JP7074142B2 - Manufacturing method of liquid crystal element - Google Patents

Description

Cross-reference of related applications

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

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

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

A PSA (Polymer Sustained Alignment) method is known as one of the alignment processing methods for liquid crystal devices (see, for example, Patent Document 1). In the PSA method, a photopolymerizable monomer is mixed in advance with a liquid crystal in the gap between a pair of substrates, and after constructing a liquid crystal cell, the photopolymerizable monomer is polymerized by irradiating ultraviolet rays with a voltage applied between the substrates. This is a technique for forming a polymer layer by forming a polymer layer and controlling the initial orientation of the liquid crystal by the polymer layer. According to this technique, it is possible to widen the viewing angle and speed up the liquid crystal molecular response, and it is possible to solve the problems of insufficient transmittance and contrast in the MVA type panel.

Further, Patent Document 1 discloses that in PSA technology, a pattern electrode patterned so as to have a comb tooth shape (also referred to as a fishbone shape) having a large number of openings (slit portions) is used as a pixel electrode. Has been done. In the liquid crystal display of Patent Document 1, a drain bus line is formed on a glass substrate on the array substrate side, and an interlayer insulating film is formed on the drain bus line. Further, a fishbone-shaped pixel electrode is formed on the interlayer insulating film, and a liquid crystal alignment film is formed on the pixel electrode. The liquid crystal alignment film usually contains a polymer component such as polyamic acid, polyimide, polyorganosiloxane, (meth) acrylic polymer, or polyamide dissolved in a solvent, and the polymer composition is applied onto a substrate to apply the solvent. Formed by removal.

Japanese Patent Application Laid-Open No. 2003-149647

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

The present disclosure has been made in view of the above problems, and in an element structure in which an interlayer insulating film, a pattern electrode, and a liquid crystal alignment film are formed in this order on a substrate, a liquid crystal element having excellent reliability can be obtained. One purpose is to provide a method for manufacturing an element.

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

（式（１）中、Ｒ^１は、炭素数２～５の１価の炭化水素基、又は当該炭化水素基における炭素－炭素結合間に「－Ｏ－」を有する１価の基である。）

（式（２）中、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子、炭素数１～６の１価の炭化水素基、又は当該炭化水素基の炭素－炭素結合間に「－Ｏ－」を有する１価の基であり、Ｒ^２とＲ^３とが互いに結合して環構造を形成してもよい。Ｒ^４は、炭素数１～６のアルキル基である。）<1> A method for manufacturing a liquid crystal element including a pair of substrates arranged to face each other, a liquid crystal layer arranged between the pair of substrates, and a pair of electrodes, wherein at least one of the pair of electrodes is , A pattern electrode having a plurality of openings, a step of forming an interlayer insulating film on at least one of the pair of substrates, a step of forming the pattern electrode on the interlayer insulating film, and a step of forming the pattern electrode on the pattern electrode. A step of forming a liquid crystal alignment film so as to be in contact with at least a part of the interlayer insulating film, wherein the liquid crystal alignment film is composed of a polymer component and at least one solvent selected from the solvent group shown below. A method for manufacturing a liquid crystal element, which is formed by using a liquid crystal aligning agent containing the above.
Solvent group:
[A] Solvent: A compound represented by the following formula (1), a compound represented by the following formula (2), N, N, 2-trimethylpropionamide, and 1,3-dimethyl-2-imidazolidinone.
[B] Solvent: Dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, 4-methoxy-4-methyl-2-pentanone, 4-hydroxy-2-butanone, 2-methyl-2-hexanol, 2 , 6-Dimethyl-4-heptanol, diisobutylketone, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

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

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

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

FIG. 1 is a diagram schematically showing a part of a liquid crystal display. FIG. 2 is a cross-sectional view schematically showing a part of the liquid crystal display of the first embodiment. FIG. 3 is a cross-sectional view schematically showing a part of the liquid crystal display of the second embodiment. FIG. 4 is a diagram showing the structure of the electrodes used in the examples. FIG. 5 is a diagram showing the structure of the electrodes used in the examples.

Hereinafter, embodiments will be described with reference to the drawings. In each of the following embodiments, the parts that are the same or equal to each other are designated by the same reference numerals, and the description thereof will be used for the parts having the same reference numerals.

(Structure of liquid crystal device 10)
The liquid crystal device 10 is a PSA (Polymer Sustained Alignment) type vertically oriented liquid crystal display element. A plurality of pixels 11 are arranged in a matrix on the display unit of the liquid crystal device 10. As shown in FIG. 1, the pixel 11 is formed in a region surrounded by scanning signal lines 12 and video signal lines 13 that intersect each other. A thin film transistor (TFT) 14 that functions as a liquid crystal display driving element is arranged in each pixel 11. As shown in FIG. 2, the liquid crystal display device 10 includes an array substrate 15, a facing substrate 16, and a liquid crystal layer 17.

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

The pixel electrode 19 is formed of a transparent conductor such as ITO. As shown in FIG. 1, the pixel electrode 19 is a pattern electrode in which a plurality of slit portions (elongated rectangular openings) 19c are provided in a planar electrode. Specifically, the pixel electrode 19 is located between a trunk line portion 19a extending in two directions orthogonal to each other, a plurality of branch line portions 19b extending diagonally from the trunk line portion 19a, and a plurality of branch line portions 19b. It is provided with a plurality of formed slit portions 19c, and has a repeating pattern of a conductive portion and a non-conductive portion. The pixel electrode 19 is electrically connected to the thin film transistor 14. The thin film transistor 14 is electrically connected to the scanning signal line 12 and the video signal line 13, and various signals are supplied.

The array substrate 15 has a structure in which the transparent substrate 18, the interlayer insulating film 21, and the pixel electrodes 19 are laminated in this order in a display region in which a plurality of pixels 11 are arranged in a matrix. The pixel electrode 19 is connected to the drain electrode 25 via a contact hole 27 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, it is possible to suppress the increase in the capacitive coupling between the pixel electrode 19 and the signal line.

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

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

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

The liquid crystal layer 17 has a negative dielectric anisotropy. The liquid crystal layer 17 has PSA layers 34 and 35, which are polymer layers, at the interface with the array substrate 15 and the interface with the opposed substrate 16, respectively. The PSA layers 34 and 35 are formed by photopolymerizing a photopolymerizable monomer previously mixed in the liquid crystal layer 17 in a state where the liquid crystal molecules are pretilt-oriented after the liquid crystal cell is constructed. In the liquid crystal device 10, the PSA layers 34 and 35 control the initial orientation of the liquid crystal molecules in the liquid crystal layer 17.

In the liquid crystal display 10, polarizing plates 36 and 37 are arranged on the outside of the array substrate 15 and the facing substrate 16, respectively. A terminal region is provided on the outer edge of the array substrate 15, and the liquid crystal device 10 is driven by connecting a driver IC or the like for driving the liquid crystal to this terminal region.

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

(Polymer component)
The main skeleton of the polymer contained in the liquid crystal alignment agent is not particularly limited, and for example, polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, polyester, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide). ) Main skeletons such as derivatives and poly (meth) acrylic polymers can be mentioned. Among these, at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane (hereinafter, also referred to as [P] polymer) is preferable. In preparing the liquid crystal alignment agent, one type of polymer may be used alone, or two or more types may be used in combination. As used herein, "(meth) acrylic" is meant to include "acrylic" and "methacrylic".

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

(Polyamic acid)
Examples of the tetracarboxylic acid dianhydride used for the synthesis of polyamic acid include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride and the like. .. Specific examples of these include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride and ethylenediaminetetraacetic acid dianhydride;
Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and the like. 2,3,5-Tricarboxycyclopentylacetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-franyl) -naphtho [1,2- c] Fran-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] Fran-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3'-(tetratetra-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane -2: 4,6: 8-dianhydride, cyclohexanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, etc.;
Aromatic tetracarboxylic acid dianhydrides include, for example, pyromellitic acid dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic acid anhydride, p-phenylenebis (trimellitic acid monoester anhydride), ethylene glycol. Bis (anhydrotrimeritate), 1,3-propylene glycol bis (anhydrotrimeritate) and the like can be mentioned, respectively, and the tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used. Can be used. The tetracarboxylic acid dianhydride may be used alone or in combination of two or more.

