KR102321076B1 - Method for manufacturing a liquid crystal element - Google Patents

Abstract

The element structure in which the interlayer insulating film, the pattern electrode, and the liquid crystal aligning film were formed in this order on a board|substrate WHEREIN: The liquid crystal element excellent in reliability is obtained. A process of forming an interlayer insulating film 21 on at least one of the pair of substrates, a process of forming a pattern electrode (pixel electrode 19) on the interlayer insulating film 21, and a process of forming an interlayer insulating film 21 on the pattern electrode ) In the manufacturing method of the liquid crystal element comprising the process of forming a liquid crystal aligning film (1st alignment film 32) so that it may contact at least a part, a liquid crystal aligning film is at least 1 sort(s) selected from a polymer component and a specific solvent group. It forms using the liquid crystal aligning agent containing the solvent of

Description

Method for manufacturing a liquid crystal element

(Cross-reference to related applications)

This application is based on Japanese Application No. 2017-223114 for which it applied on November 20, 2017, The description is used here.

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

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

As one of the alignment processing methods of a liquid crystal element, the PSA(Polymer Sustained Alignment) system is known (for example, refer patent document 1). In the PSA method, a photopolymerizable monomer is mixed in advance with a liquid crystal in a gap between a pair of substrates, a liquid crystal cell is constructed, and then the photopolymerizable monomer is polymerized by irradiating ultraviolet rays in a state where a voltage is applied between the substrates. It is a technique for forming a polymer layer and controlling the initial orientation of liquid crystal by the polymer layer. According to this technique, it is possible to expand the viewing angle and speed up the liquid crystal molecular response, and it is possible to solve the problem of insufficient transmittance and contrast in the MVA type panel.

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

Japanese Laid-Open Patent Publication No. 2003-149647

When a pattern electrode having a large number of slits is disposed on the interlayer insulating film and a liquid crystal aligning film is formed thereon, the liquid crystal aligning agent and the interlayer insulating film are in contact with the slit in the pixel region (ie, display region) of the liquid crystal device. In this case, there is a concern that the reliability of the liquid crystal device may decrease because the interlayer insulating film is affected by the liquid crystal aligning agent and its properties change, or the impurity component contained in the interlayer insulating film elutes into the liquid crystal aligning agent and the performance of the liquid crystal aligning film decreases. do.

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

In order to solve the said subject, this indication employ|adopted the following means.

<1> A method of manufacturing a liquid crystal device comprising a pair of substrates disposed 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, the step of forming an interlayer insulating film on at least one of the pair of substrates, the steps 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 liquid crystal element comprising the step of forming a liquid crystal aligning film so as to contact with manufacturing method.

Dragon Army:

[A] Solvent: A compound represented by the following formula (1), a compound represented by the following formula (2), N,N,2-trimethylpropionamide, and 1,3-dimethyl-2-imidazolidinone.

[B] Solvent: dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, 4-methoxy-4-methyl-2-pentanone, 4-hydroxy-2-butanone, 2 -Methyl-2-hexanol, 2,6-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 hydrocarbon group having “-O-” between the carbon-carbon bonds of the hydrocarbon group. group, and R ² and R ³ may be bonded to each other to form a ring structure. R ⁴ is an alkyl group having 1 to 6 carbon atoms.)

According to the 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 does not fall easily, and the liquid crystal element excellent in reliability can be obtained.

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

(Form for implementing the invention)

EMBODIMENT OF THE INVENTION Below, embodiment is demonstrated, referring drawings. In addition, in each of the following embodiments mutually, the same code|symbol is attached|subjected to the mutually same or equivalent part in drawing, and the description is invoked about the part with the same code|symbol.

(Configuration of liquid crystal device 10)

The liquid crystal device 10 is a vertical alignment type liquid crystal display element of a PSA(Polymer Sustained Alignment) system. In the display section of the liquid crystal device 10, a plurality of pixels 11 are arranged in a matrix. As shown in FIG. 1 , the pixel 11 is formed in a region surrounded by scan signal lines 12 and video signal lines 13 that intersect with each other. Each pixel 11 is provided with a thin film transistor (TFT) 14 functioning as a liquid crystal driving element. As shown in FIG. 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 scan signal line 12 , an image signal line 13 , a thin film transistor 14 , a pixel electrode 19 , and an interlayer insulating film 21 . has (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) and a drain electrode 25 connected thereto. 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. The pixel electrode 19 is a pattern electrode in which a plurality of slits (elongated rectangular openings) 19c are formed in a planar electrode as shown in FIG. 1 . 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, A plurality of slit portions 19c formed between the plurality of branch line portions 19b are provided, and a repeating pattern of a conductive portion and a non-conductive portion is provided. The pixel electrode 19 is electrically connected to the thin film transistor 14 . The thin film transistor 14 is electrically connected to the scan signal line 12 and the video signal line 13, and various signals are supplied thereto.

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 via 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 to be described later. By forming the interlayer insulating film 21, the increase in capacitive coupling between the pixel electrode 19 and the signal line is suppressed.

The counter substrate 16 includes a 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 over the plurality of pixels 11 .

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

The array substrate 15 and the counter substrate 16 are arranged with a predetermined gap (cell gap) formed so that the alignment film formation surface of the array substrate 15 and the alignment film formation surface of the counter substrate 16 face each other. The periphery of a pair of board|substrates opposingly arrange|positioned is joined by the sealing compound (not shown). As a material of a sealing compound, a well-known material (for example, thermosetting resin and photocurable resin) is used as a sealing compound for liquid crystal devices. A liquid crystal composition is filled in the space surrounded by the array substrate 15 , the counter substrate 16 , and the sealing compound, and thus the liquid crystal layer 17 is brought into contact with the first alignment layer 32 and the second alignment layer 33 . ) is placed.

The liquid crystal layer 17 has negative dielectric anisotropy. The liquid crystal layer 17 has PSA layers 34 and 35 which are polymer layers in 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 a photopolymerizable monomer mixed in advance with the liquid crystal layer 17 in a state in which the liquid crystal molecules are pretilt aligned 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, 37) are arranged outside each of the array substrate (15) and the counter substrate (16). A terminal region is formed in the outer edge of the array substrate 15, and a driver IC for driving the liquid crystal or the like is connected to the terminal region, whereby the liquid crystal device 10 is driven.

<Liquid crystal aligning agent>

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

(Polymer component)

As for the polymer contained in a liquid crystal aligning agent, the main skeleton is not specifically limited, For example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, a cellulose derivative, polyacetal, a polystyrene derivative, poly( main skeletons such as styrene-phenylmaleimide) derivatives and poly(meth)acrylic polymers. Among these, it is preferable that it is at least 1 sort(s) of polymer (hereinafter also referred to as a [P] polymer) selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane. In addition, preparation of a liquid crystal aligning agent WHEREIN: As a polymer, you may use individually by 1 type, and may use it in combination of 2 or more type. In this specification, "(meth)acryl" is a meaning including "acryl" and "methacryl."

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

(polyamic acid)

As tetracarboxylic dianhydride used for the synthesis|combination of polyamic acid, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. As these specific examples, As an aliphatic tetracarboxylic dianhydride, For example, 1,2,3,4- butanetetracarboxylic dianhydride, ethylenediamine tetraacetic acid dianhydride, etc.;

As the alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho [1,2-c] furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-fura nyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran- 2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 2,4,6, 8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-2 anhydride, cyclohexanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride and the like;

As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, p-phenylenebis(trimellitic acid monoester anhydride), ethylene glycol Bis(anhydrotrimellitate), 1,3-propylene glycol bis(anhydrotrimellitate), etc. are mentioned, respectively, tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 is used. can In addition, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

The tetracarboxylic dianhydride used for the synthesis preferably contains an alicyclic tetracarboxylic dianhydride from the viewpoint of making the solubility of the resulting polymer higher in a solvent, and includes a cyclobutane ring, a cyclopentane ring and a cyclo It is more preferable to include tetracarboxylic dianhydride (hereinafter also referred to as "specific tetracarboxylic dianhydride") having at least one ring structure selected from the group consisting of a hexane ring. It is preferable that it is 10 mol% or more with respect to the total amount of tetracarboxylic dianhydride used for the synthesis|combination of a polyamic acid, and, as for the usage ratio of specific tetracarboxylic dianhydride, it is more preferable that it is 20-100 mol%.

