TW201842172A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent whereby a liquid crystal alignment film is obtained in which the ability thereof to align liquid crystals vertically is not reduced even when the liquid crystal alignment film is exposed to excessive heating, and provides a liquid crystal alignment agent whereby a liquid crystal alignment film is obtained in which the ability thereof to align liquid crystals vertically is not reduced even when some foreign matter touches or damages the film. The present invention provides a liquid crystal alignment agent containing a diamine component containing a diamine represented by formula [1] (In formula [1], X represents a single bond or -O- or another divalent group, Y represents a group represented by formula [1-1], and Y1 through Y6 represent specific groups described in the specification.), and at least one species of polymer selected from a polyimide precursor and a polyimide that is an imidization product of the polyimide precursor, the polyimide precursor being a product of reaction with a tetracarboxylic acid component.

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 align liquid crystal vertically.

A liquid crystal display device in which a liquid crystal molecule vertically aligned with a substrate reacts due to 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 a manufacturing process. By.

In such a vertical alignment type liquid crystal display element, it is known to add a photopolymerizable compound to a liquid crystal composition in advance, and use a vertical alignment film such as a polyimide system to irradiate the liquid crystal cell while applying a voltage. A technology that accelerates the reaction speed of liquid crystal by ultraviolet rays (PSA (Polymer Sustained Alignment) system elements, see, for example, Patent Document 1 and Non-Patent Document 1).

As a liquid crystal alignment agent for this PSA system element. A liquid crystal alignment agent using a side chain having a specific ring structure has been proposed (see Patent Document 2). The specific ring structure has a high ability to vertically align liquid crystals, and a liquid crystal display element using a vertical alignment method of the liquid crystal alignment agent has good display characteristics. [Prior Art Literature] [Patent Literature]

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

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

[Problems to be Solved by the Invention]

However, in recent years, the liquid crystal display elements of the vertical alignment method have a temperature difference between different parts in the same substrate during firing due to the thinness and largeness of the substrate used, and the liquid crystal in the part that has been overheated. The ability of the alignment film to vertically align the liquid crystal is reduced, and as a result, the resulting liquid crystal display element may cause a problem that part of the display is defective. In addition, in the manufacturing process of the liquid crystal panel, the liquid crystal alignment film is in contact with the column spacer, which causes damage to the liquid crystal alignment film. It is also a problem that alignment defects (bright spots) are generated in this part.

The present invention is to provide a liquid crystal alignment agent that can obtain a liquid crystal alignment film that does not reduce the ability to vertically align liquid crystals even when exposed to excessive heating. In addition, the present invention provides a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film that does not reduce the ability to vertically align liquid crystals even if a certain foreign matter comes into contact with the film and causes damage. [Means to solve the problem]

The inventors have found that the liquid crystal alignment agent having the following constitution can achieve the object and completed the present invention. That is, the constitution of the present invention is as follows. A liquid crystal alignment agent comprising a polyfluorene imide precursor containing a reactant of a diamine component of a diamine represented by the following formula [1] and a tetracarboxylic acid component, and a polyfluorene of the fluorimidate 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, m represents an integer of 1-8. Y is a structure independently represented by the following formula [1-1].

In Formula [1-1], Y ¹ and Y ³ are each independently selected from the group consisting of a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO-, and -OCO- are at least one species. Y ² represents a single bond or-(CH ₂ ) _b- (b is an integer from 1 to 15) (however, 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- (but Y ¹ is -CONH-, Y ² and Y ³ are single bonds)). Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton and a tocopherol skeleton. Any hydrogen atom on a cyclic group can pass through an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Oxygen or fluorine atom substitution. Y ⁵ represents at least one type of cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. Any hydrogen atom on these cyclic groups can be passed through an alkyl group of 1 to 3 carbons, carbon The alkoxy group having 1 to 3, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atoms are substituted. Y ⁶ is selected from the group consisting of 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 a carbon number 1 At least one type of group consisting of fluoroalkoxy group ~ 18. n represents an integer from 0 to 4. [Effect of the invention]

According to the present invention, it is possible to provide a liquid crystal alignment agent that can obtain a liquid crystal alignment film that does not reduce the ability to vertically align liquid crystals even when exposed to excessive heating. In addition, according to the present invention, in addition to the above-mentioned effects, or in addition to the above-mentioned effects, a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film that does not reduce the ability to vertically align liquid crystals even when a certain foreign matter comes into contact with the film and causes damage may be provided. Further, according to the present invention, a liquid crystal alignment film obtained from the liquid crystal alignment agent and a method for obtaining a liquid crystal alignment film using the liquid crystal alignment agent can be provided.

The liquid crystal alignment agent of the present invention contains a diamine component containing diamine represented by the above formula [1] (hereinafter, the "diamine represented by the above formula [1] is abbreviated as" specific diamine ") and four At least one polymer selected from the polyimide precursors of the reactants of the carboxylic acid component and the polyimide of the amidine imidates (hereinafter, referred to as "specific polymers").

The specific polymer contains a specific diamine, but may have a diamine other than the specific diamine. The amount of the specific diamine and other diamines in the specific polymer can be 5 mol% to 70 mol%, preferably 10 mol% to 50 mol%, and more preferably 10 mol% to 40 mol%. Come with a specific diamine. In addition, the liquid crystal alignment agent of the present invention may contain a "polyimide precursor and / or a polyimide of a polyimide" other than a specific polymer. Hereinafter, "specific diamines" will be described, followed by diamines other than "specific diamines".

<Specific diamine> 的 The specific diamine used in the liquid crystal alignment agent of the present invention is represented by the 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, m represents an integer of 1-8. "Any combination of these" may be -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 And so on. X may preferably be a single bond, -O-, -NH-, -O- (CH ₂ ) _m -O-.

In formula [1], the position of Y with respect to X may be a meta position or an adjacent position, and may preferably be an adjacent position. 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 formula [1], and it can be any position, preferably it can be the following formula [1] -a1, [1] -a2, [1]- The position represented by a3 is more preferably [1] -a1.

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

Y is a structure independently represented by the following formula [1-1].

In Formula [1-1], Y ¹ and Y ³ are each independently selected from the group consisting of a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO-, and -OCO- are at least one species. Y ² represents a single bond or-(CH ₂ ) _b- (b is an integer from 1 to 15) (however, 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- (but Y ¹ is -CONH-, Y ² and Y ³ are single bonds)). Y ⁴ represents at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton and a tocopherol skeleton. Any hydrogen atom on a cyclic group can pass through an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Oxygen or fluorine atom substitution. Y ⁵ represents at least one type of cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. Any hydrogen atom on these cyclic groups can be passed through an alkyl group of 1 to 3 carbons, carbon The alkoxy group having 1 to 3, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atoms are substituted. Y ⁶ is selected from the group consisting of 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 a carbon number 1 At least one type of group consisting of fluoroalkoxy group ~ 18. n represents an integer from 0 to 4.

Examples of the base represented by the formula [1-1] include the following bases [1-1] -1 to [1-1] -22, but are not limited thereto. Among these, [1-1] -1 to [1-1] -4, [1-1] -8, and [1-1] -10 are preferred. In addition, * represents a position of bonding with a phenyl group in the above formula [1], the above formula [1 '], the above formula [1] -a1 to the above 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 alignment agent of this invention may have a photoreactive side chain. The "specific polymer" may have the photoreactive side chain, and a "polyimide precursor and / or a polyimide of a polyimide" of a polymer other than the "specific polymer" may also have the Photoreactive side chains. <Diamine containing a photoreactive side chain> If a photoreactive side chain is to be introduced into a polymer other than "specific polymer" and / or "specific polymer", it may be used as part of the diamine component. Sex side chain of diamine. Examples of the diamine having a photoreactive side chain include a diamine having a side chain represented by the formula [VIII] or the formula [IX], but it is not limited thereto.

The bonding position of the two amine groups (-NH ₂ ) in the formula [VIII] and the formula [IX] is not limited. Specifically, as for 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 listed. , 3, 5 positions. From the viewpoint of reactivity when synthesizing polyamic acid, among them, the position of 2,4, the position of 2,5, or the position of 3,5 are particularly preferred. When considering the ease of synthesizing diamine, it is more preferable that it is a position of 2,4 or a position of 3,5.

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 (CH ₃ )-or -N (CH ₃ ) 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 which may be substituted by a fluorine atom, and -CH ₂ -of the alkylene group may be optionally substituted by -CF ₂ -or -CH = CH-, any of the following When the groups are not adjacent, these groups may be substituted; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic or heterocyclic ring. The above-mentioned divalent carbocyclic ring or heterocyclic ring can be specifically exemplified as follows, but it is not limited thereto.

R ⁹ can be formed by a general organic synthesis method. From the viewpoint of ease of synthesis, R ⁹ 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 methacryl group, an acrylic group, or a vinyl group.

The definitions of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y _5, and Y _{6 in} the 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 having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring. The alkylene group, a divalent carbocyclic ring or a heterocyclic ring has one or more hydrogen atoms, and may also be a fluorine atom or Organic group substitution. Y ₂ , when the following groups are not adjacent, -CH ₂ -may 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 cassia hydrazone. Y ₅ is a single bond, an alkylene group having 1 to 30 carbon atoms, a divalent carbocyclic ring or a heterocyclic ring, and the alkylene group, a divalent carbocyclic ring or a heterocyclic ring having one or more hydrogen atoms can also pass through A fluorine atom or an organic group is substituted. Y ₅ , when the following groups are not adjacent, -CH ₂ -may also be substituted for these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-,- NHCONH-, -CO-. Y ₆ represents a photopolymerizable group of an acrylic group or a methacrylic group.

