JP2017193654A - Resin composition and article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of giving such a cured product that has excellent surface smoothness, essentially comprises a polyimide resin, and gives no influence or effectively suppresses influences on another composition even when the compound is deposited on the cured product, an article using the composition, particularly, a liquid crystal alignment film, and a liquid crystal display element including the film.SOLUTION: The resin composition comprises a resin represented by structural formula (a1) and a polyimide. In formula (a1), R, Rand Reach represent a hydrogen atom or an organic group having 1 to 18 carbon atoms; Rrepresents a fluorinated alkyl group or a fluoroalkylene ether chain having a plurality of fluorinated alkyl groups connected via an oxygen atom and having a carbon atom at a bonding site to Y; and Yrepresents an oxygen atom or a sulfur atom.SELECTED DRAWING: None

Description

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

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

  Since polyimide itself lacks solvent solubility, after preparing a solution containing its precursor polyamic acid and its ester, this is applied, and a process for forming the polyimide into a film by heat treatment at high temperature is performed. As an application, for example, an insulating base material of 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, automobile panels, word processors, electronic notebooks, printers, computers, televisions, clocks, advertisement display boards, as well as watches and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, and VA (vertucally aligned) type characterized by vertical alignment using TFT (thin film transistor). And IPS (in-plane switching) type / FFS (fringe field switching) type characterized by horizontal alignment.

  Among these display methods, the VA type, the CSH (color super homeotropic) type, and the like have a feature that a liquid crystal composition having a negative dielectric anisotropy (Δε) is used. On the other hand, a liquid crystal composition having a positive Δε is used in a horizontal alignment type display such as a TN type, STN type, or IPS type. In recent years, there has been reported a driving method in which a liquid crystal composition having a positive Δε is vertically aligned when no voltage is applied and an IPS type / FFS type electric field is applied to display.

  Liquid crystal display elements used in all these driving methods have a liquid crystal alignment film for aligning liquid crystal molecules according to various driving methods. In recent years, PSA (Polymer Sustained Alignment) technology and photo-alignment technology have been proposed as new technologies for imparting pretilt angle characteristics to coating films (liquid crystal alignment films) formed using liquid crystal alignment agents. Yes. In the PSA technology, a polymerizable component that is polymerized by light irradiation is mixed in the liquid crystal layer of the liquid crystal cell, and the liquid crystal cell is tilted by application of voltage, and the liquid crystal cell is irradiated with light to thereby irradiate the polymerizable component. This is a technique for controlling the molecular orientation of liquid crystal molecules by polymerization (see, for example, Patent Document 1). The photo-alignment technique is a technique for causing a film to exhibit pretilt angle characteristics by irradiating light onto a polymer thin film having a photofunctional group such as a cinnamoyl group (see, for example, Patent Document 2).

  As liquid crystal display elements are widely put into practical use for large-screen LCD TVs and high-definition mobile applications (display parts of digital cameras and mobile phones), the substrates used in comparison with the past have become larger, The unevenness of the step of the substrate is getting larger. 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 aligning agents have a certain probability that defects such as pinholes and film thickness unevenness occur in the coating film (alignment film) formed using the liquid crystal aligning agent. It is pointed out that the product yield is insufficient. The main cause of this failure is the poor solvent solubility of the aforementioned polymer such as polyimide used as the material of the alignment film. Therefore, when the polymer concentration increases during solvent volatilization, the aggregation tends to occur. It is considered because.

  In order to express the smoothness of such a coating film, it is considered effective to use an additive generally called a leveling agent, but the surface of the alignment film is directly connected to the liquid crystal composition described above. Since they are in contact with each other, it is unsuitable to use those that affect the alignment behavior of the liquid crystal composition.

  When manufacturing a liquid crystal display element using the formed substrate having a 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, an ODF (One Drop Filling) method is often applied. In this case, the liquid crystal composition must be uniformly spread on the substrate by pressure from above. When the alignment film is formed using a liquid crystal aligning agent containing a leveling agent, the leveling agent is segregated on the surface thereof, so that it is necessary to prevent the “push-out” uniformity of the liquid crystal composition from being inhibited.

Japanese Patent Application Laid-Open No. 2015-099344 JP 2009-037104 A

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

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has excellent surface smoothness during the production of a cured product by using a fluorine-based resin having a specific thermally decomposable group, and fluorine atoms are removed by heat treatment. Depending on the fact that the contained part can be removed, even if another compound is laminated on the cured product, the influence on the compound can be effectively suppressed. Therefore, for example, even when this cured product is used as a liquid crystal alignment film The present inventors have found that the liquid crystal display element does not impair the electrical characteristics and that the liquid crystal alignment performance does not deteriorate even when used for a long period of time, and the present invention has been completed.

That is, the present invention provides the following structural formula (a1)
[In Formula (a1), R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. 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 fluorine-containing thermally decomposable resin (A) having a thermally decomposable group represented by:
Polyimide (b-1) using at least tetracarboxylic dianhydride and diamine as raw materials, polyamic acid (b-2) which is a precursor of the polyimide (b-1), and ester of the polyamic acid (b-3) The resin composition characterized by containing 1 or more types of compounds (B) selected from the group which consists of these), and its hardened | cured material.

  Furthermore, this invention provides the liquid crystal display element which comprises the coating film containing the resin and polyimide which have the carboxyl group which is excellent in surface smoothness, its manufacturing method, and the said coating film as an alignment film.

  The resin composition of the present invention can give a cured product excellent in surface smoothness, particularly a coating film. The composition can be applied to 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 can be used as a liquid crystal alignment film. In this case, since a fluorine atom does not exist in a portion that is in direct contact with the liquid crystal composition, the liquid crystal display element having excellent display quality can be obtained without affecting the characteristics of the liquid crystal display element.

<Fluorine-containing thermally decomposable resin (A)>
The fluorine-containing thermally decomposable resin (A) used in the present invention has the following structural formula (a1)
[In Formula (a1), R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. 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. ]
It has the thermal decomposable group represented by these.

R ¹ , R ² and R ^{3 in the} structural formula (a1) are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and when the resin has a plurality of the thermally decomposable 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 that may have a carbon-carbon double bond, An alicyclic hydrocarbon group containing a ring structure, a hydrocarbon group having an aromatic ring which may have a substituent, or one or more of these linked by an ether bond or an ester bond It may be. In view of the thermal decomposition temperature of the fluorine-containing thermally decomposable resin (A) and easy production of the resin (A), an organic group having 1 to 9 carbon atoms is preferable. Group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group and other alkyl groups, methoxy group, ethoxy group, propyloxy group, isopropyl Mention may be made of alkoxy groups such as oxy groups, butoxy groups, phenyl groups, tolyl groups, xylyl groups, naphthyl groups, anthryl groups, and organic groups in which alkyl groups, alkoxy groups, halogen atoms, etc. are substituted on these aromatic nuclei. 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 obtained. From the viewpoint that it can be obtained, a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded, or a fluorinated alkyl group having 1 to 4 carbon atoms to which fluorine atoms are directly bonded is an oxygen atom. It is preferable that it is an ether chain connected through plural numbers. In the ether chain, the same number of carbon atoms in the fluorinated alkyl group may be connected, or different ones may be connected. Either a copolymerization format or a random copolymerization format may be used. From the viewpoint of easy availability of raw materials, ease of production of the fluorine-containing thermally decomposable resin (A), and a cured product excellent in surface smoothness, the molecular weight of the ether chain is in the range of 200 to 5,000. It is preferred that it is in the range of 300-2000.

Furthermore, R ⁴ in the structural formula (a1) is more preferably a fluorinated alkyl group, particularly preferably a fluorinated alkyl group having 4 to 6 carbon atoms to which fluorine atoms are directly bonded, and fluorine. Most preferred are fluorinated alkyl groups having 6 carbon atoms to which atoms are directly bonded.

  As said structural formula (a1), what is represented by the following is mentioned, for example.

  In the structural formula (a1), it is considered that splitting occurs between a carbonyloxy group and a carbon atom by heating a resin containing the structure, and a portion containing a fluorine atom volatilizes to become a carboxyl group. As a result, the cured product obtained by removing the fluorine atom-containing portion and curing the composition of the present invention has almost no fluorine atoms on its surface and is laminated by coating other compounds on the cured product. Even when trying to do so, it is possible to obtain a good laminate without causing repelling or the like.

  While the structural formula (a1) in the fluorine-containing thermally decomposable resin (A) used in the present invention is necessary to express the smoothness of the cured product surface of the composition as described above, the cured product surface It is also necessary that the fluorine atom-containing portion can be efficiently removed. From such a viewpoint, the content ratio of the partial structure represented by the structural formula (a1) in the fluorine-containing thermally decomposable resin (A) used in the present invention is the fluorine atom content in the resin (A). 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 in the range of 5 to 25% by mass. Most preferred. In addition, the content rate of a fluorine atom can be measured as an actual value in the ion chromatogram after combustion.

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

[In formulas (a2) and (a3), X ¹ and X ² are each a direct bond or a divalent linking group, and R ⁵¹ is a hydrogen atom, a methyl group, a group represented by the 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 it is resin which has a structural unit represented by these.

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 of 0 to 6.)

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

Examples of the fluorine-containing thermally decomposable resin (A) include a resin having a carboxyl group, wherein a part or all of the carboxyl group is the structural formula (a1). When a part of the carboxyl group is designed so as to have the structural formula (a1), the abundance ratio of the carboxyl group and the structural formula (a1) is determined by measurement of the acid value in the resin or measurement by ¹ H or ¹³ C-NMR. Can be measured.

  Further, as described above, the carboxyl group in the resin having a carboxyl group may further include, for example, a structural portion represented by the following structural formula (a4) within a range not inhibiting the effects of the present invention.

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

Examples of the organic group having 1 to 18 carbon atoms in the structural formula (a4) are the same as those described in the structural formula (a1), and the same applies to preferable organic groups. Among these, those in which R ¹¹ , R ²¹ and R ³¹ are each a hydrogen atom, R ⁴¹ is an organic group having 1 to 18 carbon atoms, and Y ¹¹ is an oxygen atom or a sulfur atom are polar with a carboxyl group This is preferable because it makes it easier to balance the surface smoothness of the resulting cured product and the ease of lamination when other compounds are laminated, and particularly the following structural formula (a4-1)

It is more preferable that it is resin which has the structure site | part represented by these.

  The number average molecular weight (Mn) of the fluorine-containing thermally decomposable resin (A) used in the present invention is the compound (B) described later, that is, polyimide (b-1) using at least tetracarboxylic dianhydride and diamine as raw materials. The compatibility with the polyamic acid (b-2), which is the precursor of the polyimide (b-1), and the ester (b-3) of the polyamic acid is good, and it is in the range of 1,000 to 50,000. Is preferable, the range of 1,500 to 20,000 is more preferable, and the range of 2,000 to 8,000 is 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 to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. GPC measurement conditions are as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” (6.0 mm ID × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + “TSK− manufactured by Tosoh Corporation” 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 rate: 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution 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”.

(Monodispersed 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 fluorine-containing thermally 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 as described above by heating. 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 is volatilized. However, in order to achieve the effect of the present invention, the ratio is 1 in an atmosphere of 180 to 300 ° C. It is preferable to stand for ˜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 heat treatment, the fluorine-containing thermally decomposable resin (A) used in the present invention is, for example, the following structural formula (c1) or (c2)
[In the formulas (c1) and (c2), X ¹ and X ² are each a direct bond or a divalent linking group, R ⁶¹ is a hydrogen atom, a methyl group, and the following structural formula (a1)
[In Formula (a1), R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. A plurality of linked fluoroalkylene ether chains, the bonding site with Y ¹ is a carbon atom, and Y ¹ is an oxygen atom or a sulfur atom. ]
R ⁶² and R ⁶³ each represent a group or a carboxyl group represented by the structural formula (a1). )
A resin having a carboxyl group (however, the fluorine atom content in the resin having a carboxyl group is 0.5 mass% or less).

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

[In the formula (1), R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. 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 of polymerizing the polymerizable monomer after obtaining a polymerizable monomer having a blocked carboxyl group by reacting with the vinyl ether compound represented by formula (1).

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

  The fluorine-containing thermally decomposable resin obtained by the production method 1, that is, a blocked carboxyl group that 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 fluorine-containing decomposable resin obtained by the production method 2, that is, a polymer composed of the polymerizable monomer (α) as a raw material, and a vinyl ether compound represented by the general formula (1) are constituent elements. Resin.