The tetracarboxylic acid dianhydride used for the synthesis preferably contains an alicyclic tetracarboxylic acid dianhydride in that the obtained polymer can be more soluble in a solvent, and preferably contains a cyclobutane ring, a cyclopentane ring and a cyclopentane ring. It is more preferable to contain a tetracarboxylic acid dianhydride having at least one ring structure selected from the group consisting of cyclohexane rings (hereinafter, also referred to as "specific tetracarboxylic acid dianhydride"). The ratio of the specific tetracarboxylic acid dianhydride used is preferably 10 mol% or more, preferably 20 to 100 mol%, based on the total amount of the tetracarboxylic acid dianhydride used for the synthesis of the polyamic acid. More preferred.

（式（Ｄ－１）中、Ｘ^I及びＸ^IIは、それぞれ独立に、単結合、－Ｏ－、＊－ＣＯＯ－、＊－ＯＣＯ－又は＊－ＮＨ－ＣＯ－（但し、「＊」を付した結合手がジアミノフェニル基と結合する。）であり、Ｒ^Ｉ及びＲ^ＩＩは、それぞれ独立に、炭素数１～３のアルカンジイル基であり、ａは０又は１であり、ｂは０～２の整数であり、ｃは１～２０の整数であり、ｎは０又は１であり、ｍは０又は１である。但し、ａ及びｂが同時に０になることはなく、Ｘ^Ｉが＊－ＮＨ－ＣＯ－の場合、ｎは０である。）
で表される化合物などを；
ジアミノオルガノシロキサンとして、例えば、１，３－ビス（３－アミノプロピル）－テトラメチルジシロキサンなどを、それぞれ挙げることができるほか、特開２０１０－９７１８８号公報に記載のジアミンを用いることができる。なお、ポリアミック酸の合成に際し、ジアミンは１種を単独で又は２種以上組み合わせて使用することができる。Examples of the diamine used for the synthesis of polyamic acid include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes and the like. Specific examples of these include, as aliphatic diamines, for example, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, etc .; alicyclic diamines. For example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), etc.;
As aromatic diamines, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-Diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) ethane, 1,3-bis (4-amino) Phenoxy) propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4'-(p-phenylenediisopropylidene) Bisaniline, 1,4-bis (4-aminophenoxy) benzene, 2,6-diaminopyridine, 3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine, 1,4-bis- (4-Aminophenyl) -piperazine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1- (4-aminophenyl) -2 , 3-Dihydro-1,3,3-trimethyl-1H-inden-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene , Cholestanyloxy-2,4-diaminobenzene, 3,5-diaminobenzoate cholestanyl, 3,5-diaminobenzoate cholestenyl, 3,5-diaminobenzoate lanostannyl, 3,6-bis (4-aminobenzoyloxy) ) Cholestan, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1, 1-Bis (4-((Aminophenyl) Methyl) Phenyl) -4- (4-Heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, N- [4- (2-Aminoethyl) Phenyl] benzene-1,4-diamine, N- [4- (Aminomethyl) Phenyl] benzene-1,4-diamine, 1,3-bis (4-aminophenityl) urea, 4 , 4'-[4,4'-Propane-1,3-diylbis (piperidine-1,4-diyl)] dianiline, 2-propynyloxy-2,4-phenylenediamine and the following formula (D-1)

(In the formula (D-1), X ^I and X ^II are independently single-bonded, -O-, * -COO-, * -OCO- or * -NH-CO- (where "*" is used. The attached bond is a diaminophenyl group.), ^{RI and R II are} independently alcandiyl groups having 1 to 3 carbon atoms, a is 0 or 1, and b is 0. It is an integer of 2 to 2, c is an integer of 1 to 20, n is 0 or 1, m is 0 or 1. However, a and b cannot be ⁰ at the same time, and XI is. * In the case of -NH-CO-, n is 0.)
Compounds represented by;
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, and diamines described in JP-A-2010-97188 can be used. In the synthesis of polyamic acid, one type of diamine can be used alone or two or more types can be used in combination.

The polyamic acid can be obtained by reacting the tetracarboxylic acid dianhydride as described above with a diamine, if necessary, with a molecular weight adjusting agent. The ratio of the tetracarboxylic acid dianhydride used in the polyamic acid synthesis reaction to the diamine is 0.2 to 2 for the acid anhydride group of the tetracarboxylic acid dianhydride with respect to 1 equivalent of the amino group of the diamine. Equivalent proportions are preferred. Examples of the molecular weight adjusting agent include acid monoanhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenylisocyanate and naphthylisocyanate. Can be mentioned. The ratio of the molecular weight adjusting agent used is preferably 20% by mass or less with respect to the total amount of the tetracarboxylic acid dianhydride and the diamine used.

The synthetic reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably −20 ° C. to 150 ° C., and the reaction time is preferably 0.1 to 24 hours.
Examples of the organic solvent used in the reaction include an aprotonic polar solvent, a phenolic solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, m-cresol, xylenol, One or more selected from the group consisting of halogenated phenol and a specific solvent described later is used as a solvent, or a mixture of one or more of these with another organic solvent (for example, butyl cellosolve, diethylene glycol diethyl ether, etc.). It is preferable to use. The amount of the organic solvent used is preferably such that the total amount of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50% by mass with respect to the total amount of the reaction solution. As described above, a reaction solution obtained by dissolving a polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal alignment agent, or the polyamic acid contained in the reaction solution may be isolated and then used for the preparation of the liquid crystal alignment agent.

(Polyimide)
The polyimide can be obtained by dehydrating and ring-closing the polyamic acid synthesized as described above to imidize it. The polyimide may be a completely imidized product in which all of the amic acid structure possessed by its precursor polyamic acid is dehydrated and ring-closed, and only a part of the amic acid structure is dehydrated and ring-closed to form an amic acid structure and an imide. It may be a partially imidized product in which a ring structure coexists. The imidization ratio of the polyimide is preferably 30% or more, more preferably 40 to 99%, still more preferably 60 to 99%. This imidization ratio is expressed as a percentage of the ratio of the number of imide ring structures to the total number of amic acid structures and the number of imide ring structures of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as necessary. In this method, as the dehydrating agent, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 0.01 to 20 mol per 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, colidine, lutidine, and triethylamine can be used. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used include organic solvents exemplified as those used for the synthesis of polyamic acids. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C., and the reaction time is preferably 1.0 to 120 hours. The obtained reaction solution may be used as it is for the preparation of the liquid crystal alignment agent, or the polyimide may be isolated and then used for the preparation of the liquid crystal alignment agent.

(Polyamic acid ester)
The polyamic acid ester is, for example, [I] a method of reacting the polyamic acid obtained by the above reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, and [III] a tetracarboxylic acid diester. It can be obtained by a method of reacting a dihalide with a diamine, or the like. Here, examples of the esterifying agent of the above [I] include methanol, ethanol and the like. The tetracarboxylic acid diester used in [II] above can be obtained by ring-opening the tetracarboxylic acid dianhydride with alcohols or the like. The tetracarboxylic acid diester dihalide used in the above [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. The obtained polyamic acid ester may have only an amic acid ester structure, or may be a partial esterified product in which an amic acid structure and an amic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be used as it is for the preparation of the liquid crystal alignment agent, or the polyamic acid ester contained in the reaction solution may be isolated and then used for the preparation of the liquid crystal alignment agent.

