TW201839053A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment film having good adhesion even after going through a low-temperature firing process, a liquid crystal alignment agent with which the liquid crystal alignment film is formed, and a liquid crystal display element provided with the liquid crystal alignment film. The present invention provides a liquid crystal alignment agent containing a component (A) and a component (B) described below, and a component (C) that is an organic solvent. Component (A): A polymer such as a polyimide, a polyamic acid, or a polyamic acid ester. Component (B): At least one compound selected from the group comprising the compound represented by formula [CL-1] and the compound represented by formula [CL-2] (in the formulas, r1 represents a hydrogen atom or a methyl group, r2 is a C2-20 straight-chain or branched-chain alkylene group or the like, the -CH2- in the structure may be replaced with -O-, r3 is a C2-20 k-valent aliphatic group or the like, Z indicates the bivalent group represented by formula (1a) (in the formula, r4 is a C1-20 straight-chain or branched-chain alkyl group or the like, and one of *1 and *2 bonds with a nitrogen atom, while the other bonds with r3) , k is a natural number between 2 and 9 inclusive, RCL1 is a hydrogen atom or a methyl group, RCL2 and RCL3 are each independently a hydrogen atom, a C1-20 straight-chain or branched-chain alkyl group, or a C1-20 straight-chain or branched-chain hydroxylalkyl group, and RCL4 is a hydroxyl group or a C1-20 straight-chain or branched-chain hydroxylalkyl group).

Description

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

The present invention relates to a liquid crystal alignment agent having good adhesion even when a low-temperature firing step is used, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film.

A flexible liquid crystal display device using a flexible resin film as a substrate has various advantages such as being thin and light, or being foldable for storage and movement, and is suitable for viewing digital content today and in the near future. However, the resin film lacks heat resistance, so it is proposed to manufacture various elements constituting a liquid crystal display element, such as a low-temperature process for a liquid crystal alignment film. Along with this process, a liquid crystal alignment film material that can be fired at low temperature is required (Patent Document 1). In addition, compared with the glass substrate, the resin film generally has a weaker impact from the outside, so the adhesiveness between the alignment film and the resin film substrate is required to be high.

As a result of the review by the present inventors with a liquid crystal alignment agent containing a conventional cross-linking agent, it was found that the adhesion of the liquid crystal alignment film obtained by low-temperature firing may be significantly reduced. Therefore, it is desired to develop a liquid crystal alignment agent and a liquid crystal alignment film that are excellent in adhesion even after low-temperature firing. For a composition suitable for forming a cured film having liquid crystal alignment, for example, there is a report in Patent Document 2 and the like. Further, for example, Patent Document 3 discloses a liquid crystal alignment film containing polycarbonate as an essential component. However, these documents are not sufficient for the purpose of providing a liquid crystal alignment agent having good adhesion even when firing at a low temperature. [Prior Art Literature] [Patent Literature]

[Patent Document 1] WO2012 / 121259. [Patent Document 2] WO2015 / 129890. [Patent Document 3] Japanese Patent Application Laid-Open No. 11-119225.

[Problems to be Solved by the Invention]

Therefore, an object of the present invention is to provide a liquid crystal alignment film having good adhesion even after a low-temperature firing process, a liquid crystal alignment agent forming the liquid crystal alignment film, and a liquid crystal display element including the liquid crystal alignment film. In addition, the object of the present invention is to provide a method for manufacturing the above-mentioned liquid crystal alignment film in addition to the above objects. [Means to solve the problem]

The inventors have found the following inventions. <1> A liquid crystal alignment agent comprising: (A) selected from the group consisting of polyimide, polyamidic acid, polyamidate, polyorganosiloxane, polyester, polyamidine, and polymerizable A polymer of at least one group of polymers of monomers of unsaturated bonds; (B) selected from compounds represented by the following formula [CL-1]; and compounds represented by the following formula [CL-2]; Groups of at least one compound (in the formula [CL-1], r ¹ represents a hydrogen atom or a methyl group, r ² represents a linear or branched alkylene group having 2 to 20 carbon atoms, and 5 to 6 carbon atoms A divalent organic group formed from an aliphatic ring or a divalent aliphatic group containing an aliphatic ring having 5 to 6 carbons. These groups may also have -CH ₂ -in the structure via -O- Instead, r ³ represents a k-valent linear or branched aliphatic group having 2 to 20 carbon atoms, a k-valent group formed from an aliphatic ring having 5 to 6 carbon atoms, or a fat containing 5 to 6 carbon atoms K-valent aliphatic groups of the group ring, these groups, -CH ₂ -in the structure may also be substituted with -O-, Z represents the following formula (1a) (wherein, r ⁴ represents a carbon number of 1 to A straight or branched alkyl group of 20, a monovalent group formed by an aliphatic ring having 5 to 6 carbon atoms, or containing carbon A divalent aliphatic group of the aliphatic ring of 5 to 6, the group of these, which is configured in the -CH ₂ - may be substituted by -O-, * 1 and * 2 represents either one of them is a nitrogen atom and Bond, and the other is a divalent group represented by a bond to r ³ ), k is a natural number of 2 to 9. In the formula [CL-2], R _CL1 is a hydrogen atom or a methyl group, R _CL2 and R _CL3 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 20 carbon atoms, and R _CL4 is a hydroxyl group or carbon number 1 A linear or branched hydroxyalkyl group to 20); and (C) an organic solvent.

[Inventive effect]

According to the present invention, it is possible to provide a liquid crystal alignment film having good adhesion even after a low-temperature firing process, a liquid crystal alignment agent forming the liquid crystal alignment film, and a liquid crystal display element including the liquid crystal alignment film. In addition, according to the present invention, in addition to the above effects, a method for manufacturing the above-mentioned liquid crystal alignment film can be provided. [Form of Implementing Invention]

This case provides a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film. Hereinafter, description will be made in order. <Liquid crystal alignment agent> The liquid crystal alignment agent of the present case contains (A) component; (B) component; and (C) component: organic solvent.

<< (A) component >> The (A) component is selected from the group consisting of polyimide, polyamidic acid, polyamidate, polyorganosiloxane, polyester, polyamidine, and polymerizable unsaturated. A polymer of at least one group of polymers of bonded monomers.

The component (A) will be described in detail below. [Polyamine acid] The polyamino acid used in the present invention can be obtained by reacting a diamine compound with a tetracarboxylic dianhydride.

<Diamine> The diamine used for the polymerization of the polyamic acid of the present invention can be represented by the following general formula (1).

A1 and A2 in the above formula (1) 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, an alkynyl group having 2 to 5 carbon atoms, and Y ₁ is a divalent organic group . From the viewpoint of liquid crystal alignment, A1 and A2 are preferably a hydrogen atom or a methyl group.

In a preferred aspect of the formula (1), the diamine is a diamine using the following formula (DA-1).

In the formula (DA-1), Y _d is a divalent organic group represented by the following formulae (Y-1) to (Y-171).

In the formula (Y-87), X ¹ is a sulfur atom, an oxygen atom, or -NH-, R ⁸ and R ⁹ are each independently a divalent organic group, and at least one of R ⁸ and R ⁹ has an aromatic ring, "- "CO-X ^1- " is preferably bonded to an aromatic ring by a bond, preferably from formulas (b-) described in paragraphs [0047] to [0048] corresponding to paragraphs of Japanese Laid-Open Publication 2015-135464. 1) A compound obtained by removing two amine groups from (b-42).

In the formula (Y-139), R1 and R2 are each ethylene, -COO-, -OCO-, -NHCO-, and -N (CH ₃ ) CO-.

In the above formula, n is an integer of 1 to 6. Preferred embodiments of one of the diamines usable in the present invention include diamines having an alkyl group and a fluorine-containing alkyl group in a side chain represented by the following formulas [Sd-1] to [Sd-4]. .

In the formula, A ¹ each independently represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group having 1 to 22 carbon atoms.

Another preferred aspect of the diamine that can be used in the present invention includes 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4 , 4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminediamine Phenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3 ' -Dicarboxylic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenyl Ethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminodiphenyl ether-3,3'-di A carboxylic acid and a diamine having a structure represented by the following formulas [4a-1] to [4a-6]. From the viewpoint of increasing the curing speed of the liquid crystal alignment film, the diamine is preferably used in combination with a diamine that imparts vertical alignment properties to be described later. These diamines are preferably 10 mol% or more, and more preferably 20 mol% or more, with respect to the entire diamine component used in the liquid crystal alignment agent.

Another preferable aspect of the diamine which can be used in the present invention includes diamines represented by the following formulas [2a-1] to [2a-9] (n each independently represents an integer of 2 to 12).

Another preferable aspect of the diamine usable in the present invention includes a diamine having a heterocyclic ring represented by the following formula (bs).

In the formula [bs], X ₁ is a divalent organic group selected from at least one group selected from the group consisting of -O-, -NQ1-, -CONQ1-, -NQ1CO-, -CH ₂ O-, and -OCO-. Q1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ₂ is a single bond or at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, and an aromatic hydrocarbon group. 1 type of divalent organic group, X ₃ is a single bond, or is selected from the group consisting of -O-, -NQ2-, -CONQ2-, -NQ2CO-, -COO-, -OCO-, and -O (CH ₂ ) m- (m is an integer from 1 to 5) at least one kind of divalent organic group in a group, Q2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X ₄ is a nitrogen-containing aromatic heterocyclic ring, and n is 1 The integer of 4 is preferably a combination described in Tables 1 to 3 in paragraphs [0036] to [0038] of International Publication WO2009 / 093707.

Another preferable aspect of the diamine usable in the present invention is a diamine having a photoreactive group represented by the following formula (PV-0).

In the formula (PV-0), X ² represents a substituent, and a structured structure represented by the following formula (2A) or the following formula (2B).

In the formula (2A) and the formula (2B), R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms (but any hydrogen atom may be substituted by a fluorine atom), or an alkane having 1 to 18 carbon atoms. An oxy group (but any of its hydrogen atoms may be replaced by a fluorine atom). A and B each independently represent a single bond or a ring structure represented by the following formula. However, any hydrogen atom in the ring structure may be substituted by an alkoxy group having 1 to 10 carbon atoms. T ¹ to T ⁴ each independently represent a single bond, an ether, an ester, an amidine, or a ketone bond. S represents a single bond or an alkylene group having 1 to 10 carbon atoms.

When vertical alignment is imparted, the diamines usable in the present invention include the two formulas [2-1] to [2-31] described in paragraphs [0033] to [0042] of International Publication WO2013 / 125595 Amines, etc. These diamines are preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more with respect to the entire diamine component. From the viewpoint of increasing the hardening speed, it is preferably 90 mol% or less, and more preferably 80 mol% or less. A more preferred diamine is at least one selected from the following formulae [2a-24] to [2a-33].

In formula (2a-32), when it is in the ortho position with respect to one amine group, R ¹ each independently represents selected from the group consisting of -O-, -OCH _2- , -CH ₂ O-, -COOCH _2- , and -CH ₂ When at least one kind of bonding group of OCO- is meta to two amine groups, R ¹ is selected from -CONH-, -NHCO-, and -CH _{2 in} addition to the bonding group shown above. -At least one kind of bonding group, R ² each independently represents a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, and Cy is selected from 4,4'-biphenyldiyl, 4,4'-phenylcyclohexyl, 4,4'-dicyclohexyl.