  Examples of the polymerizable monomer (α) having a carboxyl group include (meth) acrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinate Preferred examples include acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyltetrahydrophthalic 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 methacryloyl group and acryloyl group. “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 include oxyoctane, 3,3,4,4,5,5,6,6,6-nonafluoro-1-vinyloxyhexane, and the like. Among these, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro- from the viewpoint of good reactivity with the polymerizable monomer (α). 1-vinyloxyoctane is preferred.

  In the production method 1, after obtaining a polymerizable monomer having a blocked carboxyl group, when the polymerizable monomer is polymerized, or in the production method 2, the polymerizable monomer having a carboxyl group (α). When obtaining a polymer obtained by using a polymer, a polymerizable monomer other than the polymerizable monomer (α) is used within the range not impairing the effects of the present invention for the purpose of imparting various functions such as surface activity. (Γ) can also be used in combination to obtain a fluorine-containing thermally decomposable resin. Examples of the polymerizable monomer (γ) include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates, and dialkyl esters of fumaric acid. Or monoalkyl esters, radically polymerizable monomers having an oxyalkylene chain, and it is necessary to particularly improve the surface smoothness of the resulting cured product, and after heat treatment When the fluorine atom content may be slightly higher, a radical polymerizable monomer having a fluorinated alkyl 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, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydro And furfuryl acrylate.

  Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydro And furfuryl methacrylate.

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

  Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, propyl), N, N-dialkyl methacrylamide ( 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 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, 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 vinylate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate ,vinyl Rate, vinyl caproate, vinyl chloroacetate, vinyl di- chloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl -β- phenyl butyrate, vinyl cyclohexyl carboxylate.

  Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of the dialkyl ester or monoalkyl ester of fumaric acid include dibutyl fumarate and the like, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile, styrene, and the like.

  Examples of the radical 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. (Meth) acrylate, (poly) ethylene glycol / (poly) propylene glycol mono (meth) acrylate, (poly) (ethylene 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 (meta) ) Acrylate, (poly) butylene glycol mono (meth) acrylate, (poly) (ethylene glycol / trimethylene glycol) mono (meth) acrylate, (poly) ethylene glycol / (poly) trimethyl Glycol (mono) (poly) (propylene glycol / trimethylene glycol) mono (meth) acrylate, (poly) propylene glycol / (poly) trimethylene glycol mono (meth) acrylate, (poly) (trimethylene glycol)・ Tetramethylene glycol) mono (meth) acrylate, (poly) trimethylene glycol ・ (Poly) tetramethylene glycol mono (meth) acrylate, (poly) (butylene glycol ・ trimethylene glycol) mono (meth) acrylate, (poly) Examples include butylene glycol and (poly) trimethylene glycol mono (meth) acrylate.

  The “poly (ethylene glycol / propylene glycol)” means a random copolymer of ethylene glycol and propylene glycol, and “polyethylene glycol / polypropylene glycol” means a block copolymer of ethylene glycol and propylene glycol. The same is true for the others. “(Poly) propylene glycol” means either propylene glycol or polypropylene glycol, and the same applies to other ones. The molecular weight of the oxyalkylene chain in the radical 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 radical polymerizable monomers having an oxyalkylene chain include “NK Ester AMP-10G”, “NK Ester AMP-20G”, and “NK Ester AMP-60G” manufactured by Shin-Nakamura Chemical Co., Ltd. “Blemmer PME-100”, “Blemmer PME-200”, “Blemmer PME-400”, “Blemmer PME-4000”, “Blemmer PP-1000”, “Blemmer PP-500”, manufactured by NOF Corporation “Blemmer PP-800”, “Blemmer 70PEP-350B”, “Blemmer 55PET-800”, “Blemmer 50POEP-800B”, “Blemmer 10PPB-500B”, “Blemmer NKH-5050”, “Blemmer AP-400”, Sartomer "SR604" made by the company That.

  Examples of the radical 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 one of the following formulas (L-1) to (L-10), and Rf represents the following formula (Rf -1) to any one of (Rf-7). ]

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

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

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

  The radical 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 from the viewpoint of good compatibility with the compound (B) or other components in the resin composition 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 in a homopolymer form or a copolymer form is preferred. .

  Moreover, when obtaining the fluorine-containing thermally decomposable resin (A) used in the present invention, a vinyl ether compound other than the compound represented by the general formula (1) is converted into a vinyl ether compound represented by the general formula (1) and 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 compound; 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 such as sodium carboxylate Ether compounds, cyclic vinyl thioether compounds corresponding to these.

  In the said manufacturing method 1, the polymeric monomer ((alpha)) which has a carboxyl group, and the vinyl ether compound represented by the said General formula (1) are made to react. 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. And when polymerizing the polymerizable monomer which has the carboxyl group blocked, it can carry out on the conditions similar to the conditions which superpose | polymerize the polymerizable monomer ((alpha)) mentioned later.

  In the 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 components used in combination as necessary. Examples thereof include a method of polymerizing a radical polymerizable monomer (γ) in an organic solvent using a radical polymerization initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples 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 polymerizability. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

  In the said manufacturing method 2, the said polymer and the vinyl ether compound represented by the said General formula (1) can be made to react by heating to about 20-100 degreeC in presence of an acid catalyst, for example. By this reaction, the carboxyl group of the polymer is blocked, and a polymer having a structure represented by the structural formula (a1) is obtained.

  In the present invention, the above-mentioned fluorine-containing thermally decomposable resin (A) is used for expressing surface smoothness when obtaining a cured product, and further laminated with another compound on the surface of the cured product. When constituting a body, the laminated state can be made good. From such a point of view, in the present invention, the fluorine-containing thermally decomposable resin (A) is a polyimide (b-1) made of at least tetracarboxylic dianhydride and diamine as raw materials having good heat resistance, It is preferable to use together 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 out.

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

<Tetracarboxylic dianhydride>
As the acid anhydride used for the synthesis of polyimide, tetracarboxylic dianhydride is preferable. Examples of the tetracarboxylic dianhydride include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 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 acid 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- Xahydro-7-ethyl-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-8-ethyl-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 tetracarboxylic dianhydride, bi Cyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3-oxabisch port [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 anhydride 3,5,6 - tricarboxy-2-carboxymethyl-norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5,3,1,0 ^2,6] undecane -3,5,8, 10-tetraone, aliphatic and alicyclic tetra force rubonic acid dianhydrides such as compounds represented by the following formulas (I) and (II);

[In the formulas (I) and (II), R ⁷ and R ⁹ represent a divalent organic group having an aromatic ring, R ⁸ and R ¹⁰ , a hydrogen atom or an alkyl group, and a plurality of R ⁸ and R ¹⁰ may be the same or different. ],

Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bi (3,4-Dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride, 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 (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butane -Bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis ( Aromatic tetracarboxylic dianhydrides such as 4-hydroxyphenyl) propane-bis (anhydrotrimellitate) and compounds represented by the following formulas (2) to (5) can be exemplified. These may be used alone or in combination of two or more. In addition, the benzene ring of the aromatic dianhydride may be substituted with one or two 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-dio So-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic acid Anhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic 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 acid anhydride, 3 , 5,6-tricarboxy-2-carboxymethylnorbornane-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′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 1 , 4,5,8-Naphthalenetetracarboxylic dianhydride, when a compound represented by the following formulas (6) to (9) is used, when the resulting composition is used as a liquid crystal aligning agent, good liquid crystal alignment Sex can be expressed.

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 dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5 -Dioxotetrahydro-3-furanyl)- -Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatri Examples include cyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride, and a compound represented by the formula (6).

<Diamine>
Examples of the diamine include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, and 4,4′-diaminodiphenyl. Sulfone, 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-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethyl Indane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 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-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9 , 9-dimethyl-2,7-diaminofluorene, 9,9-bis (4-aminophenyl) 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-phenylenediisopropylidene) bisaniline, 2,2'-bis [ 4- (4-Amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-3,3′-bis (trifluoromethyl) biphenyl, 4,4′-diamino-2,2 Aromatic diamines such as' -bis (trifluoromethyl) biphenyl, 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;

1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, Tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenediethylenediamine, 4,4′-methylenebis (cyclohexylamine) ), 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and the like 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- Aminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 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 It has two primary amino groups and nitrogen atoms other than the primary amino group in the molecule, such as compounds represented by the following formulas (III) to (IV) Amines;

(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, X ² represents a divalent organic group, A plurality of X ² may be the same or different.)

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

(In the formula (V), R ¹³ represents a divalent linking group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R ¹⁴ represents a steroid A skeleton, a monovalent organic group having a group selected from a trifluoromethyl group and a fluoro group, or an alkyl group having 6 to 30 carbon atoms, wherein the steroid skeleton is a skeleton composed of a cyclopentano-perhydrophenanthrene nucleus or (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 ¹⁵ may be the same or different, p is an integer of 1 to 3, and q is It is an integer of 1-20.)

Furthermore, the compound etc. which are represented by following formula (10)-(14) can be mentioned.

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

  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 two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group).

  Among these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 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, '-(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 III) Among the compounds represented by the following formula (15), among the compounds represented by the above formula (IV), a compound represented by the following formula (16), represented by the above formula (V) Among these compounds, dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene , 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) Of these compounds, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane is preferred.

<Synthesis of polyamic acid (b-2)>
A polyamic acid (b-2) can be obtained by reacting the tetracarboxylic acid dihydrate and diamine. The ratio of the tetracarboxylic dianhydride and the diamine to be used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.001 per 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 performed in an organic solvent under a temperature condition 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 N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide. Aprotic polar solvents such as γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and 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 tetracarboxylic dianhydride and 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 Ethyl 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, isoamylpropionate, isoamylisobutyrate, diisopentyl ether.

  The use ratio of the other organic solvent is preferably 80% by mass or less, more preferably 50% by mass or less, and further 40% by mass or less with respect to the total of the above-mentioned organic solvent and the other organic solvent. Preferably there is.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the resin composition, may be used for the preparation of the resin composition after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a resin composition. Polyamic acid can be isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator. it can. The polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or a method of performing the 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, all of the amic acid structure may be dehydrated and closed to completely imidize, or only a part of the amic acid structure may be dehydrated and closed to form a partially imidized product in which the amic acid structure and the imide structure coexist. Also good. The imidation ratio of polyimide is preferably 40% or more, and more preferably 80% or more. Here, the “imidization ratio” 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 polyamic acid is (i) a method of heating polyamic acid, or (ii) dissolving 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 a method.

  The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the resulting 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 (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the polyamic acid structural unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing 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-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. 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 for the preparation of the resin composition as it is, or may be used for the preparation of the resin composition after purifying the obtained polyimide. On the other hand, in the above method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be used for the preparation of the resin composition as it is, 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 after isolating the polyimide. It may be used for the preparation of the resin composition, or may be used for the preparation of the resin composition after purifying the isolated polyimide. In order to remove the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. The isolation and purification of the polyimide can be performed by performing the same operation as described above as the isolation and purification method of the polyamic acid.

<End-modified polymer>
Each of the polyamic acid and the polyimide may be a terminal-modified polymer having a controlled molecular weight. Such a terminal-modified polymer can be synthesized by adding an appropriate molecular weight regulator such as acid monoanhydride, monoamine compound, monoisocyanate compound to the reaction system when synthesizing the polyamic acid. . Here, as the acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride , N-hexadecyl succinic acid anhydride and the like. Examples of the monoamine compound 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 . Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

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

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

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

  The tetracarboxylic acid diester used in the method (ii) can be obtained by a method of ring-opening by reacting a tetracarboxylic dianhydride with an alcohol, a method of esterifying a tetracarboxylic acid, or the like. 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 the compounds exemplified as the diamine used for 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 partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

  The resin composition of the present invention includes the above-mentioned fluorine-containing thermally decomposable resin (A), polyimide (b-1) using at least tetracarboxylic dianhydride and diamine as raw materials, and the polyimide (b-1). As long as it contains at least one compound (B) selected from the group consisting of the polyamic acid (b-2) as a precursor and the ester (b-3) of the polyamic acid, the use thereof is particularly preferable. Although it is not limited, it is excellent in surface smoothness especially in the case of a thin film, the heat treatment step after forming a coating film is essential, and pyrolysis containing fluorine atoms from the coating film surface by that step As a result of considering the feature that the functional group is removed, as a field in which the use of a leveling agent containing fluorine atoms has been difficult, it is a thin film that requires surface smoothness. It can be suitably used as a resin composition for film formation (the liquid crystal alignment agent). In particular, the surface of the coating film obtained is substantially free of fluorine atoms, so even if the surface and the liquid crystal composition are in direct contact with each other, there is no influence on the liquid crystal composition or it is effectively suppressed. This is 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 thermally decomposable resin (A) can be appropriately set according to the intended performance and application, and is not particularly limited. From the viewpoint of easily obtaining a cured product having smoothness, the fluorine-containing thermally decomposable resin (A) is usually used in a 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, particularly preferably in the range of 0.05 to 5 parts by mass.

