KR20200042002A - Method of manufacturing a liquid crystal element - Google Patents

Abstract

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 highly reliable liquid crystal device is obtained. A step of forming an interlayer insulating film 21 on at least one of the pair of substrates, a step of forming a pattern electrode (pixel electrode 19) on the interlayer insulating film 21, and an interlayer insulating film 21 on the pattern electrode A method for manufacturing a liquid crystal device comprising a step of forming a liquid crystal alignment film (first alignment film 32) so as to contact at least a portion of the liquid crystal alignment film, the polymer component and at least one selected from a specific solvent group It is formed using a liquid crystal aligning agent containing a solvent.

Description

Method of manufacturing a liquid crystal element

(Cross reference of related applications)

This application is based on the Japanese application No. 2017-223114 for which it applied on November 20, 2017, and uses the content described here.

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

As a liquid crystal device, a horizontal alignment mode using a nematic liquid crystal having a positive dielectric anisotropy and a negative dielectric anisotropy, such as TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, etc. Various devices are known, such as a vertical (homeotropic) alignment mode VA (Vertical Alignment) type liquid crystal device using a nematic liquid crystal. In addition, a liquid crystal device of a transverse electric field mode, such as an in-plane switching (IPS) type and a fringe field switching (FFS) type, in which a pair of electrodes has a cell structure formed on one substrate, is also known.

As one of the alignment treatment methods of the liquid crystal element, a PSA (Polymer Sustained Alignment) method is known (for example, see Patent Document 1). In the PSA method, a photopolymerizable monomer is premixed with a liquid crystal in a gap between a pair of substrates, and after a liquid crystal cell is constructed, ultraviolet light is irradiated with a voltage applied between the substrates to polymerize the photopolymerizable monomer. It is a technique to form a polymer layer and to 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 response of the liquid crystal molecules, and it is possible to solve the problem of insufficient transmittance and contrast in the MVA type panel.

In addition, Patent Document 1 discloses that in PSA technology, a pattern electrode patterned to have a comb shape (also referred to as a fishbone shape) having a large number of openings (slit portions) is used as a pixel electrode. 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 pixel electrode having a fishbone shape is formed on the interlayer insulating film, and a liquid crystal alignment film is formed on the pixel electrode. The liquid crystal alignment film is usually formed by dissolving a polymer component such as polyamic acid, polyimide, polyorganosiloxane, (meth) acrylic polymer, or polyamide in a solvent, and applying the polymer composition on a substrate to remove the solvent. .

Japanese Patent Publication No. 2003-149647

When a pattern electrode having a plurality of slit portions is disposed on the interlayer insulating film, and a liquid crystal alignment film is formed thereon, in the pixel region (that is, the display region) of the liquid crystal device, the liquid crystal aligning agent and the interlayer insulating film are in contact with the slit portion. In this case, there is a concern that the interlayer insulating film is affected by the liquid crystal aligning agent and its properties are changed, or the impurity component or the like contained in the interlayer insulating film is eluted with the liquid crystal aligning agent to deteriorate the performance of the liquid crystal aligning film, thereby deteriorating the reliability of the liquid crystal device. do.

The present disclosure has been made in view of the above problems, and to provide a method of manufacturing a liquid crystal device capable of obtaining a liquid crystal device having excellent reliability in an element structure in which an interlayer insulating film, a pattern electrode, and a liquid crystal alignment film are formed on a substrate in this order. For one purpose.

In order to solve the above problems, the present disclosure employs the following means.

<1> A method for manufacturing a liquid crystal device comprising a pair of substrates arranged oppositely, a liquid crystal layer disposed between the pair of substrates, and a pair of electrodes, wherein at least one of the pair of electrodes comprises a plurality of A pattern electrode having an opening, a step of forming an interlayer insulating film on at least one of the pair of substrates, a step of forming the pattern electrode on the interlayer insulating film, and at least a part of the interlayer insulating film on the pattern electrode A step of forming a liquid crystal aligning film so as to contact with, wherein the liquid crystal aligning film is formed using a liquid crystal aligning agent containing a polymer component and at least one solvent selected from the group of solvents shown below. Manufacturing method.

Solvents:

[A] Solvent: Compound represented by the following formula (1), 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-dimethyl-4-heptanol, diisobutyl ketone, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

(In 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 are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent group having "-O-" between the carbon-carbon bonds of the hydrocarbon group. Group, and R ² and R ³ may combine with each other to form a ring structure. R ⁴ is an alkyl group having 1 to 6 carbon atoms.)

According to the said structure, even if an interlayer insulating film and a liquid crystal aligning agent contact in the opening part of a pattern electrode when forming a liquid crystal aligning film, the performance of an interlayer insulating film or a liquid crystal aligning film is hard to fall, and a reliable liquid crystal element can be obtained.

1 is a diagram schematically showing a part of a liquid crystal device.
2 is a cross-sectional view schematically showing a part of the liquid crystal device of the first embodiment.
3 is a cross-sectional view schematically showing a part of the liquid crystal device of the second embodiment.
4 is a view showing the structure of an electrode used in Examples.
5 is a view showing the structure of an electrode used in Examples.

(Form for carrying out the invention)

EMBODIMENT OF THE INVENTION Hereinafter, embodiment is demonstrated, referring drawings. In addition, in each of the following embodiments, the same code | symbol is attached | subjected to the part which is the same or equivalent to each other, 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 vertically aligned liquid crystal display element of a PSA (Polymer Sustained Alignment) system. A plurality of pixels 11 are arranged in a matrix on the display portion of the liquid crystal device 10. 1, the pixel 11 is formed in the area | region surrounded by the scanning signal line 12 and the video signal line 13 which mutually intersect. In each pixel 11, a thin film transistor (TFT) 14 serving as an element for driving a liquid crystal is disposed. 2, the liquid crystal device 10 includes an array substrate 15, a counter substrate 16, and a liquid crystal layer 17.

The array substrate 15 includes a transparent substrate 18 such as a glass substrate or a plastic substrate, a scanning signal line 12, an image signal line 13, a thin film transistor 14, a pixel electrode 19, and an interlayer insulating film 21 (See FIG. 2). The thin film transistor 14 includes a gate electrode 22 made of a scan signal line 12, a semiconductor layer 23 made of silicon (Si), a source electrode 24 made of an image signal line 13, and a pixel electrode ( 19) is connected to the drain electrode 25. The thin film transistor 14 is formed by a known method such as photolithography. As a specific material constituting each part of the thin film transistor 14, a known material can be used.

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 slit portions (elongated rectangular openings) 19c are formed on a flat electrode. Specifically, the pixel electrode 19 includes a stem 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 stem line portion 19a, It has a plurality of slit portions 19c formed between the plurality of branch line portions 19b, and has a repeating pattern of the conductive portion and the non-conductive portion. 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 various signals are supplied.

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 formed in the interlayer insulating film 21. The interlayer insulating film 21 is formed by a photolithography method using a radiation-sensitive resin composition described later. By forming the interlayer insulating film 21, the increase in the capacitive coupling between the pixel electrode 19 and the signal line is suppressed.

The counter substrate 16 includes a transparent 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 in 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 formed across a plurality of pixels 11.

The first alignment layer 32 is formed on the electrode formation surface of the array substrate 15, and the second alignment layer 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 formed on a substrate using a liquid crystal alignment agent that is a polymer composition containing a polymer component. It is done. The first alignment film 32 is in contact with the interlayer insulating film 21 in at least the slit portion 19c of the display area.

The array substrate 15 and the counter substrate 16 are arranged to form a predetermined gap (cell gap) so 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 periphery of the pair of opposing substrates is joined by a sealing agent (not shown). As a material for the sealing agent, a known material (for example, a thermosetting resin or a photocurable resin) is used as the sealing agent for liquid crystal devices. A liquid crystal composition is filled in a space surrounded by the array substrate 15, the counter substrate 16, and the sealing agent, and accordingly, the liquid crystal layer 17 is brought into contact with the first alignment layer 32 and the second alignment layer 33. ).

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 each of the interface with the array substrate 15 and the interface with the counter substrate 16. The PSA layers 34 and 35 are formed by photopolymerizing the photopolymerizable monomer previously mixed into the liquid crystal layer 17 in a state in which the liquid crystal molecules are pretilt-oriented after the construction of the liquid crystal cell. In the liquid crystal device 10, the initial alignment of the liquid crystal molecules in the liquid crystal layer 17 is controlled by the PSA layers 34 and 35.

In the liquid crystal device 10, polarizing plates 36 and 37 are disposed on the outer sides of the array substrate 15 and the counter substrate 16, respectively. A terminal region is formed on an outer edge portion of the array substrate 15, and a driver IC or the like for driving liquid crystal is connected to the terminal region, thereby driving the liquid crystal device 10.