As diamine used for the synthesis|combination of polyamic acid, an aliphatic diamine, alicyclic diamine, aromatic diamine, diaminoorganosiloxane etc. are mentioned, for example. Specific examples of the aliphatic diamine include metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine) and the like;

As the aromatic diamine, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 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) C)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-indene-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6- Amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3 , 5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid lanostanyl, 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-diallylaniline, 4-aminobenzylamine, N-[ 4-(2-aminoethyl)phenyl]benzene-1,4-diamine, N-[4-(aminomethyl)phenyl]benzene-1,4-diamine, 1,3-bis(4-aminophenyl)urea , 4,4'-[4,4'-propane-1,3-diylbis(piperidin-1,4-diyl)]dianiline, 2-propynyloxy-2,4-phenylenediamine and Formula (D-1)

(In formula (D-1), X ^I and X ^II are each independently a single bond, -O-, *-COO-, *-OCO- or *-NH-CO- (provided that "*" 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, and b is an integer of 0 to 2; c is an integer from 1 to 20, n is 0 or 1, m is 0 or 1. However, a and b do not simultaneously become 0, and when X ^I is *-NH-CO-, n is 0).

compounds represented by ;

As the diaminoorganosiloxane, for example, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane etc. are mentioned, respectively, and the diamine of Unexamined-Japanese-Patent No. 2010-97188 is used. can Moreover, in the synthesis|combination of polyamic acid, 1 type can be used individually or in combination of 2 or more types of diamine.

A polyamic acid can be obtained by making the above tetracarboxylic dianhydride and diamine react with a molecular weight modifier as needed. The ratio of tetracarboxylic dianhydride and diamine used in the synthesis reaction of polyamic acid is preferably such that the acid anhydride group of tetracarboxylic dianhydride is 0.2 to 2 equivalents with respect to 1 equivalent of the amino group of the diamine. Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, monoisocyanate compounds such as phenyl isocyanate and naphthyl isocyanate, etc. can be heard It is preferable that the usage ratio of a molecular weight modifier shall be 20 mass % or less with respect to the total amount of the tetracarboxylic dianhydride and diamine to be used.

The synthesis reaction of polyamic acid is preferably performed 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, dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea, hexamethylphosphotria. At least one selected from the group consisting of mide, m-cresol, xylenol, halogenated phenol, and a specific solvent to be described later is used as the solvent, or an organic solvent different from at least one of these (e.g., butyl cell) Rosolv, diethylene glycol diethyl ether, etc.) is preferably used. It is preferable to make the usage-amount of an organic solvent into the quantity used as 0.1-50 mass % with respect to the total amount of tetracarboxylic dianhydride and diamine with respect to the total amount of a reaction solution. As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used for preparation of a liquid crystal aligning agent as it is, and after isolating the polyamic acid contained in a reaction solution, you may provide for preparation of a liquid crystal aligning agent.

(Polyimide)

A polyimide can be obtained by imidating the polyamic acid synthesize|combined as mentioned above by dehydration ring-closure. The polyimide may be a complete imidized product obtained by dehydrating and ring-closing the entire amic acid structure of the polyamic acid that is its precursor, or a partial imidized product in which only a part of the amic acid structure is dehydrated and cyclized to coexist with a amic acid structure and an imide ring structure. good. It is preferable that the imidation ratio of a polyimide is 30 % or more, It is more preferable that it is 40 to 99 %, It is still more preferable that it is 60 to 99 %. This imidation ratio shows the ratio which the number of imide ring structures occupies with respect to the sum total of the number of the male acid structures of a polyimide, and the number of imide ring structures, as a percentage. Here, an isoimide ring may be sufficient as a part of an imide ring.

The dehydration ring closure of polyamic acid is preferably performed by dissolving polyamic acid in an organic solvent, adding a dehydrating agent and dehydration ring closure catalyst to this solution, and heating as necessary. In this method, as a dehydrating agent, acid anhydrides, such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride, can be used, for example. The amount of the dehydrating agent to be used is preferably 0.01 to 20 moles with respect to 1 mole of the amic acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of the dehydrating agent used. As an organic solvent to be used, the organic solvent illustrated as what is used for the synthesis|combination of polyamic acid is mentioned. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180°C, and the reaction time is preferably 1.0 to 120 hours. The obtained reaction solution may be used for preparation of a liquid crystal aligning agent as it is, and after isolating a polyimide, you may provide for preparation of a liquid crystal aligning agent.

(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 obtain by the method of making a dihalide and diamine react, etc. 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 tetracarboxylic dianhydride with an alcohol or the like. The tetracarboxylic acid diester dihalide used in the above [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. The polyamic acid ester obtained may have only a amic acid ester structure, and the partial esterification product in which a amic acid structure and a amic ester structure coexist may be sufficient as it. The reaction solution formed by dissolving polyamic acid ester may be used for preparation of a liquid crystal aligning agent as it is, and after isolating the polyamic acid ester contained in a reaction solution, you may provide for preparation of a liquid crystal aligning agent.

The polyamic acid, polyamic acid ester, and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa·s, and a solution of 15 to 500 mPa·s, when it is made into a solution having a concentration of 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 (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer. It is the value measured in 25 degreeC with respect to a solution using the E-type rotational viscometer. About polyamic acid, polyamic acid ester, and polyimide, it is preferable that it is 500-100,000, and, as for the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC), it is more preferable that it is 1,000-50,000.

(Polyorganosiloxane)

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

Examples of the hydrolyzable silane compound used for the synthesis of polyorganosiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethane. alkoxysilane compounds such as oxysilane, trimethoxysilylpropyl succinic 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-styryltri Unsaturated bond containing alkoxysilane compounds, such as methoxysilane, etc. are mentioned. A hydrolysable silane compound can be used individually by 1 type in these or in combination of 2 or more type. In addition, in this specification, "(meth)acrylo" is a meaning including "acrylo" and "methacrylo."

As described above, the 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 moles with respect to 1 mole of the silane compound (total amount). As a catalyst to be used, an acid, an alkali metal compound, an organic base (for example, triethylamine, tetramethylammonium hydroxide, etc.), a titanium compound, a zirconium compound, etc. are mentioned, for example. Although the usage-amount of a catalyst changes with reaction conditions, such as the kind of catalyst, temperature, etc., and should be set suitably, For example, with respect to the total amount of a silane compound, Preferably it is 0.01-3 times mole. Examples of the organic solvent to be used include hydrocarbons, ketones, esters, ethers and alcohols, and among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. To [ the usage ratio of an organic solvent / 100 mass parts in total of the silane compound used for reaction ], Preferably it is 50-1,000 mass parts.

It is preferable to perform said hydrolysis and condensation reaction by heating with an oil bath etc., for example. In that case, it is preferable that heating temperature shall be 130 degrees C or less, and it is preferable that heating time shall be 0.5 to 12 hours. After completion of the reaction, polysiloxane can be obtained by removing the solvent from the organic solvent layer separated from the reaction solution.