<Liquid crystal aligning agent>
When a resin composition is used as the liquid crystal aligning agent, the compound (B) using a general tetracarboxylic 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. A polyimide film that includes a so-called rubbing treatment step in which the coating film is rubbed in a certain direction with a roll wound with a resin, and the resin after thermal decomposition of the fluorine-containing thermally decomposable resin (A) in the film, that is, the aforementioned The resin has a carboxyl group (C), and the polyimide molecular chains are anisotropically oriented in the plane of the film, or the polyimide side chains are anisotropically oriented outside the film. By doing so, the characteristic which controls an orientation of a liquid crystal molecule can be provided.

  Alternatively, in the case of a resin composition using a compound (B) made of a diamine having a vertical alignment functional group as a raw material, the obtained coating film is a vertical alignment alignment film, specifically, a polyimide film. In addition, the film contains the resin after pyrolysis of the fluorine-containing thermally decomposable resin (A), that is, the resin (C) having the carboxyl group, and the liquid crystal molecules can be vertically aligned on the film surface. The alignment film has characteristics.

  As the diamine having a vertical alignment functional group, any diamine having a vertical functional group may be used. Among them, those formed by diamines represented by the following formulas (29) to (31) are preferable. is there. In addition, these may be used independently and may be used in combination of 2 or more type.

[Wherein, X represents a single bond, —O—, —CO—, —COO—, —OCO—, —NHCO—, —CONH—, —S— or an arylene group, and R ⁴ represents a carbon number of 10 A monovalent organic group having an alkyl group of -20, a 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 each independently 1,4-cyclohexylene or 1,4-phenylene; A ⁴ is 1,4-cyclohexylene, 1,4- Phenylene or a single bond; B ¹ , B ² and B ³ are each independently a single bond or 1,2-ethylene; R ⁶ is an alkyl having 1 to 20 carbon atoms, One —CH ₂ — may be replaced by —O—. ]

In the above formula (29), examples of the alkyl group having 10 to 20 carbon atoms represented by R ⁴ include an n-decyl group, an n-dodecyl group, an n-pentadecyl group, an n-hexadecyl group, and an n-octadecyl group. , N-eicosyl 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. Groups having an alicyclic skeleton derived from cycloalkane, etc .; groups having a steroid skeleton such as cholesterol and cholestanol; and groups having a bridged alicyclic skeleton such as norbornene and adamantane. Among these, a group having a steroid skeleton is particularly preferable. The organic group having an alicyclic skeleton may be a group substituted with a halogen atom, preferably a fluorine atom, or a fluoroalkyl group, preferably a trifluoromethyl group.

Furthermore, as a group having 6 to 20 carbon atoms represented by R ⁴ in the above formula (29), for example, an n-hexyl group, an n-octyl group, an n-decyl group or the like having 6 or more carbon atoms. Straight chain 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 part or all of the atoms are substituted with a fluorine atom or a fluoroalkyl group such as a trifluoromethyl group.

  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 tolylene group, a biphenylene group, and a naphthylene group. Of these, groups represented by —O—, —COO—, and —OCO— are particularly preferable.

  Specific examples of the diamine having the group represented by the above formula (29) include dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2, Preferred examples include 4-diaminobenzene and a compound represented by the following formula.

  Specific examples of the diamine having a group represented by the above formula (30) include diamines represented by the following formulas as preferred examples.

In the above formula (31), R ⁶ is arbitrarily selected from alkyl having 1 to 20 carbon atoms, and may be linear or branched. 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, nonadecyl, eicosyl, 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. Preferred examples among these are propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like.

In the above formula (31), B ¹ , B ² , and B ³ are each independently selected from a single bond or 1,2-ethylene, but 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 The compound which has 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. Although the cis / trans isomer of 1,4-cyclohexylene may be mixed, the trans isomer is preferred.

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

  Thus, the side chain having a steroid skeleton, or 3-4 rings selected from any of 1,4-cyclohexylene and 1,4-phenylene are linear or directly via 1,2-ethylene. It is preferable to have a side chain having a structure bonded 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 independently of each other, 1,4-cyclohexylene and 1,4-phenylene. And the bonds between the 3 to 4 rings may be each independently a single bond or 1,2-ethylene. Films mainly composed of polyimides made from these compounds can be driven effectively 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 to 87 to 89.5 ° (more preferably 87.5 to 89 °). It is also effective in suppressing burn-in.

  On the other hand, after applying a photo-alignment film, that is, the resin composition of the present invention on a substrate as a liquid crystal aligning agent, the liquid crystal molecules are subjected to alignment treatment by light irradiation, particularly polarized ultraviolet irradiation, to control the alignment of liquid crystal molecules. In order to obtain an alignment film by imparting, a reaction of photodecomposition, photodimerization, or photoisomerization proceeds as a compound (B) or in a compound used in combination with the compound (B), It is necessary that there is a group to which anisotropy is imparted in the same direction as the direction or in a direction perpendicular to the polarization direction.

  Examples of such specific groups include a coumarin group, a cinnamate group, a chalcone group, an azobenzene group, a stilbene group, a benzophenone group, and a β-hydroxyester structure. Examples of the coumarin derivative include a compound represented by the following formula (32). Among them, a 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 stilbene group (absorption wavelength (λmax) 295 nm). It is preferable to use as a raw material a compound having at least one selected photofunctional group in the side chain. In addition, these photofunctional groups may be used independently and may be used in combination of 2 or more type. Moreover, these functional groups may be contained in any one of the tetracarboxylic dianhydride and diamine used as a raw material, and both may contain the same or different functional groups. As for the chalcone group, for example, any of tetracarboxylic dianhydrides and diamines described in JP-A-2002-82336 can be used. As the azobenzene type acid anhydride, any of the compounds described in JP 2012-224578 A 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 the structure of the following formula (HE-1). By having the structure of the following formula (HE-1), the polyamic acid and polyimide using the diamine as a raw material can form a double bond having excellent photoreactivity in the molecule when heated. When it is used to form a liquid crystal alignment film, it can exhibit excellent optical alignment performance.

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

  In the structure of the above formula (HE-1), a particularly preferred 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) having a β-hydroxyester structure and a structure for realizing vertical alignment of liquid crystal molecules.

In the formula (HE-2), X ₁ has the same meaning as the formula (HE-1).

In the formula (HE-2), X ₂ represents a single bond or at least one divalent linking group selected from the group consisting of ether, ester, amide, and urethane. X ₂ is preferably a single bond, an ether group, an ester group or an amide group, more preferably a single bond, an ether group or an ester group. X ₃ represents a monovalent organic group having a linear alkyl group having 3 to 20 carbon atoms or an alicyclic skeleton having 4 to 40 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, 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, Naphthyl group, anthracenyl group, cyclohexylphenyl group, n-pentyl-cyclohexylphenyl group, n-heptyl-cyclohexylphenyl group, A cyclohexyloxyphenyl group or an n-pentyl-cyclohexyloxyphenyl group is preferred, and an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, a cyclohexyl group, a cyclohexyl- An n-heptyl group, a bicyclohexyl-n-pentyl group, a cyclohexyloxyphenyl group, or an n-pentyl-cyclohexyloxyphenyl group is more preferable.

  Preferable examples of diamines include compounds 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. X ₄ is preferably a single bond, a methylene group, an ethylene group, an n-propylene group, or an n-butylene group, and more preferably a single bond or an ethylene group. X ₅ represents a single bond, an oxygen atom, * —OCO— or * —OCH ₂ — (wherein a bond marked with “*” is bonded to X ₄ ). However, when X ₄ is a single bond, X ₅ is a single bond. X ₅ is preferably a single bond, an oxygen atom, or * —OCH ₂ —, more preferably * —OCH ₂ — or an oxygen atom.

  Preferable 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 a C3-20 alkyl group 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, n-octyl group, n-nonyl A group, an n-decyl group, an n-undecyl group, or an n-dodecyl group is more preferable. 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. Xb is a linear alkyl group having 1 to 12 carbon atoms, for example, methyl group, ethyl group, 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, or n-dodecyl group are preferable, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, or n-heptyl group. Groups are more preferred.

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

[Wherein, R ¹ is a tetravalent group having an alicyclic structure, R ² is a divalent organic group, and R ²⁵ and R ²⁶ are each independently a hydrogen atom or a monovalent organic group. . ]

In particular, at least one of R ¹ , R ²⁵ , and R ²⁶ is a fluorinated alkyl group, a fluorinated alkoxy group, a fluorinated alkyl ester group, —Si (OR ³⁰ ) ₃ (wherein R ³⁰ has 1 to 4 carbon atoms) More preferred).

The tetravalent group having the alicyclic structure has a structure derived from an alicyclic tetracarboxylic acid. Examples of the alicyclic structure of R ¹ include a monocyclic cycloalkane such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring; a bicyclo [2.2.0] hexane ring, a decahydronaphthalene ring, and a bicyclo Bicyclic alkanes such as [2.2.1] heptane 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 a cyclobutane ring because of high photoalignment. Is particularly preferred.

In the above formula, R ² is a divalent organic group. For example, at least one methylene group of a divalent hydrocarbon group or a divalent hydrocarbon group may be represented by —O—, —CO—, —COO—, —NH—, —NHCO—, — Examples include groups substituted with Si (R ³⁰ ) ₂ —, —Si (OR ³⁰ ) ₂ —, etc., groups having a heterocyclic ring, 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 formula, R ²⁵ and R ²⁶ are a hydrogen atom or a monovalent organic group. As the monovalent organic group, for example, at least one methylene group of a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent hydrocarbon group having 1 to 18 carbon atoms is represented by —O— or —CO. —, —COO—, —NR—, —NRCO— (wherein R is an alkyl group), —Si (R ³⁰ ) ₂ —, —Si (OR ³⁰ ) ₂ —, etc. And a group obtained by substituting a hydrogen atom bonded to a carbon atom of 18 monovalent hydrocarbon group with a halogen atom, an alkylsilyl group, an alkoxysilyl group, or the like. R ²⁵ and R ²⁶ may be the same as or different from each other.

In the case of obtaining an alignment film from the above material, the exposure energy of light irradiation to the film during the process is preferably 100 mJ / cm ² or less, and more preferably 50 mJ / cm ² or less. Moreover, when performing the division | segmentation orientation process which divides and exposes each pixel using a light shielding mask (photomask) etc., it is still more preferable that it is 20 mJ / cm < ² > or less.

  Further, as a raw material of the compound (B) used in the present invention or in a compound used in the resin composition, it has a radical generating function for generating radicals by light irradiation and a photosensitizing function for sensitizing by light irradiation. By including the structure, a liquid crystal aligning agent for a PSA mode liquid crystal display element can be obtained. Here, the “photosensitizing function” refers to a function in which a singlet excited state is brought about by light irradiation and then an intersystem crossing is quickly caused to transition to a triplet excited state. When colliding with other molecules in this triplet excited state, the partner is changed to the excited state and returns to the ground state. This photosensitization function may coexist with a radical generation function that generates radicals by light irradiation.

  Specific examples of the specific structure include structures capable of expressing a radical generating function such as an acetophenone structure, a benzophenone structure, a xanthone structure, a fluorenone structure, a benzaldehyde structure, a fluorene structure, an anthraquinone structure, a triphenylamine structure, a carbazole structure, an alkyl Examples include phenone structure, benzoin structure, thioxanthone structure, acylphosphine oxide structure, polysilane structure, etc., and examples of structures capable of expressing the photosensitizing function include acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole Structure, nitroaryl structure (nitrobenzene structure, 1,3-dinitrobenzene structure, etc.), naphthalene structure, fluorene structure, anthracene structure, acridine structure, indole Concrete, 1,4-di-oxo-cyclohexadiene-2,5-diene structure, and the like. These structures are acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, alkylphenone, benzoin, thioxanthone, acylphosphine oxide, biphenyl, nitrobenzene, 1,3-dinitrobenzene. , Naphthalene, anthracene, acridine, indole, and 1,4-dioxocyclohexa-2,5-diene, a group consisting of groups obtained by removing 1 to 4 hydrogen atoms.