Specific examples of the diamine having a photoreactive side chain include, but are not limited to, the following. In the following formulae, X ⁹ and X ¹⁰ each independently represent a single bond, -O-, -COO-, -NHCO-, or -NH-, and Y represents a carbon atom number 1 ~ 20 of the alkyl group.

The diamine having a photoreactive side chain may include a diamine having a side chain represented by the following formula having a group that causes a photo-dimerization reaction and a group that causes a photo-polymerization reaction.

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 in accordance with the characteristics of liquid crystal alignment, pretilt angle, voltage holding characteristics, stored charge, 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.

The diamine having a photoreactive side chain is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, and particularly preferably 30 to 20 mol% of the diamine component used in the synthesis of polyamino acid. ~ 50 Mol%. In addition, examples of the diamine having a photoreactive side chain include a diamine having a site having a radical generating structure that is decomposed and generates radicals by irradiation with ultraviolet rays.

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 the group consisting of phenylene, naphthyl, and biphenyl, 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 )-,- Bonding group of CON (CH ₃ )-, -N (CH ₃ ) CO-. S is a single bond or an unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms. However, -CH ₂ -or -CF ₂ -of an alkylene group may be arbitrarily substituted by -CH = CH-. When any of the groups listed below are not adjacent, these groups may also be substituted; -O-,- COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, a divalent heterocyclic ring. 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 formula (I), the Ar group bonded to the carbonyl group is related to the absorption wavelength of ultraviolet rays. Therefore, in the case of a longer wavelength, a structure having a longer conjugate length such as a naphthyl group or a diphenyl group is preferred. Further, 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, or an amine group.

In the formula (I), if Ar has a structure such as a naphthyl group or a biphenyl group, the solubility is deteriorated, and the difficulty of synthesis is also increased. If the wavelength of ultraviolet rays is in the range of 250 nm to 380 nm, sufficient characteristics can also be obtained with phenyl groups, so phenyl groups are the best.

When R ₁ and R ₂ are each independently an alkyl group, alkoxy group, benzyl group, or phenethyl group having 1 to 10 carbon atoms, and an alkyl group or alkoxy group, R ₁ and R ₂ may be Form a ring.

In the formula (I), Q is preferably an electron-donating organic group, and more preferably the above-mentioned group. When Q is an amine derivative, it is more preferable that the carboxylic acid group and the amine group form a salt, etc. during polymerization of the polyfluorine acid of the polyfluorene imide precursor. Hydroxyl or alkoxy.

The diaminobenzene in 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 ease of synthesis, high versatility, and characteristics, the structure represented by the following formula is preferable. Moreover, n is an integer of 2-8 in the formula.

<Other diamines> 其他 Other diamine components used to obtain specific polymers may contain diamines other than the specific diamines represented by the 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 singly or in combination of two or more kinds.

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 monomer, A ₁ and A _{2 are} preferably a hydrogen atom or a methyl group. The structure of Y ₁ is exemplified 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 alignment agent of the present invention are not particularly limited, but in terms of coatability, voltage holding ratio characteristics, residual DC voltage characteristics, etc., it is particularly preferred to select (Y-7) , (Y-8), (Y-16), (Y-17), (Y-21), (Y-22), (Y-28), (Y-37), (Y-38), ( Y-60), (Y-67), (Y-68), (Y-71) ~ (Y-73), (Y-160) ~ (Y-180) selected and used in combination.

(Tetracarboxylic acid component) The tetracarboxylic acid component used to obtain a specific polymer includes tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic dihalide, tetracarboxylic acid dialkyl, or tetracarboxylic acid dioxane. Ester dihalides are also collectively referred to as tetracarboxylic acid components in the present invention. The tetracarboxylic acid component may also use 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> Examples of fluorene tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of these include the following groups [1] to [5].

[1] aliphatic tetracarboxylic dianhydride, for example, 1,2,3,4-butanetetracarboxylic dianhydride;

[2] Examples of the alicyclic tetracarboxylic dianhydride include acid dianhydrides such as the following formulae (X1-1) to (X1-13);

In the formulae (X1-1) to (X1-4), R ₃ to R ₂₃ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, 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 foregoing formula, R _M is a hydrogen atom or a methyl group, and Xa is the following A tetravalent organic group represented by the formulae (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-tri Carboxyl-2-carboxymethyl norbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.02,6] undecane-3,5,8,10- Tetraketone, etc.

[4] Examples of aromatic tetracarboxylic dianhydrides include pyromellitic anhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 3,3', 4,4'-di Phenylphosphonium tetracarboxylic dianhydride, acid dianhydride represented by the following formulae (Xb-1) to (Xb-10), and

[5] Further, acid dianhydrides represented by the formulae (X1-44) to (X1-52), and tetracarboxylic dianhydride described in Japanese Patent Application Laid-Open No. 2010-97188 can be cited.

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 alignment agent of the present invention is not particularly limited, but from the viewpoints of coatability, voltage retention characteristics, residual DC voltage characteristics, and the like, it 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'-diphenylphosphonium tetracarboxylic dianhydride, tetracarboxylic dianhydride selected from (Xb-6) and (Xb-9) are used.

<Method for producing polymer> (1) A method for producing such a polymer is generally obtained by reacting a diamine component and a tetracarboxylic acid component. Examples include reacting at least one type of tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and a derivative of tetracarboxylic acid with a diamine component composed of one or more types of diamines, and Method for obtaining polyamic acid. Specifically, a method in which polycarboxylic acid is obtained by polycondensing a tetracarboxylic dianhydride with a first- or second-stage diamine can be used.

In order to obtain polyalkylamino alkyl esters, a method of polycondensing a tetracarboxylic acid obtained by esterifying a carboxylic acid dialkyl group with a diamine of class 1 or 2 can be used. A method of polycondensing a carboxylic acid dihalide with a diamine of class 1 or 2, or a method of converting a carboxyl group of a polyamic acid into an ester. In order to obtain polyimide, a method in which the aforementioned polyamic acid or polyalkylamic acid ester is closed to form polyimide can be used.

The reaction of the diamine component and the tetracarboxylic acid component is usually performed in a solvent. The solvent used at this time is not particularly limited as long as it is capable of dissolving the produced polyimide precursor. Specific examples of the solvent used in the reaction are listed below, but are not limited to these examples. Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamidine, N, N-dimethylethyl Amidoamine, dimethylsulfinium, or 1,3-dimethyl-imidazolinone. 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] ~ solvent represented by formula [D-3].

In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ Represents an alkyl group having 1 to 4 carbon atoms.

These solvents may be used singly or in combination. Furthermore, even if it is a solvent which does not dissolve the polyfluorene imide precursor, it can also be mixed with the said solvent and used in the range which does not precipitate the generated polyfluorene imide precursor. In addition, the water in the solvent may hinder the polymerization reaction and cause hydrolysis of the produced polyimide precursor. Therefore, it is preferable to use a solvent which is 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 a solvent, and directly adding or dispersing or dissolving the tetracarboxylic acid component in a solvent may be mentioned. 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, and the like, any of these methods may be used . In addition, when a plurality of types of diamine components or tetracarboxylic acid components are used for the reaction, they may be reacted in a pre-mixed state, may be individually reacted sequentially, or the low-molecular-weight bodies subjected to the individual reactions may be mixed to form a polymer.

The temperature at which the diamine component and the tetracarboxylic acid component are polycondensed can be selected at any temperature of -20 to 150 ° C, preferably in the range of -5 to 100 ° C. The reaction can be performed at any concentration, but when the concentration is too low, it becomes difficult to obtain a polymer with a high molecular weight. 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% by mass, and more preferably 5 to 30% by mass. The reaction is performed at a high concentration in the initial stage, and a solvent may be added afterwards. In the polymerization reaction of the fluorene polyimide precursor, 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 with the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyfluorene imide precursor produced.

Polyimide is a polyimide obtained by closing the aforementioned polyimide precursor. The polyimide has a ring closure ratio (also known as amidation ratio) of amidine groups. Need to be 100%, which can be adjusted arbitrarily according to the purpose or purpose. The method for making the polyimide precursor precursor imidized includes hot imidization by directly heating the solution of the polyimide precursor, or adding a catalyst to the solution of the polyimide precursor. Mediate imidization.

The temperature at which the polyfluorene imine precursor is thermally fluorinated in the solution is 100 to 400 ° C, preferably 120 to 250 ° C, and it is preferable to remove the water generated by the fluorination reaction To the outside of the system. The catalyst of polyimide precursor can be imidized by adding alkaline catalyst and acid anhydride to the solution of polyimide precursor. Stir at -20 ~ 250 ℃, preferably 0 ~ 180 ℃. get on.

The amount of the alkaline catalyst is 0.5 to 30 mol times of the amino acid group, preferably 2 to 20 mol times, and the amount of the acid anhydride is 1 to 50 mol times of the amino acid group, preferably 3 ~ 30 mol times. Examples of the alkaline catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is particularly preferred because it has a moderate basicity for the reaction to proceed. Examples of the acetic anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. In particular, when acetic anhydride is used, it is preferable because purification after the reaction is easy. The rate of imidization, which is based on the catalyst imidation, can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When recovering the produced polyimide precursor or polyimide from a polyimide precursor or a polyimide reaction solution, the reaction solution may be put into a solvent to cause precipitation. Examples of the solvent used for the precipitation include methanol, ethanol, isopropanol, acetone, hexane, butylcythrene, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated after being put into a solvent can be recovered by filtration, and then dried at normal temperature or heating under normal pressure or reduced pressure. In addition, when the polymer recovered by precipitation is re-dissolved in the solvent 2 to 10 times, and the operation of re-precipitation recovery is performed, impurities in the polymer can be reduced. Examples of the solvent in this case include alcohols, ketones, and hydrocarbons. When three or more solvents selected from these are used, the refining efficiency is further improved, so it is preferable.