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

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

Examples of the hydrolyzable silane compound used for the synthesis of polyorganosiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and trimethoxysilylpropyl. Alkoxysilane compounds such as succinic acid anhydride, dimethyldimethoxysilane, dimethyldiethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureido Nitrogen / sulfur-containing alkoxysilane compounds such as propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (3-cyclohexylamino) propyltrimethoxysilane; 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Epoxy group-containing silane compounds such as methoxysilane; 3- (meth) acryloxipropyltrimethoxysilane, 3- (meth) acryloxipropylmethyldimethoxysilane, 3- (meth) acryloxipropylmethyldiethoxysilane, vinyltrimethoxy Examples thereof include unsaturated bond-containing alkoxysilane compounds such as silane and p-styryltrimethoxysilane. As the hydrolyzable silane compound, one of these can be used alone or in combination of two or more. In addition, in this specification, "(meth) acrylo" means to include "acrylo" and "methacrylo".

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

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

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

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

The content ratio of the [P] polymer in the liquid crystal alignment agent (total amount when two or more kinds are contained) may be 60% by mass or more with respect to the total amount of the polymer components in the liquid crystal alignment agent. It is preferably 80% by mass or more, more preferably 80% by mass or more. Further, the liquid crystal alignment agent preferably contains at least one [p] polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide in that a liquid crystal element having more excellent reliability can be obtained. .. The content ratio of the [p] polymer in the liquid crystal alignment agent (the total amount when two or more kinds are contained) may be 40% by mass or more with respect to the total amount of the polymer components in the liquid crystal alignment agent. It is preferably 60% by mass or more, 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 the formula (3), L ¹ is -O-, -CO-, -COO- * ¹ , -OCO- * ¹ , -NR ^15- , -NR ¹⁵ -CO- * ¹ , -CO-NR ¹⁵ -* ¹ , an alkanediyl group having 1 to 6 carbon atoms, -OR ^16- * ¹ or -R ¹⁶ -O- * ¹ (however, R ¹⁵ is a hydrogen atom or a monovalent group having 1 to 10 carbon atoms. It is a hydrocarbon group, R ¹⁶ is an alkanediyl group having 1 to 3 carbon atoms. “* ¹ ” indicates that it is a bond with R ^11. ). R ¹¹ and R ¹³ are Each is independently a single bond, a phenylene group or a cycloalkylene group, and R ¹² is a single bond, a phenylene group, a cycloalkylene group, -R ¹⁷ -B ^1- * ² , or -B ¹ -R ^17- * ² . (However, R ¹⁷ is a phenylene group or a cycloalkylene group, B ¹ is -COO- * ³ , -OCO- * ³ , or an alkanediyl group having 1 to 3 carbon atoms. "* ² " is R. It indicates that it is a bond with ¹³ and "* ³ " indicates that it is a bond with R ¹⁷ ). R ¹⁴ is a hydrogen atom, a fluorine atom, and an alkyl having 1 to 18 carbon atoms. A group, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a fluoroalkoxy group having 1 to 18 carbon atoms, or a hydrocarbon group having a steroid skeleton and having 17 to 51 carbon atoms, which is radically polymerized. It may have a sex group or a photoinitiator group. However, when R ¹⁴ is a hydrogen atom, a fluorine atom or a group having 1 to 3 carbon atoms, all of R ¹¹ , R ¹² and R ¹³ are single-bonded. It does not become. "*" Indicates that it is a bond.)

In the above 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 ^R14 include a cholestanyl group, a cholesteryl group, a lanostannyl group and the like. The phenylene group of R ¹¹ , R ¹² , R ¹³ and R ¹⁷ is preferably a 1,4-phenylene group, and the cycloalkylene group is preferably a 1,4-cyclohexylene group. It is preferable that at least one of R ¹¹ and R ¹³ is a phenylene group or a cycloalkylene group. R ¹² is preferably a phenylene group, a cycloalkylene group, -R ¹⁷ -B ^1- * ² , or -B ¹ -R ^17- * ² . The main skeleton of the polymer having the partial structure represented by the above formula (3) is not particularly limited, but is preferably a [P] polymer.
The content ratio of the partial structure represented by the above formula (3) in the polymer is appropriately set according to the main chain of the polymer, but from the viewpoint of sufficiently increasing the response speed of the liquid crystal, the entire polymer. It is preferably 1 to 50 mol% and more preferably 2 to 40 mol% with respect to the monomer unit.

Further, in that a liquid crystal element that does not easily generate an afterimage and has a fast response speed of the liquid crystal can be obtained, the liquid crystal alignment agent has, as a polymer component, a radical polymerizable group, a photoinitiator group, a radical polymerization prohibiting agent group, and the like. A polymer having at least one selected from the group consisting of a nitrogen-containing heterocycle (excluding the imide ring of polyimide), an amino group, and a protected amino group (hereinafter, also referred to as "specific partial structure"). Is preferably contained.

Examples of the radically polymerizable group include (meth) acryloyl group, vinyl group, allyl group, vinylphenyl group, maleimide group, vinyloxy group, ethynyl group and the like. Of these, the (meth) acryloyl group is particularly preferable because of its high reactivity.
The photoinitiator group is a site where the polymerization initiation ability is generated by light or a site having a photosensitizing effect, and the polymerization of the polymerizable component is carried out by irradiation with radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. It is a group having a structure derived from an initiating compound (photoinitiator). The photoinitiator group is preferably a group having a structure derived from a radical polymerization initiator capable of generating radicals by light irradiation. Specific examples thereof include a group having a structure derived from an acetophenone-based compound, an oxime ester-based compound, a dibenzoyl-based compound, a benzoin-based compound, a benzophenone-based compound, an alkylphenone-based compound, and an acylphosphine 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 radically polymerizable group and a photoinitiator group, it is preferable to have these groups in the side chain.
The radical polymerization inhibitor group supplements a peroxide decomposition agent that invalidates peroxy radicals and hydroperoxides generated by energy such as ultraviolet rays and heat, or a radical intermediate during polymerization to carry out the polymerization reaction. It functions as a radical trapping agent that suppresses the progress. By including the polymer having such a polymerization inhibitor group in the liquid crystal alignment film, it is possible to suppress the reaction of the photopolymerizable compound mixed in the liquid crystal layer in the liquid crystal layer by light irradiation in the PSA mode. The polymerization inhibitor group is preferably a group having at least one selected from the group consisting of a hindered amine structure, a hindered phenol structure and an aniline structure.

Examples of the nitrogen-containing heterocycle include pyrrol, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzoimidazole, purine, quinoline, isoquinoline, naphthylidine, quinoxaline, phthalazine, triazine, carbazole, aclysine and piperazine. Examples thereof include 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.

（式（Ｎ－１）中、Ｒ^５０は、水素原子又は１価の有機基である。「＊」は炭化水素基に結合する結合手である。）The amino group and the protected amino group are preferably groups represented by the following formula (N-1).

( ^In formula (N-1), R50 is a hydrogen atom or a monovalent organic group. “*” Is a bond that binds to a hydrocarbon group.)

^In the above formula (N-1), the monovalent organic group of R50 is preferably a monovalent hydrocarbon group or a protecting group. The monovalent hydrocarbon group preferably has 1 to 10 carbon atoms, and specifically, for example, a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a cycloalkyl group such as a cyclohexyl group. Group; aryl group such as phenyl group and methylphenyl; aralkyl group such as benzyl group and the like. Examples of the substituent that R ⁵⁰ may have include a halogen atom, a cyano group, an alkylsilyl group, an alkoxysilyl group and the like. ^R50 is preferably an alkyl group, a cyclohexyl group, a phenyl group or a benzyl group having 1 to 5 carbon atoms. Examples of the hydrocarbon group to which the "*" in the above formula (N-1) is bonded include an alkanediyl group, a cyclohexylene group, a phenylene group and the like.

