JP2008191270A - Composition for forming planarizing insulating film for liquid crystal display element and method for producing planarizing insulating film for liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a planarizing insulating film for a liquid crystal display element having photosensitivity and excellent transparency and heat resistance. <P>SOLUTION: The composition for forming such a planarizing insulating film for a liquid crystal display element is provided which comprises a resin (A) comprising a constitutional unit (a1) represented by general formula (a1-1) [wherein R<SP>1</SP>represents a single bond or a straight- or branched-chain alkylene group; R<SP>101</SP>represents an alkyl group; and n1 represents an integer of 0-4] and a photosensitizing agent (B). A method for producing such a planarizing insulating film for a liquid crystal display element is provided which comprises: forming a resin film on a substrate using the composition; exposing and developing the resin film to form a pattern; and baking the pattern. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composition for forming a planarizing insulating film for liquid crystal display elements and a method for producing a planarizing insulating film for liquid crystal display elements.

Conventionally, in electronic parts such as liquid crystal display elements, integrated circuit elements, solid-state imaging elements, protective films for preventing deterioration and damage and interlayer insulating films for insulating electrodes, wirings, etc. have been provided. .
In the case of an integrated circuit element, for example, a multi-layer wiring of an LSI (Large Scale Integrated Circuit Element) is formed by alternately forming and processing metal wiring that conducts electricity and an interlayer insulating film that electrically insulates them. .
In the case of a liquid crystal display element, for example, a TFT (thin film transistor) type liquid crystal display element is generally a transparent conductive circuit such as ITO (indium-tin-oxide) on a transparent substrate such as a glass substrate provided with a polarizing plate. Layers and TFTs are formed and covered with an interlayer insulating film to form a back plate (liquid crystal array substrate). On a transparent substrate such as a glass substrate provided with a polarizing plate, a black matrix layer and a color filter layer are provided as necessary. In addition, a transparent conductive circuit layer such as ITO is formed sequentially to form an upper surface plate (counter substrate), and the liquid crystal array substrate and the counter substrate are opposed to each other via a spacer, and liquid crystal is sealed between the two plates. Manufactured.

An example of the liquid crystal array substrate is shown in FIGS. FIG. 1 is a schematic top view showing one of the pixel regions of the liquid crystal array substrate 1, and FIG. 2 is a partially enlarged view of a cross section at a position AA ′ in FIG.
In general, the liquid crystal array substrate 1 includes a plurality of gate lines 3 formed on a transparent substrate 2, a plurality of source lines 4 orthogonal to the gate lines 3, and a plurality of regions (pixel regions) surrounded by them. ), Each of the transparent pixel electrodes 5 and the TFT 6 disposed on each pixel electrode 5.
The TFT 6 includes a gate 7 formed on the transparent substrate 2 and an amorphous silicon layer 9 provided above the gate 7 via an insulating film (gate insulating film) 8. The gate line 3 and the gate 7 are connected via a gate electrode 10. The source line 4 and the amorphous silicon layer 9 are connected via a source electrode. The amorphous silicon layer 9 and the pixel electrode 5 are connected via the drain electrode 11.
A transparent interlayer insulating film 12 is provided on the transparent substrate 2 so as to cover the TFT 6, the source line 4 and the gate line 5. The interlayer insulating film 12 flattens unevenness on the surface derived from the TFT 6 and the like on the interlayer insulating film 13 and the interlayer insulating film 13 with high insulating properties that directly cover the TFT 6, the source line 4 and the gate line 5. For this purpose, an interlayer insulating film (planarized insulating film) 14 is provided.
By providing the planarization insulating film, a sufficient distance between the pixel electrode and the TFT can be secured in the longitudinal cross-sectional direction, so that the pixel electrode can be provided in the entire region surrounded by the source line and the gate line, and the effective pixel range. Will increase. As a result, the aperture ratio of the liquid crystal display element is improved, which contributes to power saving and luminance improvement. Further, since the flatness of the surface of the liquid crystal array substrate is improved, spots on the liquid crystal portion can be reduced, and there is an advantage that the image quality is improved.

