TW201928478A - Method for manufacturing liquid crystal element - Google Patents

Abstract

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

Description

Manufacturing method of liquid crystal element

[Cross Reference to Related Applications]
This application is based on Japanese Patent Application No. 2017-223114 filed on November 20, 2017, and the contents thereof are incorporated herein by reference.

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

As a liquid crystal device, a Twisted Nematic (TN) type, a Super Twisted Nematic (STN) type, or the like is known and a nematic liquid crystal having positive anisotropy of dielectric properties is used. Various devices such as a horizontal alignment mode, a vertical alignment (VA) type liquid crystal device using a homeotropic alignment mode using nematic liquid crystals with negative dielectric characteristics and anisotropy. In addition, lateral electric field modes such as an in-plane switching (IPS) type and a fringe field switching (FFS) type having a unit structure provided with a pair of electrodes on one substrate are also known. LCD device.

As one of the alignment processing methods of a liquid crystal element, a polymer stabilized alignment (PSA) method is known (for example, refer to patent document 1). The PSA method is a technique in which a photopolymerizable monomer is mixed in advance with a liquid crystal in a gap between a pair of substrates to construct a liquid crystal cell, and then the photopolymerizable monomer is polymerized by irradiating ultraviolet rays while applying a voltage between the substrates. Thus, a polymer layer is formed, and the initial alignment of the liquid crystal is controlled by using the polymer layer. With this technology, the field of view can be enlarged and the response of the liquid crystal molecules can be increased, so that the problems of insufficient transmittance and contrast in a multi-domain vertical alignment (MVA) panel can be eliminated.

In addition, Patent Document 1 discloses a case where, in the PSA technology, a pattern is formed so as to form a comb-shaped package (also called a fish bone shape) having a large number of openings (slit portions). The formed pattern electrode is used as a pixel electrode. In the liquid crystal device of Patent Document 1, a drain busline is formed on a glass substrate on the array substrate side, and an interlayer insulating film is formed thereon. In addition, a fishbone-shaped pixel electrode is formed on the interlayer insulating film, and a liquid crystal alignment film is formed on the pixel electrode. The liquid crystal alignment film is generally prepared by dissolving a polymer component such as polyamic acid or polyimide, polyorganosiloxane, (meth) acrylic polymer, polyamine in a solvent, and dissolving the polymer. The composition is formed by coating a substrate and removing a solvent.
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-149647

[Problems to be Solved by the Invention]
When a pattern electrode having a large number of slits is arranged on the interlayer insulating film, and a liquid crystal alignment film is formed thereon, in a pixel region (ie, a display region) of the liquid crystal device, the liquid crystal alignment agent and the interlayer insulating film may Contact in the slit part. In this case, there are concerns that the interlayer insulating film is affected by the liquid crystal alignment agent and its characteristics are changed, or that the impurity components and the like contained in the interlayer insulating film are dissolved in the liquid crystal alignment agent and the performance of the liquid crystal alignment film is reduced. The reliability is reduced.

This invention is made in view of the said subject, and one of the objective is to provide the manufacturing method of a liquid crystal element, which can be obtained by sequentially forming an interlayer insulation film and a pattern electrode, and a liquid crystal alignment film on a board | substrate. A liquid crystal element with excellent reliability in the element structure.
[Means for solving problems]

The present invention adopts the following means in order to solve the above-mentioned problems.

<1> A method for manufacturing a liquid crystal element, the liquid crystal element comprising a pair of substrates disposed opposite to each other, a liquid crystal layer disposed between the pair of substrates, and a pair of electrodes, at least one of the pair of electrodes As a pattern electrode having a plurality of openings, the method for manufacturing a liquid crystal element includes: a step of forming an interlayer insulating film on at least one of the pair of substrates; and forming a pattern electrode on the interlayer insulating film. A step of forming a liquid crystal alignment film on the pattern electrode so as to be in contact with at least a part of the interlayer insulating film, using at least one selected from the group consisting of a solvent and a polymer component A liquid crystal alignment agent to form the liquid crystal alignment film.
Solvent group:
[A] Solvent: a compound represented by the following formula (1), a compound represented by the following formula (2), N, N, 2-trimethylpropanamine, and 1,3-dimethyl-2 -Imidazolidone.
[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, diisoamyl ether, diacetone alcohol , And propylene glycol monobutyl ether.
[Chemical 1]



(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)
[Chemical 2]



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

According to the above configuration, even when the interlayer insulating film is in contact with the liquid crystal alignment agent in the opening portion of the pattern electrode when the liquid crystal alignment film is formed, the performance of the interlayer insulation film or the liquid crystal alignment film is not easily reduced, and a liquid crystal element having excellent reliability can be obtained .

Hereinafter, embodiments will be described with reference to the drawings. In each of the following embodiments, the same or equivalent parts are denoted by the same reference numerals in the drawings, and the descriptions of the parts having the same reference numerals are referred to each other.

(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 portion of the liquid crystal device 10, a plurality of pixels 11 are arranged in a matrix. As shown in FIG. 1, the pixels 11 are formed in an area surrounded by the scanning signal lines 12 and the image signal lines 13 crossing each other. A thin film transistor (TFT) 14 that functions as a liquid crystal driving element is disposed in each pixel 11. As shown in FIG. 2, the liquid crystal device 10 includes an array substrate 15, an opposing substrate 16, and a liquid crystal layer 17.

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

The pixel electrode 19 is formed of a transparent conductor such as indium tin oxide (ITO). As shown in FIG. 1, the pixel electrode 19 is a pattern electrode in which a plurality of slits (slender rectangular openings) 19 c are provided on a planar electrode. Specifically, the pixel electrode 19 includes a main line portion 19a extending in two directions orthogonal to each other, a plurality of branch line portions 19b extending from the main line portion 19a in an oblique direction, and a plurality of branch line portions 19b formed in the plurality of branch line portions 19b. The plurality of slit portions 19c therebetween has a repeated pattern of conductive portions and non-conductive portions. The pixel electrode 19 is electrically connected to the thin film transistor 14. The thin film transistor 14 is electrically connected to the scanning signal line 12 and the image signal line 13 so as to be supplied with various signals.

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

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

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

The array substrate 15 and the opposing substrate 16 are arranged so that a predetermined gap (cell interval) is provided so that the alignment film forming surface of the array substrate 15 and the alignment film forming surface of the opposing substrate 16 face each other. The peripheral edge portions of the pair of substrates disposed opposite to each other are bonded together with a sealant (not shown). As the material of the sealant, a material known as a sealant for a liquid crystal device (for example, a thermosetting resin or a photocurable resin) can be used. A liquid crystal composition is filled in a space surrounded by the array substrate 15, the opposing substrate 16, and the sealant, whereby a liquid crystal layer 17 is disposed so as to be in contact with the first alignment film 32 and the second alignment film 33.

The liquid crystal layer 17 has a negative dielectric anisotropy. The liquid crystal layer 17 includes a PSA layer 34 and a PSA layer 35 as a polymer layer at an interface with the array substrate 15 and an interface with the opposing substrate 16, respectively. The PSA layer 34 and the PSA layer 35 are formed by photopolymerizing a photopolymerizable monomer previously mixed into the liquid crystal layer 17 and preliminarily aligning the liquid crystal molecules after the liquid crystal cell is constructed. 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 layer 34 and the PSA layer 35.

In the liquid crystal device 10, a polarizing plate 36 and a polarizing plate 37 are arranged outside each of the array substrate 15 and the opposing substrate 16. A terminal region is provided in an outer edge portion of the array substrate 15. A driver integrated circuit (IC) or the like for driving liquid crystal is connected to the terminal region to drive the liquid crystal device 10.

＜ Liquid crystal alignment agent ＞
Next, a liquid crystal alignment agent for forming a liquid crystal alignment film (a first alignment film 32 and a second alignment film 33) will be described. The liquid crystal alignment agent contains a polymer component and a solvent component.

(Polymer composition)
The main skeleton of the polymer contained in the liquid crystal alignment agent is not particularly limited, and examples thereof include polyamic acid, polyamidate, polyimide, polyorganosiloxane, polyester, and cellulose. Main skeletons such as derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylic polymers. Among these, at least one polymer (hereinafter also referred to as [P] polymerization) selected from the group consisting of polyamidic acid, polyamidate, polyimide, and polyorganosiloxane is preferred. Thing). In the preparation of the liquid crystal alignment agent, as the polymer, one kind may be used alone, or two or more kinds may be used in combination. In this specification, "(meth) acrylic acid" means the meaning of "acrylic acid" and "methacrylic acid."

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

(Polyamic acid)
Examples of the tetracarboxylic dianhydride used in the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. As specific examples of these, examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, and the like;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid. Acid dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3- Furyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione- 6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene -1,2-dicarboxylic anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride, cyclohexanetetracarboxylic dianhydride, cyclopentane Alkanetetracarboxylic dianhydride, etc .;
Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, and p-phenylene bis (trimellitic acid monoester). Anhydride), ethylene glycol bis (trimellitic anhydride ester), 1,3-propanediol bis (trimellitic anhydride ester), etc., in addition to the tetracarboxylic acid di described in Japanese Patent Laid-Open No. 2010-97188 anhydride. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

The tetracarboxylic dianhydride used in the synthesis preferably contains an alicyclic tetracarboxylic dianhydride in terms of making the obtained polymer more soluble in a solvent, and more preferably includes a cyclic structure having the following ring structure. Tetracarboxylic dianhydride (hereinafter also referred to as "specific tetracarboxylic dianhydride"): the ring structure is at least one selected from the group consisting of a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring One. The use ratio of the specific tetracarboxylic dianhydride is preferably 10 mol% or more, more preferably 20 mol% to 100 mol% with respect to the total amount of tetracarboxylic dianhydride used in the synthesis of polyamic acid. .

Examples of the diamine used in the synthesis of polyamic acid include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, and a diamine organosiloxane. Specific examples of the aliphatic diamine include m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine, and 1,3-bis (amine). Methyl) cyclohexane; etc .; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and the like;
Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diamine Diphenyl ether, 1,3-bis (4-aminophenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 9,9-bis (4-aminophenylbenzene) ) Fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4 '-(p-phenylene diisopropylidene) bisaniline, 1,4 -Bis (4-aminophenoxy) benzene, 2,6-diaminopyridine, 3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) benzidine, 1 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, bile Cholestanyloxy-3,5-diaminobenzene, Cholestanyloxy-3,5-diaminobenzene, Cholestanyloxy-3,5-diaminobenzene, Cholestane Cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate stanyl 3,5-diaminobenzoate), cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5 -diaminobenzoate), 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminobenzoyloxy) cholestane, 4- (4'-trifluoromethoxybenzene Formamyloxy) 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-diene Propylaniline, 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 (piperidine-1) , 4-diyl)] diphenylamine, 2-propynyloxy-2,4-phenylenediamine and the following formula (D-1)
[Chemical 3]



(In formula (D-1), X ^I and X ^II are each independently a single bond, -O-, * -COO-, * -OCO-, or * -NH-CO- (wherein, "*" Bond and diaminophenyl bond), R ^I and R ^II are each independently an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, and c is 1 to 20 Integer, n is 0 or 1, m is 0 or 1, where a and b will not be 0 at the same time, and n is 0 when X ^I is * -NH-CO-)
Represented compounds, etc .;
Examples of the diamine-based organosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisilaxane, etc. In addition, Japanese Patent Laid-Open No. 2010-97188 can also be used As described in Diamine. When synthesizing polyphosphonic acid, diamines can be used alone or in combination of two or more.