When a functional group such as a pretilt angle imparting group or a photo-aligning 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 polyorganosiloxane having an epoxy group, and then, the obtained epoxy group-containing polyorganosiloxane is reacted with carboxylic acid having the functional group. The reaction between the epoxy group-containing polyorganosiloxane and carboxylic acid can be performed 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, still more preferably 1,000 to 20,000. do. When the weight average molecular weight of polyorganosiloxane exists in the said range, when manufacturing a liquid crystal aligning film, it is easy to handle, and the liquid crystal aligning film which has sufficient material strength and a characteristic will be obtained.

It is preferable that it is 60 mass % or more with respect to the total amount of the polymer component in a liquid crystal aligning agent, and, as for the content rate of the [P] polymer in a liquid crystal aligning agent (total amount when 2 or more types are contained), it is more that 80 mass % or more desirable. Moreover, it is preferable that a liquid crystal aligning agent contains the [p] polymer which is at least 1 sort(s) chosen from the group which consists of a polyamic acid, polyamic acid ester, and a polyimide at the point which can obtain the liquid crystal element excellent by reliability. It is preferable that the content rate of the [p] polymer in a liquid crystal aligning agent (the total amount when 2 or more types are included) is 40 mass % or more with respect to the total amount of the polymer component in a liquid crystal aligning agent, It is 60 mass % or more more preferably.

It is preferable that at least one part of the polymer component contained in a liquid crystal aligning agent is a polymer which has a partial structure represented by 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 (provided that 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 " indicates a bond with ^{R 11. ) R 11} and R ¹³ are each independently a single bond, a phenylene group or a cycloalkylene group. and R ¹² is a single bond, a phenylene group, a cycloalkylene group, -R ¹⁷ -B ¹ -* ² , or -B ¹ -R ¹⁷ -* ² (provided that 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. “* 2} ” represents a bond with ^{R 13, and “* 3} ” ^{represents a bond with 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, or fluoro having 1 to 18 carbon atoms. It is an alkoxy group or a hydrocarbon group of 17 to 51 carbon atoms having a steroid skeleton, and may have a radical polymerizable group or a photoinitiator group, provided that R ¹⁴ is a hydrogen atom, a fluorine atom or a group having 1 to 3 carbon atoms, R ¹¹ , R ¹² and R ¹³ do not all form a single bond. "*" indicates a bond.)

In said formula (3), it is preferable that the alkanediyl group of ^L<1> , B<^1> , and the alkyl group, fluoroalkyl group, alkoxy group, and fluoroalkoxy group of ^{R<14> are linear.} Examples of the group having a steroid skeleton for R ¹⁴ include a cholestanyl group, a cholesteryl group, and a lanostanyl group. The ^{phenylene group of R 11} , R ¹² , R ¹³ and R ¹⁷ is preferably a 1,4-phenylene group, and the cycloalkylene group is preferably a 1,4-cyclohexylene group. 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 . Although the main skeleton of the polymer which has a partial structure represented by said Formula (3) is not specifically limited, It is preferable that it is a [P] polymer.

Although the content rate of the partial structure represented by said Formula (3) in a polymer is set suitably according to the main chain of a polymer, from a viewpoint of making the response speed of a liquid crystal sufficiently fast, 1-50 mol% with respect to all the monomer units of a polymer. It is preferable to set it as 2-40 mol%, and it is more preferable to set it as 2-40 mol%.

Moreover, since an afterimage is hard to generate|occur|produce and the liquid crystal element with a quick response speed of a liquid crystal can be obtained, a liquid crystal aligning agent is a radically polymerizable group, a photoinitiator group, a radical polymerization inhibitor group, nitrogen-containing heterocyclic ring as a polymer component. (However, 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”) (excluding the imide ring of the polyimide). .

As a radically polymerizable group, a (meth)acryloyl group, a vinyl group, an allyl group, a vinylphenyl group, a maleimide group, a vinyloxy group, an ethynyl group etc. are mentioned, for example. Among these, a (meth)acryloyl group is especially preferable at a point with high reactivity.

The photoinitiator group is a site that generates polymerization initiation ability by light or a site that has a photosensitizing action, and initiates polymerization of the polymerizable component by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. It is a group having a structure derived from a possible compound (photoinitiator). As a photoinitiator group, it is preferable that it is group which has a structure derived from the radical polymerization initiator which can generate|occur|produce a radical 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 group which has an acetophenone structure among these. When a polymer has at least any one of a radically polymerizable group and a photoinitiator group, it is preferable to have these groups in a side chain.

A radical polymerization inhibitor is a peroxide decomposing agent that invalidates peroxy radicals or hydroperoxides generated by energy such as ultraviolet rays or heat, or a radical trapping agent that suppresses the progress of polymerization by supplementing a radical intermediate during polymerization function as zero. By containing the polymer which has such a polymerization inhibitor group in a liquid crystal aligning film, it can suppress that the photopolymerizable compound mixed in the liquid crystal layer in PSA mode reacts by light irradiation. It is preferable that a polymerization inhibitor group is group which has at least 1 sort(s) chosen 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 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. Among these, it is preferable to have at least one selected from the group consisting of pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole and acridine.

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

(In formula (N-1), R ⁵⁰ is a hydrogen atom or a monovalent organic group. "*" is a bond bonded 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, an ethyl group, a propyl group or a butyl group; cycloalkyl groups such as a cyclohexyl group; Aryl groups, such as a phenyl group and methylphenyl; Aralkyl groups, such as a benzyl group, etc. are mentioned. Examples of the substituent R ⁵⁰ may have include a halogen atom, a cyano group, an alkylsilyl group, and an alkoxysilyl group. R ⁵⁰ is preferably an alkyl group having 1 to 5 carbon atoms, a cyclohexyl group, a phenyl group or a benzyl group. As a hydrocarbon group to which "*" in said formula (N-1) couple|bonds, an alkanediyl group, a cyclohexylene group, a phenylene group, etc. are mentioned, for example.

The protecting group is preferably a group that is released by heat, for example, a carbamate protecting group, an amide protecting group, an imide protecting group, a sulfonamide protecting group, and each of the following formulas (8-1) to (8-5) and the like that appear. Among them, a tert-butoxycarbonyl group is preferable from the viewpoint of high desorption property by heat and of reducing the amount remaining in the film of the deprotected portion.

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

Although the main skeleton of the polymer which has the said specific partial structure is not specifically limited, It is preferable that it is a [P] polymer, and it is more preferable that it is a [p] polymer. It is preferable that the content rate of the said specific partial structure in a polymer (the total amount when 2 or more types are contained) shall be 5 mol% or more with respect to all the monomer units of a polymer, and it is more preferable to set it as 10-80 mol%. desirable.

(solvent)

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

Dragon Army:

[A] Solvent: A compound represented by the following formula (1), a compound represented by the following formula (2), N,N,2-trimethylpropionamide (DMIB), and 1,3-dimethyl-2-imidazolidinone.

[B] Solvent: dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether (DME), diethylene glycol monoethyl ether, 4-methoxy-4-methyl-2-pentanone (4M4M2P), 4-hydroxy- 2-butanone (4H2B), 2-methyl-2-hexanol (2M2H), 2,6-dimethyl-4-heptanol (DIBS), diisobutyl ketone (DIBK), 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 hydrocarbon group having “-O-” between the carbon-carbon bonds of the hydrocarbon group. group, and R ² and R ³ may be bonded to each other to form a ring structure. R ⁴ is an alkyl group having 1 to 6 carbon atoms.)

・[A] About solvent

(Compound represented by Formula (1))

With respect to the compound represented by the formula (1), the ^{monovalent hydrocarbon group having 2 to 5 carbon atoms for 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 carbon-carbon bonds in the said hydrocarbon group, a C2-C5 alkoxyalkyl group is mentioned, for example.