<Liquid crystal aligning agent>

Next, the liquid crystal aligning agent used for forming a liquid crystal aligning film (1st aligning film 32, 2nd aligning 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 ( And main skeletons such as styrene-phenylmaleimide) derivatives and poly (meth) acrylic polymers. Among these, it is preferable that they are 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. In addition, in preparing a liquid crystal aligning agent, one type of polymer may be used alone, or two or more types may be used in combination. In this specification, "(meth) acrylic" means "acrylic" and "methacryl."

[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 anhydride and diamine.

(Polyamic acid)

Examples of the tetracarboxylic acid anhydride used for the synthesis of polyamic acid include aliphatic tetracarboxylic acid anhydride, alicyclic tetracarboxylic acid anhydride, aromatic tetracarboxylic acid anhydride, and the like. As specific examples of these, as aliphatic tetracarboxylic acid anhydride, for example, 1,2,3,4-butanetetracarboxylic acid anhydride, ethylenediamine tetraacetic acid 2 anhydride, and the like;

As an alicyclic tetracarboxylic acid anhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 2,3,5-tricarboxycyclopentylacetic acid 2 anhydride, 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-fura Neil) -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 acid anhydride, 2,4,6, 8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, cyclohexanetetracarboxylic acid anhydride, cyclopentanetetracarboxylic acid anhydride, and the like;

As aromatic tetracarboxylic acid anhydride, for example, pyromellitic acid anhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, p-phenylenebis (trimellitic acid monoester anhydride), ethylene glycol In addition to the bis (anhydrotrimellitate), 1,3-propylene glycol bis (anhydrotrimellitate), and the like, the tetracarboxylic acid anhydride described in JP 2010-97188 A can be used. You can. Moreover, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more type.

The tetracarboxylic acid anhydride used for synthesis is preferably from an alicyclic tetracarboxylic acid anhydride in view of being able to make the solubility of the resulting polymer higher in the solvent, and includes cyclobutane ring, cyclopentane ring, and cyclo It is more preferable to include tetracarboxylic acid dianhydride (hereinafter also referred to as "specific tetracarboxylic acid anhydride") having at least one ring structure selected from the group consisting of hexane rings. The use ratio of the specific tetracarboxylic acid anhydride is preferably 10 mol% or more, more preferably 20 to 100 mol% with respect to the total amount of tetracarboxylic acid anhydride used for the synthesis of polyamic acid.

Examples of the diamine used for the synthesis of polyamic acid include aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane, and the like. As specific examples of these, as the aliphatic diamine, for example, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane and the like; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and the like;

As an aromatic diamine, 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-aminophenoxy) propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) Si) phenyl] hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 2,6-diaminopyridine, 3, 6-diaminocarbazole, 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-indene-6- Amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholesteric Nyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholesteryl, 3,5- Diaminobenzoic acid ranstanil, 3,6-bis (4-aminobenzoyloxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1 -Bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane , 2,4-diamino-N, N-diallyaniline, 4-aminobenzylamine, N- [4- (2-aminoethyl) phenyl] benzene-1,4-diamine, N- [4- (amino Methyl) phenyl] benzene-1,4-diamine, 1,3-bis (4-aminophenyl) 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- (however, "*" The attached bond is bonded to a diaminophenyl group), R ^I and R ^II are each independently an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer from 0 to 2, c is an integer from 1 to 20, n is 0 or 1, and m is 0 or 1. However, when a and b are not 0 at the same time, when X ^I is * -NH-CO-, n is 0.)

Compounds represented by;

As the diamino organosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like can be mentioned, and the diamine described in JP 2010-97188 A can be used. You can. In addition, in the synthesis of polyamic acid, diamine can be used alone or in combination of two or more.

Polyamic acid can be obtained by reacting the above tetracarboxylic acid anhydride and diamine with a molecular weight modifier as necessary. The ratio of the tetracarboxylic acid anhydride and the diamine used in the synthesis reaction of the polyamic acid is preferably 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid anhydride relative to the amino group equivalent of the diamine. As the molecular weight modifier, for example, acid monohydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate, etc. Can be mentioned. It is preferable that the use ratio of a molecular weight modifier is 20 mass% or less with respect to the total amount of the tetracarboxylic dianhydride and diamine used.

The synthesis reaction of the 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 and hydrocarbons. Preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethyl urea, hexamethylphosphoria One or more types selected from the group consisting of mid, m-cresol, xylenol, halogenated phenol, and specific solvents described below are used as a solvent, or an organic solvent different from one or more of them (for example, butyl cell) It is preferable to use a mixture of Rosolve, diethylene glycol diethyl ether, and the like). The amount of the organic solvent used is preferably an amount such that the total amount of tetracarboxylic acid anhydride and diamine is 0.1 to 50% by mass relative to the total amount of the reaction solution. As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be provided as it is to the preparation of a liquid crystal aligning agent, or may be provided to the preparation of a liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution.

(Polyimide)

The polyimide can be obtained by imidizing the polyamic acid synthesized as described above by dehydration and ring closure. The polyimide may be a complete imide product in which the entirety of the cancerous acid structure possessed by its precursor polyamic acid is dehydrated and closed, or a partial imide in which only a part of the cancerous acid structure is dehydrated and closed to form a coexistence of the cancerous acid structure and the imide ring structure. good. It is preferable that the imidation ratio of polyimide is 30% or more, it is more preferable that it is 40-99%, and it is still more preferable that it is 60-99%. The imidation ratio is a percentage of the ratio of the number of imide ring structures to the sum of the number of imide ring structures and the number of male acid structures of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration cyclization of the polyamic acid is preferably carried out by a method in which the polyamic acid is dissolved in an organic solvent, a dehydrating agent and a dehydration cyclization catalyst are added to the solution and heated as necessary. In this method, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per 1 mol of the rock acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, rutidine and triethylamine can be used. The amount of the dehydration ring-closed catalyst is preferably 0.01 to 10 mol per 1 mol of the dehydrating agent used. Examples of the organic solvent used include organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration cyclization reaction is preferably 0 to 180 ° C, and the reaction time is preferably 1.0 to 120 hours. The obtained reaction solution may be provided to the preparation of a liquid crystal aligning agent as it is, or may be provided to the preparation of a liquid crystal aligning agent after isolation of the polyimide.

(Polyamic acid ester)

The polyamic acid ester is, for example, [I] a method of reacting the polyamic acid obtained by the above reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [III] a tetracarboxylic acid diester It can be obtained by a method of reacting dihalide with diamine, or the like. Here, as an esterification 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 of tetracarboxylic acid anhydride with alcohols 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 obtained polyamic acid ester may have only a carboxylic acid ester structure, or may be a partial esterified product in which a carboxylic acid structure and a carboxylic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be provided as it is to the preparation of the liquid crystal aligning agent, or may be provided to the preparation of the liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution.

The polyamic acid, polyamic acid ester, and polyimide obtained as described above are preferably those having a solution viscosity of 10 to 800 mPa · s, and a solution of 15 to 500 mPa · s when the concentration is 10% by mass. It is more preferable to have a viscosity. In addition, the solution viscosity (mPa · s) of the polymer is a polymer having a concentration of 10% by mass prepared using a good solvent of the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The solution is a value measured at 25 ° C using an E-type rotational viscometer. For polyamic acid, polyamic acid ester, and polyimide, the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) is preferably 500 to 100,000, and more preferably 1,000 to 50,000.

(Polyorganosiloxane)

The polyorganosiloxane can be obtained, for example, by hydrolyzing or hydrolyzing / condensing a hydrolyzable silane compound in the presence of a suitable organic solvent, water and catalyst.

Examples of the hydrolyzable silane compound used for the synthesis of the polyorganosiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltrie Alkoxysilane compounds such as methoxysilane, trimethoxysilylpropylsuccinic anhydride, dimethyldimethoxysilane, and dimethyldiethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyl Nitrogen-sulfur-containing alkoxysilane compounds such as trimethoxysilane, 3-aminopropyltriethoxysilane, and N- (3-cyclohexylamino) propyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, Epoxy group-containing silane compounds such as 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane; 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, p-styryl tree And an unsaturated bond-containing alkoxysilane compound such as methoxysilane. The hydrolyzable silane compound can be used alone or in combination of two or more. In addition, in this specification, "(meth) acrylo" means "acrylo" and "methacryl".

The above hydrolysis / condensation reaction is performed by reacting one or two or more of the silane compounds 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 mol with respect to 1 mol of the silane compound (total amount). Examples of the catalyst used include acids, alkali metal compounds, organic bases (for example, triethylamine and tetramethylammonium hydroxide), titanium compounds, and zirconium compounds. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, and the like, and should be appropriately set. For example, it is preferably 0.01 to 3 times the mole relative to the total amount of the silane compound. 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 sparingly water-soluble organic solvent. The use ratio of the organic solvent is preferably 50 to 1,000 parts by mass based on 100 parts by mass of the total amount of silane compounds used for the reaction.