Polyamic acid can be obtained by reacting the tetracarboxylic dianhydride and diamine as described above together with a molecular weight adjuster as necessary. The use ratio of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine and the acid anhydride group of the tetracarboxylic dianhydride becomes 0.2 to 2 equivalents. proportion. 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; phenyl isocyanate and isocyanate Monoisocyanate compounds such as acid naphthyl esters and the like. The use ratio of the molecular weight modifier is preferably 20% by mass or less based on the total amount of the tetracarboxylic dianhydride and diamine used.

The synthesis reaction of the 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 hour to 24 hours.
Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The preferred organic solvent is preferably selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfonium, One or more of a group consisting of γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol, halogenated phenol, and a specific solvent described later as a solvent, or use this A mixture of one or more of these with other organic solvents (eg, butyl cellosolve, diethylene glycol diethyl ether, etc.). The used amount of the organic solvent is preferably an amount of 0.1 to 50% by mass based on the total amount of the tetracarboxylic dianhydride and diamine relative to the total amount of the reaction solution. In this manner, a reaction solution obtained by dissolving polyamidic acid can be obtained. The reaction solution can be directly used in the preparation of the liquid crystal alignment agent, or the polyamic acid contained in the reaction solution can be isolated and then used in the preparation of the liquid crystal alignment agent.

(Polyimide)
The polyfluorene imine can be obtained, for example, by dehydrating and ring-closing the polyphosphonium acid synthesized as described above and fluorinating the fluorene. The polyamidoimide may be a complete phosphonium imide obtained by dehydrating and ring-closing all the phosphoamidate structures of the polyamidic acid as a precursor thereof, or may be a dehydration and ring-closing only a part of the phosphonium structure Part of the phosphonium imine compound in which the phosphonium acid structure and the phosphonium imine ring structure coexist. The polyfluorene imine preferably has a fluorinated imidization rate of 30% or more, more preferably 40% to 99%, and still more preferably 60% to 99%. This fluorene imidization ratio is a percentage which expresses the ratio of the number of fluorene imine ring structures with respect to the sum of the number of fluorene acid structures of fluorene and the number of fluorene imine structures. Here, a part of the fluorene imine ring may be an isofluorene ring.

Dehydration ring closure of polyamic acid is preferably performed by dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. In this method, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The used amount of the dehydrating agent is preferably 0.01 mol to 20 mol with respect to 1 mol of the fluoric acid structure of the polyamic acid. Examples of the dehydration ring-closing catalyst include tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine. The used amount of the dehydration closed-loop catalyst is preferably set to 0.01 to 10 mol based on 1 mol of the dehydrating agent used. Examples of the organic solvent used include organic solvents exemplified as users of synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 ° C to 180 ° C, and the reaction time is preferably 1.0 hour to 120 hours. The obtained reaction solution can be directly used for the preparation of the liquid crystal alignment agent, or the polyamic acid can be used for the preparation of the liquid crystal alignment agent after being isolated.

(Polyurethane)
The polyamidate can be obtained, for example, by the following methods: [I] a method of reacting the polyamino acid obtained by the above reaction with an esterifying agent; [II] a tetracarboxylic diester and a diamine Method of reaction; [III] A method of reacting a tetracarboxylic diester dihalide with a diamine, and the like. Here, examples of the esterifying agent of the above [I] include methanol and ethanol. The tetracarboxylic acid diester used in the above [II] can be obtained by ring-opening the 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 an appropriate chlorinating agent such as thionyl chloride. The obtained polyamidate may have only a pseudoamidate structure, or may be a partial esterified product in which a pseudoamidate structure and a pseudoamidate structure coexist. The reaction solution obtained by dissolving the polyamidate can be directly used for the preparation of the liquid crystal alignment agent, or the polyamidate contained in the reaction solution can be isolated and used for the preparation of the liquid crystal alignment agent.

The polyamidic acid, polyamidate, and polyimide obtained in the above manner are preferably those having a solution viscosity of 10 mPa · s to 800 mPa · s when the solution is made into a solution having a concentration of 10% by mass. , More preferably a solution viscosity of 15 mPa · s to 500 mPa · s. The solution viscosity (mPa · s) of the polymer is a concentration of 10% by mass based on a good solvent (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer. The polymer solution was measured at 25 ° C using an E-type rotational viscometer. As for polyamic acid, polyamic acid ester, and polyimide, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 500 to 100,000, and more preferably It is preferably 1,000 to 50,000.

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

Examples of the hydrolyzable silane compound used in the synthesis of polyorganosiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyl Alkoxysilane compounds such as trimethoxysilane, phenyltriethoxysilane, trimethoxysilylpropylsuccinic anhydride, dimethyldimethoxysilane, and dimethyldiethoxysilane; 3-mercapto Propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-fluorenylpropyltrimethoxysilane, 3-amino group Nitrogen and sulfur-containing alkoxysilane compounds such as propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (3-cyclohexylamino) propyltrimethoxysilane; 3-shrink Glyceryloxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy ring Hexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and other epoxy-containing silane compounds; 3- (meth) propylene Oxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, ethylene Unsaturated bond-containing alkoxysilane compounds such as trimethoxysilane and p-styryltrimethoxysilane. The hydrolyzable silane compound may be used alone or in combination of two or more thereof. In addition, in this specification, "(meth) acryl 醯 ~" means the meaning which contains "acryl 醯 ~" and "methacryl 醯 ~."

The hydrolysis and condensation reaction are carried out by reacting one or two or more of the silane compounds as described above with water, preferably in the presence of a suitable catalyst and an organic solvent. During the reaction, the use ratio of water is preferably 1 mol to 30 mol relative to the silane compound (total amount). Examples of the catalyst to be used include acids, alkali metal compounds, organic bases (such as triethylamine or tetramethylammonium hydroxide), titanium compounds, zirconium compounds, and the like. The amount of catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and should be appropriately set. For example, it is preferably 0.01 to 3 times mole relative to the total amount of the silane compound. Examples of the organic solvent to be used include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, it is preferable to use an organic solvent that is not water-soluble or hardly water-soluble. The use ratio of the organic solvent is preferably 50 parts by mass to 1,000 parts by mass based on 100 parts by mass of the total of the silane compound used in the reaction.

The hydrolysis and condensation reaction are preferably carried out by heating, for example, in an oil bath. In this case, the heating temperature is preferably 130 ° C. or lower, and the heating time is preferably 0.5 to 12 hours. After the reaction is completed, the solvent is removed from the organic solvent layer separated from the reaction solution, thereby obtaining a polysiloxane.

When a functional group such as a pretilt imparting group or a photo-alignment group is introduced into the side chain of the polyorganosiloxane, the synthesis method is not particularly limited, and examples thereof include the following methods: for epoxy-containing silane compounds Or, a mixture of an epoxy-containing silane compound and other silane compounds is hydrolyzed and condensed to synthesize a polyorganosiloxane having an epoxy group, and then the obtained polyorganosiloxane containing an epoxy group and the A method of reacting a carboxylic acid with a functional group, and the like. The reaction of the epoxy group-containing polyorganosiloxane with a carboxylic acid can be performed according to a conventional method.

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

The content ratio of the [P] polymer in the liquid crystal alignment agent (total amount when it contains two or more types) is preferably 60% by mass or more with respect to the total amount of the polymer components in the liquid crystal alignment agent, and more It is preferably 80% by mass or more. In addition, in terms of obtaining a liquid crystal element having more reliability, the liquid crystal alignment agent preferably contains a [p] polymer selected from the group consisting of polyamic acid and polyamic acid ester. And at least one of the group consisting of polyimide. The content ratio of the [p] polymer in the liquid crystal alignment agent (the total amount when it contains two or more types) is preferably 40% by mass or more relative to the total amount of the polymer components in the liquid crystal alignment agent. It is more preferably 60% by mass or more.

At least a part of the polymer component contained in the liquid crystal alignment agent is preferably a polymer having a partial structure represented by the following formula (3).

* -L ¹ -R ¹¹ -R ¹² -R ¹³ -R ¹⁴ ··· (3)

(In formula (3), L ¹ is -O-, -CO-, -COO- * ¹ , -OCO- * ¹ , -NR ^15- , -NR ¹⁵ -CO- * ¹ , -CO-NR ^15- * ¹ , an alkanediyl group having 1 to 6 carbon atoms, -OR ^16- * ¹ , or -R ¹⁶ -O- * ¹ (wherein R ¹⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹⁶ alkanediyl group having a carbon number of 1 to 3; "* ^1" represents a bond to R & lt ^{1 1);} R ¹¹ and R ^{13 are} each independently a single bond, phenylene or stretch cycloalkyl, R ¹² is a single Bond, phenylene, cycloalkylene, -R ¹⁷ -B ^1- * ² , or -B ¹ -R ^17- * ² (where R ¹⁷ is phenylene or cycloalkylene, and B ¹ is- COO- * ³ , -OCO- * ³ , or an alkanediyl group having 1 to 3 carbon atoms; "* ² " represents a bond with R ¹³ and "* ³ " represents a bond with R ¹⁷ ); R ¹⁴ is Hydrogen atom, fluorine atom, alkyl group having 1 to 18 carbon atoms, fluoroalkyl group having 1 to 18 carbon atoms, alkoxy group having 1 to 18 carbon atoms, fluoroalkoxy group having 1 to 18 carbon atoms, or having a steroid skeleton A hydrocarbon group having 17 to 51 carbon atoms may have a radical polymerizable group or a photoinitiator group; in the case where R ¹⁴ is a hydrogen atom, a fluorine atom, or a group having 1 to 3 carbon atoms, R ¹¹ , R ^{1 2} and R ^{13 are} not all single keys; "*" means a combination key)

In the formula (3), the alkanediyl group of L ¹ and B ¹ and the alkyl group, fluoroalkyl group, alkoxy group, and fluoroalkoxy group of R ¹⁴ are preferably linear. Examples of the group having a steroid skeleton of R ¹⁴ include a cholesteryl group, a cholesteryl group, and a lanosteryl group. R ¹¹ , R ¹² , R ¹³ and R ¹⁷ preferably have a 1,4-phenylene group, and a cycloalkyl group is preferably a 1,4-cyclohexyl group. Regarding R ¹¹ and R ¹³ , at least one of these is preferably a phenylene group or a cycloalkylene group. R ^{12 is} preferably a phenylene group, a cycloalkylene group, -R ¹⁷ -B ^1- * ² , or -B ¹ -R ^17- * ² . The main skeleton of the polymer having a partial structure represented by the formula (3) is not particularly limited, and a [P] polymer is preferred.
The content ratio of the partial structure represented by the above formula (3) in the polymer is preferably appropriately set according to the main chain of the polymer, and from the viewpoint of sufficiently increasing the response speed of the liquid crystal, it is preferably relative to the polymer. All monomer units are set to 1 mol% to 50 mol%, and more preferably 2 mol% to 40 mol%.

