JP6808963B2 - Resin composition and articles using it - Google Patents

Description

The present invention is a composition containing polyimide, which has excellent surface smoothness of the cured product, and has good stackability even when another compound is laminated on the surface to obtain a laminate. The present invention relates to a resin composition that can be suitably used for an alignment film or the like of a liquid crystal display element, and an article using the resin composition.

Due to its rigid molecular structure and strong intermolecular force, polyimide is widely used in the cutting-edge field as a material having extremely high heat resistance and mechanical and chemical strength among polymer materials.

Since polyimide itself lacks solvent solubility, a manufacturing method in which a solution containing polyamic acid, which is a precursor thereof, and an ester thereof is prepared, applied, and heat-treated at a high temperature to form a polyimide film. It is often used, and as applications, for example, an insulating base material for an electronic circuit material, a protective film for a semiconductor element, an alignment film in a liquid crystal display element, and the like are known.

Liquid crystal display elements are used in various measuring instruments such as clocks and calculators, automobile panels, word processors, electronic organizers, printers, computers, televisions, clocks, advertisement display boards and the like. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, and VA (vertucally aligned) type, which is characterized by vertical alignment using a TFT (thin film transistor). There are IPS (in-plane switching) type / FFS (fringe field switching) type, etc., which are characterized by horizontal orientation.

In these display methods, the VA type, the CSH (color super homeotropic) type, and the like are characterized by using a liquid crystal composition having a negative dielectric anisotropy (Δε). On the other hand, a liquid crystal composition having a positive Δε is used in a horizontally oriented display such as a TN type, an STN type, or an IPS type. In recent years, a drive method has also been reported in which a liquid crystal composition having a positive Δε is vertically oriented when no voltage is applied and displayed by applying an IPS type / FFS type electric field.

The liquid crystal display element used in all of these drive methods has a liquid crystal alignment film for orienting liquid crystal molecules according to various drive methods. In recent years, PSA (Polymer Sustained Alignment) technology, photoalignment technology, and the like have been proposed as new technologies for imparting pretilt angle characteristics to a coating film (liquid crystal alignment film) formed using a liquid crystal alignment agent. There is. In PSA technology, a polymerizable component that polymerizes by light irradiation is mixed in the liquid crystal layer of the liquid crystal cell, and the liquid crystal cell is irradiated with light in a state where the liquid crystal molecules are inclined by applying a voltage to obtain the polymerizable component. This is a technique for controlling the molecular orientation of liquid crystal molecules by polymerizing (see, for example, Patent Document 1). Further, the photoalignment technique is a technique for expressing a pretilt angle characteristic in a film by irradiating a polymer thin film having a photofunctional group such as a cinnamoyl group with light (see, for example, Patent Document 2).

As liquid crystal display elements are widely put into practical use in large-screen liquid crystal televisions and high-definition mobile applications (display parts of digital cameras and mobile phones), the size of the substrate used has become larger than before. The unevenness of the board step is getting bigger. Even in such a situation, it has been required to form a uniform liquid crystal alignment film on a large substrate or a step from the viewpoint of display characteristics.

However, conventionally known liquid crystal alignment agents cause defects such as pinholes and uneven film thickness in the coating film (alignment film) formed by using the liquid crystal alignment agent with a certain probability, and when manufacturing the liquid crystal alignment film. It has been pointed out that the product yield of the product is insufficient. The main cause of this defect is the poor solvent solubility of the above-mentioned polymer such as polyimide used as the material of the alignment film, and therefore, if the polymer concentration increases during solvent volatilization, the aggregation tends to occur. It is believed to be for.

In order to develop such smoothness of the coating film, it is considered effective to use an additive generally called a leveling agent, but the surface of the alignment film is directly different from the above-mentioned liquid crystal composition. Since they are in contact with each other, it is inappropriate to use a liquid crystal composition that affects the orientation behavior and the like.

When manufacturing a liquid crystal display element using a substrate having a formed liquid crystal alignment film, it is necessary to uniformly inject a liquid crystal composition corresponding to various driving methods into the liquid crystal cell. In particular, when a large substrate is used, the ODF (One Drop Filling) method is often applied. In this case, the liquid crystal composition must be uniformly spread on the substrate by the pressure from above. When an alignment film is formed using a liquid crystal alignment agent containing a leveling agent, the leveling agent is segregated on the surface thereof, so that it must be prevented from impairing the uniformity of "spreading" of the liquid crystal composition.

Japanese Unexamined Patent Publication No. 2015-099344 Japanese Unexamined Patent Publication No. 2009-037104

The problem to be solved by the present invention is a composition containing polyimide, which is excellent in surface smoothness of the cured product, and when another compound is laminated on the surface to obtain a laminate. A resin composition capable of giving a cured product that does not affect other compounds or is effectively suppressed, and an article using the resin composition, particularly a liquid crystal alignment film and a liquid crystal display element provided with the resin composition. To provide.

As a result of diligent studies to solve the above problems, the present inventor has excellent surface smoothness during the production of a cured product by using a fluorine-based resin having a specific pyrolytic group, and also heat-treats the fluorine atoms. Since the contained portion can be removed, the influence on the compound can be effectively suppressed even if another compound is laminated on the cured product. Therefore, for example, even when this cured product is used as a liquid crystal alignment film. The present invention has been completed by finding that the liquid crystal alignment performance does not deteriorate even after long-term use without impairing the electrical characteristics of the obtained liquid crystal display element.

That is, the present invention has the following structural formula (a1).
[In the formula (a1), R ¹ , R ² and R ³ are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. A plurality of fluoroalkylene ether chains are linked and the bonding site with Y ¹ is a carbon atom, and Y ¹ is an oxygen atom or a sulfur atom. ]
Fluorine-containing thermosetting resin (A) having a thermally decomposable group represented by
Polyimide (b-1) made from at least tetracarboxylic dianhydride and diamine, polyamic acid (b-2) which is a precursor of the polyimide (b-1), and ester of the polyamic acid (b-3). ), A resin composition characterized by containing one or more compounds (B) selected from the group consisting of), and a cured product thereof.

Further, the present invention provides a coating film containing a resin having a carboxyl group and a polyimide, which is excellent in surface smoothness, a method for producing the same, and a liquid crystal display element having the coating film as an alignment film.

The resin composition of the present invention can give a cured product having excellent surface smoothness, particularly a coating film. The composition can be coated on a substrate and then subjected to a certain heat treatment to remove fluorine atom-containing groups contained in the resin composition. For example, the obtained coating film is a liquid crystal alignment film. In this case, since the fluorine atom does not exist in the portion in direct contact with the liquid crystal composition, the characteristics of the liquid crystal display element are not affected, and the liquid crystal display element having excellent display quality can be obtained.

<Fluorine-containing thermosetting resin (A)>
The fluorine-containing thermosetting resin (A) used in the present invention has the following structural formula (a1).
[In the formula (a1), R ¹ , R ² and R ³ are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. A plurality of fluoroalkylene ether chains are linked and the bonding site with Y ¹ is a carbon atom, and Y ¹ is an oxygen atom or a sulfur atom. ]
It is characterized by having a pyrolytic group represented by.

R ¹ , R ² and R ^{3 in the} structural formula (a1) are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively, and when the resin has a plurality of the pyrolytic groups, they are the same. It may be a resin having a plurality of types having different structures.

Examples of the organic group having 1 to 18 carbon atoms in the structural formula (a1) include a linear or branched aliphatic hydrocarbon group which may have a carbon-carbon double bond, and a part of the fat. An alicyclic hydrocarbon group containing a ring structure, a hydrocarbon group having an aromatic ring which may have a substituent, or one or a plurality of these being linked by an ether bond, an ester bond, or the like. It may be. From the viewpoint of the thermal decomposition temperature of the fluorothermally decomposable resin (A) and the ease of production of the resin (A), it is preferable that the organic group has 1 to 9 carbon atoms, and specifically, methyl. Alkyl group such as group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, methoxy group, ethoxy group, propyloxy group, isopropyl An alkoxy group such as an oxy group and a butoxy group, a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, an anthryl group, and an organic group in which an alkyl group, an alkoxy group, a halogen atom or the like is substituted on these aromatic nuclei can be mentioned. it can. In particular, from the viewpoint of easy availability of raw materials, a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms is preferable, and a hydrogen atom is most preferable.

R ⁴ in the structural formula (a1) is a fluorinated alkyl group or a fluoroalkylene ether chain in which a plurality of fluorinated alkyl groups are linked via an oxygen atom, and a cured product having excellent surface smoothness can be easily produced. From the viewpoint that can be obtained, an alkyl fluorinated group having 1 to 6 carbon atoms directly bonded to a fluorine atom or an alkyl fluorinated group having 1 to 4 carbon atoms directly bonded to a fluorine atom is an oxygen atom. It is preferable that a plurality of ether chains are linked via. In the ether chain, a plurality of carbon atoms having the same number of carbon atoms in the alkyl fluorinated group may be linked, or different ones may be linked. If they are different, a so-called block It may be a copolymerization type or a random copolymerization type. The molecular weight of the ether chain is in the range of 200 to 5000 from the viewpoint of easy availability of raw materials, easy production of the fluorine-containing thermosetting resin (A), and easy acquisition of a cured product having excellent surface smoothness. It is preferably in the range of 300 to 2000, most preferably.

Further, as R ⁴ in the structural formula (a1), it is more preferable that it is a fluorinated alkyl group, and a fluorinated alkyl group having 4 to 6 carbon atoms to which a fluorine atom is directly bonded is particularly preferable. Most preferably, a fluorinated alkyl group having 6 carbon atoms to which the atoms are directly bonded.

Examples of the structural formula (a1) include those represented by the following.

In the structural formula (a1), it is considered that the resin containing the structure is heated to cause splitting between the carbonyloxy group and the carbon atom, and the portion containing the fluorine atom volatilizes to become a carboxyl group. As a result, the fluorine atom-containing portion is removed, and the cured product obtained by curing the composition of the present invention has almost no fluorine atoms on its surface and is laminated by applying another compound on the cured product. Even when an attempt is made, it is possible to obtain a good laminate without causing repelling or the like.

The structural formula (a1) in the fluorine-containing thermosetting resin (A) used in the present invention is necessary for exhibiting the smoothness of the cured product surface of the composition as described above, while the cured product surface. It is also necessary to be able to efficiently remove the fluorine atom-containing portion from the water. From this point of view, the content ratio of the partial structure represented by the structural formula (a1) in the fluorine-containing pyrolytic resin (A) used in the present invention is defined as the content ratio of fluorine atoms in the resin (A). It is possible to specify, and the content is preferably in the range of 1 to 35% by mass, particularly preferably in the range of 3 to 30% by mass, and preferably in the range of 5 to 25% by mass. Is most preferable. The fluorine atom content can be measured as an actually measured value by an ion chromatogram after combustion.

The fluorothermally decomposable resin (A) may be any resin having the structural unit represented by the structural formula (a1) as described above, and the overall structure thereof is not particularly limited. From the viewpoint of easy production, the following structural formula (a2) or (a3)

In [Formula ^{(a2), (a3),} X 1, X 2 is a direct bond or a divalent linking group, ^{respectively, R 51} is a hydrogen atom, a methyl group, group represented by the above general formula (a1) or It is a carboxyl group, R ⁵² is a group represented by the general formula (a1), and R ⁵³ is a group or a carboxyl group represented by the general formula (a1). ]
It is preferable that the resin has a structural unit represented by.

Examples of the divalent linking group represented by X ¹ and X ² in the structural formulas (a2) and (a3) include the following linking groups.

(M and n in the formula represent the number of repetitions and are integers from 0 to 6.)

Among these, it is preferable that the divalent linking group represented by X ^1, X ² from the viewpoint of industrial availability of raw material is of formula (X 2 ^-1), also a direct bond Is preferable. Further, in the formulas (a2) and (a3), it is more preferable that R ⁵¹ is a hydrogen atom or a methyl group.

Examples of the fluorine-containing thermosetting resin (A) include a resin having a carboxyl group in which a part or all of the carboxyl groups has the structural formula (a1). If some of the carboxyl groups are designed to be the structural formula (a1), the abundance ratio of the measurement by the acid number measurements and ^{1 H} or ^{13 C-NMR} in the resin, the carboxyl group and the structural formula (a1) It is possible to measure.

Further, the carboxyl group in the resin having a carboxyl group as described above may further include, for example, a structural portion having the following structural formula (a4) as long as the effect of the present invention is not impaired.

[In formula (a4), R ¹¹ , R ²¹ and R ³¹ are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively, and R ⁴¹ is an organic group having 1 to 18 carbon atoms, and R ³¹ and R are R. ⁴¹ may be bonded to each other to form a heterocycle having Y ¹¹ as a hetero atom, and Y ¹¹ is an oxygen atom or a sulfur atom. ]

The organic group having 1 to 18 carbon atoms in the structural formula (a4) is the same as that mentioned in the structural formula (a1), and is also the same as a preferable organic group. Among these, R ¹¹ , R ²¹ and R ³¹ are hydrogen atoms, respectively, R ⁴¹ is an organic group having 1 to 18 carbon atoms, and Y ¹¹ is an oxygen atom or a sulfur atom, which has a polarity with a carboxyl group. It is preferable because the difference between the above is large and it becomes easier to balance the surface smoothness of the obtained cured product with the ease of laminating when other compounds are laminated, and in particular, the following structural formula (a4-1).

It is more preferable that the resin has a structural portion represented by.

The number average molecular weight (Mn) of the fluorine-containing thermosetting resin (A) used in the present invention is the compound (B) described later, that is, the polyimide (b-1) made from at least tetracarboxylic acid dianhydride and diamine. , The range of 1,000 to 50,000 because the compatibility with the polyamic acid (b-2), which is a precursor of the polyimide (b-1), and the ester (b-3) of the polyamic acid is good. Is preferable, the range of 1,500 to 20,000 is more preferable, and the range of 2,000 to 8,000 is even more preferable. Similarly, the weight average molecular weight (Mw) is preferably in the range of 1,000 to 100,000, more preferably in the range of 5,000 to 70,000.

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted into polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions of GPC are as follows.

[GPC measurement conditions]
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HHR-H" (6.0 mm I.D. x 4 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-GEL GMHHR-N" (7.8 mm I.D. x 30 cm) + Tosoh Co., Ltd. "TSK-" GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: RI
Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent tetrahydrofuran (THF)
Flow velocity 1.0 ml / min Sample: A solution of 1.0 mass% tetrahydrofuran in terms of resin solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Data Analysis Version 4.30".

(Unidispersed polystyrene)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
"F-288" manufactured by Tosoh Corporation
"F-550" manufactured by Tosoh Corporation

In the fluorothermally decomposable resin (A) in the present invention, the bond between the oxygen atom and the carbon atom of the carbonyloxy group in the structural formula (a1) is broken by heating as described above. , The structural formula (a1) can be a carboxyl group, resulting in a resin (C) having a carboxyl group. Depending on the heat treatment conditions, it is possible to adjust the ratio at which the bond is broken and the fluorine atom-containing portion volatilizes, but in order to further exhibit the effects of the present invention, 1 in an atmosphere of 180 to 300 ° C. It is preferable to leave it for about 60 minutes, and the fluorine atom content in the resin can be reduced to 0.5% by mass or less by such heat treatment.

By the above-mentioned heat treatment, the fluorine-containing thermosetting resin (A) used in the present invention is, for example, the following structural formula (c1) or (c2).
[Formula (c1), in ^(c2), respectively X 1, ^{X 2} is a direct bond or a divalent linking ^{group, R 61} is a hydrogen atom, a methyl group, the following structural formulas (a1)
[In the formula (a1), R ¹ , R ² and R ³ are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. A plurality of fluoroalkylene ether chains linked together, the bonding site with Y ¹ is a carbon atom, and Y ¹ is an oxygen atom or a sulfur atom. ]
It is a group or a carboxyl group represented by, and R ⁶² and R ⁶³ are groups or carboxyl groups represented by the structural formula (a1), respectively. )
It is a resin having a carboxyl group having a structural unit represented by (however, the fluorine atom content in the resin having a carboxyl group is 0.5% by mass or less).

The fluorine-containing thermosetting resin (A) used in the present invention can be efficiently produced, for example, by the following method.
Production method 1: A polymerizable monomer (α) having a carboxyl group and the following general formula (1)

[In formula (1), R ¹ , R ² and R ³ are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. It is a plurality of linked fluoroalkylene ether chains and the bonding site with Y ¹ is a carbon atom, and Y ¹ is an oxygen atom or a sulfur atom. ]
A method in which a vinyl ether compound represented by (1) is reacted with a polymerizable monomer having a blocked carboxyl group, and then the polymerizable monomer is polymerized.

Production method 2: A method of reacting a polymer obtained by using a polymerizable monomer (α) having a carboxyl group with a vinyl ether compound represented by the general formula (1).

The fluorine-containing thermosetting resin obtained by the above-mentioned production method 1 has a blocked carboxyl group which is a reaction product of the polymerizable monomer (α) and the vinyl ether compound represented by the general formula (1). It is a resin having a polymerizable monomer as a constituent element. Further, the fluorinated degradable resin obtained by the production method 2 contains, that is, a polymer using the polymerizable monomer (α) as a raw material and a vinyl ether compound represented by the general formula (1) as constituent elements. It is a resin to be used.

Examples of the polymerizable monomer (α) having a carboxyl group include (meth) acrylic acid, itaconic acid, mesaconic acid, maleic acid, phthalic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. 2- (Meta) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinate Preferred examples thereof include acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid and the like. Among them, (meth) acrylic acid is preferable, and methacrylic acid is more preferable because it is inexpensive and easy to handle.

In the present invention, "(meth) acrylate" refers to one or both of methacrylate and acrylate, and "(meth) acryloyl group" refers to one or both of a methacryloyl group and an acryloyl group, and "(meth) acrylate". ) Acrylic acid ”refers to one or both of methacrylic acid and acrylic acid.

Examples of the vinyl ether compound represented by the general formula (1) include 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-vinyl. Examples thereof include oxyoctane, 3,3,4,4,5,5,6,6,6-nonafluoro-1-vinyloxyhexane. Above all, from the viewpoint of good reactivity with the polymerizable monomer (α), 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro- 1-Vinyloxyoctane is preferred.

When a polymerizable monomer having a blocked carboxyl group is obtained in the production method 1 and then the polymerizable monomer is polymerized, or in the production method 2, the polymerizable monomer (α) having a carboxyl group When the polymer obtained by using the above is obtained, a polymerizable monomer other than the polymerizable monomer (α) is obtained as long as the effects of the present invention are not impaired for the purpose of imparting various functions such as surface activity. A fluorothermally decomposable resin can also be obtained in combination with (γ). Examples of the polymerizable monomer (γ) include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylicamides, allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates, and dialkyl esters of fumaric acid. Classes, monoalkyl esters, radically polymerizable monomers having an oxyalkylene chain, and further, when it is necessary to particularly improve the surface smoothness of the obtained cured product, and after heat treatment. When the fluorine atom content may be slightly higher, a radically polymerizable monomer having an alkyl fluorinated group or a poly (perfluoroalkylene ether) chain may be used in combination.

Examples of the acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, chlorethyl acrylate, 2-hydroxyethyl acrylate, trimethyl propane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, and tetrahydro. Examples include full frill acrylate.

Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chlorethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, flufuryl methacrylate, and tetrahydro. Examples include full frill methacrylate.

Examples of the acrylamides include acrylamide, N-alkylacrylamide (alkyl groups having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group) and N, N-dialkylacrylamide (as alkyl groups). Has 1 to 3 carbon atoms), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

Examples of the methacrylamides include methacrylamide, N-alkylmethacrylamide (alkyl groups having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group) and N, N-dialkylmethacrylamide (alkyl groups). Examples of the alkyl group include those having 1 to 3 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide and the like.

Examples of the allyl compound include allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.). Examples thereof include allyloxyethanol.

Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, and 2-ethylbutyl vinyl ether. Hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc. Vinyl esters: vinyl bitilate, vinyl isobutylate, vinyl trimethyl acetate, vinyl diethyl acetate , Vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinylmethoxyacetate, vinylbutoxyacetate, vinyllactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Examples of the dialkyl itaconic acid include dimethyl itaconic acid, diethyl itaconic acid, and dibutyl itaconic acid. Examples of the dialkyl esters or monoalkyl esters of fumaric acid include dibutyl fumarate and the like, as well as crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleironitrile and styrene.

Examples of the radically polymerizable monomer having an oxyalkylene chain include (poly) propylene glycol mono (meth) acrylate, (poly) tetramethylene glycol (meth) acrylate, and (poly) (ethylene glycol / propylene glycol) mono. (Meta) acrylate, (Poly) ethylene glycol / (Poly) propylene glycol Mono (meth) acrylate, (Poly) (Ethethylene glycol / Tetramethylene glycol) Mono (meth) acrylate, (Poly) Ethylene glycol / (Poly) Tetramethylene Glycol mono (meth) acrylate, (poly) (propylene glycol / tetramethylene glycol) mono (meth) acrylate, (poly) propylene glycol / polytetramethylene glycol mono (meth) acrylate, (poly) (propylene glycol / butylene glycol) Mono (meth) acrylate, (poly) propylene glycol / (poly) butylene glycol Mono (meth) acrylate, (poly) (ethylene glycol / butylene glycol) mono (meth) acrylate, (poly) ethylene glycol / (poly) butylene glycol Mono (meth) acrylate, (poly) (tetraethylene glycol / butylene glycol) mono (meth) acrylate, (poly) tetraethylene glycol / (poly) butylene glycol mono (meth) acrylate, (poly) butylene glycol mono (meth) Acrylate, (poly) (ethylene glycol / trimethylene glycol) mono (meth) acrylate, (poly) ethylene glycol / (poly) trimethylene glycol mono (meth) acrylate, (poly) (propylene glycol / trimethylene glycol) mono ( Meta) acrylate, (poly) propylene glycol / (poly) trimethylene glycol mono (meth) acrylate, (poly) (trimethylene glycol / tetramethylene glycol) mono (meth) acrylate, (poly) trimethylene glycol / (poly) Examples thereof include tetramethylene glycol mono (meth) acrylate, (poly) (butylene glycol / trimethylene glycol) mono (meth) acrylate, and (poly) butylene glycol / (poly) trimethylene glycol mono (meth) acrylate.

The above-mentioned "poly (ethylene glycol / propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol / polypropylene glycol" is a block copolymer of ethylene glycol and propylene glycol. Means, and so on. "(Poly) propylene glycol" means either propylene glycol or polypropylene glycol, and so on. The molecular weight of the oxyalkylene chain in the radically polymerizable monomer having an oxyalkylene chain is preferably in the range of 200 to 2500 from the viewpoint of excellent compatibility with other resins constituting the composition. ..

Examples of commercially available products of the radically polymerizable monomer having an oxyalkylene chain include "NK ester AMP-10G", "NK ester AMP-20G" and "NK ester AMP-60G" manufactured by Shin Nakamura Chemical Industry Co., Ltd. , "Blemmer PME-100", "Blemmer PME-200", "Blemmer PME-400", "Blemmer PME-4000", "Blemmer PP-1000", "Blemmer PP-500", manufactured by Nichiyu Co., Ltd. "Blemmer PP-800", "Blemmer 70PEP-350B", "Blemmer 55PET-800", "Blemmer 50 POEP-800B", "Blemmer 10PPB-500B", "Blemmer NKH-5050", "Blemmer AP-400" Examples thereof include "SR604" manufactured by the company.

Examples of the radically polymerizable monomer having a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain include those represented by the following general formula (γ1).

[In the above general formula (γ1), R represents a hydrogen atom or a methyl group, L represents any one group of the following formulas (L-1) to (L-10), and Rf represents the following formula (Rf). -1) Represents any one group of (Rf-7). ]

N in the above formulas (Rf-1) to (Rf-4) is, for example, an integer of 1 to 6, preferably an integer of 4 to 6. In the above formula (Rf-5), m is, for example, an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23. Preferably, m is an integer of 1-5, n is an integer of 0-4, and the sum of m and n is 4-5. In the above equation (Rf-6), m is, for example, an integer of 1 to 6, n is an integer of 1 to 3, l is an integer of 1 to 20, and p is an integer of 0 to 5. Moreover, the total product of m, p and n and l is 2 to 71. Preferably, m is an integer of 1-3, n is an integer of 1-3, l is an integer of 1-6, p is an integer of 0-2, and m, p and n. The sum of the products of and l is 2-23.

Specific examples of the radically polymerizable monomer having a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain include the following polymerizable monomers (γ1-1) to (γ1-15). It can be exemplified.

N in the formulas (γ1-1) to (γ1-11) is, for example, 0 to 5. Further, n in (γ1-12) to (γ1-15) is, for example, 0 to 20.

The radically polymerizable monomer (γ) can be used alone or in combination of two or more. Among these, it is preferable to use a radically polymerizable monomer having an oxyalkylene chain in combination, particularly from the viewpoint of good compatibility with the compound (B) or other components in the resin composition to be used in combination. The number of carbon atoms in the repeating unit in the oxyalkylene chain is preferably 2 to 4, and any oxyalkylene chain of either a homopolymer type or a copolymer type is preferable. ..

Further, when the fluorine-containing thermosetting resin (A) used in the present invention is obtained, a vinyl ether compound other than the compound represented by the general formula (1) is referred to as a vinyl ether compound represented by the general formula (1). It can also be used in combination as long as the effects of the present invention are not impaired. Examples of such vinyl ether compounds include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; Aliphatic vinyl thioether compounds; 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy- 2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, 3,4-dihydro-2H-pyran-2- Cyclic vinyl ether compounds such as sodium carboxylate; corresponding cyclic vinyl thioether compounds and the like can be mentioned.

In the production method 1, the polymerizable monomer (α) having a carboxyl group is reacted with the vinyl ether compound represented by the general formula (1). As a result, a polymerizable monomer having a blocked carboxyl group is obtained. Examples of the reaction conditions include conditions for heating to about 20 to 100 ° C. in the presence of an acid catalyst. Then, when the polymerizable monomer having a blocked carboxyl group is polymerized, it can be carried out under the same conditions as the conditions for polymerizing the polymerizable monomer (α) described later.

In the above-mentioned production method 2, the method for obtaining the polymer using the polymerizable monomer (α) is not particularly limited, but for example, the polymerizable monomer (α) and other methods used in combination as necessary are used. Examples thereof include a method of polymerizing a radically polymerizable monomer (γ) in an organic solvent using a radical polymerization initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers and hydrocarbons are preferable, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate and butyl acetate, Examples thereof include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility and polymerizable property. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Further, if necessary, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethyl thioglyco-lic acid, and octyl thioglyco-lic acid can be used.

In the production method 2, the polymer and the vinyl ether compound represented by the general formula (1) can be reacted by heating to about 20 to 100 ° C. in the presence of an acid catalyst, for example. By this reaction, the carboxyl group of the polymer is blocked, and a polymer having the structure represented by the structural formula (a1) is obtained.

In the present invention, the above-mentioned fluorine-containing thermosetting resin (A) is used to exhibit surface smoothness when a cured product is obtained, and another compound is laminated on the surface of the cured product. When the body is constructed, the laminated state can be made good. From this point of view, in the present invention, the fluorothermally decomposable resin (A) is a polyimide (b-1) having good heat resistance and made of at least tetracarboxylic dianhydride and diamine as raw materials. It is preferable to use in combination with one or more compounds (B) selected from the group consisting of polyamic acid (b-2) which is a precursor of polyimide (b-1) and ester (b-3) of the polyamic acid. I found that.

The polyimide (b-1) is made of at least tetracarboxylic acid dihydrate and diamine as raw materials, and may be made by using other raw materials in combination as needed, and is made of polyamide-imide. There may be. Further, a part of the imide structure may be isoimide.

<Tetracarboxylic dianhydride>
As the acid anhydride used for the synthesis of polyimide, tetracarboxylic dianhydride is suitable. Examples of the tetracarboxylic dianhydride include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,2-dimethyl-1,2,3,4-. Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,2,3,4-tetramethyl 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4 , 5-Cyclohexanetetracarboxylic dianhydride, 3,3', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 2,3,4,5 − Tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan- 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan- 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan- 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c]- Fran-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -Fran-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] -Fran-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -Fran-1,3-dione, Bicyclo [2,2,2] -Octo-7-ene-2,3,5,6 Tet Lacarboxylic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3-oxabisik mouth [3,2,1] octane-2,4-dione- 6-Spiro-3'-( tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride Compounds 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5,3,1,0 ^2,6 ] undecane- Aliphatic and alicyclic tetrapower rubonic acid dianhydrides such as 3,5,8,10-tetraone and compounds represented by the following formulas (I) and (II);

[In formulas (I) and (II), R ⁷ and R ⁹ represent divalent organic groups having an aromatic ring, R ⁸ and R ¹⁰ , represent hydrogen atoms or alkyl groups, and a plurality of R ⁸ and R are present. ¹⁰ may be the same or different from each other. ],

Pyromellitic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic hydride, 3,3', 4,4'-biphenylsulfonetetracarboxylic hydride, 1,4,5,5 8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-Dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic acid dianhydride, 1,2,3,4-frantetracarboxylic acid dianhydride , 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (4,4'-bis (3,4-dicarboxyphenoxy) 3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'-perfluoroisopropyridene diphthalic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride Anhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m- Phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene Glycol-bis (anhydro trimellitate), propylene glycol-bis (anhydrotrimelite), 1,4-butanediol-bis (anhydrotrimerite), 1,6-hexanediol-bis (anhydro) (Trimeritate), 1,8-octanediol-bis (anhydrotrimerite), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimerite), the following formulas (2) to ( Aromatic tetracarboxylic dianhydrides such as the compound represented by 5) can be mentioned. These may be used alone or in combination of two or more. The benzene ring of the aromatic dianhydride may be substituted with one or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group).

Of these, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-) 2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5- (tetrahydro-) 2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl-5-( Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2,2,2] -oct-7-ene-2,3,5 6-Tetetracarboxylic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4 -Dione-6-Spiro-3'-(tetrakidian-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2- Dicarboxylic acid dianhydride, 3,5,6-tricarboxy-2-carboxymethyl dianbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6} ] Undecane-3,5,8,10-tetraone, pyromellitic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl Sulfontetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, the following formulas (6) to (9). When the obtained composition is used as a liquid crystal aligning agent, good liquid crystal orientation can be exhibited by using the compound represented by).

Particularly preferred are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5. -(Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5 -(Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [3,3,0] octane-2,4,6,8-tetra Carboxylic acid dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3'-( tetrahydrofuran-2', 5'-dione), 5- (2,5) −Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6- Dianoxide, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride and represented by formula (6). Compounds can be mentioned.

<Diamine>
Examples of the diamine include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfide, and 4,4'-diaminodiphenyl. Sulfur, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindan, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethyl Indan, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone , 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino) Phenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-amino) Phenyl) fluorene, bis (4-amino-2-chlorophenyl) methane, 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino -5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropi) Liden) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'-bis (trifluoromethyl) biphenyl , 4,4'-Diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -ok Aromatic diamines such as tafluorobiphenyl;

1,1-Methylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene cyclopentadienylide diamine, hexahydro-4,7-meth Noin mite range diamine, tricyclo [6.2.1.0 ^2,7] - undecylenate range diamine, 4,4'-methylenebis (cyclohexylamine ), 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, etc., aliphatic and alicyclic diamines;

2,3-Diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4 -Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3 , 5-Triazine, 2,4-diamino-6-methoxy-1,3,5-Triazine, 2,4-diamino-6-phenyl-1,3,5-Triazine, 2,4-diamino-6-methyl −S-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine , 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 3,8-diamino-6-phenylphenanthridin, 1,4-diaminopiperazin, 3, 6-Diaminoacridine, N, N'-bis (4-aminophenyl) phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N -Phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethyl-benzidine, and the following formula Diamines having two primary amino groups and nitrogen atoms other than the primary amino groups in the molecule, such as the compounds represented by each of (III) to (IV);

In formula (III), R ¹¹ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ¹ represents a divalent organic group. )

(In formula (IV), R ¹² represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ² represents a divalent organic group. A plurality of X ^2s may be the same or different.)

Mono-substituted phenylenediamines represented by the following formula (V)

(In formula (V), R ¹³ represents a divalent linking group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH- and -CO-, and R ¹⁴ is a steroid. A monovalent organic group having a group selected from a skeleton, a trifluoromethyl group and a fluoro group, or an alkyl group having 6 to 30 carbon atoms is shown. Here, the steroid skeleton is a skeleton composed of a cyclopentano-perhydrophenanthrene nucleus or a skeleton. A skeleton in which one or more of the carbon-carbon bonds are double bonds.)

Diaminoorganosiloxane represented by the following formula (VI);

(In the formula (VI), R ¹⁵ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ^15s present may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 3. It is an integer of 1 to 20.)

Further, compounds represented by the following formulas (10) to (14) can be mentioned.

[In equation (13), y is an integer of 2 to 12, and in equation (14), z is an integer of 1 to 5. ]

These diamines can be used alone or in combination of two or more. The benzene ring of the aromatic diamine may be substituted with one or more alkyl groups having 1 to 4 carbon atoms (preferably methyl groups).

Of these, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminobenzanilide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4 , 4'-Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4) -Aminophenyl) Hexafluoropropane, 4,4'-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene , 4,4'-bis (4-aminophenoxy) biphenyl, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, 2,6-diaminopyridine , 3,4-Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole , N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, the above formula Among the compounds represented by (III), the compound represented by the following formula (15), the compound represented by the above formula (IV), the compound represented by the following formula (16), and the above formula (V). Among the compounds represented, dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diamino Benzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, compounds represented by the following formulas (17) to (28), and the above formula (VI). ), 1,3-Bis (3-aminopropyl) -tetramethyldisiloxane is preferable.

<Synthesis of polyamic acid (b-2)>
A polyamic acid (b-2) can be obtained by reacting the above-mentioned tetracarboxylic acid dihydrate with a diamine. As for the ratio of tetracarboxylic acid dianhydride and diamine used in the polyamic acid synthesis reaction, the acid anhydride group of tetracarboxylic acid dianhydride is 0. To 1 equivalent of the amino group contained in the diamine. A ratio of 5 to 2 equivalents is preferable, and a ratio of 0.7 to 1.2 equivalents is more preferable.

The polyamic acid synthesis reaction is preferably carried out in an organic solvent under temperature conditions of preferably -20 to 150 ° C., more preferably 0 to 100 ° C. The reaction time is preferably 2 to 24 hours, more preferably 2 to 12 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid, but is N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide. , Gamma-butyrolactone, tetramethylurea, hexamethylphosphortriamide and other aproton polar solvents; phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol are preferred. The amount of the organic solvent used is preferably such that the total amount of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by mass with respect to the total amount of the reaction solution.

Further, other organic solvents may be used in combination as long as there is no problem in solubility. Examples of other organic solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate and acetone. , Methyl ethyl ketone, Methyl isobutyl ketone, Cyclohexanone, Methyl acetate, Ethyl acetate, Butyl acetate, Methyl methoxypropionate, Ethyl ethoxypropionate, Diethyl oxalate, Diethyl malonate, Diethyl ether, Ethylene glycol Methyl ether, Ethylene glycol Ethylene ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl 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, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene , Xylene, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether.

The proportion of the other organic solvent used is preferably 80% by mass or less, more preferably 50% by mass or less, and further 40% by mass or less, based on the total of the above-mentioned organic solvent and the other organic solvent. It is preferable to have.

As described above, a reaction solution obtained by dissolving a polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the resin composition, the polyamic acid contained in the reaction solution may be isolated and then used for the preparation of the resin composition, or the isolated polyamic acid may be purified. After that, it may be used for the preparation of the resin composition. The polyamic acid can be isolated by pouring the above reaction solution into a large amount of a poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling off the reaction solution under reduced pressure with an evaporator. it can. Further, the polyamic acid can be purified by dissolving the polyamic acid in an organic solvent again and then precipitating it in a poor solvent, or by performing a step of distilling off under reduced pressure with an evaporator once or several times.

<Synthesis of polyimide>
The polyimide (b-1) can be synthesized by dehydrating and ring-closing the polyamic acid (b-2) obtained as described above. At this time, the entire amic acid structure may be dehydrated and ring-closed to completely imidize, or only a part of the amic acid structure may be dehydrated and ring-closed to form a partially imidized product in which the amic acid structure and the imide structure coexist. May be good. The imidization ratio of the polyimide is preferably 40% or more, more preferably 80% or more. Here, the "imidization rate" refers to a numerical value representing the ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures in polyimide as a percentage. At this time, a part of the imide ring may be an isoimide ring.

The dehydration ring closure reaction of a polyamic acid is carried out by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and heating as necessary. It can be done by the method.

The reaction temperature in the method of heating the polyamic acid of (i) above is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. If the reaction temperature is less than 50 ° C., the dehydration ring closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C., the molecular weight of the obtained polyimide may decrease. The reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.

On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the above-mentioned solution of polyamic acid (ii), an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can be done. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per 1 mol of the polyamic acid structural unit. Further, as the dehydration ring closure catalyst, for example, a tertiary amine such as pyridine, collagen, lutidine, triethylamine or the like can be used. However, it is not limited to these. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring closure reaction include organic solvents exemplified as those used in the synthesis of polyamic acids. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C., more preferably 10 to 150 ° C., and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.

The polyimide obtained in the above method (i) may be used as it is for the preparation of the resin composition, or the obtained polyimide may be purified and then used for the preparation of the resin composition. On the other hand, in the above method (ii), a reaction solution containing polyimide can be obtained. This reaction solution may be used as it is for the preparation of the resin composition, or may be used for the preparation of the resin composition after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, and the polyimide is isolated. The resin composition may be prepared in the above, or the isolated polyimide may be purified and then used for the preparation of the resin composition. In order to remove the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, a method such as solvent substitution can be applied. Isolation and purification of polyimide can be carried out by performing the same operation as described above as a method for isolating and purifying polyamic acid.