<Other ingredients>
When using the resin composition of this invention as a liquid crystal aligning agent, you may contain another component as needed. 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 said epoxy group containing compound can be used in order to improve the adhesiveness with the substrate surface in a liquid crystal aligning film, and an electrical property. 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-xylenediamine, 1,3-bis (N, N -Diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglyci Le - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - may be mentioned as being preferred and cyclohexylamine. When these epoxy group-containing compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by mass or less, based on a total of 100 parts by mass of the resin components contained in the liquid crystal aligning agent. Part is more preferred.

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

  As said other component, the compound which has at least 1 oxetanyl group in a molecule | numerator other than the compound illustrated above, antioxidant, etc. can also be used.

<Solvent>
When using the resin composition of this invention as a liquid crystal aligning agent, the resin component and the other component arbitrarily mix | blended as needed, Preferably it melt | dissolves in an organic solvent, and is comprised.

  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, 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 monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl Examples include 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 aligning agent, the solid content concentration (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) takes viscosity, volatility and the like into consideration. However, it is preferably in the range of 1 to 10% by mass. That is, the liquid crystal aligning agent is applied to the substrate surface as will be described later, and 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, the film thickness of this coating film is appropriate and a good liquid crystal alignment film can be suitably obtained, and the viscosity of the liquid crystal alignment agent is It is an appropriate range and the coating characteristics are good.

  The particularly preferable solid content concentration range varies depending on the method of applying the liquid crystal aligning agent to the substrate. For example, when the spinner method is used, the solid content concentration is particularly preferably 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 thereby 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 thereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature when preparing the liquid crystal aligning agent 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 of the liquid crystal aligning 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 includes the following (i) to (ii)
(I) a first step in which the liquid crystal aligning agent of the present invention is applied on the conductive film of a pair of substrates having a conductive film, and then heated 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 with the coating film facing each other through 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>
Examples of the substrate include glass such as float glass and soda glass; and a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and poly (alicyclic olefin). As the conductive film, it is preferable to use a transparent conductive film, for example, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ) or indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ). An ITO film or the like can be used. This 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. The characteristics can be made wider.

  As a method of applying the liquid crystal aligning agent of the present invention on the formation surface of the transparent conductive film on the pair of substrates, it can be preferably performed by an offset printing method, a spin coating method, a roll coater method or an ink jet printing method. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or functional titanium is formed on the surface of the substrate surface on which the coating film is to be formed. You may give the pretreatment which apply | coats a compound etc. previously.

  After applying the liquid crystal aligning agent to the substrate, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Then, a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed. The post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. During the post-baking, the fluorine-containing thermally decomposable resin (A) described above becomes a resin (C) having a carboxyl group by removing the group containing fluorine atoms by thermal decomposition. Thus, the film thickness of the formed film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

  In addition, the Range% (maximum / minimum difference in film thickness / average film thickness) in the film thickness measurement of the reflective spectral film thickness meter of the alignment film obtained in this step can be 10% or less. As the reflective spectral film thickness meter, a reflective spectral film pressure gauge FE-3000 manufactured by Otsuka Electronics Co., Ltd. can be used, and the range of 4 cm × 4 cm in the center of the film is divided into 400 points, and the respective film thicknesses are measured. Smoothness can be evaluated by the standard deviation of thickness and Range% (maximum / minimum difference in film thickness / average film thickness). In addition, it shows that it is so smooth that Range% is small. Further, the fact that no fluorine atom is present in the film or that it is below the detection limit can be confirmed by, for example, XPS (X-ray photoelectron spectroscopy).

  By removing the organic solvent by heating after applying the liquid crystal aligning agent, a coating film to be an alignment film is formed. At this time, when 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 Further, after the coating film is formed, the film may be further heated to cause the dehydration ring-closing reaction to proceed so that the coating film is more imidized.

  The coating film thus formed is treated according to the structure of the acid anhydride and diamine used. That is, rubbing treatment, light irradiation, or both of them may be performed. In the case of a PSA type or the like, these alignment treatments may not be performed and may be directly used for the second step.

<Second step: construction of liquid crystal cell>
By preparing a substrate having a liquid crystal alignment film formed on at least one side as described above, and disposing a liquid crystal layer containing a liquid crystal composition between the substrate and the other substrate opposed to the substrate. A liquid crystal cell is manufactured. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a vacuum injection method. First, two substrates are arranged opposite to each other with a liquid crystal alignment film on the inside via 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 a liquid crystal composition into the cell gap and then sealing the injection hole. The second method is a technique called an ODF (One Drop Filling) method. For example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates, and the liquid crystal composition is dropped on predetermined locations on the liquid crystal alignment film surface, A liquid crystal cell is manufactured by laminating the other substrate, spreading the liquid crystalline 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 takes an isotropic phase and then gradually cooled to room temperature. The orientation may be removed.

  As the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as 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 not particularly limited as long as the standard components of such a liquid crystal display device are essential. is not. The liquid crystal display device may be a simple matrix liquid crystal display device, but is preferably an active matrix liquid crystal display device. The liquid crystal display device includes pixels arranged in a matrix including pixel electrodes arranged in a matrix on the liquid crystal layer side of one substrate and a common electrode arranged on the liquid crystal layer side of the other substrate. It is preferable to have. In addition, the liquid crystal layer side of one substrate may have pixels arranged in a matrix including pixel electrodes and common electrodes formed in a comb shape.

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

[In the 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 each independently —CH═CH Optionally substituted by-, -C≡C-, -O-, -CO-, -COO- or -OCO-,
A ^II1 and A ^II2 are each independently (a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more —CH ₂ — not adjacent to each other is —O And (b) a 1,4-phenylene group (one —CH═ present in the group or two or more —CH═ not adjacent to each other) is replaced with —N═. May be.)
(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 by —N═. )
The group (a), the group (b) and the group (c) are each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^II1 represents a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—. , -CH = N-N = 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, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and one or more hydrogens in the alkyl group The atom may be substituted with a fluorine atom,
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 embodiment of compound represented by 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 includes a compound represented by the following general formula (J).

  As a compound represented by general formula (i), it is preferable to contain 1 type, or 2 or more types of compounds represented by general formula (J). These compounds correspond to dielectrically positive compounds (Δε is greater than 2).

(Wherein 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 each independently —CH═CH—, — Optionally substituted 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 each independently
(A) 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced by —O—).
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —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 by —N═.
The group (a), the group (b) and the group (c) are each independently selected from the group consisting of cyano group, fluorine atom, chlorine atom, methyl group, trifluoromethyl group or trifluoro May be substituted with a methoxy group,
Z ^J1 and Z ^J2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, -COO-, -OCO- or -C≡C-
When n ^J1 is 2, 3 or 4 and a plurality of A ^J2 are present, they may be the same or different, and n ^J1 is 2, 3 or 4 and a plurality of Z ^J1 is present. If they are the same or different,
X ^J1 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 represents 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. 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. An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, 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 having 3 carbon atoms. (Propenyl group) is particularly preferred.

R ^J1 is preferably an alkyl group when emphasizing reliability, and is preferably an alkenyl group when emphasizing a decrease in viscosity.

  Further, 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 An alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which the alkenyl group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain A linear alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group 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 groups represented by any one of the formulas (R1) to (R5). (The black dot in each formula represents the carbon atom 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 independently increase Δn, and are preferably aliphatic to improve the response speed. 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 by fluorine atoms It is more preferable to represent the following structure,

It is more preferable to represent the following structure.

Z ^J1 and Z ^J2 each independently preferably represent —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond, OCH ₂ —, —CF ₂ O—, —CH ₂ CH ₂ — or a single bond is more preferable, and —OCH ₂ —, —CF ₂ O— or a single bond is particularly preferable.

X ^J1 is preferably a fluorine atom or a trifluoromethoxy group, and more preferably a fluorine atom.

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

  Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performance, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The kind of the compound to be used is, for example, one kind, two kinds, and three kinds as one embodiment. Furthermore, in another embodiment, there are four types, five types, six types, and seven or more types.

  In the liquid crystal composition, the content of the compound represented by the general formula (J) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, dripping marks, image sticking, dielectric constant. It is necessary to adjust appropriately 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%, 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% with respect to the total amount of the liquid crystal composition. Yes, 35%, 25%.

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

R ^J1 is preferably an alkyl group when emphasizing reliability, and is preferably an alkenyl group when emphasizing a decrease in viscosity.

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

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

(Wherein R ^M1 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 each independently —CH═CH—, — Optionally substituted by C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^M1 represents 0, 1, 2, 3 or 4;
A ^M1 and A ^M2 are 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 by -O- or -S- And (b) 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═).
A hydrogen atom on the group (a) and the group (b) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^M1 and Z ^M2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, -COO-, -OCO- or -C≡C-
When n ^M1 is 2, 3 or 4 and a plurality of A ^M2 are present, they may be the same or different, and n ^M1 is 2, 3 or 4 and a plurality of Z ^M1 is present If they are the same or different,
X ^M1 and X ^M3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,
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 formula (M), R ^M1 represents 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. 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. An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, 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 having 3 carbon atoms. (Propenyl group) is particularly preferred.

R ^M1 is preferably an alkyl group when emphasizing reliability, and is preferably an alkenyl group when emphasizing a decrease in viscosity.

  Further, 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 An alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which the alkenyl group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain A linear alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group 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 groups represented by any one of the formulas (R1) to (R5). (The black dot in each formula represents the carbon atom in the ring structure to which the alkenyl group is bonded.)

A ^M1 and A ^M2 are preferably aromatic when it is required to independently increase Δn, and are preferably aliphatic to improve the response speed, and 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 preferably represents a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents 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 a single bond is more preferable, and —CF ₂ O— or a single bond is particularly preferable.

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

  Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performance, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The kind of the compound to be used is, for example, one kind, two kinds, and three kinds as one embodiment. Furthermore, in another embodiment, there are four types, five types, six types, and seven or more types.

  In the liquid crystal composition, the content of the compound represented by the general formula (M) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, image sticking, dielectric constant. It is necessary to adjust appropriately 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% with respect to the total amount of the liquid crystal composition. Yes, 35%, 25%.

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

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

(Wherein 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 each independently hydrogen. An atom or a fluorine atom, Y ³¹ represents a fluorine atom or OCF ₃ , and M ^{31 to} M ³³ each independently represents 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, The two hydrogen atoms may be substituted with fluorine atoms, n ³¹ and n ³² each independently represent 0, 1 or 2, and n ⁴¹ + n ⁴² represents 1, 2 or 3.)

  Specifically, the liquid crystal compound represented by the general formula (M-1) is preferably a compound represented by the following general formula (M-1-a) to general formula (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.)
Specifically, the liquid crystal compound represented by the general formula (M-2) is preferably a compound represented by the following general formula (M-2-a) to general formula (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.)
In addition, the liquid crystal compound represented by the general formula (M) is specifically preferably the following general formula (M-3) to 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 formula (K). These compounds correspond to dielectrically positive compounds (Δε is greater than 2).

(In the formula, R ^K1 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 each independently —CH═CH—, — Optionally substituted by C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^K1 represents 0, 1, 2, 3 or 4;
A ^K1 and A ^K2 are 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 by -O- or -S- And (b) 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═).
A hydrogen atom on the group (a) and the group (b) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^K1 and Z ^K2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, -COO-, -OCO- or -C≡C-
When n ^K1 is 2, 3 or 4 and a plurality of A ^K2 are present, they may be the same or different, and n ^K1 is 2, 3 or 4 and a plurality of Z ^K1 is present If they are the same or different,
X ^K1 and X ^K3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,
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 general formula (K), R ^K1 represents 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. 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. An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, 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 having 3 carbon atoms. (Propenyl group) is particularly preferred.

^RK1 is preferably an alkyl group when importance is placed on reliability, and an alkenyl group is preferred when importance is placed on lowering viscosity.

  Further, 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 An alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which the alkenyl group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain A linear alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group 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 groups represented by any one of the formulas (R1) to (R5). (The black dot in each formula represents the carbon atom in the ring structure to which the alkenyl group is bonded.)

A ^K1 and A ^K2 are preferably aromatic when it is required to independently increase Δn, and are preferably aliphatic to improve response speed, and 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 preferably represents a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents 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 a single bond is more preferable, and —CF ₂ O— or a single bond is particularly preferable.

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

  Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performance, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The kind of the compound to be used is, for example, one kind, two kinds, and three kinds as one embodiment. Furthermore, in another embodiment, there are four types, five types, six types, and seven or more types.

  In the liquid crystal composition, the content of the compound represented by the general formula (K) is low temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, image sticking, dielectric constant. It is necessary to adjust appropriately 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% with respect to the total amount of the liquid crystal composition. Yes, 35%, 25%.