In addition, in terms of obtaining a liquid crystal element which is less likely to cause an afterimage and has a fast response speed of the liquid crystal, the liquid crystal alignment agent preferably contains a polymer selected from the group consisting of a radically polymerizable group and light. At least one of the group consisting of an initiator group, a radical polymerization inhibitor group, a nitrogen-containing heterocyclic ring (except for the fluorene imine ring of polyfluorene), an amine group, and a protected amine group One kind (hereinafter also referred to as "specific partial structure") as a polymer component.

Examples of the radical polymerizable group include (meth) acrylfluorenyl, vinyl, allyl, vinylphenyl, maleimido, vinyloxy, and ethynyl. Among these, a (meth) acrylfluorenyl group is especially preferable from a viewpoint of high reactivity.
The photoinitiator base is a site that generates polymerization initiation ability by light or a site that has photosensitization, and has a source derived from radiation that can be emitted by visible light, ultraviolet, far ultraviolet, electron beam, X-ray, and the like. A group having a structure of a compound (photoinitiator) that initiates polymerization of a polymerizable component by irradiation. As the photoinitiator group, a group having a structure derived from a radical polymerization initiator capable of generating radicals by light irradiation is preferred. Specific examples include groups having a structure derived from the following compounds: acetophenone-based compounds, oxime ester-based compounds, benzophenone-based compounds, benzoin-based compounds, benzophenone-based compounds, alkanes An acetophenone-based compound or a fluorenyl phosphine oxide-based compound. Among these, the photoinitiator group is preferably a group having an acetophenone structure. When the polymer has at least one of a radical polymerizable group and a photoinitiator group, it is preferable to have these groups in a side chain.
The radical polymerization inhibitor group inhibits the polymerization reaction as a peroxide decomposition agent that invalidates peroxide radicals or hydrogen peroxide generated by energy such as ultraviolet rays or heat, or captures radical intermediates in the middle of polymerization and inhibits the polymerization reaction. The free radical scavenger functions. By containing such a polymer having a polymerization inhibitor group in the liquid crystal alignment film, it is possible to suppress the photopolymerizable compound mixed in the liquid crystal layer in the PSA mode from reacting with light irradiation. The polymerization inhibitor group is preferably a group having at least one selected from the group consisting of a hindered amine structure, a hindered phenol structure, and an aniline structure.

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

The amine group and the protected amine group are preferably a group represented by the following formula (N-1).
[Chemical 4]



(In formula (N-1), R ⁵⁰ is a hydrogen atom or a monovalent organic group; "*" is a bonding bond 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 a carbon number of 1 to 10. Specific examples include a linear or branched alkyl group such as methyl, ethyl, propyl, and butyl; a cycloalkyl group such as cyclohexyl; benzene Aryl groups such as methyl, methylphenyl, and aralkyl groups such as benzyl. Examples of the substituent which 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. Examples of the hydrocarbon group bonded by "*" in the formula (N-1) include an alkanediyl group, a cyclohexyl group, and a phenylene group.

The protecting group is preferably a group that is detached by heat, and examples thereof include a urethane-based protecting group, a fluorenamine-based protecting group, a fluorenimine-based protecting group, a sulfonamide-based protecting group, and the following formula 8-1) to groups represented by Formula (8-5), and the like. Among them, the third protecting group is preferably a third butoxycarbonyl group in terms of high release property by heat or reducing the remaining amount of the deprotected portion in the film.
[Chemical 5]



(In the formulae (8-1) to (8-5), Ar ¹¹ is a monovalent group having 6 to 10 carbon atoms after removing one hydrogen atom from a substituted or unsubstituted aromatic ring, and R ⁶¹ is carbon Alkyl group of 1 to 12, R ⁶² is methylene or ethylene; "*" represents a bonding bond to a nitrogen atom)

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

(Solvent)
The liquid crystal alignment agent contains, as a solvent component, a specific solvent selected from at least one of a solvent group (a group including a [A] solvent and a [B] solvent) shown below.
Solvent group:
[A] Solvent: a compound represented by the following formula (1), a compound represented by the following formula (2), N, N, 2-trimethylpropanamine, and 1,3-dimethyl-2 -Imidazolidone.
[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, diisoamyl ether, diacetone alcohol , And propylene glycol monobutyl ether.
[Chemical 6]



(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)
[Chemical 7]



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

･ About [A] solvent (compound represented by formula (1))
Regarding the compound represented by the formula (1), the monovalent hydrocarbon group having 2 to 5 carbon atoms in R ¹ is preferably a chain hydrocarbon group, and examples thereof include an alkyl group, alkenyl group, and alkynyl group having 2 to 5 carbon atoms. Examples of the monovalent group having "-O-" between carbon-carbon bonds in the hydrocarbon group include an alkoxyalkyl group having 2 to 5 carbon atoms.
As specific examples of these, examples of the alkyl group having 2 to 5 carbon atoms include ethyl, propyl, butyl, and pentyl; examples of the alkenyl group having 2 to 5 carbon atoms include vinyl, 1-propylene Examples include alkynyl, 2-propenyl, 3-butenyl, and the like; examples of alkynyl having 2 to 5 carbons include ethynyl, 2-propynyl, and 2-butynyl; alkoxy having 2 to 5 carbons Examples of the alkyl group include methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, ethoxymethyl, and ethoxyethyl. These may be linear It may be branched. Among the above-mentioned groups, R ^{1 is} preferably an alkyl group or alkoxyalkyl group having 2 to 5 carbon atoms.

Specific examples of the compound represented by the formula (1) include N-ethyl-2-pyrrolidone, N- (n-propyl) -2-pyrrolidone, and N-isopropyl-2 -Pyrrolidone, N- (n-butyl) -2-pyrrolidone, N- (third 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- (third butyl) -2-pyrrolidone, N -Methoxypropyl-2-pyrrolidone. The compounds represented by the formula (1) may be used alone or in combination of two or more of these exemplified compounds.

(Compound represented by formula (2))
Regarding the compound represented by the formula (2), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms in R ² and R ³ include a chain hydrocarbon group having 1 to 6 carbon atoms and an alicyclic formula having 3 to 6 carbon atoms. A hydrocarbon group, an aromatic hydrocarbon group having 5 or 6 carbon atoms, and the like. Examples of the monovalent group having "-O-" between the carbon-carbon bonds of the hydrocarbon group include an alkoxyalkyl group having 2 to 6 carbon atoms.
As specific examples of these, examples of the chain hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl. These may be linear or branched. . Examples of the alicyclic hydrocarbon group having 3 to 6 carbon atoms include cyclopentyl, cyclohexyl, and the like; examples of the aromatic hydrocarbon group include phenyl, and the like; examples of the alkoxyalkyl group having 2 to 6 carbon include R ¹ Examples include alkoxyalkyl and the like. In addition, R ² and R ³ in formula (2) may be the same as or different from each other. In addition, R ² and R ^{3 may} be bonded to each other to form a ring with the nitrogen atom to which R ² and R ³ are bonded. Examples of the ring formed by bonding R ² and R ^{3 to} each other include, for example, a pyrrolidine ring and a piperidine ring, and monovalent chain hydrocarbon groups 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 of R ⁴ include the groups exemplified in the description of the alkyl group having 1 to 6 carbon atoms of R ² and R ³ . An alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred.

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

[A] The solvent is preferably selected from a compound represented by the above formula (1) and a compound represented by the above formula (2) in terms of further reducing the influence on the interlayer insulating film 21. And at least one selected from the group consisting of 1,3-dimethyl-2-imidazolidinone, and more preferably selected from the group consisting of the compound represented by the above formula (1) wherein R ¹ is an alkyl group having 2 to 5 carbon atoms Or at least one of the group consisting of alkoxyalkyl compounds, 3-methoxy-N, N-dimethylpropanamide and 1,3-dimethyl-2-imidazolidinone, especially It is preferably selected from the group consisting of N-ethyl-2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N- (third butyl) -2-pyrrolidone, and N-methoxypropyl At least one selected from the group consisting of 2--2-pyrrolidone, 3-methoxy-N, N-dimethylpropanilamine and 1,3-dimethyl-2-imidazolidinone.

[B] The solvent is preferably selected from the group consisting of dipropylene glycol monomethyl ether, propylene glycol diacetate, and diethylene glycol diethyl ether in terms of further reducing the influence on the interlayer insulating film 21. At least one selected from the group consisting of diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

As the solvent component, only a specific solvent may be used, or a solvent other than the specific solvent may be used in combination. Examples of the other solvents include solvents having high solubility and leveling properties of polymers (hereinafter also referred to as “first solvents”) and solvents having good wet spreadability (hereinafter also referred to as “second solvents”).
As specific examples of these, examples of the first solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, and N , N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethyl carbonate, propyl carbonate, etc .;
Examples of the second solvent include ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, and ethylene glycol ether. , Ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol diethylene glycol Methyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether acetate, isoamyl propionate, isobutyl Isoamyl acid etc. In addition, as other solvents, one of the above may be used alone, or two or more of them may be used in combination.

In the preparation of the liquid crystal alignment agent, as the specific solvent, only one of the [A] solvent and the [B] solvent can be used, but it is possible to suppress the contact between the liquid crystal alignment agent and the interlayer insulating film 21 when the liquid crystal alignment film is formed. In terms of the effect on the interlayer insulating film 21 in a state and the effect of suppressing the elution of the impurity components from the interlayer insulating film 21 is high, it is preferred to contain at least one of the [A] solvent and At least one.

From the viewpoint that the suppression effect of the interlayer insulating film 21 and the suppression effect of the elution of the impurity components from the interlayer insulating film 21 can be sufficiently obtained, and the precipitation of the polymer component is suppressed, the use ratio of the [A] solvent ( When two or more kinds are used, the total amount thereof is preferably 10% by mass or more, and more preferably 20% by mass or more with respect to the total amount of the solvent contained in the liquid crystal alignment agent. Moreover, from the viewpoint of obtaining the coating property improvement effect by the [B] solvent, the upper limit of the use ratio thereof is preferably 90% by mass or less with respect to the entire amount of the solvent contained in the liquid crystal alignment agent. It is more preferably set to 80% by mass or less. The [A] solvent may be used alone or in combination of two or more.

From the viewpoint that the influence on the interlayer insulating film 21 and the elution of impurity components from the interlayer insulating film 21 can be suppressed, and the coating property of the liquid crystal alignment agent is good, the use ratio of the [B] solvent In the case of more than one type, the total amount thereof is preferably 10% by mass or more, and more preferably 20% by mass or more with respect to the total amount of the solvent contained in the liquid crystal alignment agent. The upper limit of the use ratio is preferably 80% by mass or less, and more preferably 70% by mass or less with respect to the entire amount of the solvent contained in the liquid crystal alignment agent. The [B] solvent may be used singly, or two or more solvents may be used in combination.