Specific examples thereof include, as an alkyl group having 2 to 5 carbon atoms, an ethyl group, a propyl group, a butyl group, a pentyl group, and the like; Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group, 1-propenyl group, 2-propenyl group, 3-butenyl group and the like; Examples of the alkynyl group having 2 to 5 carbon atoms include ethynyl group, 2-propynyl group, 2-butynyl group and the like; Examples of the alkoxyalkyl group having 2 to 5 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, and an ethoxyethyl group. weather is good R ¹ is preferably an alkyl group having 2 to 5 carbon atoms or an alkoxyalkyl group among the above.

Specific examples of the compound represented by the formula (1) include N-ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(t-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2- pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and the like. Among these, N-ethyl-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-(t-butyl)-2-pyrrolidone, N-methoxypropyl-2-pyr Rollidone can be used particularly preferably. In addition, the compound represented by said Formula (1) can use the compound of these illustrations individually by 1 type or in combination of 2 or more type.

(Compound represented by Formula (2))

With respect to the compound represented by the formula (2), as the ^{monovalent hydrocarbon group having 1 to 6 carbon atoms for R 2} and R ³ , for example, a chain hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 5 or 6 carbon atoms. Moreover, as a monovalent group which has "-O-" between the carbon-carbon bonds of the said hydrocarbon group, a C2-C6 alkoxyalkyl group etc. are mentioned, for example.

Specific examples of these chain hydrocarbon groups include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group as the chain hydrocarbon group having 1 to 6 carbon atoms, and these may be linear or branched. Moreover, as a C3-C6 alicyclic hydrocarbon group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example; Examples of the aromatic hydrocarbon group include a phenyl group; Examples of the alkoxyalkyl group having 2 to 6 carbon atoms include the alkoxyalkyl group represented by R ¹ ; each can be heard. In addition, R<^2> and R<^3> in Formula (2) may mutually be same or different. In addition, R ² and R ³ may form a ring together with the nitrogen atom to which ^{R 2} and R ³ are bonded by bonding to each other. Examples of the ring formed by bonding 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 bonded 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 still more preferably a hydrogen atom or a methyl group.

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

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

[A] As the solvent, since the effect on the interlayer insulating film 21 can be made smaller, among them, the compound represented by the formula (1), the compound represented by the 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, 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 preferably at least one selected from the group consisting of N-dimethylpropanamide and 1,3-dimethyl-2-imidazolidinone, 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 especially preferable that it is at least 1 sort(s) chosen from the group which consists of -2- imidazolidinone.

[B] As the solvent, from the viewpoint of reducing the effect on the interlayer insulating film 21, dipropylene glycol monomethyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, It is preferable that it is at least 1 sort(s) chosen from the group which consists of diacetone alcohol and propylene glycol monobutyl ether.

As a solvent component, although only a specific solvent may be used, you may use together other solvents other than a specific solvent. Examples of such other solvents include solvents with high polymer solubility and leveling properties (hereinafter, also referred to as "first solvents") and solvents with favorable wet diffusion properties (hereinafter also referred to as "second solvents").

Specific examples of these include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, and N,N-dimethylacetamide as the first solvent. , 4-hydroxy-4-methyl-2-pentanone, ethylene carbonate (EC), 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 another solvent, 1 type in the above may be used individually, and 2 or more types may be mixed and used for it.

Preparation of a liquid crystal aligning agent WHEREIN: As a specific solvent, although either one of the [A] solvent and the [B] solvent may be used, when forming a liquid crystal aligning film, in the state which the liquid crystal aligning agent and the interlayer insulating film 21 contacted [A] at least one kind of solvent, [B] because the effect on the interlayer insulating film 21 can be suppressed and the effect of suppressing the elution of impurity components from the interlayer insulating film 21 is high; ] It is preferable that at least one kind of solvent is contained.

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

[B] Application of a liquid crystal aligning agent while suppressing the influence on the interlayer insulating film 21 and the elution of the impurity component from the interlayer insulating film 21, the usage ratio (the total amount when using 2 or more types) of a solvent It is preferable to set it as 10 mass % or more with respect to the whole quantity of the solvent contained in a liquid crystal aligning agent from a viewpoint of making property favorable, and it is more preferable to set it as 20 mass % or more. Moreover, it is preferable to set it as 80 mass % or less with respect to the whole quantity of the solvent contained in a liquid crystal aligning agent, and, as for the upper limit of the usage rate, it is more preferable to set it as 70 mass % or less. In addition, the [B] solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

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

In addition, when using the [A] solvent, [B] solvent, and other solvents, the use ratio of the other solvents (the total amount when two or more types are used) is a liquid crystal from the viewpoint of sufficiently obtaining the effect of the present disclosure. It is preferable to set it as 50 mass % or less with respect to the total amount of the solvent contained in an aligning agent, It is more preferable to set it as 30 mass % or less, It is more preferable to set it as 10 mass % or less, It is set to 5 mass % or less It is particularly preferred.

As for a liquid crystal aligning agent, it is especially preferable that a solvent component consists of a [A] solvent and a [B] solvent. However, in this specification, "a solvent component consists of [A] solvent and [B] solvent" contains other solvents other than [A] solvent and [B] solvent to such an extent that the effect of the present disclosure is not hindered. to allow to do

A liquid crystal aligning agent may contain other components other than a polymer component and a solvent component as needed. As another component, antioxidant, a metal chelate compound, a hardening accelerator, surfactant, a filler, a dispersing agent, a photosensitizer, etc. are mentioned, for example. 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.

Although the solid content concentration (the ratio which the total mass of components other than the solvent of a liquid crystal aligning agent occupies to the total mass of a liquid crystal aligning agent) in a liquid crystal aligning agent considers a viscosity, volatility, etc., Preferably it is 1- It is the range of 10 mass %. When solid content concentration is less than 1 mass %, the film thickness of a coating film becomes too small and it becomes difficult to obtain a favorable liquid crystal aligning film. On the other hand, when solid content concentration exceeds 10 mass %, the film thickness of a coating film becomes excessive and a favorable liquid crystal aligning film is hard to be obtained, and the viscosity of a liquid crystal aligning agent increases, and there exists a tendency for applicability|paintability to fall.

<Radiation-sensitive resin composition>

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

([Q] polymer)

[Q] The polymer preferably has a structural unit having a polymerizable group. [Q] It is preferable that the polymeric group which a polymer has is at least 1 sort(s) chosen from the group which consists of an oxetanyl group, an oxiranyl group, a (meth)acryloyl group, and a vinyl group. By having such a polymerizable group, hardening of a radiation-sensitive resin composition can be performed easily, and it is preferable at the point from which the favorable interlayer insulating film 21 can be obtained.

[Q] Although the main skeleton of the polymer is not particularly limited, it is preferably at least one selected from the group consisting of a (meth)acrylic polymer, polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane. Among these, it is especially preferable that it is a (meth)acrylic-type polymer. In addition, the (meth)acrylic polymer may have only the structural unit derived from the monomer which has a (meth)acryloyl group, The structural unit derived from the monomer which has a (meth)acryloyl group, and a (meth)acryloyl group You may have a structural unit derived from the other monomer different from the monomer which has The content rate of the structural unit derived from the other monomer in the (meth)acrylic polymer becomes like this. Preferably it is 50 mol% or less, More preferably, it is 40 mol% or less, More preferably, it is 30 mol% or less. .

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

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, a hydroxyalkyl group in which a hydrogen atom bonded to a carbon atom is substituted with an electron withdrawing group, etc. can be heard The acidic group is preferably 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 from the viewpoint of alkali developability, and a carboxy group or a phenolic group is preferable. A hydroxyl group is more preferable, and a carboxy group is especially 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 preferable, and at least one of (meth)acrylic acid and maleic anhydride is particularly preferable.

It is preferable that it is 1-50 mol%, and, as for the content rate of the 1st structural unit in [Q] polymer, it is more preferable that it is 15-30 mol% with respect to all the structural units which comprise the [Q] polymer. The 1st structural unit may be used individually by 1 type, or may combine 2 or more types.