Currently, in the manufacture of liquid crystal display elements, acrylic resins are mainly used as materials for forming an interlayer insulating film because of its excellent transparency.
In addition, as a material used for forming the interlayer insulating film, a photosensitive material is desired because of excellent workability when forming a pixel electrode or the like. For example, in the manufacture of the liquid crystal array substrate shown in FIG. 2, it is necessary to provide a hole in the interlayer insulating film in order to partially connect the TFT and the pixel electrode, but by using a photosensitive material, The processing can be easily performed.
For example, Patent Documents 1 and 2 describe a photosensitive resin composition containing an acrylic alkali-soluble resin and a photosensitive agent as a material for forming an interlayer insulating film.
JP-A-10-153854 JP 2006-259083 A

However, the material for forming an interlayer insulating film that has been proposed so far is overwhelmingly less photosensitive.
Moreover, in a liquid crystal display element, the process at high temperature may be performed at the time of manufacture of a liquid crystal display element, and high heat resistance is required, but the said photosensitive resin composition is not enough heat resistance. For example, there is an SOG (spin on glass) thin film that can form an interlayer insulating film having a heat resistance close to 400 ° C., but such a material has conventionally not been photosensitive. When using a non-photosensitive material, a resist film is formed on the insulating film, the resist film is patterned to form a resist pattern, the resist pattern is used as a mask, and then the resist is peeled off. This requires a large number of processes, and has disadvantages in terms of throughput and cost.
In particular, in the use of a planarization insulating film, since it is necessary to increase the film thickness to some extent, transparency is extremely important, and further improvement in transparency is required.
The present invention has been made in view of the above circumstances, and has a composition capable of forming a planarization insulating film for a liquid crystal display element having photosensitivity and excellent transparency and heat resistance, and the liquid crystal display element It is an object of the present invention to provide a method for manufacturing a planarization insulating film.

In order to achieve the above object, the present invention employs the following configuration.
That is, the first aspect of the present invention includes a resin (A) containing a structural unit (a1) represented by the following general formula (a1-1), and a photosensitizer (B). A composition for forming a planarizing insulating film for a liquid crystal display device.

［式中、Ｒ^１は単結合または直鎖状もしくは分岐鎖状のアルキレン基を表し、Ｒ^１０１はアルキル基を表し、ｎ１は０〜４の整数を表す。］

[Wherein, R ¹ represents a single bond or a linear or branched alkylene group, R ¹⁰¹ represents an alkyl group, and n1 represents an integer of 0 to 4. ]

  The second aspect of the present invention is a step of forming a resin film on a support using the planarization insulating film forming composition for a liquid crystal display element of the first aspect, a step of exposing the resin film, It is a method for producing a planarization insulating film for a liquid crystal display element, including a step of developing the resin film to form a pattern and a step of baking the pattern.

In the present specification and claims, the “structural unit” means a monomer unit (monomer unit) constituting a resin (polymer, copolymer).
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
The “alkylene group” includes linear, branched and cyclic divalent saturated hydrocarbon groups unless otherwise specified.
A “lower alkyl group” is an alkyl group having 1 to 5 carbon atoms.
“Exposure” is a concept that includes radiation exposure in general.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a composition capable of forming a planarization insulating film for a liquid crystal display element having photosensitivity and excellent transparency and heat resistance, and a method for producing the planarization insulating film for a liquid crystal display element.

≪Composition for flattening insulating film formation for liquid crystal display element≫
The composition for forming a planarization insulating film for a liquid crystal display element of the present invention is a resin (A) containing the structural unit (a1) represented by the general formula (a1-1) (hereinafter referred to as component (A). ) And a photosensitive agent (B) (hereinafter referred to as component (B)).
A resin film formed using such a composition is insoluble in alkali due to the presence of component (B) before exposure. When the resin film is exposed, the structure of the component (B) is changed and the alkali solubility is increased. Therefore, when alkali development is performed after exposure, the exposed portion is dissolved, while the unexposed portion remains as it is, so that a positive pattern is formed on the resin film. Then, by further baking the resin film on which the pattern is formed, a planarization insulating film having a predetermined pattern is formed.

<(A) component>
"Structural unit (a1)"
In general formula (a1-1), when R ¹ is a single bond, the benzene ring is directly bonded to the silicon atom.
The alkylene group for R ¹ preferably has 1 to 5 carbon atoms.
Examples of the linear alkylene group include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group.
Examples of the branched alkylene group include a methylethylene group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 1,1-dimethylethylene group, and 1-methylbutane. -1,4-diyl group, 2-methylbutane-1,4-diyl group, 1,2-dimethylpropane-1,3-diyl group, 1,1-dimethylpropane-1,3-diyl group, 2,2 -A dimethylpropane- 1, 3- diyl group etc. are mentioned.
R ¹ is preferably a linear alkylene group, particularly preferably a methylene group or an ethylene group.