（式（８－１）～式（８－５）中、Ａｒ^１１は、置換又は無置換の芳香環から１個の水素原子を取り除いた炭素数６～１０の１価の基であり、Ｒ^６１は炭素数１～１２のアルキル基であり、Ｒ^６２はメチレン基又はエチレン基である。「＊」は窒素原子に結合する結合手を示す。）The protecting group is preferably a group that is desorbed by heat, and for example, a carbamate-based protecting group, an amide-based protecting group, an imide-based protecting group, a sulfonamide-based protecting group, the following formulas (8-1) to (8-). Examples include the groups represented by each of 5). Of these, the tert-butoxycarbonyl group is preferable in that it has high heat-removability and reduces the residual amount in the membrane of the deprotected portion.

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

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

（式（１）中、Ｒ^１は、炭素数２～５の１価の炭化水素基、又は当該炭化水素基における炭素－炭素結合間に「－Ｏ－」を有する１価の基である。）

（式（２）中、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子、炭素数１～６の１価の炭化水素基、又は当該炭化水素基の炭素－炭素結合間に「－Ｏ－」を有する１価の基であり、Ｒ^２とＲ^３とが互いに結合して環構造を形成してもよい。Ｒ^４は、炭素数１～６のアルキル基である。）(solvent)
The liquid crystal alignment agent contains, as a solvent component, at least one specific solvent selected from the solvent group shown below (a group consisting of [A] solvent and [B] solvent).
Solvent group:
[A] Solvent: A compound represented by the following formula (1), a compound represented by the following formula (2), N, N, 2-trimethylpropionamide, and 1,3-dimethyl-2-imidazolidinone.
[B] Solvent: Dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, 4-methoxy-4-methyl-2-pentanone, 4-hydroxy-2-butanone, 2-methyl-2-hexanol, 2 , 6-Dimethyl-4-heptanol, diisobutylketone, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

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

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

-[A] Solvent (compound represented by formula (1))
Regarding the compound represented by the above formula (1), the monovalent hydrocarbon group having 2 to 5 carbon atoms of ^R1 is preferably a chain hydrocarbon group, for example, an alkyl group having 2 to 5 carbon atoms and an alkenyl. Examples include a group and an alkynyl group. Further, 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.
Specific examples of these include an ethyl group, a propyl group, a butyl group, a pentyl group and the like as an alkyl group having 2 to 5 carbon atoms; and an alkenyl group having 2 to 5 carbon atoms, for example, a vinyl group and a 1-propenyl group. , 2-Propenyl group, 3-butenyl group, etc .; as an alkynyl group having 2 to 5 carbon atoms, for example, an ethynyl group, 2-propynyl group, 2-butynyl group, etc .; as an alkoxyalkyl group having 2 to 5 carbon atoms. For example, a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, an ethoxyethyl group and the like can be mentioned, respectively, and these may be linear or branched. Among the above, R ¹ is preferably an alkyl group having 2 to 5 carbon atoms or an alkoxyalkyl group.

Specific examples of the compound represented by the above formula (1) include N-ethyl-2-pyrrolidone, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, and N- (n-). Butyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N -Methoxybutyl-2-pyrrolidone and the like can be mentioned. Among these, N-ethyl-2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, and N-methoxypropyl-2-pyrrolidone are particularly preferably used. Can be done. As the compound represented by the above formula (1), these exemplified compounds can be used alone or in combination of two or more.

(Compound represented by the formula (2))
Regarding the compound represented by the above formula (2), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms of R ² and R ³ include a chain hydrocarbon group having 1 to 6 carbon atoms and 3 to 6 carbon atoms. Examples thereof include an alicyclic hydrocarbon group of 6 and an aromatic hydrocarbon group having 5 or 6 carbon atoms. Further, 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.
Specific examples of these include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like as a chain hydrocarbon group having 1 to 6 carbon atoms, and these are linear. It may be branched or branched. Further, as the alicyclic hydrocarbon group having 3 to 6 carbon atoms, for example, a cyclopentyl group, a cyclohexyl group or the like; as an aromatic hydrocarbon group, for example, a phenyl group or the like; as an alkoxyalkyl group having 2 to 6 carbon atoms. Can, for example, list the alkoxyalkyl groups mentioned in R ¹ ; respectively. In addition, R ² and R ³ in the formula (2) may be the same or different from each other. Further, R ² and R ³ may form a ring together with the nitrogen atom to which R ² and R ³ are bonded by binding to each other. Examples of the ring formed by bonding R ² and R ³ to each other include a pyrrolidine ring and a piperidine ring, and a monovalent chain hydrocarbon group such as a methyl group is bonded to these rings. May be.
R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and further preferably a hydrogen atom or a methyl group. be.
Examples of the alkyl group having 1 to 6 carbon atoms of R ⁴ include the groups exemplified in the above description of the alkyl groups having 1 to 6 carbon atoms of R ² and R ³ . It is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

Specific examples of the compound represented by the above formula (2) include, for example, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropaneamide, 3-hexyloxy-N, N-. Examples thereof include dimethylpropaneamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and the like. The compound represented by the above formula (2) can be used alone or in combination of two or more.

[A] As the solvent, the compound represented by the above formula (1), the compound represented by the above formula (2) and 1,3-dimethyl-are particularly small in that the influence on the interlayer insulating film 21 can be made smaller. It is preferable that the compound is at least one selected from the group consisting of 2-imidazolidinone, and in the compound represented by the above formula (1), R ¹ is an alkyl group having 2 to 5 carbon atoms or an alkoxyalkyl group, 3. More preferably, it is at least one selected from the group consisting of -methoxy-N, N-dimethylpropanamide and 1,3-dimethyl-2-imidazolidinone, and N-ethyl-2-pyrrolidone, N- (n-). Pentyl) -2-pyrrolidone, N- (t-butyl) -2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide and 1,3-dimethyl-2-imidazolidi It is particularly preferable that it is at least one selected from the group consisting of non.

[B] As the solvent, among the above, dipropylene glycol monomethyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and It is preferably at least one selected from the group consisting of propylene glycol monobutyl ether.

As the solvent component, only the specific solvent may be used, but other solvents other than the specific solvent may be used in combination. As such other solvents, a solvent having high solubility and leveling property of the polymer (hereinafter, also referred to as “first solvent”) and a solvent having good wettability and spreading property (hereinafter, also referred to as “second solvent”). ).
Specific examples of these include, as a first solvent, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl. -2-Pentanone, ethylene carbonate, propylene carbonate, etc.;
As the second solvent, for example, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene Glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether acetate, Isoamylpropionate, isoamylisobutyrate and the like can be mentioned respectively. As the other solvent, one of the above may be used alone, or two or more of them may be mixed and used.

When preparing the liquid crystal alignment agent, only one of [A] solvent and [B] solvent may be used as the specific solvent, but when forming the liquid crystal alignment film, the liquid crystal alignment agent and the interlayer insulating film 21 are used. At least one of the [A] solvent and the [B] solvent are highly effective in suppressing the influence on the interlayer insulating film 21 in the state of being in contact with the interlayer insulating film 21 and suppressing the elution of impurity components from the interlayer insulating film 21. It is preferable that at least one of the above is contained.

[A] The ratio of the solvent used (the total amount when two or more kinds are used) sufficiently satisfies the effect of suppressing the influence on the interlayer insulating film 21 and the effect of suppressing the elution of the impurity component from the interlayer insulating film 21. From the viewpoint of suppressing the precipitation of the polymer component while obtaining the polymer component, the amount is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total amount of the solvent contained in the liquid crystal aligning agent. Further, the upper limit of the usage ratio is preferably 90% by mass or less, preferably 80% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent, from the viewpoint of obtaining the effect of improving the coatability by the solvent [B]. % Or less is more preferable. The solvent [A] may be used alone or in combination of two or more.

[B] The ratio of the solvent used (the total amount when two or more kinds are used) suppresses the influence on the interlayer insulating film 21 and the elution of impurity components from the interlayer insulating film 21, and the coatability of the liquid crystal alignment agent. From the viewpoint of improving the above, the amount is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total amount of the solvent contained in the liquid crystal alignment agent. The upper limit of the usage ratio is preferably 80% by mass or less, more preferably 70% by mass or less, based on the total amount of the solvent contained in the liquid crystal alignment agent. The solvent [B] may be used alone or in combination of two or more.