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

It is preferable that it is 1-15 mol%, and, as for the content rate of the 2nd structural unit in [Q] polymer, it is more preferable that it is 3-10 mol% with respect to all the structural units which comprise the [Q] polymer. The 2nd structural unit may be used individually by 1 type, or may combine 2 or more types.

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 it can improve developing adhesion and resistance to heat and peeling solution. It is preferable that it is a structural unit derived from at least 1 sort(s) of compound selected from the group which consists of styrene, (alpha)-methylstyrene, 4-methylstyrene, and 4-hydroxystyrene from a possible point.

It is preferable that it is 25-80 mol%, and, as for the content rate of the 3rd structural unit in [Q] polymer, it is more preferable that it is 30-65 mol% with respect to all the structural units which comprise the [Q] polymer. The 3rd structural unit may be used individually by 1 type, or may combine 2 or more types.

Moreover, the [Q] polymer may further have other structural units other than a 1st structural unit, a 2nd structural unit, and a 3rd structural unit. As such a structural unit, alkyl (meth)acrylate etc. are mentioned, for example.

[Q] The polymer can be synthesized by using a monomer that provides the first to third structural units or the like, according to conventional methods such as radical polymerization. About the detail of a synthesis|combination condition, it can set suitably with reference to the various conditions of Unexamined-Japanese-Patent No. 2015-92233, for example.

([R] photosensitizer)

[R] As the photosensitizer, at least one selected from the group consisting of a radical photopolymerization initiator, a photoacid generator and a photobase generator can be preferably used.

As these specific examples, As an optical radical polymerization initiator, For example, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, etc.;

As the photoacid generator, for example, an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carbonic acid ester compound, a quinonediazide compound, etc. ;

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

[R] The use ratio of the photosensitizer changes with the kind of compound to be used. For example, in the case of a radical photopolymerization initiator, 1-40 mass parts is preferable with respect to 100 mass parts of [Q] polymers, and it is more preferable to set it as 5-30 mass parts.

0.1-50 mass parts is preferable with respect to 100 mass parts of [Q] polymers, and, as for the usage ratio of a photo acid generator, 1-30 mass parts is more preferable.

0.1-20 mass parts is preferable with respect to 100 mass parts of [Q] polymers, and, as for the usage ratio of a photobase generator, it is more preferable that it is 1-10 mass parts.

The radiation-sensitive resin composition can 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] photosensitive agent. Each of these optional components may be used individually by 1 type, and may be used in combination of 2 or more type.

A radiation-sensitive resin composition is prepared by mixing other arbitrary components mix|blended as needed other than the [Q] polymer and the [R] photosensitive agent. The radiation-sensitive resin composition is preferably dissolved in a suitable solvent and used in a solution state. 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, a ketone, ester, etc. are mentioned.

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 mass% from the viewpoint of applicability, stability, etc. of the radiation-sensitive resin composition obtained, 10 The quantity used as -40 mass % is more preferable.

(Manufacturing method of liquid crystal device 10)

The liquid crystal device 10 can be manufactured by a method including the following steps A to E.

Step A: A step of forming an interlayer insulating film 21 on a substrate.

Step B: A step of forming the pixel electrode 19 on the interlayer insulating film 21 .

Process C: A process 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 constructing a liquid crystal cell by arranging the array substrate 15 and the counter substrate 16 to face each other with a liquid crystal layer containing a photopolymerizable monomer interposed therebetween.

Process E: The process of irradiating light to a liquid crystal cell.

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, a thin film transistor 14, a scanning signal line ( 12), an image signal line 13 is formed. Next, the radiation-sensitive resin composition for forming an interlayer insulating film is applied on the thin film transistor 14 and the signal line formation surface in the transparent substrate 18 to form the interlayer insulating film 21 (Step A).

Although the application method of the radiation-sensitive resin composition is not specifically limited, For example, appropriate methods, such as the spray method, the roll coating method, the spin coating method, the slit coating method, the bar coating method, the inkjet coating method, are employable. Among these, the spin coating method or the slit coating method is preferable at the point which can form the film|membrane of uniform thickness. After application of the radiation-sensitive resin composition, the coated surface is preferably heated (pre-baked) and, if necessary, the coating film is exposed through a photomask having a predetermined pattern, followed by development and post-baking. An interlayer insulating film 21 as a film is obtained. As for various conditions for forming the interlayer insulating film 21, the conditions described in, for example, Japanese Patent Application Laid-Open No. 2015-92233 can be adopted.

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

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

At the subsequent process C, first, a liquid crystal aligning agent is apply|coated on the board|substrate with an electrode, Preferably, a coating film is formed on a board|substrate by heating an application surface. On the electrode formation surface, application|coating of the liquid crystal aligning agent to a board|substrate becomes like this. Preferably the offset printing method, the spin coating method, the roll coater method, the flexographic printing method, or the inkjet printing method is performed. After apply|coating a liquid crystal aligning agent, for purposes, such as liquid flow prevention of the apply|coated liquid crystal aligning agent, Preferably, preliminary heating (prebaking) is performed. Pre-baking temperature becomes like this. Preferably it is 30-200 degreeC, and pre-baking time becomes like this. Preferably it is 0.25 to 10 minutes. After that, the solvent is completely removed and, if necessary, a calcination (post-baking) step is performed for the purpose of thermal imidization of the amic acid structure present in the polymer. The baking temperature (post-baking temperature) at this time becomes like this. Preferably it is 80-300 degreeC, and post-baking time becomes like this. Preferably it is 5-200 minutes. Thus, the thickness of the film|membrane formed becomes like this. Preferably it is 0.001-1 micrometer. After apply|coating a liquid crystal aligning agent on a board|substrate, the coating film used as a liquid crystal aligning film or a liquid crystal aligning film is formed by removing an organic solvent.

Here, a liquid crystal aligning agent is apply|coated on the electrode formation surface of the board|substrate in which the pattern electrode (pixel electrode 19) which has many slit part 19c on the interlayer insulating film 21 was formed. Therefore, the liquid crystal aligning agent in a liquid state comes into contact with the interlayer insulating film 21 through the opening of the slit part 19c. The liquid crystal alignment film (first alignment film 32 ) formed on the substrate is in contact with the interlayer insulating film 21 through the slit portion 19c in the display region of the liquid crystal device 10 .

Moreover, although the coating film formed above may be used as a liquid crystal aligning film as it is, you may perform the process (orientation process) which provides liquid-crystal orientation ability. As the alignment treatment, for example, a rubbing treatment in which a coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, cotton, or a liquid crystal aligning agent is applied to a coating film formed on a substrate by irradiating light to the coating film The photo-alignment process etc. which provide orientation ability are mentioned.

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

The liquid crystal layer 17 drips or apply|coats a liquid crystal composition on one board|substrate to which the sealing compound was apply|coated, for example, After that, the method (ODF system) of bonding the other board|substrate, or a cell gap is interposed. The periphery of a pair of substrates arranged to face each other is joined by a sealing agent, and the liquid crystal composition is injected and filled into the substrate surface and the cell gap surrounded by the sealing agent, followed by sealing the injection hole or the like. It is preferable to remove the flow orientation at the time of liquid-crystal filling by performing the annealing process in which the liquid crystal used further heats to the temperature which takes an isotropic phase with respect to the obtained liquid crystal cell, and then cools it slowly to room temperature.

As a photopolymerizable monomer, the compound which has two or more (meth)acryloyl groups at the point with high polymerizability by light can be used preferably. Specific examples thereof include, for example, 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. It is preferable that the compounding ratio of a photopolymerizable monomer shall be 0.1-0.5 mass % with respect to the total amount of the liquid-crystal composition used for formation of the liquid-crystal layer 17. In addition, as a photopolymerizable monomer, you may use individually by 1 type, and may use it in combination of 2 or more type.