<Terminal-modified polymer>
The polyamic acid and the polyimide may be end-modified polymers having a controlled molecular weight, respectively. Such a terminal-modified polymer can be synthesized by adding an appropriate molecular weight modifier such as an acid monoanhydride, a monoamine compound, or a monoisocyanate compound to the reaction system when synthesizing a polyamic acid. .. Here, examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic acid anhydride, n-dodecylsuccinic acid anhydride, and n-tetradecylsuccinic acid anhydride. , N-Hexadecylsuccinic anhydride and the like. Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n. -Dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine and the like can be mentioned. .. Examples of the monoisocyanate compound include phenylisocyanate and naphthylisocyanate.

The ratio of the molecular weight modifier used is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total amount of the tetracarboxylic dianhydride and the diamine used in synthesizing the polyamic acid. is there.

<Polyamic acid ester (b-3)>
The polyamic acid ester (b-3) is, for example, (i) a method of reacting the polyamic acid obtained by the above synthesis reaction with an esterifying agent, (ii) reacting a tetracarboxylic acid diester with a diamine. It can be obtained by a method, (iii) a method of reacting a tetracarboxylic acid diester dihalide with a diamine, or the like.

Examples of the esterifying agent used in the method (i) include hydroxyl group-containing compounds, acetal-based compounds, halides, and epoxy group-containing compounds. Specific examples of these include, for example, alcohols such as methanol, ethanol and propanol, and phenols such as phenol and cresol as hydroxyl group-containing compounds; for example, N, N-dimethylformamide diethyl acetal, N, as acetal compounds. N-diethylformamide diethyl acetal and the like; as halides such as methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like; containing epoxy groups. Examples of the compound include propylene oxide and the like.

The tetracarboxylic dianester used in the method (ii) can be obtained by a method of reacting a tetracarboxylic dianhydride with alcohols to open a ring, a method of esterifying a tetracarboxylic acid, or the like. Further, the tetracarboxylic acid diester dihalide used in the method (iii) can be obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate halogenating agent such as thionyl chloride.

Examples of the diamine used in the methods (ii) and (iii) include compounds exemplified as diamines used in the synthesis of the polyamic acid (b-2). The polyamic acid ester (b-3) may have only an amic acid ester structure, or may be a partial esterified product in which the amic acid structure and the amic acid ester structure coexist.

The resin composition of the present invention comprises the above-mentioned fluorothermally decomposable resin (A), a polyimide (b-1) made from at least tetracarboxylic dianhydride and diamine, and the above-mentioned polyimide (b-1). Any compound (B) containing one or more compounds (B) selected from the group consisting of the polyimide polyamic acid (b-2) as a precursor and the ester (b-3) of the polyamic acid may be contained, and the application thereof is particularly high. Although not limited, the surface smoothness is particularly excellent in the case of forming a thin film, the heat treatment step after forming the coating film is indispensable, and the process causes thermal decomposition containing fluorine atoms from the surface of the coating film. As a result of considering the feature that the sex group is removed, the alignment film in the liquid crystal display element is a field in which it has been difficult to use a leveling agent containing a fluorine atom, although it is a thin film that requires surface smoothness. It can be suitably used as a resin composition (liquid crystal aligning agent) for forming. In particular, since the surface of the obtained coating film contains almost no fluorine atoms, even if the surface and the liquid crystal composition come into direct contact with each other, there is no effect on the liquid crystal composition or it is effectively suppressed. The point obtained is also one of the reasons why it is suitable as a liquid crystal aligning agent.

In the resin composition of the present invention, the blending ratio of the above-mentioned fluorine-containing thermosetting resin (A) can be appropriately set according to the desired performance and application, and is not particularly limited, but is a general surface. From the viewpoint that a cured product having smoothness can be easily obtained, the fluorothermosetting resin (A) is usually used in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the solid content in the resin composition. It is preferably used in the range of 0.03 to 8 parts by mass, and particularly preferably in the range of 0.05 to 5 parts by mass.

<Liquid crystal alignment agent>
When a resin composition is used as the liquid crystal aligning agent, the compound (B) made of a general tetracarboxylic acid dianhydride and diamine as raw materials is a cloth made of fibers such as nylon, rayon, and cotton at the time of forming the alignment film. By including a so-called rubbing treatment step of rubbing the coating film in a certain direction with a roll wrapped with a polyimide film, the polyimide film is a resin after thermal decomposition of the fluorothermally decomposable resin (A) in the film, that is, the above-mentioned. The polyimide molecular chain is eccentrically oriented in the plane of the film, or the side chain of the polyimide is eccentrically oriented outside the plane of the film, which contains the resin (C) having a carboxyl group of. By doing so, it is possible to impart the property of controlling the orientation of the liquid crystal molecules.

Alternatively, if the resin composition is a resin composition using the compound (B) made from a diamine having a vertically oriented functional group, the obtained coating film is a vertically oriented alignment film, specifically, a polyimide film. Therefore, the film contains the heat-decomposed resin (A) of the fluorine-containing thermally decomposable resin (A), that is, the resin (C) having the above-mentioned carboxyl group, and the liquid crystal molecules can be vertically oriented on the film surface. It becomes an alignment film with characteristics.

The diamine having a vertically oriented functional group may be any diamine having a vertical functional group, and among them, those formed by diamines represented by the following formulas (29) to (31) are preferable. is there. These may be used alone or in combination of two or more.

[In the formula, X is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S- or an arylene group, and R ⁴ has 10 carbon atoms. It is a monovalent organic group having an alkyl group of ~ 20 and an alicyclic skeleton having 4 to 40 carbon atoms or a monovalent organic group having a fluorine atom having 6 to 20 carbon atoms. R ⁵ is a divalent organic group having an alicyclic skeleton having 4 to 40 carbon atoms. In formula (31), A ¹ , A ² and A ³ are independently 1,4-cyclohexylene or 1,4-phenylene; A ⁴ is 1,4-cyclohexylene, 1,4-. Phenylene or single bond; B ¹ , B ² and B ³ are independent single bonds or 1,2-ethylene, respectively; R ⁶ is an alkyl having 1 to 20 carbon atoms in this alkyl. One −CH ₂₋ may be replaced by −O−. ]

In the above formula (29), the alkyl group of 10 to 20 carbon atoms represented by ^{R 4,} for example, n- decyl group, n- dodecyl group, n- pentadecyl, n- hexadecyl group, n- octadecyl , N-eikosyl group and the like.

Examples of the organic group having an alicyclic skeleton having 4 to 40 carbon atoms represented by R ⁴ in the above formula (29) and R ⁵ in the above formula (30) include cyclobutane, cyclopentane, cyclohexane and cyclodecane. Such as a group having an alicyclic skeleton derived from cycloalkane; a group having a steroid skeleton such as cholesterol and cholestanol; a group having an alicyclic skeleton such as norbornene and adamantan. Among these, a group having a steroid skeleton is particularly preferable. The organic group having the alicyclic skeleton may be a group substituted with a halogen atom, preferably a fluorine atom, a fluoroalkyl group, and preferably a trifluoromethyl group.

Furthermore, the group having a fluorine atom having 6 to 20 carbon atoms represented by ^{R 4} in the formula (29), for example, n- hexyl, n- octyl group, a carbon number of 6 or more, such as n- decyl Linear alkyl group; Alicyclic hydrocarbon group having 6 or more carbon atoms such as cyclohexyl group and cyclooctyl group; Hydrogen in organic group such as aromatic hydrocarbon group having 6 or more carbon atoms such as phenyl group and biphenyl group Examples thereof include a group in which a part or all of an atom is replaced with a fluoroalkyl group such as a fluorine atom or a trifluoromethyl group.

Further, X in the above formula (29) and the above formula (30) is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S- or an arylene group. Examples of the arylene group include a phenylene group, a trilene group, a biphenylene group, and a naphthylene group. Of these, the groups represented by -O-, -COO-, and -OCO- are particularly preferable.

Specific examples of the diamine having a group represented by the above formula (29) include dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2, 4-Diaminobenzene, a compound represented by the following formula, can be mentioned as preferable.

Further, as a specific example of the diamine having a group represented by the above formula (30), the diamine represented by each of the following formulas can be mentioned as preferable.

In the above formula (31), R ⁶ is arbitrarily selected from alkyl having 1 to 20 carbon atoms, and may be linear or branched. Also, one −CH ₂₋ may be replaced by −O−. Specific examples are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecil, eicocil, isopropyl, isobutyl, sec-. Butyl, t-butyl, isopentyl, neopentyl, t-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, isohexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl , 4-Ethylpentyl, 2,4-dimethylhexyl, 2,3,5-triethylheptylmethoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl , Methoxyhexyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl, hexyloxypentyl, hexyloxyhexyl and the like. Of these, preferred examples are propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecylic, dodecyl, tridecylic, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecylic, eikosyl and the like.

Further, in the above formula (31), B ¹ , B ² and B ³ are independently selected from single bond or 1,2-ethylene, respectively, but of 1,2-ethylene in the above formula (31). The number is preferably 0 or 1.

Further, in the above formula (31), as very particularly preferred compounds, the ^{R 6, A 1, A 2} , A 3, A 4, B 1, B 2 and ^{B 3} illustrated in Tables 1-3 below Compounds having a combination can be mentioned. In each table, B represents 1,4-phenylene, Ch represents 1,4-cyclohexylene, − represents a single bond, and E represents 1,2-ethylene. The cis / trans isomers of 1,4-cyclohexylene may be mixed, but the trans isomer is preferred.

Further, as a specific example of the diamine having a group represented by the above formula (31), the diamine represented by the following formula can be mentioned as preferable.

Thus, the side chain with the steroid skeleton or 3-4 rings selected from any of 1,4-cyclohexylene and 1,4-phenylene are linear, either directly or via 1,2-ethylene. It is preferable to have a side chain having a structure bound to. That is, it has a side chain having a structure in which 3 to 4 rings are linearly bonded, and the 3 to 4 rings are independent of each other, 1,4-cyclohexylene and 1,4-phenylene, respectively. The bond between the above 3 to 4 rings may be a single bond or 1,2-ethylene independently of each other. A film containing polyimide as a raw material made of these compounds can be effectively driven as a VATN mode by using this as an alignment film, and the average pretilt angle of the liquid crystal layer is suitable for the VATN mode. It can be stabilized at 87-89.5 ° (more preferably 87.5-89 °). It is also effective in suppressing burn-in.

On the other hand, after applying a photoalignment film, that is, the resin composition of the present invention as a liquid crystal alignment agent on a substrate, the alignment treatment is performed by light irradiation, particularly polarized ultraviolet irradiation to control the orientation of liquid crystal molecules. In order to obtain an imparted alignment film, either photolysis, photodimerization, or photoisomerization proceeds as compound (B) or in a compound used in combination with compound (B), and polarized light is formed. It is necessary that there is a group that imparts anisotropy in the same direction as the direction or in the direction perpendicular to the polarization direction.

Examples of such a specific group include a coumarin group, a cinnamate group, a chalcone group, an azobenzene group, a stilbene group, a benzophenone group, a β-hydroxyester structure and the like. Examples of the coumarin derivative include compounds represented by the following formula (32). Among them, from the group consisting of a cinnamate group (absorption wavelength (λmax) 270 nm), a chalcone group (absorption wavelength (λmax) 300 nm), an azobenzene group (absorption wavelength (λmax) 350 nm) and a stillben group (absorption wavelength (λmax) 295 nm). It is preferable to use a compound having at least one selected photofunctional group in the side chain as a raw material. In addition, these photofunctional groups may be used individually or in combination of 2 or more types. Further, either one of the tetracarboxylic dianhydride or the diamine used as a raw material may contain these functional groups, and both may contain the same or different functional groups. As for the chalcone group, for example, any of the tetracarboxylic dianhydrides and diamines listed in JP-A-2002-82336 can be used. As the azobenzene-type acid anhydride, any of the compounds listed in JP2012-224578A can be used.

The β-hydroxyester structure can be represented by the following formula (HE).

In particular, the compound having a β-hydroxyester structure as a diamine preferably has a structure of the following formula (HE-1). By having the structure of the following formula (HE-1), in the polyamic acid and polyimide using the diamine as a raw material, a double bond having excellent photoreactivity can be formed in the molecule when heated. When used for forming a liquid crystal alignment film, it can exhibit excellent photoalignment performance.

In the above formula (HE-1), X ₁ is a monocyclic ring having 5 or 6 atoms, two adjacent monocyclic rings having 5 or 6 atoms, and a bicyclic ring having 8 to 10 atoms. Represents an unsubstituted or substituted, carbocyclic or heterocyclic aromatic group selected from the system and the group consisting of a tricyclic ring system having 13 or 14 atoms.

In the structure of the above formula (HE-1), a particularly preferable structure is a structure represented by the following formula (HE-1-1).

Further, the diamine preferably has a structure of the following formula (HE-2), which has a β-hydroxyester structure and also has a structure for realizing vertical orientation of liquid crystal molecules.

In the above formula (HE-2), X ₁ is synonymous with the above formula (HE-1).

In the above formula (HE-2), X ₂ represents a single bond or at least one divalent bonding group selected from the group consisting of ether, ester, amide, and urethane. As X ₂ , a single bond, an ether group, an ester group or an amide group is preferable, and a single bond, an ether group or an ester group is more preferable. X ₃ represents a monovalent organic group having an alicyclic skeleton linear alkyl group or a C 4 to 40 3 to 20 carbon atoms. However, the hydrogen atom of this alkyl group may be replaced with a fluorine atom. Examples of X ₃ include n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and n-undecyl group. Group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, adamantyl group, spiro [5.5] Undecyl group, bicyclo [2.2.2] octyl group, bicyclo [2.2.1] heptyl group, cyclohexyl-n-heptyl group, bicyclohexyl-n-pentyl group, phenyl group, A naphthyl group, anthrasenyl group, cyclohexylphenyl group, n-pentyl-cyclohexylphenyl group, n-heptyl-cyclohexylphenyl group, cyclohexyloxyphenyl group, or n-pentyl-cyclohexyloxyphenyl group is preferable, and n-octyl group, n- Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, cyclohexyl group, cyclohexyl-n-heptyl group, bicyclohexyl-n-pentyl group, cyclohexyloxyphenyl group, or n-pentyl-cyclohexyloxy A phenyl group is more preferred.

Preferred examples of the diamine include a compound represented by the following formula (DA).

In the above formula (DA), X ₁ , X ₂ , and X ₃ are the same as described above. X ₄ represents a single bond, a methylene group or an alkylene group having 2 to 6 carbon atoms. However, this alkylene group may be substituted with a hydroxyl group. The X _4, a single bond, a methylene group, an ethylene group, n- propylene, n- butylene group, more preferably a single bond, or an ethylene group is more preferable. X ₅ represents a single bond, an oxygen atom, * -OCO- or * -OCH _2- (where the bond with the "*" bonds to X ₄ ). However, when X ₄ is a single bond, X ₅ is a single bond. As X ₅ , a single bond, an oxygen atom, or * -OCH ₂ -is preferable, and * -OCH _2- or an oxygen atom is more preferable.

Preferred examples of the diamine compound represented by the above formula (DA) include diamine compounds represented by the following formulas (DA-1) to (DA-8).

In the above formulas (DA-1) to (DA-8), Ra is an alkyl group having 3 to 20 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. Xa is a linear alkyl group having 3 to 16 carbon atoms, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-. Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group or n-hexadecyl group are preferable, and n-octyl group and n-nonyl group are preferable. More preferred are groups, n-decyl groups, n-undecyl groups, or n-dodecyl groups. Rb is an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. As Xb, a linear alkyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, n- An octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, or an n-dodecyl group is preferable, and an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, or an n-heptyl group is preferable. Groups are more preferred.

In order to cause photodecomposition, for example, a polyimide having the following structure can be used.

[In the formula, R ¹ is a tetravalent group having an alicyclic structure, R ² is a divalent organic group, and R ²⁵ and R ²⁶ are independently hydrogen atoms or monovalent organic groups, respectively. .. ]

In particular, at least one of R ¹ , R ²⁵ , and R ²⁶ is an alkyl fluorinated group, an alkoxy fluorinated group, an alkyl fluorinated ester group, and −Si (OR ³⁰ ) ₃ (however, R ³⁰ has 1 to 4 carbon atoms. It is more preferably the alkyl group of.).

The tetravalent group having an alicyclic structure has a structure derived from an alicyclic tetracarboxylic acid. Examples of the alicyclic structure of R ¹ include monocyclic cycloalkanes such as cyclobutane ring, cyclopentane ring, cyclohexane ring, and cyclooctane ring; bicyclo [2.2.0] hexane ring, decahydronaphthalene ring, and bicyclo. Examples thereof include bicyclic alkanes such as [2.2.1] heptan ring and bicyclo [2.2.2] octane ring. Among these, the alicyclic structure of R1 is preferably a cyclobutane ring, a cyclopentane ring, a cyclohexane ring or a bicyclo [2.2.0] hexane ring, and is preferably a cyclobutane ring, in terms of high photoorientity. Is particularly preferable.

In the above formula, R ² is a divalent organic group. To give an example, for example, at least one methylene group of a divalent hydrocarbon group and a divalent hydrocarbon group is -O-, -CO-, -COO-, -NH-, -NHCO-,-. Examples thereof include a group substituted with Si (R ³⁰ ) _2- , −Si (OR ³⁰ ) _2-, etc., a group having a heterocycle, and the like. In R ² , the hydrogen atom bonded to the carbon atom of the hydrocarbon group may be substituted with a halogen atom, an alkylsilyl group, an alkoxysilyl group or the like.

In the above formula, R ²⁵ and R ²⁶ are hydrogen atoms or monovalent organic groups. As the monovalent organic group, for example, at least one methylene group of a monovalent hydrocarbon group having 1 to 18 carbon atoms and a monovalent hydrocarbon group having 1 to 18 carbon atoms is used as −O—, −CO. -, -COO-, -NR-, -NRCO- (where R is an alkyl group), -Si (R ³⁰ ) _2- , -Si (OR ³⁰ ) _2-, etc. Examples thereof include a group formed by substituting a hydrogen atom bonded to a carbon atom of a monovalent hydrocarbon group of 18 with a halogen atom, an alkylsilyl group, an alkoxysilyl group or the like. R ²⁵ and R ²⁶ may be the same or different from each other.

When an alignment film is obtained from the above material, the exposure energy of light irradiation to the film is preferably 100 mJ / cm ² or less, and more preferably 50 mJ / cm ² or less during the process. Further, when performing the division orientation processing in which each pixel is divided and exposed by using a light-shielding mask (photomask) or the like, it is more preferably 20 mJ / cm ² or less.

Further, it has a radical generation function of generating radicals by light irradiation and a photosensitizing function of exhibiting a sensitizing effect by light irradiation as a raw material of the compound (B) used in the present invention or in a compound used in combination in a resin composition. By including the structure, it can be used as a liquid crystal alignment agent for a PSA mode liquid crystal display element. Here, the "photosensitizing function" refers to a function of rapidly transitioning to a triplet excited state by causing intersystem crossing after becoming a singlet excited state by irradiation with light. When it collides with another molecule in this triplet excited state, it changes the partner to the excited state and returns to the ground state. This photosensitizing function may coexist with a radical generation function that generates radicals by light irradiation.