The use ratio of the specific solvent (in the case of using two or more kinds) is from the viewpoint that the effect of suppressing the influence on the interlayer insulating film 21 and the effect of reducing the elution of impurity components from the interlayer insulating film 21 can be sufficiently obtained. Total amount) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, more preferably 90% by mass or more with respect to the entire amount of the solvent contained in the liquid crystal alignment agent. The content is 95% by mass or more.

In addition, in the case where the [A] solvent, the [B] solvent, and other solvents are used, from the viewpoint of fully obtaining the effects of the present invention, the ratio of the use of the other solvents (the total amount when two or more kinds are used) ) Is preferably 50% by mass or less, more preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass relative to the total amount of the solvent contained in the liquid crystal alignment agent. Mass% or less.
The liquid crystal alignment agent is particularly preferably such that the solvent component includes a [A] solvent and a [B] solvent. However, in the present specification, the "solvent component includes [A] solvent and [B] solvent", and it is allowable to contain solvents other than [A] solvent and [B] solvent to such an extent that the effects of the present invention are not hindered.

In addition to the polymer component and the solvent component, the liquid crystal alignment agent may contain other components as necessary. Examples of the other components include an antioxidant, a metal chelate compound, a hardening accelerator, a surfactant, a filler, a dispersant, and a photosensitizer. The blending ratio of other components can be appropriately selected depending on each compound within a range that does not impair the effect of the present invention.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) may be appropriately selected in consideration of viscosity and volatility, and is preferably 1% by mass. A range of -10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small, and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film is too large, and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent increases, and the coating property tends to decrease.

＜ Radiosensitive resin composition ＞
Next, the radiation-sensitive resin composition 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 contains a structural unit having a polymerizable group. [Q] The polymerizable group possessed by the polymer is preferably at least one selected from the group consisting of oxetanyl, oxetanyl, (meth) acrylfluorenyl, and vinyl. By having such a polymerizable group, curing of the radiation-sensitive resin composition can be easily performed, and a good interlayer insulating film 21 can be obtained, which is preferable in this respect.

[Q] The main skeleton of the polymer is not particularly limited, but it is preferably selected from the group consisting of (meth) acrylic polymers, polyamic acid, polyamidate, polyimide, and polyorganosiloxane At least one of the groups. Among these, a (meth) acrylic polymer is particularly preferable. The (meth) acrylic polymer may contain only a structural unit derived from a monomer having a (meth) acrylfluorenyl group, or may contain a structural unit derived from a monomer having a (meth) acrylfluorenyl group. And a structural unit derived from another monomer different from the monomer having a (meth) acrylfluorenyl group. The content ratio of the structural unit derived from other monomers in the (meth) acrylic polymer is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less.

Specifically, the [Q] polymer preferably contains a first structural unit having an acidic group, a second structural unit having an oxetanyl group or an oxetanyl group, and a polymer formed with the first structural unit and The polymer having a third structural unit having a different main chain structure as the second structural unit.

Examples of the acidic group of the first structural unit include a carboxyl group, a sulfo group, a phenolic hydroxyl group, a phosphate group, a sulfonic acid group, a phosphonic acid group, a sulfonamido group, and a hydrogen atom bonded to a carbon atom. Electron-based hydroxyalkyl and the like. As the acidic group, in terms of alkali developability, these are preferably a carboxyl group, a sulfo group, a phenolic hydroxyl group, a fluorine-containing alcoholic hydroxyl group, a phosphate group, a sulfonic acid group, a phosphonic acid group, or a combination thereof. , More preferably a carboxyl group or a phenolic hydroxyl group, and even more preferably a carboxyl group.

The first structural unit is preferably a structural unit derived from at least one compound selected from the group consisting of (meth) acrylic acid or unsaturated carboxylic anhydride, and more preferably at least one of (meth) acrylic acid and maleic anhydride .
The content ratio of the first structural unit in the [Q] polymer is preferably 1 mol% to 50 mol%, and more preferably 15 mol% to 30 mol relative to all the structural units constituting the [Q] polymer. ear%. The first structural unit may be a single type, or two or more types may be combined.

The second structural unit is preferably derived from glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, and glycidyl ether of 4-hydroxybutyl (meth) acrylate. And a structural unit of at least one compound in the group consisting of 3- (meth) acrylfluorenyloxymethyl-3-ethyloxetane.
The content ratio of the second structural unit in the [Q] polymer is preferably 1 mol% to 15 mol%, and more preferably 3 mol% to 10 mol relative to all the structural units constituting the [Q] polymer. ear%. The second structural unit may be a single type or a combination of two 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 that of the first structural unit and the second structural unit, and can develop development adhesion and resistance to heat or a peeling solution. In a more favorable aspect, a structural unit derived from at least one compound selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene, and 4-hydroxystyrene is preferable. .
The content ratio of the third structural unit in the [Q] polymer is preferably 25 mol% to 80 mol%, and more preferably 30 mol% to 65 mol relative to all the structural units constituting the [Q] polymer. ear%. The third structural unit may be a single type, or two or more types may be combined.

In addition, the [Q] polymer may further have a structural unit other than the first structural unit, the second structural unit, and the third structural unit. Examples of such a structural unit include an alkyl (meth) acrylate.
[Q] The polymer can be synthesized according to a conventional method such as radical polymerization using a monomer that provides the first structural unit to the third structural unit. For details of the synthesis conditions, for example, various conditions described in Japanese Patent Laid-Open No. 2015-92233 can be appropriately set.

([R] Photosensitizer)
As the [R] photosensitizer, at least one selected from the group consisting of a photoradical polymerization initiator, a photoacid generator, and a photobase generator can be preferably used.
As specific examples of these, examples of the photo-radical polymerization initiator include O-fluorenyl oxime compounds, acetophenone compounds, and biimidazole compounds;
Examples of the photoacid generator include an oxime sulfonate compound, an onium salt, a sulfonylimine compound, a halogen-containing compound, a diazomethane compound, a sulfonium compound, a sulfonate compound, a carboxylic acid ester compound, and a quinone diester. Nitrogen compounds, etc .;
Examples of the photobase generator include transition metal complexes such as cobalt, o-nitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, and europium Oxyimines and the like.
[R] The use ratio of the photosensitizer varies depending on the kind of compound used. For example, in the case of a photoradical polymerization initiator, it is preferably 1 to 40 parts by mass, and more preferably 5 to 30 parts by mass based on 100 parts by mass of the [Q] polymer. .
With respect to 100 parts by mass of the [Q] polymer, the use ratio of the photoacid generator is preferably from 0.1 to 50 parts by mass, and more preferably from 1 to 30 parts by mass.
With respect to 100 parts by mass of the [Q] polymer, the use ratio of the photoacid agent is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass.

In addition to the [Q] polymer and the [R] photosensitizer, the radiation-sensitive resin composition may further contain a hardening accelerator, a polymerizable unsaturated compound, a surfactant, a storage stabilizer, and an adhesion promoter. Each of these arbitrary components may be used alone, or two or more of them may be used in combination.

The radiation-sensitive resin composition can be prepared by mixing a [Q] polymer and a [R] photosensitizer, and other optional ingredients prepared as needed. The radiation-sensitive resin composition is preferably dissolved in an appropriate solvent and used in a solution state. Examples of the solvent include alcohols, glycol ethers, glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, and propylene glycol. Monoalkyl ethers, propylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, ketones, esters, and the like.
Regarding the content of the solvent, from the viewpoints of coatability and stability of the obtained radiation-sensitive resin composition, it is preferable that the total concentration of each component other than the solvent of the radiation-sensitive resin composition is 5 masses. The amount of% to 50% by mass is more preferably an amount of 10% to 40% by mass.

(Manufacturing method of the 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 the substrate.
Step B: a step of forming a pixel electrode 19 on the interlayer insulating film 21.
Step C: A step of forming a liquid crystal alignment film (first alignment film 32) on the pixel electrode 19 so as to be in contact with a part of the interlayer insulating film 21.
Step D: A step of arranging the array substrate 15 and the opposite substrate 16 to face each other with a liquid crystal layer containing a photopolymerizable monomer interposed therebetween to construct a liquid crystal cell.
Step E: a step of irradiating the liquid crystal cell with light.

When manufacturing the liquid crystal device 10 shown in FIGS. 1 and 2, first, a thin film transistor 14, a scanning signal line 12, and an image are formed on a transparent substrate 18 such as a glass substrate by a known method such as a photolithography method. Signal line 13. Then, a radiation-sensitive resin composition for forming an interlayer insulating film is coated on the formation surface of the thin film transistor 14 and the signal line in the transparent substrate 18 to form an interlayer insulating film 21 (step A).

The coating method of the radiation-sensitive resin composition is not particularly limited, and suitable methods such as a spray method, a roll coating method, a spin coating method, a slit coating method, a bar coating method, and an inkjet coating method can be used. Among these methods, a spin coating method or a slit coating method is preferable because a film having a uniform thickness can be formed. After the coating of the radiation-sensitive resin composition, it is preferable to heat (pre-bake) the coated surface and, if necessary, expose the coating film through a photomask having a predetermined pattern, and then perform development and post-treatment. By baking, there is obtained an interlayer insulating film 21 as a cured film. Regarding various conditions when the interlayer insulating film 21 is formed, the conditions described in, for example, Japanese Patent Laid-Open No. 2015-92233 can be adopted.

In the next step B, a pixel electrode 19 is formed on the interlayer insulating film 21 formed in step A in the transparent substrate 18. The pixel electrode 19 is formed of a ITO (indium tin oxide) film and an indium zinc oxide (Indium Zinc Oxide) film having a film thickness of 50 nm to 200 nm, more preferably 100 nm to 150 nm by a conventional method such as sputtering. (IZO) film, and then patterned into a fishbone shape (also known as "comb shape") by photolithography. Thereby, a fish-bone pixel electrode 19 is formed on the substrate, and an array substrate 15 is fabricated.

Separately from the above, on a transparent substrate 28 such as a glass substrate, a color filter layer 29, an overcoat layer (not shown), and a common electrode 31 are sequentially formed using a conventional method such as a photolithography method. Opposite substrate 16.

In the next step C, first, a liquid crystal alignment agent is coated on the substrate on which the electrodes are formed, and it is preferable to heat the coating surface to form a coating film on the substrate. The application of the liquid crystal alignment agent to the substrate is preferably performed on the electrode formation surface by a lithographic printing method, a spin coating method, a roll coater method, a flexographic printing method, or an inkjet printing method. After the liquid crystal alignment agent is applied, it is preferable to perform pre-heating (pre-baking) for the purpose of preventing dripping of the applied liquid crystal alignment agent. The pre-baking temperature is preferably 30 ° C to 200 ° C, and the prebaking time is preferably 0.25 minutes to 10 minutes. After that, the sintering (post-baking) step is performed for the purpose of completely removing the solvent and thermally imidate the sulfamic acid structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and the post-baking time is preferably 5 minutes to 200 minutes. The thickness of the thus formed film is preferably 0.001 μm to 1 μm. After the liquid crystal alignment agent is applied on the substrate, the organic solvent is removed, thereby forming a liquid crystal alignment film or a coating film that becomes a liquid crystal alignment film.