It is preferable to perform the said hydrolysis-condensation reaction by heating, for example with an oil bath. At that time, the heating temperature is preferably 130 ° C or lower, and the heating time is preferably 0.5 to 12 hours. After completion of the reaction, the polysiloxane can be obtained by removing the solvent to the organic solvent layer fractionated from the reaction solution.

When a functional group such as a pretilt angle imparting group or a photo-alignment group is introduced into the side chain of the polyorganosiloxane, the synthesis method thereof is not particularly limited, for example, an epoxy group-containing silane compound or an epoxy group-containing silane compound and other And a method in which a mixture of silane compounds is hydrolyzed and condensed to synthesize a polyorganosiloxane having an epoxy group, and then the obtained epoxy group-containing polyorganosiloxane is reacted with a carbon acid having the functional group. The reaction of the epoxy group-containing polyorganosiloxane and carbon acid can be carried out according to a known method.

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

The content ratio of the [P] polymer in the liquid crystal aligning agent (total amount when two or more kinds are contained) is preferably 60% by mass or more, and more preferably 80% by mass or more, with respect to the total amount of the polymer components in the liquid crystal aligning agent. desirable. Moreover, it is preferable that a liquid crystal aligning agent contains the [p] polymer which is at least 1 sort (s) selected from the group which consists of polyamic acid, polyamic acid ester, and polyimide from the point which can obtain a liquid crystal element excellent by reliability. The content ratio of the [p] polymer in the liquid crystal aligning agent (when two or more are included) is preferably 40% by mass or more, and 60% by mass or more, with respect to the total amount of the polymer components in the liquid crystal aligning agent. It is more preferable.

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 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, -OR ^16- * ¹ , or -R ¹⁶ -O- * ¹ (where R ¹⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹⁶ is an alkanediyl group having a carbon number of 1 to 3. "* ^1", it indicates that sonin combination with R ^11. is). R ¹¹ and R ¹³ are, each independently, a single bond, phenylene group or cycloalkyl group , R ¹² is a single bond, a phenylene group, a cycloalkylene group, -R ¹⁷ -B ^1- * ² , or -B ¹ -R ^17- * ² (where R ¹⁷ is a phenylene group or a cycloalkylene group, B ¹ is -COO- * ³ , -OCO- * ³ , or an alkanediyl group having 1 to ^3. C. "* ² " indicates a bonding group with R ^13, and "* ³ " indicates R ¹⁷ and of binding indicates that sonin.) a. R ¹⁴ is, seen in the alkyl group, having 1 to 18 carbon atoms as a hydrogen atom, a fluorine atom, an alkyl, fluoroalkyl having 1 to 18 carbon atoms having a carbon number of 1 to 18 Group, an alkoxy group, or a hydrocarbon group of a carbon number of 17-51 with a steroid skeleton, the radical polymerization may have a group or photoinitiation raised. However, R ¹⁴ is a hydrogen atom, a fluorine atom or a carbon number of fluoroalkyl having 1 to 18 carbon atoms In the case of a group of 1 to 3, all of R ¹¹ , R ¹² and R ¹³ do not form a single bond. "*" Indicates a bonding hand.)

In the formula (3), the alkanediyl group of L ¹ and B ¹ and the alkyl group, fluoroalkyl group, alkoxy group and fluoroalkoxy group of R ¹⁴ are preferably linear. Examples of the group having a steroid skeleton of R ¹⁴ include cholstanyl group, cholesteryl group, and lanostaniyl group. The phenylene group of R ¹¹ , R ¹² , R ¹³ and R ¹⁷ is preferably 1,4-phenylene group, and the cycloalkylene group is preferably 1,4-cyclohexylene group. It is preferable that at least one of R ¹¹ and R ¹³ is a phenylene group or a cycloalkylene group. R ¹² is preferably a phenylene group, a cycloalkylene group, -R ¹⁷ -B ^1- * ² , or -B ¹ -R ^17- * ² . The main skeleton of the polymer having a partial structure represented by the formula (3) is not particularly limited, but is preferably a [P] polymer.

The content ratio of the partial structure represented by the formula (3) in the polymer is appropriately set depending on the main chain of the polymer, but from the viewpoint of sufficiently fastening the response speed of the liquid crystal, it is 1 to 50 mol% relative to the total monomer units of the polymer. It is preferable to be, and it is more preferable to be 2 to 40 mol%.

In addition, since a residual image is hardly generated and a liquid crystal element having a high response speed of liquid crystal can be obtained, the liquid crystal aligning agent is a polymer component, a radical polymerizable group, a photoinitiator group, a radical polymerization inhibitor group, a nitrogen-containing heterocycle (However, except for the imide ring of the polyimide), it is preferable to contain a polymer having at least one selected from the group consisting of an amino group and a protected amino group (hereinafter also referred to as "specific partial structure"). .

Examples of the radical polymerizable group include (meth) acryloyl group, vinyl group, allyl group, vinylphenyl group, maleimide group, vinyloxy group, and ethynyl group. Of these, a (meth) acryloyl group is particularly preferred because of its high reactivity.

The photoinitiator is a site that generates a polymerization initiation ability by light or a site that has a light-sensitizing action, and initiates polymerization of the polymerizable component by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet rays, electron beams, and X-rays. It is a group which has a structure derived from a possible 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 And the like. It is preferable that a photoinitiator group is a group which has an acetophenone structure among these. When the polymer has at least one of a radically polymerizable group and a photoinitiator group, it is preferable to have these groups in a side chain.

The radical polymerization inhibitor group captures radicals that inhibit the progress of the polymerization reaction by supplementing a peroxide decomposing agent that neutralizes peroxy radicals or hydroperoxides generated by energy such as ultraviolet rays or heat, or a radical intermediate during polymerization. It functions as zero. By containing the polymer having such a polymerization inhibitor group in the liquid crystal alignment film, it is possible to suppress the photopolymerizable compound mixed in the liquid crystal layer in the PSA mode from reacting by light irradiation. It is preferable that a polymerization inhibitor group is a group which has at least 1 sort (s) selected from the group which consists of a hindered amine structure, a hindered phenol structure, and an aniline structure.

Examples of the nitrogen-containing heterocycle include, for example, pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzoimidazole, purine, quinoline, isoquinoline, naphthyridine, quinoxaline, And phthalazine, triazine, carbazole, acridine, piperidine, piperazine, pyrrolidine, and hexamethyleneimine. Especially, it is preferable to have at least 1 sort (s) selected from the group which consists of pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole, and acridine.

It is preferable that the said amino group and protected amino group are groups represented by following formula (N-1).

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

In the 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 specifically, for example, a linear or branched alkyl group such as a methyl group, ethyl group, propyl group or butyl group; Cycloalkyl groups such as cyclohexyl groups; Aryl groups such as phenyl group and methylphenyl; And aralkyl groups such as benzyl groups. As a substituent which R ⁵⁰ may have, a halogen atom, a cyano group, an alkylsilyl group, an alkoxysilyl group, etc. are mentioned, for example. 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 formula (N-1) binds include an alkanediyl group, a cyclohexylene group, and a phenylene group.

The protecting group is preferably a group that is desorbed by heat, and for example, each of a carbamate-based protecting group, an amide-based protecting group, an imide-based protecting group, a sulfonamide-based protecting group, and the following formulas (8-1) to (8-5) And groups appearing. Especially, a tert-butoxycarbonyl group is preferable at the point which has high desorption property by heat, and the residual amount in the film | membrane of the deprotected part is small.

(In Formulas (8-1) to (8-5), Ar ¹¹ is a monovalent group having 6 to 10 carbon atoms, wherein one hydrogen atom is removed from a substituted or unsubstituted aromatic ring, and R ⁶¹ is 1 to 1 carbon atom. 12 is an alkyl group, and R ⁶² is a methylene group or an ethylene group. "*" Represents a bond that binds to a nitrogen atom.)

The main skeleton of the polymer having the 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 specific partial structure in the polymer (when two or more are contained, the total amount thereof) is preferably 5 mol% or more relative to the total monomer units of the polymer, and more preferably 10 to 80 mol%. desirable.

(solvent)

As a solvent component, a liquid crystal aligning agent contains the specific solvent which is at least 1 sort (s) selected from the solvent group shown below (group consisting of [A] solvent and [B] solvent).

Solvents:

[A] Solvent: Compound represented by the following formula (1), 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-dimethyl-4-heptanol, diisobutyl ketone, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

(In 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 are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent group having "-O-" between the carbon-carbon bonds of the hydrocarbon group. Group, and R ² and R ³ may combine with each other to form a ring structure. R ⁴ is an alkyl group having 1 to 6 carbon atoms.)