In the subsequent step E, the liquid crystal cell obtained in the step D is irradiated with light. Light irradiation to the liquid crystal cell may be performed in a state in which no voltage is applied between the electrodes, may be performed in a state in which a predetermined voltage not driven by the liquid crystal molecules in the liquid crystal layer 17 is applied, or liquid crystal molecules are driven It may be carried out in a state in which a predetermined voltage to be applied is applied between the electrodes. Preferably, light is irradiated in a state in which a voltage is applied between the electrodes of the pair of substrates. The voltage to be applied can be, for example, 5 to 50 V of direct current or alternating current. As the light to be irradiated, for example, although ultraviolet rays and visible rays containing light having a wavelength of 150 to 800 nm can be used, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. When the radiation used is linearly polarized light or partially polarized light, the light irradiation direction may be performed from a direction perpendicular to the substrate surface, may be performed from an inclined direction, or a combination thereof may be performed. When irradiating a non-polarized radiation, an irradiation direction is made into an oblique direction.

As a light source of irradiated light, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser etc. can be used, for example. In addition, the ultraviolet rays in the above 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 amount of light irradiated is preferably 1,000 to 200,000 J/m 2 , 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 in which a polarizing film called “H film” in which iodine is absorbed while stretching and oriented polyvinyl alcohol is sandwiched by a cellulose acetate protective film, or a polarizing plate composed 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. Although it is not clear why such an effect was obtained, as one reason, the specific solvent used for preparation of the liquid crystal aligning agent has a small effect on the interlayer insulating film 21, and thus the performance degradation of the interlayer insulating film 21 is suppressed. can think In particular, in the PSA technique, in order to improve the response characteristic of the MVA mode, a fine stripe-shaped electrode pattern of, for example, a few micrometers is formed. When such a fine electrode pattern is formed on a substrate, when the liquid crystal aligning agent comes into contact with the interlayer insulating film 21 and the interlayer insulating film 21 swells and the thickness of the film changes slightly, the pixel electrode 19 is also easily deformed. , it is conceivable that a decrease in device performance may be caused. In this respect, it is estimated that, according to the specific solvent, the swelling of the interlayer insulating film 21 is suppressed, so that the influence on the pixel electrode 19 can be reduced as much as possible, thereby sufficiently suppressing the decrease in device performance. Moreover, 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 to the liquid crystal aligning agent from the interlayer insulating film 21 can be suppressed, and the fall of element performance was fully suppressed by this. guessed

(Second embodiment)

Next, 2nd Embodiment is demonstrated centering on the point of difference from 1st Embodiment. This embodiment is different from the first embodiment in that the color filter layer is formed on the array substrate 15 .

3 is a cross-sectional view schematically showing a part of the device structure of the second embodiment. The liquid crystal device 10 shown in FIG. 3 has a structure in which an array substrate 15 and a counter substrate 16 are disposed to face each other with a liquid crystal layer 17 interposed therebetween, similarly to the liquid crystal device of the first embodiment. The array substrate 15 includes a TFT 14 on a transparent substrate 18 , and a color filter layer 29 including a coloring pattern 29a and an interlayer insulating film 29b . The coloring pattern 29a is constituted by 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 protecting the coloring pattern 29a and forming the pixel electrode 19 exhibiting excellent characteristics. The pixel electrode 19 is disposed on the interlayer insulating film 29b.

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

(Other embodiment)

- 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 the pattern electrode. A pattern electrode and an interlayer insulating film may be formed also 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 use as various display apparatuses, such as a mobile phone, a smart phone, various monitors, a liquid crystal TV, and an information display, a light control apparatus, etc.

Example

EXAMPLES Hereinafter, although embodiment of this invention is described in more detail based on an Example, this invention is not interpreted limitedly by a 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 methods.

[Imidation rate of polyimide]

The polyimide solution was poured into pure water, and the resulting precipitate was dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ^<1> H-NMR spectrum, the imidation rate [%] was calculated|required by following formula (1).

Imidization ratio [%] = (1-(A ¹ /(A ² ×α))) × 100 … (One)

(In formula (1), A ¹ is the peak area derived from protons of the NH group appearing in the vicinity of 10 ppm of the chemical shift, A ² is the peak area derived from other protons, and α is the 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]

A weight average molecular weight is a polystyrene conversion value measured by the gel permeation chromatography in the following conditions.

Column: TSKgelGRCXLII manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40℃

Pressure: 68kgf/cm2

[epoxy equivalent]

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

The abbreviation used in the following examples is shown. In addition, below, the compound represented by Formula X may be simply represented as "compound X".

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

(1) Synthesis of [Q] polymer

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

8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were charged to a flask provided with a cooling tube and a stirrer. 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 are added, and after nitrogen substitution, the temperature of the solution is raised to 70 ° C. while gradually stirring. , a solution containing a polymer (Q-1) was obtained by polymerization by holding the temperature for 5 hours. The Mw of the polymer (Q-1) was 8000.

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

8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were charged to a flask provided with a cooling tube and a stirrer. 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 parts by mass of n-lauryl methacrylate After adding part and nitrogen substitution, the temperature of the solution was raised to 70 degreeC, stirring slowly, and the solution containing the polymer (Q-2) was obtained by superposing|polymerizing by holding|maintaining this temperature for 5 hours. The Mw of polymer (Q-2) was 8000.

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

8 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were charged to a flask provided with a cooling tube and a stirrer. 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, and nitrogen After substitution, the temperature of the solution was raised to 70° C. while stirring slowly, and polymerization was carried out by holding this temperature for 5 hours to obtain a solution containing a polymer (Q-3). The Mw of polymer (Q-3) was 8000.

(2) Preparation of radiation-sensitive resin composition

[Preparation Example 1]

To a solution containing the polymer (Q-1) obtained in Synthesis Example 1 (an amount equivalent to 100 parts by mass (solid content) of the polymer (Q-1)), 1,2-octanedione 1-[4-(phenyl) Thio)-2-(O-benzoyloxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF) was added in 20 parts by mass, and further a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD (trademark) DPHA, the Nippon Kayaku company make) 100 mass parts was added, and it mixed. After adding and dissolving diethylene glycol ethyl methyl ether so that solid content concentration might be set to 30 mass %, it filtered with the membrane filter of diameter 0.2 micrometer, and the radiation-sensitive resin composition (V-1) was prepared.

[Preparation Examples 2 to 4]

The radiation-sensitive resin compositions (V-2) to (V-4) were prepared in the same manner as in Preparation Example 1, except that the compounding composition was changed as described in Table 1 below. In addition, in following Table 1, "-" means that the said component is not mix|blended (the same also about the following table|surface).

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 moles)

U-1: mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku)

2. Synthesis of polymer (for liquid crystal aligning agent)

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

100 mol parts of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, 20 mol parts of cholestanyloxy-2,4-diaminobenzene as diamine, 50 mol parts of 3,5-diaminobenzoic acid And 30 mol parts of compound (d-8) were melt|dissolved in N-methyl- 2-pyrrolidone (NMP), it reacted at room temperature for 6 hours, and the solution containing 20 mass % of polyamic acids was obtained. Then, pyridine and acetic anhydride were added to the obtained polyamic acid solution, and chemical imidation was performed. The reaction solution after chemical imidation was concentrated, and it prepared with NMP so that a density|concentration might be 10 mass %. The imidation ratio of the obtained polyimide (referred to as polymer (PI-1)) was about 75%.

[Synthesis Examples 6 to 8]

A polyimide (polymer (PI-2) to polymer (PI-4)) was synthesized in the same manner as in Synthesis Example 5 except that the types and amounts of tetracarboxylic dianhydride and diamine to be used were changed as shown in Table 2 below. In addition, in Table 2, the numerical value in parentheses shows the usage ratio [molar part] of each compound with respect to a total of 100 molar parts of tetracarboxylic dianhydride used for the synthesis|combination of a polymer.