A more specific method for producing the polyalkylamino alkyl ester of the present invention is shown in the following (1) to (3). (1) A method for producing by the esterification reaction of polyamidic acid, which is to produce polyamidic acid from a diamine component and a tetracarboxylic acid component, and perform a chemical reaction on its carboxyl group (COOH group), that is, an esterification reaction, In order to produce a polyalkylamino ester. The esterification reaction is a reaction of polyamine and an esterifying agent in the presence of a solvent at a temperature of -20 to 150 ° C (preferably 0 to 50 ° C) for 30 minutes to 24 hours (preferably 1 to 4 hours). method.

The esterification agent is preferably one which can be easily removed after the esterification reaction, and examples thereof include N, N-dimethylformamide dimethyl acetal and N, N-dimethylformamide diethyl Acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di- t-butylacetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazine Alkenes, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, and the like. The amount of the esterifying agent is preferably 2 to 6 mol equivalents relative to 1 mol of the repeating unit of the polyamic acid. Among them, 2 to 4 mole equivalents are preferred.

The solvent used for the said esterification reaction is a solvent used for the reaction of the said diamine component and the tetracarboxylic-acid component from a viewpoint of the solubility of a polyamic acid in a solvent. Among them, N, N-dimethylformamidine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferred. These solvents may be used singly 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% by mass from the viewpoint that the precipitation of the polyamic acid is unlikely to occur. Among them, 5 to 20% by mass is preferable.

(2) A method for producing by reacting a diamine component with a tetracarboxylic acid diester dichloride. Specifically, it is a method in which a diamine component and a tetracarboxylic acid diester dichloride are present in the presence of a base and a solvent. A method of reacting at -20 to 150 ° C (preferably 0 to 50 ° C) for 30 minutes to 24 hours (preferably 1 to 4 hours). As the scopolamine, pyridine, triethylamine, 4-dimethylaminopyridine, and the like can be used. Among them, since the reaction proceeds mildly, pyridine is particularly preferred. 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. Especially preferred is 2 to 3 times mole.

From the viewpoint of the solubility of the obtained polymer, that is, the alkyl polyamidate to a solvent, the solvent may be a solvent used for the reaction of the diamine component and the tetracarboxylic acid component. Among them, N, N-dimethylformamidine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferred. These solvents may be used singly or in combination of two or more. The concentration of the polyalkylene alkylate in the solvent during the hydrazone reaction is preferably 1 to 30% by mass from the viewpoint that the precipitation of the polyalkylamino alkyl ester is unlikely to occur. Among them, 5 to 20% by mass is preferable. In addition, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used in the production of the polyalkylamino alkyl ester is preferably dehydrated as much as possible. Furthermore, the reaction is preferably performed in a nitrogen environment to prevent the incorporation of external gases.

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

As the condensing agent, 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 Urethane tetrafluoroborate, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethylurenium hexafluorophosphate, (2,3-dihydro-2 -Thio-3-benzoxazolyl) diphenylphosphonate and the like. The amount of the condensing agent is preferably 2 to 3 times mole, and particularly preferably 2 to 2.5 times mole compared to the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the alkali used is preferably an amount that can be easily removed after the polycondensation reaction, and is preferably 2 to 4 times mole, more preferably 2 to 3 times mole, relative to the diamine component. From the viewpoint of the solubility of the obtained polymer, that is, the alkyl polyamidate in a solvent, the solvent used in the polycondensation reaction includes the solvent used in the reaction of the aforementioned diamine component and tetracarboxylic acid component. Among them, N, N-dimethylformamidine, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferred. These solvents may be used alone or in combination of two or more.

In the polycondensation reaction, the reaction proceeds efficiently by adding a Lewis acid as an additive. The Lewis acid is preferably a lithium halide such as lithium chloride or lithium bromide. The amount of the Lewis acid used is preferably 0.1 to 10 times the mole compared to the diamine component. Among them, 2.0 to 3.0 times the mole is preferred.

When recovering the polyalkylamine from the solution of the polyalkylamine obtained by the methods (1) to (3) above, the reaction solution may be put into a solvent to precipitate it. Examples of the solvent used for the precipitation include water, methanol, ethanol, 2-propanol, hexane, butyl cyperidine, acetone, and toluene. The polymer which is put into the solvent and precipitated is preferably washed several times with the above-mentioned solvent for the purpose of removing the aforementioned additives and catalysts. After washing, filtering and recovering, the polymer can be dried under normal pressure or reduced pressure, at normal temperature or by heating. In addition, by repeating the operation of re-dissolving the polymer precipitated and recovered in the solvent 2 to 10 times, and re-precipitating and recovering, the impurities in the polymer can be reduced. The fluorene polyalkylamino ester is preferably the production method of (2) or (3).

<Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention may be a solution containing the above-mentioned specific polymer, and is preferably used to form a liquid crystal alignment film. The content of the polymer in the liquid crystal alignment agent is preferably 2 to 10% by mass, and more preferably 3 to 8% by mass.

All the polymer components in the liquid crystal alignment agent of the present invention may be all the specific polymers of the present invention, or other polymers other than them may be mixed. Other polymers include, in addition to polyimide and polyimide precursors, cellulose polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamines, and polysiloxanes. Alkanes, etc. The content of other polymers other than these is preferably 1 to 90% by mass and more preferably 30 to 80% of the resin components contained in the liquid crystal alignment agent.

The good solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is one that can dissolve the specific polymer of the present invention. Specific examples of the solvent used for the liquid crystal alignment agent are listed below, but they are not limited to these examples. Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamidine, N, N-dimethylethyl Amidoamine, dimethylsulfinium, or 1,3-dimethyl-imidazolinone. 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] ~ solvent represented by formula [D-3]. One kind of the good solvent may be used, or it may be used in a more suitable combination and ratio in accordance with a coating method or the like.良 The good solvent in the liquid crystal alignment agent of the present invention is preferably 20 to 99% by mass of the entire solvent contained in the liquid crystal alignment agent. Among them, 20 to 90% by mass is preferable. More preferably, it is 30 to 80% by mass.

In the liquid crystal alignment agent of the present invention, a solvent (also referred to as a poor solvent) that improves the coating property or surface smoothness of the liquid crystal alignment film when the liquid crystal alignment agent is applied can be used. Specific examples are listed below. Examples include 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, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol , 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,6-dimethyl-4-heptanol, 1,2-ethylene glycol, 1,2-propylene glycol , 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl -2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropyl ether, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol Dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4 -Hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone 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) ethanol, ethylene glycol monobutyl ether, ethylene glycol Monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furan methanol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol , Propylene glycol monomethyl ether acetate, dipropylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl Ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, Ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethyl Glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3 -Ethyl ethoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methyl Propyl oxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, the aforementioned formula [D-1] ~ [D-3] Solvents shown.

Among them, particularly preferred combinations of solvents 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, γ-butyrolactone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether; N-methyl-2 -Pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone Propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanone; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether 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 Esters and dipropylene glycol dimethyl ether. 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 solvent contained in the liquid crystal alignment agent. The type and content of such a solvent are appropriately selected depending on the coating device, coating conditions, and coating environment of the liquid crystal alignment agent.

The liquid crystal alignment agent of the present invention may contain, in addition to the above, a polymer other than the polymer described in the present invention, a dielectric body for the purpose of changing electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film, and the like. A silane coupling agent for the purpose of improving the adhesion between a liquid crystal alignment film and a substrate, a crosslinkable compound for the purpose of improving the hardness or density of a film when used as a liquid crystal alignment film, and a polymerizable compound for firing a coating film. A fluorene imidation accelerator and the like for the purpose of the fluorene imidization caused by the heating of the fluorene imine precursor to efficiently proceed.

Examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate include compounds containing functional silanes and compounds containing epoxy groups. Examples of the compounds include 3-aminopropyltrimethoxysilane and 3-aminopropyltriamine. Ethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2 -Aminoamino) -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 Acid ester, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxy Silane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-amine Propyl triethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraepoxypropyl -2,4-hexanediol, N, N, N ', N',-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-glycidylamino) (Meth) cyclohexane or N, N, N ', N',-tetraepoxypropyl-4, 4'-diaminodiphenylmethane and the like.

In addition, in the liquid crystal alignment agent of the present invention, in order to improve the mechanical strength of the liquid crystal alignment film, the following additives may be added.

The aforementioned additive is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. When the content is less than 0.1 parts by mass, the effect cannot be expected, and when it exceeds 30 parts by mass, the alignment of the liquid crystal is reduced, 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 it. For example, a cured film obtained by applying the liquid crystal alignment agent of the present invention to a substrate and then drying and firing as required may be directly used as the liquid crystal alignment film. The cured film may be rubbed, irradiated with polarized light or light of a specific wavelength, etc., treated with an ion beam, or irradiated with UV as a PSA alignment film while a voltage is applied to the liquid crystal display element after the liquid crystal is filled. It is particularly 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 plates, polycarbonate, poly (meth) acrylate, polyether, polyarylate, and polyurethane can be used. Ester, polyfluorene, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triethylfluorene cellulose, diethylfluorene cellulose , Plastic substrates such as cellulose acetate butyrate. From the viewpoint of simplifying the manufacturing process, it is preferable to use a substrate formed with an ITO electrode or the like for liquid crystal driving. Moreover, in a reflective liquid crystal display element, as long as it is only on a single-sided substrate, an opaque object such as a silicon wafer may be used, and an electrode such as aluminum may be used as a material that reflects light.