· [A] Solvent

(Compound represented by Formula (1))

For the compound represented by the formula (1), the monovalent hydrocarbon group having 2 to 5 carbon atoms in R ¹ is preferably a chain hydrocarbon group, and examples thereof include an alkyl group having 2 to 5 carbon atoms, an alkenyl group, and an alkynyl group. Moreover, as a monovalent group which has "-O-" between the carbon-carbon bonds in the said hydrocarbon group, the C2-C5 alkoxyalkyl group is mentioned, for example.

As a specific example of these, as a C2-C5 alkyl group, For example, an ethyl group, a propyl group, a butyl group, a pentyl group, etc .; Examples of the alkenyl group having 2 to 5 carbon atoms include vinyl group, 1-propenyl group, 2-propenyl group, and 3-butenyl group; As an alkynyl group having 2 to 5 carbon atoms, for example, ethynyl group, 2-propynyl group, 2-butynyl group, and the like; Examples of the alkoxyalkyl group having 2 to 5 carbon atoms include, for example, methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, ethoxymethyl group, ethoxyethyl group, and the like. The weather may be good. As R ¹ , it is preferable that it is a C2-C5 alkyl group or an alkoxyalkyl group among the above.

Specific examples of the compound represented by the 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- And pyrrolidone, N-ethoxyethyl-2-pyrrolidone, and N-methoxybutyl-2-pyrrolidone. Among these, N-ethyl-2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N-methoxypropyl-2-pi Rollidone can be used particularly preferably. Moreover, the compound represented by said Formula (1) can use these exemplary compounds individually by 1 type or in combination of 2 or more type.

(Compound represented by Formula (2))

About the compound represented by the formula (2), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms of R ² and R ³ include, for example, a linear hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, And aromatic hydrocarbon groups having 5 or 6 carbon atoms. Moreover, as a monovalent group which has "-O-" between the carbon-carbon bonds of the said hydrocarbon group, the C2-C6 alkoxyalkyl group etc. are mentioned, for example.

As a specific example of these, as a C1-C6 linear hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. are mentioned, For example, These may be linear or branched. Moreover, as an alicyclic hydrocarbon group of 3-6 carbon atoms, For example, cyclopentyl group, cyclohexyl group, etc .; As an aromatic hydrocarbon group, For example, a phenyl group etc .; Examples of the alkoxyalkyl group having 2 to 6 carbon atoms include, for example, an alkoxyalkyl group contained in R ¹ ; Each can be lifted. In addition, R ² and R ³ in Formula (2) may be the same or different from each other. Further, R ² and R ³ may be bonded 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 of R ² and R ³ to each other include a pyrrolidine ring and a piperidine ring, and a monovalent chain hydrocarbon group such as a methyl group may be bound to these rings.

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, and more preferably a hydrogen atom or a methyl group.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁴ include groups exemplified in the description of the alkyl group having 1 to 6 carbon atoms in R ² and R ³ . Preferably, it is a C1-C4 alkyl group, More preferably, it is a methyl group or an ethyl group.

As a specific example of the compound represented by said formula (2), 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-hexyloxy-N, N, for example -Dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide, and the like. Moreover, the compound represented by said formula (2) can be used individually by 1 type or in combination of 2 or more type.

[A] As a solvent, since the effect on the interlayer insulating film 21 can be made smaller, among them, the compound represented by the above formula (1), the compound represented by the above formula (2) and 1,3-dimethyl-2 -It is preferable that it is at least 1 sort (s) selected from the group which consists of imidazolidinone, and in the compound represented by said formula (1), R <^1> is a C2-C5 alkyl group or an alkoxyalkyl group, 3-methoxy-N, It is more preferable that it is at least one member selected from the group consisting of 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-dimethylpropanamide and 1,3-dimethyl It is particularly preferable that it is at least one member selected from the group consisting of -2-imidazolidinone.

[B] As a solvent, since the effect on the interlayer insulating film 21 can be made smaller, among the above, dipropylene glycol monomethyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, It is preferable that it is at least 1 sort (s) selected from the group which consists of diacetone alcohol and propylene glycol monobutyl ether.

As a solvent component, you may use only a specific solvent, but you may use together other solvents other than a specific solvent. Examples of such other solvents include solvents having high solubility and leveling properties of the polymer (hereinafter also referred to as "first solvent") and solvents having good wet diffusivity (hereinafter also referred to as "second solvent").

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, and the like;

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, isoamyl propionate, isoamyl isobutylate, etc. are mentioned, respectively. In addition, as other solvents, one of the above may be used alone, or two or more of them may be mixed and used.

In the preparation of the liquid crystal aligning agent, as the specific solvent, only one of the [A] solvent and the [B] solvent may be used, but the liquid crystal aligning agent and the interlayer insulating film 21 are in contact with each other when forming the liquid crystal aligning film. At least one of the [A] solvents and [B], since the effect on the interlayer insulating film 21 can be suppressed and the effect of suppressing the elution of the impurity component from the interlayer insulating film 21 is high. ] It is preferable that at least one solvent is contained.

[A] The use ratio of the solvent (when two or more kinds are used, the total amount thereof) is obtained while sufficiently obtaining the effect of suppressing the effect on the interlayer insulating film 21 and the effect of suppressing the elution of impurity components from the interlayer insulating film 21. , From the viewpoint of suppressing precipitation of the polymer component, the total amount of the solvent contained in the liquid crystal aligning agent is preferably 10% by mass or more, and more preferably 20% by mass or more. Moreover, it is preferable to set it as 90 mass% or less with respect to the total amount of the solvent contained in a liquid crystal aligning agent from the viewpoint of obtaining the improvement effect of coatability with a [B] solvent, and the upper limit of the use ratio is 80 mass% It is more preferable to do the following. In addition, [A] solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

[B] The use ratio of the solvent (when two or more types are used, the total amount thereof) suppresses the influence on the interlayer insulating film 21 and the elution of the impurity component from the interlayer insulating film 21, and also applies a liquid crystal aligning agent. From the viewpoint of improving the properties, the total amount of the solvent contained in the liquid crystal aligning agent is preferably 10% by mass or more, and more preferably 20% by mass or more. Moreover, it is preferable that it is 80 mass% or less with respect to the total amount of the solvent contained in a liquid crystal aligning agent, and, as for the upper limit of the use ratio, it is more preferable that it is 70 mass% or less. Moreover, [B] solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

The use ratio of a specific solvent (when two or more types are used, the total amount thereof) is a viewpoint to sufficiently obtain the effect of suppressing the effect on the interlayer insulating film 21 and the effect of reducing the dissolution of impurity components from the interlayer insulating film 21. In, with respect to the total amount of the solvent contained in the liquid crystal aligning agent, it is preferably 50 mass% or more, more preferably 70 mass% or more, even more preferably 90 mass% or more, and 95 mass% It is particularly preferable to set the above.

In addition, when using the solvent [A], the solvent [B], and other solvents, the use ratio of the other solvents (the total amount when two or more solvents are used) is a liquid crystal from the viewpoint of sufficiently obtaining the effects of the present disclosure. The total amount of the solvent contained in the alignment agent is preferably 50% by mass or less, more preferably 30% by mass or less, more preferably 10% by mass or less, and 5% by mass or less It is particularly preferred.

It is particularly preferable that the liquid crystal aligning agent is composed of a [A] solvent and a [B] solvent. However, in this specification, "the solvent component consists of [A] solvent and [B] solvent" contains the solvents other than [A] solvent and [B] solvent to such an extent that the effects of the present disclosure are not disturbed. Is to allow.

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

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 and volatility, but is preferably 1 to It is the range of 10 mass%. When the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, making it 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 excessive, so that it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent tends to increase and the coating property tends to decrease.

<Sensitive radiation 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] photosensitive agent.

([Q] polymer)

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

The main skeleton of the [Q] polymer is not particularly limited, but it is preferably at least one selected from the group consisting of (meth) acrylic polymer, polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane. Among these, it is particularly preferable that it is a (meth) acrylic polymer. In addition, the (meth) acrylic polymer may have only a structural unit derived from a monomer having a (meth) acryloyl group, a structural unit derived from a monomer having a (meth) acryloyl group, and a (meth) acryloyl group You may have a structural unit derived from other monomers different from the monomer which has. The content ratio of the structural unit derived from other monomers in the (meth) acrylic polymer is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less. .

Specifically, the polymer [Q] has 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. It is preferably a polymer having a third structural unit to be formed.

Examples of the acidic group of the first structural unit include 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, and a hydroxyalkyl group in which hydrogen atoms bonded to carbon atoms have been replaced with electron withdrawing groups. Can be lifted. As the acidic group, from the viewpoint of alkali developability, among these, a carboxyl 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, and a carboxyl group or phenolic The hydroxyl group is more preferable, and the carboxyl group is particularly preferable.

