WO2019097902A1

WO2019097902A1 - Method for manufacturing liquid crystal element

Info

Publication number: WO2019097902A1
Application number: PCT/JP2018/037583
Authority: WO
Inventors: 隆一奥田; 裕介植阪; 小山　貴由
Original assignee: Jsr株式会社
Priority date: 2017-11-20
Filing date: 2018-10-09
Publication date: 2019-05-23
Also published as: CN111108433B; KR20200042002A; KR102321076B1; JPWO2019097902A1; TWI776974B; JP7074142B2; CN111108433A; TW201928478A

Abstract

The present invention makes it possible to obtain a liquid crystal element that exhibits superior reliability with an element structure in which an interlayer insulating film, patterned electrodes, and a liquid crystal alignment film are formed in this order on a substrate. In a method for manufacturing a liquid crystal element, the method including: a step for forming an interlayer insulating film 21 on at least one of a pair of substrates; a step for forming patterned electrodes (pixel electrodes 19) on the interlayer insulating film 21; and a step for forming a liquid crystal alignment film (first alignment film 32) on the patterned electrodes such that the liquid crystal alignment film is in contact with at least a portion of the interlayer insulating film 21, the liquid crystal alignment film is formed by using a liquid crystal alignment agent containing a polymer component and at least one kind of solvent selected from a specific set of solvents.

Description

Method of manufacturing liquid crystal device

Cross-reference to related applications

This application is based on Japanese Patent Application No. 2017-223114 filed on November 20, 2017, the contents of which are incorporated herein by reference.

The present disclosure relates to a method of manufacturing a liquid crystal element.

As a liquid crystal device, a horizontal alignment mode using a nematic liquid crystal having a positive dielectric anisotropy represented by a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type or the like, or a negative dielectric anisotropy Various devices are known such as a VA (Vertical Alignment) liquid crystal device using a nematic liquid crystal having a vertical alignment (homeotropic) alignment mode. In addition, a liquid crystal device of a lateral electric field mode such as an IPS (In-Plane Switching) type or an FFS (Fringe Field Switching) type having a cell structure in which a pair of electrodes is provided on one substrate is also known.

As one of alignment processing methods of liquid crystal elements, a PSA (Polymer Sustained Alignment) method is known (see, for example, Patent Document 1). In the PSA method, a photopolymerizable monomer is mixed in advance with liquid crystal in the gap between a pair of substrates, and after a liquid crystal cell is constructed, ultraviolet light is irradiated in a state where a voltage is applied between the substrates to polymerize the photopolymerizable monomer. To form a polymer layer and control the initial alignment of the liquid crystal by the polymer layer. According to this technique, it is possible to increase the viewing angle and speed up the liquid crystal molecule response, and to solve the problem of the insufficient transmittance and contrast in the MVA type panel.

Further, Patent Document 1 discloses that, in the PSA technology, a pattern electrode patterned to have a comb-tooth shape (also referred to as a fishbone shape) having a large number of openings (slit portions) is used as a pixel electrode. It is done. In the liquid crystal device of Patent Document 1, a drain bus line is formed on a glass substrate on the array substrate side, and an interlayer insulating film is formed thereon. Further, a fishbone-shaped pixel electrode is formed on the interlayer insulating film, and a liquid crystal alignment film is formed on the pixel electrode. The liquid crystal alignment film generally dissolves polymer components such as polyamic acid, polyimide, polyorganosiloxane, (meth) acrylic polymer, polyamide and the like in a solvent, applies the polymer composition on a substrate and It is formed by removing.

Japanese Patent Application Publication No. 2003-149647

When a pattern electrode having a large number of slits is disposed on an interlayer insulating film and a liquid crystal alignment film is formed thereon, the liquid crystal alignment agent and the interlayer insulating film are formed in the slit in the pixel region (that is, the display region) of the liquid crystal device. And contact. In this case, the characteristics of the interlayer insulating film may change due to the influence of the liquid crystal aligning agent, or impurity components contained in the interlayer insulating film may be eluted into the liquid crystal aligning agent to deteriorate the performance of the liquid crystal alignment film. There is a concern that the reliability of the liquid crystal device may be reduced.

The present disclosure has been made in view of the above problems, and in a device structure in which an interlayer insulating film, a pattern electrode, and a liquid crystal alignment film are formed in this order on a substrate, a liquid crystal that can obtain a liquid crystal device with excellent reliability. It is an object to provide a method of manufacturing a device.

The present disclosure adopts the following means in order to solve the problems.

<1> A method of manufacturing a liquid crystal device, comprising: a pair of substrates disposed opposite to each other, a liquid crystal layer disposed between the pair of substrates, and a pair of electrodes, wherein at least one of the pair of electrodes is A pattern electrode having a plurality of openings, forming an interlayer insulating film on at least one of the pair of substrates, forming the pattern electrode on the interlayer insulating film, and forming the pattern electrode on the pattern electrode. Forming a liquid crystal alignment film to be in contact with at least a part of the interlayer insulating film, the liquid crystal alignment film comprising: a polymer component; and at least one solvent selected from the following solvent group: The manufacturing method of a liquid crystal element formed using the liquid crystal aligning agent containing.
Solvent group:
[A] Solvent: a compound represented by the following formula (1), a compound represented by the following formula (2), N, N, 2-trimethylpropionamide, and 1,3-dimethyl-2-imidazolidinone.
[B] Solvent: dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, 4-methoxy-4-methyl-2-pentanone, 4-hydroxy-2-butanone, 2-methyl-2-hexanol, 2 6, 6-dimethyl-4-heptanol, diisobutyl ketone, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

In the formula (1), R ¹ is a monovalent hydrocarbon group having 2 to 5 carbon atoms, or a monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group. )

(In formula (2), R ² and R ³ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or “—O— between carbon-carbon bonds of the hydrocarbon group. R ² and R ³ may be bonded to each other to form a ring structure. R ⁴ is an alkyl group having 1 to 6 carbon atoms.

According to the above configuration, when forming the liquid crystal alignment film, even if the interlayer insulating film and the liquid crystal alignment agent come in contact with each other at the opening of the pattern electrode, the performance of the interlayer insulating film or the liquid crystal alignment film does not easily deteriorate. An excellent liquid crystal element can be obtained.

FIG. 1 is a view schematically showing a part of a liquid crystal device. FIG. 2 is a cross-sectional view schematically showing a part of the liquid crystal device according to the first embodiment. FIG. 3 is a cross-sectional view schematically showing a part of the liquid crystal device of the second embodiment. FIG. 4 is a view showing the structure of the electrode used in the example. FIG. 5 is a view showing the structure of the electrode used in the example.

Embodiments will be described below with reference to the drawings. In addition, in the following each embodiment, the same code | symbol is attached | subjected to the mutually same or equal part in the figure, and the description is used about the part of the same code | symbol.

(Configuration of Liquid Crystal Device 10)
The liquid crystal device 10 is a vertical alignment type liquid crystal display element of a PSA (Polymer Sustained Alignment) type. In the display unit of the liquid crystal device 10, a plurality of pixels 11 are arranged in a matrix. As shown in FIG. 1, the pixels 11 are formed in a region surrounded by the scanning signal lines 12 and the video signal lines 13 which cross each other. In each pixel 11, a thin film transistor (TFT) 14 that functions as a liquid crystal driving element is disposed. As shown in FIG. 2, the liquid crystal device 10 includes an array substrate 15, an opposing substrate 16, and a liquid crystal layer 17.

The array substrate 15 has a transparent substrate 18 such as a glass substrate or a plastic substrate, scanning signal lines 12, video signal lines 13, thin film transistors 14, pixel electrodes 19, and an interlayer insulating film 21 (see FIG. 2). The thin film transistor 14 includes a gate electrode 22 formed of the scanning signal line 12, a semiconductor layer 23 formed of silicon (Si), a source electrode 24 formed of the video signal line 13, and a drain electrode 25 connected to the pixel electrode 19. It consists of The thin film transistor 14 is provided by a known method such as photolithography. A known material can be used as a specific material that constitutes each part of the thin film transistor 14.

The pixel electrode 19 is formed of a transparent conductor such as ITO. As shown in FIG. 1, the pixel electrode 19 is a pattern electrode in which a plurality of slits (long and narrow rectangular openings) 19 c are provided on a planar electrode. Specifically, the pixel electrode 19 is provided between a trunk line portion 19a extending in two directions orthogonal to each other, a plurality of branch line portions 19b extending in an oblique direction from the trunk line portion 19a, and a plurality of branch line portions 19b. A plurality of formed slit portions 19c are provided, and a repeated pattern of a conductive portion and a nonconductive portion is provided. The pixel electrode 19 is electrically connected to the thin film transistor 14. The thin film transistor 14 is electrically connected to the scanning signal line 12 and the video signal line 13 and is supplied with various signals.

The array substrate 15 has a structure in which a transparent substrate 18, an interlayer insulating film 21 and a pixel electrode 19 are stacked in this order in a display area in which a plurality of pixels 11 are arranged in a matrix. The pixel electrode 19 is connected to the drain electrode 25 through a contact hole 27 provided in the interlayer insulating film 21. The interlayer insulating film 21 is formed by photolithography using a radiation sensitive resin composition described later. By providing the interlayer insulating film 21, the increase in capacitive coupling between the pixel electrode 19 and the signal line is suppressed.

The counter substrate 16 includes a glass substrate 28, a color filter layer 29, an overcoat layer (not shown) as an insulating layer, and a common electrode 31. The color filter layer 29 is composed of sub-pixels colored with red (R), green (G) and blue (B). The color filter layer 29 is produced by a known method such as photolithography. The common electrode 31 is a planar electrode formed of a transparent conductor such as ITO, and is provided across the plurality of pixels 11.

A first alignment film 32 is formed on the electrode formation surface of the array substrate 15, and a second alignment film 33 is formed on the electrode formation surface of the counter substrate 16. The first alignment film 32 and the second alignment film 33 are liquid crystal alignment films that regulate the alignment of liquid crystal molecules in the liquid crystal layer 17, and are substrates using a liquid crystal alignment agent that is a polymer composition containing a polymer component. It is formed on top. The first alignment film 32 is in contact with the interlayer insulating film 21 at least in the slit portion 19 c in the display area.