In the above formula, R ₃ represents -O- or -CH ₂ O-, Cy ₂ is synonymous with the aforementioned Cy, R ⁷ each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms, and 1,4- The cis-trans isomer of cyclohexyl represents the trans isomer. In addition to the diamines listed above, 4- (2- (methylamino) ethyl) aniline or the diamine described in Japanese Patent Application Laid-Open No. 2010-97188 can also be used. Among the photoreactive diamines, the following compounds are preferred from the viewpoint of photoreactivity and the like.

In the C _n H _{2n + 1} portion of the particularly preferred diamine compounds exemplified in the above formulae, n represents an integer of 0 to 18.

<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, such as 1,2,3,4-butane tetracarboxylic dianhydride, etc .; [2] Alicyclic tetracarboxylic dianhydride, such as the following formula (X1-1) ~ (X1-13) (In the formulae (X1-1) ~ (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, and an alkyl group having 2 to 6 carbon atoms. Alkenyl, alkynyl having 2 to 6 carbon atoms, monovalent organic group having 1 to 6 carbon atoms containing fluorine atom, or phenyl group may be the same or different. In the foregoing formula, R _M is a hydrogen atom or a methyl group Xa is an acid dianhydride such as a tetravalent organic group represented by the following formulae (Xa-1) to (Xa-7);

[3] 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran -2 ', 5'-dione), 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [ 5.3.1.02,6] Undecane-3,5,8,10-tetraone, etc .;

[4] Aromatic tetracarboxylic dianhydrides, such as pyromellitic anhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, 3,3', 4,4'-diphenyl Hydrazone tetracarboxylic dianhydride, acid dianhydride represented by the following formulae (Xb-1) to (Xb-10); and

[5] In addition, 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.

Moreover, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

<The manufacturing method of a polyamic acid> The polyamic acid used by this invention can be synthesize | combined by a conventional method (for example, refer to international publication WO2014 / 034792).

The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone in terms of the solubility of monomers and polymers. Use 1 type or mix 2 or more types. The concentration of the polymer is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass from the viewpoint that the polymer is not easily precipitated and a high molecular weight body can be obtained.

[Polyamidate] The polyamidate used in the present invention can be obtained as follows.

<Manufacturing method of polyamidate> The polyamidate used in the present invention can be synthesized by the following (1) polyamic acid, and (2) a polyfluorene synthesized from a tetracarboxylic acid diester and a diamine. Any of the conventional methods (e.g., International Publication Gazette WO2014 / 034792) for the case of urethane or (3) the case of synthesis by reaction of tetracarboxylic acid diester dichloride and diamine.

The tetracarboxylic diester can be represented by the following reaction formula (wherein R ¹ is an alkyl group having 1 to 5 carbon atoms, and A is a tetravalent organic group derived from the aforementioned tetracarboxylic dianhydride). The carboxylic dianhydride is produced by a conventional method (for example, refer to International Publication 2010/092989) by reacting with an alcohol having 1 to 5 carbon atoms represented by R ¹ OH.

Among the tetracarboxylic acid diesters of the present invention, a compound represented by [5-p-1] is preferred from the viewpoint of obtaining a high molecular weight and low-dispersion polyamidate.

The tetracarboxylic acid diester dichloride can be produced, for example, by a conventional method of chlorinating the aforementioned tetracarboxylic acid dialkyl ester (for example, refer to International Publication WO2010 / 092989).

From the viewpoint of obtaining a high molecular weight and low-dispersed polyamidate, the tetracarboxylic acid diester dichloride is preferably of the formula [5-Cl] (In the above formula (5-Cl), A is the same as the above formula ( 5) A compound having the same meaning as A).

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of the solubility of the polyamidate. These solvents can be used alone or in combination of two or more. The polymer concentration during synthesis is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass from the viewpoint that the polymer is not easily precipitated and a high molecular weight body can be obtained.

Among the above-mentioned three synthetic methods of polyamic acid esters, since high-molecular-weight poly (fluorinated acid esters) can be obtained, the synthetic method of (2) or (3) above is particularly preferred. [Polyimide] The polyimide used in the present invention can be obtained by a conventional method (for example, refer to International Publication WO2013 / 125595).

The polyfluorene imine may be a complete fluorinated imine compound in which the fluorinated amino acid structure of the polyfluorinated acid or the fluorinated amino acid structure of the polyfluorinated acid ester is completely dehydrated and closed, or may be only fluorinated. Part of the sulfamic acid or sulfonate structure undergoes dehydration ring closure, and the fluorinated acid structure or the fluorinated acid ester structure and the fluorinated imine ring structure coexist in part of the fluorinated imide. The polyimide to be used preferably has a fluorinated imidization rate of 20% or more. From the viewpoint of ensuring solubility in a solvent, it is preferably 90% or less, and more preferably 60% or less. The ratio of fluorene imine is relative to the total number of fluorinated acid structure or fluorinated acid ester structure of polyfluorene and the number of fluorinated imine ring structure. Presenter. Here, a part of the fluorene imine ring may be an isofluorene ring.

[Polyorganosiloxane] The polyorganosiloxane of the present invention can be obtained, for example, by a conventional method of hydrolyzing and condensing a hydrolyzable silane compound (for example, refer to International Publication WO2009 / 025386).

Examples of the silane compound used in the synthesis of polyorganosiloxane include tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldiethoxy Alkoxysilane compounds such as silane; 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (3-cyclohexylamine ) Azine-sulfur-containing alkoxysilane compounds such as propyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Epoxy-containing silane compounds such as glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane; 3- (methyl Propyl) propenyloxypropyltrimethoxysilane, 3- (meth) propenyloxypropylmethyldimethoxysilane, 3- (meth) propenyloxypropylmethyldiethoxy Unsaturated bond-containing alkoxysilane compounds such as trisilane and vinyltriethoxysilane; trimethoxysilylpropylsuccinic anhydride and the like. The hydrolyzable silane compound may be used singly or in combination of two or more kinds. In addition, "(meth) acryloxy" means the meaning of "acryloxy" and "methacryloxy".

For the polyorganosiloxane according to the present invention, the weight average molecular weight (Mw) measured by GPC in terms of polystyrene is preferably in the range of 100 to 50,000, and more preferably in the range of 200 to 10,000.

Among the polyorganosiloxanes of the present invention, polyorganosiloxanes having repeating units represented by the following formula (P-Si-Ep) are preferred.

In the formula (P-Si-Ep), X ¹ is an epoxy group containing the following formula (X ¹ -1) or (X ¹ -2) (where "*" represents a bonding bond), and Y ¹ is Hydroxyl, alkoxy having 1 to 10 carbons, alkyl having 1 to 20 carbons or aryl having 6 to 20 carbons.

Among the polyorganosiloxanes of the present invention, a carboxylic acid having a liquid crystal alignment group is preferably a cinnamic acid derivative (Cn-1) or (Cn-2) described below, from the viewpoint of exerting the effects of the present invention.

[Polyester] The polyester used in the present invention can be obtained, for example, by reacting a dicarboxylic acid with a diepoxy compound. Here, the above-mentioned diepoxy compounds are, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1 In addition to hexamethylene glycol diglycidyl ether, diepoxy compounds described in Japanese Patent Application Laid-Open No. 2013-113937 can be cited.

The ratio of the diepoxy compound to the dicarboxylic acid compound used in the polyester synthesis reaction is 1 equivalent to the carboxyl group contained in the dicarboxylic compound, and the epoxy group of the diepoxy compound is 0.2 equivalent to 2 equivalents. Good, more preferably from 0.3 to 1.2 equivalents.

The reaction of the dicarboxylic acid and the diepoxy compound is preferably carried out in the presence of an organic solvent. Examples of the organic solvent used include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazolinone, Aprotic polar solvents such as dimethyl sulfene, γ-butyrolactone, tetramethylurea, Hexamethylphosphoric triamide; m-cresol, xylenol, phenol, halogenated phenol, etc. Phenol-based solvents.

In this way, a solution containing a polyester as the polymer (A) can be obtained. This reaction solution can be directly supplied for the preparation of the liquid crystal alignment agent, or the polyester contained in the reaction solution can be isolated, the liquid crystal alignment agent can be prepared, or the isolated polyester can be purified, and the liquid crystal alignment agent can be supplied. Of modulation. Isolation and purification of polyesters can be performed according to conventional methods.

The polyester obtained in this way has a polystyrene-equivalent number average molecular weight (Mn) measured by GPC, so that the formed liquid crystal alignment film has good liquid crystal alignment and a viewpoint of ensuring the stability of the liquid crystal alignment over time. It is preferably 250 to 500,000, more preferably 500 to 100,000, and even more preferably 1,000 to 50,000.

[Polyfluorene] The polyfluorene used in the present invention can be obtained, for example, by a method of reacting a dicarboxylic acid with a diamine. Here, it is preferable that the dicarboxylic acid is reacted with diamine after performing chlorination using an appropriate chlorinating agent such as thionyl chloride.

The dicarboxylic acid used in the synthesis of polyamines is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, and fumaric acid. Carboxylic acids; dicarboxylic acids with alicyclic structure, such as cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4, 4'-biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-carbonyl dibenzoic acid, 4-carboxycinnamic acid, p-phenylene diacrylic acid, etc. Cyclic dicarboxylic acids; etc. Moreover, a dicarboxylic acid can be used individually by 1 type or in combination of 2 or more types. The diamine used in the synthesis of the polyfluorene of the present invention can be obtained by using at least a part of the diamine used in the above polyfluorene imide precursor. In addition, other diamines may be used in combination during the synthesis. Diamines can be used alone or in combination of two or more.

The ratio of the dicarboxylic acid and the diamine used in the synthesis reaction of the polyamine is 1 equivalent to the amine group of the diamine, and it is preferable that the carboxyl group of the dicarboxylic acid is 0.2 to 2 equivalents. The reaction between a dicarboxylic acid (preferably a chlorinated dicarboxylic acid) and a diamine is preferably performed in an organic solvent in the presence of a base. As the organic solvent, for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylmethylene, N-methyl-2-pyrrolidone, etc. can be preferably used. The amount of the organic solvent used is 100 parts by weight, and preferably 400 to 900 parts by weight based on the total amount of the dicarboxylic acid and the diamine. The base used in the reaction is preferably a tertiary amine such as pyridine, triethylamine, N-ethyl-N, N-diisopropylamine, or the like. The amount of base used is 1 mole, preferably 2 to 4 moles, relative to the diamine. In this way, a reaction solution obtained by dissolving polyfluorene is obtained. This reaction solution can be directly used for the preparation of the liquid crystal alignment agent, or the polyamine contained in the reaction solution can be used for the preparation of the liquid crystal alignment agent after being isolated.

The polyamine of the present invention has a weight average molecular weight (Mw) of polystyrene equivalent measured by GPC, preferably 1,000 to 500,000, and more preferably 5,000 to 300,000.

[Polymer having a polymerizable unsaturated bond] Polymerizable unsaturated polymer having a monomer having a polymerizable unsaturated bond (hereinafter also referred to as "polymer (PAc)") Examples of the bond include (meth) acrylfluorenyl, vinyl, styryl, and maleimido. Specific examples of the monomer having such a polymerizable unsaturated bond include unsaturated carboxylic acids such as (meth) acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, and vinylbenzoic acid: ( Alkyl (meth) acrylate cycloalkyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3,4-epoxy (meth) acrylate Unsaturated carboxylic acid esters such as butyl ester, 4-hydroxybutyl glycidyl acrylate, etc .: Unsaturated polycarboxylic acid anhydrides such as maleic anhydride: (meth) acrylic compounds; styrene, methylstyrene, Aromatic vinyl compounds such as divinylbenzene; conjugated diene compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene; N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and other compounds containing maleimide; and the like. The monomer having a polymerizable group unsaturated bond may be used singly or in combination of two or more kinds.