As the first structural unit, a structural unit derived from at least one compound selected from the group consisting of (meth) acrylic acid or unsaturated carboxylic acid anhydride is preferred, and at least one of (meth) acrylic acid and maleic anhydride is particularly preferred.

[Q] The content ratio of the first structural unit in the polymer is preferably 1 to 50 mol%, more preferably 15 to 30 mol%, relative to the total structural units constituting the [Q] polymer. The first structural unit may be used alone or in combination of two or more.

Examples of the second structural unit include (meth) acrylic acid glycidyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3- (meth) acrylic. A structural unit derived from at least one compound selected from the group consisting of monooxymethyl-3-ethyloxetane is preferred.

[Q] The content ratio of the second structural unit in the polymer is preferably 1 to 15 mol%, more preferably 3 to 10 mol%, relative to the total structural units constituting the [Q] polymer. 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 that forms a main chain structure different from the first structural unit and the second structural unit, but the adhesion to development and the resistance to heat and peeling solutions can be improved. It is preferable that it is a structural unit derived from at least 1 type of compound chosen from the group which consists of styrene, (alpha) -methylstyrene, 4-methylstyrene, and 4-hydroxystyrene.

[Q] The content ratio of the third structural unit in the polymer is preferably 25 to 80 mol%, more preferably 30 to 65 mol%, relative to the total structural units constituting the [Q] polymer. The third structural unit may be used alone or in combination of two or more.

In addition, the [Q] polymer may further have other structural units other than the first structural unit, the second structural unit, and the third structural unit. As such a structural unit, (meth) acrylic-acid alkyl etc. are mentioned, for example.

[Q] The polymer can be synthesized according to a conventional method such as radical polymerization using monomers that impart first to third structural units or the like. The details of the synthesis conditions can be appropriately set, for example, with reference to various conditions described in JP-A-2015-92233.

([R] photosensitizer)

As the [R] photosensitive agent, at least one selected from the group consisting of a photo-radical polymerization initiator, a photo acid generator and a photo base generator can be preferably used.

As specific examples of these, examples of the photo-radical polymerization initiator include O-acyloxime compounds, acetophenone compounds, and biimidazole compounds;

As a photo acid generator, for example, oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carbonic acid ester compounds, quinonediazide compounds, etc. ;

Examples of the photobase generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, and acyloxyiminos, respectively. have.

The ratio of the [R] photosensitizer used varies depending on the type of compound used. For example, in the case of a photo-radical polymerization initiator, 1 to 40 parts by mass is preferable, and more preferably 5 to 30 parts by mass, with respect to 100 parts by mass of the [Q] polymer.

The use ratio of the photoacid generator is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the [Q] polymer.

The use ratio of the photobase generator is preferably 0.1 to 20 parts by mass, 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 aid in addition to the above-mentioned [Q] polymer and [R] photosensitizer. These arbitrary components may be used individually by 1 type, or may be used in combination of 2 or more type.

The radiation-sensitive resin composition is prepared by mixing, in addition to the [Q] polymer and the [R] photosensitive agent, other optional components to be blended as necessary. The radiation-sensitive resin composition is preferably dissolved in a suitable solvent and used in solution. Examples of the solvent include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, and propylene glycol alkyl ether. Acetate, propylene glycol monoalkyl ether propionate, ketone, ester, and the like.

The content of the solvent is preferably an amount such that the total concentration of each component excluding the solvent of the radiation-sensitive resin composition is 5 to 50% by mass, from the viewpoint of coatability, stability, and the like of the resulting radiation-sensitive resin composition, 10 The amount which becomes -40 mass% is more preferable.

(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.

Step A: The step of forming the interlayer insulating film 21 on the substrate.

Step B: The 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 contact a part of the interlayer insulating film 21.

Step D: A step of arranging the array substrate 15 and the counter substrate 16 to face each other via a liquid crystal layer containing a photopolymerizable monomer to construct a liquid crystal cell.

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, on a transparent substrate 18 such as a glass substrate, the thin film transistor 14 and the scanning signal line (by a known method such as a photolithography method) 12), an image signal line 13 is formed. Subsequently, on the formation surface of the thin film transistor 14 and the signal line in the transparent substrate 18, a radiation-sensitive resin composition for forming an interlayer insulating film is applied to form the interlayer insulating film 21 (step A).

The method for applying the radiation-sensitive resin composition is not particularly limited, and suitable methods such as a spray method, a roll coating method, a spin coating method, a slit coating method, a bar coating method, and an inkjet coating method can be adopted, for example. Of these, a spin coating method or a slit coating method is preferable because a film having a uniform thickness can be formed. After application of the radiation-sensitive resin composition, curing is preferably performed by heating (pre-baking) the coated surface, exposing the coating film via a photomask having a predetermined pattern as necessary, and then developing and post-baking. An interlayer insulating film 21 as a film is obtained. As for the various conditions when forming the interlayer insulating film 21, for example, the conditions described in JP-A-2015-92233 can be adopted.

In the subsequent step B, the pixel electrode 19 is formed on the interlayer insulating film 21 formed in step A of the transparent substrate 18. The pixel electrode 19 forms an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film having a film thickness of 50 to 200 nm, more preferably 100 to 150 nm, using a known method such as sputtering. Then, it is patterned into a fishbone shape (also referred to as a "comb shape") by photolithography. Accordingly, a fishbone-type pixel electrode 19 is formed on the substrate, thereby fabricating the array substrate 15.

In addition, the color filter layer 29, the overcoat layer (not shown), and the common electrode 31 are formed on a transparent substrate 28 such as a glass substrate using a known method such as a photolithography method. Formed in this order, the counter substrate 16 is produced.

In the subsequent step C, first, a liquid crystal aligning agent is applied onto a substrate on which an electrode is formed, and a coating film is preferably formed on the substrate by heating the coated surface. The liquid crystal aligning agent is applied to the substrate on the electrode formation surface, preferably by an offset printing method, a spin coating method, a roll coater method, a flexo printing method or an inkjet printing method. After the liquid crystal aligning agent is applied, preheating (pre-baking) is preferably performed for the purpose of preventing liquid flow of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, and the pre-baking time is preferably 0.25 to 10 minutes. Thereafter, a sintering (post-baking) step is carried out with the aim of completely removing the solvent and thermally imidizing the acid structure present in the polymer, if necessary. The firing 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 apply | coating a liquid crystal aligning agent on a board | substrate, by removing an organic solvent, the liquid crystal aligning film or the coating film used as a liquid crystal aligning film is formed.

Here, a liquid crystal aligning agent is applied onto the interlayer insulating film 21 on the electrode formation surface of the substrate on which the pattern electrode (pixel electrode 19) having a plurality of slit portions 19c is formed. Therefore, the liquid crystal aligning agent in a liquid state contacts 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 via the slit portion 19c in the display area of the liquid crystal device 10.

Moreover, although the coating film formed above may be used as it is as a liquid crystal aligning film, you may perform the process (orientation process) which gives liquid crystal aligning ability. As the alignment treatment, for example, rubbing treatment of rubbing the coating film in a predetermined direction with a roll of cloth made of fibers such as nylon, rayon, or cotton, or irradiating the coating film formed on the substrate with a liquid crystal aligning agent to irradiate the coating film with liquid crystal And a photo-alignment treatment for imparting alignment ability.

In the subsequent process D, the interlayer insulating film 21, the pixel electrode 19 and the first alignment film 32 are formed in this order, the array substrate 15, and the common electrode 31 and the second alignment film 33 are in this order. The opposing substrates 16 formed of are arranged so that the alignment film forming surfaces of each other face each other. Between the array substrate 15 and the counter substrate 16, a liquid crystal layer 17 in which a photopolymerizable monomer is mixed is disposed, thereby constructing a liquid crystal cell.

The liquid crystal layer 17 is, for example, dropped or coated with a liquid crystal composition on one substrate coated with a sealing agent, and thereafter, a method of bonding the other substrate (ODF method) or via a cell gap. Then, the peripheral portions of the pair of substrates facing each other are bonded by a sealing agent, and the liquid crystal composition is injected and filled into a cell gap surrounded by the substrate surface and the sealing agent, and then formed by a method of sealing the injection hole. For the obtained liquid crystal cell, it is preferable to further remove the flow orientation during liquid crystal charging by heating to a temperature at which the used liquid crystal takes an isotropic phase and then slowly cooling to room temperature.

As a 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 di (meth) acrylate having a biphenyl structure, di (meth) acrylate having a phenyl-cyclohexyl structure, and di (meth) acrylate having a 2,2-diphenylpropane structure. , Di (meth) acrylate having a diphenylmethane structure, dithio (meth) acrylate having a diphenylthioether structure, and the like. The blending ratio of the photopolymerizable monomer is preferably 0.1 to 0.5% by mass relative to the total amount of the liquid crystal composition used for forming the liquid crystal layer 17. Moreover, as a photopolymerizable monomer, 1 type may be used individually and may be used in combination of 2 or more type.