The ratio of the specific solvent used (the total amount when two or more kinds are used) sufficiently obtains 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. From the viewpoint, it is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and 95% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent. It is particularly preferable that the mass is 70% or more.

Further, when the [A] solvent, the [B] solvent and the other solvent are used, the ratio of the other solvent used (the total amount when two or more kinds are used) sufficiently obtains the effect of the present disclosure. From the viewpoint, it is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 10% by mass or less with respect to the total amount of the solvent contained in the liquid crystal aligning agent. It is particularly preferable that the content is% by mass or less.
It is particularly preferable that the liquid crystal alignment agent has a solvent component of [A] solvent and [B] solvent. However, in the present specification, "the solvent component is composed of [A] solvent and [B] solvent" does not mean that the [A] solvent and other solvents other than the [B] solvent do not interfere with the effect of the present disclosure. It is permissible to contain it to a certain extent.

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

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferable. It is in the range of 1 to 10% by mass. When the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes excessive and it is difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coatability deteriorates. Tend to do.

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

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

[Q] The main skeleton of the polymer is not particularly limited, but it is preferably at least one selected from the group consisting of (meth) acrylic polymers, polyamic acids, polyamic acid esters, polyimides, and polyorganosiloxanes. Among these, a (meth) acrylic polymer is particularly preferable. The (meth) acrylic polymer may have only a structural unit derived from a monomer having a (meth) acryloyl group, or may have a structure derived from a monomer having a (meth) acryloyl group. It may have a unit and a structural unit derived from another monomer different from the monomer having a (meth) acryloyl 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, still more preferably 30 mol% or less. Is.

Specifically, the [Q] polymer has a first structural unit having an acidic group, a second structural unit having an oxetanyl group or an oxylanyl group, and a main structural unit different from the first structural unit and the second structural unit. It is preferably a polymer having a third structural unit forming a chain structure.

As the acidic group of the first structural unit, a carboxy group, a sulfo group, a phenolic hydroxyl group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonamide group, and a hydrogen atom bonded to a carbon atom are electron-withdrawing groups. Examples thereof include a substituted hydroxyalkyl group. As the acidic group, among these, a carboxy group, a sulfo group, a phenolic hydroxyl group, a fluorine-containing alcoholic hydroxyl group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group or a combination thereof is preferable from the viewpoint of alkali developability. A carboxy group or a phenolic hydroxyl group is more preferable, and a carboxy group is particularly preferable.

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

The second structural unit includes glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3- (meth) acryloyloxymethyl-3-. Structural units derived from at least one compound selected from the group consisting of ethyloxetane are preferred.
The content ratio of the second structural unit in the [Q] polymer is preferably 1 to 15 mol%, preferably 3 to 10 mol%, based on the total structural units constituting the [Q] polymer. More preferred. The second structural unit may be one type alone 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 the first structural unit and the second structural unit, but is not particularly limited as long as it has development adhesion and resistance to heat and a peeling solution. It is preferable that the structural unit is derived from at least one compound selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene, and 4-hydroxystyrene in that
The content ratio of the third structural unit in the [Q] polymer is preferably 25 to 80 mol%, preferably 30 to 65 mol%, based on the total structural units constituting the [Q] polymer. More preferred. The third structural unit may be one type alone or a combination of two or more types.

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

([R] Photosensitizer)
[R] As the 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.
Specific examples of these include, for example, O-acyloxime compounds, acetophenone compounds, biimidazole compounds and the like as photoradical polymerization initiators;
As the photoacid generator, for example, an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, a quinonediazide compound and the like;
Examples of the photobase generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamate, α, α-dimethyl-3,5-dimethoxybenzyl carbamate, acyloxyimino and the like.
[R] The proportion of the photosensitive agent used varies depending on the type of the compound used. For example, in the case of a photoradical polymerization initiator, it is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the [Q] polymer.
The proportion of the photoacid generator used is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the [Q] polymer.
The ratio of the photoacid-base agent used is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the [Q] polymer.

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

The radiation-sensitive resin composition is prepared by mixing the [Q] polymer and the [R] photosensitive agent, as well as other optional components to be blended as necessary. The radiation-sensitive resin composition is preferably dissolved in a suitable solvent and used in a solution state. Examples of the solvent include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, and propylene glycol monoalkyl ether. Propylene, ketones, esters and the like can be mentioned.
Regarding the content of the solvent, from the viewpoint of coatability, stability, etc. of the obtained radiation-sensitive resin composition, the total concentration of each component excluding the solvent of the radiation-sensitive resin composition is 5 to 50% by mass. The amount is preferable, and an amount of 10 to 40% by mass is more preferable.

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

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

The method for applying the radiation-sensitive resin composition is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method, a slit coating method, a bar coating method, or an inkjet coating method can be adopted. Of these, the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed. After coating the radiation-sensitive resin composition, the coated surface is preferably heated (prebaked), and if necessary, the coating film is exposed to the coating film through a photomask having a predetermined pattern, and then developed and post-baked. As a result, the interlayer insulating film 21 as a cured film is obtained. As for various conditions for forming the interlayer insulating film 21, for example, the conditions described in Japanese Patent Application Laid-Open No. 2015-92233 can be adopted.

In the subsequent step B, the pixel electrode 19 is formed on the interlayer insulating film 21 formed in the step A of the transparent substrate 18. The pixel electrode 19 is formed with an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film having a film thickness of 50 to 200 nm, more preferably 100 to 150 nm by using a known method such as a sputtering method, and then a photo. It is patterned into a fishbone shape (also referred to as "comb tooth shape") by a lithography method. As a result, the fishbone type pixel electrode 19 is formed on the substrate, and the array substrate 15 is manufactured.

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

In the subsequent step C, first, a liquid crystal alignment agent is applied onto the substrate on which the electrodes are formed, and preferably the coated surface is heated to form a coating film on the substrate. The liquid crystal alignment agent is applied to the substrate on the electrode forming surface, preferably by an offset 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, preheating is preferably performed for the purpose of preventing the applied liquid crystal alignment agent from dripping. The prebake temperature is preferably 30 to 200 ° C., and the prebake time is preferably 0.25 to 10 minutes. Then, a firing (post-baking) step is carried out for the purpose of completely removing the solvent and, if necessary, thermally imidizing the amic acid structure present in the polymer. The firing temperature (post-baking temperature) at this time is preferably 80 to 300 ° C., and the post-baking time is preferably 5 to 200 minutes. The thickness of the film thus formed is preferably 0.001 to 1 μm. After applying the liquid crystal alignment agent on the substrate, the organic solvent is removed to form a liquid crystal alignment film or a coating film to be a liquid crystal alignment film.

Here, the liquid crystal alignment agent is applied on the electrode forming surface of the substrate on which the pattern electrode (pixel electrode 19) having a large number of slit portions 19c is formed on the interlayer insulating film 21. Therefore, the liquid liquid crystal alignment agent comes into 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 via the slit portion 19c in the display region of the liquid crystal device 10.
The coating film formed above may be used as it is as a liquid crystal alignment film, or may be subjected to a treatment (alignment treatment) for imparting a liquid crystal alignment ability. Alignment treatment includes rubbing treatment in which the coating film is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, and cotton, and light irradiation is applied to the coating film formed on the substrate using a liquid crystal alignment agent. Examples thereof include a photo-alignment treatment for imparting a liquid crystal alignment ability to the coating film.

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

The liquid crystal layer 17 is, for example, a method of dropping or applying a liquid crystal composition onto one substrate coated with a sealant and then laminating the other substrate (ODF method), or arranged so as to face each other via a cell gap. The peripheral edges of the pair of substrates are bonded together with a sealant, and the liquid crystal composition is injected and filled in the surface of the substrate and the cell gap surrounded by the sealant, and then formed by a method of sealing the injection holes or the like. It is preferable that the obtained liquid crystal cell is further heated to a temperature at which the liquid crystal used is isotropic, and then subjected to an annealing treatment of slowly cooling to room temperature to remove the flow orientation at the time of filling the liquid crystal.