The application method of the liquid crystal alignment agent is not particularly limited, and examples thereof include printing methods such as screen printing, lithographic printing, and flexographic printing; inkjet methods, spray methods, and roll coating methods; or dipping, roll coating, and narrow coating methods. Seam applicator, spinner, etc. In terms of productivity, the transfer printing method is widely used industrially, and it can be suitably used in the present invention.

The coating film formed by applying the liquid crystal alignment agent by the method described above can be fired to become a cured film. The drying step after applying the liquid crystal alignment agent is not necessarily necessary, but when the time from coating to firing of each substrate is not fixed, or when firing is not performed immediately after coating, the drying step is preferably performed. This drying is only required to remove the solvent to such an extent that the shape of the coating film is not deformed by the transportation of the substrate or the like, and the drying means is not particularly limited. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., and drying for 0.5 to 30 minutes, preferably 1 to 5 minutes.

The firing temperature of the coating film formed by applying the liquid crystal alignment agent is not limited, and 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. The heating can be performed by a generally known method such as a hot plate, a hot air circulation furnace, an infrared furnace, or the like.

The thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, and more preferably 20 to 200 nm.

After the liquid crystal display element has a liquid crystal alignment film formed on the substrate by the above method, a liquid crystal cell can be produced by a known method. A specific example of a liquid crystal display element is a liquid crystal display element of a vertical alignment method, which includes a liquid crystal cell having two substrates arranged in an opposite arrangement, a liquid crystal layer provided between the substrates, and a liquid crystal layer provided 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 liquid crystal display element of a vertical alignment method, which includes a liquid crystal cell. The liquid crystal cell is formed by applying a liquid crystal alignment agent on two substrates and firing to form a liquid crystal alignment film. An alignment film is arranged so that two substrates face each other, and a liquid crystal layer made 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 while applying a voltage to the liquid crystal alignment film and the liquid crystal layer while reacting to form a vertical alignment. Significantly superior PSA system liquid crystal display element.

The substrate of a liquid crystal display element is not particularly limited as long as it is a substrate with high transparency. Generally, it is a substrate on which a transparent electrode for driving liquid crystal is formed on the substrate. Specific examples include the same substrates described in the liquid crystal alignment film. It is also possible to use a substrate provided with a conventional electrode pattern or protrusion pattern. However, in the PSA type liquid crystal display element, since a liquid crystal alignment agent containing the polyfluorene imide polymer of the present invention is used, it is on one side. The substrate can be formed with a line / slit electrode pattern of, for example, 1 to 10 μm, and can also be operated in a structure in which a slit pattern or a protrusion pattern is not formed on the opposing substrate. With the structure of the liquid crystal display element, the manufacturing process can be simplified. Process can get high transmittance.

In addition, a high-performance element such as a TFT type element is one in which an element such as a transistor is formed between an electrode for liquid crystal driving and a substrate. In the case of a transmissive liquid crystal display element, generally, a substrate as described above is used, but in the case of a reflective liquid crystal display element, as long as it is only a single-sided substrate, an opaque substrate such as a silicon wafer can also be used. In this case, the electrode formed on the substrate may be made of 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 conventional liquid crystal materials used in the vertical alignment method can be used, such as negative liquid crystals such as MLC-6608, MLC-6609, and MLC-3023 manufactured by Merck. . In the case of a PSA system liquid crystal display device, for example, a liquid crystal containing a polymerizable compound represented by the following formula can be used.

The method of sandwiching a liquid crystal layer between two substrates includes a known method. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are spread on the liquid crystal alignment film of one substrate, and the other side is bonded so that the surface on the side where the liquid crystal alignment film is formed becomes the inner side. The substrate is a method of injecting and sealing liquid crystal under reduced pressure. Alternatively, a pair of substrates having a liquid crystal alignment film formed thereon can be used. After the spacers such as beads are spread on the liquid crystal alignment film of one substrate, the liquid crystal can be dropped, and then the surface on the side where the liquid crystal alignment film is formed can become the inside. The method of bonding the substrate of the other side and sealing is used to produce a liquid crystal cell. The thickness of the spacer is preferably 1 to 30 μm, and more preferably 2 to 10 μm.

The step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between electrodes provided on a substrate, and A method of irradiating ultraviolet rays under the electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, and preferably 5 to 20 Vp-p. The amount of ultraviolet radiation is, for example, 1 to 60 J, and preferably 40 J or less. The amount of ultraviolet radiation is small, which can reduce the decrease in reliability caused by the destruction of the components constituting the liquid crystal display element, and reduce the ultraviolet irradiation time, and the manufacturing efficiency. Increase, so it is more suitable.

As described above, when a voltage is applied to the liquid crystal alignment film and the liquid crystal layer while irradiating ultraviolet rays, the polymerizable compound reacts to form a polymer. With the polymer, the direction in which the liquid crystal molecules are tilted is memorized, thereby accelerating the obtained liquid crystal. 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, a polyimide precursor having a side chain that vertically aligns the liquid crystal and a photoreactive side chain, and the polyimide precursor The photoreactive side chains of at least one polymer selected from the polyfluorene imine obtained by fluoridation can react with each other, or the photoreactive side chains of the polymer react with the polymerizable compound. The response speed of the obtained liquid crystal display element can be accelerated. [Example]

Examples are given below to explain the present invention in more detail, but the present invention is not limited to these. The abbreviations of the compounds used are shown below. (Liquid crystal) MLC-3023 (Merck, 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] 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 type diamine compound) 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] Compound 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-cyclobutane tetracarboxylic dianhydride D2: bicyclic [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride D3: pyromellitic dianhydride D4: 2,3,5-tricarboxycyclopentylacetic dianhydride D5: 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride

(Solvent) NMP: N-methyl-2-pyrrolidone BCS: ethylene glycol monobutyl ether NEP: N-ethyl-2-pyrrolidone (crosslinking agent) E1: represented by the following formula (E1) Crosslinking agent (additive) E2: 3-picolylamine

(Molecular weight measurement) The molecular weights of the polyimide precursor and polyimide are measured using a normal temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Corporation), and a column (KD-803, KD -805) (manufactured by Shodex), and measured as follows. Column temperature: 50 ° C Eluent: N, N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr ･ H ₂ O) 30mmol / L (liter), anhydrous crystal of phosphonium phosphate (o- Phosphoric acid) 30mmol / L, Tetrahydrofuran (THF) 10ml / L) Flow rate: 1.0ml / Standard calibration line sample: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) Manufactured by Cao Corporation) and polyethylene glycol (molecular weight; approximately 12,000, 4,000, and 1,000) (made by Polymer Laboratories).

(Measurement of Polyimide Imidization Rate) 20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, ϕ5 (made by Kusano Science Co., Ltd.)), and deuteration was added. Dimethyl sulfene (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixed product) (0.53 ml) was applied to completely dissolve. This solution was used to measure a proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500) (manufactured by Datum Corporation). The hydrazone imidization rate is determined based on protons from structures that have not changed before and after hydrazone imidization. The peak integral value of the proton is used, and the NH group from hydrazone is present around 9.5 to 10.0 ppm. The integral value of the proton wave peak is obtained by the following formula.醯 Imination ratio (%) = (1-α ･ x / y) × 100 In the above formula, x is the integral value of the proton peak derived from the NH group of the amino acid, y is the integral value of the peak of the reference proton, and α is The ratio of the number of reference protons to one of the NH matrix protons of amidine (amidation ratio of 0%) for polyammonium acid.

(Viscosity measurement) In the synthesis example or 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 and a conical rotor TE. -1 (1 ° 34 ', R24), measured at a temperature of 25 ° C.

W-A1 ~ W-A3 and W-A4 ~ W-A10 are novel compounds not disclosed in the literature, etc. The synthesis method is described in detail below. The products described in the following Synthesis Examples 1 to 3 and Synthesis Examples 4 to 10 were identified by ¹ H-NMR analysis (the analysis conditions are as follows). Apparatus: Varian NMR System 400 NB (400 MHz). Measurement solvents: CDCl ₃ , DMSO-d ₆ . Reference material: Tetramethylsilane (TMS) (δ0.0 ppm for ¹ H).