Specific examples of the specific structure include an acetophenone structure, a benzophenone structure, a xantone structure, a fluorene structure, a benzaldehyde structure, a fluorene structure, an anthraquinone structure, a triphenylamine structure, a carbazole structure, and an alkyl as a structure capable of expressing a radical generation function. Examples thereof include a phenone structure, a benzoin structure, a thioxanthone structure, an acylphosphine oxide structure, a polysilane structure, and the like, and examples of the structure capable of exhibiting a photosensitizing function include an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, and carbazole. Structure, nitroaryl structure (nitrobenzene structure, 1,3-dinitrobenzene structure, etc.), naphthalene structure, fluorene structure, anthracene structure, aclydin structure, indol structure, 1,4-dioxocyclohexa-2,5-diene structure, etc. Can be mentioned. Each of these structures includes acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, alkylphenone, benzoin, thioxanthone, acylphosphine oxide, biphenyl, nitrobenzene, 1,3-dinitrobenzene. , Naphthalene, anthracene, acrydin, indol, 1,4-dioxocyclohexa-2,5-diene, which is a structure composed of groups obtained by removing 1 to 4 hydrogen atoms.

<Other ingredients>
When the resin composition of the present invention is used as a liquid crystal alignment agent, it may contain other components if necessary. Examples of such other components include compounds having at least one epoxy group in the molecule (hereinafter, referred to as “epoxy group-containing compound”), functional silane compounds, and the like.

The epoxy group-containing compound can be used to improve the adhesiveness and electrical properties of the liquid crystal alignment film to the substrate surface. For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin. Diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N', N'-tetraglycidyl-m-xylene diamine, 1,3-bis (N, N) -Diglycidyl aminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine and the like can be mentioned as preferable ones. When these epoxy group-containing compounds are added to the liquid crystal alignment agent, the blending ratio thereof is preferably 40 parts by mass or less, preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total resin components contained in the liquid crystal alignment agent. Part is more preferable.

The functional silane compound can be used for the purpose of improving the printability of the liquid crystal alignment agent. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-3 Aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl Methyl -3,6-diazanonanate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane , 3-Glycydoxypropyltrimethoxysilane and the like. When these functional silane compounds are added to the liquid crystal alignment agent, the blending ratio thereof is preferably 2 parts by mass or less, preferably 0.02 to 0.2 parts by mass, based on 100 parts by mass of the total resin components in the liquid crystal alignment agent. Part is more preferable.

As the above-mentioned other components, in addition to the compounds exemplified above, a compound having at least one oxetanyl group in the molecule, an antioxidant and the like can also be used.

<Solvent>
When the resin composition of the present invention is used as a liquid crystal alignment agent, the resin component and other components optionally blended are preferably dissolved in an organic solvent.

Examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone and ethylene. Glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, Ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl 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, dipropylene glycol Examples thereof include monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate and the like. These can be used alone or in admixture of two or more.

When the resin composition of the present invention is used as a liquid crystal alignment agent, the solid content concentration (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) takes into consideration viscosity, volatility, etc. It is appropriately selected, but it is preferably in the range of 1 to 10% by mass. That is, the liquid crystal alignment agent is applied to the surface of the substrate as described later, and is preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film. At this time, when the solid content concentration is in the range of 1 to 10% by mass, a good liquid crystal alignment film having an appropriate film thickness can be preferably obtained, and the viscosity of the liquid crystal alignment agent is high. It is in an appropriate range and the coating characteristics are good.

The range of particularly preferable solid content concentration varies depending on the method of applying the liquid crystal alignment agent to the substrate. For example, in the case of the spinner method, it is particularly preferable that the solid content concentration is in the range of 1.5 to 4.5% by mass. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by mass, and the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by mass and the solution viscosity is in the range of 3 to 15 mPa · s. The temperature at which the liquid crystal aligning agent is prepared is preferably 10 to 50 ° C, more preferably 20 to 30 ° C.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment film of the present invention is formed by the liquid crystal alignment agent prepared as described above, and the liquid crystal display element of the present invention includes the liquid crystal alignment film. The manufacturing method of the liquid crystal display element is as follows (i) to (ii).
(I) The first step of applying the liquid crystal alignment agent of the present invention onto the conductive film of a pair of substrates having a conductive film, and then heating the conductive film to form a coating film.
(Ii) A second step of constructing a liquid crystal cell by arranging a pair of substrates on which the coating film is formed so as to face each other so that the coating films face each other via a liquid crystal layer containing a liquid crystal compound.
including. Hereinafter, each of these steps will be described in detail.

<First step: Formation of coating film>
As the substrate, for example, a transparent substrate made of glass such as float glass or soda glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (aliphatic olefin) can be used. As the conductive film, it is preferable to use a transparent conductive film, for example, tin oxide NESA film made of (SnO ₂₎ (US PPG registered trademark), indium oxide - consisting of tin oxide _{(In 2} O 3 -SnO ₂₎ An ITO film or the like can be used. The conductive film is preferably a patterned conductive film partitioned into a plurality of regions. With such a conductive film, when a voltage is applied between the conductive films, the direction of the pretilt angle of the liquid crystal molecules can be changed for each region by applying a different voltage in each region, whereby the viewing angle can be changed. It is possible to make the characteristics wider.

The method of applying the liquid crystal aligning agent of the present invention on the surfaces of the pair of substrates on which the transparent conductive film is formed can be preferably performed by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. When applying the liquid crystal alignment agent, in order to further improve the adhesiveness between the substrate surface and the transparent conductive film and the coating film, the functional silane compound and functional titanium are applied to the surface of the substrate on which the coating film should be formed. Pretreatment to apply a compound or the like in advance may be performed.

After the liquid crystal alignment agent is applied to the substrate, preheating is preferably performed for the purpose of preventing the applied liquid crystal alignment agent from dripping. The prebake temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. After that, a firing (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amic acid structure present in the polymer. The post-bake temperature is preferably 80-300 ° C, more preferably 120-250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. During this post-baking, the above-mentioned fluorine-containing thermosetting resin (A) becomes a resin (C) having a carboxyl group by removing groups containing fluorine atoms by thermal decomposition. The film thickness of the film formed in this way is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

Further, the Range% (maximum minimum value difference of film thickness / average film thickness) in the film thickness measurement of the reflection spectroscopic film thickness meter of the alignment film obtained by this step can be 10% or less. As the reflection spectroscopic film thickness meter, a reflection spectroscopic film thickness meter FE-3000 manufactured by Otsuka Electronics Co., Ltd. can be used. The range of 4 cm x 4 cm in the center of the film is divided into 400 points, and the film thickness of each is measured. Smoothness can be evaluated by the standard deviation of the thickness and the Range% (maximum and minimum difference in film thickness / average film thickness). The smaller the Range%, the smoother it is. Further, it can be confirmed by, for example, XPS (X-ray photoelectron spectroscopy) that the fluorine atom does not exist in the film or is below the detection limit.

By removing the organic solvent by heating after applying the liquid crystal alignment agent, a coating film to be an alignment film is formed. At this time, if the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imide ring structure and an amic acid structure, The dehydration ring closure reaction may be allowed to proceed by further heating after the coating film is formed to obtain a more imidized coating film.

The coating film formed in this manner is treated according to the structures of the acid anhydride and diamine used. That is, rubbing treatment, light irradiation, or both of them may be performed, and in the case of PSA type or the like, these orientation treatments may not be performed and may be directly subjected to the second step.

<Second step: Construction of liquid crystal cell>
By preparing a substrate on which a liquid crystal alignment film is formed on at least one side as described above and arranging a liquid crystal layer containing a liquid crystal composition between the substrate and the other substrate arranged opposite to the substrate. Manufactures liquid crystal cells. For example, the following two methods can be mentioned for manufacturing a liquid crystal cell. The first method is a vacuum injection method. First, two substrates are placed facing each other with the liquid crystal alignment film inside through a gap (cell gap), and the peripheral portions of the two substrates are bonded together using a sealant, and are partitioned by the substrate surface and the sealant. A liquid crystal cell is manufactured by injecting and filling the liquid crystal composition into the cell gap and then sealing the injection hole. The second method is a method called an ODF (One Drop Filling) method. After applying, for example, an ultraviolet light-curable sealant to a predetermined position on one of the two substrates, and further dropping the liquid crystal composition onto several predetermined locations on the liquid crystal alignment film surface, the liquid crystal composition is added dropwise. A liquid crystal cell is manufactured by laminating the other substrate, spreading the liquid crystal composition over the entire surface of the substrate, and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealant.

Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal composition used is isotropic, and then slowly cooled to room temperature to allow the liquid crystal to flow during liquid crystal filling. The orientation may be removed.

As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used. The liquid crystal composition will be described later.

<Liquid crystal display device>
The configuration of the liquid crystal display device using the liquid crystal display element of the present invention is particularly limited as long as the standard components of such a liquid crystal display device are indispensable. is not. The liquid crystal display device may be a simple matrix type liquid crystal display device, but is preferably an active matrix type liquid crystal display device. The liquid crystal display device is a pixel arranged in a matrix including pixel electrodes arranged in a matrix on the liquid crystal layer side of one substrate and common electrodes arranged on the liquid crystal layer side of the other substrate. It is preferable to have. Further, the liquid crystal layer side of one of the substrates may have pixels arranged in a matrix including a comb-shaped pixel electrode and a common electrode.

<Liquid crystal composition>
The liquid crystal composition used in the liquid crystal display device of the present invention preferably contains one or more compounds represented by the general formula (i).

[In formula (i), R ^II1 represents an alkyl group having 1 to 10 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independently −CH = CH. It may be replaced by −, −C≡C−, −O−, −CO−, −COO− or −OCO−.
A ^II1 and ^{A II2} each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - is -O (May be replaced with −) and (b) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other is replaced with -N =. May be done.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One -CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. )
Representing a group selected from the group consisting of, the above group (a), group (b) and group (c) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, respectively.
Z ^II1 is a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 -, - CF 2 O- , -CH = NN = CH-, -CH = CH-, -CF = CF- or -C≡C-
Y ^II1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 10 carbon atoms, one or non-adjacent two or more -CH 2 in the alkyl group _- is independently It may be substituted with -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and one or more hydrogens in the alkyl group. Atoms may be substituted with fluorine atoms,
m ^II1 each represents 1, 2, 3 or ^4, if ^{m II1} is representative of the 2, 3 or 4, ^{A II1} and ^{Z II1} there is a plurality may be the same or different. ]

<First aspect of the compound represented by the general formula (i)>
The compound represented by the general formula (i) is a so-called p-type liquid crystal compound having a positive dielectric anisotropy, and examples thereof include a compound represented by the following general formula (J).

As the compound represented by the general formula (i), it is preferable to contain one or more compounds represented by the general formula (J). These compounds are dielectrically positive compounds (Δε is greater than 2).

(In the formula, R ^J1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independently −CH = CH−, −. It may be replaced by C≡C−, −O−, −CO−, −COO− or −OCO−.
n ^J1 represents 0, 1, 2, 3 or 4
A ^J1 , A ^J2 and A ^J3 are independent of each other.
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =) and (c). Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2) , 3,4-Tetrahydronaphthalene-2,6-Diyl group One -CH = or two or more non-adjacent -CH = may be replaced with -N =).
Represents a group selected from the group consisting of, and the above groups (a), group (b) and group (c) are independently cyano groups, fluorine atoms, chlorine atoms, methyl groups, trifluoromethyl groups or trifluoro groups. It may be substituted with a methoxy group,
Z ^J1 and ^{Z J2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O-, Represents -COO-, -OCO- or -C≡C-
When n ^J1 is 2, 3 or 4 and there are a plurality of A ^J2s , they may be the same or different, and when n ^J1 is 2, 3 or 4 and there are a plurality of Z ^J1s. If so, they may be the same or different,
^XJ1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )
In the general formula ^{(J), R J1} is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, alkenyloxy of alkenyl or 2 to 8 carbon atoms having from 2 to 8 carbon atoms The group is preferable, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferable. Alkyl groups having 1 to 5 or alkenyl groups having 2 to 5 carbon atoms are more preferable, alkyl groups having 2 to 5 carbon atoms or alkenyl groups having 2 to 3 carbon atoms are further preferable, and alkenyl groups having 3 carbon atoms are more preferable. (Propenyl group) is particularly preferable.

Preferably R ^J1 is an alkyl group in the case of emphasizing reliability, it is preferred when emphasizing a reduction in viscosity is an alkenyl group.

When the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and carbon are used. An alkoxy group having 4 to 5 atoms is preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, a linear alkyl group having 1 to 5 carbon atoms or a straight chain is used. Alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from the groups represented by any of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure to which the alkenyl group is bonded.)

A ^J1 , A ^J2 and A ^J3 are preferably aromatic when it is required to increase Δn independently, and are preferably aliphatic in order to improve the response rate, and trans-. 1,4-Cyclohexylene group, 1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene It preferably represents a -2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, which are substituted with fluorine atoms. It may be more preferable to represent the following structure.

It is more preferable to represent the following structure.

Z ^J1 and Z ^J2 independently represent -CH ₂ O-, -OCH _2- , -CF ₂ O-, -CH ₂ CH _2- , -CF ₂ CF _2- or single bond, respectively. OCH _2- , -CF ₂ O-, -CH ₂ CH _2- or single bond is more preferred, and -OCH _2- , -CF ₂ O- or single bond is particularly preferred.

^XJ1 is preferably a fluorine atom or a trifluoromethoxy group, preferably a fluorine atom.

n ^J1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when focusing on improvement of Δε, and preferably 1 or 2 when focusing on Tni. ..

The types of compounds that can be combined are not particularly limited, but they are used in combination according to desired performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, and three types as one embodiment. Further, in another embodiment, there are 4 types, 5 types, 6 types, and 7 or more types.

In the liquid crystal composition, the content of the compound represented by the general formula (J) is solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, seizure, dielectric constant. It is necessary to make appropriate adjustments according to the required performance such as anisotropy.

The lower limit of the preferable content of the compound represented by the general formula (J) with respect to the total amount of the liquid crystal composition is 1%, 10%, 20%, 30%, and 40%. , 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferable content is, for example, 95%, 85%, 75%, 65%, 55%, and 45% in one form with respect to the total amount of the liquid crystal composition. Yes, 35%, 25%.

When a composition having a low viscosity and a high response speed is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when a composition having a high Tni of the composition and good temperature stability is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the above lower limit value and raise the upper limit value.

Preferably R ^J1 is an alkyl group in the case of emphasizing reliability, it is preferred when emphasizing a reduction in viscosity is an alkenyl group.

As the compound represented by the general formula (J), the compound represented by the general formula (M) and the compound represented by the general formula (K) are preferable.

The liquid crystal composition preferably contains one or more compounds represented by the general formula (M). These compounds are dielectrically positive compounds (Δε is greater than 2).

^{(Wherein, R M1} represents an alkyl group having 1 to 8 carbon atoms, one or non-adjacent two or more -CH ₂ in the alkyl group - are each independently -CH = CH -, - It may be replaced by C≡C−, −O−, −CO−, −COO− or −OCO−.
n ^M1 represents 0, 1, 2, 3 or 4
^AM1 and ^AM2 are independent of each other
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- (May be) and (b) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
Represents a group selected from the group consisting of, and the hydrogen atoms on the above groups (a) and (b) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ^M1 and ^{Z M2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O-, Represents −COO−, −OCO− or −C≡C−
When n ^M1 is 2, 3 or 4 and there are a plurality of ^AM2 , they may be the same or different, and when n ^M1 is 2, 3 or 4 and there are a plurality of Z ^M1s. If so, they may be the same or different,
X ^M1 and X ^M3 independently represent a hydrogen atom, a chlorine atom or a fluorine atom, respectively.
X ^M2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )
In the general formula (M), ^RM1 is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy having 2 to 8 carbon atoms. The group is preferable, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferable. Alkyl groups having 1 to 5 or alkenyl groups having 2 to 5 carbon atoms are more preferable, alkyl groups having 2 to 5 carbon atoms or alkenyl groups having 2 to 3 carbon atoms are further preferable, and alkenyl groups having 3 carbon atoms are more preferable. (Propenyl group) is particularly preferable.

Preferably R ^M1 is an alkyl group in the case of emphasizing reliability, it is preferred when emphasizing a reduction in viscosity is an alkenyl group.

When the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and carbon are used. An alkoxy group having 4 to 5 atoms is preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, a linear alkyl group having 1 to 5 carbon atoms or a straight chain is used. Alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from the groups represented by any of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure to which the alkenyl group is bonded.)

Preferably when it is desired A ^M1 and A ^M2 is to increase the Δn each independently is an aromatic, preferably to improve the response speed is an aliphatic, trans-1,4 -Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2, 3-Difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It is preferable to represent a diyl group, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably to represent the following structure.

It is more preferable to represent the following structure.

Z ^M1 and ^{Z M2} each _{independently -CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CF 2 O-, -CH ₂ CH _2- or single bond is more preferred, and -CF ₂ O- or single bond is particularly preferred.

n ^M1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when focusing on improvement of Δε, and preferably 1 or 2 when focusing on Tni. ..

The types of compounds that can be combined are not particularly limited, but they are used in combination according to desired performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, and three types as one embodiment. Further, in another embodiment, there are 4 types, 5 types, 6 types, and 7 or more types.

In the liquid crystal composition, the content of the compound represented by the general formula (M) is solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, seizure, dielectric constant. It is necessary to make appropriate adjustments according to the required performance such as anisotropy.

The lower limit of the preferable content of the compound represented by the formula (M) with respect to the total amount of the liquid crystal composition is 0%, 1%, 10%, 20%, and 30%. Yes, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferable content is, for example, 95%, 85%, 75%, 65%, 55%, and 45% in one form with respect to the total amount of the liquid crystal composition. Yes, 35%, 25%.

When a composition having a low viscosity and a high response speed is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when the Tni of the liquid crystal composition is kept high and a composition having good temperature stability is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the above lower limit value and raise the upper limit value.

Specifically, the liquid crystal compound represented by the general formula (M) is preferably the following general formula (M-1) and general formula (M-2).

(In the formula, R ³¹ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ³¹ and X ³² are independently hydrogen. Representing an atom or a fluorine atom, Y ³¹ represents a fluorine atom or OCF ₃ , and M ^{31 to} M ³³ independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group. One or two -CH _{2- in the} trans-1,4-cyclohexylene group may be substituted with -O- so that the oxygen atom is not directly adjacent, and one or two in the phenylene group or The two hydrogen atoms may be substituted with fluorine atoms, where n ³¹ and n ³² independently represent 0, 1 or 2, and n ⁴¹ + n ⁴² represent 1, 2 or 3).

The liquid crystal compound represented by the general formula (M-1) is preferably a compound represented by the following general formulas (M-1-a) to (M-1-f).

^{(Wherein, R 31, X 31, X} 32 and ^{Y 31} are as defined ^{R 31, X 31,} X ³² and ^{Y 31} in the general formula ^{(M), X} 34 ~X ³⁹ are each independently Represents a hydrogen atom or a fluorine atom.)
The liquid crystal compound represented by the general formula (M-2) is preferably a compound represented by the following general formulas (M-2-a) to (M-2-n).

^{(Wherein, R 31, X 31, X} 32 and ^{Y 31} are as defined ^{R 31, X 31,} X ³² and ^{Y 31} in the general formula ^{(M), X} 34 ~X ³⁹ are each independently Represents a hydrogen atom or a fluorine atom.)
Further, the liquid crystal compound represented by the general formula (M) is preferably from the following general formula (M-3) to the general formula (M-26).