Here, on the interlayer insulating film 21, a liquid crystal alignment agent is applied on an electrode formation surface of a substrate on which a pattern electrode (pixel electrode 19) having a large number of slit portions 19c is formed. Therefore, the liquid crystal alignment agent is in contact with the interlayer insulating film 21 through the opening of the slit portion 19c. The liquid crystal alignment film (first alignment film 32) formed on the substrate is in contact with the interlayer insulating film 21 through the slit portion 19 c in the display area of the liquid crystal device 10.
In addition, the coating film formed in the above may be used as a liquid crystal alignment film directly, or a treatment (alignment treatment) for imparting liquid crystal alignment ability may be applied. Examples of the alignment treatment include a rubbing treatment in which a coating film is rubbed in a certain direction by a roller wound with a cloth including fibers such as nylon, rayon, and cotton, and the use of a liquid crystal alignment agent. A light alignment process or the like that irradiates a coating film formed on a substrate with light to give the coating film liquid crystal alignment ability.

In the next step D, the array substrate 15 in which the interlayer insulating film 21, the pixel electrode 19, and the first alignment film 32 are sequentially formed, and the opposite substrate 16 in which the common electrode 31 and the second alignment film 33 are sequentially formed. It is arrange | positioned so that the mutually forming film formation surface may face each other. A liquid crystal layer 17 in which a photopolymerizable monomer is mixed is disposed between the array substrate 15 and the counter substrate 16 to construct a liquid crystal cell.

The liquid crystal layer 17 is formed by, for example, a method of dropping or coating a liquid crystal composition on one of the substrates coated with a sealant, and then bonding the other substrate (One Drop Filling (ODF) ) Method); Or, the peripheral edges of a pair of substrates which are arranged to face each other across the cell interval are bonded with a sealant, and a liquid crystal composition is injected and filled into the cell interval surrounded by the substrate surface and the sealant, and then injected. Methods for sealing holes, etc. Preferably, the obtained liquid crystal cell is further subjected to an annealing treatment in which the liquid crystal used is slowly cooled to room temperature after being heated to a temperature at which the liquid crystal used becomes an isotropic phase, thereby removing the flow alignment during the filling of the liquid crystal.

As the photopolymerizable monomer, a compound having two or more (meth) acrylfluorenyl groups can be preferably used in terms of high polymerizability by light. Specific examples thereof include a di (meth) acrylate having a biphenyl structure, a di (meth) acrylate having a phenyl-cyclohexyl structure, and a di (meth) acrylate having a 2,2-diphenylpropane structure. Di (meth) acrylate, di (meth) acrylate having a diphenylmethane structure, di-thio (meth) acrylate having a diphenylsulfide structure, and the like. The blending ratio of the photopolymerizable monomer is preferably 0.1% by mass to 0.5% by mass with respect to the entire amount of the liquid crystal composition used in the formation of the liquid crystal layer 17. Furthermore, as the photopolymerizable monomer, one kind may be used alone, or two or more kinds may be used in combination.

In the next step E, the liquid crystal cell obtained in step B is irradiated with light. The light irradiation of the liquid crystal cell may be performed in a state where no voltage is applied between the electrodes, or in a state where a predetermined voltage that does not drive the liquid crystal molecules in the liquid crystal layer 17 is applied, or may be applied between the electrodes. The liquid crystal molecules are driven under a predetermined voltage. The light irradiation is preferably performed in a state where a voltage is applied between the electrodes provided on the pair of substrates. The applied voltage may be, for example, 5 V to 50 V DC or AC. As the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used, and ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable. Regarding the direction of light irradiation, when the used radiation is linearly polarized light or partially polarized light, the light may be irradiated from a direction perpendicular to the substrate surface, or may be irradiated from an oblique direction, or a combination of these may be used for irradiation. When irradiating non-polarized light, the irradiation direction is an oblique direction.

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

Then, the polarizing plate 36 and the polarizing plate 37 are bonded to the outer surface of the liquid crystal cell, thereby obtaining the liquid crystal device 10. Examples of the polarizing plate 36 and the polarizing plate 37 include a polarizing plate in which a polarizing film called an “H film” is sandwiched by a cellulose acetate protective film, or a polarizing plate including the H film itself. The film is made by absorbing iodine while orienting the polyvinyl alcohol.

In this embodiment, the first alignment film 32 is formed using a liquid crystal alignment agent containing a specific solvent as a solvent component. With this, even when the first alignment film 32 is in contact with the interlayer insulating film 21 via the slit portion 19c, a liquid crystal device 10 having excellent reliability can be obtained. Although the reason for obtaining such an effect is uncertain, it is considered that, as a reason, the specific solvent used in the preparation of the liquid crystal alignment agent has little effect on the interlayer insulating film 21, thereby reducing the performance degradation of the interlayer insulating film 21. . Especially in the PSA technology, in order to improve the response characteristics of the MVA mode, for example, an electrode pattern having a fine stripe shape of several μm is formed. In the case where such a fine electrode pattern is formed on a substrate, it is considered that if the interlayer insulating film 21 swells due to the contact between the liquid crystal alignment agent and the interlayer insulating film 21, the thickness of the film slightly changes. Deformation is also easy to occur, resulting in degradation of element performance. In this regard, it is speculated that the swelling of the interlayer insulating film 21 is suppressed by using a specific solvent, and the influence on the pixel electrode 19 can be minimized, so that the reduction in element performance can be sufficiently suppressed. In addition, it is also estimated that in a state where the liquid crystal alignment agent is in contact with the interlayer insulating film 21, the elution of the impurity components from the interlayer insulating film 21 to the liquid crystal alignment agent can be suppressed, thereby sufficiently reducing the degradation of the device performance.

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

3 is a cross-sectional view schematically showing a part of an element structure of a second embodiment. Similarly to the liquid crystal device of the first embodiment, the liquid crystal device 10 shown in FIG. 3 has a structure in which the array substrate 15 and the opposing substrate 16 are arranged to face each other with the liquid crystal layer 17 interposed therebetween. The array substrate 15 includes a TFT 14 and a color filter layer 29 including a colored pattern 29 a and an interlayer insulating film 29 b on a transparent substrate 18. The coloring pattern 29 a includes sub-pixels colored in red (R), green (G), and blue (B), and is produced by a conventional 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 provided for the purpose of protecting the colored pattern 29a and forming the pixel electrode 19 exhibiting excellent characteristics. The pixel electrode 19 is disposed on the interlayer insulating film 29b.

In this case, the first alignment film 32 is also formed on the electrode formation surface of the substrate on which the fish-bone pattern electrode (pixel electrode 19) is formed on the interlayer insulating film 29b. Therefore, the first alignment film 32 is in the slit portion 19c. The middle is in contact with the interlayer insulating film 29b. In this regard, by forming the first alignment film 32 using the liquid crystal alignment agent described above, a liquid crystal device 10 having excellent reliability can be obtained.

(Other embodiments)
In the above-mentioned first embodiment, the pixel electrode 19 on the array substrate 15 side is a pattern electrode, and the interlayer insulating film 21 and the first alignment film 32 are in contact with each other in the slit portion 19c. A pattern electrode and an interlayer insulating film are provided, and the pattern electrode and the interlayer insulating film are brought into contact with each other in the slit portion.

The liquid crystal device 10 of the present invention detailed above can be effectively applied to various uses, such as a clock, a portable game machine, a word processor, a notebook personal computer, a navigation system, a video camera, a personal digital assistant (Personal Digital Assistant (PDA)), digital cameras, mobile phones, smart phones, various monitors, LCD TVs, information displays, and other display devices, or dimming devices.

[Example]
Hereinafter, embodiments of the present invention will be described in more detail based on examples, but the present invention is not limitedly explained by the following examples.

In the following examples, the following methods were used to measure the fluorene imidization rate of polyfluorene imine in the polymer solution, the solution viscosity of the polymer solution, the weight average molecular weight of the polymer, and the epoxy equivalent.
[Perylene imidation rate of polyimide]
The solution of polyfluoreneimide was poured into pure water, and the obtained precipitate was dried under reduced pressure at room temperature, and then dissolved in deuterated dimethylsulfine, and tetramethylsilane was used as a reference substance in the chamber. ¹ H-Nuclear Magnetic Resonance (NMR) was measured at room temperature. Based on the obtained ¹ H-NMR spectrum, the fluorene imidization ratio [%] was determined by the following formula (1).
醯 Imination ratio [%] = (1- (A ¹ / (A ² × α)) × 100… (1)
(In formula (1), A ¹ is the peak area of the NH-derived protons appearing near the chemical shift of 10 ppn, A ² is the peak area of the other protons, and α is the polymer precursor (polyfluorene). Proton ratio of other protons relative to one proton in NH group)
[Polymer average molecular weight]
The weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.
Column: made by Tosoh Corporation, TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Epoxy equivalent]
The epoxy equivalent is measured by the hydrochloric acid-methyl ethyl ketone method described in Japanese Industrial Standards (JIS) C 2105.

The abbreviations used in the following examples are shown. In addition, the compound represented by Formula X may be simply expressed as "compound X" below.
[Chemical 8]



[Chemical 9]



[Chemical 10]



[Chemical 11]

1. Preparation of radiation-sensitive resin composition (for formation of interlayer insulation film) (1) Synthesis of [Q] polymer
[Synthesis Example 1: Synthesis of Polymer (Q-1)]
A flask equipped with a cooling tube and a stirrer was charged with 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ether. Next, 25 parts by mass of methacrylic acid, 45 parts by mass of 3,4-epoxycyclohexyl methacrylate, and 30 parts by mass of styrene were charged, and after nitrogen substitution, the solution was gradually stirred while being stirred. The temperature was increased to 70 ° C, and the temperature was maintained for 5 hours to perform polymerization, thereby obtaining a solution containing the polymer (Q-1). The Mw of the polymer (Q-1) was 8,000.

[Synthesis Example 2: Synthesis of Polymer (Q-2)]
A flask equipped with a cooling tube and a stirrer was charged with 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ether. Then, 15 parts by mass of methacrylic acid, 40 parts by mass of 3,4-epoxycyclohexyl methacrylate, 20 parts by mass of styrene, 15 parts by mass of tetrahydrofurfuryl methacrylate, and 10 parts by mass were charged. After mass parts of n-lauryl methacrylate was replaced with nitrogen, the temperature of the solution was raised to 70 ° C while slowly stirring, and the temperature was maintained for 5 hours to perform polymerization, thereby obtaining a polymer-containing polymer (Q-2 )The solution. The Mw of the polymer (Q-2) was 8,000.