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

<Synthesis of compound [1] and compound [2]> In tetrahydrofuran (165.6g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (41.1g) , 135 mmol) and triethylamine (31.5 g), and methylsulfonyl chloride (33.2 g) was dropped under ice-cooled conditions in a nitrogen environment, and reacted for 1 hour to obtain compound [1]. Next, p- (trans-4-heptylcyclohexyl) phenol (77.8g) dissolved in tetrahydrofuran (246.6g) was added, and after stirring at 40 ° C for 1 hour, a solution dissolved in pure water (233g) was added at the same temperature. Potassium hydroxide (41.0 g) was 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 heated and dissolved in tetrahydrofuran (574 g) at 50 ° C, and methanol (328 g) was added to precipitate crystals. 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 carbon (5.94 g) were fed and reacted at room temperature in a hydrogen environment. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure, so that the total internal weight became 145 g. Next, methanol (297 g) was added to the concentrated solution, followed by ice-cold stirring, and then filtered and dried 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 of Synthesis Example 2 W-A2 >>

<Synthesis of compound [3]> In tetrahydrofuran (327.2 g), 4,4'-dinitro-2,2'-diphthalic acid (40.9 g, 123 mmol) and p- (trans-4- Heptylcyclohexyl) phenol (72.1g), 4-dimethylaminopyridine (1.50g), 1- (3-dimethylaminopropyl) -3-ethyl was added at room temperature in a nitrogen environment 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. The obtained crude product was dissolved in tetrahydrofuran (245 g) by heating at 60 ° C. The insoluble matter was removed by filtration, and the total internal weight was reduced to 232 g by concentration under reduced pressure. Then, methanol (163 g) was added to precipitate crystals. After stirring under ice-cooling conditions, the compound [3] was obtained by filtration and drying 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 carbon (8.80 g) were fed, and the temperature was at room temperature in a hydrogen environment. 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, followed by ice-cold stirring, and then 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 of Synthesis Example 3 W-A3 >>

<Synthesis of compound [4] and compound [5]> To toluene (366 g), 4- (trans-4-heptylcyclohexyl) -benzoic acid (73.1 g, 242 mmol) and N, N-dimethylformate were added. Methylformamide (0.73 g), and thionyl chloride (35.9 g) was dropped under a nitrogen environment 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 [4]. Next, in tetrahydrofuran (210g), 4,4'-dinitro-1,1'-biphenyl-2,2'-dimethanol (35.0g, 115mmol) and triethylamine (26.8g) were fed, The compound [4] dissolved in tetrahydrofuran (73.1 g) was dripped under nitrogen-cooled conditions. 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 slurry was washed with methanol (291 g) at room temperature, and the slurry was washed with ethyl acetate (175 g) at room temperature, and then 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), 8.47 ppm (d, 2H, J = 2.4Hz).

〈Synthesis of W-A3〉 In tetrahydrofuran (484g) and methanol (161g), compound [5] (80.5g, 92.2mmol) and 3% platinum carbon (6.44g) were added and reacted at room temperature in a hydrogen environment. . After the reaction was completed, platinum and carbon were removed by filtration, and the solvent was removed by concentration under reduced pressure, so that the total internal weight became 96.6 g. Next, methanol (322 g) was added to the concentrated solution to precipitate crystals, and the mixture was cooled with ice and stirred to obtain a crude product by filtration. Next, the obtained crude product was dissolved by heating with ethyl acetate (322 g) at 60 ° C., methanol (700 g) was added, and crystals were precipitated under ice-cooling conditions, and then 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 of Synthesis Example 4 W-A4 >>

<Synthesis of compound [6] and compound [7]> To toluene (134 g), trans, trans-4'-pentylbiscyclohexyl-4-carboxylic acid (26.7 g, 95.1 mmol) and N, N- Dimethylformamide (0.401 g) was dropwise added thionyl chloride (13.6 g, 114 mmol) under a nitrogen environment at 50 ° C. After dripping, after reacting at the same temperature for 1 hour, the reaction solution was concentrated under reduced pressure to obtain a 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 dropped under ice-cooled conditions in a nitrogen environment. After completion of the dropping, the reaction temperature was set to room temperature, and the reaction was carried out for 17 hours. After the reaction, the reaction solution was added to pure water (731 g) to precipitate crystals. After filtration, washing with pure water and washing with methanol, the crude product was recovered. Next, the obtained crude product was heated and dissolved in toluene (56.0 g), and hexane (112 g) was added to precipitate crystals. After stirring at room temperature, filtration and drying were performed to obtain compound [7] (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 (136g) and methanol (34.0g), compound [7] (17.0g, 20.6mmol) and 3% platinum carbon (1.36g) were fed, and under room temperature conditions in a hydrogen environment The reaction took about 41 hours. After completion of the reaction, the total internal weight was adjusted to 40 g by filtration and concentration under reduced pressure. Next, methanol (68.0 g) was added to precipitate crystals, and then 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 of Synthesis Example 5 W-A5 >>

<Synthesis of compound [8]> To toluene (227 g), trans-1-bromo-4- (4-heptylcyclohexyl) benzene (45.4 g, 135 mmol) and lithium bis (trimethylsilyl) were added. Amidine (about 26% tetrahydrofuran solution, about 1.30 mol / L, 218 mL), tri-tert-butyl fluorene tetrafluoroborate (1.58 g, 5.44 mmol), bis (dibenzylideneacetone) palladium (0) ( 3.14 g, 5.46 mmol), and reacted for 17 hours at room temperature under nitrogen environment. After the reaction was completed, a 5.7 mol / L hydrochloric acid aqueous solution (80.0 mL) was added to precipitate crystals, and the hydrochloride salt of the 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), and the solution was separated with a 3.0 mol / L sodium hydroxide aqueous solution (200 g). The organic phase was further saturated with Wash with saline. Next, activated carbon (brand: special egret, 2.27g) was added to the organic phase and stirred, and then the activated carbon was removed by filtration. The obtained filtrate was concentrated under reduced pressure to obtain an oily compound. The oily compound was dispersed in hexane (100 g), and crystals were precipitated under dry ice / ethanol cooling conditions, and then 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]> To tetrahydrofuran (120 g) and dichloromethane (60.0 g), 4,4'-dinitro-2,2'-diphthalic 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-ethylcarbodifluoride The imine hydrochloride (20.0 g, 104 mmol) was reacted at room temperature under a nitrogen environment for 14 hours. After the reaction was completed, it 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 dehydrated with magnesium sulfate. Next, the organic phase was concentrated under reduced pressure to give a total internal weight of 112 g, and then methanol (120 g) was added to precipitate crystals. 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 (140g) and methanol (56.0g), compound [9] (28.0g, 33.2mmol) and 5% palladium on carbon (2.10g) were fed, and under room temperature in a hydrogen environment. The reaction takes about 3 days. After the reaction was completed, palladium on 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, and then 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 of Synthesis Example 6 W-A6 >>

<Synthesis of compound [10]> To tetrahydrofuran (113 g) and dichloromethane (113 g), 4,4'-dinitro-2,2'-diphthalic 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 at room temperature under a nitrogen environment for 18 hours. After the reaction was completed, dichloromethane (375 g) was added to the reaction solution, and the organic phase was washed three times with saturated saline (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 the crude product was obtained by filtration. The obtained crude product was recrystallized twice from a mixed solution of chloroform (500 g) and methanol (600 g), and 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 (320g) and methanol (80.8g), compound [10] (40.4g, 37.8mmol) and 5% palladium carbon (3.03g) were fed, and under room temperature conditions in a hydrogen environment. The reaction takes about 3 days. After the reaction was completed, palladium on 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, and then 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), 6.95-6.97 ppm (m, 2H), 7.26-7.28 ppm (m, 2H)

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

<Synthesis of compound [11] and compound [12]> To 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 dropped under ice-cooled conditions under a nitrogen environment. After completion of the dropping, the compound [11] was obtained by stirring at 40 ° C for 3 hours due to the reaction temperature. 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 the compound [11]. (85.0% product, 45.1g, 683mmol), heated to 50 ° C for 39 hours. After the reaction was completed, 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), filtered again, and washed with methanol. The obtained crystal crude product was heated and dissolved in tetrahydrofuran (600 g) at 60 ° C, and methanol (400 g) was added to precipitate crystals. After stirring at room temperature, the 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 (741g) and methanol (155g), compound [12] (77.7g, 110mmol) and 3% platinum carbon (6.22g) were added, and reacted at room temperature under a hydrogen environment. About 2 days. After the reaction was completed, platinum was removed by filtration, and the filtrate was concentrated under reduced pressure. To the obtained concentrated crude product was added tetrahydrofuran (122 g), which was dissolved by heating at 60 ° C, and acetonitrile (159 g) was added to precipitate crystals. After stirring at room temperature, filtration and drying were performed to obtain W-A7 (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 of Synthesis Example 8 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 dropped under ice-cooled conditions under a nitrogen environment. After the dropwise addition, the compound [11] was obtained by stirring at 40 ° C for 3 hours due to the reaction temperature. Next, 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)) were added to the reaction solution of the compound [11]. 714 mmol) and heated to 50 ° C for 39 hours. After completion of the reaction, the reaction solution was poured into pure water (660 g), and the mixture was subjected to liquid separation extraction with chloroform (588 g × 4 times). The recovered organic phase was concentrated under reduced pressure, and 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 then filtered. The crystal was washed with a pure water / methanol = 1/1 mixed solvent (118 g) and methanol (118 g × 2 times), 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 (325g) and methanol (65.0g), compound [13] (65.0g, 105mmol) and 3% platinum carbon (5.20g) were fed, and at room temperature in a hydrogen environment The reaction takes about 2 days. After the reaction was completed, the platinum and carbon were removed by filtration and concentrated under reduced pressure. The crude product was heated and dissolved in tetrahydrofuran (70.4 g) at 60 ° C, and methanol (130 g) was added to precipitate crystals. After stirring at room temperature, filtration was performed. The crystal was washed with methanol (130 g × 2 times), and the filter cake was dried to obtain W-A8 (yield: 54.2 g, 96.7 mmol, yield: 92%). ¹ H-NMR (400MHz) in CDCl ₃ : 1.19-1.28ppm (m, 2H), 1.31-1.41ppm (m, 8H), 1.70-1.73ppm (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 of Synthesis Example 9 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) , 68.7 mmol) and triethylamine (15.3 g, 151 mmol), and the ethylsulfonyl chloride (18.6 g, 145 mmol) was dropped under ice-cooled conditions in a nitrogen environment. After the dropwise addition, the compound [11] was obtained by stirring at 40 ° C for 3 hours due to the reaction temperature. Next, 4-[(trans, trans) -4'-pentyl [1,1'-biscyclohexyl] -4-yl] phenol (48.6) 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, followed by filtration and washing 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, and methanol (100 g) was added to precipitate crystals. After stirring at room temperature, the 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), 7.39 ppm (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 (361g) and methanol (90.2g), compound [14] (45.1g, 48.7mmol) and 3% platinum carbon (3.60g) were fed, and the pressure was 40 at 0.4MPa hydrogen pressure. 40 The reaction was carried out at a temperature of 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 wash the slurry. Next, the crude product obtained by filtration was heated and dissolved in tetrahydrofuran (180g) at 60 ° C, ethyl acetate (120g) was added, and crystals were precipitated by stirring at room temperature, and then filtered and dried to obtain 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 of Synthesis Example 10 W-A10 >>