In the subsequent step E, light is irradiated to the liquid crystal cell obtained in step D. Light irradiation to the liquid crystal cell may be performed in a state in which no voltage is applied between the electrodes, or may be performed in a state in which a predetermined voltage that is not driven by the liquid crystal molecules in the liquid crystal layer 17 is applied, or the liquid crystal molecules are driven. You may perform it in the state which applied the prescribed voltage between electrodes. Preferably, light is irradiated while a voltage is applied between the electrodes of the pair of substrates. The voltage to be applied can be, for example, DC or AC of 5 to 50V. As the light to be irradiated, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. When the radiation to be used is linearly polarized or partially polarized, the direction of irradiation of light may be performed from a direction perpendicular to the substrate surface, from an inclined direction, or a combination thereof. When irradiating non-polarized radiation, the irradiation direction is set to the inclined direction.

As the light source of the irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. In addition, ultraviolet rays in the above-described preferred wavelength range can be obtained by means of using a light source in combination with, for example, a filter diffraction grating or the like. The irradiation amount of light is preferably 1,000 to 200,000 J / m 2, and more preferably 1,000 to 100,000 J / m 2.

And the liquid crystal device 10 is obtained by bonding the polarizing plates 36 and 37 to the outer surface of a liquid crystal cell. Examples of the polarizing plates 36 and 37 include a polarizing plate sandwiched between a protective film of cellulose acetate and a polarizing plate called an "H film" which absorbs iodine while stretching and aligning polyvinyl alcohol, or a polarizing plate made of the H film itself. have.

In this embodiment, the 1st alignment film 32 is formed using the liquid crystal aligning agent containing a specific solvent as a solvent component. Accordingly, even when the first alignment film 32 is in contact with the interlayer insulating film 21 via the slit portion 19c, the liquid crystal device 10 having excellent reliability can be obtained. It is not clear why this effect was obtained, but as one reason, the specific solvent used for the preparation of the liquid crystal aligning agent has a small effect on the interlayer insulating film 21, thereby suppressing the deterioration of the performance of the interlayer insulating film 21. Can think. In particular, in the PSA technique, in order to improve the response characteristics of the MVA mode, an electrode pattern of a fine stripe shape of, for example, about several μm is formed. When such a fine electrode pattern is formed on a substrate, if the interlayer insulating film 21 swells due to the liquid crystal aligning agent contacting the interlayer insulating film 21 and the thickness of the film changes slightly, the pixel electrode 19 is easily deformed. , It is considered that it causes the deterioration of device performance. According to this point and a specific solvent, it is estimated that the effect on the pixel electrode 19 can be reduced as much as possible by suppressing the swelling of the interlayer insulating film 21, thereby sufficiently suppressing the deterioration of device performance. Further, in the state in which the liquid crystal aligning agent is in contact with the interlayer insulating film 21, the elution of the impurity component from the interlayer insulating film 21 to the liquid crystal aligning agent can be suppressed, thereby sufficiently suppressing the deterioration of device performance. I guess.

(Second embodiment)

Next, the second embodiment will be mainly described with respect to differences from the first embodiment. This embodiment differs from the first embodiment in that a color filter layer is formed on the array substrate 15.

3 is a cross-sectional view schematically showing a part of the device structure according to the second 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 opposite to each other via the liquid crystal layer 17, similarly to the liquid crystal device of the first embodiment. The array substrate 15 has a TFT 14 on a transparent substrate 18, a color filter layer 29 composed of a coloring pattern 29a and an interlayer insulating film 29b. The coloring pattern 29a is composed of sub-pixels colored in red (R), green (G), and blue (B), and is produced by a known method such as photolithography. The interlayer insulating film 29b is formed using the radiation-sensitive resin composition described in the first embodiment. This interlayer insulating film 29b is formed for the purpose of forming the pixel electrode 19 showing excellent characteristics while protecting the coloring pattern 29a. The pixel electrode 19 is disposed on the interlayer insulating film 29b.

Also in this case, the first alignment layer 32 is formed by forming the first alignment layer 32 on the electrode formation surface of the substrate on which the fishbone-shaped pattern electrode (pixel electrode 19) is formed on the interlayer insulating film 29b. In the slit portion 19c, the interlayer insulating film 29b is brought into contact. By forming this point and the 1st alignment film 32 using the liquid crystal aligning agent mentioned above, the liquid crystal device 10 excellent in reliability is obtained.

(Other embodiments)

In the first embodiment, the interlayer insulating film 21 and the first alignment film 32 were in contact with each other in the slit portion 19c, using the pixel electrode 19 on the array substrate 15 side as a pattern electrode. A pattern electrode and an interlayer insulating film may also be formed on the electrode 16 side, 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 above can be effectively applied to various uses, for example, a watch, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, It can be used as various display devices such as mobile phones, smart phones, various monitors, liquid crystal TVs, information displays, and dimming devices.

Example

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

In the following examples, the imidation ratio of the polyimide in the polymer solution, the weight average molecular weight of the polymer, and the epoxy equivalent were measured by the following method.

[Imidization 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, dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidation rate [%] was determined by the following formula (1).

Imidation rate [%] = (1-(A ¹ / (A ² × α))) x 100. (One)

(In Formula (1), A ¹ is a peak area derived from a proton of an NH group appearing near 10 ppm of chemical shift, A ² is a peak area derived from other protons, and α is a polymer precursor (polyamic acid). It is the ratio of the number of other protons to one proton of the NH group.)

[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 Corporation, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ℃

Pressure: 68kgf / ㎠

[Epoxy equivalent]

The epoxy equivalent was measured by the hydrochloric acid-methylethylketone method described in JIS C 2105.

The symbol used in the following example is shown. In addition, in the following, the compound represented by Formula X may be simply referred to as "compound X".

1. Preparation of radiation-sensitive resin composition (for forming an interlayer insulating film)

(1) [Q] Synthesis of polymer

[Synthesis Example 1: Synthesis of polymer (Q-1)]

To a flask equipped with a cooling tube 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 methacrylic acid, and 30 parts by mass of styrene were added, and after nitrogen substitution, the temperature of the solution was raised to 70 ° C while gradually stirring. , A solution containing the polymer (Q-1) was obtained by maintaining and maintaining this temperature for 5 hours. The polymer (Q-1) had an Mw of 8000.

[Synthesis Example 2: Synthesis of polymer (Q-2)]

To a flask equipped with a cooling tube 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 methacrylic acid, 20 parts by mass of styrene, 15 parts by mass of tetrahydrofurfuryl methacrylate, and 10 mass of n-lauryl methacrylate The solution was added, and after nitrogen substitution, the temperature of the solution was raised to 70 ° C while stirring slowly, and the temperature was kept for 5 hours and polymerized to obtain a solution containing the polymer (Q-2). The polymer (Q-2) had an Mw of 8000.

[Synthesis Example 3: Synthesis of polymer (Q-3)]

To a flask equipped with a cooling tube 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 were added to nitrogen. After substitution, the temperature of the solution was raised to 70 ° C while stirring slowly, and the polymer was stored and polymerized for 5 hours to obtain a solution containing the polymer (Q-3). Mw of the polymer (Q-3) was 8000.

(2) Preparation of radiation-sensitive resin composition

[Preparation Example 1]

To a solution containing polymer (Q-1) obtained in Synthesis Example 1 (amount equivalent to 100 parts by mass (solid content) of polymer (Q-1)), 1,2-octanedione 1- [4- (phenyl Thio) -2- (O-benzoyloxime)] (Irgacure (registered trademark) OXE01, manufactured by BASF), 20 parts by mass, and further a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) was added and mixed with 100 parts by mass. Diethylene glycol ethyl methyl ether was added and dissolved so that the solid content concentration was 30 mass%, followed by filtration through a membrane filter having a diameter of 0.2 µm 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 addition, in Table 1, "-" means that the said component is not mix | blended (it is the same also about the following table).

In Table 1, the abbreviation of a compound is as showing below.

R-1: 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure (registered trademark) OXE01, manufactured by BASF)

R-2: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinone Condensate of diazide-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. Synthesis of polymer (for liquid crystal aligning agent)

[Synthesis Example 5: Synthesis of polymer (PI-1)]

As tetracarboxylic acid anhydride, 100 mol parts of 2,3,5-tricarboxycyclopentyl acetic acid 2 anhydride, and as diamine, 20 mol parts of cholestanyloxy-2,4-diaminobenzene, 50 mol parts of 3,5-diaminobenzoic acid And, 30 mol parts of the compound (d-8) was dissolved in N-methyl-2-pyrrolidone (NMP), and reacted 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, and chemical imidization was performed. The reaction solution after chemical imidation was concentrated, and it was prepared by NMP so that the concentration may be 10 mass%. The imidation ratio of the obtained polyimide (referred to as polymer (PI-1)) was about 75%.