The polymer (PAc) is preferably a polymer containing a monomer of a (meth) acrylic compound from the viewpoints of transparency, material strength, and the like. When the polymer (PAc) is synthesized, the usage ratio of the (meth) acrylic compound is relative to the total amount of the monomers used in the synthesis, preferably 50 mol% or more, more preferably 60 mol% or more, and More preferably, it is 70 mol or more.

When manufacturing a vertical alignment type liquid crystal display element, a photoreactive monomer represented by the structure of the following formula (3m) -1 may be used.

In the formula (3m) -1, Mc represents a polymerizable unsaturated bond such as a (meth) acrylfluorenyl group, a vinyl group, a styryl group, a maleimide group, or the like, and Sb is a linear or Branched alkylene, divalent aromatic group or divalent alicyclic group, Md is single bond, divalent heterocyclic ring, trivalent heterocyclic ring, tetravalent heterocyclic ring, substituted or unsubstituted Branched 1 to 10 carbon alkyl groups, divalent aromatic groups, trivalent aromatic groups, tetravalent aromatic rings, divalent alicyclic groups, trivalent alicyclic groups, tetravalent Alicyclic group, divalent condensed cyclic group, trivalent condensed cyclic group or tetravalent condensed cyclic group, each group is unsubstituted, or more than one hydrogen atom may be fluorine atom, chlorine atom, Cyano, methyl, or methoxy substituted, d is an integer of 1 to 3, and Z is an oxygen atom or a sulfur atom. Xa and Xb are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, and R ₁ is a single bond, an oxygen atom, -COO- or -OCO-, preferably a single bond, -COO- or -OCO-, R ₂ is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group, and R ₃ is a single bond and an oxygen atom , -COO- or -OCO-, R ₄ is a linear or branched alkyl group having 1 to 40 carbon atoms or a monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group, and R ₅ is a carbon number An alkyl group of 1 to 3, an alkoxy group of 1 to 3 carbon atoms, a fluorine atom or a cyano group, preferably a methyl group, a methoxy group or a fluorine atom, a is an integer of 0 to 3, and b is an integer of 0 to 4 Integer.

Examples of the monomer represented by the formula (3m) -1 include, but are not limited to, the following.

The usage ratio of the above-mentioned photoreactive monomers is relative to the total amount of the monomers used synthetically, preferably 10 to 95 mol, more preferably 10 to 90 mol%, and still more preferably 20 to 70 mol%.

The polymer (PAc) can be obtained, for example, by polymerizing a monomer having a polymerizable group unsaturated bond in the presence of a polymerization initiator. Polymerization initiator used, such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis An azo compound such as (4-methoxy-2,4-dimethylvaleronitrile) is preferred. The use ratio of the polymerization initiator is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of the total monomer used in the reaction. The polymerization reaction is preferably performed in an organic solvent. Examples of the organic solvent used in the reaction include alcohols, ethers, ketones, amidines, esters, and hydrocarbon compounds. Diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate are preferred. The used amount of the organic solvent (a) is a total amount of monomers used in the reaction (b), and is preferably an amount of 0.1 to 60% by mass based on the total amount (a + b) of the reaction solution.

According to a preferred aspect of the present invention, the component (A) is selected from the group consisting of polymers of polyimide, polyamidic acid, polyamidate, and a monomer having a polymerizable unsaturated bond. At least one polymer.

In a more preferred aspect of the present invention, the component (A) is derived from a tetracarboxylic acid selected from the group consisting of at least one group consisting of tetracarboxylic dianhydride, tetracarboxylic diester, and tetracarboxylic diester dichloride. A polymer obtained by reacting a substance with a diamine. In this case, the tetracarboxylic dianhydride, the tetracarboxylic diester, and the tetracarboxylic diester dichloride are preferably selected from the group consisting of the aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic A structure of at least one group of a group of tetracarboxylic dianhydrides, and tetracarboxylic diesters and tetracarboxylic diester dichlorides. More preferably, it includes a structure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, a cyclohexane ring structure, and a benzene ring structure. Specifically, from the viewpoint of the solubility of a solvent, the polyamidic acid and the polyamidate or polyimide obtained by subjecting them to polyimidization is preferably the aforementioned formula (X1-1). ~ (X1-3), (X1-6) ~ (X1-12), (Xa-1) ~ (Xa-2), pyromellitic anhydride, 4,4 '-(hexafluoroisopropylidene) Diphthalic anhydride, (Xb-6) ~ (Xb-8), (X1-44), (X1-47) ~ (X1-52), more preferably (X1-1) ~ (X1-3 ), (X1-6) ~ (X1-12), (Xa-1) ~ (Xa-2), (Xb-6) ~ (Xb-8), (X1-44), (X1-49).

A more preferred form of the tetracarboxylic acid derivative includes a compound selected from the group consisting of compounds represented by the following formulae (X1-1-1) to (X1-1-6),

Contains compounds represented by the above formulae (X1-6) to (X1-9), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid di Anhydride, pyromellitic anhydride, a compound represented by (Xb-6) and at least one compound (T) of a group of these tetracarboxylic diesters and tetracarboxylic diester dichlorides are particularly preferred.

The use amount of these preferred compounds (T) (the total amount when two or more kinds are used) is relative to the total amount of tetracarboxylic dianhydride and its derivatives used in the synthesis of polyamic acid, preferably 10 Molar% or more, more preferably 20 Molar% or more, and even more preferably 30 Molar% or more.

The molecular weights of the polyamidic acid, polyamidate, and polyimide described in the present invention are weight average molecular weights, preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

<<< Amount of component >> (A) component is 1 to 15% by weight when the total amount of the liquid crystal alignment agent is set to 100% by weight, preferably 1 to 8% by weight, and more preferably 1.5 to 7% by weight.

<(B) component> The liquid crystal aligning agent system of this case contains (B) component. (B) component is at least one compound selected from the group consisting of a compound represented by the following formula [CL-1] and a compound represented by the following formula [CL-2]. By containing these compounds, when a liquid crystal alignment film is formed from a liquid crystal alignment agent, the adhesion between the liquid crystal alignment film and the substrate can be improved, and / or the adhesion between the liquid crystal alignment film and a member provided directly above it can be improved. Sex.

(CL-1) In the formula, r ¹ represents a hydrogen atom or a methyl group, and r ² represents an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms and a fat having 5 to 6 carbon atoms. A bivalent organic group formed from a family ring, or a divalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms. These groups may be replaced by -O _2- r ³ represents a k-valence formed by a k-valent aliphatic group having 2 to 20 carbon atoms, a k-valent straight or branched chain alkylene group having 2 to 20 carbon atoms, and an aliphatic ring having 5 to 6 carbon atoms. Or a k-valent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms. These groups may be substituted with -CH ₂ -in the structure, and more preferably represent 2 to 6 carbon atoms. A k-valent aliphatic group of 10 is more preferably a k-valent alkyl group having 2 to 10 carbon atoms, Z represents a divalent group represented by the above formula (1a), and k is 2 or more and 9 or less, preferably 2 to 6 The natural number. In formula (1a), r ⁴ represents an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, A monovalent group formed by an aliphatic ring having 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms. These groups may also have -CH ₂ -in the structure. Substituted by -O-, preferably methyl. * 1 and * 2 indicate that either is a bond to a nitrogen atom, and the other indicates a bond to r ³ .

Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of r ² include a divalent group obtained by removing one hydrogen atom from an alkyl group having 2 to 20 carbon atoms. Specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, and n- Pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-tri Methyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n -Tetradecyl, n-pentadecyl, n-hexadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl, n-icosyl, cyclopentyl Radicals, cyclohexyl radicals, and one or more of these radicals, the radicals of which are bonded within a range of 20 carbon atoms, and one or more of these radicals are substituted by a methyl group or a non-adjacent plural methyl group. Examples of the group which is an ether bond are listed.

A monovalent radical formed by an aliphatic ring having 5 to 6 carbons in the definition of r ² , such as cyclopentyl and cyclohexyl; etc. In the definition of r ² includes 1 of an aliphatic ring having 5 to 6 carbons Examples of the valence aliphatic group include an alkyl group containing a cyclopentyl ring or a cyclohexane ring.

A specific example of a k-valent aliphatic group having 2 to 20 carbon atoms in the definition of r ^{3 can} be obtained from an alkyl group having 2 to 20 carbon atoms and then removing 1 to (k-1) hydrogen atoms. k-valent basis. The alkyl group having 2 to 20 carbon atoms is synonymous with the definition of r ² described above. In the definition of r ³ , a k-valent group formed from an aliphatic ring having 5 to 6 carbon atoms can be exemplified by a k-valent group formed by removing a k hydrogen atom from a cyclopentyl ring or a cyclohexane ring. base. The k-valent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms in the definition of r ³ includes, for example, a k-valent alkyl group containing a cyclopentyl ring or a cyclohexane ring.

The combination of r ² and r ³ is particularly preferred from the viewpoints of availability of raw materials, such that r 2 is an ethylene group, and r ³ is an n-hexyl group.

the definition of r ⁴ carbon atoms in the alkyl group of 1 to 20, in addition to an alkyl group having a carbon number in the definition of r2 of 2 to 20 include a methyl group, the carbon number of 5 to 6 in the definition of the r ⁴ Examples of the monovalent group formed by an aliphatic ring include cyclopentyl and cyclohexyl; and the monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms in the definition of r ⁴ includes, for example, An alkyl group including a cyclopentyl ring or a cyclohexane ring, and the like.

In the formula (CL-2), R _CL1 is a hydrogen atom or a methyl group, and R _CL2 and R _CL3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a hydroxyalkyl group having 1 to 20 carbon atoms. Is an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 20 carbon atoms, more preferably a straight or branched alkyl group having 1 to 10 carbon atoms or a straight or branched chain alkyl group having 1 to 20 carbon atoms A hydroxyalkyl group, R _CL4 is a hydroxy group or a hydroxyalkyl group having 1 to 20 carbon atoms, preferably a hydroxy group or a hydroxyalkyl group having 1 to 10 carbon atoms, more preferably a hydroxy group or a linear or branched chain having 1 to 6 carbon atoms. Hydroxyalkyl.

Specific examples of the alkyl group having 1 to 20 carbon atoms in R _CL2 and R _CL3 include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and s-butyl. Group, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl- n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1-ethyl-n-butyl , 1,1,2-trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl , N-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl and Examples of n-icosyl are listed. In addition, n indicates normal, i indicates iso, s indicates second, and t indicates tertiary.

Specific examples of the hydroxyalkyl group having 1 to 20 carbon atoms in R _CL2 and R _CL3 are preferably those in which the terminal of the alkyl group is substituted with a hydroxy group, and hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl, 12 -Hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl, 15-hydroxypentadecyl, 16-hydroxyhexadecyl, 17-hydroxyhexadecyl, 18-hydroxy Octadecyl, 19-hydroxynonadecyl and 20-hydroxy eicosyl are listed as examples.

The compounds represented by the formula (CL-1) include the following (MA-M1) to (MA-M3), but are not limited thereto.

Among the compounds listed above, (MA-M1) and (MA-M3) are preferred, and (MA-M1) is more preferred.

The compounds represented by the formula (CL-2) include the following (G-M1) to (G-M4), but are not limited thereto.

Among the compounds listed above, (G-M1), (G-M2), and (G-M4) are preferred, and (G-M1) is more preferred.

<<< Amount of (B) component >> 中 In the liquid crystal alignment agent of the present case, the component (B) is 0.1 to 50 parts by weight, preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight with respect to the component (A). It is 0.1 to 20 parts by weight.