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

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

<Synthesis of compound [17]> To 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. A crude product (20.0 g) of the 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, and the slurry was washed with methanol (66.0 g) and pure water (67.0 g) respectively, and then filtered and dried to obtain compound [17] (yield: 4.23 g, 4.75 mmol, product Yield: 4.1% (yield based on the compound [15] fed). 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), 1.84-1.87 ppm (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 (28.8g) and methanol (7.5g), compound [17] (3.60g, 4.04mmol) and 3% platinum carbon (0.290g) were added. Stir at 40 ° C for 3 hours under pressure. After the reaction was completed, the platinum and carbon were removed by filtration and concentrated under reduced pressure. The crude product was added with ethyl acetate and methanol to precipitate crystals. After stirring at room temperature, filtration was performed, followed by drying 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 polyfluorene-imide-based 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) in NMP (36.2 g ), And after reacting at 60 ° C for 3 hours, D1 (1.78 g, 9.10 mmol) was added and reacted at 40 ° C for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 840 mPa ･ s. NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (4.43 g) and pyridine (1.37 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (382 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (1). The polyimide has a perylene imidation ratio of 76.4%, a number average molecular weight of 16,165, and a weight average molecular weight of 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. Then, D1 (1.84 g, 9.38 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 658 mPa ･ s. NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (4.38 g) and pyridine (1.36 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (382 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (2). The polyimide has a fluorene imidization rate of 75.8%, a number average molecular weight of 15,430, and a weight average molecular weight of 45,756.

[Synthesis Example 3] (1) 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. Then, D1 (1.84 g, 9.38 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of this polyamic acid solution, it was 656 mPa ･ s. NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (4.32 g) and pyridine (1.34 g) were added as the imidization catalyst and reacted at 80 ° C 3 hours. This reaction solution was poured into methanol (382 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (3). The polyimide had a fluorene imidation rate of 74.7%, a number average molecular weight of 13,340, and a weight average molecular weight of 41,948.

[Control Synthesis Example 1] 溶解 Dissolve D2 (1.50g, 6.0mmol), C2 (1.83g, 12.0mmol), C3 (2.18g, 9.0mmol), and A1 (3.43g, 9.0mmol) in NMP (41.1g) After reacting at 60 ° C for 3 hours, D3 (1.31 g, 6.0 mmol) was added, followed by D1 (3.47 g, 17.7 mmol) and NMP (13.71 g), and reacting at 25 ° C for 10 hours to obtain a polyamic acid solution. (2) NMP was added to the polyamidic acid solution (50 g), diluted to 6.5% by mass, and then acetic anhydride (11.1 g) and pyridine (3.4 g) were added as the phosphonium imidization catalyst, and reacted at 60 ° C for 3 hours. This reaction solution was poured into methanol (700 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (4). The polyimide has a fluorene imidation ratio of 79%, a number average molecular weight of 11,000, and a weight average molecular weight of 24,000.

[Comparative Synthesis Example 1] (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. D1 (2.19 g, 11.2 mmol) was added, and it reacted at 40 degreeC for 3 hours, and obtained the polyamic-acid solution of the resin solid content concentration of 20 mass%. After measuring the viscosity of the polyamic acid solution, it was 680 mPa ･ s. NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (4.64 g) and pyridine (1.44 g) were added as the imidization catalyst and reacted at 80 ° C 3 hours. This reaction solution was poured into methanol (382 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (R1). The polyimide has a fluorene imidization rate of 75.1%, a number average molecular weight of 15,322, and a weight average molecular weight of 45,800.

[Synthesis Example 5] (1) 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. Then, D1 (1.92 g, 9.80 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 783 mPa ･ s. NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (3.86 g) and pyridine (1.20 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (233 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (5). The polyimide had a fluorene imidation ratio of 76.7%, a number average molecular weight of 14,399, and a weight average molecular weight of 38,573.

[Synthesis Example 6] (1) 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) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 769 mPa ･ s. NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, acetic anhydride (3.83 g) and pyridine (1.19 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (232 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (6). The polyimide has a hydrazone imidization rate of 73.4%, a number average molecular weight of 13,841, and a weight average molecular weight of 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, 23.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 658 mPa ･ s. NMP was added to the obtained polyamic acid solution (75.0 g), diluted to 6.5% by mass, and then acetic anhydride (18.2 g) and pyridine (5.6 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (7). The polyimide has a fluorene imidization rate of 72.9%, a number average molecular weight of 13,362, and a weight average molecular weight of 38,725.

[Synthesis Example 8] (2) 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. Then, D1 (4.71 g, 24.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 725 mPa ･ s. NMP was added to the obtained polyamic acid solution (75.0 g), diluted to 6.5% by mass, and then acetic anhydride (16.5 g) and pyridine (5.1 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (8). The polyimide has a fluorene imidization rate of 73.1%, a number average molecular weight of 13,628, and a weight average molecular weight of 39,937.

[Synthesis Example 9] D2 (6.26g, 25.0mmol), W-A8 (7.01g, 12.5mmol), and C1 (4.06g, 37.5mmol) were mixed in NMP (66.1g), and reacted at 60 ° C for 3 hours. Then, D1 (4.71 g, 24.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 674 mPa ･ s. NMP was added to the obtained polyamic acid solution (75.0 g), diluted to 6.5% by mass, and then acetic anhydride (17.2 g) and pyridine (5.3 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (9). The polyimide has a fluorinated imidization rate of 73.2%, a number average molecular weight of 10,425, and a weight average molecular weight of 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. Then, D1 (4.71 g, 24.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 823 mPa ･ s. NMP was added to the obtained polyamic acid solution (75.0 g), diluted to 6.5% by mass, and then acetic anhydride (20.7 g) and pyridine (6.4 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The polyimide had a fluorene imidization rate of 71.5%, a number average molecular weight of 13,732, and a weight average molecular weight of 38,921.

[Synthesis Example 11] (1) 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. Then, D1 (1.84 g, 9.40 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 695 mPa ･ s. NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6.5% by mass, and then acetic anhydride (4.35 g) and pyridine (1.35 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (235 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (11). The polyimide had a fluorene imidization rate of 76.1%, a number average molecular weight of 12,913, and a weight average molecular weight of 39,182.

[Synthesis Example 12] (2) D2 (25.0 g, 100 mmol), W-A1 (37.9 g, 50.0 mmol), C3 (12.1 g, 50.0 mmol), C8 (33.0 g, 100 mmol) were mixed in NMP (432 g), and After reacting at 60 ° C. for 3 hours, D1 (18.8 g, 96.0 mmol) was added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 721 mPa ･ s. NMP was added to the obtained polyamic acid solution (100 g), diluted to 6.5% by mass, acetic anhydride (16.0 g) and pyridine (4.96 g) were added as the imidization catalyst, and the reaction was carried out at 80 ° C. 3 hour. This reaction solution was poured into methanol (1150 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (12). The polyimide has a fluorene imidization rate of 75.1%, a number average molecular weight of 14,736, and a weight average molecular weight of 39,645.

[Synthesis Example 13] D2 (25.0g, 100mmol), W-A1 (37.9g, 50.0mmol), C6 (20.5g, 60.0mmol), C8 (6.61g, 20,0mmol), C7 (27.9g, 70 (0mmol) was mixed with NMP (471g), and after reacting at 60 ° C for 3 hours, D1 (18.8g, 96.0mmol) was added and reacted at 40 ° C for 3 hours to obtain a polyamine solution having a resin solid content concentration of 20% by mass . After measuring the viscosity of the polyamic acid solution, it was 771 mPa ･ s. NMP was added to the obtained polyamic acid solution (100 g), diluted to 6.5% by mass, and then acetic anhydride (14.9 g) and pyridine (4.63 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hour. This reaction solution was poured into methanol (1150 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained polyfluorene imide powder (13). The polyimide has a fluorene imidation rate of 76.2%, a number average molecular weight of 15,835, and a weight average molecular weight of 39,145.

[Synthesis Example 14] D2 (25.0g, 100mmol), W-A1 (37.9g, 50.0mmol), C6 (17.0g, 50.0mmol), C8 (16.5g, 50.0mmol), C3 (12.1g, 50.0mmol ) Was mixed with NMP (434 g), and after reacting at 60 ° C for 3 hours, D1 (18.8 g, 96.0 mmol) was added and reacted at 40 ° C for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 701 mPa ･ s. NMP was added to the obtained polyamic acid solution (100 g), diluted to 6.5% by mass, acetic anhydride (16.0 g) and pyridine (4.97 g) were added as the imidization catalyst, and the reaction was carried out at 80 ° C. 3 hour. This reaction solution was poured into methanol (1150 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyfluorene imide powder (14). The polyimide has a fluorene imidation rate of 74.8%, a number average molecular weight of 17,635, and a weight average molecular weight of 41,647.