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

70 mole parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 30 mole parts of 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and cholestanyloxy- as diamine 20 mole parts of 2,4-diaminobenzene, 30 mole parts of compound (d-12), 40 mole parts of 4,4'-diaminodiphenylmethane, and 4,4'-[4,4'-propane-1,3- 10 mol parts of diylbis(piperidine-1,4-diyl)]dianiline were dissolved in NMP, and reaction was performed at room temperature for 6 hours to obtain a solution containing 20% by mass of polyamic acid. The polyamic acid obtained here was used as a polymer (PAA-1).

[Synthesis Example 10]

Polyamic acid (referred to as polymer (PAA-2)) was synthesized in the same manner as in Synthesis Example 9 except that the types and amounts of tetracarboxylic dianhydride and diamine to be used were changed as shown in Table 2 below.

[Synthesis Example 11]

100 g of compound (s-1), 500 g of methyl isobutyl ketone, and 10 g of triethylamine were put into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, and the mixture was mixed at room temperature. Next, 100 g of deionized water was added dropwise in a dropping funnel over 30 minutes, followed by reaction at 80°C for 6 hours while stirring under reflux. After completion of the reaction, the organic layer is taken out, washed with a 0.2 mass % aqueous ammonium nitrate solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to obtain reactive polyorganosiloxane (ESSQ-1) was obtained as a viscous transparent liquid. ^{As a result of performing 1} H-NMR analysis on this reactive polyorganosiloxane, a peak based on an epoxy group was obtained around a chemical shift (δ) = 3.2 ppm, and it was confirmed that a side reaction of the epoxy group did not occur during the reaction. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane (ESSQ-1) was 3000, and the epoxy equivalent was 190 g/mol.

[Synthesis Examples 12 and 13]

A reactive polyorganosiloxane (polymer (ESSQ-2) and polymer (ESSQ-3)) was synthesized in the same manner as in Synthesis Example 11 except that the type and amount of the monomer to be used was 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 a total of 100 molar parts of the monomer used for the synthesis|combination of a polymer.

[Synthesis Example 14]

In a 500 mL three-neck flask, 10.0 g of reactive polyorganosiloxane (ESSQ-1), 300 g of methyl isobutyl ketone as a solvent, 16 g of compound (c-1) and 16 g of compound (c-3) as a modified component, 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 with water 3 times, the organic layer was dried using magnesium sulfate, and then the solvent was distilled off to obtain 75 g of polymerizable group-containing polyorganosiloxane (PSQ-1). . The weight average molecular weight Mw of the obtained polymer was 6000.

[Synthesis Examples 15 and 16]

Polymerizable group-containing polyorganosiloxane (polymer (PSQ-2) and polymer (PSQ-3) in the same manner as in Synthesis Example 14 except that the types and amounts of reactive polyorganosiloxane and modified components used were changed as shown in Table 4 below. )) was synthesized. In Table 4, the numerical value in parentheses shows the use ratio [molar part] of each compound with respect to a total of 100 molar parts of the monomer used for the synthesis|combination of a polymer.

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

[Example 1]

(1) Preparation of liquid crystal aligning agent

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

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

With respect to 10 g of nematic liquid crystal (Merck Corporation, MLC-6608), the compound represented by the following formula (RM-1) is added so that 0.3 mass % of the total amount of the total constituents of the liquid crystal composition is added and mixed to form a liquid crystal composition (LC-1) was obtained.

(3) Manufacture of liquid crystal display element

After apply|coating the radiation-sensitive resin composition (V-1) on a glass substrate ("Corning 7059" (made by Corning)) using a spinner, prebaking is performed in 90 degreeC clean oven for 10 minutes, and a glass substrate A coating film having a thickness of 2.0 µm was formed thereon, respectively. Next, using a UV (ultraviolet) exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ), 100 mJ of UV light was irradiated through a pattern mask. Then, using the tetramethylammonium hydroxide aqueous solution (developing solution) of the density|concentration of 2.38 mass %, the developing process for 100 second was performed by the puddle method at 25 degreeC. After the development treatment, the coating film was washed in running water for 1 minute with ultrapure water, dried to form a patterned coating film on the substrate, and then cured by heating (post-baking) in an oven at 230° C. for 30 minutes. Next, using Canon Co., Ltd. product PLA-501F exposure machine (ultra-high pressure mercury lamp), it exposed at the exposure amount of 500 J/m<2> to the whole surface of each coating film without interposing a photomask. Then, it post-baked at 230 degreeC for 30 minutes, each coating film was hardened, and the interlayer insulating film was formed.

Next, on the glass substrate on which the interlayer insulating film was formed, the ITO electrode patterned in the shape of a fishbone was formed. In this Example, the electrode pattern of the ITO electrode was made into the fishbone shape of line/space = 3.5 micrometers/3.5 micrometers. The electrode pattern of the ITO electrode used here was shown in FIG. Moreover, the glass substrate which has an ITO electrode which does not have a pattern was prepared by performing similar 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 having no pattern.

Then, after spin coating the liquid crystal aligning agent (W-1) on each electrode formation surface of a pair of substrates, heating (pre-baking) for 1 minute on a hot plate at 80° C. to remove the solvent, and then, It heated (post-baking) for 15 minutes on a 230 degreeC hotplate, and formed the coating film with an average film thickness of 100 nm. About this coating film, after performing ultrasonic cleaning for 1 minute in ultrapure water, it dried for 10 minutes in 100 degreeC clean oven, and obtained a pair of board|substrates which have a liquid crystal aligning film.

Next, an epoxy resin adhesive having an aluminum oxide sphere having a diameter of 5.5 μm is applied to the outer edge of the ITO surface of the glass substrate having a patterned ITO electrode, and then, on the inner surface of the epoxy resin adhesive, a liquid crystal composition (LC-1) was added dropwise at 6 points (2 points vertically x 3 points horizontally, the interval between each point was 10 mm, up and down, left and right, and the application amount of each point was 0.6 mg). The liquid crystal cell was manufactured by superimposing and crimping|bonding this board|substrate so that this board|substrate and another glass board|substrate might oppose, and hardening|curing the adhesive agent. About the obtained liquid crystal cell, the liquid crystal cell for evaluation was produced by performing ultraviolet irradiation and annealing according to "PSA process-1" mentioned later.

(PSA Process-1)

With respect to the liquid crystal cell, an alternating current of 20 Vpp with a frequency of 60 Hz is applied between the electrodes, and in a state in which the liquid crystal is driven, an ultraviolet irradiation device using a metal halide lamp as a light source is used to irradiate an ultraviolet ray of 80 mW for 50 seconds. Then, in the state in which no voltage is applied, 3.5 mW ultraviolet-ray is irradiated for 30 minutes using the ultraviolet irradiation apparatus which used the metal halide lamp as a light source.

Finally, a liquid crystal cell is put into a 120 degreeC clean oven for 10 minutes, and it anneals. In addition, the irradiation amount is the value measured using the photometer measured with wavelength 365nm reference|standard.

(4) Evaluation of voltage retention ratio (VHR)

The liquid crystal cell for evaluation prepared in (3) above is placed in a thermostat, and a voltage of 5 V is applied at 60° C. with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage retention rate (VHR) 167 milliseconds after the application is released. ) was measured by "VHR-1" manufactured by Toyo Technica. At this time, a case where the VHR was 96% or higher was “very good (◎)”, a case where the VHR was 93% or more and less than 96% was “good (○)”, and a case where the VHR was 90% or more and less than 93% was “possible (Δ)”. , the case where it was less than 90 % was evaluated as "defect (x)". As a result, in this Example, VHR = 97%, and evaluation was "very good (double-circle)".