In formula (a1-1), the bonding position of the hydroxyl group in the benzene ring is not particularly limited, but the para position is preferable with respect to the bonding position of R ¹ .

The benzene ring in general formula (a1-1) may have R ¹⁰¹ as a substituent. “Having R ¹⁰¹ ” means that part or all of the hydrogen atoms bonded to the carbon atoms constituting the benzene ring are substituted with R ¹⁰¹ .
As the alkyl group for R ¹⁰¹ , an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, and an isopentyl group. And neopentyl group. Industrially, a methyl group or an ethyl group is preferable.
n1 is an integer of 0 to 4, 0 or 1 is preferable, and 0 is particularly preferable.

As the structural unit (a1), one type may be used alone, or two or more types may be used in combination.
In the component (A), the proportion of the structural unit (a1) is preferably 10 mol% or more, more preferably 25 mol% or more, more preferably 30 mol, based on the total of all the structural units constituting the component (A). % Or more is more preferable. When it is 20 mol% or more, the alkali solubility after exposure is improved, and a good pattern can be formed. The upper limit is not particularly limited, but is preferably 80 mol% or less, and most preferably 75 mol% or less.

  The component (A1) may contain a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include the structural units (a2) to (a5) shown below.

"Structural unit (a2)"
The component (A) preferably further contains a structural unit (a2) represented by the following general formula (a2-1). Thereby, the alkaline dissolution inhibitory effect improves and it becomes unnecessary to add a large amount of (B) component.

［式中、Ｒ^２は芳香族炭化水素基またはアルキル基を表す。］

[Wherein R ² represents an aromatic hydrocarbon group or an alkyl group. ]

Examples of the aromatic hydrocarbon group for R ² include a group in which one hydrogen atom has been removed from an aromatic ring that may or may not have a substituent.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like.
Examples of the substituent that the aromatic ring may have include the same substituents as those exemplified as the substituent that the benzene ring in formula (a1-1) may have.
As the aromatic hydrocarbon group for R ² , a phenyl group or a phenanthryl group is particularly preferable.

The alkyl group for R ² may be linear, branched or cyclic.
The linear alkyl group preferably has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.
The branched alkyl group preferably has 3 to 5 carbon atoms, such as 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, 1-methylbutyl. Group, 2-methylbutyl group, 3-methylbutyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group and the like.
The cyclic alkyl group preferably has 3 to 10 carbon atoms in the basic ring (the number of carbon atoms constituting the ring), more preferably a cyclopentyl group or a cyclohexyl group. In the cyclic alkyl group, a substituent may be bonded to the basic ring, and examples of the substituent include the same as those for R ¹⁰¹ in formula (a1-1).
As the alkyl group for R ² , a linear alkyl group having 3 to 5 carbon atoms is particularly preferable.

As the structural unit (a2), one type may be used alone, or two or more types may be used in combination.
In the component (A), the proportion of the structural unit (a2) is preferably in the range of 5 to 80 mol%, more preferably 10 to 75 mol%, based on the total of all structural units constituting the component (A). Preferably, 20 to 70 mol% is more preferable. The effect by containing a structural unit (a2) is fully acquired as it is more than the lower limit of the said range, and a balance with another structural unit is favorable when it is below an upper limit.

"Structural unit (a3)"
The structural unit (a3) is a structural unit represented by the following general formula (a3-1).

［式中、Ｒ^３は単結合または直鎖状もしくは分岐鎖状のアルキレン基を表し、Ｒ^４は直鎖状または分岐鎖状のアルキル基を表し、Ｒ^１０３はアルキル基を表し、ｎ３は０〜４の整数を表す。］

[Wherein R ³ represents a single bond or a linear or branched alkylene group, R ⁴ represents a linear or branched alkyl group, R ¹⁰³ represents an alkyl group, and n3 represents 0 Represents an integer of ~ 4. ]

Examples of R ³ include the same as R ¹ in formula (a1-1).
Examples of R ⁴ include the same as the linear alkyl group and the branched alkyl group mentioned as the alkyl group for R ² in formula (a2-1).
Examples of R ¹⁰³ and n3 in the general formula (a3-1) include the same as R ¹⁰¹ and n1 in the general formula (a1-1).