[Synthesis Example 3: Synthesis of Polymer (Q-3)]
A flask equipped with a cooling tube and a stirrer was charged with 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ether. Then, 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-cyclohexyl were charged. After the maleimidine was replaced with nitrogen, the temperature of the solution was raised to 70 ° C. while slowly stirring, and the temperature was maintained for 5 hours to perform polymerization, thereby obtaining a solution containing a polymer (Q-3). The Mw of the polymer (Q-3) was 8,000.

(2) Preparation of radiation-sensitive resin composition
[Preparation Example 1]
To the polymer (Q-1) -containing solution (the amount of the polymer (Q-1) equivalent to 100 parts by mass (solid content)) obtained in the above Synthesis Example 1 was added 20 parts by mass of 1,2- Octanedione 1- [4- (phenylthio) -2- (O-benzylidene oxime)] (Irgacure (registered trademark) OXE01 manufactured by BASF), and then added to 100 Part of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) and mixed. Diethylene glycol ethyl methyl ether was added so as to have a solid content concentration of 30% by mass and dissolved, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive resin composition (V-1).
[Preparation Example 2 to Preparation Example 4]
The formula composition was changed to those described in Table 1 below, and except for this point, a radiation-sensitive resin composition (V-2) to a radiation-sensitive resin composition (V-4) were prepared in the same manner as in Preparation Example 1. . In addition, in Table 1 below, "-" means that the component is not blended (the same is true in the following table).

[Table 1]

The abbreviations of the compounds in Table 1 are shown below.
R-1: 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzylideneoxime)] (manufactured by BASF, Irgacure (registered Trademark) OXE01)
R-2: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol (1.0 mole), and 1 Condensate of 2,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol)
U-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.)

2. Synthesis of polymer (for liquid crystal alignment agent)
[Synthesis Example 5: Synthesis of Polymer (PI-1)]
100 mol parts of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride, and 20 mol parts of cholestoxy-2,4-diaminobenzene as diamine. , 50 mol parts of 3,5-diaminobenzoic acid, and 30 mol parts of compound (d-8) are dissolved in N-methyl-2-pyrrolidone (NMP) The reaction was performed at room temperature for 6 hours to obtain a solution containing 20% by mass of polyamic acid. Next, pyridine and acetic anhydride were added to the obtained polyfluorenic acid solution, and chemical imidization was performed. The reaction solution after chemical imidization was concentrated and prepared by NMP so that the concentration became 10% by mass. The polyimide of the obtained polyimide (referred to as a polymer (PI-1)) had an imidization ratio of about 75%.
[Synthesis example 6 to synthesis example 8]
A polyfluorene imine (polymer (PI-2) was synthesized in the same manner as in Synthesis Example 5 except that the types and amounts of the tetracarboxylic dianhydride and diamine used were changed to those shown in Table 2 below. ~ Polymer (PI-4)). In addition, in Table 2, the numerical value in parentheses shows the usage ratio [mole part] of each compound with respect to the total 100 mole parts of the tetracarboxylic dianhydride used for polymer synthesis.

[Synthesis Example 9: Synthesis of Polymer (PAA-1)]
70 mol of 2,3,5-tricarboxycyclopentylacetic dianhydride as tetracarboxylic dianhydride and 30 mol of 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and 20 moles of cholestoxy-2,4-diaminobenzene as diamine, 30 moles of compound (d-12), and 40 moles of 4,4'-diaminodiphenylmethane And 10 mol portions of 4,4 '-[4,4'-propane-1,3-diylbis (piperidine-1,4-diyl)] diphenylamine were dissolved in NMP and carried out at room temperature. After 6 hours of reaction, a solution containing 20% by mass of polyamic acid was obtained. The polyamidic acid obtained here was made into a polymer (PAA-1).
[Synthesis example 10]
The polycarboxylic acid was synthesized in the same manner as in Synthesis Example 9 except that the types and amounts of the tetracarboxylic dianhydrides and diamines used were changed to those shown in Table 2 below (this was made into a polymer ( PAA-2)).

[Table 2]

[Synthesis Example 11]
A reaction vessel including a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube was charged with 100 g of the compound (s-1), 500 g of methyl isobutyl ketone, and 10 g of triethylamine. Mix at temperature. Next, after 30 minutes, 100 g of deionized water was added dropwise from the dropping funnel, and the reaction was performed at 80 ° C. for 6 hours while stirring under reflux. After the reaction was completed, the organic layer was taken out and washed with a 0.2% by mass ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a viscous transparent liquid. Reactive polyorganosiloxane (ESSQ-1). ¹ H-NMR analysis was performed on this reactive polyorganosiloxane, and as a result, it was confirmed that an epoxy-based peak can be obtained near the chemical shift (δ) = 3.2 ppm, and that no epoxy group was generated during the reaction. reaction. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane (ESSQ-1) was 3000, and the epoxy equivalent was 190 g / mole.
[Synthesis Example 12, Synthesis Example 13]
Reactive polyorganosiloxane (polymer (ESSQ-2) and polymer) were synthesized in the same manner as in Synthesis Example 11 except that the types and amounts of the monomers used were changed to those shown in Table 3 below. (ESSQ-3)). In Table 3, the numerical values in parentheses represent the use ratio [mole parts] of each compound with respect to the total 100 mole parts of the monomers used in the synthesis of the polymer.

[table 3]

[Synthesis Example 14]
A 500 mL three-necked flask was charged with 10.0 g of reactive polyorganosiloxane (ESSQ-1), 300 g of methyl isobutyl ketone as a solvent, 16 g of a compound (c-1) as a modified component, and 16 g of the compound (c-3) and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro (Stock)) as a catalyst were stirred at 100 ° C. for 48 hours to perform a reaction. After the reaction, ethyl acetate was added to the reaction mixture, the obtained solution was washed three times with water, and the organic layer was dried with magnesium sulfate, and then the solvent was distilled off to obtain a polyorganosiloxane containing a polymerizable group ( PSQ-1) 75 g. The weight average molecular weight Mw of the obtained polymer was 6000.
[Synthesis Example 15, Synthesis Example 16]
A polyorganosiloxane containing a polymerizable group was synthesized in the same manner as in Synthesis Example 14 except that the types and amounts of the reactive polyorganosiloxane and the modified components used were changed to those shown in Table 4 below. Alkane (Polymer (PSQ-2) and Polymer (PSQ-3)). In Table 4, the numerical value in parentheses represents the use ratio [mole part] of each compound with respect to the total 100 mole parts of the monomers used in polymer synthesis.

[Table 4]

3. Evaluation of liquid crystal alignment agent and liquid crystal display element
[Example 1]
(1) Preparation of liquid crystal alignment agent in a solution containing polymer (PI-1) as a polymer component to become polymer (PI-1): polymer (PSQ-1) = 95: 5 (mass ratio) Add the polymer (PSQ-1), and then add NMP, Diethylene Glycol Diethyl Ether (DEDG), and Diacetone Alcohol (DAA) as solvents, and stir thoroughly to make a solvent. A solution having a composition of NMP: DEDG: DAA = 50: 30: 20 (mass ratio) and a solid content concentration of 6.5% by mass. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (W-1).

(2) Preparation of liquid crystal composition (LC-1): 0.3 g of nematic liquid crystal (Merck, MLC-6608, manufactured by Merck Co., Ltd.) relative to the total amount of all constituent components of the liquid crystal composition A compound represented by the following formula (RM-1) was added and mixed as a mass% to obtain a liquid crystal composition (LC-1).
[Chemical 12]

(3) Manufacture of liquid crystal display elements Using a spinner, a radiation-sensitive resin composition (V-1) was coated on a glass substrate ("Corning 7059" (Corning)), and then applied at 90 ° C. Pre-bake for 10 minutes in a clean oven at ℃ to form a coating film with a thickness of 2.0 μm on the glass substrate. Then, a UV (ultraviolet) exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ) was used to irradiate 100 mJ of UV light through a pattern mask. Then, a tetramethylammonium hydroxide aqueous solution (developing solution) having a concentration of 2.38% by mass was subjected to a development treatment at 25 ° C. for 100 seconds by a liquid coating method. After the development process, the coating film was washed with flowing water for 1 minute with ultrapure water, dried to form a patterned coating film on the substrate, and then heated (post-baking) at 230 ° C for 30 minutes in an oven to make Its hardened. Next, the entire surface of each coating film was exposed using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon (stock) at an exposure amount of 500 J / m ² without using a mask. Then, after 30 minutes of post-baking at 230 degreeC, each coating film was hardened, and the interlayer insulation film was formed.

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

Next, the liquid crystal alignment agent (W-1) was spin-coated on the electrode formation surfaces of the pair of substrates, and then heated (pre-baked) on a heating plate at 80 ° C for 1 minute to remove the solvent, and then heated on a heating plate at 230 ° C Heat up (post-bake) for 15 minutes to form a coating film with an average film thickness of 100 nm. This coating film was subjected to ultrasonic cleaning in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a pair of substrates having a liquid crystal alignment film.

Next, an epoxy resin adhesive containing a zirconia ball having a diameter of 5.5 μm was coated on the outer edge of the ITO surface of the glass substrate including the patterned ITO electrode, and then the inside of the epoxy resin adhesive was applied. Liquid crystal composition (LC-1) was added dropwise on the surface at 6 points (2 vertical points × 3 horizontal points, the interval between the points was set to 10 mm above and below, and the coating amount at each point was set to 0.6 mg). This substrate and another glass substrate were overlapped and crimped in an opposing manner, and the adhesive was hardened to produce a liquid crystal cell. The obtained liquid crystal cell was subjected to ultraviolet irradiation and annealing in accordance with the "PSA process-1" described later, thereby producing a liquid crystal cell for evaluation.
(PSA process-1)
For the liquid crystal cell, an AC 20 Vpp at a frequency of 60 Hz was applied between the electrodes, and an ultraviolet irradiation device using a metal halide lamp as a light source was irradiated with 80 mW of ultraviolet rays for 50 seconds while the liquid crystal was being driven. Then, in a state where no voltage was applied, an ultraviolet irradiation device using a metal halide lamp as a light source was irradiated with 3.5 mW of ultraviolet rays for 30 minutes. Finally, the liquid crystal cell was annealed in a clean oven at 120 ° C for 10 minutes. In addition, an irradiation amount is a value measured using the light quantity meter measured with the wavelength 365 nm reference | standard.

(4) Evaluation of voltage holding ratio (VHR) The liquid crystal cell for evaluation manufactured in the above (3) was placed in a thermostatic bath, and 5 V was applied at 60 ° C for 60 microseconds and a span of 167 milliseconds. After the voltage was applied, a "VHR-1" manufactured by Toyo Technica was used to measure the voltage holding rate (VHR) after 167 milliseconds after the release was applied. At this time, a case where the VHR is 96% or more is evaluated as "very good (◎)", a case where it is 93% or more and less than 96% is evaluated as "good (○)", and it is 90% or more and less than 93% The case was evaluated as "OK (△)", and the case below 90% was evaluated as "Defective (×)". As a result, VHR = 97% in this example, which is an evaluation of ◎ very good (◎) ｣.