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

  Specifically, the liquid crystal compound represented by 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 each independently hydrogen. An atom or a fluorine atom, Y ⁴¹ represents a fluorine atom or OCF ₃ , and M ^{41 to} M ⁴³ each independently represents 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, The two hydrogen atoms may be substituted with fluorine atoms, n ⁴¹ and n ⁴² each independently represents 0, 1 or 2, and n ⁴¹ + n ⁴² represents 1, 2 or 3.)

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

  Specifically, 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 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, specifically, the liquid crystal compound represented by the general formula (K) is preferably the following general formula (K-3) to 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 embodiment of compound represented by 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 includes compounds represented by the following general formulas (LC1) and (LC2). it can.

  The compound represented by the general formula (i) preferably contains one or more compounds selected from the compound group represented by the general formula (N-1) to the general formula (N-3).

(In the formula, R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or non-adjacent 2 in the alkyl group _Two or more —CH ₂ — may be each 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 each independently (a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or adjacent to each other). Two or more —CH ₂ — that are not present may be replaced by —O—.)
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —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 by —N═.
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
^{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═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—,
^XN21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents —CH ₂ — or an oxygen atom,
^nN11 , ^nN12 , ^nN21 , ^nN22 , ^nN31 and ^nN32 each independently represent an integer of 0 to 3, but ^nN11 + ^nN12 , ^nN21 + ^nN22 and ^nN31 + ^nN32 are each independently 1, 2 or ^3, if ^{a N11 ~A N32, Z N11 ~Z} N32 there are multiple, they may be the same or different. However, the compound represented by general formula (N-1) in general formula (N-2) and general formula (N-3) is excluded, and in general formula (N-3), general formula (N-2) The compound represented by is 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 the absolute value thereof is greater than 2). Although applicable, it is preferable that Δε is negative and the absolute value thereof is larger than 3.

In the general formulas (N-1), (N-2), and (N-3), R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31, and R ^N32 each independently represent 1 to 8 carbon atoms. An alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and the number of 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, 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 more preferable, and an alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable. In particular, by using a combination of a compound in which at least one of R ^N11 and R ^N12 represents an alkenyl group and a compound represented by the general formula (I), a decrease in voltage holding ratio (VHR) is remarkably suppressed. be able to. Similarly, by using a compound in which at least one of R ^N21 and R ^N22 represents an alkenyl group and a compound represented by the general formula (I) in combination, a decrease in voltage holding ratio (VHR) is remarkably suppressed. In addition, by using a combination of a compound in which at least one of R ^N31 and R ^N32 represents an alkenyl group and a compound represented by the general formula (I), the voltage holding ratio (VHR) is decreased. Can be remarkably suppressed.

  Further, 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 An alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which the alkenyl group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain A linear alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group 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 groups represented by any one of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31, and A ^N32 are preferably aromatic when it is required to increase Δn independently, and in order to improve the response speed, fat A 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-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Preferred, it is more preferable that represents the following structures,

More preferably, it represents 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.

^XN21 is preferably a fluorine atom.

T ^N31 is preferably an oxygen atom.

n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are preferably 1 or 2, a combination in which n ^N11 is 1 and n ^N12 is 0, a combination in which n ^N11 is 2 and n ^N12 is 0, n ^A combination in which ^N11 is 1 and n ^N12 is 1, a combination in which n ^N11 is 2 and n ^N12 is 1, a combination in which n ^N21 is 1 and n ^N22 is 0, n ^N21 is 2 and n ^N22 is n A combination in which n ^N31 is 1 and n ^N32 is 0, and a combination in which n ^N31 is 2 and n ^N32 is 0 are preferable.

  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%, 30 %, 40%, 50%, 55%, 60%, 65%, 70%, 75%, and 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It 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%, 30 %, 40%, 50%, 55%, 60%, 65%, 70%, 75%, and 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It 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%, 30 %, 40%, 50%, 55%, 60%, 65%, 70%, 75%, and 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

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

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

(In the formula, A ⁱ¹¹ , A ⁱ¹² and A ⁱ¹³ each independently represents a 1,4-cyclohexylene group or a 1,4-phenylene group, but one existing in the 1,4-cyclohexylene group) of -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S-, it 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 Z represents the same meaning as ^N12 .)

  The compound represented by General Formula (i-1) is preferably a compound represented by General Formula (i-1A), General Formula (i-1B), or General Formula (i-1C).

(In the formula, R ^N11 , R ^N12 , A ⁱ¹¹ and Z ⁱ¹ each independently represent the same meaning as R ^N11 , R ^N12 , A ⁱ¹¹ and Z ⁱ¹ in formula (i-1)).

^{(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 Represents.)

(In the formula, m ⁱ¹³ represents 1, and 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 (i-1). , R ^N12 , A ⁱ¹¹ , A ⁱ¹² , A ⁱ¹³ , Z ⁱ¹ , Z ⁱ² and m ⁱ¹¹ represent the same meaning.)

  As a compound represented by general formula (i-1A), the compound represented by the following general formula (i-1A-1)-general formula (i-1A-4) is preferable.

(In the formula, R ^N11 and R ^N12 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (i-1).)

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

(In the formula, R ^N11 and R ^N122 each independently represent the same meaning as R ^N11 and R ^N12 in General Formula (i-1).)

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

(In the formula, R ^N11 and R ^N122 each independently represent the same meaning as R ⁱ¹ and R ⁱ² in formula (i-1).)

  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 two or more compounds selected from the compound group represented by i-1C) may be contained, or represented by general formula (i-1A), general formula (i-1B), or general formula (i- One or more compounds each represented by 1C) may be contained. It is preferable to contain 1 type, 2 or more types of compounds represented by general formula (i-1A) and general formula (i-1B), and it is more preferable to contain 2 to 10 types.

  More specifically, general formula (i-1A), general formula (i-1B) and general formula (i-1C) are general formula (i-1A-1), general formula (i-1B-1) and general formula (i-1B-1). It is preferable to contain 1 type, or 2 or more types of compounds chosen from the compound group represented by Formula (i-1C-1), and the compound represented by General Formula (i-1A-1) and General Formula (i It is more preferably a combination of compounds represented by -1B-1).

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

(In the formula, A ⁱⁱ¹ and A ⁱⁱ² each independently represents a 1,4-cyclohexylene group or a 1,4-phenylene group, but one —CH present in the 1,4-cyclohexylene group) ₂ or two or more non-adjacent —CH ₂ — may be replaced by —O— or —S—, and one hydrogen atom present in the 1,4-phenylene group is each independently 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 general formula (ii-1), it is preferable to contain 1 type, or 2 or more types of compounds represented by 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.)}

  It is preferable that the compound represented by general formula (ii-1) is a compound represented by general formula (II-2A) or 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, A ⁱⁱ¹¹ and A ⁱⁱ¹¹ each independently represent a 1,4-cyclohexylene group or a 1,4-phenylene group, but one —CH present in the 1,4-cyclohexylene group) ₂ or two or more non-adjacent —CH ₂ — may be replaced by —O— or —S—, and one hydrogen atom present in the 1,4-phenylene group is each independently (It may be substituted with a fluorine atom or a chlorine atom, and R ^N11 and R ^N12 represent the same meaning as R ^N11 and R ^N12 in formula (ii).)

  As a compound represented by general formula (ii-1A), the compound represented by the following general formula (ii-1A-1) and general formula (ii-1A-2) is 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 formula (ii-1B-1) to general formula (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 general formula (ii), but the compound group represented by general formula (ii-1A) and general formula (ii-1B). 1 type or 2 types or more may be contained, and the compound represented by general formula (ii-1A) and general formula (ii-1B) may be contained respectively 1 or more types. It is preferable to contain 2 to 10 compounds represented by general formula (ii-1A) and 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). 1B) preferably contains one or more compounds selected from the group of compounds represented by general formula (ii-1B-1) and general formula (ii-1B-2). General formula (ii- A combination of the compounds represented by 1A-1) and the general formula (ii-1B-1) is more preferable.

  Moreover, it is preferable to contain 1 type, or 2 or more types of compounds represented by the following general formula (LC3-b) as general formula (N-1).

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

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

(In the formula, R ^N11 and R ^N12 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)

The combination of R ^N11 and R ^N12 is not particularly limited, but both represent an alkyl group, both represent an alkenyl group, one represents an alkyl group, the other represents an alkenyl group, and either one represents It is preferable that one represents an alkyl group, the other represents alkoxy, and one represents an alkyl group and the other represents an alkenyloxy group, both represent an alkyl group, and both represent an alkenyl group. It is more preferable that it represents.

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

(In the formula, R ^N11 and R ^N12 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)

  The compound represented by General Formula (N-2) is preferably a compound selected from the group of compounds represented by General Formulas (N-2-1) to (N-2-3).

(In the formula, R ^N211 and R ^N22 each independently represent the same meaning as R ^N211 and R ^N22 in General Formula (N-2).)

  The compound represented by General Formula (N-3) is preferably a compound selected from the group of compounds represented by General Formulas (N-3-1) and (N-3-2).

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

(In the formula, R ^N31 and R ^N32 each independently represent the same meaning as R ^N31 and R ^N32 in formula (N-3).)

<Third embodiment of the compound represented by the general formula (i)>
A so-called nonpolar liquid crystal compound having a dielectric anisotropy of about 0, and a compound represented by the following general formula (L) can be given.

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

(Wherein, R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently May be substituted 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 represent (a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more —CH ₂ — not adjacent to each other). May be replaced with -O-.
(B) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —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 by —N═.
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and Z ^L2 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═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—,
When n ^L1 is 2 or 3, and a plurality of A ^L2 are present, they may be the same or different, and when n ^L1 is 2 or 3, and a plurality of Z ^L3 are present, May be the same or different, but excludes compounds represented by general formula (J), general formula (N-1), general formula (N-2) and general formula (N-3). )

  Although the compound represented by general formula (L) may be used independently, it can also be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to desired properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of compound to be used is, for example, one kind as one embodiment. Alternatively, in another embodiment, there are 2 types, 3 types, 4 types, 5 types, 6 types, 7 types, 8 types, 9 types, 10 types or more is there.

  In the liquid crystal composition, the content of the compound represented by the general formula (L) is low temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, image sticking, dielectric constant. It is necessary to adjust appropriately 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 upper limit of the preferable content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, and 25%.

  When a composition that keeps the viscosity of the liquid crystal composition low and has a fast response speed is necessary, the above lower limit value is preferably high and the upper limit value is preferably high. Further, when a composition having a high temperature stability and a high temperature stability is required, it is preferable that the 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 driving voltage low, it is preferable that the above lower limit value is lowered and the upper limit value is low.

When importance is attached to reliability, R ^L1 and R ^L2 are preferably both alkyl groups, and when importance is placed on reducing the volatility of the compound, it is preferably an alkoxy group, and importance is placed on viscosity reduction. In this case, at least one is preferably an alkenyl group.

R ^L1 and R ^L2 are a linear alkyl group having 1 to 5 carbon atoms or a linear alkyl group having 1 to 4 carbon atoms when the ring structure to which R ^L1 is bonded is a phenyl group (aromatic). When the ring structure to which the alkoxy group and the alkenyl group having 4 to 5 carbon atoms are bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, a straight chain having 1 to 5 carbon atoms is preferable. An alkyl group, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group 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 groups represented by any one of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

In particular, by using a combination of a compound in which at least one of R ^L1 and R ^L2 represents an alkenyl group and a compound represented by the general formula (I), a decrease in voltage holding ratio (VHR) is remarkably suppressed. be able to.

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

A ^L1 , A ^L2, and A ^L3 are preferably aromatic when it is required to increase Δn, and are preferably aliphatic for improving the response speed, and are each 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 preferably represents a diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, more preferably represents the following structure,

More preferably, it represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

Z ^L1 and Z ^L2 are preferably single bonds when the 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, R ^L1 and R ^L2 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L).)

R ^L11 and R ^L12 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. . Although the compound represented by general formula (L-1) can also be used independently, it can also be used in combination of 2 or more compounds. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound to be used is, for example, one kind as one embodiment, two kinds, three kinds, four kinds, and five kinds or more.

  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 that keeps the viscosity of the liquid crystal composition low and has a fast response speed is necessary, the above lower limit value is preferably high and the upper limit value is preferably 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 medium and the upper limit value is medium. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the 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 formula (L-1-1.11) to the formula (L-1-1.13). Is preferable, and is preferably a compound represented by Formula (L-1-1.12) or Formula (L-1-1.13), and particularly represented by Formula (L-1-1.13). It is preferable that it is a compound.