As the structural unit (a3), one type of structural unit may be used alone, or two or more types may be used in combination.
When the structural unit (a3) is contained, the proportion of the structural unit (a3) in the component (A) is preferably 5 to 50 mol% with respect to the total of all the structural units constituting the component (A). 30 mol% is more preferable.

"Structural unit (a4)"
The structural unit (a4) is a structural unit represented by the following general formula (a4-1).

［式中、Ｒ^５は単結合または直鎖状もしくは分岐鎖状のアルキレン基を表し、Ｒ^６は直鎖状または分岐鎖状のアルキル基を表し、Ｒ^１０４はアルキル基を表し、ｎ４は０〜４の整数を表す。］

[Wherein, R ⁵ represents a single bond or a linear or branched alkylene group, R ⁶ represents a linear or branched alkyl group, R ¹⁰⁴ represents an alkyl group, and n4 represents 0. Represents an integer of ~ 4. ]

Examples of R ⁵ include the same as R ¹ in formula (a1-1).
Examples of R ⁶ include the same as the linear alkyl group and the branched alkyl group mentioned as the alkyl group for R ² in formula (a2-1).
Examples of R ¹⁰⁴ and n4 in general formula (a4-1) include the same as R ¹⁰¹ and n1 in general formula (a1-1).

As the structural unit (a4), one type may be used alone, or two or more types may be used in combination.
When the structural unit (a4) is contained, the proportion of the structural unit (a4) in the component (A) is preferably 5 to 50 mol% with respect to the total of all the structural units constituting the component (A). 30 mol% is more preferable.

"Structural unit (a5)"
The structural unit (a5) is a structural unit represented by the following general formula (a5-1).

［式中、Ｒ^７は単結合または直鎖状もしくは分岐鎖状のアルキレン基を表し、Ｒ^８は直鎖状または分岐鎖状のアルキル基を表し、Ｒ^１０５はアルキル基を表し、ｎ５は０〜４の整数を表す。］

[Wherein, R ⁷ represents a single bond or a linear or branched alkylene group, R ⁸ represents a linear or branched alkyl group, R ¹⁰⁵ represents an alkyl group, and n5 represents 0. Represents an integer of ~ 4. ]

Examples of R ⁷ include the same as R ¹ in formula (a1-1).
Examples of R ⁸ include the same as the linear alkyl group and the branched alkyl group mentioned as the alkyl group for R ² in formula (a2-1).
Examples of R ¹⁰⁵ and n5 in general formula (a5-1) include the same as R ¹⁰¹ and n1 in general formula (a1-1), respectively.

As the structural unit (a5), one type of structural unit may be used alone, or two or more types may be used in combination.
When the structural unit (a5) is contained, the proportion of the structural unit (a5) in the component (A) is preferably 5 to 50 mol% with respect to the total of all the structural units constituting the component (A). 30 mol% is more preferable.

The weight average molecular weight (Mw) of component (A) (polystyrene conversion by gel permeation chromatography (hereinafter sometimes abbreviated as GPC, hereinafter the same)) is not particularly limited, but 2000 to 15000 is Preferably, 2500 to 10,000 are more preferable. By setting it as this range, the solubility to an organic solvent becomes favorable.
Moreover, although Mw / number average molecular weight (Mn) is not specifically limited, Preferably it is 1.0-6.0, More preferably, it is 1.0-2.0. By setting it as this range, resolution and pattern shape become favorable.
The component (A) can be produced, for example, by the method described in Japanese Patent No. 2567984.

<(B) component>
The component (B) is not particularly limited as long as it is generally used as a photosensitizer in a positive resist composition.
In the present invention, the component (B) is preferably a compound having a naphthoquinonediazide group (a quinonediazide group-containing compound).
Examples of the quinonediazide group-containing compound include esterified products of a naphthoquinonediazidesulfonic acid compound and a phenol compound.