The array substrate 15 and the counter substrate 16 are arranged with a predetermined gap (cell gap) such that the alignment film forming surface of the array substrate 15 and the alignment film forming surface of the counter substrate 16 face each other. The peripheral portions of the pair of opposed substrates are bonded together by a sealing agent (not shown). As a material of the sealing agent, a known material (for example, a thermosetting resin or a photocurable resin) is used as the sealing agent for a liquid crystal device. The liquid crystal composition is filled in a space surrounded by the array substrate 15, the counter substrate 16 and the sealing agent, whereby the liquid crystal layer 17 is disposed in contact with the first alignment film 32 and the second alignment film 33. It is done.

The liquid crystal layer 17 has negative dielectric anisotropy. The liquid crystal layer 17 has PSA layers 34 and 35 which are polymer layers at the interface with the array substrate 15 and the interface with the counter substrate 16 respectively. The PSA layers 34 and 35 are formed by photopolymerizing photopolymerizable monomers previously mixed in the liquid crystal layer 17 in a state in which liquid crystal molecules are pretilted and aligned after construction of a liquid crystal cell. In the liquid crystal device 10, the initial alignment of liquid crystal molecules in the liquid crystal layer 17 is controlled by the PSA layers 34 and 35.

In the liquid crystal device 10,

polarizers

36 and 37 are disposed outside the array substrate 15 and the counter substrate 16, respectively. A terminal area is provided at the outer edge of the array substrate 15. A liquid crystal device 10 is driven by connecting a driver IC or the like for driving liquid crystal to the terminal area.

<Liquid crystal alignment agent>
Next, the liquid crystal aligning agent used in order to form a liquid crystal aligning film (1st alignment film 32, 2nd alignment film 33) is demonstrated. The liquid crystal aligning agent contains a polymer component and a solvent component.

(Polymer component)
The main skeleton of the polymer contained in the liquid crystal aligning agent is not particularly limited. For example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) Main skeletons of derivatives, poly (meth) acrylic polymers and the like). Among these, at least one polymer (hereinafter, also referred to as [P] polymer) selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane is preferable. In addition, in preparation of a liquid crystal aligning agent, it may be used individually by 1 type as a polymer, and may be used combining 2 or more types. In the present specification, "(meth) acrylic" is meant to include "acrylic" and "methacrylic".

[P] The method for synthesizing the polymer is not particularly limited. For example, when the [P] polymer is a polyamic acid, the polyamic acid can be obtained by reacting tetracarboxylic acid dianhydride with a diamine.

(Polyamic acid)
Examples of tetracarboxylic acid dianhydrides used in the synthesis of polyamic acids include aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aromatic tetracarboxylic acid dianhydrides. . As specific examples of these, as aliphatic tetracarboxylic acid dianhydride, for example, 1,2,3,4-butanetetracarboxylic acid dianhydride, ethylenediaminetetraacetic acid dianhydride etc .;
Examples of alicyclic tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid 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, 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 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8- Dianhydride, cyclohexanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride etc .;
As aromatic tetracarboxylic acid dianhydride, for example, pyromellitic acid dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, p-phenylene bis (trimellitic acid monoester anhydride), ethylene glycol In addition to bis (anhydrotrimellitate), 1,3-propylene glycol bis (anhydrotrimellitate), etc., tetracarboxylic acid dianhydrides described in JP-A-2010-97188 can be mentioned. It can be used. In addition, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

The tetracarboxylic acid dianhydride used in the synthesis preferably contains an alicyclic tetracarboxylic acid dianhydride from the viewpoint that the solubility of the resulting polymer in a solvent can be further increased, and a cyclobutane ring, a cyclopentane ring and It is more preferable to include a tetracarboxylic acid dianhydride having at least one ring structure selected from the group consisting of cyclohexane rings (hereinafter, also referred to as “specific tetracarboxylic acid dianhydride”). The use ratio of the specific tetracarboxylic acid dianhydride is preferably 10 mol% or more, preferably 20 to 100 mol%, with respect to the total amount of tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid. More preferable.

Examples of the diamine used for the synthesis of the polyamic acid include aliphatic diamines, alicyclic diamines, aromatic diamines, diamino organosiloxanes and the like. As specific examples of these, as aliphatic diamines, for example, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane and the like; alicyclic diamines As, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) etc .;
As aromatic diamines, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-Diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) ethane, 1,3-bis (4-amino) Phenoxy) propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) Bisaniline, 1,4-bis (4-aminophenoxy) benzene, 2,6-diaminopyridine, 3,6-diaminocar Azole, N, N'-bis (4-aminophenyl) -benzidine, 1,4-bis- (4-aminophenyl) -piperazine, 1- (4-aminophenyl) -2,3-dihydro-1,3 , 3-Trimethyl-1H-inden-5-amine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 3,5-diaminobenzoic acid Acid, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, 3,5-diaminobenzoic acid Acid cholestenyl acid, lanostanyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 4- (4'-trifluoromethoxy) 1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) ) -4- (4-Heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, N- [4- (2-aminoethyl) phenyl] benzene-1,4- Diamine, N- [4- (aminomethyl) phenyl] benzene-1,4-diamine, 1,3-bis (4-aminophenytyl) urea, 4,4 '-[4,4'-propane-1, 3-Diylbis (piperidine-1,4-diyl)] dianiline, 2-propynyloxy-2,4-phenylenediamine and the following formula (D-1)

(In Formula (D-1), X ^I and X ^II each independently represent a single bond, -O-, * -COO-, * -OCO- or * -NH-CO- (where "*" represents subjected the bond is bound to the diamino phenyl group.), and, R ^I and R ^II are each independently an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is 0 C is an integer of 1 to 20, n is 0 or 1, and m is 0 or 1. However, a and b do not simultaneously become 0, and X ^I is In the case of * -NH-CO-, n is 0.)
Compounds and the like;
Examples of diaminoorganosiloxanes include, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and diamines described in JP-A-2010-97188 can be used. In the synthesis of the polyamic acid, one kind of diamine may be used alone, or two or more kinds thereof may be used in combination.

The polyamic acid can be obtained by reacting the above-mentioned tetracarboxylic acid dianhydride and diamine with a molecular weight modifier as required. The ratio of tetracarboxylic acid dianhydride and diamine used in the synthesis reaction of the polyamic acid is such that the acid anhydride group of tetracarboxylic acid dianhydride is 0.2 to 2 per 1 equivalent of amino group of diamine. The ratio which becomes equivalent is preferable. Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate. It can be mentioned. The proportion of the molecular weight modifier used is preferably 20% by mass or less based on the total amount of tetracarboxylic acid dianhydride and diamine used.

The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and the reaction time is preferably 0.1 to 24 hours.
Examples of the organic solvent used for the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like. Preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, One or more selected from the group consisting of halogenated phenols and specific solvents described later are used as a solvent, or a mixture of one or more of these and other organic solvents (eg, butyl cellosolve, diethylene glycol diethyl ether, etc.) It is preferred to use The amount of the organic solvent used is preferably such that the total amount of tetracarboxylic acid dianhydride and diamine is 0.1 to 50% by mass with respect to the total amount of the reaction solution. As described above, a reaction solution in which the polyamic acid is dissolved is obtained. This reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparation of a liquid crystal aligning agent after the polyamic acid contained in the reaction solution is isolated.

(Polyimide)
The polyimide can be obtained by dehydration ring closure and imidization of the polyamic acid synthesized as described above. The polyimide may be a completely imidized product obtained by dehydrating and ring closing all of the amic acid structure of the precursor polyamic acid, and only a part of the amic acid structure may be dehydrating and ring closing, and the amic acid structure and the imide. It may be a partial imidate in which ring structures coexist. The imidation ratio of the polyimide is preferably 30% or more, more preferably 40 to 99%, and still more preferably 60 to 99%. The imidation ratio is a percentage representing the ratio of the number of imide ring structures to the total number of amic acid structures of polyimide and the number of imide ring structures. Here, part of the imide ring may be an isoimide ring.

The dehydration ring closure of polyamic acid is preferably carried out by a method of dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and heating as necessary. In this method, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride and the like can be used. The amount of the dehydrating agent used is preferably 0.01 to 20 moles per mole of the polyamic acid's amic acid structure. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydrating ring-closing catalyst used is preferably 0.01 to 10 moles relative to 1 mole of the dehydrating agent used. As an organic solvent to be used, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C., and the reaction time is preferably 1.0 to 120 hours. The obtained reaction solution may be used as it is for preparation of a liquid crystal aligning agent, or may be used for preparing a liquid crystal aligning agent after isolating a polyimide.

(Polyamic acid ester)
The polyamic acid ester is, for example, a method of reacting a polyamic acid obtained by the above reaction with an esterification agent, a method of reacting a [II] tetracarboxylic acid diester with a diamine, a [III] tetracarboxylic acid diester It can be obtained by a method of reacting a dihalide with a diamine, or the like. Here, as an esterifying agent of said [I], methanol, ethanol etc. are mentioned, for example. The tetracarboxylic acid diester used in the above [II] can be obtained by ring-opening tetracarboxylic acid dianhydride with an alcohol or the like. The tetracarboxylic acid diester dihalide used in the above [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. The resulting polyamic acid ester 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 reaction solution obtained by dissolving the polyamic acid ester may be used as it is for the preparation of a liquid crystal aligning agent, or the polyamic acid ester contained in the reaction solution may be isolated for the preparation of a liquid crystal aligning agent.

The polyamic acid, polyamic acid ester and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s when this is made into a solution with a concentration of 10% by mass, preferably 15 to 500 mPa. More preferably, it has a solution viscosity of s. In addition, the solution viscosity (mPa · s) of the above-mentioned polymer is a polymer solution having a concentration of 10% by mass prepared using a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer. It is the value measured at 25 ° C. using an E-type viscometer. The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) for polyamic acid, polyamic acid ester and polyimide is preferably 500 to 100,000, and 1,000 to 50,000. Is more preferred.

(Polyorganosiloxane)
Polyorganosiloxane can be obtained, for example, by hydrolysis or hydrolysis / condensation of a hydrolyzable silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst.