[Synthesis Example 15] 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) ) Was mixed with NMP (455 g), and reacted at 60 ° C. for 15 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 662 mPa ･ s. NMP was added to the obtained polyamic acid solution (100 g), diluted to 6.5% by mass, then acetic anhydride (17.9 g) and pyridine (5.55 g) were added as the imidization catalyst, and reacted at 100 ° C for 3 hour. The reaction solution was poured into methanol (1160 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained polyfluorene imide powder (15). The polyimide had a fluorene imidization rate of 71.7%, a number average molecular weight of 13,329, and a weight average molecular weight of 40,527.

[Synthesis Example 16] (2) 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). After reacting at 60 ° C for 3 hours, D5 (14.3 g, 40.0 mmol), followed by D1 (11.0 g, 56.0 mmol) and NMP (100 g), and reacted at 25 ° C for 10 hours to obtain a polyamic acid solution. (1) NMP was added to the polyamino acid solution (100 g), diluted to 6.5% by mass, and then acetic anhydride (21.0 g) and pyridine (6.52 g) were added as the phosphonium imidization catalyst, and reacted at 80 ° C for 3 hours. This reaction solution was poured into methanol (1170 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (16). The polyimide had a imidation ratio of 75.8%, a number average molecular weight of 14,679, and a weight average molecular weight of 35747.

[Synthesis Example 17] (2) D2 (25.0g, 100mmol), C6 (50.0g, 120mmol), C9 (15.1g, 60.0mmol), W-A1 (15.1g, 20.0mmol) were dissolved in NMP (385g), and After reacting at 60 ° C. for 3 hours, D1 (18.8 g, 96.0 mmol) and NMP (75.3 g) were added and reacted at 40 ° C. for 3 hours to obtain a polyamic acid solution having a resin solid content concentration of 20% by mass. After measuring the viscosity of the polyamic acid solution, it was 753 mPa ･ s. (1) NMP was added to the polyamidic acid solution (100 g), diluted to 6.5% by mass, acetic anhydride (17.6 g) and pyridine (5.47 g) were added as the imidization catalyst, and the reaction was performed at 80 ° C for 3 hours. This reaction solution was poured into methanol (1160 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 60 degreeC, and obtained the polyfluorene imide powder (17). The polyimide had a fluorene imidization rate of 71.1%, a number average molecular weight of 17635, and a weight average molecular weight of 38427.

[Comparative Synthesis Example 2] (1) 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. D1 (4.90 g, 25.0 mmol) was added, and it reacted at 40 degreeC for 12 hours, and obtained the polyamic-acid solution of the resin solid content concentration of 20 mass%. After measuring the viscosity of the polyamic acid solution, it was 338 mPa ･ s. NMP was added to the obtained polyamic acid solution (75.0 g), diluted to 6.5% by mass, and then acetic anhydride (15.0 g) and pyridine (4.6 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (R2). This polyfluorene imine has a hydrazone imidization rate of 73.0%, a number average molecular weight of 10,175, and a weight average molecular weight of 23,642.

[Comparative Synthesis Example 3] (1) 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. D1 (4.90 g, 25.0 mmol) was added, and it reacted at 40 degreeC for 12 hours, and obtained the polyamic-acid solution of the resin solid content concentration of 20 mass%. After measuring the viscosity of the polyamic acid solution, it was 446 mPa ･ s. NMP was added to the obtained polyamic acid solution (75.0 g), diluted to 6.5% by mass, and then acetic anhydride (18.3 g) and pyridine (5.7 g) were added as the imidization catalyst, and reacted at 80 ° C. 3 hours. This reaction solution was poured into methanol (1000 ml), and the obtained precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyfluorene imide powder (R3). The polyimide has a perylene imidation ratio of 72.2%, a number average molecular weight of 11,636, and a weight average molecular weight of 24,624. The composition of the polyfluorene imide powder obtained in the fluorene synthesis examples and comparative synthesis examples is summarized in Table 1.

<Preparation of a liquid crystal alignment treatment agent> In Examples and Comparative Examples, examples of preparation of a liquid crystal alignment treatment agent are described. The liquid crystal alignment treatment agents obtained in the examples and comparative examples were used to produce a liquid crystal display element and perform various evaluations.

<Example 1> NMP (28.2 g) was added to the polyfluorene imine powder (1) (3.00 g) obtained in Synthesis Example 1, and stirred at 70 ° C. for 24 hours to dissolve. 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). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and a uniform solution was confirmed.

<Example 2> and <Example 3> 中 In Example 1, polyimide powders (2) and (3) were used instead of polyimide powder (1), and they were obtained in the same procedure as in Example 1. Liquid crystal alignment treatment agents (V-2) and (V-3). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and a uniform solution was confirmed.

<Control 1> 中 In Example 1, the polyimide powder (4) obtained in Control Synthesis Example 1 was used instead of the polyimide powder (1), and a liquid crystal alignment treatment agent was obtained in the same procedure as in Example 1. (V-4). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and a uniform solution was confirmed.

<Example 4> 3.0 g of the liquid crystal alignment treatment agent (V-1) obtained in Example 1 was mixed as the first component, and the liquid crystal alignment treatment agent (V-4) obtained in Control 1 was mixed as the second component 7.0 g, and a liquid crystal alignment treatment agent (V-5) was obtained by stirring for 1 hour.

<Example 5> ~ <Example 6> 中 In Example 4, a liquid crystal alignment treatment agent (V-2) or (V-3) was used in place of the liquid crystal alignment treatment agent (V-1). As a first component, borrow In the same procedure as in Example 4, liquid crystal alignment treatment agents (V-6) and (V-7) were obtained.

<Comparative Example 1> NMP (28.2g) and BCS (18.8g) were added to polyimide powder (R1) (3.00g) obtained in Comparative Synthesis Example 1, and stirred at 70 ° C for 24 hours to obtain a liquid crystal alignment treatment. Agent (R-V1). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and a uniform solution was confirmed. Using the obtained liquid crystal alignment treatment agent (R-V1), production of a liquid crystal display element, evaluation of vertical alignment, evaluation of a pretilt angle, evaluation of a voltage holding ratio, and evaluation of afterimage characteristics were performed.

<Example 7> NMP (22.0 g) was added to the polyfluorene imine powder (5) (3.00 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. To this solution, 3.0 g of E2 (1 wt% NMP solution) and BCS (20.0 g) were added, followed by stirring at room temperature for 5 hours to obtain a liquid crystal alignment treatment agent (V-8). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and a uniform solution was confirmed.

<Examples 8 to 13, 15 to 17, 19, 20, and Comparative Examples 2 to 4> In the same manner as in Example 7, Synthesis Examples 6 to 11, 13 to 15, 17, and Comparative Synthesis Examples 1 to 3 were used. The polyimide powders (6) to (11), (13) to (15), (17), (R1 to R3), and (4) obtained in Synthesis Example 1 were controlled to prepare a liquid crystal alignment treatment agent (V -9 ~ V-21), (R-V2 ~ R-V4).

<Example 14> NEP (22.0 g) was added to the polyfluorene imine powder (12) (3.00 g) obtained in Synthesis Example 12, and the mixture was stirred at 70 ° C. for 24 hours to dissolve. NEP (3.0g) and BCS (20.0g) were added to this solution, and it stirred at room temperature for 5 hours, and obtained the liquid-crystal aligning agent (V-15). No abnormality such as turbidity or precipitation was observed in the liquid crystal alignment treatment agent, and a uniform solution was confirmed.

<Example 18> The polyfluorene imine powder (16) obtained in Synthesis Example 16 was also subjected to the same operation as in Example 14 to obtain a liquid crystal alignment film treatment agent (V-19).

<Example 21> 3.0 g of the liquid crystal alignment treatment agent (V-15) obtained in Example 14 as the first component, and the liquid crystal alignment treatment agent (V-19) obtained in Example 18 as the second component were mixed. 7.0 g of the cross-linking agent E1, which is 5% by weight relative to the resin component in the liquid crystal alignment film, was stirred for 1 hour to obtain a liquid crystal alignment treatment agent (W-2).

<Examples 22 to 24> (1) For the liquid crystal alignment treatment agents (V-16) to (V-21) obtained in Examples 15 to 20, the same operation as in Example 21 was performed to obtain a liquid crystal alignment treatment agent (W-3 ) ~ (W-5).

Using the liquid crystal alignment treatment agent obtained in the example and the liquid crystal alignment treatment agent obtained in the comparative example, the production of a liquid crystal display element, the evaluation of the vertical alignment, the scratch test, the evaluation of the pretilt angle, the evaluation of the voltage holding ratio, the residual Evaluation of image characteristics.

<Production of the liquid crystal display element for measuring the voltage holding ratio> 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 diameter 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 an ITO electrode, which was washed with pure water and IPA (isopropanol) and was 40 mm x 30 mm. Then, heat treatment was performed on a hot plate at 70 ° C. for 90 seconds, and in a thermal cycle type clean oven at 230 ° C. for 30 minutes to obtain an ITO substrate with a liquid crystal alignment film with a thickness of 100 nm. Prepare two obtained ITO substrates with a liquid crystal alignment film, and apply a 4 μm-diameter bead spacer to the liquid crystal alignment film surface of one of the substrates (Nippon Kasei Kasei Kasei Co., Ltd., silk ball, SW-D1) . Next, the periphery was coated with a sealant (XN-1500T manufactured by Mitsui Chemicals). Next, the side of the other substrate on which the liquid crystal alignment film is formed is used as an inner side, and after bonding to the previous substrate, the sealing material is hardened to form an empty cell. Liquid crystal MLC-3023 (trade name, manufactured by Merck) was injected into the empty cell by a reduced pressure injection method to prepare a liquid crystal cell. After applying a DC voltage of 15V to the obtained liquid crystal cell, an ultraviolet irradiation device using a high-pressure mercury lamp as a light source was used to irradiate ultraviolet rays at a wavelength of 365 nm with a bandpass filter of 15 J / cm ² to obtain a vertical alignment type liquid crystal display element. In addition, the measurement of the amount of ultraviolet irradiation was performed by using a UV-M03A receiver connected to UV-35 manufactured by ORC Corporation.