As the photopolymerizable monomer, a compound having two or more (meth) acryloyl groups can be preferably used because it is highly polymerizable by light. Specific examples thereof include di (meth) acrylate having a biphenyl structure, di (meth) acrylate having a phenyl-cyclohexyl structure, di (meth) acrylate having a 2,2-diphenylpropane structure, and di (meth) acrylate having a diphenylmethane structure. Examples thereof include (meth) acrylate and di-thio (meth) acrylate having a diphenylthioether structure. The blending ratio of the photopolymerizable monomer is preferably 0.1 to 0.5% by mass with respect to the total amount of the liquid crystal composition used for forming the liquid crystal layer 17. As the photopolymerizable monomer, one type may be used alone, or two or more types may be used in combination.

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

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

Then, the liquid crystal device 10 is obtained by bonding the polarizing plates 36 and 37 to the outer surface of the liquid crystal cell. The polarizing plates 36 and 37 include a polarizing plate in which a polarizing film called “H film” in which polyvinyl alcohol is stretched and oriented to absorb iodine and sandwiched between a cellulose acetate protective film, or a polarizing plate made of the H film itself, or the like. Can be mentioned.

In the present embodiment, the first alignment film 32 is formed by using a liquid crystal alignment agent containing a specific solvent as a solvent component. As a result, the liquid crystal display device 10 having excellent reliability can be obtained even when the first alignment film 32 is in contact with the interlayer insulating film 21 via the slit portion 19c. The reason why such an effect was obtained is not clear, but one reason is that the specific solvent used for preparing the liquid crystal alignment agent has a small effect on the interlayer insulating film 21, thereby suppressing the deterioration of the performance of the interlayer insulating film 21. It is possible that it was done. In particular, in the PSA technique, in order to improve the response characteristics of the MVA mode, for example, a fine striped electrode pattern of about several μm is formed. When such a fine electrode pattern is formed on the substrate, when the liquid crystal alignment agent comes into contact with the interlayer insulating film 21, the interlayer insulating film 21 swells and the thickness of the film changes even slightly, and the pixel electrode 19 also has a change. Deformation is likely to occur, which may lead to deterioration of element performance. In this respect, according to the specific solvent, it is presumed that the influence on the pixel electrode 19 can be reduced as much as possible by suppressing the swelling of the interlayer insulating film 21, and thus the deterioration of the element performance can be sufficiently suppressed. It is also speculated that the elution of the impurity component from the interlayer insulating film 21 to the liquid crystal alignment agent could be suppressed in the state where the liquid crystal alignment agent was in contact with the interlayer insulating film 21, and thus the deterioration of the device performance could be sufficiently suppressed. Will be done.

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

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

Also in this case, the first alignment film 32 is formed on the electrode forming surface of the substrate on which the fishbone-shaped pattern electrode (pixel electrode 19) is formed on the interlayer insulating film 29b, whereby the first alignment film 32 is formed. Will come into contact with the interlayer insulating film 29b at the slit portion 19c. In this respect, by forming the first alignment film 32 using the above-mentioned liquid crystal alignment agent, a highly reliable liquid crystal device 10 can be obtained.

(Other embodiments)
In the first embodiment, the pixel electrode 19 on the array substrate 15 side is used as a pattern electrode, and the interlayer insulating film 21 and the first alignment film 32 are in contact with each other at the slit portion 19c, but the pattern is also on the counter electrode 16 side. An electrode and an interlayer insulating film may be provided so that the pattern electrode and the interlayer insulating film are in contact with each other at the slit portion.

The liquid crystal display 10 of the present invention described in detail above can be effectively applied to various applications, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcoder, a PDA, a digital camera, and a mobile phone. , Smartphones, various monitors, liquid crystal televisions, various display devices such as information displays, dimming devices, and the like.

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

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

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

1. 1. Preparation of radiation-sensitive resin composition (for forming an interlayer insulating film) (1) [Q] Synthesis of polymer [Synthesis Example 1: Synthesis of polymer (Q-1)]
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 ethyl ether. Subsequently, 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, substituted with nitrogen, and then the temperature of the solution was raised to 70 ° C. with gentle stirring. A solution containing the polymer (Q-1) was obtained by polymerizing while maintaining the temperature for 5 hours. The Mw of the polymer (Q-1) was 8000.

[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 ethyl ether. Subsequently, 15 parts by mass of methacrylic acid, 40 parts by mass of 3,4-epoxycyclohexyl methacrylate, 20 parts by mass of styrene, 15 parts by mass of tetrahydrofurfuryl methacrylate, and 10 parts by mass of n-lauryl methacrylate were charged, substituted with nitrogen, and then slowly. The temperature of the solution was raised to 70 ° C. while stirring, and the temperature was maintained for 5 hours for polymerization to obtain a solution containing the polymer (Q-2). The Mw of the polymer (Q-2) was 8000.

[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 ethyl ether. Subsequently, 40 parts by mass of glycidyl methacrylate, 20 parts by mass of 4- (α-hydroxyhexafluoroisopropyl) styrene, 10 parts by mass of styrene, and 30 parts by mass of N-cyclohexylmaleimide were charged, replaced with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and the temperature was maintained for 5 hours for polymerization to obtain a solution containing the polymer (Q-3). The Mw of the polymer (Q-3) was 8000.

(2) Preparation of Radiation Sensitive Resin Composition [Preparation Example 1]
In the solution containing the polymer (Q-1) obtained in Synthesis Example 1 (the amount of the polymer (Q-1) corresponding to 100 parts by mass (solid content)), 1,2-octanedione1- Add 20 parts by mass of [4- (phenylthio) -2- (O-benzoyloxime)] (BASF's Irgacure (registered trademark) OXE01), and further add a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD). (Registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) was added in an amount of 100 parts by mass and mixed. Diethylene glycol ethylmethyl ether was added and dissolved so that the solid content concentration became 30% by mass, and then the mixture was filtered through a membrane filter having a diameter of 0.2 μm to prepare a radiation-sensitive resin composition (V-1).
[Preparation Examples 2 to 4]
Radiation-sensitive resin compositions (V-2) to (V-4) were prepared in the same manner as in Preparation Example 1 except that the compounding composition was changed as shown in Table 1 below. In addition, in Table 1 below, "-" means that the corresponding component is not blended (the same applies to the table below).

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

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

[Synthesis Example 9: Synthesis of Polymer (PAA-1)]
70 mol parts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid dianhydride, 30 mol parts of 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, and choles as diamine. 20 mol parts of tanyloxy-2,4-diaminobenzene, 30 mol parts of compound (d-12), 40 mol parts of 4,4'-diaminodiphenylmethane, and 4,4'-[4,4'-propane-1, 3-Diylbis (piperidin-1,4-diyl)] 10 mol parts of dianiline was dissolved in NMP and reacted at room temperature for 6 hours to obtain a solution containing 20% by mass of polyamic acid. The polyamic acid obtained here was used as a polymer (PAA-1).
[Synthesis Example 10]
Polyamic acid (this is referred to as a polymer (PAA-2)) is synthesized in the same manner as in Synthesis Example 9 except that the types and amounts of tetracarboxylic acid dianhydride and diamine used are changed as shown in Table 2 below. did.