Examples of hydrolyzable silane compounds used for the synthesis of polyorganosiloxanes include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane and trimethoxysilylpropyl. Alkoxysilane compounds such as succinic anhydride, dimethyldimethoxysilane, dimethyldiethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureido Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (3-cyclohexylamino) propylto Nitrogen and sulfur containing alkoxysilane compounds such as methoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy Epoxy group-containing silane compounds such as cyclohexyl) ethyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyl Examples thereof include unsaturated bond-containing alkoxysilane compounds such as dimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, p-styryltrimethoxysilane and the like. The hydrolyzable silane compounds can be used alone or in combination of two or more of them. In the present specification, “(meth) acrylo” is a meaning including “acrylo” and “methacrylo”.

The above-mentioned hydrolysis / condensation reaction is carried out by reacting one or more silane compounds as described above with water, preferably in the presence of a suitable catalyst and an organic solvent. In the reaction, the proportion of water used is preferably 1 to 30 moles relative to 1 mole of the silane compound (total amount). As a catalyst to be used, an acid, an alkali metal compound, an organic base (for example, triethylamine, tetramethyl ammonium hydroxide etc.), a titanium compound, a zirconium compound etc. can be mentioned, for example. The amount of catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and should be set appropriately. For example, it is preferably 0.01 to 3 times the molar amount of the total amount of silane compounds. . Examples of the organic solvent to be used include hydrocarbons, ketones, esters, ethers, alcohols and the like, and among these, it is preferable to use a water insoluble or poorly water soluble organic solvent. The proportion of the organic solvent used is preferably 50 to 1,000 parts by mass with respect to a total of 100 parts by mass of the silane compound used for the reaction.

The above hydrolysis / condensation reaction is preferably carried out, for example, by heating with an oil bath or the like. At that time, the heating temperature is preferably 130 ° C. or less, and the heating time is preferably 0.5 to 12 hours. After completion of the reaction, the solvent can be removed from the organic solvent layer separated from the reaction solution to obtain a polysiloxane.

When functional groups such as a pretilt angle imparting group and a photoalignable group are introduced into the side chain of the polyorganosiloxane, the synthesis method is not particularly limited. For example, epoxy group-containing silane compounds or epoxy group-containing silane compounds Hydrolysis condensation of a mixture of this and other silane compounds to synthesize an epoxy group-containing polyorganosiloxane, and then reacting the obtained epoxy group-containing polyorganosiloxane with a carboxylic acid having the above functional group And the like. The reaction of the epoxy group-containing polyorganosiloxane with the carboxylic acid can be carried out according to a known method.

The polyorganosiloxane preferably has a polystyrene equivalent weight average molecular weight (Mw) measured by GPC in the range of 500 to 100,000, more preferably in the range of 1,000 to 30,000, 1, More preferably, it is from 000 to 20,000. When the weight average molecular weight of the polyorganosiloxane is in the above range, it is easy to handle when producing a liquid crystal alignment film, and a liquid crystal alignment film having sufficient material strength and characteristics can be obtained.

The content ratio of the [P] polymer in the liquid crystal aligning agent (total amount when two or more are contained) is 60% by mass or more based on the total amount of the polymer components in the liquid crystal aligning agent Preferably, it is 80% by mass or more. In addition, it is preferable that the liquid crystal aligning agent contains at least one kind of [p] polymer, which is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, in that a liquid crystal element more excellent in reliability can be obtained. . The content ratio of the [p] polymer in the liquid crystal aligning agent (in the case of containing two or more, the total amount thereof) is 40% by mass or more based on the total amount of the polymer components in the liquid crystal aligning agent Preferably, it is 60% by mass or more.

It is preferable that at least a part of the polymer component contained in the liquid crystal aligning agent is a polymer having a partial structure represented by the following formula (3).
* -L ¹ -R ¹¹ -R ¹² -R ¹³ -R ¹⁴ (3)
(In the formula ^(3), L ¹ ^{is, -O -, - CO -,} - COO- * 1, -OCO- * 1, -NR 15 -, - NR 15 -CO- * 1, -CO-NR 15 -* ¹ , an alkanediyl group having 1 to 6 carbon atoms, -O-R ^16- * ¹ , or -R ¹⁶ -O- * ¹ (provided that R ¹⁵ is a hydrogen atom or a monovalent group having 1 to 10 carbon atoms) a hydrocarbon ^{group, R 16} is an alkanediyl group of 1 to 3 carbon atoms. ^{"* 1"} ^indicates that the bond between ^{R 11.)} a is ^{.R 11} and ^{R 13,} each independently represent a single bond, a phenylene group or a cycloalkylene ^{group, R 12} represents a single bond, a phenylene group, a cycloalkylene ^{^{^{group, -R 17 -B 1 - * 2}}} , or ^-B 1 ^-R 17 - ^{* 2} ^{(However, R 17} is a phenylene group or a cycloalkylene group, ^{B 1} is -CO -. ^* 3, -OCO- ^{* 3,} or alkanediyl group having a carbon number of 1 to 3 ^{"* 2"} ^indicates that the bond to ^{R 13,} ^{"* ^3",} and ^{R 17} R ¹⁴ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. Or a fluoroalkoxy group having 1 to 18 carbon atoms or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton, and may have a radically polymerizable group or a photoinitiator group, provided that R ¹⁴ is In the case of a hydrogen atom, a fluorine atom or a group having 1 to 3 carbon atoms, all of R ¹¹ , R ¹² and R ¹³ will not be single bonds. "*" Indicates that it is a bond.)

In the above formula (3), the L ¹ and B ¹ alkanediyl groups, and the R ¹⁴ alkyl group, fluoroalkyl group, alkoxy group and fluoroalkoxy group are preferably linear. Examples of the group having a steroid skeleton of R ¹⁴ include cholestanyl group, cholesteryl group, lanostanyl group and the like. The phenylene group of R ¹¹ , R ¹² , R ¹³ and R ¹⁷ is preferably a 1,4-phenylene group, and the cycloalkylene group is preferably a 1,4-cyclohexylene group. Among R ¹¹ and R ¹³ , at least one of them is preferably a phenylene group or a cycloalkylene group. R ¹² is a phenylene group, a cycloalkylene ^group, -R 17 ^-B 1 - ^{* 2,} or ^-B 1 ^-R 17 - is preferably a ^{* 2.} The main skeleton of the polymer having a partial structure represented by the above formula (3) is not particularly limited, but is preferably a [P] polymer.
The content ratio of the partial structure represented by the above formula (3) in the polymer is appropriately set according to the main chain of the polymer, but from the viewpoint of sufficiently increasing the response speed of the liquid crystal, the entire content of the polymer The amount is preferably 1 to 50 mol%, and more preferably 2 to 40 mol%, based on the monomer unit.

In addition, a liquid crystal aligning agent has a radical polymerizable group, a photoinitiator group, a radical polymerization inhibitor group, and a polymer component as a polymer component, in that a liquid crystal element in which an afterimage hardly occurs and a response speed of liquid crystal can be obtained A polymer having at least one selected from the group consisting of nitrogen-containing heterocycles (but excluding the imide ring possessed by polyimide), an amino group, and a protected amino group (hereinafter, also referred to as “specific partial structure”) Is preferably contained.

Examples of the radical polymerizable group include (meth) acryloyl group, vinyl group, allyl group, vinylphenyl group, maleimide group, vinyloxy group, ethynyl group and the like. Among these, a (meth) acryloyl group is particularly preferable in terms of high reactivity.
The photoinitiator group is a site that generates polymerization initiation ability by light or a site having a photosensitizing function, and polymerizes a polymerizable component by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a group having a structure derived from a startable compound (photoinitiator). The photoinitiator group is preferably a group having a structure derived from a radical polymerization initiator capable of generating radicals by light irradiation. Specifically, for example, a group having a structure derived from an acetophenone compound, an oxime ester compound, a dibenzoyl compound, a benzoin compound, a benzophenone compound, an alkylphenone compound, or an acylphosphine oxide compound can be mentioned. . Among these, the photoinitiator group is preferably a group having an acetophenone structure. When the polymer has at least one of a radically polymerizable group and a photoinitiator group, it is preferable to have these groups in the side chain.
The radical polymerization inhibitor group is a polymerization initiator by capturing a peroxide decomposition agent that neutralizes the peroxy radical or hydroperoxide generated due to energy such as ultraviolet light and heat, or a radical intermediate during polymerization. It functions as a radical scavenger that suppresses the progress. By including a polymer having such a polymerization inhibitor group in the liquid crystal alignment film, it is possible to suppress the reaction of the photopolymerizable compound mixed in the liquid crystal layer in the PSA mode with light irradiation. The polymerization inhibitor group is preferably a group having at least one selected from the group consisting of a hindered amine structure, a hindered phenol structure and an aniline structure.

Examples of the nitrogen-containing heterocycle include pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinoline, naphthyridine, quinoxaline, phthalazine, triazine, carbazole, acridine, piperidine, And piperazine, pyrrolidine, hexamethyleneimine and the like. Among them, it is preferable to have at least one selected from the group consisting of pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole and acridine.

The amino group and the protected amino group are preferably a group represented by the following formula (N-1).

(In formula (N-1), R ⁵⁰ is a hydrogen atom or a monovalent organic group. “*” Is a bond that bonds to a hydrocarbon group.)

In the above formula (N-1), the monovalent organic group of R ⁵⁰ is preferably a monovalent hydrocarbon group or a protecting group. The monovalent hydrocarbon group preferably has 1 to 10 carbon atoms, and specific examples thereof include linear or branched alkyl groups such as methyl, ethyl, propyl and butyl; and cycloalkyl such as cyclohexyl and the like And groups; aryl groups such as phenyl group and methylphenyl; and aralkyl groups such as benzyl group. Examples of the substituent which R ⁵⁰ may have include a halogen atom, a cyano group, an alkylsilyl group, an alkoxysilyl group and the like. R ⁵⁰ is preferably an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, a phenyl group or a benzyl group. Examples of the hydrocarbon group to which “*” in the above formula (N-1) is bonded include alkanediyl group, cyclohexylene group, phenylene group and the like.

The protective group is preferably a group which is released by heat, and examples thereof include a carbamate type protective group, an amide type protective group, an imide type protective group, a sulfonamide type protective group, and the following formulas (8-1) to (8-) Groups represented by each of 5) and the like can be mentioned. Among them, tert-butoxycarbonyl group is preferable in that it is highly removable by heat and in that the remaining amount of the deprotected portion in the film is reduced.