Examples of the naphthoquinonediazide sulfonic acid compound include naphthoquinone-1,2-diazide-5-sulfonic acid and naphthoquinone-1,2-diazide-4-sulfonic acid.
Examples of the phenol compound include polyhydroxybenzophenone compounds such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone;
Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, Bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5- Dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, Bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyl Nylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4- Hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) ) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenyl Methane, bis (5-cyclohexyl-4-hydro Trisphenol compounds such as shea-2-methylphenyl) -3,4-dihydroxyphenyl methane;
Linear type 3 such as 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol Nuclear phenolic compounds;
1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy-5-methylbenzyl) ) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl)- 4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl- 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4- Loxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2-hydroxy-) 5-methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [2,5-dimethyl-3- ( Linear tetranuclear phenolic compounds such as 2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane;
2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5 Linear type 5 such as -methylbenzyl] -6-cyclohexylphenol and 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol Linear polyphenol compounds such as nuclear phenol compounds;
Bis (2,3-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4′-hydroxyphenylmethane, 2- (2,3,4- Trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3′-fluoro-4′-hydroxyphenyl) propane, 2- ( 2,4-dihydroxyphenyl) -2- (4′-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4′-hydroxypheny) ) Propane, 2- (2,3,4-hydroxyphenyl) -2- (4'-hydroxy-3 ', bisphenol type compounds such as 5'-dimethylphenyl) propane;
1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl]- Polynuclear branched compounds such as 4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;
Examples thereof include condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane.

An esterified product of a naphthoquinone diazide sulfonic acid compound and a phenol compound is, for example, the above-mentioned phenol compound and naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazide-4-sulfonyl chloride, dioxane, etc. In an appropriate solvent, in the presence of an alkali such as triethanolamine, alkali carbonate or alkali hydrogencarbonate, and a part or all of the hydroxyl group can be esterified.

The esterified product preferably has an esterification rate of 40 to 100%, and more preferably 50 to 100%. The esterification rate can be determined by [(number of hydroxyl groups esterified) / (total number of hydroxyl groups (of phenol compound) before esterification)] × 100.

Other quinonediazide group-containing compounds other than those described above can also be used.
Other quinonediazide group-containing compounds include, for example, orthoquinonediazides such as orthobenzoquinonediazide, orthonaphthoquinonediazide, orthoanthraquinonediazide; nucleus-substituted derivatives thereof (for example, orthonaphthoquinonediazidesulfonate esters, etc.); orthoquinonediazidesulfonyl chloride, Compounds having a hydroxyl group or an amino group (for example, phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, hydroxyl group partially Reaction products with gallic acid, aniline, p-aminodiphenylamine, etc., which are esterified or etherified, and the like.

These may be used alone or in combination of two or more.
As the component (B), an esterified product of a phenol compound represented by the following general formula (b-1) and a naphthoquinone diazide sulfonic acid compound is particularly preferable.

［式中、Ｒ^１１〜Ｒ^２０はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基または炭素原子数１〜６のアルコキシ基を表し；Ｒ^２２〜Ｒ^２５はそれぞれ独立に水素原子または炭素原子数１〜６のアルキル基を表し；Ｒ^２１は水素原子または炭素原子数１〜６のアルキル基を表し、Ｑ^１は水素原子、炭素数１〜６のアルキル基または下記一般式（ｂ−２）で表される基を表すか、またはＲ^２１の末端とＱ^１の末端とが結合して炭素数２〜５のアルキレン基を形成してもよく；ａ、ｂは１〜３の整数を表し；ｄ、ｅは０〜３の整数を表し；ｈ、ｉはｈ＋ｉ＝０〜３となる整数を表す。］

[Wherein, R ^{11 to} R ²⁰ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; R ^{22 to} R ²⁵ each independently represent Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ²¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the following general formula The group represented by the formula (b-2) may be represented, or the terminal of R ^{21 and} the terminal of Q ¹ may be bonded to form an alkylene group having 2 to 5 carbon atoms; D represents an integer of 0 to 3; h and i represent an integer of h + i = 0 to 3; ]

［式中、Ｒ^２６及びＲ^２７はそれぞれ独立に水素原子、ハロゲン原子、炭素原子数１〜６のアルキル基または炭素原子数１〜６のアルコキシ基を表し；ｃは１〜３の整数を表す。］

[Wherein R ²⁶ and R ²⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; c represents an integer of 1 to 3] . ]

Examples of the halogen atom in R ^{11 to} R ²⁰ , R ²⁶ and R ²⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group in R ^{11 to} R ²⁷ may be linear, branched or cyclic, and is particularly preferably a methyl group or a cyclohexyl group.
When bonded and the end of the terminal and to ^{Q 1} R ²¹ form an alkylene group having 2 to 5 carbon atoms, and ^{Q 1,} and ^{R 21,} the carbon atoms between ^{Q 1, R 21} A cyclic alkyl group having 3 to 6 carbon atoms is formed.