[Synthesis Example 11]
100 g of compound (s-1), 500 g of methyl isobutyl ketone, and 10 g of triethylamine were charged in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux cooling tube, and mixed at room temperature. Then, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and then the reaction was carried out at 80 ° C. for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out, washed with a 0.2 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 reactive polyorganosiloxane (reactive polyorganosiloxane). ESSQ-1) was obtained as a viscous transparent liquid. When ¹ H-NMR analysis was performed on this reactive polyorganosiloxane, a peak based on an epoxy group was obtained near chemical shift (δ) = 3.2 ppm, and no side reaction of the epoxy group occurred during the reaction. It was confirmed that. The obtained reactive polyorganosiloxane (ESSQ-1) had a weight average molecular weight Mw of 3000 and an epoxy equivalent of 190 g / mol.
[Synthesis Examples 12, 13]
Reactive polyorganosiloxanes (polymer (ESSQ-2) and polymer (ESSQ-3)) were synthesized in the same manner as in Synthesis Example 11 except that the type and amount of the monomers used were changed as shown in Table 3 below. .. In Table 3, the numerical values in parentheses represent the ratio [molar portion] of each compound to 100 mol parts in total of the monomers used for the synthesis of the polymer.

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

3. 3. Evaluation of liquid crystal alignment agent and liquid crystal display element [Example 1]
(1) Preparation of liquid crystal alignment agent A polymer (PSQ-1) is added to a solution containing a polymer (PI-1) as a polymer component, and a polymer (PI-1): polymer (PSQ-1) =. In addition to the ratio of 95: 5 (mass ratio), NMP, diethylene glycol diethyl ether (DEDG) and diacetone alcohol (DAA) were further added as solvents, and the mixture was sufficiently stirred, and the solvent composition was NMP: DEDG: DAA = 50 :. A solution was prepared at 30:20 (mass ratio) and a solid content concentration of 6.5% by mass. A liquid crystal alignment agent (W-1) was prepared by filtering this solution using a filter having a pore size of 1 μm.

(2) Preparation of liquid crystal composition (LC-1) With respect to 10 g of nematic liquid crystal (MLC-6608 manufactured by Merck Group), the compound represented by the following formula (RM-1) is the total amount of all the constituents of the liquid crystal composition. The liquid crystal composition (LC-1) was obtained by adding the mixture in an amount of 0.3% by mass based on the amount of the liquid crystal composition (LC-1).

(3) Manufacture of liquid crystal display element After applying the radiation-sensitive resin composition (V-1) on a glass substrate (“Corning 7059” (manufactured by Corning)) using a spinner, in a clean oven at 90 ° C. Pre-baking was performed for 10 minutes to form a coating film having a thickness of 2.0 μm on the glass substrate. Then, using a UV (ultraviolet) exposure machine (TOPCON Deep-UV exposure machine TME-400PRJ), 100 mJ of UV light was irradiated through the pattern mask. Then, using a tetramethylammonium hydroxide aqueous solution (developing solution) having a concentration of 2.38% by mass, a developing process was carried out at 25 ° C. for 100 seconds by a liquid filling method. After the development treatment, the coating film is washed with ultrapure water for 1 minute under running water, dried to form a patterned coating film on the substrate, and then heated (post-baked) at 230 ° C. for 30 minutes in an oven to cure. I let you. Next, using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Inc., the entire surface of each coating film was exposed to an exposure amount of 500 J / m ² without using a photomask. Then, post-baking was performed at 230 ° C. for 30 minutes to cure each coating film, and an interlayer insulating film was formed.

Next, an ITO electrode patterned in a fishbone shape was formed on a glass substrate on which an interlayer insulating film was formed. In this embodiment, the electrode pattern of the ITO electrode is a fishbone shape with line / space = 3.5 μm / 3.5 μm. The electrode pattern of the ITO electrode used here is shown in FIG. Further, by performing the same operation, a glass substrate having an ITO electrode having no pattern was prepared. Of these pair of substrates, a 3.5 μm column spacer was formed on the electrode-side surface of the glass substrate having the ITO electrode having no pattern.

Next, a liquid crystal alignment agent (W-1) was spin-coated on each electrode forming surface of the pair of substrates, and then heated (prebaked) on a hot plate at 80 ° C. for 1 minute to remove the solvent, and then 230. It was heated (post-baked) on a hot plate at ° C. for 15 minutes to form a coating film having an average film thickness of 100 nm. This coating film was ultrasonically washed in ultrapure water for 1 minute and then dried in a 100 ° C. clean oven for 10 minutes to obtain a pair of substrates having a liquid crystal alignment film.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm was applied to the outer edge of the ITO surface of the glass substrate having the patterned ITO electrode, and then the liquid crystal composition (the liquid crystal composition () was applied to the inner surface of the epoxy resin adhesive. LC-1) was dropped at 6 points (2 points in the vertical direction × 3 points in the horizontal direction, the interval between the points was 10 mm in the vertical and horizontal directions, and the coating amount of each point was 0.6 mg). This substrate and another glass substrate were overlapped and pressure-bonded so as to face each other, and the adhesive was cured to produce a liquid crystal cell. The obtained liquid crystal cell was irradiated with ultraviolet rays and annealed according to "PSA process-1" described later to prepare a liquid crystal cell for evaluation.
(PSA process-1)
An AC 20Vpp having a frequency of 60 Hz is applied between the electrodes of the liquid crystal cell, and while the liquid crystal is being driven, an ultraviolet irradiation device using a metal halide lamp as a light source is used to irradiate 80 mW of ultraviolet rays for 50 seconds. Subsequently, with no voltage applied, an ultraviolet irradiation device using a metal halide lamp as a light source is used to irradiate 3.5 mW of ultraviolet rays for 30 minutes.
Finally, the liquid crystal cell is placed in a clean oven at 120 ° C. for 10 minutes for annealing. The irradiation amount is a value measured using a photometer measured based on a wavelength of 365 nm.

(4) Evaluation of voltage retention rate (VHR) The evaluation liquid crystal cell manufactured in (3) above is placed in a constant temperature bath, and a voltage of 5 V is applied at 60 ° C. for an application time of 60 microseconds and a span of 167 milliseconds. After that, the voltage holding ratio (VHR) 167 milliseconds after the application was released was measured by "VHR-1" manufactured by Toyo Technica. At this time, when the VHR was 96% or more, it was "very good (◎)", when it was 93% or more and less than 96%, it was "good (○)", and when it was 90% or more and less than 93%. Was evaluated as “OK (Δ)”, and when it was 90% or less, it was evaluated as “Defective (×)”. As a result, in this example, VHR = 97%, which was an evaluation of "very good (⊚)".

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

In Table 5, the numerical values in parentheses in the polymer column indicate the mixing ratio [parts by mass] of each polymer with respect to the total 100 parts by mass of the polymer components used for preparing the liquid crystal alignment agent. The numerical value in the solvent composition column indicates the mixing ratio [parts by mass] of each compound with respect to 100 parts by mass of the whole solvent used for preparing the liquid crystal alignment agent. The abbreviations for solvents are as follows (the same applies to Table 6 below).
NMP: N-Methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone DMI: 1,3-dimethyl-2-imidazolidinone EQM: 3-methoxy-N, N-dimethylpropanamide BC: Butyl cellosolve DEDG: Diethylene glycol Diethyl Ether PGDAc: Propylene Glycol Diacetate DPM: Dipropylene Glycol Monomethyl Ether DAA: Diacetone Alcohol PG: Propylene Glycol Monobutyl Ether DIPE: Diisopentyl Ether

As shown in Table 5, in Examples 1 to 22 in which the liquid crystal alignment film was formed using the liquid crystal alignment agent containing the specific solvent, Comparative Example 1 in which the liquid crystal alignment film was formed using the liquid crystal alignment agent not containing the specific solvent. A liquid crystal display element with higher reliability than that of, 2 was obtained. Among these, Examples 1 to 18 using the liquid crystal alignment agent containing the solvent [A] and the solvent [B] were evaluated as "very good" and were particularly excellent.