^{(Wherein, R 31, X 31, X} 32 and ^{Y 31} are as defined ^{R 31, X 31,} X ³² and ^{Y 31} in the general formula ^{(M), X} 34 ~X ³⁹ are each independently Represents a hydrogen atom or a fluorine atom.)

The liquid crystal composition preferably contains one or more compounds represented by the general formula (K). These compounds are dielectrically positive compounds (Δε is greater than 2).

(In the formula, ^RK1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ −s in the alkyl group are independently −CH = CH−, −. It may be replaced by C≡C−, −O−, −CO−, −COO− or −OCO−.
n ^K1 represents 0, 1, 2, 3 or 4
^AK1 and ^AK2 are independent of each other
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- (May be) and (b) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
Represents a group selected from the group consisting of, and the hydrogen atoms on the above groups (a) and (b) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ^K1 and ^{Z K2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O-, Represents −COO−, −OCO− or −C≡C−
If n ^K1 is a 2, 3 or 4 ^{A K2} there are multiple, they may be different even in the ^{same, n K1} is a 2, 3 or 4 ^{Z K1} there are multiple If so, they may be the same or different,
X ^K1 and X ^K3 independently represent a hydrogen atom, a chlorine atom or a fluorine atom, respectively.
X ^K2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )
In the general formula (K), ^RK1 is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy having 2 to 8 carbon atoms. The group is preferable, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferable. Alkyl groups having 1 to 5 or alkenyl groups having 2 to 5 carbon atoms are more preferable, alkyl groups having 2 to 5 carbon atoms or alkenyl groups having 2 to 3 carbon atoms are further preferable, and alkenyl groups having 3 carbon atoms are more preferable. (Propenyl group) is particularly preferable.

Preferably R ^K1 is an alkyl group in the case of emphasizing reliability, it is preferred when emphasizing a reduction in viscosity is an alkenyl group.

When the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and carbon are used. An alkoxy group having 4 to 5 atoms is preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, a linear alkyl group having 1 to 5 carbon atoms or a straight chain is used. Alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from the groups represented by any of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure to which the alkenyl group is bonded.)

Preferably when it is desired A ^K1 and A ^K2 is to increase the Δn each independently is an aromatic, preferably to improve the response speed is an aliphatic, trans-1,4 -Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2, 3-Difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It is preferable to represent a diyl group, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably to represent the following structure.

It is more preferable to represent the following structure.

Z ^K1 and ^{Z K2} are each _{independently -CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CF 2 O-, -CH ₂ CH _2- or single bond is more preferred, and -CF ₂ O- or single bond is particularly preferred.

n ^K1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when focusing on improvement of Δε, and preferably 1 or 2 when focusing on Tni. ..

The types of compounds that can be combined are not particularly limited, but they are used in combination according to desired performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, and three types as one embodiment. Further, in another embodiment, there are 4 types, 5 types, 6 types, and 7 or more types.

In the liquid crystal composition, the content of the compound represented by the general formula (K) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, seizure, and dielectric constant. It is necessary to make appropriate adjustments according to the required performance such as anisotropy.

The lower limit of the preferable content of the compound represented by the formula (K) with respect to the total amount of the liquid crystal composition is 1%, 10%, 20%, 30%, and 40%. Yes, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferable content is, for example, 95%, 85%, 75%, 65%, 55%, and 45% in one form with respect to the total amount of the liquid crystal composition. Yes, 35%, 25%.

When a composition having a low viscosity and a high response speed is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when the Tni of the liquid crystal composition is kept high and a composition having good temperature stability is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the above lower limit value and raise the upper limit value.

Specifically, the liquid crystal compound represented by the general formula (K) is preferably the following general formula (K-1) and general formula (K-2).

(In the formula, R ⁴¹ represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ⁴¹ and X ⁴² are independently hydrogen. Representing an atom or a fluorine atom, Y ⁴¹ represents a fluorine atom or OCF ₃ , and M ^{41 to} M ⁴³ independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group. One or two -CH _{2- in the} trans-1,4-cyclohexylene group may be substituted with -O- so that the oxygen atom is not directly adjacent, and one or two in the phenylene group or The two hydrogen atoms may be substituted with fluorine atoms, where n ⁴¹ and n ⁴² independently represent 0, 1 or 2, and n ⁴¹ + n ⁴² represent 1, 2 or 3).

The liquid crystal compound represented by the general formula (K-1) is preferably a compound represented by the following general formulas (K-1-a) to (K-1-d).

^{(Wherein, R 41, X 41, X} 42 and ^{Y 41} are as defined ^{R 41, X 41,} X ⁴² and ^{Y 41} in the general formula ^{(K), X} 44 ~X ⁴⁹ are each independently Represents a hydrogen atom or a fluorine atom.)

The liquid crystal compound represented by the general formula (K-2) is preferably a compound represented by the following general formula (K-2-a) to the general formula (K-2-g).

^{(Wherein, R 41, X 41, X} 42 and ^{Y 41} are as defined ^{R 41, X 41,} X ⁴² and ^{Y 41} in the general formula ^{(K), X} 44 ~X ⁴⁹ are each independently Represents a hydrogen atom or a fluorine atom.)
Further, the liquid crystal compound represented by the general formula (K) is preferably from the following general formula (K-3) to the general formula (K-5).

^{(Wherein, R 41, X 41, X} 42 and ^{Y 41} are as defined ^{R 41, X 41,} X ⁴² and ^{Y 41} in the general formula ^{(K), X} 44 ~X ⁴⁹ are each independently Represents a hydrogen atom or a fluorine atom.)

<Second aspect of the compound represented by the general formula (i)>
The compound represented by the general formula (i) is a so-called n-type liquid crystal compound having a negative dielectric anisotropy, and examples thereof include compounds represented by the following general formulas (LC1) and general formula (LC2). it can.

As the compound represented by the general formula (i), it is preferable to contain one or more compounds selected from the compound group represented by the general formulas (N-1) to (N-3).

(In the formula, ^RN11 , ^RN12 , ^RN21 , ^RN22 , ^RN31 and ^RN32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two non-adjacent ones. More than one −CH ₂₋ may be independently substituted by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are independently (a) 1,4-cyclohexylene groups (one -CH _2- or adjacent to each other in this group). No two or more -CH _2- may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =) and (c). Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2) , 3,4-Tetrahydronaphthalene-2,6-Diyl group One -CH = or two or more non-adjacent -CH = may be replaced with -N =).
Representing a group selected from the group consisting of, the above group (a), group (b) and group (c) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, respectively.
^{Z N11, Z N12, Z N21} , Z N22, Z N31 and ^{Z N32} are each independently a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O- , -COO-, -OCO-, -OCF _2- , -CF ₂ O-, -CH = NN = CH-, -CH = CH-, -CF = CF- or -C≡C-
X ^N21 represents a hydrogen atom or a fluorine atom.
^TN31 represents −CH _2- or oxygen atom,
n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 each independently represent an integer of 0 to 3, but n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are independent of each other. When it is 1, 2 or 3, and there are a plurality of A ^{N11 to} A ^N32 and Z ^{N11 to} Z ^N32 , they may be the same or different. However, the compounds represented by the general formula (N-1) in the general formula (N-2) and the general formula (N-3) are excluded, and the general formula (N-2) in the general formula (N-3) is excluded. The compounds represented by are excluded. )
The compounds represented by the general formulas (N-1), (N-2) and (N-3) are dielectrically negative compounds (the sign of Δε is negative and its absolute value is larger than 2). Although applicable, it is preferred that the compound has a negative Δε and an absolute value greater than 3.

In the general formulas (N-1), (N-2) and (N-3), ^RN11 , ^RN12 , ^RN21 , ^RN22 , ^RN31 and ^RN32 are independent of each other and have 1 to 8 carbon atoms. Alkyl group, alkoxy group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms or alkenyloxy group having 2 to 8 carbon atoms is preferable, and the alkyl group having 1 to 5 carbon atoms and the number of carbon atoms are preferable. An alkoxy group having 1 to 5 atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is preferable. More preferably, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is further preferable, and an alkenyl group (propenyl group) having 3 carbon atoms is particularly preferable. Among them, by using a compound in which at least one or more of ^RN11 and ^RN12 represents an alkenyl group and a compound represented by the general formula (I) in combination, a decrease in voltage retention (VHR) is remarkably suppressed. be able to. Similarly, by using a compound in which at least one or more of ^RN21 and ^RN22 represents an alkenyl group and a compound represented by the general formula (I) in combination, a decrease in voltage retention (VHR) is significantly suppressed. it can, also, by using in combination with a compound which represents at least one or more alkenyl groups R ^N31 and R ^N32, a compound represented by the general formula (I), the decrease in voltage holding ratio (VHR) Can be remarkably suppressed.

When the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and carbon are used. An alkoxy group having 4 to 5 atoms is preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, a linear alkyl group having 1 to 5 carbon atoms or a straight chain is used. Alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from the groups represented by any of the formulas (R1) to (R5). (The black dots in each equation represent carbon atoms in the ring structure.)

A ^N11 , ^AN12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are preferably aromatics when it is required to increase Δn independently, and fats are used to improve the response rate. It is preferably a group, and is preferably a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, 3,5. -Difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1 , 4-Diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, which are preferably represented as follows. It is more preferable to represent the structure of

It is more preferable to represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

^{Z N11, Z N12, Z N21} , Z N22, Z N31 and ^{Z N32} _-CH 2 each _{independently O -, - CF 2 O -} , - CH 2 CH 2 -, - CF 2 CF 2 - or a single bond preferably represents _{an, -CH 2 O -, - CH} 2 CH 2 - or a single bond is more preferable, _-CH 2 O-or a single bond is particularly preferred.

Fluorine atom is preferable for X ^N21 .

Oxygen atom is preferable for ^TN31 .

n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are preferably 1 or 2, n ^N11 is 1 and n ^N12 is 0, n ^N11 is 2 and n ^N12 is 0, n ^{The combination of N11} being 1 and ^nN12 being 1, the combination of ^nN11 being 2 and ^nN12 being 1, the combination of ^nN21 being 1 and ^nN22 being 0, ^nN21 being 2 and ^nN22 being A combination of 0, a combination of n ^N31 of 1 and n ^N32 of 0, and a combination of n ^N31 of 2 and n ^N32 of 0 are preferred.

The lower limit of the preferable content of the compound represented by the formula (N-1) with respect to the total amount of the liquid crystal composition is 0%, 1%, 10%, 20%, and 30. %, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%. Is.

The lower limit of the preferable content of the compound represented by the formula (N-2) with respect to the total amount of the liquid crystal composition is 0%, 1%, 10%, 20%, and 30. %, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%. Is.

The lower limit of the preferable content of the compound represented by the formula (N-3) with respect to the total amount of the liquid crystal composition is 0%, 1%, 10%, 20%, and 30. %, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%. Is.

When a composition that keeps the viscosity of the liquid crystal composition low and has a high response speed is required, it is preferable that the above lower limit value is low and the upper limit value is low. Further, when a composition having a high Tni of the liquid crystal composition and good temperature stability is required, it is preferable that the lower limit value is low and the upper limit value is low. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is high and the upper limit value is high.

The liquid crystal composition preferably contains one or more compounds represented by the general formula (i-1) as the general formula (N-1).

(In the formula, A ⁱ¹¹ , A ⁱ¹² and A ⁱ¹³ independently represent a 1,4-cyclohexylene group or a 1,4-phenylene group, respectively, but one present in the 1,4-cyclohexylene group. of -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S-, is one of the hydrogen atoms present in the 1,4-phenylene group, respectively It may be independently substituted with a fluorine atom or a chlorine atom, and Z ⁱ¹ is -OCH _2- , -CH ₂ O-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- or -CF ₂ CF ₂ - ^{represents, m i11} and ^{m i12} are each independently 0 or ^{1, R N11,} R ^N12 and ^{Z N12 is, R} N11, ^{R N12} and in the general formula (N-1) each independently It has the same meaning as Z ^N12 .)

The compound represented by the general formula (i-1) is preferably a compound represented by the general formula (i-1A), the general formula (i-1B) or the general formula (i-1C).

^(Wherein, R ^N11, R ^{N12, A i11} and ^{Z i1} represent the same meaning as ^{R N11, R N12, A i11} and ^{Z i1} in the general formula (i1) independently.)

^{(Wherein, R N11, R N12, A i11} , A i12 and ^{Z i1} are the same meaning as ^{R N11, R N12, A i11} , A i12 and ^{Z i1} in the general formula (i1) independently Represent.)

^{(Wherein, m i13} represents ^{1, R N11, R N12,} A i11, A i12, A i13, Z i1, Z i2 and ^{m i11} are each independently ^{R N11} in the general formula (i1) represents the same meaning as ^{R N12, a i11, a i12} , a i13, Z i1, Z i2 and ^{m i11.)}

As the compound represented by the general formula (i-1A), the compounds represented by the following general formulas (i-1A-1) to (i-1A-4) are preferable.

(In the formula, ^RN11 and ^RN12 independently represent the same meanings as ^RN11 and ^RN12 in the general formula (i-1), respectively.)

The compound represented by the general formula (i-1B) is preferably a compound represented by the following general formulas (i-1B-1) to (i-1B-7).

^{(Wherein, R N11} and ^{R N122} has the same meaning as ^{R N11} and ^{R N12} are independently in Formula (i-1).)

The compound represented by the general formula (i-1C) is preferably a compound represented by the following general formulas (i-1C-1) to (i-1C-4), and is preferably a compound represented by the general formula (i-1C-4). It is more preferable that the compound is represented by -1C-1) and the general formula (i-1C-2).

(In the formula, ^RN11 and ^RN122 independently represent the same meanings as R ⁱ¹ and R ⁱ² in the general formula (i-1), respectively.)

The liquid crystal composition preferably contains one or more compounds represented by the general formula (i-1), but the general formula (i-1A), the general formula (i-1B) or the general formula ( One or more compounds selected from the compound group represented by i-1C) may be contained, and the general formula (i-1A), the general formula (i-1B) or the general formula (i-) may be contained. One or more compounds represented by 1C) may be contained in each. It is preferable to contain one or more compounds represented by the general formula (i-1A) and the general formula (i-1B), and more preferably 2 to 10 kinds.

More specifically, the general formula (i-1A), the general formula (i-1B) and the general formula (i-1C) are the general formula (i-1A-1), the general formula (i-1B-1) and the general formula. It is preferable to contain one or more compounds selected from the compound group represented by the formula (i-1C-1), and the compound represented by the general formula (i-1A-1) and the general formula (i). It is more preferable that the combination of compounds represented by -1B-1) is used.

The liquid crystal composition preferably contains one or more compounds represented by the general formula (ii) as the general formula (LC3).

^(Wherein, A ^{ii1, A ii2} represents an independently 1,4 cyclohexylene group or 1,4-phenylene group cyclohexylene, one -CH present in a 1,4-cyclohexylene group _Two or more -CH _2- or non-adjacent -CH _2- may be replaced by -O- or -S-, and one hydrogen atom present in the 1,4-phenylene group is independent of each other. It may be substituted by a fluorine atom or a chlorine ^{atom, m ii1} and ^{m ii2} independently represents 1 or ^{2, R N11} and ^{R N12} is, ^{R N11} and in the general formula (N-1) each independently represent the same meaning as R ^N12.)

As the general formula (ii-1), it is preferable to contain one or more compounds represented by the general formula (ii-1).

^(Wherein, it represents the same meaning as R ^N11, R ^{N12, A ii1} and ^{m ii1} is ^R N11 in the general formula ^{(ii), R N12, A} ii1 and ^{m ii1.)}

The compound represented by the general formula (ii-1) is preferably a compound represented by the general formula (II-2A) or the general formula (II-2B).

^{(Wherein, R N11,} R ^N12 and ^{A ii1} have the same meanings as ^{R N11, R N12} and ^{A ii1} in formula (ii).)

(In the formula, ^Aii11 and ^Aii11 independently represent a 1,4-cyclohexylene group or a 1,4-phenylene group, respectively, but one -CH present in the 1,4-cyclohexylene group. _Two or more -CH _2- or non-adjacent -CH _2- may be replaced with -O- or -S-, and one hydrogen atom present in the 1,4-phenylene group is independent of each other. It may be substituted by a fluorine atom or a chlorine ^{atom, R N11} and ^{R N12} in the general formula (ii) represents the same meaning as ^{R N11} and ^{R N12.)}

As the compound represented by the general formula (ii-1A), the compounds represented by the following general formulas (ii-1A-1) and general formula (ii-1A-2) are preferable.

^{(Wherein, R N11} and ^{R N12} are the same as defined ^{R N11} and ^{R N12} in the general formula (ii).)

The compound represented by the general formula (ii-1B) is preferably a compound represented by the following general formulas (ii-1B-1) to (ii-1B-3).

^{(Wherein, R N11} and ^{R N12} are the same as defined ^{R N11} and ^{R N12} in the general formula (ii).)

The liquid crystal composition preferably contains one or more compounds represented by the general formula (ii), but the compound group represented by the general formula (ii-1A) and the general formula (ii-1B). One or more compounds selected from the above may be contained, or one or more compounds represented by the general formula (ii-1A) and the general formula (ii-1B) may be contained. It is preferable to contain 2 to 10 kinds of compounds represented by the general formula (ii-1A) and the general formula (ii-1B).

More specifically, the general formula (ii-1A) preferably contains one or more compounds selected from the compound group represented by the general formula (ii-1A-1), and the general formula (ii-). 1B) preferably contains one or more compounds selected from the compound group represented by the general formula (ii-1B-1) and the general formula (ii-1B-2), and the general formula (ii-). It is more preferable that the combination of the compounds represented by 1A-1) and the general formula (ii-1B-1) is used.

Further, as the general formula (N-1), it is preferable to contain one or more compounds represented by the following general formula (LC3-b).

^{(Wherein, R N11, R N12, A N11} , A N12 and ^{Z N11} are each independently the same meaning in the general formula (N-1) and ^{R N11, R N12, A N11} , A N12 and ^{Z N11} X ^{LC3b1 to} X ^LC3b4 represent hydrogen atoms or fluorine atoms, but at least one combination of X ^LC3b1 and X ^LC3b2 , or X ^LC3b3 and X ^LC3b4 both represents a fluorine atom, and m ^LC3b1 represents 0 or 1. However, in the general formula (LC3-b), the compounds represented by the general formula (i-1) and the general formula (ii) are excluded.)

As the general formula (LC3-b), it is preferable to represent the following general formulas (LC3-b1) to general formulas (LC3-b10).

(In the formula, ^RN11 and ^RN12 independently represent the same meanings as ^RN11 and ^RN12 in the general formula (N-1).)

The combination of ^RN11 and ^RN12 is not particularly limited, but both represent an alkyl group, both represent an alkenyl group, one represents an alkyl group, and the other represents an alkenyl group. It is preferable that one represents an alkyl group and the other represents an alkoxy, and one of them represents an alkyl group and the other represents an alkenyloxy group, both of which represent an alkyl group, and both of which represent an alkenyl group. It is more preferable that it represents.

Further, as the general formula (LC3-b), it is preferable to represent the following general formula (LC3-c).

(In the formula, ^RN11 and ^RN12 independently represent the same meanings as ^RN11 and ^RN12 in the general formula (N-1).)