  In addition, the compound represented by the general formula (L-1-1) is a compound selected from the compound group represented by the formula (L-1-1.21) to the formula (L-1-1.24). Preferably, it is a compound represented by the formula (L-1-1.22) to the formula (L-1-1.24). In particular, the compound represented by the formula (L-1-1.22) is preferable because the response speed of the liquid crystal composition is particularly improved. Moreover, when calculating | requiring Tni higher than a response speed, it is preferable to use the compound represented by a formula (L-1-1.23) or a formula (L-1-1.24).

  Moreover, the compound represented by general formula (L-1-1) is a compound chosen from the compound group represented by Formula (L-1-1.31) and Formula (L-1-1.41). Preferably there is.

  Moreover, it is preferable that the compound represented by general formula (L-1) is a compound represented by general formula (L-1-2).

(Wherein R ¹²¹ and R ¹²² each independently represents 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 formula (L-1-2.1) to the formula (L-1-2.12). Are preferable, and a compound represented by Formula (L-1-2.1), Formula (L-1-2.3), or Formula (L-1-2.4) is preferable. In particular, the compound represented by the formula (L-1-2.1) is preferable because the response speed of the liquid crystal composition is particularly improved. When obtaining Tni higher than the response speed, the equation (L-1-2.3), the equation (L-1-2.4), the equation (L-1-2.11), and the equation (L- It is preferable to use the compound represented by 1-2.12). Total of compounds represented by formula (L-1-2.3), formula (L-1-2.4), formula (L-1-2.11) and formula (L-1-2.12) The content of is not preferably 20% or more in order to improve the solubility at low temperatures.

  Moreover, it is preferable that the compound represented by general formula (L-1) is a compound chosen from the compound group represented by general formula (L-1-3) and / or (L-1-4). .

(In the formula, R ⁱⁱ³¹ and R ⁱⁱ⁴¹ each independently represent the same meaning as R ⁱⁱ² in the general formula (L).)
Moreover, it is preferable that the compound represented by general formula (L) is a compound represented by the following general formula (L-2) to general formula (L-11). The liquid crystal composition preferably contains one or more compounds represented by general formula (L-2) to general formula (L-11) as the compound represented by general formula (L).

(Wherein R ^L31 and R ^L32 are an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, R ^L32 is an alkyl group having 1 to 5 carbon atoms, and 1 to C atoms) 5 represents an alkoxyl group, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms.)

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

In the compounds represented by general formula (L-4), general formula (L-7), and general formula (L-8), R ^L31 is an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms. 5 alkenyl group having, preferably R ^L32 is an alkoxy group having 5 alkyl group or a carbon number of 1 1 to 5 carbon atoms, that R ^L31 is an alkenyl group having 2 to 5 carbon atoms More preferably, it is more preferably an alkenyl group having 2 or 3 carbon atoms. In the compound represented by the general formula (L-6), R ^L31 and R ^L32 each independently represent 1 to 5 carbon atoms. And an alkenyl group having 2 to 5 carbon atoms.

  Moreover, as a compound represented by general formula (L), 1 type, or 2 or more types of compounds represented by general formula (L-12), general formula (L-13), or general formula (L-14) are contained. It is also preferable to do.

^{(Wherein, R L51} and ^{R L52} are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms 2 to 5 carbon ^{atoms, X L51} and X ^L52 each independently represents a fluorine atom or a hydrogen atom, and one of X ^L51 and X ^L52 is a fluorine atom, and the other is a hydrogen atom.)

  Moreover, as a compound represented by general formula (L), you may contain 1 type, or 2 or more types of compounds represented by general formula (L-16.1) to general formula (L-16.3). .

  Moreover, you may contain 1 type, or 2 or more types of compounds represented by general formula (N-001) as a compound represented by general formula (L).

Wherein R ^N1 and R ^N2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 2 to 8 carbon atoms. L ¹ and L ² each independently represents a hydrogen atom, a fluorine atom, CH ₃ or CF ₃ (except that both L ¹ and L ² represent a fluorine atom).
R ^N1 and R ^N2 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) at 25 ° C. of 1.5 to 20.0. 1.5 to 18.0 is more preferable, 1.5 to 15.0 is more preferable, 1.5 to 11 is further preferable, and 1.5 to 8 is particularly preferable.

  The liquid crystal composition having a positive 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 is preferable to contain the compound represented by the general formula (M) and the compound represented by the general formula (L-1), and the general formula (M-1) and / or the general formula (M -2) and a compound represented by the general formula (L-1-1) are preferably contained.

  The total content of the compound represented by the general formula (J) and the compound represented by the general formula (L) of the liquid crystal composition is preferably 5% or more as a lower limit in the composition, 80 %, Preferably 85% or more, preferably 88% or more, preferably 90% or more, preferably 92% or more, 95% or more. It is preferable to contain 97% or more, preferably 98% or more, preferably 99% or more, and substantially free from other compounds. Further, the upper limit value is preferably 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and substantially contains other compounds. Preferably not. The term “substantially” means that an unintentionally contained compound such as impurities inevitably generated during production is excluded.

  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 a lower limit in the composition, Preferably 80% or more, preferably 85% or more, preferably 88% or more, preferably 90% or more, preferably 92% or more, preferably 95% or more It is preferable to contain 97% or more, preferably 98% or more, preferably 99% or more, and substantially free from other compounds. Further, the upper limit value is preferably 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and substantially contains other compounds. Preferably not.

  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 a lower limit in the composition. Preferably, containing 10% or more, preferably containing 13% or more, preferably containing 15% or more, preferably containing 18% or more, preferably containing 20% or more, more than 23% 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, preferably 40% or more. Further, the upper limit value is preferably 95% or less, preferably 90% or less, preferably 88% or less, preferably 85% or less, and preferably 83% or less. 80% or less, preferably 78% or less, preferably 75% or less, preferably 73% or less, preferably 70% or less, preferably 68% or less Preferably 65% or less, preferably 63% or less, preferably 60% or less, preferably 55% or less, preferably 50% or less, It is preferable to contain 40% or less.

  The liquid crystal composition preferably has a negative dielectric anisotropy (Δε) at 25 ° C., and the dielectric anisotropy (Δε) at 25 ° C. is from −2.0 to −8.0. -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) includes compounds represented by general formula (N-1) to general formula (N-3) and a compound represented by general formula (L). It is preferable to contain. More specifically, it is preferable to contain the compound represented by general formula (N-1) and the compound represented by general formula (L-1), and the compound represented by general formula (N-1) And a compound represented by the general formula (L-1-1).

  The total content of the compound represented by the general formula (N-1) to the general formula (N-3) and the compound represented by the general formula (L) of the liquid crystal composition is a lower limit value in the composition. 5% or more, preferably 80% or more, preferably 85% or more, preferably 88% or more, preferably 90% or more, preferably 92% or more It is preferable to contain 95% or more, preferably 97% or more, preferably 98% or more, preferably 99% or more, and substantially free of other compounds. Is preferred. Further, the upper limit value is preferably 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and substantially contains other compounds. Preferably not.

  The total content of the compound represented by the general formula (N-1) and the compound represented by the general formula (L) of the liquid crystal composition is preferably 5% or more as a lower limit in the composition. 80% or more, preferably 85% or more, preferably 88% or more, preferably 90% or more, preferably 92% or more, preferably 95% or more It is preferable to contain 97% or more, preferably 98% or more, preferably 99% or more, and substantially free from other compounds. Further, the upper limit value is preferably 90% or less, preferably 95% or less, preferably 98% or less, preferably 99% or less, and substantially contains other compounds. Preferably not.

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

  The liquid crystal composition may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, an infrared absorber, a polymerizable monomer, or a light stabilizer (HALS) in addition to the above-described compounds. Good.

  For example, the liquid crystal composition may contain a liquid crystal compound having a dielectric anisotropy (Δε) at 25 ° C. of +2.0 to +50.0 as a normal nematic liquid crystal or smectic liquid crystal. Although it is 0 to 50% by mass, it is preferably 1 to 30% by mass, preferably 3 to 30% by mass, and preferably 5 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 monofunctional polymerizable compounds having one reactive group and polyfunctional polymerizable compounds having two or more reactive groups such as bifunctional or trifunctional You may contain above. 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 by light.

  Among the polymerizable compounds having a reactive group, specific examples of the polymerizable compound having a monofunctional reactive group include the following general formula (VI):

(In the formula, X ³ represents a hydrogen atom or a methyl group, and Sp ³ represents a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _t — (wherein t is 2 to 2). Represents an integer of 7 and an oxygen atom is bonded to an aromatic ring.), V is a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic group having 5 to 30 carbon atoms. An alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is 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 by an oxygen atom in a range not adjacent to each other), or may be substituted by a cyclic substituent, and 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 general formula (VI), X ³ represents a hydrogen atom or a methyl group. However, when importance is attached to the reaction rate, a hydrogen atom is preferred, and when importance is placed on reducing the residual amount of reaction, a methyl group is preferred. preferable.

In the general formula (VI), Sp ³ represents a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _t — (wherein t represents an integer of 2 to 7, Represents a bond to an aromatic ring), but the carbon chain is preferably not so long, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or 1 to 3 carbon atoms is preferable. An alkylene group is more preferred. Also, Sp ³ is -O- _{(CH 2) t} - may represent a, t is preferably 1 to 5, 1 to 3 is more preferable.

  In the 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 an alkylene group in the polyvalent alkylene group. May be substituted with an oxygen atom in a range where the oxygen atoms are not adjacent to each other, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom within a range where the oxygen atoms are not adjacent to each other) .) Or may be substituted with a cyclic substituent, and is preferably substituted with two or more cyclic substituents.

  More specifically, the polymerizable compound represented by the general formula (VI) is represented by 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 each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other, -CO-, -COO- or -OCO- may be substituted, and one or more hydrogen atoms in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group. May be)
A ³ and A ⁶ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group do not have oxygen atoms directly bonded to each other) And each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 17 carbon atoms).
A ⁴ and A ⁷ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group do not have oxygen atoms directly bonded to each other) And each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group of 1 to 9 carbon atoms)
p represents 1 to 10,
B ¹ , B ² and B ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are In addition, the oxygen atoms may be independently substituted with an oxygen atom, —CO—, —COO—, or —OCO— as those in which oxygen atoms are not directly bonded to each other, and one or two or more of the alkyl groups may be substituted. A hydrogen atom may be independently substituted with a halogen atom or a trialkoxysilyl group having 3 to 6 carbon atoms).

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

(Wherein A ⁸ represents a hydrogen atom or a methyl group,
6-membered rings T ¹ , T ² and T ³ are each independently

(Where q represents an integer of 1 to 4),
q represents 0 or 1,
Y ¹ and Y ² are each independently a single bond, —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-
Y ³ represents a single bond, —COO— or —OCO—,
B ⁸ represents a hydrocarbon group having 1 to 18 carbon atoms. And a compound represented by

  Furthermore, the polymerizable compound represented by the general formula (VI) specifically includes the general formula (X1c)

(Wherein R ⁷⁰ represents a hydrogen atom or a methyl group, and R ⁷¹ represents a hydrocarbon group having a condensed ring).

  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 each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —O—. (CH ₂ ) _s — (wherein s represents an integer of 2 to 7 and an oxygen atom is bonded to an aromatic ring), and U is a linear or branched chain having 2 to 20 carbon atoms. 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 the oxygen atom is not adjacent to each other. -20 alkyl group (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent) or a cyclic substituent, and k is an integer of 1-5. The polymerizable compound represented by .

In the general formula (VII), X ¹ and X ² each independently represent a hydrogen atom or a methyl group. However, when importance is attached to the reaction rate, a hydrogen atom is preferable, and importance is placed on reducing the reaction residual amount. In this case, a methyl group is preferred.

In the general formula (VII), Sp ¹ and Sp ² are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s — (wherein s is 2 to 7 In which the oxygen atom is bonded to the aromatic ring. However, the carbon chain is preferably not so 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 3 carbon atoms is more preferable. Further, when Sp ¹ and Sp ² represent —O— (CH ₂ ) _s —, s is preferably 1 to 5, more preferably 1 to 3, and at least one of Sp ¹ and Sp ² is a single bond. More preferably, it is particularly preferable that both are single bonds.

  In the 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 an alkylene group in the polyvalent alkylene group. May be substituted with an oxygen atom in a range where the oxygen atoms are not adjacent to each other, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom within a range where the oxygen atoms are not adjacent to each other) ), May be substituted with a cyclic substituent, and is preferably substituted with two or more cyclic substituents.