  (B) As for the compounding quantity of a component, 5-200 mass parts is preferable with respect to 100 weight part of (A) component, 5-100 mass parts is more preferable, 5-50 mass parts is more preferable, 10-20 mass parts Is most preferred. When it is at least the lower limit of the above range, the sensitivity, resolution and the like are improved, and when it is at most the upper limit, the transparency, insulation, low dielectric constant and the like of the resulting film are improved.

<Acid generator (C)>
The composition for forming a planarization insulating film for a liquid crystal display element of the present invention is an acid generator (C) that generates an acid upon irradiation (exposure) of radiation as an optional component, as long as the effects of the present invention are not impaired. (Hereinafter referred to as the component (C)). By including the component (C), sensitivity, resolution and the like are improved.
The component (C) is not particularly limited, and those that have been proposed as acid generators for chemically amplified resists can be used. Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and poly (bissulfonyl) diazomethanes. There are various known diazomethane acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like.

  Examples of the onium salt acid generator include acid generators represented by the following general formula (c-0).

［式中、Ｒ^５１は、直鎖、分岐鎖若しくは環状のアルキル基、または直鎖、分岐鎖若しくは環状のフッ素化アルキル基を表し；Ｒ^５２は、水素原子、水酸基、ハロゲン原子、直鎖若しくは分岐鎖状のアルキル基、直鎖若しくは分岐鎖状のハロゲン化アルキル基、または直鎖若しくは分岐鎖状のアルコキシ基であり；Ｒ^５３は置換基を有していてもよいアリール基であり；ｕ”は１〜３の整数である。］

[Wherein R ⁵¹ represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group; R ⁵² represents a hydrogen atom, a hydroxyl group, a halogen atom, linear or A branched alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group; R ⁵³ is an optionally substituted aryl group; u "Is an integer from 1 to 3.]

In General Formula (c-0), R ⁵¹ represents a linear, branched, or cyclic alkyl group, or a linear, branched, or cyclic fluorinated alkyl group.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
The fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. The fluorination rate of the fluorinated alkyl group (ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. Those in which all hydrogen atoms are substituted with fluorine atoms are preferred because the strength of the acid is increased.
R ⁵¹ is most preferably a linear alkyl group or a fluorinated alkyl group.

R ⁵² represents a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group, a linear or branched alkyl halide group, or a linear or branched alkoxy group.
In R ⁵² , examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
In R ⁵² , the alkyl group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
In R ⁵² , the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms. Examples of the alkyl group herein are the same as the “alkyl group” in R ⁵² . Examples of the halogen atom to be substituted include the same as those described above for the “halogen atom”. In the halogenated alkyl group, it is desirable that 50 to 100% of the total number of hydrogen atoms are substituted with halogen atoms, and it is more preferable that all are substituted.
In R ⁵² , the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.
Among these, R ⁵² is preferably a hydrogen atom.

R ⁵³ is an aryl group which may have a substituent, and examples of the structure of the basic ring (matrix ring) excluding the substituent include a naphthyl group, a phenyl group, an anthryl group, and the like. From the viewpoint of absorption of exposure light such as ArF excimer laser, a phenyl group is desirable.
Examples of the substituent include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group).
As the aryl group for R ^53, an aryl group having no substituent is more preferable.
u ″ is an integer of 1 to 3, preferably 2 or 3, and particularly preferably 3.

  Preferable examples of the acid generator represented by the general formula (c-0) include the following.

  Moreover, as another onium salt type acid generator of the acid generator represented by general formula (c-0), the compound represented by the following general formula (c-1) or (c-2) is mentioned, for example. .

［式中、Ｒ^１”〜Ｒ^３”，Ｒ^５”〜Ｒ^６”は、それぞれ独立に、アリール基またはアルキル基を表し；Ｒ^４”は、直鎖、分岐または環状のアルキル基またはフッ素化アルキル基を表し；Ｒ^１”〜Ｒ^３”のうち少なくとも１つはアリール基を表し、Ｒ^５”〜Ｒ^６”のうち少なくとも１つはアリール基を表す。］

[Wherein, R ¹ ″ to R ³ ″ and R ⁵ ″ to R ⁶ ″ each independently represents an aryl group or an alkyl group; R ⁴ ″ represents a linear, branched or cyclic alkyl group or fluorinated group. Represents an alkyl group; at least one of R ¹ ″ to R ³ ″ represents an aryl group, and at least one of R ⁵ ″ to R ⁶ ″ represents an aryl group.]