The compound represented by the general formula (N-2) is preferably a compound selected from the compound group represented by the general formulas (N2-1) to (N-2-3).

^{(Wherein, R N211} and ^{R N22} are each independently the same meaning as ^{R N211} and ^{R N22} in the general formula (N-2).)

The compound represented by the general formula (N-3) is preferably a compound selected from the compound group represented by the general formulas (N-3-1) and (N-3-2).

The compound represented by the general formula (N-3-1) is the following compound.

^{(Wherein, R N31} and ^{R N32} are each independently the same meaning as ^{R N31} and ^{R N32} in the general formula (N-3).)

<Third aspect of the compound represented by the general formula (i)>
It is a so-called non-polar liquid crystal compound having a dielectric anisotropy of about 0, and examples thereof include compounds represented by the following general formula (L).

The liquid crystal composition preferably contains one or more compounds represented by the general formula (L). The compound represented by the general formula (L) corresponds to a dielectrically substantially neutral compound (the value of Δε is -2 to 2).

(Wherein, R ^L1 and R ^L2 represent each independently an alkyl group having 1 to 8 carbon atoms, one or non-adjacent two or more -CH 2 in the alkyl group _- is independently It may be replaced by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
n ^L1 represents 0, 1, 2 or 3
A ^{L1, A L2,} and ^{A L3} each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - May be replaced with -O-.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =) and (c). Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2) , 3,4-Tetrahydronaphthalene-2,6-Diyl group One -CH = or two or more non-adjacent -CH = may be replaced with -N =).
Representing a group selected from the group consisting of, the above group (a), group (b) and group (c) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, respectively.
Z ^L1 and ^{Z L2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
If n ^L1 is 2 or 3 and there are a plurality of A ^L2s , they may be the same or different, and if n ^L1 is 2 or 3 and there are a plurality of Z ^L3s , they may be the same or different. May be the same or different, except for compounds represented by the general formula (J), the general formula (N-1), the general formula (N-2) and the general formula (N-3). )

The compound represented by the general formula (L) may be used alone, or may be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to desired performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The type of compound used is, for example, one type as one embodiment. Alternatively, in another embodiment, there are two types, three types, four types, five types, six types, seven types, eight types, nine types, and ten or more types. is there.

In the liquid crystal composition, the content of the compound represented by the general formula (L) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, seizure, and dielectric constant. It is necessary to make appropriate adjustments according to the required performance such as anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L) with respect to the total amount of the liquid crystal composition is 0%, 1%, 10%, 20%, and 30%. Yes, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, and 25%.

When a composition having a low viscosity and a high response speed is required, it is preferable that the above lower limit value is high and the upper limit value is high. Further, when a composition having a high Tni of the liquid crystal composition and good temperature stability is required, it is preferable that the above lower limit value is high and the upper limit value is high. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is low and the upper limit value is low.

Both ^RL1 and ^RL2 are preferably alkyl groups when reliability is important, and alkoxy groups are preferable when reducing the volatility of the compound is important, and reduction of viscosity is important. It is preferable that at least one of them is an alkenyl group.

^RL1 and ^RL2 are linear alkyl groups having 1 to 5 carbon atoms and linear carbon atoms 1 to 4 when the ring structure to which they are bonded is a phenyl group (aromatic). The alkoxy group and the alkenyl group having 4 to 5 carbon atoms are preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, the linear carbon atom number is 1 to 5. Alkyl groups, linear alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from the groups represented by any of the formulas (R1) to (R5). (The black dots in each equation represent carbon atoms in the ring structure.)

Above all, by using in combination with a compound which represents at least one or more alkenyl groups R ^L1 and R ^L2, and a compound represented by the general formula (I), suppressing a decrease in voltage holding ratio (VHR) significantly be able to.

n ^L1 is preferably 0 when the response speed is important, 2 or 3 is preferable for improving the upper limit temperature of the nematic phase, and 1 is preferable for balancing these. Further, in order to satisfy the properties required for the liquid crystal composition, it is preferable to combine compounds having different values.

Preferably A ^L1, A ^L2, and A ^L3 if it is required to increase the Δn is aromatic, preferably to improve the response speed is an aliphatic, independently trans - 1,4-Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group , 1,4-Cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 It is preferable to represent a −diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably to represent the following structure.

It is more preferable to represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

Z ^L1 and Z ^L2 are preferably single-bonded when response speed is important.
The number of halogen atoms in the molecule is preferably 0 or 1.

The compound represented by the general formula (L) is preferably a compound selected from the compounds represented by the general formula (L-1).

(In the formula, ^RL1 and ^RL2 independently represent the same meanings as ^RL1 and ^RL2 in the general formula (L)).

R ^L11 and ^RL12 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .. The compound represented by the general formula (L-1) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, three types, four types, and five or more types as one embodiment.

The lower limit of the preferable content is 1%, 2%, 3%, 5%, 7%, 10%, and 15% with respect to the total amount of the liquid crystal composition. Yes, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%. The upper limit of the preferable content is 95%, 90%, 85%, 80%, 75%, 70%, and 65% with respect to the total amount of the liquid crystal composition. Yes, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%.

When a composition having a low viscosity and a high response speed is required, it is preferable that the above lower limit value is high and the upper limit value is high. Further, when a composition having a high Tni of the liquid crystal composition and good temperature stability is required, it is preferable that the lower limit value is moderate and the upper limit value is moderate. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is low and the upper limit value is low.

The compound represented by the general formula (L-1) is preferably a compound represented by the general formula (L-1-1).

^{(Wherein, R L11} represents a hydrogen atom or a methyl ^{group, R L2} represents the same meaning as ^{R L2} in Formula (L).)

The compound represented by the general formula (L-1-1) is a compound selected from the compound group represented by the formulas (L-1-1.11) to (L-1-1.13). Is preferable, and the compound is preferably represented by the formula (L-1-1.12) or the formula (L-1-1.13), and in particular, the compound is represented by the formula (L-1-1.13). It is preferably a compound.

The compound represented by the general formula (L-1-1) is a compound selected from the compound group represented by the formulas (L-1-1.21) to (L1-1.24). It is preferable that the compound is represented by the formulas (L-1-1.22) to (L1-1.24). In particular, the compound represented by the formula (L-1-1.22) is preferable because it particularly improves the response speed of the liquid crystal composition. Further, when obtaining Tni higher than the response speed, it is preferable to use a compound represented by the formula (L-1-1.23) or the formula (L1-1.24).

The compound represented by the general formula (L-1-1) is a compound selected from the compound group represented by the formula (L-1-1.31) and the formula (L1-1.41). It is preferable to have.

The compound represented by the general formula (L-1) is preferably a compound represented by the general formula (L-1-2).

(In the formula, R ¹²¹ and R ¹²² independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)

The compound represented by the general formula (L-1-2) is a compound selected from the compound group represented by the formulas (L-1-2-2.1) to (L-1-2.12). Is preferable, and it is preferable that the compound is represented by the formula (L-1-2.1), the formula (L-1-2.3) or the formula (L-1-2.4). In particular, the compound represented by the formula (L-1-2.1) is preferable because it particularly improves the response speed of the liquid crystal composition. Further, when obtaining a Tni higher than the response speed, the formula (L-1-2.3), the formula (L-1-2.4), the formula (L-1-2.11) and the formula (L-) are obtained. It is preferable to use the compound represented by 1-2.12). The sum of the compounds represented by the formulas (L-1-2.3), (L-1-2.4), (L-1-2.11) and (L-1-2-2.12). The content of is not preferably 20% or more in order to improve the solubility at low temperature.

Further, the compound represented by the general formula (L-1) is preferably a compound selected from the compound group represented by the general formula (L-1-3) and / or (L-1-4). ..

(R ^{ii 31} and R ^{ii 41} in the formula independently represent the same meaning as R ⁱⁱ 2 in the general formula (L)).
Further, the compound represented by the general formula (L) is preferably a compound represented by the following general formulas (L-2) to (L-11). The liquid crystal composition preferably contains one or more compounds represented by the general formulas (L-2) to (L-11) as the compounds represented by the general formula (L).

(In the formula, ^RL31 and ^RL32 are alkyl groups having 1 to 5 carbon atoms or alkenyl groups having 2 to 5 carbon atoms, and ^RL32 are alkyl groups having 1 to 5 carbon atoms and 1 to 5 carbon atoms. Represents an alkoxyl group of 5, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms.)

The compound represented by the general formula (L) is a compound selected from the general formula (L-4), the general formula (L-6), the general formula (L-7) and the general formula (L-8). Is more preferable, and it is more preferable that the compound is selected from the general formula (L-6), the general formula (L-7) and the general formula (L-8), and the general formula (L-7) and the general formula (L-) are more preferable. It is more preferable that the compound is selected from 8), and it is also preferable that the compound is selected from the general formula (L-6) and the general formula (L-8). More specifically, when a large Δn is required, the compound is preferably selected from the general formula (L-6), the general formula (L-8) and the general formula (L-11).

Further, in the compounds represented by the general formula (L-4), the general formula (L-7) and the general formula (L-8), ^RL31 is an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms. ^RL32 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and ^RL31 is preferably an alkenyl group having 2 to 5 carbon atoms. More preferably, it is more preferably an alkenyl group having 2 or 3 carbon atoms, and in the compound represented by the general formula (L-6), ^RL31 and ^RL32 are independently 1 to 5 carbon atoms, respectively. It is preferably an alkyl group or an alkenyl group having 2 to 5 carbon atoms.

Further, as the compound represented by the general formula (L), one or more compounds represented by the general formula (L-12), the general formula (L-13) or the general formula (L-14) are contained. It is also preferable to do so.

(In the formula, ^RL51 and ^RL52 independently represent an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, respectively, and X ^L51 and X ^L52 independently represents a fluorine atom or a hydrogen atom, and any one of ^XL51 and ^XL52 is a fluorine atom and the other one is a hydrogen atom.)

Further, as the compound represented by the general formula (L), one or more compounds represented by the general formula (L-16.1) to the general formula (L-16.3) may be contained. ..

Further, as the compound represented by the general formula (L), one or more compounds represented by the general formula (N-001) may be contained.

(In the formula, ^RN1 and ^RN2 are independently alkyl groups having 1 to 8 carbon atoms, alkoxyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, or alkenyl groups having 2 to 8 carbon atoms, respectively. L ¹ and L ² independently represent a hydrogen atom, a fluorine atom, CH ₃ or CF ₃ , except for those in which both L ¹ and L ² represent a fluorine atom.)
^RN1 and ^RN2 preferably represent an alkyl group having 1 to 5 carbon atoms.

The liquid crystal composition preferably has a positive dielectric anisotropy (Δε) at 25 ° C., and preferably has a dielectric anisotropy (Δε) of 1.5 to 20.0 at 25 ° C. , 1.5 to 18.0 is more preferred, 1.5 to 15.0 is more preferred, 1.5 to 11 is even more preferred, and 1.5 to 8 is particularly preferred.

The liquid crystal composition having a positive value of dielectric anisotropy (Δε) preferably contains a compound represented by the general formula (J) and a compound represented by the general formula (L). More specifically, it preferably contains a compound represented by the general formula (M) and a compound represented by the general formula (L-1), and the general formula (M-1) and / or the general formula (M). It is preferable to contain the compound represented by -2) and the compound represented by the general formula (L-1-1).

The total content of the compound represented by the general formula (J) and the compound represented by the general formula (L) in the liquid crystal composition is preferably 5% or more as the lower limit value, and is preferably 80. % Or more is preferable, 85% or more is preferably contained, 88% or more is preferably contained, 90% or more is preferably contained, 92% or more is preferably contained, and 95% or more is contained. Is preferable, 97% or more is preferably contained, 98% or more is preferably contained, 99% or more is preferably contained, and substantially no other compound is contained. Further, as an upper limit value, it is preferably contained in an amount of 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and substantially contains other compounds. It is preferable not to do so. Substantially means excluding unintentionally contained compounds such as impurities that are inevitably generated during production.

The total content of the compound represented by the general formula (M) and the compound represented by the general formula (L) in the liquid crystal composition is preferably 5% or more as the lower limit value in the composition. It is preferably contained in an amount of 80% or more, preferably 85% or more, preferably 88% or more, preferably 90% or more, preferably 92% or more, and 95% or more. It is preferable to contain 97% or more, preferably 98% or more, preferably 99% or more, and substantially no other compound. Further, as an upper limit value, it is preferably contained in an amount of 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and substantially contains other compounds. It is preferable not to do so.

The total content of the compound represented by the general formula (J) and the compound represented by the general formula (L-1) in the liquid crystal composition may be 5% or more as the lower limit value in the composition. Preferably, it is preferably contained in an amount of 10% or more, preferably 13% or more, preferably 15% or more, preferably 18% or more, preferably 20% or more, and preferably 23% or more. It is preferably contained, preferably 25% or more, preferably 28% or more, preferably 30% or more, preferably 33% or more, and preferably 35% or more. , 38% or more is preferable, and 40% or more is preferable. Further, as the upper limit value, it is preferably contained in an amount of 95% or less, preferably 90% or less, preferably 88% or less, preferably 85% or less, and preferably 83% or less. , 80% or less is preferable, 78% or less is preferably contained, 75% or less is preferably contained, 73% or less is preferably contained, 70% or less is preferably contained, and 68% or less is contained. It is preferably contained in an amount of 65% or less, preferably 63% or less, preferably 60% or less, preferably 55% or less, and preferably 50% or less. It is preferably contained in an amount of 40% or less.

The liquid crystal composition preferably has a negative dielectric anisotropy (Δε) at 25 ° C. and has a dielectric anisotropy (Δε) of −2.0 to −8.0 at 25 ° C. Is preferable, -2.0 to -6.0 is preferable, -2.0 to -5.0 is more preferable, and -2.5 to -4.0 is particularly preferable.

The liquid crystal composition having a negative dielectric anisotropy (Δε) is a compound represented by the general formulas (N-1) to (N-3) and a compound represented by the general formula (L). Is preferably contained. More specifically, it is preferable to contain a compound represented by the general formula (N-1) and a compound represented by the general formula (L-1), and a compound represented by the general formula (N-1). And it is preferable to contain a compound represented by the general formula (L-1-1).

The total content of the compounds represented by the general formulas (N-1) to (N-3) and the compounds represented by the general formula (L) in the liquid crystal composition is set as the lower limit value in the composition. It is preferably contained in an amount of 5% or more, preferably 80% or more, preferably 85% or more, preferably 88% or more, preferably 90% or more, and 92% or more. It is preferably 95% or more, 97% or more, 98% or more, 99% or more, and substantially no other compound. Is preferable. Further, as an upper limit value, it is preferably contained in an amount of 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and substantially contains other compounds. It is preferable not to do so.

The total content of the compound represented by the general formula (N-1) and the compound represented by the general formula (L) in the liquid crystal composition is preferably 5% or more as the lower limit value in the composition. , 80% or more is preferable, 85% or more is preferably contained, 88% or more is preferably contained, 90% or more is preferably contained, 92% or more is preferably contained, and 95% or more is contained. It is preferable to contain 97% or more, 98% or more, 99% or more, and substantially no other compound. Further, as an upper limit value, it is preferably contained in an amount of 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and substantially contains other compounds. It is preferable not to do so.

The total content of the compound represented by the general formula (J) and the compound represented by the general formula (L-1) in the liquid crystal composition is preferably 5% or more as the lower limit value in the composition. It is preferably contained in an amount of 10% or more, preferably 13% or more, preferably 15% or more, preferably 18% or more, preferably 20% or more, and preferably 23% or more. It is preferable to contain 25% or more, preferably 28% or more, preferably 30% or more, preferably 33% or more, and preferably 35% or more. It is preferably contained in an amount of 38% or more, and preferably 40% or more. Further, as the upper limit value, it is preferably contained in an amount of 95% or less, preferably 90% or less, preferably 88% or less, preferably 85% or less, and preferably 83% or less. , 80% or less is preferable, 78% or less is preferably contained, 75% or less is preferably contained, 73% or less is preferably contained, 70% or less is preferably contained, and 68% or less is contained. It is preferably contained in an amount of 65% or less, preferably 63% or less, preferably 60% or less, preferably 55% or less, and preferably 50% or less. It is preferably contained in an amount of 40% or less.

The liquid crystal composition has a refractive index anisotropy (Δn) at 25 ° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. More specifically, it is preferably 0.10 to 0.13 when dealing with a thin cell gap, and preferably 0.08 to 0.10. When dealing with a thick cell gap.

The liquid crystal composition has a viscosity (η) at 25 ° C. of 10 to 50 mPa · s, more preferably 10 to 40 mPa · s, and particularly preferably 10 to 35 mPa · s.

The liquid crystal composition has a rotational viscosity (γ ₁ ) at 25 ° C. of 60 to 130 mPa · s, more preferably 60 to 110 mPa · s, and particularly preferably 60 to 100 mPa · s.

The liquid crystal composition has a nematic phase-isotropic liquid phase transition temperature (T _ni ) of 60 ° C to 120 ° C, more preferably 70 ° C to 100 ° C, and particularly preferably 70 ° C to 85 ° C.

In addition to the above-mentioned compounds, the liquid crystal composition may contain ordinary nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, infrared absorber, polymerizable monomer, light stabilizer (HALS) and the like. Good.

For example, the liquid crystal composition may contain a liquid crystal compound having a dielectric constant anisotropy (Δε) at 25 ° C. of +2.0 to +50.0 as a normal nematic liquid crystal or smectic liquid crystal, and the content thereof is Although it is 0% by mass to 50% by mass, it is preferably 1% by mass to 30% by mass, preferably 3% by mass to 30% by mass, and preferably 5% by mass to 20% by mass.

For example, the liquid crystal composition may contain 0.01 to 2% by mass of a polymerizable compound such as a biphenyl derivative or a terphenyl derivative as a polymerizable monomer.

As the polymerizable monomer, one or two kinds of a monofunctional polymerizable compound having one reactive group and a polyfunctional polymerizable compound having two or more reactive groups such as bifunctional or trifunctional are used. The above may be contained. The polymerizable compound having a reactive group may or may not contain a mesogenic moiety.

In the polymerizable compound having a reactive group, the reactive group is preferably a substituent having a polymerizable property with light.

Among the polymerizable compounds having a reactive group, the polymerizable compound having a monofunctional reactive group is specifically represented by the following general formula (VI).

(In the formula, X ³ represents a hydrogen atom or a methyl group, Sp ³ is a single bond, an alkylene group having 1 to 8 carbon atoms or −O− (CH ₂ ) _t − (in the formula, t is 2 to 2). It represents an integer of 7, and the oxygen atom is bound to the aromatic ring.), Where V is a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent ring having 5 to 30 carbon atoms. Although it represents a substituent, the alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which oxygen atoms are not adjacent to each other, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group is an oxygen atom). May be substituted with an oxygen atom in a non-adjacent range) or with a cyclic substituent, W represents a hydrogen atom, a halogen atom or an alkylene group having 1 to 8 carbon atoms). The polymerizable compound represented is preferred.

In the above general formula (VI), X ³ represents a hydrogen atom or a methyl group, but a hydrogen atom is preferable when the reaction rate is important, and a methyl group is used when reducing the reaction residual amount is important. preferable.