<(C) component: Organic solvent> The liquid crystal alignment agent of this case contains an organic solvent as (C) component. (2) The organic solvent is not particularly limited as long as it has the property of dissolving the components (A) and (B). The organic solvent is preferably any solvent that is suitable for a low-temperature firing process.

Examples of the organic solvent of the component (C) in this case include solvents belonging to the following groups A and B, but are not limited thereto. In addition, these may be used individually by 1 type or in combination.

<Group A> 溶剂 Solvents belonging to Group A, when the above polyimide, polyamidic acid, polyamidate, polyorganosiloxane, polyester, polyamidine, and polymerizable unsaturated are raised In the case of solubility of a polymer such as a bonded monomer, it is preferable to use a solvent (also referred to as group A) shown below.

For example, selected from N-methyl-2-pyrrolidone, a compound represented by the following formula (NP), a compound represented by the following (NAm), γ-butyrolactone, γ-valerolactone, 1,3-dimethyl 2-imidazolinone, a solvent of at least one of the group.

In formula (NP), R ¹ is a monovalent hydrocarbon group having 2 to 5 carbon atoms, or a monovalent group having "-O-" between carbon-carbon bonds in the hydrocarbon group. In formula (NAm), R ² and R ³ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a carbon-carbon bond between the hydrocarbon groups, and have a monovalent group of "-O-", R ² and R ³ may be bonded to each other to form a ring structure. R ⁴ is an alkyl group having 1 to 6 carbon atoms), and these solvents are those which dissolve the polymer in the liquid crystal alignment agent.

Specific examples of the compound represented by the formula (NP) include N-ethyl-2-pyrrolidone, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, and N- ( n-butyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N- Ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone and the like.

Specific examples of the compound represented by the above formula (NAm) include, for example, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3 -Hexyloxy-N, N-dimethylpropanamide, isopropoxy-N-isopropyl-propanamide, n-butoxy-N-isopropyl-propanamine and the like.

The solvent A group is selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolinone, 3- Butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N-dimethylpropanamide, isopropyl At least one kind of compound in the group consisting of propoxy-N-isopropyl-propionamine and n-butoxy-N-isopropyl-propionamine is more preferable, and more preferably selected from the group consisting of N-methyl A compound of at least one kind of 2-pyrrolidone, γ-butyrolactone, and 1,3-dimethyl-2-imidazolinone.

<Group B> The viewpoint that the liquid crystal alignment agent of the present invention can improve the coating property of the liquid crystal alignment agent to the substrate and increase the drying speed of the liquid crystal alignment agent even if it is fired at a low temperature. ), A compound represented by the following formula (Sol-2), a solvent represented by the following formula (a), methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentane Ketone, 1-butanol, tert-butanol, 1-pentanol, 2-methyl-1-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-ethyl 1-butanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methyl Cyclohexanol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 1-methylpentane Ethyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, propylene carbonate, vinyl carbonate, furfuryl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, pyruvate A compound represented by methyl ester, ethyl pyruvate, or diisobutyl ketone (hereinafter, referred to as group B) is preferable. A compound containing at least one selected from the group consisting of a compound represented by the following formula (Sol-1) and a compound represented by the following formula (Sol-2) is preferred.

In the formula (Sol-1), Ys ⁷ and Ys ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent chain hydrocarbon group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. A monovalent alicyclic hydrocarbon group of 6 and a monovalent aromatic hydrocarbon group of 1 to 6 carbon atoms. More preferred is an alkyl group having 1 to 6 carbon atoms. Xs ¹ is an oxygen atom or -COO-. Xs ² is a single bond or a carbonyl group, Rs ⁷ is an alkanediyl group having 2 to 4 carbon atoms, and the alkanediyl group of R _S ⁷ may be linear or branched. Ethyl, 1,3-propanediyl, 1,2-propanediyl, 1,4-butanediyl, 1,3-butanediyl, and the like. R _s ^{7 is} preferably ethylene, 1,3-propanediyl, or 1,4-butanediyl. ns ¹ is an integer from 1 to 3. When ns ¹ is 2 or 3, the complex Rs ⁷ may be the same or different, and is preferably 1 or 2. In the formula (Sol-2), Zs ¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkanediyl group, and examples thereof include methyl, ethyl, 1,3-propanediyl, and 1, 4-Butyldiyl and the like. Ys ⁹ and Ys ¹⁰ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 6 carbon atoms and a monovalent alicyclic group having 1 to 6 carbon atoms. Hydrocarbon groups and monovalent aromatic hydrocarbon groups having 1 to 6 carbon atoms. More preferred is an alkyl group having 1 to 6 carbon atoms.

In the formula, R ₁ and R ₂ are each independently a linear or branched alkyl group having 1 to 8 carbon atoms. However, R ₁ + R ₂ is an integer greater than 3.

Group B is selected from the group consisting of a compound represented by the formula (Sol-1), a solvent represented by the formula (Sol-2), and a formula (a), methyl ethyl ketone, cyclohexanone, and cyclopentanone. , 4-hydroxy-4-methyl-2-pentanone, 1-butanol, tert-butanol, 1-pentanol, 2-methyl-1-butanol, neopentyl alcohol, 1-hexanol, 2 -Methyl-1-pentanol, 2-ethyl-1-butanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol , 2-methylcyclohexanol, 3-methylcyclohexanol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, 2-pentanone, 3-pentanone, 2-hexanone, 2- Heptone, 4-heptanone, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, propylene carbonate, vinyl carbonate, furfuryl alcohol, n-acetic acid Butyl ester, methyl pyruvate, ethyl pyruvate, and diisobutyl ketone are preferably at least one type of compound, and is more preferably selected from the compound represented by the above formula (Sol-1), and the above formula (Sol-2), the above formula (a), methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, dipropyl ether, dibutyl ether, dihexane Ether, 2-pentanone, 3-pentanone 2-hexanone, 2-heptanone, 4-heptanone, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, propylene carbonate, ethylene carbonate Ester diisobutyl ketone is a compound of at least one type of compound. Most preferably, it is a compound selected from the group consisting of a compound represented by the formula (Sol-1) and a compound represented by the formula (Sol-2).

Specific examples of the solvent represented by the formula (Sol-1) include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, and ethylene glycol. Monobutyl ether (butyl cellosolve), ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol mono Diethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetate, ethylene glycol, 1,4-butanediol, 3-ethoxybutyl acetate Specific examples of the solvent represented by (Sol-2) include methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, and ethyl-3- Ethoxypropionate, methyl-3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, and the like.

Preferred specific examples of the formulae (Sol-1) to (Sol-2) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, and ethylene glycol-i-propyl ether. , Ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetic acid Ester, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate.

A preferred solvent for the above formula (a) includes diisobutyl methanol.

In the liquid crystal alignment agent of the present invention, it is preferable to use the A group and the B group in combination. At this time, the B group is preferably 5 to 95% by mass or less of the total solvent contained in the liquid crystal alignment agent, and more preferably 5 to 80 Mass% or less, and more preferably 30 to 80 mass% or less. The group A is preferably 5 to 95% by mass of the entire solvent contained in the liquid crystal alignment agent, more preferably 20 to 95% by mass, and still more preferably 20 to 70% by mass.

<<< Components other than (A) component to (C) component >> 之 The liquid crystal alignment agent of the present case may suitably contain components other than the components (A) to (C) described above.

<Other crosslinkable compounds> Components other than (A) component to (C) component have epoxy groups, isocyanate groups, and oxa groups as described in paragraphs [0109] to [0113] of International Publication WO2016 / 047771. Cyclobutane or cyclocarbonate-based compounds, or compounds having at least one group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group, or a compound having a blocked isocyanate group may be used. Compounds (these may also be collectively referred to as other crosslinkable compounds).

Examples of the compound having a blocked isocyanate group include the following formulae (bl-1) to (bl-3).

The above is an example of other crosslinkable compounds and is not limited to these. Moreover, the other crosslinkable compound used for the liquid crystal aligning agent of this invention may be 1 type, and 2 or more types may be combined.

The content of the other crosslinkable compound in the liquid crystal alignment agent of the present invention is preferably 0.1 to 150 parts by mass relative to 100 parts by mass of the entire polymer component. Among them, in order to perform the effect of the crosslinking reaction, it is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the polymer component. More preferably, it is 1 to 50 parts by mass.

<Other optional components> 之 As the liquid crystal alignment agent of the present invention, a compound that improves the uniformity of the film thickness of the liquid crystal alignment film or the surface smoothness when the liquid crystal alignment agent is applied can be used.化合物 Compounds that increase the uniformity or surface smoothness of the film thickness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and non-ionic surfactants. Specific examples thereof include the surfactants described in paragraph [0117] of International Publication WO2016 / 047771. The amount of the surfactant used is 100 parts by mass, preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the entire polymer component contained in the liquid crystal alignment agent.

In addition, the liquid crystal alignment agent may be added with a compound that promotes the charge movement in the liquid crystal alignment film and promotes the disappearance of the charge on the device. [M1] to a nitrogen-containing heterocyclic amine compound represented by the formula [M156]. This amine compound can be directly added to the liquid crystal alignment agent, but it is better to add it after forming a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. This solvent is not particularly limited as long as it dissolves the specific polymer (A).

In the liquid crystal alignment agent of the present invention, in addition to the above-mentioned weak solvent, crosslinkable compound, resin film, compound that enhances film thickness uniformity or surface smoothness of the liquid crystal alignment film, and compound that promotes disappearance of charge, the present invention may also be added. Polymers other than the polymers described, silane coupling agents for the purpose of improving the adhesion between the alignment film and the substrate, and the firing of the polyimide precursor by heating the polyimide efficiently during firing The purpose of chemical conversion is imidization promoter.

The liquid crystal alignment agent of this case has the form of the solution containing the said (A) component-(C) component.液晶 The liquid crystal alignment agent used in the present invention is a solution in which a polymer having a specific structure is dissolved in an organic solvent.

The concentration of the polymer of the liquid crystal alignment agent used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but from the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by weight or more. From the viewpoint of storage stability of the solution, it is preferably 10% by weight or less.

The liquid crystal alignment agent in this case can be appropriately changed by setting the thickness of the coating film by setting the solid content concentration (the ratio of the total weight of components other than the (C) component of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent). However, from the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by weight or more, and from the viewpoint of storage stability of the solution, 10% by weight or less is preferable.

A particularly preferable range of the solid content concentration varies depending on a method for applying a liquid crystal alignment agent to a substrate. For example, when the spin coater method is used, the polymer concentration is particularly preferably in the range of 1.5 to 4.5% by weight. When the printing method is used, the solid content concentration is in the range of 3 to 9% by weight, and the solution viscosity is particularly preferably set in the range of 12 to 50 mPa ･ s. When the inkjet method is used, the solid content concentration is set to a range of 1 to 5 wt%, and the solution viscosity is particularly preferably set to a range of 3 to 15 mPa ･ s.

According to another aspect of the present invention, a liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention can be provided.

In addition, according to another aspect of the present invention, a method for manufacturing a liquid crystal alignment film may be provided, which includes the following steps: 涂布 the step of applying the liquid crystal alignment agent of the present invention on a substrate to form a coating film, and the aforementioned coating A step of applying light to the coating film in a state where the film is not in contact with the liquid crystal layer or in a state where the film is in contact with the liquid crystal layer.

In addition, according to another aspect of the present invention, a liquid crystal display element may be provided which includes the liquid crystal alignment film of the present invention or a liquid crystal alignment film obtained by the aforementioned manufacturing method of the present invention. Details are as follows.