  In the general formula (VII), U specifically preferably represents the following formula (VII-1) to formula (VII-5), and the formula (VII-1) to formula (VII-3) It is more preferable to represent, 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, at least one of the Sp ¹ and Sp ² preferably represents a single bond, and it is also preferable that both are single bonds.

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

  More specifically, the general formula (P)

It is preferable to contain 1 type, or 2 or more types of the polymeric compound represented by these.

In General Formula (P), X ²⁰¹ and X ²⁰² each independently represent a hydrogen atom, a methyl group, or a —CF ₃ group. X ²⁰¹ and X ²⁰² are each preferably a diacrylate derivative that is a hydrogen atom, and a dimethacrylate derivative that is both a methyl group, and a compound in which one is a hydrogen atom and the other is a methyl group. A preferred compound can be used depending on the application, but in the PSA display element, the polymerizable compound represented by the general formula (P) preferably has at least one methacrylate derivative, and preferably has two.

In General Formula (P), Sp ²⁰¹ and Sp ²⁰² are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s — (wherein s is 2 to 7). And an oxygen atom is bonded to the ring. Sp ²⁰¹ and Sp ²⁰² are preferably at least one is a single bond in a PSA type liquid crystal display device, and both are compounds having a single bond or one is a single bond and the other is an alkylene having 1 to 8 carbon atoms. It is preferably a group or —O— (CH ₂ ) _s —. In this case, an alkylene group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4.

In the general formula (P), M ²⁰¹ , M ²⁰² and M ²⁰³ each independently represent a trans-1,4-cyclohexylene group (one or non-adjacent two or more —CH ₂ — in the group represents May be substituted by -O- or -S-), 1,4-phenylene group (one or two or more non-adjacent -CH = in the group may be substituted by -N =). 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene- Represents a 2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and each hydrogen atom in the group independently represents a fluorine atom, a -CF ₃ group, or a carbon atom number. 1 to 10 alkyl groups, 1 to 1 carbon atom It may be substituted by 0 alkoxyl group or any one of formulas (R-1) to (R-15).

In General Formula (P), Z ²⁰¹ and Z ²⁰² each independently represent —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, — 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 — (wherein Y ¹ and Y ² each independently represents a fluorine atom or a hydrogen atom), —C≡C— or a single bond -COO-, -OCO-, -CH = CH-COO-,- H = 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 a single bond is preferable, —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 preferable.

In the general formula (P), n ²⁰¹ represents 0, 1 or 2, and 0 or 1 is preferable. However, when there are a plurality of M ²⁰² and Z ²⁰² , 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, more 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 preferred.

More specifically, when n ²⁰¹ is 0 in the general formula (P), the ring structure between Sp ²⁰¹ and Sp ²⁰² is preferably the formula (XXa-1) to the formula (XXa-5), The formula (XXa-1) to the formula (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 connected to Sp ²⁰¹ or Sp ²⁰² .

  The polymerizable compound represented by the general formula (P) containing these skeletons is suitable for a PSA type liquid crystal display element because of its alignment regulating power after polymerization, and a good alignment state is obtained, thereby suppressing display unevenness. There is an effect that does not occur at all.

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

In the general formula (XX-10) from the formula (XX-1), ^{Sp xx} is an alkylene group or -O- _{(CH 2)} 1 to 8 carbon atoms _s - (wherein, s is an integer of 2 to 7 And an oxygen atom is bonded to the ring).

In formula (XX-1) to general formula (XX-10), the hydrogen atom in the 1,4-phenylene group is further —F, —Cl, —CF ₃ , —CH ₃ , or formula (R-1). To optionally substituted by any of formula (R-15).

In the general formula (P), when n ²⁰¹ is 1, for example, a polymerizable compound such as the formula (P31) to the formula (P48) is preferable.

Hydrogen atoms of the 1,4-phenylene group and in the naphthalene radical of the formula (P48) from the formula (P31) _{further, -F, -Cl, -CF 3,} -CH 3, wherein the formula (R-1) It may be substituted by any of (R-15).

  The polymerizable compound represented by the general formula (P) containing these skeletons is suitable for a PSA type liquid crystal display element because of its alignment regulating power after polymerization, and a good alignment state is obtained, thereby suppressing display unevenness. There is an effect that does not occur at all.

In the case where n ²⁰¹ is 1 in the general formula (P) and there are a plurality of formulas (R-1) or (R-2), for example, polymerizable compounds such as formulas (P301) to (P316) preferable.

Hydrogen atoms in the 1,4-phenylene group and naphthalene group in the formula (P316) from equation (P301) further, -F, _-Cl, -CF 3, may be substituted by -CH _3.

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

  The antioxidant is preferably a hindered phenol represented by general formula (H-1) to general formula (H-4).

In general formula (H-1) to general formula (H-4), R ^H1 represents 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 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 two or more hydrogen atoms present in the group may be each independently substituted with a fluorine atom or a chlorine atom. More specifically, it is 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. An alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms is more preferable.

In General Formula (H-4), ^MH4 represents an alkylene group having 1 to 15 carbon atoms (one or two or more —CH ₂ — in the alkylene group may be — O—, —CO—, —COO—, —OCO— may be substituted.), —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—, a single bond, a 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or a trans-1,4-cyclohexylene group. Preferably an alkylene group having 1 to 14 carbon atoms, In consideration of the viscosity, a large number of carbon atoms is preferable, but in consideration of the viscosity, the number of carbon atoms is preferably not too large. Therefore, the number of carbon atoms is more preferably 2 to 12, more preferably 3 to 10. 4 to 10 carbon atoms are more preferred, 5 to 10 carbon atoms are more preferred, and 6 to 10 carbon atoms are more preferred.

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

In general formula (H-1) to general formula (H-4), one or two or more non-adjacent —CH ₂ — in the 1,4-cyclohexylene group is replaced by —O— or —S—. May be. In addition, each hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.

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

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

  A liquid crystal display device using the above liquid crystal composition has no display defects or is suppressed and has excellent display quality and high response speed. In particular, as an active matrix driving liquid crystal display device, 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.

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

Synthesis Example 1 [Synthesis of fluorine-containing thermally decomposable resin (A-1)]
Into a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 26.8 g of acrylic acid and 3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluoro-1-vinyloxyoctane (30.0 g) was charged, and the mixture was stirred for 21 hours at room temperature [20 to 28 ° C.] in a dry air stream. Next, 0.003 g of methoquinone and 107.6 g of diisopropyl ether were added, and 161.4 g of a saturated aqueous sodium carbonate solution and 161.4 g of ion-exchanged water were added to separate the layers. Next, after taking out the upper layer, 161.4 g of ion-exchanged water was added for liquid separation. Furthermore, 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).

  A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 50 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 80 ° C. while stirring in a nitrogen stream. Next, a monomer solution obtained 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 Two kinds of dripping solutions with a polymerization initiator solution obtained by dissolving 1.5 g of 2,2′-azobis (methyl isobutyrate) in 17 g of propylene glycol monomethyl ether acetate are set in separate dripping apparatuses, and the inside of the flask is set to 80. While maintaining the temperature at 0 ° C., the dropwise addition was started at the same time, and each was dropped over 3 hours. After completion of 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 the fluorine-containing thermally decomposable resin (A-1). The molecular weight of the obtained fluorine-containing thermally decomposable resin (A-1) was measured by GPC (polystyrene equivalent molecular weight). As a result, 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 thermally decomposable resin (A-2)]
Into a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 26.8 g of acrylic acid and 3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluoro-1-vinyloxyoctane (30.0 g) was charged, and the mixture was stirred for 21 hours at room temperature [20 to 28 ° C.] in a dry air stream. Next, 0.003 g of methoquinone and 107.6 g of diisopropyl ether were added, and 161.4 g of a saturated aqueous sodium carbonate solution and 161.4 g of ion-exchanged water were added to separate the layers. Next, after taking out the upper layer, 161.4 g of ion-exchanged water was added for liquid separation. Furthermore, after taking out the upper layer, the solvent was removed to obtain a polymerizable monomer having a blocked carboxyl group.

  A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 50 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 80 ° C. while stirring in a nitrogen stream. Next, a monomer solution in which 17.5 g of the polymerizable monomer having a blocked carboxyl group and 32.5 g of propylene glycol polybutylene glycol monomethacrylate are dissolved in 40 g of propylene glycol monomethyl ether acetate, and 2 as a radical polymerization initiator are used. , 2'-azobis (methyl isobutyrate) 0.5g and a polymerization initiator solution in which 17g of propylene glycol monomethyl ether acetate was dissolved were set in separate dropping devices, and the flask was heated to 80 ° C. While maintaining, dropping was started simultaneously, and the monomer solution was dropped over 3 hours and the initiator solution was dropped over 4 hours. After completion of 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 the fluorine-containing thermally decomposable resin (A-2). The molecular weight of the obtained fluorine-containing thermally decomposable resin (A-2) was measured by GPC (polystyrene equivalent molecular weight). As a result, 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 thermally decomposable resin (A-3)]
Into a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 26.8 g of acrylic acid and 3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluoro-1-vinyloxyoctane (30.0 g) was charged, and the mixture was stirred for 21 hours at room temperature [20 to 28 ° C.] in a dry air stream. Next, 0.003 g of methoquinone and 107.6 g of diisopropyl ether were added, and 161.4 g of a saturated aqueous sodium carbonate solution and 161.4 g of ion-exchanged water were added to separate the layers. Next, after taking out the upper layer, 161.4 g of ion-exchanged water was added for liquid separation. Furthermore, 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).

  A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 75 g of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 80 ° C. while stirring in 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 Two types of dropping solutions of a polymerization initiator solution prepared by dissolving 2.5 g of 2,2′-azobis (methyl isobutyrate) in 25 g of propylene glycol monomethyl ether acetate were set in separate dropping devices, and the inside of the flask was set to 80. While maintaining the temperature at 0 ° C., the dropwise addition was started at the same time, and each was dropped over 3 hours. After completion of the dropwise addition, 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 the fluorine-containing thermally decomposable resin (A-3). The molecular weight of the obtained fluorine-containing thermally decomposable resin (A-3) was measured by GPC (polystyrene equivalent molecular weight). As a result, 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 polyamideimide resin]
In a flask equipped with a stirrer, a thermometer and a condenser, 540.3 g of 1,3-dimethyl-2-imidazolidinone (DMI), 15.7 g of tolylene diisocyanate, 4,4'-diisocyanate-3,3'- Dimethyl-1,1′-biphenyl 95.0 g, trimellitic anhydride 76.8 g, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride 32.2 g were charged, and heat was generated while stirring. The temperature was raised to 140 ° C. over 2 hours, and the reaction was carried out at this temperature for 22 hours. The reaction proceeded with the foaming of carbon dioxide, and the system became a yellow transparent liquid. A solution of a polyamideimide resin (1) having a resin solid content of 28% with a viscosity at 25 ° C. of 9 Pa · s and a solution acid value of 10 (mgKOH / g) was obtained. In addition, as a result of measurement by 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 Corporation as a curing agent is added to 100 parts by mass of the DMI solution of the polyamideimide resin (1), and 1,2-dimethylimidazole as a catalyst is added to the solid content by 0.1%. The resin solution was prepared by adding mass% and diluting to 35 mass% using DMI. 0.0088 parts of a 20% solution of the fluorine-containing thermally decomposable resins (A-1) to (A-3) obtained in Synthesis Example 1 and 3.75 parts of DMI are mixed with 5.0 parts of this solution. Thus, a resin composition was prepared.

Example 2 [Production of cured product]
The resin composition obtained in Example 1 was spin-coated on a 10 cm × 10 cm Cr-plated glass plate at 1000 rpm for 3 seconds and 3000 rpm for 30 seconds, then dried at 100 ° C. for 30 minutes, and then at 200 ° C. Heating was performed for 1 hour to form a cured film.

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

<Evaluation method of smoothness of coating film>
Using the coating films obtained in Example 2 and Comparative Example 1, the surface smoothness was evaluated according to the following.
Using a reflective spectral film pressure gauge FE-3000 manufactured by Otsuka Electronics Co., Ltd., a range of 4 cm × 4 cm in the center of the coating film was divided into 400 points, and each film thickness was measured. The smoothness was evaluated based on the measured standard deviation of the film thickness and 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 influence of the fluorine-containing thermally decomposable resin on the liquid crystal composition, the following test was performed.
Preparation of liquid crystal samples: Samples before and after heat treatment of the fluorine-containing thermally decomposable resin obtained in the synthesis example, and samples before and after heat treatment of Fluorosurfactant Megafac F-554 manufactured by DIC Corporation were prepared as the following liquid crystal composition. A composition containing 1.0% by mass and 0.1% by mass with respect to each was prepared and subjected to pressure filtration using a 0.2 micron filter to obtain a liquid crystal sample. The heat treatment was performed by leaving in a hot air dryer set at 230 ° C. for 30 minutes.
The prepared liquid crystal sample was sealed in a cell for measuring voltage holding ratio (VHR), and VHR was measured.
VHR: Voltage holding ratio (%) at 60 Hz at 60 ° C. and an applied voltage of 5 V

  The following abbreviations are used to describe the compounds constituting the liquid crystal composition.