In formula (c-1), R ¹ ″ to R ³ ″ each independently represents an aryl group or an alkyl group. At least one of R ¹ ″ to R ³ ″ represents an aryl group. Of R ¹ ″ to R ³ ″, two or more are preferably aryl groups, and most preferably all of R ¹ ″ to R ³ ″ are aryl groups.
The aryl group for R ¹ ″ to R ³ ″ is not particularly limited, and is, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl groups, alkoxy groups It may or may not be substituted with a group, a halogen atom or the like. The aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.
The alkyl group that may be substituted for the hydrogen atom of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Is most preferred.
The alkoxy group that may be substituted with a hydrogen atom of the aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and most preferably a methoxy group or an ethoxy group.
The halogen atom that may be substituted for the hydrogen atom of the aryl group is preferably a fluorine atom.
The alkyl group for R 1 ^{"~R 3",} is not particularly limited, for example, a straight, include alkyl groups such as branched or cyclic. It is preferable that it is C1-C5 from the point which is excellent in resolution. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decanyl group. A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost.
Among these, R ¹ ″ to R ³ ″ are most preferably a phenyl group or a naphthyl group, respectively.

R ⁴ ″ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group is a cyclic group as indicated by R ¹ ″ and preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and 6 carbon atoms. Most preferably, it is -10.
The fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. The fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%. Particularly, all the hydrogen atoms are substituted with fluorine atoms. It is preferable because the strength of the acid is increased.
R ⁴ ″ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.

In formula (c-2), R ⁵ ″ to R ⁶ ″ each independently represents an aryl group or an alkyl group. At least one of R ⁵ ″ to R ⁶ ″ represents an aryl group. It is preferable that all of R ⁵ ″ to R ⁶ ″ are aryl groups.
As the aryl group for R ⁵ ″ to R ⁶ ″, the same as the aryl groups for R ¹ ″ to R ³ ″ can be used.
As the alkyl group for R ⁵ ″ to R ⁶ ″, the same as the alkyl groups for R ¹ ″ to R ³ ″ can be used.
Among these, it is most preferable that all of R ⁵ ″ to R ⁶ ″ are phenyl groups.
^{R 4} in the formula (c-2) "as the ^{R 4} in the formula (c-1)" are the same as those for.

  Specific examples of the onium salt acid generator represented by the formula (c-1) or (c-2) include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert-butylphenyl) iodonium. Trifluoromethanesulfonate or nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, tri (4-methylphenyl) sulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or the same Nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium trifluoromethanesulfonate, and its hepta Fluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of diphenylmonomethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutane Sulfonate, trifluoromethanesulfonate of (4-methylphenyl) diphenylsulfonium, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, trifluoromethane sulfonate of (4-methoxyphenyl) diphenylsulfonium, its heptafluoropropane sulfonate or its nonafluorobutane Sulfonate, tri (4-tert-butyl) phenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutanesulfonate, diphenyl (1- (4-methoxy) naphthyl) sulfonium trifluoromethanesulfonate, its heptafluoropropane Sulfonate or its nonafluorobutane sulfonate, di (1-naphthyl) phenylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate. In addition, onium salts in which the anion portion of these onium salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.

  In addition, in the general formula (c-1) or (c-2), an onium salt-based acid generator in which the anion moiety is replaced with an anion moiety represented by the following general formula (c-3) or (c-4) Can also be used (the cation moiety is the same as (c-1) or (c-2)).

［式中、Ｘ”は、少なくとも１つの水素原子がフッ素原子で置換された炭素数２〜６のアルキレン基を表し；Ｙ”、Ｚ”は、それぞれ独立に、少なくとも１つの水素原子がフッ素原子で置換された炭素数１〜１０のアルキル基を表す。］

[Wherein X ″ represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Y ″ and Z ″ each independently represent at least one hydrogen atom as a fluorine atom; Represents an alkyl group having 1 to 10 carbon atoms and substituted with

X ″ is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, Preferably it is C3.
Y ″ and Z ″ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably It is C1-C7, More preferably, it is C1-C3.
The carbon number of the alkylene group of X ″ or the carbon number of the alkyl group of Y ″ and Z ″ is preferably as small as possible because the solubility in the resist solvent is good within the above carbon number range.
In addition, in the alkylene group of X ″ or the alkyl group of Y ″ and Z ″, the strength of the acid increases as the number of hydrogen atoms substituted with fluorine atoms increases, and high-energy light or electron beam of 200 nm or less The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all. Are a perfluoroalkylene group or a perfluoroalkyl group in which a hydrogen atom is substituted with a fluorine atom.