<Liquid crystal alignment film / liquid crystal display element> 液晶 A liquid crystal alignment film can be manufactured by using the above-mentioned liquid crystal alignment agent. The liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited, and it can be applied to TN (Twisted Nematic) type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type (IPS Type), FFS (Fringe Field Switching) type, optically compensated bending mode (Optically Compensated Bend: OCB type) and other various operation modes.

The liquid crystal display element of the present invention can be manufactured by, for example, a step including the following steps (1-1) to (1-3). Step (1-1) differs depending on the desired operation mode using the substrate. Steps (1-2) and (1-3) are common to each operation mode.

[Step (1-1): Formation of Coating Film] First, the liquid crystal alignment agent of the present invention is coated on a substrate, and then a coating film can be formed on the substrate by heating the coating surface. (1-1A) For example, when manufacturing a TN-type, STN-type, or VA-type liquid crystal display element, first, a pair of two substrates provided with a patterned transparent conductive film is used as a pair, and a surface is formed on each of the transparent conductive films. It is preferable that the prepared liquid crystal alignment agent is applied by a lithographic method, a spin coating method, a roll coater method, or an inkjet printing method, respectively. For the substrate, for example, glass such as float glass, soda glass, or the like can be used. Transparent substrate made of plastic. The transparent conductive film provided on one surface of the substrate may be a NESA film (registered trademark of the United States PPG Corporation) made of stannous oxide (SnO ₂ ), or an indium-tin oxide (In ₂ O ₃ -SnO ₂ ) Into an ITO film. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching can be used after forming a patternless transparent conductive film; when forming a transparent conductive film, a pattern having a desired pattern can be used. Masking methods; etc. In the application of the liquid crystal alignment agent, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a surface of the coating film may be formed on the substrate surface, and a functional silane compound or a functional layer may be applied in advance. Pre-treatment of a titanium compound.

After the liquid crystal alignment agent is applied, it is preferable to perform preheating (pre-baking) for the purpose of preventing liquid flow of the applied liquid crystal alignment agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-baking time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Then, after the solvent is completely removed, if necessary, the firing (post-baking) step may be performed for the purpose of performing the hot-imidization of the pyrimide structure present in the polymer. The firing temperature (post-baking temperature) at this time is preferably 80 to 300 ° C, and more preferably 120 to 250 ° C. The post-baking time is preferably 5 to 200 minutes, and more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μm.

(1-1B) When manufacturing an IPS-type or FFS-type liquid crystal display element, the electrode formation surface of a substrate provided with an electrode formed by a transparent conductive film or a metal film patterned with a 栉 歯 pattern, and no electrode is provided. A liquid crystal alignment agent is applied to one surface of the opposite substrate, and then each coating surface is heated to form a coating film. At this time, regarding the material of the substrate and the transparent conductive film used, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or metal film, the pre-treatment of the substrate, and the preferred film thickness of the formed coating film It is the same as the above (1-1A). As the metal film, for example, a film made of a metal such as chromium can be used.

In any of the cases (1-1A) and (1-1B), after the liquid crystal alignment agent is applied to the substrate, the liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film can be formed by removing the organic solvent. At this time, after the coating film is formed, the polyamic acid, the polyamic acid ester, and the polyfluorene imide prepared in the liquid crystal alignment agent of the present invention are subjected to dehydration and ring-closing reaction by reheating. Aminated coating.

[Step (1-2): Treatment for imparting alignment energy] (1) When manufacturing a TN, STN, IPS or FFS type liquid crystal display device, the liquid crystal display element formed in the above step (1-1) is provided with the alignment energy. Processing. Thereby, the alignment of the liquid crystal molecules can be imparted to the coating film to become a liquid crystal alignment film. Examples of the treatment for imparting alignment energy include a rubbing treatment in which a coating film is rubbed with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton, and the coating film is irradiated with polarized or non-polarized radiation. Light alignment processing. In addition, when manufacturing a VA-type liquid crystal display element, the coating film formed in the above step (1-1) can be directly used as a liquid crystal alignment film, but the coating film can also be subjected to a treatment for imparting alignment energy.

When the liquid crystal alignment can be imparted to the coating film by the photo-alignment treatment, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used to irradiate the coating film. When the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, the substrate may be irradiated in a direction perpendicular to the substrate surface, may be irradiated in an oblique direction, or a combination of these may be used. When irradiating non-polarized light, the direction of irradiation is oblique. The light source used may be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or an excimer laser. Ultraviolet rays in a preferred wavelength range can be obtained by a means such as a combination of a light source with a filter, a diffraction grid, or the like. The radiation dose is preferably 10 to 5,000 mJ / cm ² , and more preferably 30 to 2,000 mJ / cm ² . The coating film may be irradiated with light to increase the reactivity, while the coating film is being heated. The temperature during heating is usually 30 to 250 ° C, preferably 40 to 200 ° C, and more preferably 50 to 150 ° C. In addition, when using ultraviolet rays having a wavelength of 150 to 800 nm, the light-irradiated film obtained in the above steps may be used directly as a liquid crystal alignment film, but the light-irradiated film may be fired. The firing temperature at this time is preferably 80 to 300 ° C, and more preferably 120 to 250 ° C. The firing time is preferably 5 to 200 minutes, and more preferably 10 to 100 minutes. The light alignment process here corresponds to the process of light irradiation in a state where it is not in contact with the liquid crystal layer.

In addition, for the liquid crystal alignment film after the rubbing treatment, a part of the liquid crystal alignment film is irradiated with ultraviolet rays to change a pretilt angle of a part of the liquid crystal alignment film or a resist film is formed on a part of the surface of the liquid crystal alignment film. After the rubbing treatment is performed in a direction different from the previous rubbing treatment, the resist film is removed, and the liquid crystal alignment film may also have different liquid crystal alignment capabilities in each region. In this case, the field of view characteristics of the obtained liquid crystal display element can be improved. A liquid crystal alignment film suitable for a VA type liquid crystal display element can also be used for a PSA (Polymer sustained alignment) type liquid crystal display element.

[Step (1-3): Construction of Liquid Crystal Cell] (1) (1-3A) Prepare two substrates on which the liquid crystal alignment film is formed as described above, and arrange the liquid crystal between the two substrates disposed oppositely to produce a liquid crystal cell. When manufacturing a liquid crystal cell, the following two methods are mentioned, for example. The first method is a conventionally known method. First, the respective liquid crystal alignment films are opposed to each other, and the two substrates are arranged to face each other via a gap (liquid crystal layer gap). The peripheral portions of the two substrates are bonded with a sealant, and the liquid crystal layer gap on the substrate surface and the sealant Inside, after filling and filling the liquid crystal, the injection hole is closed to manufacture a liquid crystal cell. The second method is a method called the One Drop Fill (ODF) method. In a specific place on one of the two substrates on which a liquid crystal alignment film is formed, for example, a UV-curable sealant is applied. Then, after dropping the liquid crystal at a certain number of places on the liquid crystal alignment film surface, the liquid crystal alignment film faces the other substrate, and is bonded to another substrate, and at the same time, the liquid crystal is extended to the entire surface of the substrate, and then the substrate is fully irradiated with ultraviolet light, so that The sealant hardens, producing liquid crystal cells. Regardless of the method used, the liquid crystal cell manufactured as described above is preferably heated until the liquid crystal used has an isotropic phase temperature, and then slowly cooled to room temperature to remove the flow alignment during liquid crystal filling.

As the sealant, for example, an epoxy resin containing a hardener and alumina balls as a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable. For example, Schiff base liquid crystals, azoxy liquid crystals, and liquid crystals can be used. Benz-based liquid crystal, phenylcyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal (terphenyl) -based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, and bicyclooctane-based liquid crystal , Cubic liquid crystal (cubane) and the like. In addition, cholesteric liquid crystals such as cholestery chloride, cholesteryl nonanoate, and cholesteryl carbonate may be added to these liquid crystals. Chiral agents sold under the names "C-15" and "CB-15" (Merck); p-decoxybenzylidene-p-amino-2-methylbutyl cinnamate, etc. Strong dielectric liquid crystal and so on. The liquid crystal may further include an anisotropic dye. The term "dye" refers to a substance that can absorb or deform at least part or all of the light in the visible light range, for example, in the wavelength range of 400nm to 700nm. The term "anisotropic dye" refers to at least the aforementioned visible light range. An anisotropically absorbable substance in part or all of the range. By using the aforementioned dye, the color feeling of the liquid crystal cell can be adjusted. The type of the anisotropic dye is not particularly limited, and for example, a black dye or a color dye can be used. The ratio of the anisotropic dye to the liquid crystal can be appropriately selected within a range that does not impair the physical properties of the object. For example, the anisotropic dye may contain anisotropy in a ratio of 0.01 to 5 parts by weight relative to 100 parts by weight of the liquid crystal compound. Dye, but the aforementioned ratio may be changed to a more appropriate range if necessary.

(1-3B) When manufacturing a PSA type liquid crystal display element, a liquid crystal cell is constructed in the same manner as in the above (1-3A), except that a photopolymerizable compound is injected or dropped together with the liquid crystal. Then, the liquid crystal cell is irradiated with a voltage applied between the conductive films having a pair of substrates. Here, the applied voltage may be, for example, 5 to 50V DC or AC. In addition, as the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferred. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a heavy hydrogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the like can be used. The ultraviolet rays in the above-mentioned preferable wavelength range can be obtained by means such as a combination of a light source with a filter, a diffraction grid, or the like. Light irradiation amount, preferably 100mJ / cm ² or more and less than 20,000mJ / cm ^2, more preferably 100 ~ 10,000mJ / cm ^2.

(1-3C) When a liquid crystal alignment agent containing a compound (polymer or additive) having a photopolymerizable group is used to form a coating film on a substrate, a liquid crystal cell can be constructed by the same method as in (1-3A) above. A method of manufacturing a liquid crystal display element by applying light to a liquid crystal cell in a state where a voltage is applied between the conductive films of a pair of substrates. According to this method, the advantages of the PSA mode can be realized with less light exposure. The liquid crystal cell may be irradiated with light in a state where the liquid crystal is driven by applying a voltage, or may be performed in a state where a low voltage to which the liquid crystal is not driven is applied. The applied voltage may be, for example, DC or AC of 0.1 to 30V. The conditions for irradiating light can be applied to the above (1-3B). The light irradiation treatment here corresponds to the light irradiation treatment in a state of being in contact with the liquid crystal layer.

In addition, by bonding a polarizing plate to the outer surface of the liquid crystal cell, a liquid crystal display element of the present invention can be obtained. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include a polarizing film called "H film" while extending the orientation of polyvinyl alcohol and absorbing iodine, or a polarizing plate sandwiched with a protective film of cellulose acetate or A polarizing plate made of H film.

The liquid crystal display element of the present invention can be applied to various devices such as clocks, portable games, typewriters, notebook personal computers, car navigation systems, video recorders, PDAs, digital cameras, mobile phones, smart phones, various Various display devices such as monitors, LCD TVs, and information displays.

As described above, by using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film with good adhesiveness can be obtained even if low-temperature firing is performed.

