically contacted as in the scratch test, the damage to the alignment film was small and good vertical alignment was maintained. [Industrial Availability]

The liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention can be suitably used for the liquid crystal display element. In addition, these elements are also used in liquid crystal displays for display purposes, and furthermore, dimming windows or shutters for controlling the transmission and blocking of light.

Claims (5)

A diamine represented by the following formula [1] (in formula [1], X represents a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -(CH ₂ ) _m -, -SO ₂ -, and a divalent organic group formed by any combination of these, m represents an integer from 1 to 8, and Y represents the structure of the following formula [1-1] independently; In -1], Y ¹ and Y ³ each independently represent a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH- , -NHCO-, -COO- and -OCO- at least one of the group; Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15) (only, Y ¹ or Y When ³ is a single bond and -(CH ₂ ) _a -, Y ² is a single bond, and Y ¹ is selected from -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO- At least one species of the group formed, and/or Y ³ is at least one species selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO- and -OCO- When Y ² is a single bond or -(CH ₂ ) _b - (but, when Y ¹ is -CONH-, Y ² and Y ³ are single bonds)); Y ⁴ represents a group selected from benzene ring, cyclohexane ring and At least one divalent cyclic group of a heterocyclic group, or a divalent organic group with 17 to 51 carbon atoms having a steroid skeleton and a tocopherol skeleton, and any hydrogen atom on the aforementioned cyclic group can be changed to a number of carbon atoms. 1~3 alkyl group, 1~3 carbon number alkoxy group, 1~3 carbon number fluorine-containing alkyl group, 1~3 carbon number fluorine-containing alkoxy group or fluorine atom substitution; Y ⁵ represents selected from free ring At least one cyclic group of the group consisting of a hexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups may be converted to an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, Fluorine-containing alkyl group with 1-3 carbon atoms, fluorine-containing alkoxy group with carbon number 1-3 or fluorine atom substitution; Y ⁶ represents selected from alkyl group with carbon number 1-18, alkenyl group with carbon number 2-18, At least one of the group consisting of a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having a carbon number of 1 to 18, and a fluorine-containing alkoxy group having a carbon number of 1 to 18; n represents an integer of 0 to 4);

. A diamine represented by the following formula [1] (in formula [1], X represents a single bond, -O-, -C(CH ₃ ) ₂ -, -NH-, -CO-, -(CH ₂ ) _k -, -SO ₂ -, and a divalent organic group formed by any combination of these, k represents an integer of 1 to 8, and Y is independently selected from the following formulae [1-1]-1 to [1 The group formed by -1]-22 (in the formula, * represents the position of bonding with the phenyl group in the aforementioned formula [1], m represents an integer from 1 to 15, and n represents an integer from 0 to 18)),

. A diamine represented by any one of the following formulas W-A1～W-A10,

. A polymer comprising a polyimide precursor and a polyimide of a diamine component and a tetracarboxylic acid component of the reaction product of the diamine as claimed in any one of claims 1 to 3 At least one selected from amines. The polymer according to claim 4, wherein the diamine component further contains a diamine represented by the following formula [2] (in the formula [2], A ₁ and A ₂ each independently represent a hydrogen atom, or a carbon number of 1 ~5 alkyl group, carbon number 2~5 alkenyl group, or carbon number 2~5 alkynyl group, Y ₁ represents a divalent organic group),

.