In the above general formula (VI), Sp ³ represents a single bond, an alkylene group having 1 to 8 carbon atoms or −O− (CH ₂ ) _t − (in the formula, t represents an integer of 2 to 7, and an oxygen atom. Is bonded to an aromatic ring), but the carbon chain is preferably not very long, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or an alkylene group having 1 to 5 carbon atoms is preferable. An alkylene group is more preferred. Also, when Sp ³ represents −O− (CH ₂ ) _t −, t is preferably 1 to 5, more preferably 1-3.

In the above general formula (VI), V represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and is an alkylene group in the polyvalent alkylene group. May be substituted with an oxygen atom in a range in which the oxygen atom is not adjacent, or an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted in the range in which the oxygen atom is not adjacent). ) Or may be substituted with a cyclic substituent, preferably substituted with two or more cyclic substituents.

More specifically, the polymerizable compound represented by the general formula (VI) has the general formula (X1a).

(In the formula, A ¹ represents a hydrogen atom or a methyl group.
A ² is a single bond or an alkylene group having 1 to 8 carbon atoms (one or two or more methylene groups in the alkylene group are independent oxygen atoms, assuming that the oxygen atoms are not directly bonded to each other. It may be substituted with −CO−, −COO− or −OCO−, and one or more hydrogen atoms in the alkylene group are independently substituted with a fluorine atom, a methyl group or an ethyl group, respectively. May be),
A ³ and A ⁶ are independently hydrogen atoms, halogen atoms, or alkyl groups having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl groups do not directly bond oxygen atoms to each other. As such, they may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkyl group are independently halogens. It may be substituted with an atom or an alkyl group having 1 to 17 carbon atoms.)
A ⁴ and A ⁷ are independently hydrogen atoms, halogen atoms, or alkyl groups having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl groups do not directly bond oxygen atoms to each other. As such, they may be independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkyl group are independently halogens. It may be substituted with an atom or an alkyl group having 1 to 9 carbon atoms.)
p represents 1 to 10
B ¹ , B ² and B ³ are independently hydrogen atoms and linear or branched alkyl groups having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl groups are , The oxygen atoms may be independently substituted with oxygen atoms, -CO-, -COO- or -OCO-, assuming that they do not bond directly to each other, and one or more of the alkyl groups. The hydrogen atom may be independently substituted with a halogen atom or a trialkylsilyl group having 3 to 6 carbon atoms.)).

Further, the polymerizable compound represented by the general formula (VI) is specifically represented by the general formula (X1b).

(Wherein, A ⁸ represents a hydrogen atom or a methyl group,
The 6-membered rings T ¹ , T ² and T ³ are independent of each other.

(However, q represents an integer from 1 to 4).
q represents 0 or 1 and represents
Y ¹ and Y ² are independently single-coupled, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -C≡C-, -CH = CH- _{, -CF = CF -, - (} CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH 2 = CHCH 2 CH 2 - or _-CH 2 _CH 2 CH = CH-, representing
Y ³ represents a single bond, -COO- or -OCO-,
B ⁸ represents a hydrocarbon group having 1 to 18 carbon atoms. ) Can also be mentioned.

Further, the polymerizable compound represented by the general formula (VI) is specifically represented by the general formula (X1c).

(In the formula, R ⁷⁰ represents a hydrogen atom or a methyl group, and R ⁷¹ represents a hydrocarbon group having a condensed ring.) Examples thereof also include compounds represented by.

Further, among the polymerizable compounds having a reactive group, the polymerizable compound having a polyfunctional reactive group is represented by the following general formula (VII).

(In the formula, X ¹ and X ² independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or −O−. (CH ₂ ) represents _s − (in the formula, s represents an integer of 2 to 7 and an oxygen atom is bonded to an aromatic ring), and U represents a linear or branched number of carbon atoms 2 to 20. It represents a valent alkylene group or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and the alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which oxygen atoms are not adjacent to each other, and the number of carbon atoms is 5. It may be substituted with an alkyl group of ~ 20 (the alkylene group in the group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent) or a cyclic substituent, and k is an integer of 1 to 5. The polymerizable compound represented by (represented) is preferable.

In the above general formula (VII), X ¹ and X ² independently represent a hydrogen atom or a methyl group, but when the reaction rate is important, the hydrogen atom is preferable, and it is important to reduce the reaction residual amount. If this is the case, a methyl group is preferable.

In the above general formula (VII), Sp ¹ and Sp ² are independently single bonds, an alkylene group having 1 to 8 carbon atoms, or −O− (CH ₂ ) _s − (in the formula, s is 2 to 7). It represents an integer of, and the oxygen atom is bound to the aromatic ring.) However, the carbon chain is preferably not very long, and a single bond or an alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or a single bond or An alkylene group having 1 to 3 carbon atoms is more preferable. Also, when Sp ¹ and Sp ² represent −O− (CH ₂ ) _s −, s is preferably 1 to 5, more preferably 1-3, and at least one of Sp ¹ and Sp ² is a single bond. It is more preferable that there is a single bond, and it is particularly preferable that both are single bonds.

In the above general formula (VII), U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and is an alkylene group in the polyvalent alkylene group. May be substituted with an oxygen atom in a range in which the oxygen atom is not adjacent, or an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted in the range in which the oxygen atom is not adjacent). ), May be substituted with a cyclic substituent, preferably substituted with two or more cyclic substituents.

In the above general formula (VII), specifically, U preferably represents the following formulas (VII-1) to formulas (VII-5), and formulas (VII-1) to formulas (VII-3). It is more preferable to represent it, and it is particularly preferable to represent the formula (VII-1).

(In the formula, both ends shall be bonded to Sp ¹ or Sp ^2. )

When U has a ring structure, it is preferable that at least one of Sp ¹ and Sp ² represents a single bond, and it is also preferable that both are single bonds.

In the above general formula (VII), k represents an integer of 1 to 5, but it is preferably a bifunctional compound in which k is 1, or a trifunctional compound in which k is 2, and more preferably a bifunctional compound. ..

More specifically, the general formula (P)

It is preferable to contain one or more polymerizable compounds represented by.

In the general formula (P), X ²⁰¹ and X ²⁰² each independently represent a hydrogen atom, a methyl group, or -CF ₃ groups. As X ²⁰¹ and X ²⁰² , a diacrylate derivative having a hydrogen atom and a dimethacrylate derivative having a methyl group are preferable, and a compound having one hydrogen atom and the other methyl group is also preferable. A preferable compound can be used depending on the application, but in the PSA display device, the polymerizable compound represented by the general formula (P) preferably has at least one methacrylate derivative, and preferably has two.

In the general formula (P), Sp ²⁰¹ and Sp ²⁰² are independently single bonds, an alkylene group having 1 to 8 carbon atoms or −O− (CH ₂ ) _s − (in the formula, s is 2 to 7). Represents an integer of, and the oxygen atom shall be bonded to the ring.) In the PSA type liquid crystal display element, Sp ²⁰¹ and Sp ²⁰² preferably have at least one single bond, and are either a compound having a single bond or an alkylene having a single bond and the other having 1 to 8 carbon atoms. It is preferably a group or −O− (CH ₂ ) _s −, in which case an alkylene group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4.

In formula ^{(P), M 201, M} 202 and ^{M 203} are each independently trans-1,4-cyclohexylene group (two or more -CH of one or non-adjacent in groups ₂ - -O- or -S- may be substituted), 1,4-phenylene group (one in the group or two or more non-adjacent -CH = may be substituted by -N = Good), 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- It represents a 2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the hydrogen atoms in the groups are independently fluorine atoms, -CF ₃ groups, and the number of carbon atoms. It may be substituted by either an alkyl group of 1 to 10, an alkoxyl group having 1 to 10 carbon atoms, or a formula (R-1) to a formula (R-15).

In the general formula (P), Z ²⁰¹ and Z ²⁰² are independently -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -,-, respectively. CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO -, -CH _2- OCO-, -CY ¹ = CY ^2- (In the equation, Y ¹ and Y ² independently represent a fluorine atom or a hydrogen atom), -C ≡ C- or a single bond. , -COO-, -OCO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -C≡C- or single bond is preferred, -COO-, -OCO-,- CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -,- CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO- or a single bond is more preferred.

In the general formula (P), n ²⁰¹ represents 0, 1 or 2, but 0 or 1 is preferable. However, when a plurality of M ²⁰² and Z ²⁰² exist, they may be different or the same.

At least one polymerizable compound represented by the general formula (P) may be contained, preferably 1 to 5 types, and further preferably 1 to 3 types.

The content of the general formula (P) is preferably 0.01 to 2.00% by mass, more preferably 0.05 to 1.00% by mass, and 0.10 to 0.50% by mass. It is particularly preferable to have.

More specifically, when n ²⁰¹ is 0 in the general formula (P), the ring structure between Sp ²⁰¹ and Sp ²⁰² is preferably from formula (XXa-1) to formula (XXa-5). The formulas (XXa-1) to (XXa-3) are more preferable, and the formula (XXa-1) or the formula (XXa-2) is particularly preferable. However, both ends of the equation shall be coupled to Sp ²⁰¹ or Sp ²⁰² .

The polymerizable compound represented by the general formula (P) containing these skeletons has an optimum orientation regulating force after polymerization for a PSA type liquid crystal display element, and a good orientation state can be obtained, so that display unevenness is suppressed. There is an effect that is done or does not occur at all.

From the above, as the polymerizable monomer, compounds represented by formulas (XX-1) to general formulas (XX-10) are preferable, and formulas (XX-1) to formulas (XX-4) are more preferable.

From the formula (XX-1) to the general formula (XX-10), Sp ^xx is an alkylene group having 1 to 8 carbon atoms or −O− (CH ₂ ) _s − (in the formula, s is an integer from 2 to 7). It represents, and the oxygen atom shall be bonded to the ring.)

From the formula (XX-1) to the general formula (XX-10), the hydrogen atom in the 1,4-phenylene group is further added to -F, -Cl, -CF ₃ , -CH ₃ , and formula (R-1). May be replaced by any of the formulas (R-15).

When n ²⁰¹ is 1 in the general formula (P), for example, polymerizable compounds of formulas (P31) to (P48) are preferable.

The hydrogen atoms in the 1,4-phenylene group and the naphthalene group in the formulas (P31) to (P48) are further changed from -F, -Cl, -CF ₃ , -CH ₃ , and formula (R-1). It may be replaced by any of (R-15).

The polymerizable compound represented by the general formula (P) containing these skeletons has an optimum orientation regulating force after polymerization for a PSA type liquid crystal display element, and a good orientation state can be obtained, so that display unevenness is suppressed. There is an effect that is done or does not occur at all.

When n ²⁰¹ is 1 in the general formula (P) and there are a plurality of formulas (R-1) or (R-2), for example, a polymerizable compound such as the formulas (P301) to (P316) can be used. preferable.

The hydrogen atoms in the 1,4-phenylene group and the naphthalene group in the formulas (P301) to (P316) may be further substituted with -F, -Cl, -CF ₃ , and -CH ₃ .

As the polymerizable compound represented by the general formula (P), for example, polymerizable compounds represented by the formulas (Ia-1) to (Ia-31) are also preferable.

Further, as the antioxidant, hindered phenol represented by the general formula (H-1) to the general formula (H-4) is preferable.

In the general formulas (H-1) to (H-4), ^RH1 is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. It represents an alkenyloxy group having 2 to 10 carbon atoms, one -CH ₂ present in the radical - or non-adjacent two or more -CH ₂ - are each independently -O- or -S- In addition, one or more hydrogen atoms existing in the group may be independently substituted with a fluorine atom or a chlorine atom, respectively. More specifically, it may be an alkyl group having 2 to 7 carbon atoms, an alkoxyl group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. It is more preferably an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.

In the general formula (H-4), ^MH4 is an alkylene group having 1 to 15 carbon atoms (one or two or more -CH ₂ − in the alkylene group is -CH ₂ − so that oxygen atoms are not directly adjacent to each other. It may be replaced with O-, -CO-, -COO-, -OCO-), -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-,- OCF _2- , -CF ₂ CF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-,- C≡C−, single bond, 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or trans-1,4-cyclohexylene group. It is expressed that it is preferably an alkylene group having 1 to 14 carbon atoms, and a large number of carbon atoms is preferable in consideration of volatility, but it is preferable that the number of carbon atoms is not too large in consideration of viscosity. The number of carbon atoms is more preferably 2 to 12, the number of carbon atoms is 3 to 10, the number of carbon atoms is 4 to 10, the number of carbon atoms is 5 to 10, and the number of carbon atoms is 6 to 10.

In the general formula (H-1) to the general formula (H-4), one in the 1,4-phenylene group or two or more non-adjacent -CH = may be replaced by -N =. Further, the hydrogen atom in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.

In the general formula (H-1) to the general formula (H-4), one in the 1,4-cyclohexylene group or two or more non-adjacent −CH ₂ − are replaced by −O− or −S−. It may have been. Further, the hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.

More specifically, for example, formulas (H-11) to formulas (H-15) can be mentioned.

The liquid crystal composition may contain 1 mass ppm or more of the antioxidant, but is preferably 10 mass ppm or more, preferably 20 mass ppm or more, and preferably 50 mass ppm or more. The upper limit of the content of the antioxidant is 10000 mass ppm, but 1000 mass ppm is preferable, 500 mass ppm is preferable, and 100 mass ppm is preferable.

The liquid crystal display element using the above liquid crystal composition has no or suppressed display defects, has excellent display quality, and has a high response speed. In particular, as an active matrix-driven liquid crystal display element, for example, a TN type, It can be applied to OCB type, VA type, VA-IPS type, PSVA type, PSA type, FFS type, IPS type or ECB type. The PSVA type and the PSA type are substantially synonymous.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.

Synthesis Example 1 [Synthesis of Fluorine-Containing Thermosetting Resin (A-1)]
In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 26.8 g of acrylic acid and 3,3,4,4,5,5,6,6,7,7,8,8,8- 30.0 g of tridecafluoro-1-vinyloxyoctane was charged, and the mixture was stirred at room temperature [20 to 28 ° C.] for 21 hours under a dry air stream. Next, 0.003 g of methquinone and 107.6 g of diisopropyl ether were added, 161.4 g of a saturated aqueous sodium carbonate solution and 161.4 g of ion-exchanged water were added to separate the liquids. Then, after taking out the upper layer, 161.4 g of ion-exchanged water was added to separate the liquids. Further, after taking out the upper layer, the solvent was removed to obtain a polymerizable monomer having a blocked carboxyl group represented by the general formula (1).

50 g of propylene glycol monomethyl ether acetate was charged as a solvent into a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. Next, a monomer solution prepared by dissolving 17.5 g of the polymerizable monomer having a blocked carboxyl group and 32.5 g of polypropylene glycol monomethacrylate in 40.0 g of propylene glycol monomethyl ether acetate (PGMEA) and a radical polymerization initiator. As a result, 1.5 g of 2,2'-azobis (methyl isobutyrate) was dissolved in 17 g of propylene glycol monomethyl ether acetate, and two types of dropping solutions with a polymerization initiator solution were set in separate dropping devices, and the inside of the flask was 80. The dropping was started at the same time while keeping the temperature at ° C., and each was dropped over 3 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 10 hours, and then propylene glycol monomethyl ether acetate was further added to obtain a propylene glycol monomethyl ether acetate solution containing 20% by mass of a fluorine-containing pyrolytic resin (A-1). As a result of measuring the molecular weight of the obtained fluorothermosetting resin (A-1) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,500, the weight average molecular weight was 9,000, and the maximum molecular weight was 90,000. ..

Synthesis Example 2 [Synthesis of Fluorine-Containing Thermosetting Resin (A-2)]
In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 26.8 g of acrylic acid and 3,3,4,4,5,5,6,6,7,7,8,8,8- 30.0 g of tridecafluoro-1-vinyloxyoctane was charged, and the mixture was stirred at room temperature [20 to 28 ° C.] for 21 hours under a dry air stream. Next, 0.003 g of methquinone and 107.6 g of diisopropyl ether were added, 161.4 g of a saturated aqueous sodium carbonate solution and 161.4 g of ion-exchanged water were added to separate the liquids. Then, after taking out the upper layer, 161.4 g of ion-exchanged water was added to separate the liquids. Further, after removing the upper layer, the solvent was removed to obtain a polymerizable monomer having a blocked carboxyl group.

50 g of propylene glycol monomethyl ether acetate was charged as a solvent into a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. Next, a monomer solution prepared by dissolving 17.5 g of the polymerizable monomer having a blocked carboxyl group and 32.5 g of propylene glycol polybutylene glycol monomethacrylate in 40 g of propylene glycol monomethyl ether acetate, and 2 as a radical polymerization initiator. , 2'-Azobis (methyl isobutyrate) 0.5 g dissolved in 17 g of propylene glycol monomethyl ether acetate and a polymerization initiator solution are set in separate dropping devices, and the temperature inside the flask is set to 80 ° C. The dropping was started at the same time while maintaining the temperature, and the monomer solution was added dropwise over 3 hours and the initiator solution was added dropwise over 4 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 10 hours, and then propylene glycol monomethyl ether acetate was further added to obtain a propylene glycol monomethyl ether acetate solution containing 20% by mass of a fluorine-containing pyrolytic resin (A-2). As a result of measuring the molecular weight of the obtained fluorothermally decomposable resin (A-2) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,900, the weight average molecular weight was 28,000, and the maximum molecular weight was 300,000. .. The fluorine atom content was 18% as a result of measurement by ion chromatography after combustion.

Synthesis Example 3 [Synthesis of Fluorine-Containing Thermosetting Resin (A-3)]
In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 26.8 g of acrylic acid and 3,3,4,4,5,5,6,6,7,7,8,8,8- 30.0 g of tridecafluoro-1-vinyloxyoctane was charged, and the mixture was stirred at room temperature [20 to 28 ° C.] for 21 hours under a dry air stream. Next, 0.003 g of methquinone and 107.6 g of diisopropyl ether were added, 161.4 g of a saturated aqueous sodium carbonate solution and 161.4 g of ion-exchanged water were added to separate the liquids. Then, after taking out the upper layer, 161.4 g of ion-exchanged water was added to separate the liquids. Further, after taking out the upper layer, the solvent was removed to obtain a polymerizable monomer having a blocked carboxyl group represented by the general formula (1).

75 g of propylene glycol monomethyl ether acetate was charged as a solvent into a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. Next, a monomer solution prepared by dissolving 18.0 g of the polymerizable monomer having a blocked carboxyl group and 32.0 g of polyethylene glycol monomethacrylate in 50.0 g of propylene glycol monomethyl ether acetate (PGMEA) and a radical polymerization initiator. As a result, 2.5 g of 2,2'-azobis (methyl isobutyrate) was dissolved in 25 g of propylene glycol monomethyl ether acetate, and two types of diluents with a polymerization initiator solution were set in separate dropping devices, and the inside of the flask was 80. The dropping was started at the same time while keeping the temperature at ° C., and each was dropped over 3 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 10 hours, and then propylene glycol monomethyl ether acetate was further added to obtain a propylene glycol monomethyl ether acetate solution containing 20% by mass of a fluorine-containing pyrolytic resin (A-3). As a result of measuring the molecular weight of the obtained fluorothermosetting resin (A-3) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 1,500, the weight average molecular weight was 10,000, and the maximum molecular weight was 90,000. ..