[Example]

The following examples illustrate the present invention in more detail, but the present invention is not limited to these. The abbreviations of the compounds used are as follows. (Liquid crystal) LC-V1: MLC-6608 (Merck) LC-I1: MLC-2041 (Merck) LC-I2: MLC-7026-100 (Merck)

(Diamine component) A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene A2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene A3: 1,3-diamino-4- {4- [trans-4- (trans-4- n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene A4: a diamine compound represented by the formula [A4] A5: 1,3-diamino-4-octadecyloxybenzene A6: 1,3- Diamino-4-hexadecyloxybenzene A8: N- (2,4-diaminophenyl) -4- (trans-4-heptylcyclohexyl) benzamide (formula [A8] (Represented compound)

B1: 3,5-diaminobenzoic acid B2: 2,4-diamino-N, N-diallylaniline (diamine compound represented by the following formula [B2])

C1: p-phenylenediamine C2: m-phenylenediamine C3: 1,5-bis (4-aminophenoxy) pentane C4: 1,3-bis (4-aminophenethyl) urea C5 : 4- (2- (methylamino) ethyl) aniline (compound represented by formula [C5]) C6: compound represented by formula [C6] C7: 1,2-bis (4-aminophenoxy) Ethane C8: 4,4'-diaminodiphenylmethane DA-N-A6: 4,4'-diaminodiphenylamine DA-N-A7: bis (4-aminophenyl)- N-methylamine

(Tetracarboxylic acid component) D1: 1,2,3,4-cyclobutane tetracarboxylic dianhydride D2: bicyclic [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride D3: Tetracarboxylic dianhydride represented by formula [D3] D4: Tetracarboxylic dianhydride represented by formula [D4] D5: Tetracarboxylic dianhydride represented by formula [D5] D6: 1, 2, 3, 4-butane Alkanetetracarboxylic dianhydride D7: pyromellitic dianhydride D8: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride D9: 2,4-bis (methoxycarbonyl) cyclobutane-1 , 3-dicarboxylic acid (compound represented by formula [D9]) D10: 2,5-bis (methoxycarbonyl) benzene-1,4-dicarboxylic acid (compound represented by formula [10].)

(Condensing agent) DMT-MM: 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholin-4-ium

(Adhesive compound) G-M1: Adhesive compound represented by formula [G-M1] MA-M1: Adhesive compound represented by formula [MA-M1]

(Other adhesive compounds) K1: Compound represented by formula [K1]

K2: 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

(Solvent) NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone DMI: 1,3-dimethyl-2-imidazolinone PGME: propylene glycol Monomethyl ether ECS: ethylene glycol monoethyl ether BCS: ethylene glycol monobutyl ether PB: propylene glycol monobutyl ether EC: diethylene glycol monoethyl ether EEP: ethyl-3-ethoxypropionate DEDE: diethylene glycol Alcohol diethyl ether DME: Dipropylene glycol dimethyl ether DEME: Diethylene glycol dimethyl ether DPM: Dipropylene glycol monomethyl ether

(Molecular weight measurement) The molecular weights of the polyimide precursor and polyimide were 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 ℃ Eluent: N, N'-dimethylformamide (additive is lithium bromide-hydrate (LiBr ･ H ₂ O) 30mmol / L (liter), anhydrous crystal of phosphoric acid (o-phosphoric acid) ) Is 30mmol / L, tetrahydrofuran (THF) is 10ml / L) Flow rate: 1.0ml / min Standard sample for calibration line production: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (East Manufactured by Tsao Corporation) and polyethylene glycol (molecular weight; approximately 12,000, 4,000, and 1,000) (manufactured 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 deuterated diamine was added. Methyl sulfene (DMSO-d ⁶ , 0.05% by mass TMS (tetramethylsilane) mixed product) (0.53 ml), completely dissolved by applying ultrasonic waves. This solution was used to measure a proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500) (manufactured by Japan Electronics Datum Corporation). The hydrazone imidization rate is based on protons from structures that have not changed before and after hydrazone imidization, and the peak protons from this proton are integrated with the proton peaks from the NH group of sulfamic acid appearing around 9.5 to 10.0 ppm. The value is obtained by the following formula.醯 Imidization rate (%) = (1-α ･ x / y) × 100 In the above formula, x is the integrated value of the proton peak derived from the NH group of the amino acid, and y is the integrated value of the peak of the standard proton, α The ratio of the number of reference protons to one NH matrix proton of amidine (in the case of amidinium imidization rate of 0%).

[Synthesis of polyfluorene-imide-based polymer] <Synthesis Example 1> D1 (3.32g, 16.9mmol), A1 (3.26g, 8.57mmol), B1 (1.04g, 6.84mmol), and C2 (0.19g, 1.76) mmol) was mixed with NEP (23.4 g), and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 25% by mass. The number average molecular weight of this polyamic acid was 23,200, and the weight average molecular weight was 70,100.

<Synthesis Example 2> (1) D2 (4.29 g, 17.1 mmol), A2 (6.76 g, 17.1 mmol) and B1 (2.61 g, 17.1 mmol) were mixed in NMP (33.9 g), and the reaction was performed at 50 ° C for 2 hours. , D1 (3.29 g, 16.8 mmol) and NMP (17.0 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25% by mass. This polyamic acid had a number average molecular weight of 23,800 and a weight average molecular weight of 69,500.

<Synthesis Example 3> Into the polyamic acid solution (2) (30.5 g) obtained by the synthesis method of Synthesis Example 2, NMP was added, and after diluting to 6% by mass, acetic anhydride (a fluorinated imidization catalyst) was added ( 3.90 g) and pyridine (2.41 g), and reacted at 70 ° C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (3). The polyimide has a fluorene imidization rate of 61%, a number average molecular weight of 21,900, and a weight average molecular weight of 59,900.

<Synthesis Example 4> to Synthesis Example <11> Polyimide powders (4) to (9), (11) were obtained in the same manner as in Synthesis Example 2 and Synthesis Example 3 except that the composition was changed to that shown in Table 1. And a polyamic acid solution (10) having a resin solid content concentration of 25% by mass.

As described above, the polyfluorene-based polymers obtained in Synthesis Examples 1 to 11 are shown in Table 1. In addition, in the polyfluorene imine powders of Synthesis Examples 4 to 11, the number average molecular weight and weight average molecular weight are shown in Table 2, respectively.

<Synthesis Example 12> D1 (19.61 g, 0.1 mol) as a tetracarboxylic acid component and DA-N-A6 (18.73 g, 0.094 mol) as a diamine component were mixed in NMP (345.1 g), and room temperature The reaction was carried out for 5 hours to obtain a polyamic acid solution (12) having a resin solid content concentration of 10% by mass. The number average molecular weight of this polyamic acid was 14,100, and the weight average molecular weight was 29,500.

<Synthesis Example 13> D1 (34.47 g, 0.18 mol) as a tetracarboxylic acid component, DA-N-A7 (28.38 g, 0.13 mol), and C3 (16.40 g, 0.057 mol) as a diamine component were used in NMP. In (713.25 g), the reaction was performed at room temperature for 1 hour to obtain a polyamic acid solution (13) having a resin solid content concentration of 10% by mass. This polyamic acid had a number average molecular weight of 13,300 and a weight average molecular weight of 27,800.

<Synthesis Example 14> D9 (2.03 g, 7.80 mmol) as tetracarboxylic acid, D10 (1.02 g, 3.60 mmol), C4 (1.07 g, 3.60 mmol) as diamine component, and C1 (0.79 g, 7.20 mmol) ), A8 (0.49 g, 1.20 mmol), triethylamine (0.61 g, 0.0060 mol) as a base, DMT-MM (9.96 g, 36.0 mmol) as a condensing agent, in NMP (84.4 g), in The reaction was allowed to proceed at room temperature for 3.5 hours to obtain a polyamidate solution. This polyamidate solution was put into 550 g of methanol, and the precipitated solid matter was recovered. Furthermore, after washing this solid substance several times with methanol, it dried under reduced pressure at 100 degreeC, and obtained the powder (14) of a polyamidate. The polyamidate had a number average molecular weight of 16,478 and a weight average molecular weight of 39,754.

<Synthesis Example 15> 5 C5 (2.83 g, 18.8 mmol), C4 (5.61 g, 18.8 mmol), and C3 (2.70 g, 9.40 mmol) as diamine components were added to NMP (126 g), and nitrogen was added while feeding. Stir to dissolve. While stirring this diamine solution, D1 (8.84 g, 45.1 mmol) as a tetracarboxylic acid component was added, and then NMP was added so that the resin solid content concentration became 10% by mass. Under a nitrogen environment, the mixture was stirred at room temperature for 2 hours. A polyamic acid solution (15) was obtained. This polyamic acid had a number average molecular weight of 15,600 and a weight average molecular weight of 38,400.

<Synthesis Example 16> (1) C1 (45.96 g, 0.425 mmol) and C6 (17.80 g, 0.075 mol) as diamine components were added to NMP (1390 g), and dissolved while being fed with nitrogen. While stirring this diamine solution, D5 (107.83 g, 0.481 mol) was added, and then NMP was added so that the resin solid content concentration became 10% by mass, and the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (16). The number average molecular weight of this polyamic acid was 12,629, and the weight average molecular weight was 29,521.

<Synthesis Example 17> C7 (79.4 g, 0.33 mol) and DA-N-A6 (64.8 g, 0.33 mol) as diamine components were added to NMP (911 g) and GBL (911 g), and the nitrogen Stir to dissolve. While stirring this diamine solution, D1 (65.0g, 0.33mol) was added, and after stirring at room temperature for 2 hours, D8 (86.1g, 0.29mol) was added, and then NMP (390g) and GBL (390g), nitrogen Under an environment, stirring was performed at 40 ° C. for 30 hours to obtain a polyamic acid solution (17) having a resin solid content concentration of 10%. The number average molecular weight of this polyamic acid solution was 15,773, and the weight average molecular weight was 31,242.

<Synthesis Example 18> (4) D4 (30.03 g, 0.100 mol) as a tetracarboxylic acid component, C1 (9.19 g, 0.085 mol), and A6 (5.23 g, 0.015 mol) as a diamine component are contained in NMP (252 g). The reaction was performed at 50 ° C. for 24 hours to obtain a polyamic acid solution having a resin solid content concentration of 15% by mass. 50NMP was added to 50 g of this polyphosphonic acid solution to dilute it to 5% by mass, and pyridine (8.0 g) and acetic anhydride (17.2 g) were added as the phosphonium imidization catalyst, and reacted at 40 ° C. for 3 hours. This solution was poured into 600 ml of methanol, and the obtained precipitate was filtered and obtained, and dried to obtain a white polyimide powder (18). The polyimide has an imidization ratio of 83%, a number average molecular weight of 9,834, and a weight average molecular weight of 21,659.

<Synthesis Example 19> (1) D1 (9.81 g, 0.05 mol), D7 (9.60 g, 0.044 mol) as a tetracarboxylic acid component, and C8 (19.83 g, 0.100 mol) as a diamine component in NMP (222 g), The reaction was performed at room temperature for 5 hours to obtain a polyamic acid solution (19) having a resin solid content concentration of 15% by mass. This polyamic acid had a number average molecular weight of 10,893 and a weight average molecular weight of 25,972.

[Preparation of liquid crystal alignment treatment agent] 例 Examples of preparation of the liquid crystal alignment treatment agent are described in the Examples and Comparative Examples. Using the liquid crystal alignment treatment agents obtained in the examples and comparative examples, "production of liquid crystal display elements", "evaluation of liquid crystal alignment", "evaluation of adhesion of liquid crystal alignment films", or "peeling test" were performed.