[Example 2 to Example 22, Comparative Example 1, Comparative Example 2]
The types and amounts of the polymers and solvents used were changed as described in Table 5 below, except that the same operations as described above were performed to prepare liquid crystal alignment agents, respectively. In addition, the aspect of changing the radiation-sensitive resin composition used in the production of the interlayer insulating film to the composition shown in Table 5 below, and the aspect of using the liquid crystal alignment agent prepared in each example to produce a liquid crystal alignment film Other than that, a liquid crystal cell for evaluation was manufactured in the same manner as described above, and the voltage retention was evaluated using the obtained liquid crystal cell for evaluation. The results are shown in Table 5 below.

[table 5]

In Table 5, the numerical value in parentheses of the polymer column indicates the blending ratio [mass parts] of each polymer with respect to 100 parts by mass of the total polymer components used in the preparation of the liquid crystal alignment agent. The numerical value in the solvent composition column indicates a compounding ratio [parts by mass] of each compound with respect to 100 parts by mass of the entire solvent used in the preparation of the liquid crystal alignment agent. The abbreviations of the solvents are as follows (the same applies to the following Table 6).
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: diisoamyl ether

As shown in Table 5, in Examples 1 to 22 in which a liquid crystal alignment film is formed using a liquid crystal alignment agent containing a specific solvent, a comparative example can be obtained as compared with a liquid crystal alignment film formed using a liquid crystal alignment agent not containing a specific solvent. 1. Comparative Example 2 is a liquid crystal display element having superior reliability. Of these, Examples 1 to 18 using a liquid crystal alignment agent containing a [A] solvent and a [B] solvent were particularly excellent in the evaluation of "very good".

Furthermore, in Examples 1 to 22 described above, the liquid crystal display element was manufactured and evaluated in the same manner as described above except that the pattern of the ITO electrode included in the glass substrate was changed to the pattern shown in FIG. 5. As a result, the same effects as described above were obtained in any of the examples.

[Example 23]
(1) Evaluation of ITO wiring deformation N-ethyl-2-pyrrolidone (NEP) and diethylene glycol diethyl ether (DEDG) were mixed and sufficiently stirred to prepare a solvent composition of NEP: DEDG = 50: 50 ( Mass ratio) Evaluation solvent (Z-1).
In addition, a glass substrate provided with a pattern electrode including ITO on the interlayer insulating film was prepared by performing the same operation as in (3) of the first embodiment. This glass substrate was immersed in an evaluation solvent (Z-1) at 80 ° C for 30 minutes, and the degree of swelling of the interlayer insulating film and the degree of deformation of the ITO electrode were evaluated using the criteria shown below. In the case of contact with the solvent component of the liquid crystal alignment agent, the smaller the swelling of the interlayer insulating film and the smaller the deformation of the electrode, the smaller the influence of the solvent on the interlayer insulating film and the ITO electrode, and the better the guarantee of the It can be said that it is preferable as a solvent of a liquid crystal alignment agent because of its reliability. As a result, this example was evaluated as "A".
(Evaluation criteria)
A: No swelling of the interlayer insulating film and no abnormality of the electrodes
B: Swelling of the interlayer insulating film is visible, but the electrode is normal
C: Slight abnormalities such as electrode deformation due to swelling of the interlayer insulating film
D: Severe abnormalities such as electrode disconnection due to swelling of the interlayer insulating film

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

[TABLE 6]

According to the results in Table 6, in Examples 23 to 44 in which a specific solvent was used, no swelling of the interlayer insulating film was observed, or even if swelling occurred, its degree was small and no abnormality of the electrode was seen. From these results, it can be seen that, even when a liquid crystal alignment film is formed on a fine-strip electrode pattern according to a specific solvent, the shape of the electrode is not easily changed, and the reliability of the liquid crystal element can be guaranteed.

1‧‧‧ITO electrode

2‧‧‧ Slit

3‧‧‧ light-shielding film

10‧‧‧ LCD device

11‧‧‧ pixels

12‧‧‧scan signal line

13‧‧‧Image signal line

14‧‧‧ Thin Film Transistor / TFT

15‧‧‧Array substrate

16‧‧‧ Opposite substrate

17‧‧‧LCD layer

18‧‧‧ transparent substrate

19‧‧‧ pixel electrode

19a‧‧‧Mainline Department

19b‧‧‧ Branch Line Department

19c‧‧‧Slit

21‧‧‧Interlayer insulation film

22‧‧‧Gate electrode

23‧‧‧Semiconductor layer

24‧‧‧Source electrode

25‧‧‧ Drain electrode

27‧‧‧ contact hole

28‧‧‧ glass substrate / transparent substrate

29‧‧‧ color filter layer

29a‧‧‧colored pattern

29b‧‧‧Interlayer insulation film

31‧‧‧Common electrode

32‧‧‧The first alignment film

33‧‧‧Second alignment film

34, 35‧‧‧PSA layer (alignment control layer)

36, 37‧‧‧ polarizing plates

FIG. 1 is a view schematically showing a part of a liquid crystal device.

FIG. 2 is a cross-sectional view schematically showing a part of the liquid crystal device according to the first embodiment.

3 is a cross-sectional view schematically showing a part of a liquid crystal device according to a second embodiment.

FIG. 4 is a diagram showing a configuration of an electrode used in the example.

FIG. 5 is a diagram showing a configuration of an electrode used in the example.

Claims (8)