In the formulas (8-1) to (8-5), Ar ¹¹ is a monovalent group having 6 to 10 carbon atoms in which one hydrogen atom has been removed from a substituted or unsubstituted aromatic ring, and ⁶¹ represents an alkyl group having 1 to 12 carbon atoms, R ⁶² represents a methylene group or an ethylene group, and "*" represents a bond bonded to a nitrogen atom.)

The main skeleton of the polymer having the above specific partial structure is not particularly limited, but it is preferably a [P] polymer, and more preferably a [p] polymer. The content ratio of the above-mentioned specific partial structure in the polymer (the total amount of two or more when it is contained) is preferably 5 mol% to the total monomer units of the polymer, and 10 to 80 mol%. It is more preferable to do.

(solvent)
The liquid crystal aligning agent contains, as a solvent component, at least one specific solvent selected from the group of solvents shown below (a group consisting of [A] solvent and [B] solvent).
Solvent group:
[A] Solvent: a compound represented by the following formula (1), a compound represented by the following formula (2), N, N, 2-trimethylpropionamide, and 1,3-dimethyl-2-imidazolidinone.
[B] Solvent: dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, 4-methoxy-4-methyl-2-pentanone, 4-hydroxy-2-butanone, 2-methyl-2-hexanol, 2 6, 6-dimethyl-4-heptanol, diisobutyl ketone, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

-[A] solvent (compound represented by formula (1))
In the compound represented by the above formula (1), the monovalent hydrocarbon group having 2 to 5 carbon atoms of R ¹ is preferably a chain hydrocarbon group, and for example, an alkyl group having 2 to 5 carbon atoms, alkenyl And alkynyl groups. In addition, as the monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group, for example, an alkoxyalkyl group having 2 to 5 carbon atoms can be mentioned.
Specific examples thereof include, as the alkyl group having 2 to 5 carbon atoms, for example, an ethyl group, a propyl group, a butyl group, a pentyl group and the like; and an alkenyl group having 2 to 5 carbon atoms, for example, a vinyl group and 1-propenyl group 2-propenyl group, 3-butenyl group, etc. as an alkynyl group having 2 to 5 carbon atoms, such as ethynyl group, 2-propynyl group, 2-butynyl group, etc. as an alkoxyalkyl group having 2 to 5 carbon atoms, For example, a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group etc. can be mentioned respectively, These may be linear or branched. Among the above, R ¹ is preferably an alkyl group having 2 to 5 carbon atoms or an alkoxyalkyl group.

Specific examples of the compound represented by the above formula (1) include, for example, N-ethyl-2-pyrrolidone, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-) Butyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N And-methoxybutyl-2-pyrrolidone and the like. Among these, N-ethyl-2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone and N-methoxypropyl-2-pyrrolidone are particularly preferably used. Can. In addition, the compound represented by the said Formula (1) can be used individually by 1 type or in combination of 2 or more types of these exemplary compounds.

(Compound represented by formula (2))
As the monovalent hydrocarbon group having 1 to 6 carbon atoms for R ² and R ^{3 in} the compound represented by the above formula (2), for example, a linear hydrocarbon group having 1 to 6 carbon atoms, 3 to 6 carbon atoms Examples thereof include six alicyclic hydrocarbon groups and aromatic hydrocarbon groups having 5 or 6 carbon atoms. Further, examples of the monovalent group having “—O—” between carbon-carbon bonds of the hydrocarbon group include, for example, an alkoxyalkyl group having 2 to 6 carbon atoms.
As specific examples of these, as the chain hydrocarbon group having 1 to 6 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and the like can be mentioned, and these are linear Or may be branched. Further, examples of the alicyclic hydrocarbon group having 3 to 6 carbon atoms include, for example, a cyclopentyl group and a cyclohexyl group; and examples of an aromatic hydrocarbon group include, for example, a phenyl group and the like; and an alkoxyalkyl group having 2 to 6 carbon atoms. For example, the alkoxyalkyl group mentioned for R ¹ and the like can be mentioned respectively. R ² and R ³ in the formula (2) may be the same or different. In addition, R ² and R ³ may bond to each other to form a ring together with the nitrogen atom to which R ² and R ³ are bonded. Examples of the ring formed by bonding R ² and R ³ to each other include a pyrrolidine ring, a piperidine ring and the like, and a monovalent chain hydrocarbon group such as a methyl group is bonded to these rings. It may be
R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, still more preferably a hydrogen atom or a methyl group is there.
Examples of the alkyl group having 1 to 6 carbon atoms of R ⁴ include the groups exemplified in the description of the alkyl group having 1 to 6 carbon atoms of R ² and R ³ above. Preferably, it is an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

Specific examples of the compound represented by the above formula (2) include, for example, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N- Dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and the like. In addition, the compound represented by the said Formula (2) can be used individually by 1 type or in combination of 2 or more types.

[A] Among the solvents, the compound represented by the above formula (1), the compound represented by the above formula (2), and 1,3-dimethyl-in that the influence on the interlayer insulating film 21 can be further reduced. A compound selected from the group consisting of 2-imidazolidinone, preferably a compound represented by the above formula (1), wherein R ¹ is an alkyl group having 2 to 5 carbon atoms or an alkoxyalkyl group, It is more preferable that it is at least one selected from the group consisting of -methoxy-N, N-dimethylpropanamide and 1,3-dimethyl-2-imidazolidinone, and N-ethyl-2-pyrrolidone, N- (n- Pentyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropane It is particularly preferable that it is at least one selected from the group consisting of imid and 1,3-dimethyl-2-imidazolidinone.

[B] Among the above solvents, dipropylene glycol monomethyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and diacetone alcohol, as the solvent, in that the influence on interlayer insulating film 21 can be further reduced. It is preferably at least one selected from the group consisting of propylene glycol monobutyl ether.

As a solvent component, although only a specific solvent may be used, you may use together other solvents other than a specific solvent. As such other solvents, it is also referred to as a solvent having high polymer solubility and leveling ability (hereinafter, also referred to as "first solvent"), and a solvent having good wettability and spreadability (hereinafter, "second solvent"). Can be mentioned.
As specific examples of these, as the first solvent, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl -2-pentanone, ethylene carbonate, propylene carbonate etc.
As the second solvent, for example, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, 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 monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether acetate Iso Mill propionate, isoamyl isobutyrate, etc., can be exemplified respectively. In addition, as another solvent, 1 type in the above may be used independently, and 2 or more types may be mixed and used.

When preparing the liquid crystal aligning agent, only one of the [A] solvent and the [B] solvent may be used as the specific solvent, but when forming the liquid crystal alignment film, the liquid crystal aligning agent and the interlayer insulating film 21 In addition, at least one of the [A] solvent and the [B] solvent is capable of suppressing the influence exerted on the interlayer insulating film 21 in the state where it is in contact and at the same time the elution of the impurity component from the interlayer insulating film 21 can be suppressed. It is preferable that at least one of

[A] The proportion of the solvent used (total amount when two or more are used) is sufficient to suppress the effect on the interlayer insulating film 21 and the effect of suppressing the elution of the impurity component from the interlayer insulating film 21. From the viewpoint of suppressing the precipitation of the polymer component while obtaining, the content is preferably 10% by mass or more, and more preferably 20% by mass or more based on the total amount of the solvent contained in the liquid crystal aligning agent. The upper limit of the use ratio is preferably 90% by mass or less, based on the total amount of the solvent contained in the liquid crystal aligning agent, from the viewpoint of obtaining the effect of improving the coatability by the [B] solvent, and 80% It is more preferable to make it% or less. In addition, [A] solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

[B] The proportion of the solvent used (total amount when two or more are used) has an effect on the interlayer insulating film 21 and suppresses the elution of the impurity component from the interlayer insulating film 21 and the coatability of the liquid crystal aligning agent From the viewpoint of making the property better, the content is preferably 10% by mass or more, and more preferably 20% by mass or more based on the total amount of the solvent contained in the liquid crystal aligning agent. The upper limit of the use ratio is preferably 80% by mass or less, and more preferably 70% by mass or less, based on the total amount of the solvent contained in the liquid crystal aligning agent. In addition, a [B] solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

The ratio of use of the specific solvent (total amount when two or more types are used) sufficiently achieves the effect of suppressing the influence on the interlayer insulating film 21 and the effect of reducing the elution of the impurity component from the interlayer insulating film 21 From the viewpoint, the content is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on the total amount of the solvent contained in the liquid crystal aligning agent. It is particularly preferable to set it as mass% or more.

Moreover, when [A] solvent, [B] solvent, and other solvents are used, the proportions of use of the other solvents (the total amount of two or more solvents used) sufficiently obtain the effects of the present disclosure. From the viewpoint, the content is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 10% by mass or less, based on the total amount of the solvent contained in the liquid crystal aligning agent. It is particularly preferable to set the content to less than mass%.
In the liquid crystal aligning agent, it is particularly preferable that the solvent component is composed of the [A] solvent and the [B] solvent. However, in the present specification, “the solvent component is composed of the [A] solvent and the [B] solvent” does not interfere with the effects of the present disclosure other solvents other than the [A] solvent and the [B] solvent. It is acceptable to contain to some extent.

The liquid crystal aligning agent may contain other components as necessary in addition to the polymer component and the solvent component. Examples of the other components include antioxidants, metal chelate compounds, curing accelerators, surfactants, fillers, dispersants, and photosensitizers. The blend ratio of the other components can be appropriately selected according to each compound, as long as the effects of the present disclosure are not impaired.

The solid content concentration in the liquid crystal aligning agent (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) is appropriately selected in consideration of viscosity, volatility, etc. It is in the range of 1 to 10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small, and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coating property decreases. Tend to

Radiation-sensitive resin composition
Next, the radiation sensitive resin composition used to form the interlayer insulating film 21 will be described in detail. This radiation sensitive resin composition contains a [Q] polymer and a [R] photosensitizer.

([Q] polymer)
[Q] The polymer preferably has a structural unit having a polymerizable group. [Q] The polymerizable group contained in the polymer is preferably at least one selected from the group consisting of an oxetanyl group, an oxiranyl group, a (meth) acryloyl group, and a vinyl group. By having such a polymerizable group, curing of the radiation sensitive resin composition can be easily performed, which is preferable in that a favorable interlayer insulating film 21 can be obtained.