[Synthesis Examples 6 to 8]

Polyimide (polymer (PI-2) to polymer (PI-4)) was synthesized in the same manner as in Synthesis Example 5 except that the type and amount of tetracarboxylic acid anhydride and diamine used were changed as shown in Table 2 below. In addition, in Table 2, the numerical value in parenthesis shows the use ratio [molar part] of each compound with respect to 100 mol part of the total tetracarboxylic dianhydride used for the synthesis of a polymer.

[Synthesis Example 9: Synthesis of Polymer (PAA-1)]

70 mol parts of 2,3,5-tricarboxycyclopentyl acetic anhydride as tetracarboxylic acid anhydride, 30 mol parts of 1,2,3,4-cyclopentane tetracarboxylic acid anhydride, and cholestanyloxy- as diamine 20 parts by mole of 2,4-diaminobenzene, 30 parts by mole of compound (d-12), 40 parts by mole of 4,4'-diaminodiphenylmethane, and 4,4 '-[4,4'-propane-1,3- Diylbis (piperidine-1,4-diyl)] 10 mol parts of 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 the polymer (PAA-1).

[Synthesis Example 10]

Polyamic acid (which is referred to as polymer (PAA-2)) was synthesized in the same manner as in Synthesis Example 9 except that the type and amount of tetracarboxylic acid anhydride and diamine used were changed as shown in Table 2 below.

[Synthesis Example 11]

To a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux cooling tube, 100 g of compound (s-1), 500 g of methyl isobutyl ketone, and 10 g of triethylamine were added and mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise to the dropping funnel over 30 minutes, and then reacted at 80 ° C for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out, washed with a 0.2% by mass aqueous solution of ammonium nitrate until the water after washing was neutral, and then distilled off the solvent and water under reduced pressure, thereby making the reactive polyorganosiloxane (ESSQ-1) Was obtained as a viscous transparent liquid. As a result of performing ¹ H-NMR analysis of this reactive polyorganosiloxane, it was confirmed that a peak based on an epoxy group was obtained near the chemical shift (?) = 3.2 ppm, and no side reaction of the epoxy group occurred during the reaction. The obtained reactive polyorganosiloxane (ESSQ-1) had a weight average molecular weight Mw of 3000 and an epoxy equivalent of 190 g / mol.

[Synthesis Examples 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 the monomer used were changed as shown in Table 3 below. In addition, in Table 3, the numerical value in parenthesis shows the use ratio [molar part] of each compound with respect to 100 mol part of the total monomer used for the synthesis of a 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 modified component, and 16 g of compound (c-3), Then, 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) was added as a catalyst, and the reaction was performed at 100 ° C under stirring for 48 hours. After completion of the reaction, the solution obtained by adding ethyl acetate to the reaction mixture was washed three times, the organic layer was dried using magnesium sulfate, and then the solvent was distilled off to obtain 75 g of a polymerizable group-containing polyorganosiloxane (PSQ-1). . The weight average molecular weight Mw of the obtained polymer was 6000.

[Synthesis Examples 15, 16]

The polymerizable group-containing polyorganosiloxane (polymer (PSQ-2) and polymer (PSQ-3) was used in the same manner as in Synthesis Example 14, except that the type and amount of the reactive polyorganosiloxane and modified component used were changed as shown in Table 4 below. )). In Table 4, numerical values in parentheses indicate the use ratio [molar parts] of each compound to 100 mol parts of the total monomers used for the synthesis of the polymer.

3. Evaluation of liquid crystal aligning agent and liquid crystal display element

[Example 1]

(1) Preparation of liquid crystal aligning agent

To the solution containing the polymer (PI-1) as the polymer component, the polymer (PSQ-1) was added so that the polymer (PI-1): polymer (PSQ-1) = 95: 5 (mass ratio), and further a solvent. As a solution of NEP, diethylene glycol diethyl ether (DEDG) and diacetone alcohol (DAA), and sufficiently stirred, the solvent composition is NEP: DEDG: DAA = 50: 30: 20 (mass ratio), a solid content solution of 6.5 mass% As was. The liquid crystal aligning agent (W-1) was prepared by filtering this solution using a filter having a pore diameter of 1 µm.

(2) Preparation of liquid crystal composition (LC-1)

For 10 g of nematic liquid crystals (MLC-6608 manufactured by Merck, Inc.), the compound represented by the following formula (RM-1) is added so as to be 0.3% by mass relative to the total amount of the total constituents of the liquid crystal composition, and the liquid crystal composition is mixed. (LC-1).

(3) Production of liquid crystal display elements

After applying the radiation-sensitive resin composition (V-1) on a glass substrate ("Corning 7059" (manufactured by Corning)) using a spinner, pre-baking is performed in a clean oven at 90 DEG C for 10 minutes, and then the glass substrate A coating film having a film thickness of 2.0 µm was formed on each. Subsequently, UV light was irradiated at 100 mJ through a pattern mask using a UV (ultraviolet) exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ). Thereafter, a developing treatment was performed at 25 ° C for 100 seconds by a puddle method using an aqueous solution of tetramethylammonium hydroxide (developer) at a concentration of 2.38% by mass. After the developing treatment, the coating film was washed with running water for 1 minute with ultrapure water, dried to form a patterned coating film on the substrate, and then heated (post-baked) at 230 ° C for 30 minutes in an oven to cure. Next, using a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Co., Ltd., the entire surface of each coating film was exposed at an exposure amount of 500 J / m 2 without interposing a photomask. Thereafter, post-baking was performed at 230 ° C for 30 minutes to cure each coating film to form an interlayer insulating film.

Subsequently, an ITO electrode patterned in a fishbone shape was formed on a glass substrate on which an interlayer insulating film was formed. In this embodiment, the electrode pattern of the ITO electrode was formed into a fishbone shape with line / space = 3.5 μm / 3.5 μm. The electrode pattern of the ITO electrode used here is shown in FIG. 4. In addition, a glass substrate having an ITO electrode having no pattern was prepared by performing the same operation. Among these pair of substrates, a 3.5 µm column spacer was formed on the electrode side surface of a glass substrate having an ITO electrode without a pattern.

Subsequently, after spin-coating the liquid crystal aligning agent (W-1) on each electrode formation surface of the pair of substrates, the solvent was removed by heating (pre-baking) on a hot plate at 80 ° C. for 1 minute, and thereafter, Heating (post-baking) was performed on a hot plate at 230 ° C for 15 minutes to form a coating film having an average film thickness of 100 nm. This coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water, and then dried in a 100 ° C clean oven for 10 minutes to obtain a pair of substrates having a liquid crystal alignment film.

Next, after applying an epoxy resin adhesive having an aluminum oxide sphere having a diameter of 5.5 µm on the outer edge of the ITO surface of a glass substrate having a patterned ITO electrode, a liquid crystal composition (LC-1) was applied to the inner surface of the epoxy resin adhesive. Was added 6 points (vertical 2 points x horizontal 3 points, the interval between each point was 10 mm up and down, left and right, and the coating amount of each point was 0.6 mg). A liquid crystal cell was produced by pressing and bonding each other so that the substrate and the other glass substrate were opposed to each other and curing the adhesive. The liquid crystal cell for evaluation was produced about the obtained liquid crystal cell by performing ultraviolet irradiation and annealing according to "PSA process-1" mentioned later.

(PSA Process-1)

To the liquid crystal cell, 20 Vpp of alternating current at a frequency of 60 Hz was applied between the electrodes, and while the liquid crystal was driven, 80 mW of ultraviolet light was irradiated for 50 seconds using an ultraviolet irradiation device using a metal halide lamp as the light source. Subsequently, 3.5 mW of ultraviolet light is irradiated for 30 minutes by using an ultraviolet irradiation device using a metal halide lamp as the light source without applying a voltage.

Finally, the liquid crystal cell is put in a clean oven at 120 ° C for 10 minutes, and annealing is performed. In addition, irradiation amount is the value measured using the photometer measured based on the wavelength 365nm.

(4) Evaluation of voltage retention (VHR)

The evaluation liquid crystal cell prepared in (3) was placed in a constant temperature bath, and a voltage of 5 V at 60 ° C. was applied at an application time of 60 microseconds and a span of 167 milliseconds, followed by a voltage retention of 167 milliseconds after release of the application (VHR) ) Was measured by "VHR-1" manufactured by TOYO TECHNIQUE CORPORATION. At this time, when the VHR was 96% or more, "very good (◎)", when 93% or more and less than 96% were "good (○)", when 90% or more and less than 93% were "possible (△)" , It was evaluated as "poor (x)" when it was less than 90%. As a result, in this example, VHR = 97%, and the evaluation was "very good (◎)".