[Production of liquid crystal display elements] (Production of vertical alignment type liquid crystal display elements) The liquid crystal alignment treatment agents (V-1) to (V-9) obtained in the examples and the liquid crystal alignment treatment agent (R-V1) obtained in the comparative examples ) ~ (R-V2) Pressurize filtration using a membrane filter with a pore size of 1 μm. The obtained solution was spin-coated on the ITO surface of a glass substrate (length: 100 mm, width: 100 mm, thickness: 0.7 mm) with an ITO electrode washed with pure water and IPA (isopropanol) at 100 × 100 mm. Heat treatment was performed on a hot plate at 100 ° C. for 2 minutes, and in a thermal cycle type cleaning oven, at 210 ° C. for 10 minutes to obtain an ITO substrate with a liquid crystal alignment film having a thickness of 100 nm. Two obtained ITO substrates with a liquid crystal alignment film were prepared, and a spacer of 6 μm was coated on the liquid crystal alignment film surface of one of the substrates. Secondly, the surroundings were coated with a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.). Then, the aforementioned liquid crystal composition (LC-V1) is dropped onto the liquid crystal alignment film surface of the substrate by an ODF (One Drop Filling) method, and then the liquid crystal alignment film interface of the other substrate is bonded to face each other to make a sealant. It was hardened, and the vertical alignment type liquid crystal display element was obtained. The obtained liquid crystal display element was heated at 110 ° C. for 1 hour, left at room temperature for a while, and used for each evaluation.

(Production of FFS-type liquid crystal display element) <Friction alignment treatment> The liquid crystal alignment treatment agents (I-10) to (I-13), (I-15) to (I-18) and Comparative Examples obtained in the examples The liquid crystal alignment treatment agents (R-I3) to (R-I4) are subjected to pressure filtration using a membrane filter having a pore size of 1 μm. Next, a glass substrate with an electrode substrate and a columnar spacer having a height of 4 μm, which is formed with an electrode substrate and an ITO film as described in paragraphs [0060] to [0062] of International Publication (WO2014-084364), is prepared using pure water and IPA (isopropanol) was washed. The pressure-filtered liquid crystal alignment agent was spin-coated on the substrate, heated on a hot plate at 80 ° C for 2 minutes, and heat-treated in a cleaning cycle at 230 ° C for 30 minutes to obtain a film thickness It is a 100 nm coated film substrate.

This coated film substrate was rubbed with a rayon cloth (YA-20R manufactured by Yoshikawa Chemical Industry) (roller diameter: 120 nm, number of rotations of the roller: 1000 rpm, moving speed: 20 mm / sec, and push-in length: 0.4 mm), and then was ultrasonicated in pure water After processing for 1 minute, the substrate was washed, air drops were removed, and then dried at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film. (1) Take the above two substrates as a set, print a sealant on the substrate, and attach the other substrate so that the alignment direction of the liquid crystal alignment film faces and the alignment direction becomes 0 °, and then harden the sealant. Next, the aforementioned liquid crystal composition (LC-I1) was injected by a reduced-pressure injection method, and the injection port was sealed to obtain an FFS-type liquid crystal display element. The obtained liquid crystal display element was heated at 110 degreeC for 1 hour, and left to stand at room temperature overnight, and then used for each evaluation.

<Photo-alignment treatment> (1) The liquid crystal alignment treatment agent (I-14) obtained in the example was subjected to pressure filtration using a thin-film filter having a pore diameter of 1 μm. Next, a glass substrate with an electrode substrate and a columnar spacer having a height of 4 μm, which is formed with an electrode substrate and an ITO film as described in paragraphs [0060] to [0062] of International Publication (WO2014-084364), is prepared using pure water and IPA (isopropanol) was washed. The pressure-filtered liquid crystal alignment agent was spin-coated on the substrate, and heated on a hot plate at 80 ° C. for 2 minutes, and then heat-treated at 230 ° C. for 30 minutes to obtain a film thickness. It is a 100 nm coated film substrate.

The coating film surface of this coating film substrate was irradiated with ultraviolet light 800 mJ / cm ^{2 with a} wavelength of 254 nm and a linearly polarized light having an extinction ratio of 26: 1 through a polarizing plate. This substrate was heat-treated at 230 ° C for 30 minutes using a thermal cycle type cleaning oven to obtain a substrate with a liquid crystal alignment film. The above two substrates are used as a set, and a sealant is printed on the substrate so that the other liquid crystal alignment film faces face each other and the alignment direction becomes 0 °, and then the other substrate is bonded, and then the sealant is hardened. Next, liquid crystal (LC-I2) was injected by a reduced-pressure injection method, and the injection port was sealed to obtain an FFS-type liquid crystal display element. Then, the obtained liquid crystal display element was heated at 110 ° C. for 1 hour, and left at room temperature overnight, and then used in each evaluation.

[Evaluation of liquid crystal display element] (Liquid crystal alignment) 液晶 The liquid crystal alignment of the liquid crystal display element was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to confirm whether the liquid crystal is aligned horizontally or vertically. Specifically, those who did not see any defect due to the liquid crystal due to flow were evaluated as good.评价 The evaluation results of the liquid crystal alignment of the liquid crystal display element are shown in Table 3.

(Adhesiveness of liquid crystal alignment film) The liquid crystal alignment treatment agents (V-1) to (V-6), (I-7) to (I-13) obtained in the examples, and the liquid crystal alignment treatment agent obtained in the comparative examples (R-V1) to (R-V2) are filtered under pressure using a membrane filter with a pore size of 1 μm. The aforementioned liquid crystal alignment treatment agent was coated on a glass substrate (length: 100 mm, width: 100 mm, thickness: 0.7 mm) with an ITO electrode, washed with pure water and IPA (isopropyl alcohol), 100 × 100 mm, and heated. The plate was heat-treated at 80 ° C for 2 minutes. In addition to Comparative Examples 3 and 7, a thermal cycle type cleaning oven was heat-treated at 120 ° C for 10 minutes. Comparative Examples 3 and 7 were heat-treated at 210 ° C for 10 minutes to make 2 pieces. ITO substrate with liquid crystal alignment film with a film thickness of 100 nm. On one of the substrates, a bead spacer of 6 μm was coated, and then a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of the other substrate so that the overlapping width of the substrates became 1 cm. These substrates. At this time, the amount of the sealant was adjusted so that the diameter of the sealant after bonding was 3 mm. After the two bonded substrates were fixed with a jig, they were thermally cured at 150 ° C. for 1 hour to produce a test sample substrate for this evaluation.

Next, the substrate of this test sample was fixed with a desktop precision universal testing machine (AGS-X 500N) (manufactured by Shimadzu Corporation), and the end portions of the upper and lower substrates were fixed, and then the upper portion of the substrate was pushed in to measure the stress during peeling ( N), that is, peel stress (N). Evaluation means that the larger the value of the peeling stress (N), the more excellent the sealant and the adhesion to the underlying substrate (Table 3 shows the value of the peeling stress (N)).

<Example 1> NEP (22.7g) and BCS (20.8g) were added to a polyamic acid solution (1) (7.43g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1, and the temperature was 50 ° C. Stir for 5 hours. Then, MA-M1 (0.56 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (V-1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-1), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed. In the following Examples 2 to 16 and Comparative Examples 1 to 8, the production of the liquid crystal display element and various evaluations were performed in the same manner. The results of the examples and comparative examples are shown in Table 3.

<Example 2> (1) NMP (27.3g) and BCS (25.5g) were added to a polyamic acid solution (2) (9.80g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2, and the temperature was 50 ° C. Stir for 5 hours. Then, G-M1 (0.74 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (V-2). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-2), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 3> A peeling test was performed using the liquid crystal alignment treatment agent obtained by the method of Example 2.

<Example 4> Polyimide powder (3) (2.33 g) obtained in Synthesis Example 3 was added with NMP (35.4 g) and BCS (24.2 g) and stirred at 70 ° C. for 24 hours to dissolve. Then, MA-M1 (0.23 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (V-3). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-3), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 5> 剥离 Using the liquid crystal alignment treatment agent (V-3) obtained by the method of Example 4, a peeling test was performed.

<Example 6> (1) NEP (32.8 g) and PB (18.2 g) were added to the polyfluorene imine powder (3) (1.86 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. Then, MA-M1 (0.09 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (V-4). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-4), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 7> γ To the polyfluorene imine powder (3) (1.65 g) obtained in Synthesis Example 3, γ-BL (6.40 g) and PGME (42.5 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, G-M1 (0.08 g) and K1 (0.08 g) were added to this solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (V-5). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-5), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 8> (1) To the polyfluorene imine powder (4) (2.55 g) obtained in Synthesis Example 4, NEP (34.0 g), BCS (12.4 g), and PB (14.6 g) were added, and the mixture was stirred at 70 ° C for 24 hours. Let it dissolve in hours. Then, MA-M1 (0.08 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (V-6). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-6), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 9> γ To the polyfluorene imine powder (3) (1.65 g) obtained in Synthesis Example 3, γ-BL (6.40 g) and PGME (42.5 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Then, MA-M1 (0.05 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (V-7). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-7), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 10> γ To the polyfluorene imine powder (3) (1.65 g) obtained in Synthesis Example 3, γ-BL (6.40 g) and PGME (42.5 g) were added, and the mixture was dissolved by stirring at 70 ° C for 24 hours. Then, MA-M1 (0.08 g) and K1 (0.08 g) were added to this solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (V-8). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-8), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 11> γ Poly-imide powder (3) (1.65 g) obtained in Synthesis Example 3 was added with γ-BL (6.40 g) and PGME (42.5 g) and stirred at 70 ° C for 24 hours to dissolve. Then, MA-M1 (0.08g) and G-M1 (0.08g) were added to the solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (V-9). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-9), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 12> Into the polyamic acid solution (12) (20.0g) of the resin solid content concentration of 10% by mass obtained in Synthesis Example 12, GBL (6.00g), DMI (6.00g), and EEP (8.00 g), and stirred at 50 ° C for 5 hours. Then, MA-M1 (0.60 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (I-10). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (I-10), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 13> GBInto a polyamic acid solution (13) (20.0g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 13, GBL (12.0g) and DEDE (8.00g) were added, and the temperature was 50 ° C. Stir for 5 hours. Then, G-M1 (0.60 g) was added to this solution, and the mixture was stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (I-11). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (I-11), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 14> (1) GBL (30.0 g) and DME (8.00 g) were added to the powder (14) (2.0 g) of the polyamidate obtained in Synthesis Example 14, and stirred at 50 ° C. for 5 hours. Then, MA-M1 (0.20 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (I-12). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (I-12), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

〈Example 15〉 LInto a polyamic acid solution (15) (20.0g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 15, GBL (12.0g) and DEME (8.00g) were added, and the temperature was 50 ° C. Stir for 5 hours. Then, G-M1 (0.20 g) was added to this solution and stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (I-13). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (I-13), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

〈Example 16〉 LInto the polyamic acid solution (16) (20.0g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 16, GBL (12.0g) and DEME (8.00g) were added, and the temperature was 50 ° C. Stir for 5 hours. Then, MA-M1 (0.10 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (I-14). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (I-14), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 17> GBInto a polyamic acid solution (17) (20.0 g) having a resin solid content concentration of 10% by mass obtained in Synthesis Example 17, GBL (16.0 g) and DPM (4.00 g) were added, and the temperature was 50 ° C. Stir for 5 hours. Then, G-M1 (0.10 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (I-15). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (I-15), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 18> to <Example 20> A composition as shown in Table 3 was used. As in Example 17, an adhesive compound and other adhesive compounds were added to obtain a liquid crystal alignment treatment agent (I-16). ~ (I-18). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agents (I-16) to (I-18), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 21> A liquid crystal alignment agent (V-19) was obtained in the same manner as in Example 7 except that K2 was used instead of K1. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-19), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 22> A liquid crystal alignment agent (V-20) was obtained in the same manner as in Example 10 except that K2 was used instead of K1. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (V-20), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Example 23> 3.00 g of the polyfluorene imine powder (18) obtained in Synthesis Example 18 was dissolved in GBL (34.50 g) and stirred at 50 ° C. for 20 hours to dissolve. Then, GBL was added to make the concentration of polyimide in this solution 6% by mass, and the mixture was stirred at 50 ° C for 20 hours. To the polyamic acid solution (19) (40.0 g) having a resin solid content concentration of 15% by mass obtained in Synthesis Example 19, NMP, GBL, and BCS were added to prepare polyamic acid to 6 mass% and NMP to 20% by mass, GBL by 59% by mass, and BCS by 15% by mass. 20 Mix 20 g of the polyfluorene imine solution prepared above and 80 g of the polyfluorinated acid dilute solution, stir at room temperature for 20 hours, and then add G-M1 (0.30 g) to obtain a liquid crystal alignment agent (T-20). The liquid crystal alignment treatment agent did not observe abnormalities such as turbidity or precipitation, and was confirmed to be a uniform solution. Using the obtained liquid crystal alignment agent (T-20), except that the alignment direction was 90 °, and bonding was performed, a liquid crystal display element and an adhesiveness evaluation substrate were obtained in the same manner as in Example 16, and then a liquid crystal display element was produced. Evaluation of liquid crystal alignment, evaluation of adhesion of liquid crystal alignment film.