The main skeleton of the polymer [Q] is not particularly limited, but is preferably at least one selected from the group consisting of (meth) acrylic polymers, polyamic acids, polyamic esters, polyimides, and polyorganosiloxanes. Among these, (meth) acrylic polymers are particularly preferable. The (meth) acrylic polymer may have only a structural unit derived from a monomer having a (meth) acryloyl group, or a structure derived from a monomer having a (meth) acryloyl group You may have a unit and the structural unit derived from the other monomer different from the monomer which has a (meth) acryloyl group. The content ratio of structural units derived from other monomers in the (meth) acrylic polymer is preferably 50 mol% or less, more preferably 40 mol% or less, and still more preferably 30 mol% or less. It is.

Specifically, the [Q] polymer is mainly composed of a first structural unit having an acidic group, a second structural unit having an oxetanyl group or an oxiranyl group, and a main component different from the first structural unit and the second structural unit. It is preferable that it is a polymer which has the 3rd structural unit which forms chain structure.

As an acidic group which a 1st structural unit has, a carboxy group, a sulfo group, a phenolic hydroxyl group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonamide group, the hydrogen atom couple | bonded with the carbon atom serves as an electron withdrawing group Examples thereof include substituted hydroxyalkyl groups and the like. Among these, a carboxy group, a sulfo group, a phenolic hydroxyl group, a fluorine-containing alcoholic hydroxyl group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group or a combination thereof is preferable as the acidic group from the viewpoint of alkali developability. A carboxy group or a phenolic hydroxyl group is more preferable, and a carboxy group is particularly preferable.

The first structural unit is preferably a structural unit derived from at least one compound selected from the group consisting of (meth) acrylic acid or unsaturated carboxylic acid anhydride, and at least one of (meth) acrylic acid and maleic anhydride is preferred. Particularly preferred.
The content ratio of the first structural unit in the [Q] polymer is preferably 1 to 50 mol%, preferably 15 to 30 mol%, with respect to all structural units constituting the [Q] polymer. More preferable. The first structural unit may be used alone or in combination of two or more.

As the second structural unit, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3- (meth) acryloyloxymethyl-3- Preferred is a structural unit derived from at least one compound selected from the group consisting of ethyl oxetane.
The content ratio of the second structural unit in the [Q] polymer is preferably 1 to 15 mol%, and preferably 3 to 10 mol%, with respect to all structural units constituting the [Q] polymer. More preferable. The second structural unit may be used alone or in combination of two or more.

The third structural unit is not particularly limited as long as it is a structural unit derived from a monomer forming a main chain structure different from the first structural unit and the second structural unit, but the development adhesion and the resistance to heat and peeling solution It is preferable that it is a structural unit derived from at least one compound selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene, and 4-hydroxystyrene, in that it can be better.
The content ratio of the third structural unit in the [Q] polymer is preferably 25 to 80 mol%, more preferably 30 to 65 mol%, based on all structural units constituting the [Q] polymer. More preferable. The third structural unit may be used alone or in combination of two or more.

The [Q] polymer may further have other structural units other than the first structural unit, the second structural unit, and the third structural unit. Examples of such structural units include alkyl (meth) acrylate and the like.
[Q] The polymer can be synthesized according to a conventional method such as radical polymerization using a monomer giving the first to third structural units and the like. The details of the synthesis conditions can be appropriately set with reference to, for example, various conditions described in JP-A-2015-92233.

([R] photosensitizer)
[R] As the photosensitizer, at least one selected from the group consisting of photo radical polymerization initiators, photo acid generators and photo base generators can be preferably used.
As specific examples of these, as a photo radical polymerization initiator, for example, O-acyl oxime compound, acetophenone compound, biimidazole compound etc .;
Examples of the photoacid generator include oxime sulfonate compounds, onium salts, sulfoneimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, quinonediazide compounds and the like;
Examples of the photobase generator include transition metal complexes such as cobalt, ortho-nitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, and acyloxyiminos.
[R] The proportion of the photosensitizer used varies depending on the type of compound to be used. For example, in the case of a photo radical polymerization initiator, it is preferably 1 to 40 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the [Q] polymer.
The proportion of the photoacid generator used is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the [Q] polymer.
The use ratio of the photoacid base is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the [Q] polymer.

The radiation sensitive resin composition may further contain a curing accelerator, a polymerizable unsaturated compound, a surfactant, a storage stabilizer, and an adhesion assistant, in addition to the above-mentioned [Q] polymer and [R] photosensitizer. Can. Each of these optional components may be used alone or in combination of two or more.

The radiation sensitive resin composition is prepared by mixing other optional components blended as needed in addition to the [Q] polymer and the [R] photosensitizer. The radiation sensitive resin composition is preferably dissolved in a suitable solvent and used in a solution state. As the solvent, for example, alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether Propionates, ketones, esters and the like can be mentioned.
The total concentration of the components excluding the solvent of the radiation sensitive resin composition is 5 to 50% by mass from the viewpoint of the coatability, stability, etc. of the radiation sensitive resin composition to be obtained Preferably, the amount is 10 to 40% by mass.

(Method of Manufacturing Liquid Crystal Device 10)
The liquid crystal device 10 can be manufactured by a method including the following steps A to E.
Process A: A process of forming an interlayer insulating film 21 on a substrate.
Step B: A step of forming the pixel electrode 19 on the interlayer insulating film 21.
Step C: A step of forming a liquid crystal alignment film (first alignment film 32) on the pixel electrode 19 so as to be in contact with a part of the interlayer insulating film 21.
Step D: A step of forming a liquid crystal cell by opposingly arranging the array substrate 15 and the opposite substrate 16 via a liquid crystal layer containing a photopolymerizable monomer.
Step E: A step of irradiating the liquid crystal cell with light.

In order to manufacture the liquid crystal device 10 shown in FIGS. 1 and 2, first, thin film transistors 14, scanning signal lines 12, and video signal lines 13 are formed on a transparent substrate 18 such as a glass substrate by a known method such as photolithography. Form. Subsequently, on the surface of the transparent substrate 18 on which the thin film transistor 14 and the signal line are to be formed, a radiation sensitive resin composition for forming an interlayer insulating film is applied to form an interlayer insulating film 21 (Step A).

Although the application method of the radiation sensitive resin composition is not particularly limited, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method, a slit coating method, a bar coating method, an inkjet coating method can be adopted. Among these, the spin coating method or the slit coating method is preferable in that a film having a uniform thickness can be formed. After application of the radiation sensitive resin composition, the coated surface is preferably heated (prebaked), and if necessary, exposed to light through a photomask having a predetermined pattern, followed by development and postbaking. Thus, the interlayer insulating film 21 as a cured film is obtained. As the various conditions for forming the interlayer insulating film 21, for example, the conditions described in JP-A-2015-92233 can be adopted.

In the subsequent process B, the pixel electrode 19 is formed on the interlayer insulating film 21 formed in the process A of the transparent substrate 18. The pixel electrode 19 is formed by forming an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film with a film thickness of 50 to 200 nm, more preferably 100 to 150 nm, using a known method such as sputtering. It is patterned in a fish bone shape (also referred to as “comb shape”) by a lithography method. Thereby, the fishbone-type pixel electrode 19 is formed on the substrate, and the array substrate 15 is manufactured.

Further, separately from the above, a color filter layer 29, an overcoat layer (not shown) and a common electrode 31 are formed in this order on a transparent substrate 28 such as a glass substrate using a known method such as photolithography. , And the opposing substrate 16 are manufactured.

In the subsequent step C, first, a liquid crystal aligning agent is applied on the substrate on which the electrode is formed, and preferably a coated surface is formed to form a coating film on the substrate. The application of the liquid crystal aligning agent to the substrate is preferably performed by an offset printing method, a spin coating method, a roll coater method, a flexographic printing method, or an ink jet printing method on the electrode formation surface. After the application of the liquid crystal alignment agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal alignment agent. The prebake temperature is preferably 30 to 200 ° C., and the prebake time is preferably 0.25 to 10 minutes. Thereafter, a baking (post-baking) step is carried out to completely remove the solvent and, if necessary, thermally imidize the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time is preferably 80 to 300 ° C., and the post-baking time is preferably 5 to 200 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm. After the liquid crystal aligning agent is applied onto the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film to be the liquid crystal alignment film.

Here, a liquid crystal aligning agent is applied on the electrode formation surface of the substrate on which the pattern electrode (pixel electrode 19) having a large number of slits 19c is formed on the interlayer insulating film 21. Therefore, the liquid crystal alignment agent in liquid form comes in contact with the interlayer insulating film 21 through the opening of the slit portion 19c. The liquid crystal alignment film (first alignment film 32) formed on the substrate is in contact with the interlayer insulating film 21 in the display region of the liquid crystal device 10 via the slit portion 19c.
In addition, although the coating film formed above may be used as a liquid crystal aligning film as it is, you may perform the process (alignment process) which provides liquid crystal aligning ability. For example, rubbing treatment is performed by rubbing the coating film in a fixed direction with a roll wound with a cloth made of fibers such as nylon, rayon and cotton, or light irradiation to the coating film formed on the substrate using a liquid crystal alignment agent. The optical alignment processing etc. which carry out and provide liquid crystal aligning ability to a coating film are mentioned.

In the subsequent step D, the array substrate 15 on which the interlayer insulating film 21, the pixel electrode 19 and the first alignment film 32 are formed in this order, and the opposing substrate 16 on which the common electrode 31 and the second alignment film 33 are formed in this order The alignment film forming surfaces are arranged to face each other. A liquid crystal layer 17 in which a photopolymerizable monomer is mixed is disposed between the array substrate 15 and the counter substrate 16 to construct a liquid crystal cell.

The liquid crystal layer 17 is, for example, a method in which a liquid crystal composition is dropped or applied onto one of the substrates coated with a sealing agent, and then the other substrate is bonded (ODF method). Peripheral portions of the pair of substrates are attached by a sealing agent, and the liquid crystal composition is injected and filled in a cell gap surrounded by the substrate surface and the sealing agent, and then the injection holes are formed by a method such as sealing. The obtained liquid crystal cell is further heated to a temperature at which the liquid crystal used has an isotropic phase, and then annealing treatment is preferably performed to gradually cool to room temperature to remove the flow alignment at the time of filling the liquid crystal.