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

Except for having changed the kind and quantity of the polymer and solvent to be used like following Table 5, operation similar to the above was performed, and the liquid crystal aligning agent was prepared, respectively. In addition, except that the radiation-sensitive resin composition used for preparation of the interlayer insulating film was changed to the composition shown in Table 5 below, and the liquid crystal aligning film was produced using the liquid crystal aligning agent prepared in each example, it was carried out in the same manner as above for evaluation While manufacturing the 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 compounding ratio [mass part] of each polymer with respect to a total of 100 mass parts of the polymer component used for preparation of a liquid crystal aligning agent. The numerical value of the solvent composition column shows the compounding ratio [mass part] of each compound with respect to all 100 mass parts of the solvent used for preparation of a liquid crystal aligning agent. The abbreviation of the solvent is as follows (the same is true for 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, Comparative Example 1 in which a liquid crystal aligning film was formed using the liquid crystal aligning agent which does not contain a specific solvent in Examples 1-22 which formed the liquid crystal aligning film using the liquid crystal aligning agent containing a specific solvent The liquid crystal display element excellent in 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, it was evaluation of "very favorable", and was especially excellent.

In Examples 1-22, except that the pattern of the ITO electrode of the glass substrate was changed to the pattern shown in Fig. 5, a liquid crystal display element was manufactured and evaluated in the same manner as above, and as a result, in any Example The effect similar to the above was acquired.

[Example 23]

(1) Evaluation of ITO wiring strain

N-ethyl-2-pyrrolidone (NEP) and diethylene glycol diethyl ether (DEDG) are mixed and thoroughly stirred, and the solvent composition is NEP: DEDG = 50: 50 (mass ratio) evaluation solvent (Z-1) ) was prepared.

Further, by performing the same operation as in (3) of Example 1, a glass substrate in which a pattern electrode made of ITO was disposed on the interlayer insulating film was prepared. This glass substrate was immersed in 80 degreeC solvent (Z-1) for evaluation for 30 minutes, and the criteria shown below evaluated the swelling degree of an interlayer insulating film and the deformation|transformation degree of an ITO electrode. When the liquid crystal aligning agent is brought into contact with the solvent component, the smaller the swelling of the interlayer insulating film and the smaller the deformation of the electrode, the less the influence of the solvent on the interlayer insulating film and the ITO electrode, and the reliability of the liquid crystal element can be ensured, so that the liquid crystal It can be said that it is suitable as a solvent for an aligning agent. As a result, this Example was evaluated as "A".

(Evaluation standard)

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

B: Swelling of the interlayer insulating film is seen, but there is no abnormality in the electrode

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

D: Serious abnormalities such as disconnection of electrodes due to swelling of the interlayer insulating film

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

Except for changing the solvent composition and the type of the radiation-sensitive resin composition to be used as shown in Table 6 below, the same operation as above was performed, and ITO wiring strain was evaluated for each solvent. The results are shown in Table 6 below.

From the results in Table 6, in Examples 23 to 44 in which the specific solvent was used, swelling of the interlayer insulating film was not observed, or even if it swelled, the degree was small, and no abnormality of the electrode was observed. From these results, according to the specific solvent, even when a liquid crystal aligning film was formed on the electrode pattern of fine stripe shape, it turned out that the shape of an electrode is hard to change, and the reliability of a liquid crystal element can be ensured.

1: ITO electrode
2: slit part
3: light shield
10: liquid crystal device
14: thin film transistor
15: array substrate
16: opposing substrate
17: liquid crystal layer
19: pixel electrode
19c: slit part
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, the method comprising:
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 patterned electrode on the interlayer insulating film;
On the pattern electrode, comprising the step of forming a liquid crystal alignment film so as to contact at least a portion of the interlayer insulating film,
The interlayer insulating film is formed using a radiation-sensitive resin composition containing a [Q] polymer and a [R] photosensitizer,
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 an agent that forms a main chain structure different from the first structural unit and the second structural unit a polymer having 3 structural units,
The first structural unit is a structural unit derived from at least one compound selected from the group consisting of (meth)acrylic acid and unsaturated carboxylic acid anhydride,
The second structural unit is, (meth)acrylic acid glycidyl, (meth)acrylic acid 3,4-epoxycyclohexylmethyl, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3-(meth)acryl a structural unit derived from at least one compound selected from the group consisting of royloxymethyl-3-ethyloxetane;
The manufacturing method of the liquid crystal element which forms the said liquid crystal aligning film using the liquid crystal aligning agent containing a polymer component and the at least 1 sort(s) of solvent chosen from the solvent group shown below.
Dragon Army:
[A] Solvent: a compound represented by the following formula (1), a compound represented by the following formula (2), N,N,2-trimethylpropionamide, and 1,3-dimethyl-2-imidazolidinone
[B] Solvent: dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, 4-methoxy-4-methyl-2-pentanone, 4-hydroxy-2-butanone, 2 -Methyl-2-hexanol, 2,6-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 the 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 hydrocarbon group having “-O-” between the carbon-carbon bonds of the hydrocarbon group. group, and R ² and R ³ may be bonded to each other to form a ring structure; R ⁴ is an alkyl group having 1 to 6 carbon atoms) According to claim 1,
The liquid crystal element further comprising the step of forming an orientation control layer for controlling the orientation of the liquid crystal in the liquid crystal layer on the interface on each substrate side in the liquid crystal layer by polymerizing the photopolymerizable monomer mixed in the liquid crystal layer. manufacturing method. According to claim 1,
The manufacturing method of the liquid crystal element in which the said liquid crystal aligning agent contains at least 1 type of the said [A] solvent, and at least 1 type of the said [B] solvent. 4. 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) chosen from the group which consists of polyamic acid, polyamic acid ester, a polyimide, and polyorganosiloxane, The manufacturing method of a liquid crystal element. 4. The method according to any one of claims 1 to 3,
The liquid crystal aligning agent contains at least one [p] polymer selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide,
The method for producing a liquid crystal device, wherein the polymer [p] has a partial structure derived from a tetracarboxylic acid derivative having at least one ring structure selected from the group consisting of a cyclobutane ring, a cyclopentane ring and a cyclohexane ring. 4. The method according to any one of claims 1 to 3,
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 (however, excluding the imide ring of the polyimide), an amino group, and a protected amino group The manufacturing method of the liquid crystal element containing the polymer which has 1 type. 4. The method according to any one of claims 1 to 3,
The manufacturing method of a liquid crystal element in which the said liquid crystal aligning agent contains the polymer which has a partial structure represented by 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 (provided that 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 (provided that 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} " is a group with 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, or a fluoroalkoxy group having 1 to 18 carbon atoms. , or a C17-C51 hydrocarbon group having a steroid skeleton, and may have a radical polymerizable group or a photoinitiator group, provided that R ¹⁴ is a hydrogen atom, a fluorine atom or a group having 1 to 3 carbon atoms, R ¹¹ , R ^{All of 12} and R ¹³ do not form a single bond; "*" indicates that it is a bond) 4. The method according to any one of claims 1 to 3,
A method for manufacturing a liquid crystal element, wherein a liquid crystal driving element and a color filter layer are formed on a substrate on which the interlayer insulating film is formed. delete 4. The method according to any one of claims 1 to 3,
The method for producing a liquid crystal element, wherein the [Q] polymer has at least one selected from the group consisting of a (meth)acryloyl group and a vinyl group. 4. The method according to any one of claims 1 to 3,
The said [R] photosensitizer is at least 1 sort(s) selected from the group which consists of a radical photopolymerization initiator, a photoacid generator, and a photobase generator, The manufacturing method of the liquid crystal element. delete delete delete 4. The method according to any one of claims 1 to 3,
The method for manufacturing a liquid crystal device, wherein 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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