A method for manufacturing a liquid crystal element, the liquid crystal element includes a liquid crystal layer between substrates and substrates, and a pair of electrodes At least one of them is a pattern electrode having a plurality of openings, and the method for manufacturing the liquid crystal element includes: A step of forming a pattern electrode; and a step of removing the pattern electrode from the pattern electrode䵔 ᆁ 鱶 斚 忿 ఀ 㰀 斚 忿 ఀ 㰀 love 爀 ⼀ 㸀 ⁏ curse 爀 ⼀ 㸀 ⁏ ꑽ 䑎 ⵶ 蒁  ᅎ ⹮ 뙒 ⹮ 뙒 ⹮ 뙒 ⹮ 뙒 葭 뉦 䵔 ᅒ 酏 ⹮ 뙒扢 ၢ 䂏  뉦 䵔 ᆁ 鳿 ఀ 㰀 䵔 ᆁ 鳿 ఀ 㰀 䵔 ᆁ 鳿 ఀ 㰀ᙔࡲ coconut ᙔࡲ ᙔࡲ Ⰰ Ⰰ㈀ ⵎ ॵ㉗ 祈 ᦑ 꾀 侮 쨀 ㄀ Ⰰ㌀ ⵎ 豵 ㉗ 切 ⴀ㈀ ⵔ꩕ ᅕ ㊑ Ŏ ᥎ 貑 ᥎ 貑 ᥎ 貑 ᥎ 貑 ᥎ 貑 ᥎ 貑 豵 ㊑ 貑 貑 貑 貑 貑 貑 貑 貑 貑 깎 妑 Teng Ketone, 4-hydroxy-2-butanone, 2-methyl-2- Hexanol, 2,6-dimethyl-4-heptanol, diisobutyl ketone, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentene, etc. 깎 Ƒ 髿 ᬀ 㰀 깎 Ƒ 髿 ᬀ 㰀 爀 ⼀ 㸀 ꀀ 㰀 爀 ⼀ 㸀 ꀀ 㰀 爀 ⼀ 㸀 㰀 爀 ⼀ 㸀 㰀 爀 ⼀ 㸀 㰀 bowl 洀 most 眀 bowl 㴀 ∀ ㄀ ㈀ 㘀 ∀ 栀 climbing 㴀 ∀ 㠀 㘀 ∀ 昀 bowl 氀 climbing 氀 bowl 㴀 ∀ most ㄀ ⸀ 樀 瀀 ㄀ ⸀ 樀 瀀 ∀ 洀 洀 洀 ⴀ 昀 漀 爀 洀 愀 琀 㴀 ∀ 樀 瀀 ⴀ 昀 漀 爀 洀 愀 琀 㴀 ∀ 樀 瀀 ⴀ 昀 漀 爀 洀 愀 琀 㴀 ∀ 樀 瀀 ∀ 㸀 㰀 ⼀ ∀ 㸀 㰀 ⼀ ∀ 㸀 㰀 ⼀ ∀ 㸀 㰀 ⼀ ∀ 㸀 㰀 ⼀ 洀 爀 ⼀ 㸀 ꀀ 㰀 爀 ⼀ 㸀 ࿿ ࠀ ㇿ ॎⷿ ఀ 爀 ⼀ 㸀 ࿿ ࠀ ㇿ ॎⷿ ఀ 爀 ⼀ 㸀 ࿿ ࠀ ㇿ ॎⷿ ఀ 爀 ⼀ 㸀 ࿿ ࠀ ㇿ ॎⷿ ఀ 1 ե 뱢 䂏  祈 ⵶ 葸 대 ⵸ 뎓 疕 鍑 睧 र ఀ ⴀ 伀 ⴰ 's 1-valent base; 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 having "-O- ぶ 萀 ㅐ 綾 﫿 ఀ" between carbon-carbon bonds of the hydrocarbon group.㰀 猀 甀 瀀 㸀 ㈀ 㰀 ⼀ 猀 甀 瀀 㺂܀ 㰀 猀 甀 瀀 㸀 ㈀ 㰀 ⼀ 猀 甀 瀀 㺂܀ 㰀 猀 甀 瀀 㸀 ㈀ 㰀 ⼀ 猀 甀 瀀 㺂܀ 㰀 猀 甀 瀀 㸀 ㌀ 㰀 ⼀ 猀 甀 瀀 㹓  铨 畽 傀 ౟ 扢 ၴ 끽 偩 쯿 ᬀ 㰀 猀 甀 瀀 㸀 ㌀ 㰀 ⼀ 猀 甀 瀀 㹓  铨 畽 傀 ౟ 扢 ၴ 끽 偩 쯿 ᬀ瀀 㹰 멸덥 砀 ㇿ 帀 㙶 葰  侮 Ȁ 㰀 ⼀ 挀 氀 愀 bowl 洀 㸀 㰀 挀 氀 愀 bowl 洀 漀 爀 top 洀 漀 爀 as described in item 1 The method for manufacturing a liquid crystal element further includes the steps of: forming an interface on each substrate side of the liquid crystal layer to control the alignment of the liquid crystal by polymerizing a photopolymerizable monomer mixed in the liquid crystal layer. Alignment control layer. Such as applying for a patent Enzymes (⸰Ȁ 㰀 ⼀ 挀 氀 愀) (⸰Ȁ 㰀 ⼀ 挀 氀 愀) (洀 漀 爀) (洀 漀 爀) (洀 漀 爀) (1) to (3) A method for manufacturing a liquid crystal element, wherein the liquid crystal alignment agent contains a P polymer selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyorganosiloxane At least one of the group consisting of alkanes. If you apply for a patent  ㆀ 媑 꾀 晴 ƀ 媑 꾀 晴 ƀ 媑 꾀 晴 ƀ 媑 꾀 晴 ƀ 媑 꾀 晴 ⻿ ఀ 㰀 ⻿ ఀ 㰀 ⻿ ఀ 㰀 爀 ⼀ 㸀 ⁢ 䂏  炀 婔 ࡲ 楑 睧 ८ 爀 ⼀ 㸀 ⁢ 䂏  炀 婔 ࡲ 楑 睧 ८  ꞑ 碈 䵵 ꞑ 碈 䵵 ꞑ 碈 䵵Search for at least one ring structure in the group consisting of alkane ring and cyclohexane ring. If you apply for a patent碁  ㆁ  ㅗ 婢 婔 ࡠ❗ 侮 ő 䦍 睙 쭒 䦍 睙 쭒 侮 Ɓ ㅗ 婢 婔 ࡢ 酒 㙒 㙒 侮 Ŕ⭬⹶ 蒖 뀰 ƀ 練 侮 œ 쩽 鍏 쩽 鍏蒁  ᅎ z ⻿ ᭢ 䂏 ⭬⹶ 蒖 � 끎 ⷿಀ 媑 꽎 麀 謁 䁑 睧 ॶ 蒑 꽎 麀 充 낖 摙 ᘰȀ 㰀 ⼀ 挀 氀 愀 洀 㸀 㰀 挀 氀 愀 끎 ⷿಀ 媑 꽎 麀 謁 䁑 睧 ॶ 蒑 꽎 麀 充 낖 摙 ᘰȀ 㰀 ⼀ 挀 氀 愀 洀 㸀 㰀 挀 氀 愀 洀 漀 爀 洀 漀 爀 most 愀 洀≻Ⰰ 㞘 Ԁ∀ 㹙 艵 ㎊ 쭜 ࡒ⥻ 쑗 The method for manufacturing a liquid crystal element according to any one of items 1 to 6, wherein the liquid crystal alignment agent contains a portion having a portion represented by the following formula (3) Structured polymer: * -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 , alkanediyl group having 1 to 6 carbon atoms, -OR ^16- * ¹ , or -R ¹⁶ -O- * ^1, wherein, R ¹⁵ is a hydrogen atom or a monovalent hydrocarbon group having a carbon number of 1 to 10, R ¹⁶ alkanediyl group having a carbon number of 1 to 3; "* ¹ yo Lang Sha vase with a small mouth㪂܀ knife㰀㸀 ㄀ ㄀ 㰀 ⼀ 猀 甀 瀀 㹶 葽 偔 ࢓ 痿 ᬀ 刀 㰀 猀 甀 瀀 㸀 ㄀ ㄀ 㰀 ⼀ 猀 甀 瀀 㹓 쨀 刀 㰀 猀 甀 瀀 㸀 ㄀ ㌀ 㰀 ⼀ 猀 甀 瀀 㹒 ْ╳ 桺 쭗 ば 멕꺓 田ŏ 㢂  謁 Տ 㡴 끰  﫿 ఀ 刀 㰀 猀 甀 瀀 㸀 ㄀ ㈀ 㰀 ⼀ 猀 甀 瀀 㹰 멕꺓 田 ŏ 㢂  侮 ŏ 㡴 끰  侮 Ā ⴀ 刀 㰀 猀 甀 瀀 㸀 ㄀ 㜀 㰀 ⼀ 猀 甀 瀀 㸀Ⴀ 䈀 㰀 猀 甀 瀀 㸀 ㄀ 㰀 ⼀ 猀 甀 瀀 㸀 ⴀ⨀ 㰀 猀 甀 瀀 㸀 ㈀ 㰀 ⼀ 猀 甀 瀀 㸰 Ţ Ԁ ⴀ 䈀 㰀 猀 甀 瀀 㸀 ㄀ 㰀 ⼀ 猀 甀 瀀 㸀 ⴀ 刀 㰀 猀 甀 瀀 㸀㄀ 㜀 㰀 ⼀ 猀 甀 瀀 㸀 ⴀ⨀ 㰀 猀 甀 瀀 㸀 ㈀ 㰀 ⼀ 猀 甀 瀀 㻿 ౑ 癎 ⷿఀ 刀 㰀 猀 甀 瀀 㸀 ㄀ 㜀 㰀 ⼀ 猀 甀 瀀 㹰 멏 㢂  謁 Տ 㡴 끰  﫿 ఀ 䈀㰀 Sha vase with a small mouth You 㸀 ㄀ 㰀 ⼀ Sha vase with a small mouth You 㹰 먀 ა 䌀 astir astir ა⨀ 㰀 Sha vase with a small mouth You 㸀 ㌀ 㰀 ⼀ Sha vase with a small mouth You 㸰 Ā ა 䌀 astir astir ა⨀ 㰀 Sha vase with a small mouth You 㸀 ㌀ 㰀 ⼀ Sha vase with a small mouth You 㸰 Ţ ո 덥 砀 ㇿ 帀 ㍶ 葰  豗 﫿 ᬰ ఀ⨀ 㰀 猀 甀 瀀 㸀 ㈀ 㰀 ⼀ 猀 甀 瀀 㸰 indicates a bond with R ¹³ , "* ³よ 桹 㪂܀ 刀 㰀 猀 甀 瀀 㸀 ㄀ 㜀 㰀 ⼀猀 甀 瀀 㹶 葽 偔 ࢓ 痿 ᬀ 刀 㰀 猀 甀 瀀 㸀 ㄀ 㐀 㰀 ⼀ 猀 甀 瀀 㹰 멬 ⭓ 齛 倰 Ŭὓ齛 倰 Ÿ 덥 砀 ㇿ 帀 ㄀ 㡶 葰  侮 ὰ 侮 ὰ 侮 ὰ 侮 덥 砀 ㇿ 帀 ㄀ 㡶 葰 ❗ 侮 덥 砀 ㇿ 帀 ㄀ 㡶 葰 ❗ 侮 덥 砀 ㇿ 帀 ㄀ 㡶 덥 砀 ㇿ 帀 ㄀ 㡶 덥 砀 ㇿ 帀 ㄀ 㡶 덥 砀 ㇿ 帀 ㄀ 㡶 덥 砀 ㇿ 帀 ㄀ 㡶 덥 砀 ㇿ 帀 ㄀ 㡶 덥 砀 ㇿ 帀 ㄀ 㡶幖 晴 螚 ꡧ 뙶 葸 덥 砀 ㄀ 㟿 帀 㔀 ㅶ 葰  﫿 ౎ꙓ 睧 ঁ ㅗ 婢 婔 ࡠ❗ 謁 Ց 䦍 睙 쭒 幖 晴 螚 ꡧ 뙶 葸 덥 砀 ㄀ 㟿 帀 㔀 ㅶ 葰  﫿 ౎ꙓ 睧 ঁ ㅗ 婢 婔 ࡠ❗ 謁 Ց 䦍 睙 쭒 﫿 ᭑ 癎 ⷿ౥ 밀 刀 﫿 ᭑ 癎 ⷿ౥ 밀練 ᡶ 着 練 ᡶ 参 앬셎 ௿ ఀ 刀 㰀 猀 甀 瀀 㸀 ㄀ ㄀ 㰀 ⼀ 猀 甀 瀀 㸰 Ā 刀 㰀 猀 甀 瀀 㸀 ㄀ ㈀ 㰀 ⼀ 猀 甀瀀 㹓 쨀 刀 㰀 猀 甀 瀀 㸀 ㄀ ㌀ 㰀 ⼀ 猀 甀 瀀 㹎 will all be single keys; "* よ 桹 㩽 偔 ࢓ 田 Ȁ 㰀 ⼀ 挀 氀 愀 bowl 洀 㸀 㰀 挀 氀 愀 bowl 洀 漀 爀 the most (Pan Pan) The method for manufacturing a liquid crystal element according to any one of items 1 to 7, wherein the substrate on which the interlayer insulating film is formed is also 뉦 䕒 핵 ⡑ 䍎  쩟 䕒 핵 ⡑ 䍎  쩟 牯 䥲 䝜 搰 Ȁ 㰀 ⼀ 挀 氀 愀 䥲 䝜 搰 Ȁ 㰀 ⼀ 挀 氀 愀 䥲 䝜 搰 Ȁ 㰀 ⼀ 挀 氀 愀 洀 㸀 㰀 挀 氀 愀 洀 㸀 㰀 挀 氀 愀 洀 漀 爀 洀 漀 爀 洀 漀 爀 洀 漀 爀The method for manufacturing a liquid crystal element according to any one of items 1 to 8, wherein the Interlayer insulating film is formed using a radiation-sensitive resin composition comprising a polymer Q and R of the photosensitive agent. If you apply for a patent  꽗 禎 쩎 奰  謁 䁽 䑢 ၶ 葿 ꑽ 䑎 ⵶ 蒁  ᅎ z⸰Ȁ 㰀 ⼀ 挀 氀 愀 bowl 洀 㸀 㰀 挀 氀 愀 bowl 洀 漀 爀 most 愀 洀 climb 㴀 ≻Ⰰ ㄀ ㆘ Ԁ∀ 㹙 艵㎊ 쭜 ࡒ⥻ 쑗 The method for manufacturing a liquid crystal element according to item 9 or 10, wherein the R photosensitizer is selected from the group consisting of a photoradical polymerization initiator, a photoacid generator, and a photobase generator At least one of the group. Such as applying for a patent睧 ६➖ 끎 ŗ 謁 լ➖ 끎 ᥗ 勇 葻 Ⰰ㉽ 偩 쭕깑 䌰 Ŏ 쩟 扢 ႂ ݢ 䂏 Ⰰ ㅽ 偩 쭕깑 䍓 쩢 䂏 Ⰰ㉽ 偩 쭕깑 䍎 끎 ᥗ 勇 葻 Ⰰ㉽ 偩 쭕깑 䌰 Ŏ 쩟 扢 ႂ ݢ 䂏 Ⰰ ㅽ 偩 쭕깑 䍓 쩢 䂏 Ⰰ㉽ 偩 쭕깑 䍎 The third structural unit of the same main chain structure polymer. For example, the patent application A structural unit of at least one compound in a group. If you apply for a patent漰 Ā ⡵㉗ 切 ⥎ᥰ 砀 ㌀Ⰰ 㐀 ⵴ 끬 ❴ 끝  冀 ㊑ 漰 Ā 㐀 ⵿ꕗ 祈 ŗ 切 ⡵㉗ 切 ⥎ᥰ Monument 潾 ⹬ 㑵 ᡬ 릑 腾 쨀 ㌀ⴀ ⡵㉗ 切 ⥎ᥰ 꽗 𤋮 ❗ 冀 ㉗ 切 ⴀ㌀ ⵎ 套 𤋮 ➖ 끎 Ű 䁽 䑢 ၶ 葿 ꑽ 䑎 ⵶ 蒁  ᅎ z⹓ᙔࡲ 楶 葽 偩 쭕깑 䌰 Ȁ 㰀 ⼀ 挀 氀 愀 bowl 洀 㸀 㰀 挀 氀 愀 bowl 洀 漀(爀 最 愀 洀) The method for manufacturing a liquid crystal element according to any one of items 12 to 14, wherein the third structural unit is derived from A structural unit of at least one compound selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene, and 4-hydroxystyrene.