As the photopolymerizable monomer, a compound having two or more (meth) acryloyl groups can be preferably used, from the viewpoint of high polymerizability by light. Specific examples thereof include, for example, di (meth) acrylate having a biphenyl structure, di (meth) acrylate having a phenyl-cyclohexyl structure, di (meth) acrylate having a 2,2-diphenylpropane structure, and di having a diphenylmethane structure. Examples include (meth) acrylates and di-thio (meth) acrylates having a diphenyl thioether structure. The proportion of the photopolymerizable monomer is preferably 0.1 to 0.5% by mass relative to the total amount of the liquid crystal composition used to form the liquid crystal layer 17. As the photopolymerizable monomer, one type may be used alone, or two or more types may be used in combination.

In the subsequent step E, the liquid crystal cell obtained in step B is irradiated with light. The light irradiation to the liquid crystal cell may be performed in a state where no voltage is applied between the electrodes, may be performed in a state where a predetermined voltage not driving liquid crystal molecules in the liquid crystal layer 17 is applied, or the liquid crystal molecules are driven. And a predetermined voltage may be applied between the electrodes. Preferably, light irradiation is performed in a state where a voltage is applied between the electrodes of the pair of substrates. The voltage to be applied may be, for example, 5 to 50 V direct current or alternating current. As the light to be irradiated, for example, ultraviolet light and visible light including light of a wavelength of 150 to 800 nm can be used, but ultraviolet light including light of a wavelength of 300 to 400 nm is preferable. When the radiation used is linearly polarized light or partially polarized light, the light may be emitted from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When non-polarized radiation is irradiated, the irradiation direction is oblique.

As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. can be used, for example. In addition, the ultraviolet-ray of said preferable wavelength area can be obtained by the means etc. which use a light source, for example together with a filter diffraction grating etc. The light irradiation amount is preferably 1,000 to 200,000 J / m ² , and more preferably 1,000 to 100,000 J / m ² .

Then, the

polarizing plates

36 and 37 are attached to the outer surface of the liquid crystal cell to obtain the liquid crystal device 10. As the

polarizing plates

36 and 37, a polarizing plate called a “H film” obtained by absorbing iodine while drawing and orienting polyvinyl alcohol is sandwiched by a cellulose acetate protective film, or a polarizing plate made of the H film itself, etc. Can be mentioned.

In the present embodiment, the first alignment film 32 is formed using a liquid crystal alignment agent containing a specific solvent as a solvent component. Thereby, even when the first alignment film 32 is in contact with the interlayer insulating film 21 through the slit portion 19 c, the liquid crystal device 10 having excellent reliability can be obtained. The reason why such an effect is obtained is not clear, but one of the reasons is that the specific solvent used for the preparation of the liquid crystal alignment agent has little influence on the interlayer insulating film 21 and thereby the performance deterioration of the interlayer insulating film 21 is suppressed It is thought that it was done. In particular, in PSA technology, in order to improve the response characteristics of the MVA mode, for example, a fine stripe-like electrode pattern of about several μm is formed. When such a fine electrode pattern is formed on the substrate, the liquid crystal aligning agent contacts the interlayer insulating film 21, and when the interlayer insulating film 21 swells and the thickness of the film slightly changes, the pixel electrode 19 is also formed. It is conceivable that deformation is likely to occur, leading to a decrease in device performance. In this respect, according to the specific solvent, the swelling of the interlayer insulating film 21 can be suppressed, and the influence on the pixel electrode 19 can be reduced as much as possible, whereby it is presumed that the deterioration of the device performance can be sufficiently suppressed. In addition, it is presumed that the elution of the impurity component from the interlayer insulating film 21 to the liquid crystal aligning agent can be suppressed in the state where the liquid crystal aligning agent is in contact with the interlayer insulating film 21 and thereby the deterioration of the element performance can be sufficiently suppressed. Be done.

Second Embodiment
Next, the second embodiment will be described focusing on differences from the first embodiment. The present embodiment is different from the first embodiment in that a color filter layer is provided on the array substrate 15.

FIG. 3 is a cross-sectional view schematically showing a part of the element structure of the second embodiment. Similar to the liquid crystal device of the first embodiment, the liquid crystal device 10 shown in FIG. 3 has a structure in which the array substrate 15 and the counter substrate 16 are disposed to face each other via the liquid crystal layer 17. The array substrate 15 has the TFT 14 and the color filter layer 29 configured to include the colored pattern 29 a and the interlayer insulating film 29 b on the transparent substrate 18. The colored pattern 29a is composed of sub-pixels colored with red (R), green (G) and blue (B), and is produced by a known method such as photolithography. The interlayer insulating film 29 b is formed using the radiation sensitive resin composition described in the first embodiment. The interlayer insulating film 29 b is provided for the purpose of protecting the colored pattern 29 a and forming the pixel electrode 19 exhibiting excellent characteristics. The pixel electrode 19 is disposed on the interlayer insulating film 29 b.

Also in this case, the first alignment film 32 is formed on the electrode formation surface of the substrate in which the fishbone-shaped pattern electrode (pixel electrode 19) is formed on the interlayer insulating film 29b. Is in contact with the interlayer insulating film 29b at the slit portion 19c. In this respect, by forming the first alignment film 32 using the liquid crystal alignment agent described above, the liquid crystal device 10 having excellent reliability can be obtained.

(Other embodiments)
In the first embodiment, the pixel electrode 19 on the array substrate 15 side is used as a pattern electrode, and the interlayer insulating film 21 and the first alignment film 32 are in contact with each other in the slit portion 19c. An electrode and an interlayer insulating film may be provided, and the pattern electrode and the interlayer insulating film may be in contact with each other in the slit portion.

The liquid crystal device 10 of the present invention described in detail above can be effectively applied to various applications, for example, watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones It can be used as various display devices such as smartphones, various monitors, liquid crystal televisions, information displays, light control devices and the like.

Hereinafter, although an embodiment of the present invention is described in more detail based on an example, the present invention is not limitedly interpreted by the following example.

In the following examples, the imidation ratio of the polyimide in the polymer solution, the solution viscosity of the polymer solution, the weight average molecular weight of the polymer, and the epoxy equivalent were measured by the following methods.
[Imidation rate of polyimide]
The solution of the polyimide was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. The imidation ratio [%] was determined from the obtained ¹ H-NMR spectrum by the following formula (1).
Imidation ratio [%] = (1− (A ¹ / (A ² × α))) × 100 (1)
(In the formula (1), A ¹ is a proton-derived peak area of an NH group appearing in the vicinity of a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of a polymer (polyamic acid It is the number ratio of other protons to one proton of NH group in).
[Weight average molecular weight of polymer]
The weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Corp. TSKgel GRC XLII
Solvent: Tetrahydrofuran Temperature: 40 ° C.
Pressure: 68 kgf / cm ²
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

The abbreviations used in the following examples are shown. In the following, the compound represented by the formula X may be simply referred to as “compound X”.

1. Preparation of radiation sensitive resin composition (for formation of interlayer insulating film) (1) Synthesis of [Q] polymer [Synthesis example 1: Synthesis of polymer (Q-1)]
In a flask equipped with a condenser and a stirrer, 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were charged. Subsequently, 25 parts by mass of methacrylic acid, 45 parts by mass of 3,4-epoxycyclohexyl methacrylate and 30 parts by mass of styrene are charged, and after nitrogen substitution, the temperature of the solution is raised to 70 ° C. while gently stirring. Polymerization was carried out by maintaining the temperature for 5 hours to obtain a solution containing a polymer (Q-1). The Mw of the polymer (Q-1) was 8,000.

Synthesis Example 2: Synthesis of Polymer (Q-2)
In a flask equipped with a condenser and a stirrer, 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were charged. Subsequently, 15 parts by mass of methacrylic acid, 40 parts by mass of 3,4-epoxycyclohexyl methacrylate, 20 parts by mass of styrene, 15 parts by mass of tetrahydrofurfuryl methacrylate, and 10 parts by mass of n-lauryl methacrylate are charged and replaced with nitrogen, and then relaxed. The temperature of the solution was raised to 70.degree. C., and the temperature was maintained for 5 hours while performing polymerization to obtain a solution containing a polymer (Q-2). The Mw of the polymer (Q-2) was 8,000.

Synthesis Example 3: Synthesis of Polymer (Q-3)
In a flask equipped with a condenser and a stirrer, 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were charged. Subsequently, 40 parts by mass of glycidyl methacrylate, 20 parts by mass of 4- (α-hydroxyhexafluoroisopropyl) styrene, 10 parts by mass of styrene and 30 parts by mass of N-cyclohexylmaleimide are charged, and after substituting with nitrogen, they are gently stirred. The temperature of the solution was raised to 70 ° C., and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution containing a polymer (Q-3). Mw of the polymer (Q-3) was 8,000.

(2) Preparation of radiation sensitive resin composition [Preparation Example 1]
In a solution containing the polymer (Q-1) obtained in the above Synthesis Example 1 (an amount corresponding to 100 parts by mass (solid content) of the polymer (Q-1)), 1,2-octanedione 1- 20 parts by mass of [4- (phenylthio) -2- (O-benzoyloxime)] (manufactured by BASF, IRGACURE (registered trademark) OXE01) was added, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD) 100 parts by mass of (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.) was added and mixed. Diethylene glycol ethyl methyl ether was added and dissolved so that the solid content concentration was 30% by mass, followed by filtration with a membrane filter of 0.2 μm in diameter to prepare a radiation sensitive resin composition (V-1).
Preparation Examples 2 to 4
Radiation sensitive resin compositions (V-2) to (V-4) were prepared in the same manner as in Preparation Example 1 except that the composition was changed as described in Table 1 below. In Table 1 below, "-" means that the corresponding component is not blended (the same applies to the following tables).