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

[Example 23]
(1) Evaluation of ITO wiring deformation N-ethyl-2-pyrrolidone (NEP) and diethylene glycol diethyl ether (DEDG) were mixed and sufficiently stirred, and the solvent composition was evaluated as NEP: DEDG = 50: 50 (mass ratio). A solvent (Z-1) was prepared.
Further, by performing the same operation as in (3) of Example 1, a glass substrate having a pattern electrode made of ITO arranged on an interlayer insulating film was prepared. 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 according to the criteria shown below. The smaller the swelling of the interlayer insulating film and the smaller the deformation of the electrode when it comes into contact with the solvent component of the liquid crystal alignment agent, the smaller the influence of the solvent on the interlayer insulating film and the ITO electrode, and the reliability of the liquid crystal element can be ensured. It can be said that it is suitable as a solvent for a liquid crystal alignment agent. As a result, this example was evaluated as "A".
(Evaluation criteria)
A: No swelling of the interlayer insulating film and no abnormality of the electrode B: Swelling of the interlayer insulating film is observed, but no abnormality of the electrode C: There is a slight abnormality such as deformation of the electrode due to swelling of the interlayer insulating film D: Between layers There is a serious abnormality such as disconnection of the electrode due to swelling of the insulating film.

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

From the results shown in Table 6, in Examples 23 to 44 using the specific solvent, no swelling of the interlayer insulating film was observed, or even if the interlayer insulating film swelled, the degree of swelling was small, and no abnormality was observed in the electrodes. From these results, it was found that, according to the specific solvent, the shape of the electrode does not easily change even when the liquid crystal alignment film is formed on the fine striped electrode pattern, and the reliability of the liquid crystal element can be ensured.

1 ... ITO electrode, 2 ... Slit portion, 3 ... Light-shielding film, 10 ... Liquid crystal device, 14 ... Thin film transistor, 15 ... Array substrate, 16 ... Opposing substrate, 17 ... Liquid crystal layer, 19 ... Pixel electrode, 19c ... Slit portion, 21 ... Interlayer insulating film, 29 ... Color filter layer, 29a ... Colored pattern, 29b ... Interlayer insulating film, 31 ... Common electrode, 32 ... First alignment film, 33 ... Second alignment film, 34, 35 ... PSA layer (Orientation control) layer)

Claims (11)

A method for manufacturing a liquid crystal element including a pair of substrates arranged to face each other, a liquid crystal layer arranged between the pair of substrates, and a pair of electrodes.
At least one of the pair of electrodes is a pattern electrode having a plurality of openings.
A step of forming an interlayer insulating film on at least one of the pair of substrates,
The step of forming the pattern electrode on the interlayer insulating film and
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 is included.
The interlayer insulating film is formed by using a radiation-sensitive resin composition containing a [Q] polymer and an [R] photosensitive agent.
The [Q] polymer forms a backbone structure different from the first structural unit having an acidic group, the second structural unit having an oxetanyl group or an oxylanyl group, and the first structural unit and the second structural unit. It is a polymer having a third structural unit and
The first structural unit is a structural unit derived from at least one compound selected from the group consisting of (meth) acrylic acid and unsaturated carboxylic acid anhydride.
The second structural unit is glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3- (meth) acryloyloxymethyl-3-. It is a structural unit derived from at least one compound selected from the group consisting of ethyloxetane.
A method for manufacturing a liquid crystal element, wherein the liquid crystal alignment film is formed by using a liquid crystal alignment agent containing a polymer component and at least one solvent selected from the solvent group shown below.
Solvent group:
[A] Solvent: A compound represented by the following formula (1), a compound represented by the following formula (2), N, N, 2-trimethylpropionamide, and 1,3-dimethyl-2-imidazolidinone.
[B] Solvent: Dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, 4-methoxy-4-methyl-2-pentanone, 4-hydroxy-2-butanone, 2-methyl-2-hexanol, 2 , 6-Dimethyl-4-heptanol, diisobutylketone, propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, diacetone alcohol, and propylene glycol monobutyl ether.

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

(In the formula (2), R ² and R ³ are independently each of a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or "-O-" between carbon-carbon bonds of the hydrocarbon group. , And R ² and R ³ may be bonded to each other to form a ring structure. R ⁴ is an alkyl group having 1 to 6 carbon atoms.) The claim further comprises a step of forming an orientation control layer for controlling the orientation of the liquid crystal at the interface on each substrate side in the liquid crystal layer by polymerizing the photopolymerizable monomer mixed in the liquid crystal layer. The method for manufacturing a liquid crystal element according to 1. The method for manufacturing a liquid crystal element according to claim 1 or 2, wherein the liquid crystal alignment agent contains at least one of the [A] solvent and at least one of the [B] solvent. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the liquid crystal alignment agent contains at least one [P] polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane. A method for manufacturing a liquid crystal element. The liquid crystal alignment agent contains at least one [p] polymer selected from the group consisting of polyamic acid, polyamic acid ester and polyimide.
Any of claims 1 to 4, wherein the [p] polymer has a partial structure derived from a tetracarboxylic acid derivative having at least one ring structure selected from the group consisting of a cyclobutane ring, a cyclopentane ring and a cyclohexane ring. The method for manufacturing a liquid crystal element according to item 1. The liquid crystal alignment agent comprises a radical polymerizable group, a photoinitiator group, a radical polymerization prohibiting agent group, a nitrogen-containing heterocycle (excluding the imide ring of polyimide), an amino group, and a protected amino group. The method for producing a liquid crystal element according to any one of claims 1 to 5, which contains a polymer having at least one selected from the group. The method for manufacturing a liquid crystal element according to any one of claims 1 to 6, wherein the liquid crystal alignment agent contains a polymer having a partial structure represented by the following formula (3).
* -L ¹ -R ¹¹ -R ¹² -R ¹³ -R ¹⁴ ... (3)
(In the formula (3), L ¹ is -O-, -CO-, -COO- * ¹ , -OCO- * ¹ , -NR ^15- , -NR ¹⁵ -CO- * ¹ , -CO-NR ¹⁵ -* ¹ , an alkanediyl group having 1 to 6 carbon atoms, -OR ^16- * ¹ or -R ¹⁶ -O- * ¹ (however, R ¹⁵ is a hydrogen atom or a monovalent group having 1 to 10 carbon atoms. It is a hydrocarbon group, R ¹⁶ is an alkanediyl group having 1 to 3 carbon atoms. “* ¹ ” indicates that it is a bond with R ^11. ). R ¹¹ and R ¹³ are Each is independently a single bond, a phenylene group or a cycloalkylene group, and R ¹² is a single bond, a phenylene group, a cycloalkylene group, -R ¹⁷ -B ^1- * ² , or -B ¹ -R ^17- * ² . (However, R ¹⁷ is a phenylene group or a cycloalkylene group, B ¹ is -COO- * ³ , -OCO- * ³ , or an alkanediyl group having 1 to 3 carbon atoms. "* ² " is R. It indicates that it is a bond with ¹³ and "* ³ " indicates that it is a bond with R ¹⁷ ). R ¹⁴ is a hydrogen atom, a fluorine atom, and an alkyl having 1 to 18 carbon atoms. A group, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a fluoroalkoxy group having 1 to 18 carbon atoms, or a hydrocarbon group having a steroid skeleton and having 17 to 51 carbon atoms, which is radically polymerized. It may have a sex group or a photoinitiator group. However, when R ¹⁴ is a hydrogen atom, a fluorine atom or a group having 1 to 3 carbon atoms, all of R ¹¹ , R ¹² and R ¹³ are single-bonded. It does not become. "*" Indicates that it is a bond.) The method for manufacturing a liquid crystal element according to any one of claims 1 to 7, wherein a liquid crystal drive element and a color filter layer are formed on a substrate forming the interlayer insulating film. The method for producing a liquid crystal element according to any one of claims 1 to 8, wherein the [Q] polymer has at least one selected from the group consisting of a ( meth) acryloyl group and a vinyl group. The liquid crystal element according to any one of claims 1 to 9, wherein the [R] photosensitive agent is at least one selected from the group consisting of a photoradical polymerization initiator, a photoacid generator, and a photobase generator. Manufacturing method. The third structural unit is any one of claims 1 to 10 , which is a structural unit derived from at least one compound selected from the group consisting of styrene, α-methylstyrene, 4-methylstyrene, and 4-hydroxystyrene. The method for manufacturing a liquid crystal element according to item 1.

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