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

As the VHR measurement cell, one of the following two types of cells was used.
VHR cell 1:
After firing a horizontal alignment film (SE-7492, manufactured by Nissan Chemical Co., Ltd.) on a transparent glass substrate with an ITO electrode and rubbing it, a bead spacer is used so that the liquid crystal alignment is antiparallel and the substrate spacing is 3.5 μm. Horizontally oriented cell assembled by bonding edges with thermosetting resin.
VHR cell 2:
After firing a vertical alignment film (JALS-2096, manufactured by JSR Corporation) on a transparent glass substrate with an ITO electrode, the edge portion is bonded with a thermosetting resin through a bead spacer so that the substrate spacing is 3.5 μm. Assembled vertical alignment cell.

  VHR measurement was performed in the same manner except that the liquid crystal composition LC1 was changed to LC2 to LC4. In each case, the sample after the heat treatment of the fluorine-containing thermally decomposable resin (A-2) was reduced to 0.00. 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 can effectively suppress the influence on the liquid crystal composition.

  A similar test was conducted with 0.1% of the fluorine-containing thermally decomposable resins (A-1) and (A-3) instead of the fluorine-containing thermally decomposable resin (A-2). It was 0 to 97.9%, and the same result as that of the fluorine-containing thermally decomposable resin (A-2) was obtained.

  When VHR measurement was performed in the same manner except that the liquid crystal composition LC5 was replaced with LC6, 0.1% by mass of the sample after heat treatment of the fluorine-containing thermally 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 can effectively suppress the influence on the liquid crystal composition.

  As a result of conducting the same test with 0.1% of the fluorine-containing thermally decomposable resins (A-1) and (A-3) instead of the fluorine-containing thermally decomposable resin (A-2), the measured value was 98. 7 and 98.9%, which are the same results as those of the fluorine-containing thermally decomposable resin (A-2).

Synthesis Example 5 [Preparation of alignment agent for rubbing alignment film formation]
29,80 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 14.16 g of p-phenylenediamine and 1.04 g of a 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. Thereafter, the solid 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 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 give a solid content concentration of 5.0. After obtaining a mass% solution, 0.1% of the fluorine-containing thermally decomposable resin obtained in the synthesis example is blended in terms of solid content, and then filtered through a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent. did.

Example 3 [Production of alignment film and liquid crystal display element]
Application of the liquid crystal aligning agent obtained in Synthesis Example 3 on a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spinner (rotation speed: 2000 rpm, application time: 1 minute) And it dried at 200 degreeC for 1 hour, and formed the coating film with a dry film thickness of 0.08 micrometer. The range% of the obtained film was 3% or less. When the surface was analyzed by XPS, fluorine atoms were not detected.

  Liquid crystal alignment is performed by rubbing the formed coating film surface with a rubbing machine equipped with a roll wrapped with a rayon cloth, with a bristles indentation length of 0.2 mm, a roll rotation speed of 200 rpm, and a rubbing frequency of twice. A film was formed. Two substrates having a liquid crystal alignment film were prepared, and an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3 μm was applied to the outer edge of each substrate by screen printing, and then rubbed in each liquid crystal alignment film The two substrates were placed facing each other with a gap so that the directions were antiparallel, and the outer edges were pressed together to cure the adhesive. Thereafter, nematic liquid crystal “MLC-2001” (manufactured by Merck) is injected and filled into the cell gap defined by the adhesive on the surface and outer edge of the two substrates, and then the injection hole is bonded with epoxy. A liquid crystal cell was constructed by sealing with an agent. Thereafter, a polarizing plate was bonded to 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, thereby producing a liquid crystal display element.

  It was good when the image sticking of the obtained liquid crystal display element was confirmed visually. The results of VHR measurement were 98.8%, (A-2) 98.9%, and (A-3) 98.8% in the system using the fluorine-containing thermally decomposable resin (A-1).

Comparative Example 2
In Example 3, instead of the fluorine-containing thermally decomposable resin (A-1), a liquid crystal aligning agent was prepared using MegaFuck F-554, and an alignment film was produced 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 produced using this, it was confirmed that image sticking occurred. The VHR was 93.2%.

Example 4 [Production of Vertical Alignment Film and Liquid Crystal Display Element]
The fluorine-containing thermally decomposable resin obtained in the synthesis example is dissolved in 0.1 parts by mass in terms of solid content in 100 parts of a polyimide solution (JALS2131-R6; manufactured by JSR) containing 3% of a polyimide precursor, and slitted. A substrate having an ITO electrode having a pattern was spin coated. Thereafter, the alignment film was heated to 200 ° C. to cure the polyimide precursor, thereby forming a 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, fluorine atoms were not detected. A liquid crystal display element was produced by sandwiching the LC5 liquid crystal composition between the substrate and a substrate having a transparent electrode by a dropping method. The image sticking was good when visually confirmed. In the system using the fluorine-containing thermally decomposable resin (A-1), they were 98.5%, (A-2) 98.6%, and (A-3) 98.8%.

Comparative Example 3
An alignment film and a liquid crystal display device were produced in the same manner as in Example 4 except that MegaFac F-554 was used instead of the fluorine-containing thermally decomposable resin (A-1). The range% of the coating film was 3% or less, but VHR was not measured because it was confirmed that seizure occurred.

  Example 5 [Production of photo-alignment film and liquid crystal display element]

4,4′-Diaminotolane (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 with a viscosity of 33 mPa · s was obtained. 3 g of varnish A was weighed into a sample bottle and BC was added to make 5 g. Furthermore, 0.1% by mass of the fluorine-containing thermally decomposable resin obtained in the synthesis example was added and mixed in terms of solid content. About 3% by mass of this polyamic acid solution was dropped on a transparent glass substrate provided with an ITO electrode on one side and applied by a spinner method (2,300 rpm, 15 seconds). After the coating, the substrate was heated at 80 ° C. for 5 minutes to evaporate the solvent, and then irradiated with linearly polarized light through the polarizing plate (energy of about 5 J / cm ^{2 at} 365 nm). The substrate after the light irradiation was heat-treated in an oven at 230 ° C. for 30 minutes to obtain a photo-alignment film having a thickness of about 60 nm. The range% of the film was 3% or less.

  The two substrates on which the above-mentioned photo-alignment film is formed on the ITO electrode are arranged so that the polarization directions of the linearly polarized light irradiated to the respective photo-alignment films are parallel to each other and the surface on which the photo-alignment film is formed A liquid crystal display element having a cell thickness of 3 μm was assembled by forming a gap for injecting the liquid crystal composition between the opposed photo-alignment films. Liquid crystal composition A shown below was injected into this cell.

  When this liquid crystal cell A was observed with the naked eye, so-called flow alignment in which the liquid crystals were aligned along the direction in which the liquid crystals flowed was slightly observed. This liquid crystal cell A was subjected to an isotropic treatment at 110 ° C. for 30 minutes and cooled to room temperature. When this liquid crystal cell A was observed with a microscope, liquid crystal alignment defects were not observed. In the system using the fluorine-containing thermally decomposable resin (A-1), they were 99.0%, (A-2) 98.8%, and (A-3) 98.8%.

Comparative Example 4
An alignment film and a liquid crystal display device were produced in the same manner as in Example 5 except that MegaFac F-554 was used instead of the fluorine-containing thermally decomposable resin (A-1). The range% of the coating film was within 3%, but VHR was not measured because it was confirmed that a liquid crystal alignment defect had occurred.

Example 6 [Production of photo-alignment film and liquid crystal display element]
0.820 g (3.66 mmol) of 2,3,5-tricarboxycyclopentylacetic acid-1,2: 3,4-dianhydride was added to 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 was added to the solution . Stirring was then carried out for 2 hours at 0 ° C. The mixture was then allowed to react for 21 hours at room temperature. After the polymer mixture was diluted with 18 mL of THF, precipitated into 800 mL of water and dried at room temperature under vacuum, 2.76 g of polyamic acid in the form of a white powder was obtained. Solid polyamic acid is mixed with NMP, stirred well until dissolved, and butylcellulose (BC) as the second solvent is added to convert the fluorine-containing thermally decomposable resin (A-1) to solid content The final solution was obtained by sufficiently stirring the composition to obtain 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 for 30 seconds at a spin speed of 2700 rpm. After spin coating, the substrate was subjected to a firing procedure consisting of 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 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 ° to the normal of the substrate surface. The polarization plane exists in a plane extending in the normal line of the substrate and the light propagation direction. The applied exposure dose was 22.6 mJ / cm ² . After exposure to LPUV, the two substrates were assembled such that the exposed polymer layer was facing the inside of the cell. The substrates are adjusted relative to each other such that the induced orientation directions are parallel to each other (corresponding to an antiparallel rubbed arrangement when oriented by a rubbing procedure). When the cell was filled with a liquid crystal MLC6610 (Merck KGA) having negative dielectric anisotropy, the liquid crystal in the cell showed a clear homeotropic alignment. The tilt angle is 87.56 ° using the crystal rotation method, VHR is 99.0% in the system using the fluorine-containing thermally decomposable resin (A-1), and (A-2) is 99.3% ( A-3) It was 98.9%.

Comparative Example 5
An alignment film and a liquid crystal display device were produced in the same manner as in Example 6 except that MegaFac F-554 was used instead of the fluorine-containing thermally decomposable resin (A-1). The range% of the coating film was 3% or less, but VHR was not measured because it was confirmed that a liquid crystal alignment defect was generated.

Claims (12)

The following structural formula (a1)
[In Formula (a1), R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. 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 fluorine-containing thermally decomposable resin (A) having a thermally decomposable group represented by:
Polyimide (b-1) using at least tetracarboxylic dianhydride and diamine as raw materials, polyamic acid (b-2) which is a precursor of the polyimide (b-1), and ester of the polyamic acid (b-3) And at least one compound (B) selected from the group consisting of: The fluorine-containing thermally decomposable resin (A) is represented by the following structural formula (a2) or (a3)
[In formulas (a2) and (a3), X ¹ and X ² are each a direct bond or a divalent linking group, and R ⁵¹ is a hydrogen atom, a methyl group, a group represented by the 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 resin composition according to claim 1, which is a resin having a structural unit represented by:   The resin composition according to claim 1 or 2, wherein the fluorine-containing thermally decomposable resin (A) has a fluorine atom content of 1 to 35 mass%.   The resin composition according to any one of claims 1 to 3, wherein the fluorine-containing thermally decomposable resin (A) is used in a range of 0.01 to 10 parts by mass with respect to 100 parts by mass of a solid content in the resin composition. object.   It is a liquid crystal aligning agent, The resin composition of any one of Claims 1-4   Hardened | cured material which consists of a resin composition of any one of Claims 1-4.   The coating film containing resin (C) which has a carboxyl group, and a polyimide.   8. The coating film according to claim 7, wherein Range% (maximum difference in film thickness / average film thickness) in film thickness measurement by a reflection spectral film thickness meter is 10% or less. The resin (C) having a carboxyl group is represented by the following structural formula (c1) or (c2)
[In the formulas (c1) and (c2), X ¹ and X ² are each a direct bond or a divalent linking group, R ⁶¹ is a hydrogen atom, a methyl group, and the following structural formula (a1)
[In Formula (a1), R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is a fluorinated alkyl group or a fluorinated alkyl group via an oxygen atom. A plurality of linked fluoroalkylene ether chains, the bonding site with Y ¹ is a carbon atom, and Y ¹ is an oxygen atom or a sulfur atom. ]
R ⁶² and R ⁶³ each represent a group or a carboxyl group represented by the structural formula (a1). ]
The coating film according to claim 7 or 8, wherein the content of fluorine atoms in the resin (C) having a structural unit represented by formula (C) is 0.5% by mass or less.   The coating film according to any one of claims 7 to 9, which is a liquid crystal alignment film.   After apply | coating the resin composition of any one of Claims 1-4 on a base material, it heat-processes in the atmosphere for 1 to 60 minutes at 180-300 degreeC, The manufacturing method of the coating film characterized by the above-mentioned. .   The liquid crystal display element which comprises the coating film of any one of Claims 7-10 as a liquid crystal aligning film.