<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 diameter of 1 μm. The obtained solutions were spin-coated on ITO electrode substrates (length: 35 mm) with ITO electrode patterns having a pixel size of 200 μm × 600 μm washed with pure water and IPA (isopropanol) and a line / gap of 3 μm. (Horizontal: 30mm, thickness: 0.7mm), and the ITO surface of a glass substrate (vertical: 35mm, horizontal: 30mm, thickness: 0.7mm) with an ITO electrode patterned on a light spacer with a height of 3.2 μm, Heat treatment was performed on a hot plate at 70 ° C. for 90 seconds, and in a thermal cycle type clean oven at 230 ° C. for 30 minutes 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 side of the other substrate on which the liquid crystal alignment film is formed is used as the inner side, and after bonding to the previous substrate, the sealing material is hardened to form an empty cell. Liquid crystal MLC-3023 (trade name, manufactured by Merck) was injected into the empty cell by a reduced pressure injection method to prepare a liquid crystal cell. After that, a DC voltage of 15 V was applied to the obtained liquid crystal cell, and all the pixel regions were driven, and an ultraviolet irradiation device using a high-pressure mercury lamp as a light source was used to irradiate ultraviolet rays through a band-pass filter with a wavelength of 365 nm. cm ² to obtain a vertical alignment type liquid crystal display element. The measurement of the amount of ultraviolet radiation was used by a UV-M03A receiver connected to UV-35 manufactured by ORC. Further, in Examples 1 to 3 and Comparative Example 1, in addition to the above-mentioned standard conditions, the heat treatment was set to 230 ° C. for 120 minutes as a severe condition to form a liquid crystal alignment film. A vertical alignment type liquid crystal display element was produced under the same conditions.

<Evaluation> (Vertical Alignment) The liquid crystal alignment of the liquid crystal display device was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon), and it was confirmed whether the liquid crystal is aligned vertically. Specifically, those who did not see the defect caused by the liquid crystal flow or the highlight caused by the alignment defect were rated as good. The evaluation results are shown in Table 2.

(Voltage holding rate) After applying the voltage of 1 V to the liquid crystal display element for the voltage holding rate evaluation prepared above at an application time of 60 microseconds and an interval of 1667 milliseconds, the voltage after 1667 milliseconds after the release of the application was measured. Retention rate (%). As the measurement device, 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 Mingling Technica Co., Ltd.), among the liquid crystal display elements prepared for evaluation of the pre-tilt angle, no defective liquid crystal display element due to liquid crystal flow was measured. The evaluation results are shown in Table 2.

(After-image characteristics) Using the liquid crystal display element for after-image evaluation prepared as described above, an AC voltage of 60 Hz and 20 Vp-p was applied to two diagonal regions of the four pixel regions and driven at a temperature of 168 ° C for 168 hour. After that, all 4 pixel regions were driven by an AC voltage of 5Vp-p, and the brightness difference of the pixels was visually observed. The state where the difference in brightness was hardly recognized was good. The evaluation results are shown in Table 3.

(Scratch test) 刮 The alignment film surface of the substrate with a polyimide coating film obtained in the example was subjected to a scratch test using UMT-2 (manufactured by Bruker AXS Co., Ltd.). The sensor of UMT-2 is FVL, and a 1.6mm sapphire ball is installed at the front end of the scraping part. In a state where the front end of the scraping part is brought into contact with the surface of the liquid crystal alignment film with a load of 1 mN, it takes 100 seconds to change the range of 0.5 mm in length and 2.0 mm in length and change the load from 1 mN to 20 mN to perform a scratch test. At this time, the moving direction of the front end of the scraping part is back and forth in the lateral direction, and the moving speed is performed at 5.0 mm / sec. The movement of the scratch area in the vertical direction is 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) was dropped onto the liquid crystal alignment film surface subjected to the scratch test. Contrary to this, the liquid crystal alignment film faces are superimposed on each other and the substrate with the liquid crystal alignment film obtained in Example 1 is interspersed with 4 μm spacers, and the dropped MLC-3022 is sandwiched. With a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon), the polarizing axis of the upper and lower polarizing plates was 90 ° (orthogonal polarizer), and the part where the scratch test was performed was observed to see whether light was transmitted. Table 6 shows the state where no bright spot or light leakage was seen at all, the state where a little bright spot or light leakage was seen at all, and the state where the entire scratched part became light leakage was ×.

[Table 4]

[table 5]

The above results are specifically compared with 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 is even severe. Under the conditions, the pretilt angle does not change, and the liquid crystal alignment is good. In addition, as shown in Table 5, it can be seen that the results of Examples 4 to 6 in which the liquid crystal alignment treatment agent (V-4) was mixed were excellent in afterimage characteristics. Further, from this example, it can be seen that the liquid crystal alignment film obtained by using a specific side chain type diamine has excellent stability of the pretilt angle even when fired under severe conditions. In addition, it was confirmed that even when there is physical contact with the liquid crystal alignment film as in the scratch test, the alignment film has less damage, and good vertical alignment can be maintained. [Industrial availability]

A liquid crystal display element using a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention can be suitably used for a liquid crystal display element. In addition, these devices also have liquid crystal displays for display purposes, and then control the transmission and blocking of light, such as dimming windows or shutters.

Claims (9)

A liquid crystal alignment agent comprising a polyfluorene imide precursor containing a reactant of a diamine component of a diamine represented by the following formula [1] and a tetracarboxylic acid component and a polyfluorene imine of the fluorimidate. At least one polymer selected: 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 of 1 to 8, and Y is a structure that independently represents the following formula [1-1]; in formula [1-1] , Y ¹ and Y ³ are each independently selected from the group consisting of a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO- At least one of the groups formed by -COO- and -OCO-; Y ² represents a single bond or-(CH ₂ ) _b- (b is an integer from 1 to 15) (but Y ¹ or Y ³ is a single bond And-(CH ₂ ) _a- , Y ² is a single bond, and Y ¹ is selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO-, and -OCO- When at least one of Y and / or Y ³ is at least one selected from the group consisting of -O-, -CH ₂ O-, -CONH-, -NHCO-, -COO-, and -OCO-, Y ² Is a single bond or-(CH ₂ ) _b- (However, when Y ¹ is -CONH-, Y ² and Y ³ are single bonds); Y ⁴ represents At least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton and a tocopherol skeleton, and the aforementioned cyclic group Any of the above hydrogen atoms can be passed through an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms 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. Any hydrogen atom on these cyclic groups may pass through a carbon number of 1 to 3. Alkyl group, alkoxy group with 1 to 3 carbon atoms, fluorinated alkyl group with 1 to 3 carbon atoms, fluorinated alkoxy group with 1 to 3 carbon atoms or fluorine atom substitution; Y ⁶ means selected from the group consisting of 1 to 18 carbon atoms A group of alkyl groups, alkenyl groups having 2 to 18 carbon atoms, fluorine-containing alkyl groups having 1 to 18 carbon atoms, alkoxy groups having 1 to 18 carbon atoms, and fluorine-containing alkoxy groups having 1 to 18 carbon atoms. At least 1 type; n represents an integer from 0 to 4; . For example, the liquid crystal alignment agent of claim 1, wherein the diamine represented by the aforementioned formula [1] is represented by the following formula [1 ']; . For example, the liquid crystal alignment agent of claim 1 or claim 2, wherein the diamine represented by the aforementioned formula [1] is represented by the following formula [1] -a1, the following formula [1] -a2, or the following formula [1]- a3 means; The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the diamine represented by the aforementioned formula [1] is represented by the following formula [1] -a1-1, and the following formula [1] -a2-1 ~ The formula [1] -a2-4, the following formula [1] -a3-1, or the following formula [1] -a3-2 are represented; The liquid crystal alignment agent according to any one of claims 1 to 4, wherein Y represented by the structure of the foregoing formula [1-1] is represented by the following formulas [1-1] -1 to [1-1] -22 (formula In the formula, * represents the position of the phenyl bond in the formula [1], the formula [1 '], the formula [1] -a1 to the formula [1] -a3, and m represents an integer of 1 to 15, n represents any integer from 0 to 18); The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the diamine component further contains a diamine represented by the following formula [2] (in the formula [2], A ₁ and A ₂ are each independently represented 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; Y ₁ represents a divalent organic group); . A liquid crystal alignment film is formed using the liquid crystal alignment agent according to any one of claims 1 to 6. A method for manufacturing a liquid crystal alignment film, which comprises a step of applying a liquid crystal alignment agent according to any one of claims 1 to 6 on a substrate to form a coating film; a step of firing the aforementioned coating film; and The step of aligning the obtained film is performed to form a liquid crystal alignment film. A liquid crystal display element includes a liquid crystal alignment film as claimed in claim 7; or a liquid crystal alignment film obtained by the manufacturing method as claimed in claim 8.