Synthesis Example 4 [Synthesis of Polyamide-imide Resin]
In a flask equipped with a stirrer, thermometer and condenser, 540.3 g of 1,3-dimethyl-2-imidazolidinone (DMI) and 15.7 g of tolylene diisocyanate, 4,4'-diisocyanate-3,3'- 95.0 g of dimethyl-1,1'-biphenyl, 76.8 g of trimellitic anhydride, and 32.2 g of benzophenone-3,3', 4,4'-tetracarboxylic dianhydride were charged, and heat was generated while stirring. After raising the temperature to 140 ° C. over 2 hours, the reaction was carried out at this temperature for 22 hours. The reaction proceeded with the foaming of carbon dioxide gas, and the inside of the system became a yellow transparent liquid. A solution of a polyamide-imide resin (1) having a viscosity of 9 Pa · s at 25 ° C. and a resin solid content of 28% and a solution acid value of 10 (mgKOH / g) was obtained. Moreover, as a result of the measurement of gel permeation chromatography, the weight average molecular weight was 10,000.

Example 1 [Preparation of resin composition]
7.25 parts by mass of epoxy resin EPICLON 850-S manufactured by DIC Co., Ltd. was added as a curing agent to 100 parts by mass of the DMI solution of the polyamide-imide resin (1), and 1,2-dimethylimidazole as a catalyst was 0.1 based on the solid content. The resin solution was prepared by adding mass% and diluting to 35 mass% with DMI. 0.0088 parts and 3.75 parts of DMI were mixed with 5.0 parts of this solution with a 20% solution of the fluorine-containing thermosetting resins (A-1) to (A-3) obtained in Synthesis Example 1. To prepare a resin composition.

Example 2 [Preparation of cured product]
The resin composition obtained in Example 1 was spin-coated on a 10 cm × 10 cm Cr-plated glass plate at a rotation speed of 1000 rpm for 3 seconds and 3000 rpm for 30 seconds, dried at 100 ° C. for 30 minutes, and then at 200 ° C. It was heated under the condition of 1 hour to form a coating film as a cured product.

Comparative Example 1 [Preparation of a coating film with a composition containing no fluorine-containing thermosetting resin]
A comparative control resin composition was prepared in the same manner as in Example 1 except that a fluorine-containing thermosetting resin was not used, and a coating film was prepared in the same manner as in Example 2 using this.

<Evaluation method for coating film smoothness>
Using the coating films obtained in Example 2 and Comparative Example 1, the smoothness of the surface was evaluated as follows.
Using a reflection spectroscopic film pressure gauge FE-3000 manufactured by Otsuka Electronics Co., Ltd., the area of 4 cm × 4 cm in the center of the coating film was divided into 400 points, and the film thickness of each was measured. The smoothness was evaluated by the standard deviation of the measured film thickness and the Range% (maximum / minimum difference in film thickness / average film thickness). (The smaller the Range%, the smoother it is.)

Test Example In order to directly evaluate the effect of the fluorine-containing thermosetting resin on the liquid crystal composition, the following test was conducted.
Preparation of liquid crystal sample: The sample before and after the heat treatment of the fluorothermally decomposable resin obtained in the synthesis example and the sample before and after the heat treatment of the fluorine-based surfactant Megafuck F-554 manufactured by DIC Corporation are used as the following liquid crystal compositions. Compositions containing 1.0% by mass and 0.1% by mass were prepared, respectively, and pressure-filtered using a 0.2 micron filter to prepare a liquid crystal sample. The heat treatment was performed by leaving it in a hot air dryer set at 230 ° C. for 30 minutes.
The prepared liquid crystal sample was enclosed in a cell for measuring voltage retention (VHR), and VHR was measured.
VHR: Voltage retention rate (%) at 60 Hz at 60 ° C and an applied voltage of 5 V.

The following abbreviations are used to describe the compounds that make up the liquid crystal composition.

The measured characteristics of the liquid crystal composition in the table are as follows.
TNI: Nematic phase-isotropic liquid phase transition temperature (° C)
Refractive index anisotropy at Δn: 25 degrees (also known as birefringence)
Permittivity anisotropy at Δε: 25 degrees Rotational viscosity coefficient (mPa · s) at γ1: 25 degrees

As the VHR measurement cell, one of the following two types of cells was used.
VHR cell 1:
A horizontally aligned film (SE-7492, manufactured by Nissan Chemical Co., Ltd.) is fired on a transparent glass substrate with an ITO electrode, and after rubbing treatment, the liquid crystal orientation is antiparallel and the substrate spacing is 3.5 μm via a bead spacer. A horizontally oriented cell assembled by adhering the edges with a thermosetting resin.
VHR cell 2:
After firing a vertically oriented film (JALS-2096, manufactured by JSR Corporation) on a transparent glass substrate with an ITO electrode, the edges are bonded with a thermosetting resin via a bead spacer so that the substrate spacing is 3.5 μm. Assembled vertically oriented cell.

The VHR measurement was carried out in the same manner except that the liquid crystal composition LC1 was changed to LC2 to LC4. In all cases, the sample after the heat treatment of the fluorothermally decomposable resin (A-2) was obtained as 0. In the system in which 1% by mass was added, the measured value was 97.3 to 97.6%, and it was confirmed that the compound after thermal decomposition could effectively suppress the influence on the liquid crystal composition.

As a result of conducting the same test using the fluorine-containing thermosetting resins (A-1) and (A-3) as 0.1% instead of the fluorine-containing thermosetting resin (A-2), the measured value was 97. It was 0 to 97.9%, and the same result as that of the fluorine-containing thermosetting resin (A-2) was obtained.

When VHR measurement was performed in the same manner except that the liquid crystal composition was changed to LC6 instead of LC5, 0.1% by mass of the heat-treated sample of the fluorothermally decomposable resin (A-2) was added. The measured value in the VHR cell 2 was 98.8%, and it was confirmed that the compound after thermal decomposition could effectively suppress the influence on the liquid crystal composition.

As a result of conducting the same test using the fluorine-containing thermosetting resins (A-1) and (A-3) as 0.1% instead of the fluorine-containing thermosetting resin (A-2), the measured value was 98. It was 7 and 98.9%, and the same result as that of the fluorine-containing thermosetting resin (A-2) was obtained.

Synthesis Example 5 [Preparation of Alignment Agent for Rubbing Treatment Alignment Film Formation]
29.80 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 14.16 g of p-phenylenediamine and 1.04 g of the compound represented by the following formula were dissolved in 405 g of N-methyl-2-pyrrolidone. The solution was reacted at 60 ° C. for 6 hours. The resulting reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Then, the solid substance was separated, washed with methyl alcohol, and dried under reduced pressure at 40 ° C. for 15 hours to obtain 40.25 g of polyamic acid (b-2-1).

6.0 g of the polyamic acid (b-2-1) obtained in Synthesis Example 5 and 0.3 g of polyethylene glycol diglycidyl ether (molecular weight of about 400) were dissolved in 120 g of γ-butyrolactone to have a solid content concentration of 5.0. A liquid crystal alignment agent is prepared by obtaining a mass% solution, blending 0.1% of the fluorothermally decomposable resin obtained in the synthetic example in terms of solid content, and then filtering with a filter having a pore size of 1 μm. did.

Example 3 [Manufacturing of alignment film and liquid crystal display element]
The liquid crystal alignment agent obtained in Synthesis Example 3 is applied using a spinner on a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm (rotation speed: 2000 rpm, coating time: 1 minute). Then, it was dried at 200 ° C. for 1 hour to form a coating film having a dry film thickness of 0.08 μm. The Range% of the obtained film was 3% or less. When the surface was analyzed by XPS, no fluorine atom was detected.

The formed coating film surface is oriented by applying a rubbing treatment using a rubbing machine equipped with a roll wrapped with a rayon cloth to have a hair-foot pushing length of 0.2 mm, a roll rotation speed of 200 rpm, and two rubbing times. A film was formed. Two substrates having a liquid crystal alignment film are prepared, and an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3 μm is applied to the outer edge of each substrate by a screen printing method, and then rubbing on each liquid crystal alignment film. The two substrates were placed facing each other with a gap so that the directions were opposite to each other, and the outer edges were crimped to cure the adhesive. After that, the nematic liquid crystal "MLC-2001" (manufactured by Merck Co., Ltd.) was injected and filled into the cell gap partitioned by the adhesive on the surface and the outer edge of the two substrates, and then the injection holes were epoxy-based bonded. A liquid crystal cell was formed by sealing with an agent. Then, a liquid crystal display element was manufactured by laminating a polarizing plate on the outer surface of the liquid crystal cell so that the polarization direction coincided with the rubbing direction of the liquid crystal alignment film formed on one surface of the substrate.

When the burn-in of the obtained liquid crystal display element was visually confirmed, it was good. The results of VHR measurement were 98.8% in the system using the fluorine-containing thermosetting resin (A-1), 98.9% in the same (A-2), and 98.8% in (A-3).

Comparative Example 2
In Example 3, a liquid crystal alignment agent was prepared using Megafuck F-554 instead of the fluorine-containing thermosetting resin (A-1), and an alignment film was prepared in the same manner as in Example 3. The Range% of the obtained film was 3% or less. When the surface was analyzed by XPS, fluorine atoms were detected. Furthermore, when a liquid crystal display element was manufactured using this, it was confirmed that seizure had occurred. The VHR was 93.2%.

Example 4 [Manufacturing of Vertical Alignment Film and Liquid Crystal Display Element]
The fluorothermosetting resin obtained in the synthesis example was dissolved in 100 parts of a polyimide solution (JALS2131-R6; manufactured by JSR Corporation) containing 3% of a polyimide precursor in an amount of 0.1% by mass in terms of solid content, and slit. A substrate having an ITO electrode having a pattern was spin coated. Then, the alignment film was heated to 200 ° C. and the polyimide precursor was cured to form the polyimide alignment film. The average film thickness of the alignment film was 110 nm, and the Range% was 3% or less. When the surface was analyzed by XPS, no fluorine atom was detected. A liquid crystal display element was produced by sandwiching the liquid crystal composition of LC5 between the substrate and a substrate having a transparent electrode by a dropping method. The seizure was good as a result of visual confirmation. In the system using the fluorine-containing thermosetting resin (A-1), it was 98.5%, (A-2) 98.6%, and (A-3) 98.8%.

Comparative Example 3
In Example 4, the alignment film and the liquid crystal display element were produced in the same manner except that Megafvck F-554 was used instead of the fluorine-containing thermosetting resin (A-1). The Range% of the coating film was 3% or less, but VHR was not measured because it was confirmed that seizure had occurred.

Example 5 [Manufacturing of photoalignment film and liquid crystal display element]

4,4'-Diaminotran (1.2534 g, 6.018 mmol) was dissolved in NMP (N-methyl-2-pyrrolidone, 22.5 g), PMDA (0.5901 g, 3.009 mmol) and CBTA (0. 6564 g (3.009 mmol) was added while keeping the temperature below room temperature. After stirring for 2 hours, BC (ethylene glycol monobutyl ether, 22.5 g) was added. The viscosity of this product was 350 mPa · s. When this solution was stirred at 60 ° C. for about 4 hours, a varnish having a viscosity of 33 mPa · s was obtained. 3 g of varnish A was weighed in a sample bottle, and BC was added to make 5 g. Further, 0.1% by mass of the fluorine-containing thermosetting resin obtained in the synthetic example was added in terms of solid content and mixed. This about 3% by mass polyamic acid solution was dropped onto a transparent glass substrate provided with an ITO electrode on one side, and applied by the spinner method (2,300 rpm, 15 seconds). After coating, the substrate was heated at 80 ° C. for 5 minutes to evaporate the solvent, and then linearly polarized light was irradiated through the polarizing plate (energy of about 5 J / cm ^{2 at} 365 nm). The substrate after light irradiation was heat-treated in an oven at 230 ° C. for 30 minutes to obtain a photoalignment film having a film thickness of about 60 nm. The Range% of the membrane was 3% or less.

The two substrates on which the above photoalignment film is formed on the ITO electrode are placed on the surface on which the photoalignment film is formed so that the polarization directions of the linearly polarized light irradiated to each photoalignment film are parallel. A liquid crystal display element having a cell thickness of 3 μm was assembled by forming and matching gaps for injecting the liquid crystal composition between the opposing photoalignment films. The liquid crystal composition A shown below was injected into this cell.

When the liquid crystal cell A was visually observed, a so-called flow orientation in which the liquid crystals were lined up along the direction in which the liquid crystals flowed was slightly observed. The liquid crystal cell A was subjected to isotropic treatment at 110 ° C. for 30 minutes and cooled to room temperature. When this liquid crystal cell A was observed with a microscope, no liquid crystal orientation defect was observed. In the system using the fluorine-containing thermosetting resin (A-1), it was 99.0%, (A-2) 98.8%, and (A-3) 98.8%.

Comparative Example 4
In Example 5, the alignment film and the liquid crystal display element were produced in the same manner except that Megafvck F-554 was used instead of the fluorine-containing thermosetting resin (A-1). The Range% of the coating film was within 3%, but VHR was not measured because it was confirmed that the orientation defect of the liquid crystal had occurred.

Example 6 [Manufacturing of photoalignment film and liquid crystal display element]
0.820 g (3.66 mmol) of 2,3,5-tricarboxycyclopentylacetic acid-1,2: 3,4-dianhydride in 2.014 g (3.66 mmol) of 2 in 6.56 mL of NMP. -(2,4-diaminophenyl) ethyl (2E) -3- (4- {difluoro [4- (4,4,4-trifluorobutoxy) phenyl] methoxy} phenyl) prop-2-enoate solution was added. .. Then, stirring was carried out at 0 ° C. for 2 hours. The mixture was then reacted at room temperature for 21 hours. The polymer mixture was diluted with 18 mL of THF, precipitated in 800 mL of water and dried under vacuum at room temperature to give 2.76 g of polyamic acid in the form of a white powder. Solid polyamic acid is mixed with NMP, stirred well until dissolved, and butyl cellulose (BC), which is a second solvent, is added to convert the fluorothermally decomposable resin (A-1) into solid content. The composition was sufficiently stirred to obtain a final solution, thereby obtaining a 4.5% solution of polyamic acid. The solvent ratio of NMP to butyl cellulose is 1: 1. The polymer solution was spin-coated on two ITO-coated glass substrates at a spin rate of 2700 rpm for 30 seconds. The substrate was subjected to a firing procedure consisting of spin coating, pre-baking at 130 ° C. for 5 minutes, and post-baking at a temperature of 200 ° C. for 40 minutes. The thickness of the obtained layer was about 70 nm, and the Range% was 3% or less. The substrate with the polymer layer coated side up was exposed to linearly polarized UV light (LPUV) at an angle of incidence of 40 ° with respect to the normal of the substrate surface. The plane of polarization exists in the normal of the substrate and in a plane extending in the direction of light propagation. The applied exposure dose was 22.6 mJ / cm ² . After exposure to LPUV, the two substrates were assembled so that the exposed polymer layer was facing the inside of the cell. The substrates are adjusted relative to each other so that the induced orientation directions are parallel to each other (corresponding to an antiparallel-rubbed arrangement when oriented by the rubbing procedure). When the cell was capillary-filled with a liquid crystal MLC6610 (Merck KGA) having a negative dielectric anisotropy, the liquid crystal in the cell showed a clear homeotropic orientation. The tilt angle was 87.56 ° using the crystal rotation method, VHR was 99.0% in the system using the fluorothermosetting resin (A-1), and (A-2) 99.3%. A-3) It was 98.9%.

Comparative Example 5
In Example 6, the alignment film and the liquid crystal display element were produced in the same manner except that Megafvck F-554 was used instead of the fluorine-containing thermosetting resin (A-1). Although the Range% of the coating film was 3% or less, VHR was not measured because it was confirmed that the alignment defect of the liquid crystal had occurred.

Claims (9)

The following structural formula (a1)
[In the formula (a1), R ¹ , R ² and R ³ are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. A plurality of fluoroalkylene ether chains are linked and the bonding site with Y ¹ is a carbon atom, and Y ¹ is an oxygen atom or a sulfur atom. ]
Fluorine-containing thermosetting resin (A) having a thermally decomposable group represented by
Polyimide (b-1) made from at least tetracarboxylic dianhydride and diamine, polyamic acid (b-2) which is a precursor of the polyimide (b-1), and ester of the polyamic acid (b-3). A liquid crystal aligning agent , which is a resin composition containing one or more compounds (B) selected from the group consisting of). However, the fluorothermally decomposable resin (A) having a pyrolytic group represented by the structural formula (a1) is a gel permeation chromatography (column type: TSK gel Super (Tosoh), developing solvent: tetrahydrofuran). , Column temperature: 40 ° C., Flow rate (sample injection amount): 10 μl, Device name: HLC-8220 GPC (Tosoh), Calibration curve base resin: Polystyrene resin) Weight average molecular weight obtained by measuring 1900, 2600, 3200, Excludes those that are 5500 and 12000. The fluorine-containing thermosetting resin (A) has the following structural formula (a2) or (a3).
In [Formula ^{(a2), (a3),} X 1, X 2 is a direct bond or a divalent linking group, ^{respectively, R 51} is a hydrogen atom, a methyl group, group represented by the above general formula (a1) or It is a carboxyl group, R ⁵² is a group represented by the general formula (a1), and R ⁵³ is a group or a carboxyl group represented by the general formula (a1). ]
The liquid crystal alignment agent according to claim 1, which is a resin having a structural unit represented by. The liquid crystal alignment agent according to claim 1 or 2, wherein the fluorine atom content of the fluorine-containing thermosetting resin (A) is 1 to 35% by mass. The liquid crystal orientation according to any one of claims 1 to 3, wherein the fluorine-containing thermosetting resin (A) is used in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the solid content in the resin composition. Agent . A cured product made of the liquid crystal alignment agent according to any one of claims 1 to 4. A liquid crystal alignment film containing a resin (C) having a carboxyl group and a polyimide .
The resin (C) having a carboxyl group has the following structural formula (c1) or (c2).
[Formula (c1), in ^(c2), respectively X 1, ^{X 2} is a direct bond or a divalent linking ^{group, R 61} is a hydrogen atom, a methyl group, the following structural formulas (a1)
[In the formula (a1), R ¹ , R ² and R ³ are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. A plurality of fluoroalkylene ether chains linked together, the bonding site with Y ¹ is a carbon atom, and Y ¹ is an oxygen atom or a sulfur atom. ]
It is a group or a carboxyl group represented by, and R ⁶² and R ⁶³ are groups or carboxyl groups represented by the structural formula (a1), respectively. ]
A liquid crystal alignment film having a structural unit represented by and having a fluorine atom content of 0.5% by mass or less in the resin (C) having a carboxyl group. The liquid crystal alignment film according to claim 6, wherein the Range% (maximum minimum value difference of film thickness / average film thickness) in the film thickness measurement of the reflection spectroscopic film thickness meter is 10% or less. A method for producing a coating film, which comprises applying the liquid crystal alignment agent according to any one of claims 1 to 4 onto a substrate, and then heat-treating the liquid crystal alignment agent at 180 to 300 ° C. in an atmosphere of 1 to 60 minutes. .. A liquid crystal display element comprising the liquid crystal alignment film according to claim 6 or 7 .