<Example 24> A liquid crystal alignment treatment agent (T-22) was obtained in the same manner as in Example 23 except that MA-M1 was used instead of G-M1. The liquid crystal alignment treatment agent did not observe abnormalities such as turbidity or precipitation, and was confirmed to be a uniform solution. Using the obtained liquid crystal alignment agent (T-22), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Comparative Example 1> Into a polyamic acid solution (1) (7.43 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1, NEP (22.7 g) and BCS (20.8 g) were added, and the temperature was 50 ° C. After stirring for 5 hours, a liquid crystal alignment treatment agent (R-V1) was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (R-V1), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Comparative Example 2> Into a polyamic acid solution (1) (7.43 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1, NEP (22.7 g) and BCS (20.8 g) were added, and the temperature was 50 ° C. Stir for 5 hours. Then, K1 (0.18 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (R-V2). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (R-V2), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Comparative Example 3> The temperature of the thermal cycle type cleaning oven was set to 210 ° C and heat treatment was performed for 10 minutes. The same procedure as in Comparative Example 2 was used to produce a liquid crystal display device, evaluate the alignment of the liquid crystal, and adhere the liquid crystal alignment film. Evaluation.

<Comparative Example 4> A peeling test was performed using the liquid crystal alignment treatment agent obtained by the method of Comparative Example 1.

<Comparative Example 5> Into the polyamic acid solution (12) (20.0g) of the resin solid content concentration of 10% by mass obtained in Synthesis Example 12, GBL (6.00g), DMI (6.00g), and EEP (8.00 g) After stirring at 50 degreeC for 5 hours, the liquid-crystal aligning agent (R-I3) was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (R-I3), a peeling test was performed.

<Comparative Example 6> GBInto the polyamic acid solution (12) (20.0g) of the resin solid content concentration of 10% by mass obtained in Synthesis Example 12, GBL (6.00g), DMI (6.00g), and EEP (8.00 g), and stirred at 50 ° C for 5 hours. Then, K1 (0.20 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (R-I4). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (R-I4), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Comparative Example 7> The temperature of the thermal cycle type cleaning oven was set to 210 ° C and the heat treatment was performed for 10 minutes. The same procedure as in Comparative Example 6 was performed to produce a liquid crystal display element, evaluate the alignment of the liquid crystal, and adhere the liquid crystal alignment film. Evaluation.

<Comparative Example 8> GBInto the polyamic acid solution (12) (20.0g) of the resin solid content concentration of 10% by mass obtained in Synthesis Example 12, GBL (6.00g), DMI (6.00g), and EEP (8.00 g), and stirred at 50 ° C for 5 hours. Then, K1 (0.60 g) was added to this solution, and it stirred at 25 degreeC for 2 hours, and obtained the liquid-crystal aligning agent (R-I5). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (R-I5), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed. Moreover, the peeling test was performed about Examples 3, 5 and Comparative Example 4. The peel test was performed as follows.

<Comparative Example 9> A liquid crystal alignment agent (R-T6) was obtained in the same manner as in Example 23 except that G-M1 was not added.异常 No abnormality such as turbidity or precipitation was observed in this alignment treatment agent, and it was confirmed to be a uniform solution. Using the obtained liquid crystal alignment treatment agent (R-T6), production of a liquid crystal display element, evaluation of liquid crystal alignment, and evaluation of adhesion of a liquid crystal alignment film were performed.

<Peel test> (1) The liquid crystal alignment treatment agent () obtained in the example and the liquid crystal alignment treatment agent () obtained in the comparative example were subjected to pressure filtration using a membrane filter having a pore size of 1 μm. The aforementioned liquid crystal alignment treatment agent was coated on a 100 × 100mm PET film substrate (length: 100mm, width: 100mm, thickness: 50um) with an ITO electrode, and was heat-treated on a hot plate at 120 ° C. for 5 minutes, and then cut into 100 pieces. × 20mm, two ITO substrates with a liquid crystal alignment film with a film thickness of 100nm were fabricated.涂布 A 30 μm bead spacer was coated on one of the substrates, and a sealant (723K1 manufactured by Mitsui Chemicals) was printed on the liquid crystal alignment film of the other substrate, and the substrates were overlapped and bonded. At this time, the amount of the sealant was adjusted so that the area of the sealant after bonding was 50 × 10 mm.

After the two bonded substrates were fixed with a jig, they were irradiated with ultraviolet light at 3 J / cm ² , and then thermally cured at 120 ° C. for 1 hour to produce a test sample substrate for this evaluation. Then, using a desktop precision universal testing machine (AGS-X 500N) (manufactured by Shimadzu Corporation) for the substrate of this test sample, the end portions of the upper and lower substrates were fixed, and the stress (N / 25mm) was measured in the upward direction. , Which is the peel strength (N / 25mm). The evaluation is that the larger the value of the peeling stress (N / 25mm), the better the sealant and the adhesion to the underlying substrate (Table 3 shows the value of the peeling stress (N / 25mm)).

From the above results, it can be seen that the liquid crystal display element system using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has good liquid crystal alignment, and the adhesiveness of the liquid crystal alignment film is higher than that obtained from the liquid crystal alignment treatment agent of the comparative example. In the case of a liquid crystal alignment film, the result is higher adhesion. Specifically, the examples including the adhesive compound of the present invention are compared with the comparative examples not including the adhesive compound of the present invention, that is, a comparison between Example 1 and Comparative Example 1, and a comparison between Example 12 and Comparative Example. Comparison of 6 ~ 8. In addition, in comparison with a liquid crystal alignment film obtained by using a liquid crystal alignment treatment agent having a diamine having a vertical alignment (in the table, a side chain type diamine), the use of a diamine having a horizontal alignment (a main chain type The result is that the adhesion of the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of amine) is high. Specifically, the comparison between Example 1 and Example 12. In addition, when another adhesive compound is introduced into the liquid crystal alignment treatment agent of the present invention, it becomes a liquid crystal display element having more excellent adhesion with the liquid crystal alignment film. Specifically, the comparison between Example 6 and Example 7 and Example 10. [Industrial availability]

The liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention can be applied to display elements of various liquid crystal modes. In addition, these elements can also be used in liquid crystal displays for display purposes, and dimming windows or light shutters that control the transmission and blocking of light.

Claims (7)

A liquid crystal alignment agent, comprising: (A) selected from the group consisting of polyimide, polyamidic acid, polyamidate, polyorganosiloxane, polyester, polyamido, and having a polymerizable unsaturated bond A polymer of at least one group of polymers of monomers; (B) selected from compounds represented by the following formula [CL-1]; and compounds represented by the following formula [CL-2]; At least one kind of compound (in the formula [CL-1], r ¹ represents a hydrogen atom or a methyl group, r ² represents a linear or branched alkylene group having 2 to 20 carbon atoms, and an aliphatic group having 5 to 6 carbon atoms A divalent organic group formed by a ring, or a divalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms. These groups may be substituted with -CH ₂ -in the structure, r ³ represents a k-valent linear or branched aliphatic group having a carbon number of 2 to 20, a k-valent group formed of an aliphatic ring having a carbon number of 5 to 6, or an aliphatic ring having a carbon number of 5 to 6 k-valent aliphatic groups, these groups, -CH ₂ -in the structure may also be replaced by -O-, Z represents the following formula (1a) (wherein, r ⁴ represents a carbon number of 1 to 20) A chain or branched alkyl group, a monovalent group formed by an aliphatic ring having 5 to 6 carbon atoms, or an alkyl group containing 5 to 6 carbon atoms A monovalent aliphatic group of an aliphatic ring. These groups may be substituted with -CH ₂ -in the structure. -1 and * 2 indicate that either of them is a bond with a nitrogen atom. , The other is a divalent radical represented by a bond with r ³ ), k is a natural number of 2 to 9; in the formula [CL-2], R _CL1 is a hydrogen atom or a methyl group, R _CL2 and R _{CL3 is} independent of each other as a hydrogen atom, a straight or branched alkyl group having 1 to 20 carbon atoms or a straight or branched chain hydroxyalkyl group having 1 to 20 carbon atoms, and R _CL4 is a hydroxyl group or a straight chain of 1 to 20 carbon atoms Chain or branched hydroxyalkyl); and (C) organic solvents; . The liquid crystal alignment agent according to claim 1, wherein the component (A) is at least one selected from the group consisting of a polymer of polyimide, polyamic acid, polyamic acid ester, and a monomer having a polymerizable unsaturated bond. A polymer. The liquid crystal alignment agent according to claim 1 or 2, wherein the component (A) is a tetracarboxylic acid selected from the group consisting of at least one selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic diester, and tetracarboxylic diester dihalide. A polymer obtained by the reaction of an acid derivative and a diamine. The aforementioned tetracarboxylic acid derivative includes a polymer having at least one selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, a cyclohexane ring structure, and a benzene ring structure. Compound. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the component (C) has a component selected from the group consisting of the following formulae (Sol-1) and (Sol-2) (in the formula (Sol-1), Y _s ⁷ And Y _s ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, X _s ¹ is an oxygen atom or -COO-, X _s ² is a single bond or a carbonyl group, and R _s ⁷ is 2 to 4 carbon atoms Alkyl diyl, n _s ¹ is an integer of 1 to 3 (when n _s ¹ is 2 or 3, the plural R _s ⁷ may be the same or different) In the formula (Sol-2), Z _s ¹ is a carbon number of 1 to A divalent hydrocarbon group of 6, Y _s ⁹ and Y _s ¹⁰ are each independently at least one of a group consisting of a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, . A liquid crystal alignment film is formed using the liquid crystal alignment agent according to any one of claims 1 to 4. A method for manufacturing a liquid crystal alignment film, which comprises the following steps: 步骤 a step of applying a liquid crystal alignment agent according to any one of claims 1 to 4 on a substrate to form a coating film, and the coating film is not in contact with the liquid crystal layer A step of applying light to the coating film in a state of being in contact with the liquid crystal layer or in a state of being in contact with the liquid crystal layer. A liquid crystal display element includes: a liquid crystal alignment film according to claim 5; or a liquid crystal alignment film obtained by the manufacturing method according to claim 6.