In Table 1, the abbreviation of the compounds is as follows.
R-1: 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] (manufactured by BASF Irgacure (registered trademark) OXE01)
R-2: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide- Condensate with 5-sulfonic acid chloride (2.0 mol) U-1: mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)

2. Polymer synthesis (for liquid crystal aligning agent)
Synthesis Example 5 Synthesis of Polymer (PI-1)
100 moles of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid dianhydride, 20 moles of cholestanyloxy-2,4-diaminobenzene as diamine, 50 moles of 3,5-diaminobenzoic acid A molar part and 30 molar parts of compound (d-8) were dissolved in N-methyl-2-pyrrolidone (NMP), and reaction was carried out at room temperature for 6 hours to obtain a solution containing 20% by mass of polyamic acid. Subsequently, pyridine and acetic anhydride were added to the obtained polyamic acid solution to carry out chemical imidation. The reaction solution after chemical imidization was concentrated and prepared with NMP so that the concentration was 10% by mass. The imidation ratio of the obtained polyimide (referred to as polymer (PI-1)) was about 75%.
Synthesis Examples 6 to 8
A polyimide (polymer (PI-2) to polymer (PI-4)) was prepared in the same manner as in Synthesis Example 5 except that the type and amount of tetracarboxylic acid dianhydride and diamine used were changed as shown in Table 2 below. Was synthesized. In Table 2, the numerical values in the parentheses represent the use ratio [mol part] of each compound to the total of 100 mol parts of tetracarboxylic acid dianhydride used in the synthesis of the polymer.

Synthesis Example 9 Synthesis of Polymer (PAA-1)
70 molar parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid dianhydride, and 30 molar parts of 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, and coreless as diamine 20 mol parts of tanyloxy-2,4-diaminobenzene, 30 mol parts of compound (d-12), 40 mol parts of 4,4′-diaminodiphenylmethane, and 4,4 ′-[4,4′-propane-1, Ten parts by mole of 3-diylbis (piperidine-1,4-diyl) dianiline was dissolved in NMP and reacted at room temperature for 6 hours to obtain a solution containing 20% by mass of polyamic acid. The polyamic acid obtained here was used as a polymer (PAA-1).
Synthesis Example 10
A polyamic acid (this is referred to as a polymer (PAA-2)) is synthesized in the same manner as in Synthesis Example 9 except that the type and amount of tetracarboxylic acid dianhydride and diamine used are changed as shown in Table 2 below. did.

Synthesis Example 11
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100 g of compound (s-1), 500 g of methyl isobutyl ketone and 10 g of triethylamine were charged and mixed at room temperature. Next, 100 g of deionized water was added dropwise over 30 minutes from the dropping funnel, and then reaction was performed at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer is taken out and washed with a 0.2 mass% aqueous ammonium nitrate solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to obtain a reactive polyorganosiloxane ( The ESSQ-1) was obtained as a viscous transparent liquid. ¹ H-NMR analysis of this reactive polyorganosiloxane shows that a peak based on epoxy group is obtained around chemical shift (δ) = 3.2 ppm, and no side reaction of epoxy group occurs during the reaction That was confirmed. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane (ESSQ-1) was 3000, and the epoxy equivalent was 190 g / mol.
[Synthesis example 12, 13]
Reactive polyorganosiloxanes (polymer (ESSQ-2) and polymer (ESSQ-3)) were synthesized in the same manner as in Synthesis Example 11 except that the type and amount of monomers used were changed as shown in Table 3 below. . In Table 3, the numerical values in the parentheses represent the use ratio [mol part] of each compound to the total 100 mol parts of the monomers used for the synthesis of the polymer.

Synthesis Example 14
In a 500 mL three-necked flask, 10.0 g of reactive polyorganosiloxane (ESSQ-1), 300 g of methyl isobutyl ketone as a solvent, 16 g of compound (c-1) as a modifying component and 16 g of compound (c-3), As a catalyst, 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) was charged, and the reaction was performed at 100 ° C. for 48 hours with stirring. After completion of the reaction, a solution obtained by adding ethyl acetate to the reaction mixture is washed three times with water, dried using magnesium sulfate, and then the solvent is distilled off to obtain a polymerizable group-containing polyorganosiloxane (PSQ). Obtained 75 g of -1). The weight average molecular weight Mw of the obtained polymer was 6000.
Synthesis Examples 15 and 16
Polymerizable group-containing polyorganosiloxane (polymer (PSQ-2) and polymer) in the same manner as in Synthesis Example 14 except that the type and amount of reactive polyorganosiloxane and modifying component used were changed as shown in Table 4 below. (PSQ-3)) was synthesized. In Table 4, the numerical values in the parenthesis represent the use ratio [mol part] of each compound to the total 100 mol parts of the monomers used for the synthesis of the polymer.

3. Evaluation of Liquid Crystal Alignment Agent and Liquid Crystal Display Device [Example 1]
(1) Preparation of Liquid Crystal Alignment Agent In a solution containing a polymer (PI-1) as a polymer component, a polymer (PSQ-1) is prepared by using a polymer (PI-1): a polymer (PSQ-1) = Further, NMP, diethylene glycol diethyl ether (DEDG) and diacetone alcohol (DAA) are added as a solvent so as to be 95: 5 (mass ratio), and the mixture is sufficiently stirred, and the solvent composition is NMP: DEDG: DAA = 50: It was set as a solution of 30:20 (mass ratio) and solid content concentration 6.5 mass%. The solution was filtered using a filter with a pore size of 1 μm to prepare a liquid crystal aligning agent (W-1).

(2) Preparation of Liquid Crystal Composition (LC-1) To 10 g of Nematic Liquid Crystal (MLC-6608, manufactured by Merck), the compound represented by the following formula (RM-1) is the total amount of all components of the liquid crystal composition The liquid crystal composition (LC-1) was obtained by adding so as to be 0.3% by mass with respect to and mixing.

(3) Production of Liquid Crystal Display Device After the radiation sensitive resin composition (V-1) was applied on a glass substrate ("Corning 7059" (manufactured by Corning)) using a spinner, it was then carried out in a clean oven at 90.degree. Prebaking was performed for 10 minutes to form a coating film having a film thickness of 2.0 μm on a glass substrate. Then, 100 mJ of UV light was irradiated through a pattern mask using a UV (ultraviolet) exposure device (TOPCON Deep-UV exposure device TME-400PRJ). Thereafter, using a tetramethylammonium hydroxide aqueous solution (developing solution) having a concentration of 2.38% by mass, development was carried out at 25 ° C. for 100 seconds by the liquid deposition method. After development processing, the coated film is washed with running ultrapure water for 1 minute with running water, dried to form a patterned coated film on a substrate, and then heated (post-baked) at 230 ° C. for 30 minutes in an oven for curing I did. Next, using a PLA-501F exposure apparatus (super high pressure mercury lamp) manufactured by Canon Inc., the entire surface of each coating was exposed at an exposure amount of 500 J / m ² without using a photomask. Thereafter, post-baking was performed at 230 ° C. for 30 minutes to cure each coating film, thereby forming an interlayer insulating film.

Next, an ITO electrode patterned in a fishbone shape was formed on the glass substrate on which the interlayer insulating film was formed. In this example, the electrode pattern of the ITO electrode was in a fishbone shape of line / space = 3.5 μm / 3.5 μm. The electrode pattern of the ITO electrode used here is shown in FIG. Moreover, the glass substrate which has an ITO electrode which does not have a pattern was prepared by performing the same operation. Of the pair of substrates, a 3.5 μm column spacer was formed on the electrode side surface of a glass substrate having an ITO electrode having no pattern.

Subsequently, after spin-coating a liquid crystal aligning agent (W-1) on the electrode formation surface of each of a pair of board | substrates, heating (prebaking) is carried out for 1 minute on a hot plate at 80 degreeC, Then, 230 The film was heated (post-baked) on a hot plate for 15 minutes to form a coating having an average film thickness of 100 nm. The coated film was subjected to ultrasonic cleaning in ultrapure water for 1 minute and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a pair of substrates having a liquid crystal alignment film.

Next, after applying an aluminum oxide sphere-containing epoxy resin adhesive having a diameter of 5.5 μm to the outer edge of the ITO surface of the glass substrate having a patterned ITO electrode, a liquid crystal composition (the inner surface of the epoxy resin adhesive) LC-1) was dropped at 6 points (2 points vertically × 3 points horizontally, the distance between the points was 10 mm in the vertical and horizontal directions, and the amount of application at each point was 0.6 mg). The substrate and another glass substrate were laminated so as to face each other and pressed, and the adhesive was cured to manufacture a liquid crystal cell. The obtained liquid crystal cell was irradiated with ultraviolet light and annealed in accordance with “PSA process 1” described later to prepare a liquid crystal cell for evaluation.
(PSA process-1)
For the liquid crystal cell, an alternating current 20 Vpp of frequency 60 Hz is applied between the electrodes, and while the liquid crystal is driven, ultraviolet light of 80 mW is irradiated for 50 seconds using an ultraviolet irradiation device using a metal halide lamp as a light source. Subsequently, in a state where no voltage is applied, 3.5 mW of ultraviolet light is irradiated for 30 minutes using an ultraviolet irradiation device using a metal halide lamp as a light source.
Finally, the liquid crystal cell is placed in a clean oven at 120 ° C. for 10 minutes to perform annealing. The irradiation amount is a value measured using an actinometer measured at a wavelength of 365 nm.

(4) Evaluation of voltage holding ratio (VHR) The liquid crystal cell for evaluation manufactured in (3) above is placed in a thermostatic chamber, and a voltage of 5 V is applied at 60 ° C. for 60 microseconds and a span of 167 milliseconds. After that, the voltage holding ratio (VHR) after 167 milliseconds from the release of the application was measured using “VHR-1” manufactured by Toyo Corporation. At this time, "very good (◎)" when VHR is 96% or more, "good (○)" when 93% or more and less than 96%, and 90% or more and less than 93% The case where it was "Poor" (△) and 90% or less was evaluated as "Defect (x)". As a result, in this example, VHR = 97%, which is an evaluation of “very good (◎)”.

[Examples 2 to 22, Comparative Examples 1 and 2]
The same procedure as described above was carried out except that the type and amount of the polymer and solvent used were changed as shown in Table 5 below, to prepare liquid crystal aligning agents. Moreover, except that the radiation sensitive resin composition used for preparation of the interlayer insulating film was changed to the composition shown in Table 5 below and that the liquid crystal alignment film was prepared using the liquid crystal aligning agent prepared in each example The liquid crystal cell for evaluation was manufactured in the same manner as described above, and the voltage holding ratio was evaluated using the obtained liquid crystal cell for evaluation. The results are shown in Table 5 below.