[Examples 2 to 22, Comparative Examples 1 and 2]

A liquid crystal aligning agent was prepared respectively by performing the same operation as described above except that the type and amount of the polymer and solvent used were changed as shown in Table 5 below. In addition, except for the fact that the radiation-sensitive resin composition used for the production 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, it was evaluated as in the above. While manufacturing a liquid crystal cell, voltage retention was evaluated using the obtained liquid crystal cell for evaluation. The results are shown in Table 5 below.

In Table 5, the numerical value in parentheses of the polymer column shows the blending ratio [parts by mass] of each polymer to 100 parts by mass of the total of the polymer components used in the preparation of the liquid crystal aligning agent. The numerical value of the solvent composition column shows the compounding ratio [mass part] of each compound with respect to 100 mass parts of all the solvents used for preparation of a liquid crystal aligning agent. The abbreviations for the solvent 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

DEDG: 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 1-22 in which the liquid crystal aligning film was formed using the liquid crystal aligning agent containing a specific solvent, Comparative Example 1 in which the liquid crystal aligning film was formed using the liquid crystal aligning agent not containing a specific solvent. , A liquid crystal display element with better reliability than 2 was obtained. Among these, in Examples 1-18 using the liquid crystal aligning agent containing the [A] solvent and the [B] solvent, evaluation of "very good" was particularly excellent.

In addition, in Examples 1 to 22, as a result of manufacturing and evaluating a liquid crystal display device in the same manner as 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 above was obtained.

[Example 23]

(1) Evaluation of ITO wiring strain

N-ethyl-2-pyrrolidone (NEP) and diethylene glycol diethyl ether (DEDG) were mixed and thoroughly stirred to obtain a solvent composition for evaluation of NEP: DEDG = 50: 50 (mass ratio) (Z-1) ).

Moreover, the glass substrate which arrange | positioned the pattern electrode which consists of ITO on the interlayer insulating film was prepared by performing operation similar to (3) of Example 1 above. The glass substrate was immersed in an evaluation solvent (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 by the criteria shown below. When the contact between the solvent component of the liquid crystal aligning agent and the swelling of the interlayer insulating film is small and the deformation of the electrode is small, the effect of the solvent on the interlayer insulating film and the ITO electrode is less, and the reliability of the liquid crystal element can be ensured. It can be said that it is suitable as a solvent of an alignment agent. As a result, this example was evaluated for "A".

(Evaluation standard)

A: No swelling of the interlayer insulating film and no abnormality of the electrode

B: Although the swelling of the interlayer insulating film was observed, there was no abnormality in the electrode.

C: slight abnormality such as deformation of the electrode due to swelling of the interlayer insulating film

D: There is a serious abnormality such as disconnection of the electrode due to swelling of the interlayer insulating film.

[Examples 24 to 44, Comparative Examples 3 and 4]

The same operation as described above was performed except that the solvent composition and the type of the radiation-sensitive resin composition used were changed as shown in Table 6 below, and the ITO wiring strain was evaluated for each solvent. Table 6 shows the results.

From the results of Table 6, in Examples 23 to 44 using a specific solvent, swelling of the interlayer insulating film was not observed, or even when swelling was small, the abnormality of the electrode was not observed. From these results, it was found that, according to a specific solvent, even when a liquid crystal alignment film was formed on a fine stripe-shaped electrode pattern, the shape of the electrode was difficult to change, thereby ensuring the reliability of the liquid crystal element.

1: ITO electrode
2: Slit part
3: Light shielding film
10: liquid crystal device
14: thin film transistor
15: array substrate
16: opposing substrate
17: liquid crystal layer
19: pixel electrode
19c: slit
21: interlayer insulating film
29: color filter layer
29a: coloring pattern
29b: interlayer insulating film
31: common electrode
32: first alignment layer
33: second alignment layer
34, 35: PSA layer (orientation control layer)

Claims (15)

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;
And forming a liquid crystal alignment layer on the pattern electrode so as to contact at least a portion of the interlayer insulating layer,
The said liquid crystal aligning film is formed using a liquid crystal aligning agent containing a polymer component and at least 1 sort (s) of solvent chosen from the solvent group shown below, The manufacturing method of a liquid crystal element.
Solvents:
[A] Solvent: Compound represented by the following formula (1), 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-dimethyl-4-heptanol, diisobutyl ketone, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether

(In 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 are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent group having "-O-" between the carbon-carbon bonds of the hydrocarbon group. Group, and R ² and R ³ may combine with each other to form a ring structure; R ⁴ is an alkyl group having 1 to 6 carbon atoms) According to claim 1,
A method of manufacturing a liquid crystal element further comprising the step of forming an alignment control layer for controlling the alignment of the liquid crystals at an interface on each substrate side of the liquid crystal layer by polymerizing the photopolymerizable monomer mixed in the liquid crystal layer. . The method according to claim 1 or 2,
The said liquid crystal aligning agent contains at least 1 sort (s) of the said [A] solvent, and at least 1 sort (s) of the said [B] solvent, The manufacturing method of a liquid crystal element. The method according to any one of claims 1 to 3,
The said liquid crystal aligning agent contains the [P] polymer which is at least 1 sort (s) selected from the group which consists of polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane, The manufacturing method of a liquid crystal element. The method according to any one of claims 1 to 4,
The said liquid crystal aligning agent contains the polymer [p] which is at least 1 sort (s) selected from the group which consists of polyamic acid, polyamic acid ester, and polyimide,
The [p] polymer has a partial structure derived from a tetracarboxylic acid derivative having at least one ring structure selected from the group consisting of a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. The method according to any one of claims 1 to 5,
The liquid crystal aligning agent is at least selected from the group consisting of a radically polymerizable group, a photoinitiator group, a radical polymerization inhibitor group, a nitrogen-containing heterocycle (except for the imide ring of the polyimide), an amino group, and a protected amino group. The manufacturing method of a liquid crystal element containing the polymer which has 1 type. The method according to any one of claims 1 to 6,
The said liquid crystal aligning agent contains the polymer which has a partial structure represented by following formula (3), The manufacturing method of a liquid crystal element.
* -L ¹ -R ¹¹ -R ¹² -R ¹³ -R ¹⁴ … (3)
(In 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, -OR ^16- * ¹ , or -R ¹⁶ -O- * ¹ (where R ¹⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹⁶ is an alkanediyl group having 1 to 3 carbon atoms; “* ¹ ” represents a bond with R ¹¹ ); R ¹¹ and R ¹³ are each independently a single bond, a phenylene group or a cycloalkylene group , R ¹² is a single bond, a phenylene group, a cycloalkylene group, -R ¹⁷ -B ^1- * ² , or -B ¹ -R ^17- * ² (where R ¹⁷ is a phenylene group or a cycloalkylene group, B ¹ is -COO- * ³ , -OCO- * ³ , or an alkanediyl group having 1 to ³ carbon atoms; "* ² " represents a bond with R ^13, and "* ³ " represents R ¹⁷ R ¹⁴ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, 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 a hydrogen atom, a fluorine atom or 1 to 1 carbon atom; When the group is 3, all of R ¹¹ , R ¹² and R ¹³ are not single-bonded; `` * '' indicates a bonding hand) The method according to any one of claims 1 to 7,
A method for manufacturing a liquid crystal element, wherein a liquid crystal driving element and a color filter layer are formed on a substrate forming the interlayer insulating film. The method according to any one of claims 1 to 8,
The interlayer insulating film is formed using a radiation-sensitive resin composition containing a [Q] polymer and a [R] photosensitizer, and a method for manufacturing a liquid crystal device. The method of claim 9,
The said [Q] polymer has at least 1 sort (s) selected from the group which consists of an oxetanyl group, an oxiranyl group, a (meth) acryloyl group, and a vinyl group, The manufacturing method of a liquid crystal element. The method of claim 9 or 10,
The said [R] photosensitive agent is at least 1 sort (s) selected from the group which consists of a photo-radical polymerization initiator, a photo acid generator, and a photo base generator, The manufacturing method of a liquid crystal element. The method according to any one of claims 9 to 11,
The [Q] polymer is a first structural unit having an acidic group, a second structural unit having an oxetanyl group or an oxiranyl group, and a agent forming a main chain structure different from the first structural unit and the second structural unit. The manufacturing method of a liquid crystal element which is a polymer which has three structural units. The method of claim 12,
The said 1st structural unit is a structural unit derived from at least 1 type of compound chosen from the group which consists of (meth) acrylic acid and unsaturated carboxylic acid anhydride, The manufacturing method of a liquid crystal element. The method of claim 12 or 13,
The second structural unit includes (meth) acrylic acid glycidyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3- (meth) acrylic. A method for producing a liquid crystal device, which is a structural unit derived from at least one compound selected from the group consisting of royloxymethyl-3-ethyloxetane. The method according to any one of claims 12 to 14,
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.

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