In Table 5, the numerical values in the parenthesis of the polymer column show the proportions [parts by mass] of each polymer with respect to a total of 100 parts by mass of the polymer components used for the preparation of the liquid crystal aligning agent. The numerical values in the solvent composition column indicate the blending proportions (parts by mass) of the respective compounds with respect to 100 parts by mass of the solvent used for the preparation of the liquid crystal aligning agent. Abbreviated solvents are as follows (the same applies to Table 6 below).
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone DMI: 1,3-dimethyl-2-imidazolidinone EQM: 3-methoxy-N, N-dimethylpropanamide BC: butyl cellosolve DE DG: diethylene glycol Diethyl ether PGDAc: Propylene glycol diacetate DPM: Dipropylene glycol monomethyl ether DAA: Diacetone alcohol PG: Propylene glycol monobutyl ether DIPE: Diisopentyl ether

As shown in Table 5, in Examples 1 to 22 in which the liquid crystal alignment film was formed using the liquid crystal alignment agent containing the specific solvent, the liquid crystal alignment film was formed using the liquid crystal alignment agent not containing the specific solvent. The liquid crystal display device was more reliable than the above. Among these, in Examples 1 to 18 in which the liquid crystal aligning agent containing the [A] solvent and the [B] solvent was used, it was evaluated as "very good" and was particularly excellent.

Furthermore, in Examples 1 to 22 above, the liquid crystal display element was manufactured and evaluated in the same manner as described above except that the pattern of the ITO electrode of the glass substrate was changed to the pattern shown in FIG. The same effect as described above was obtained in

[Example 23]
(1) Evaluation of deformation of ITO wiring N-ethyl-2-pyrrolidone (NEP) and diethylene glycol diethyl ether (DEDG) are mixed and sufficiently stirred, and the solvent composition is evaluated as NEP: DEDG = 50: 50 (mass ratio) A solvent (Z-1) was prepared.
Moreover, the glass substrate which distributed the pattern electrode which consists of ITO on the interlayer insulation film was prepared by performing operation similar to (3) of the said Example 1. FIG. The glass substrate was immersed in a solvent for evaluation (Z-1) at 80 ° C. for 30 minutes, and the degree of swelling of the interlayer insulating film and the degree of deformation of the ITO electrode were evaluated according to the criteria shown below. The smaller the swelling of the interlayer insulating film and the smaller the deformation of the electrode when contacted with the solvent component of the liquid crystal aligning agent, the smaller the influence of the solvent on the interlayer insulating film and the ITO electrode is, and the reliability of the liquid crystal element can be secured. And as a solvent for liquid crystal alignment agents. As a result, this example was an evaluation of "A".
(Evaluation criteria)
A: There is no swelling of the interlayer insulating film and no abnormality of the electrode B: Swelling of the interlayer insulating film is observed but there is no abnormality in the electrode Swelling of insulating film causes serious abnormality such as disconnection of electrode

[Examples 24 to 44, Comparative Examples 3 and 4]
The same procedure as described above was carried out except that the solvent composition and the type of radiation sensitive resin composition used were changed as shown in Table 6 below, and the ITO wiring deformation was evaluated for each solvent. The results are shown in Table 6 below.

From the results in Table 6, in Examples 23 to 44 in which the specific solvent was used, swelling of the interlayer insulating film was not observed or the degree was small even if swelling was observed, and no abnormality of the electrode was observed. From these results, it was found that according to the specific solvent, even when the liquid crystal alignment film is formed on the fine stripe-shaped electrode pattern, the shape of the electrode hardly changes, and the reliability of the liquid crystal element can be secured.

DESCRIPTION OF SYMBOLS 1 ... ITO electrode, 2 ... slit part, 3 ... light shielding film, 10 ... liquid crystal device, 14 ... thin-film transistor, 15 ... array substrate, 16 ... opposing board | substrate, 17 ... liquid crystal layer, 19 ... pixel electrode, 19c ... slit part, 21 ... interlayer insulating film, 29 ... color filter layer, 29a ... colored pattern, 29b ... interlayer insulating film, 31 ... common electrode, 32 ... first alignment film, 33 ... second alignment film, 34, 35 ... PSA layer (alignment control layer)

Claims

A method of manufacturing a liquid crystal device, comprising: a pair of substrates disposed opposite to each other; a liquid crystal layer disposed between the pair of substrates; and a pair of electrodes,
At least one of the pair of electrodes is a pattern electrode having a plurality of openings,
Forming an interlayer insulating film on at least one of the pair of substrates;
Forming the pattern electrode on the interlayer insulating film;
Forming a liquid crystal alignment film on the pattern electrode so as to be in contact with at least a part of the interlayer insulating film,
The manufacturing method of a liquid crystal element which forms the said liquid crystal aligning film using the liquid crystal aligning agent containing a polymer component and at least 1 type of solvent chosen from the solvent group shown below.
Solvent group:
[A] Solvent: a compound represented by the following formula (1), a compound represented by the following formula (2), N, N, 2-trimethylpropionamide, and 1,3-dimethyl-2-imidazolidinone.
[B] Solvent: dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, 4-methoxy-4-methyl-2-pentanone, 4-hydroxy-2-butanone, 2-methyl-2-hexanol, 2 6, 6-dimethyl-4-heptanol, diisobutyl ketone, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

In the formula (1), R 1 is a monovalent hydrocarbon group having 2 to 5 carbon atoms, or a monovalent group having “—O—” between carbon-carbon bonds in the hydrocarbon group. )

(In formula (2), R 2 and R 3 each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or “—O— between carbon-carbon bonds of the hydrocarbon group. R 2 and R 3 may be bonded to each other to form a ring structure. R 4 is an alkyl group having 1 to 6 carbon atoms.
The method further includes the step of forming an alignment control layer for controlling the alignment of the liquid crystal at the interface on each substrate side in the liquid crystal layer by polymerizing the photopolymerizable monomer mixed in the liquid crystal layer. The manufacturing method of the liquid crystal element as described in 1.
The method according to claim 1, wherein the liquid crystal aligning agent contains at least one of the [A] solvent and at least one of the [B] solvent.
The said liquid crystal aligning agent contains the [P] polymer which is at least 1 type chosen from the group which consists of a polyamic acid, polyamic acid ester, a polyimide, and a polyorganosiloxane, It is described in any one of Claims 1-3. Method of manufacturing liquid crystal element.
The liquid crystal aligning agent contains a [p] polymer which is at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide,
The polymer according to any one of claims 1 to 4, wherein the polymer [p] has a partial structure derived from a tetracarboxylic acid derivative having at least one ring structure selected from the group consisting of cyclobutane ring, cyclopentane ring and cyclohexane ring. A manufacturing method of a liquid crystal element given in one paragraph.
The liquid crystal aligning agent comprises a radical polymerizable group, a photoinitiator group, a radical polymerization inhibitor group, a nitrogen-containing heterocycle (but excluding the imide ring possessed by the polyimide), an amino group, and a protected amino group. The method for producing a liquid crystal device according to any one of claims 1 to 5, comprising a polymer having at least one selected from the group consisting of
The method for producing a liquid crystal device according to any one of claims 1 to 6, wherein the liquid crystal aligning agent contains a polymer having a partial structure represented by the following formula (3).
* -L 1 -R 11 -R 12 -R 13 -R 14 (3)
(In the formula (3), L 1 is, -O -, - CO -, - COO- * 1, -OCO- * 1, -NR 15 -, - NR 15 -CO- * 1, -CO-NR 15 -* 1 , an alkanediyl group having 1 to 6 carbon atoms, -O-R 16- * 1 , or -R 16 -O- * 1 (provided that R 15 is a hydrogen atom or a monovalent group having 1 to 10 carbon atoms) a hydrocarbon group, R 16 is an alkanediyl group of 1 to 3 carbon atoms. "* 1" indicates that the bond between R 11.) a is .R 11 and R 13, each independently represent a single bond, a phenylene group or a cycloalkylene group, R 12 represents a single bond, a phenylene group, a cycloalkylene group, -R 17 -B 1 - * 2 , or -B 1 -R 17 - * 2 (However, R 17 is a phenylene group or a cycloalkylene group, B 1 is -CO -. * 3, -OCO- * 3, or alkanediyl group having a carbon number of 1 to 3 "* 2" indicates that the bond to R 13, "* 3", and R 17 R 14 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. Or a fluoroalkoxy group having 1 to 18 carbon atoms or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton, and may have a radically polymerizable group or a photoinitiator group, provided that R 14 is In the case of a hydrogen atom, a fluorine atom or a group having 1 to 3 carbon atoms, all of R 11 , R 12 and R 13 will not be single bonds. "*" Indicates that it is a bond.)
The method for manufacturing a liquid crystal device according to any one of claims 1 to 7, wherein a liquid crystal driving element and a color filter layer are formed on a substrate on which the interlayer insulating film is formed.
The liquid crystal device according to any one of claims 1 to 8, wherein the interlayer insulating film is formed using a radiation sensitive resin composition containing a [Q] polymer and a [R] photosensitizer. Production method.
The method for manufacturing a liquid crystal device according to claim 9, wherein the [Q] polymer has at least one selected from the group consisting of oxetanyl group, oxiranyl group, (meth) acryloyl group and vinyl group.
The method for producing a liquid crystal device according to claim 9, wherein the [R] photosensitizer is at least one selected from the group consisting of photo radical polymerization initiators, photo acid generators, and photo base generators.
The [Q] polymer forms a main chain structure different from the first structural unit having an acidic group, the second structural unit having an oxetanyl group or an oxiranyl group, and the first structural unit and the second structural unit. The method for producing a liquid crystal device according to any one of claims 9 to 11, which is a polymer having a third structural unit.
The method of manufacturing a liquid crystal device according to claim 12, wherein the first structural unit is a structural unit derived from at least one compound selected from the group consisting of (meth) acrylic acid and unsaturated carboxylic acid anhydride.
The second structural unit is glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3- (meth) acryloyloxymethyl-3- The method for producing a liquid crystal device according to claim 12 or 13, which is a structural unit derived from at least one compound selected from the group consisting of ethyl oxetane.
The third structural unit is a structural unit derived from at least one compound selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene, and 4-hydroxystyrene. A manufacturing method of a liquid crystal element given in one paragraph.