  In this specification, the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (C-1), and has a property of generating an acid upon irradiation with radiation. is there. Such oxime sulfonate-based acid generators are frequently used for chemically amplified resist compositions, and can be arbitrarily selected and used.

（式（Ｂ−１）中、Ｒ^３１、Ｒ^３２はそれぞれ独立に有機基を表す。）

(In formula (B-1), R ³¹ and R ³² each independently represents an organic group.)

The organic groups of R ³¹ and R ³² are groups containing carbon atoms, and atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms (fluorine atoms, chlorine atoms, etc.), etc.) You may have.
As the organic group for R ³¹ , a linear, branched, or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. There is no restriction | limiting in particular as this substituent, For example, a fluorine atom, a C1-C6 linear, branched or cyclic alkyl group etc. are mentioned. Here, “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
As an alkyl group, C1-C20 is preferable, C1-C10 is more preferable, C1-C8 is more preferable, C1-C6 is especially preferable, and C1-C4 is the most preferable. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable. The partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. Means an alkyl group substituted with Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.
The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, a partially or completely halogenated aryl group is particularly preferable. The partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms. Means an aryl group substituted with.
R ³¹ is particularly preferably an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms which has no substituent.

As the organic group for R ³² , a linear, branched, or cyclic alkyl group, aryl group, or cyano group is preferable. As the alkyl group and aryl group for R ^32, the same alkyl groups and aryl groups as those described above for R ³¹ can be used.
R ³² is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.

  More preferable examples of the oxime sulfonate-based acid generator include compounds represented by the following general formula (C-2) or (C-3).

［式（Ｃ−２）中、Ｒ^３３は、シアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３４はアリール基である。Ｒ^３５は置換基を有さないアルキル基またはハロゲン化アルキル基である。］

[In Formula (C-2), R ³³ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁴ is an aryl group. R ³⁵ represents an alkyl group having no substituent or a halogenated alkyl group. ]

［式（Ｃ−３）中、Ｒ^３６はシアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３７は２または３価の芳香族炭化水素基である。Ｒ^３８は置換基を有さないアルキル基またはハロゲン化アルキル基である。ｐ”は２または３である。］

[In the formula (C-3), R ³⁶ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁷ is a divalent or trivalent aromatic hydrocarbon group. ^R38 is an alkyl group having no substituent or a halogenated alkyl group. p ″ is 2 or 3.]

In the general formula (C-2), the alkyl group or halogenated alkyl group having no substituent for R ³³ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and carbon atoms. Numbers 1 to 6 are most preferable.
R ³³ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group.
The fluorinated alkyl group for R ³³ is preferably such that the hydrogen atom of the alkyl group is 50% or more fluorinated, more preferably 70% or more, and still more preferably 90% or more.

As the aryl group of R ³⁴ , one hydrogen atom is removed from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or a phenanthryl group. And a heteroaryl group in which a part of carbon atoms constituting the ring of these groups is substituted with a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom. Among these, a fluorenyl group is preferable.
The aryl group of R ³⁴ may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. The alkyl group or halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.

The alkyl group or halogenated alkyl group having no substituent for R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
R ³⁵ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group.
The fluorinated alkyl group in R ³⁵ preferably has 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more fluorinated. This is preferable because the strength of the acid is increased. Most preferred is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.

In the general formula (C-3), the alkyl group or halogenated alkyl group having no substituent for R ³⁶ is the same as the alkyl group or halogenated alkyl group having no substituent for R ^33. Is mentioned.
Examples of the divalent or trivalent aromatic hydrocarbon group for R ³⁷ include groups obtained by further removing one or two hydrogen atoms from the aryl group for R ³⁴ .
Examples of the alkyl group or halogenated alkyl group having no substituent of R ³⁸ include the same alkyl groups or halogenated alkyl groups having no substituent as R ³⁵ described above.
p ″ is preferably 2.

Specific examples of the oxime sulfonate acid generator include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitrobenzenesulfonyloxy). Imino) -benzylcyanide, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -benzylcyanide, α- (benzenesulfonyloxyimino) -4-chlorobenzylcyanide, α- (benzenesulfonyl) Oxyimino) -2,4-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,6-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -4-methoxybenzyl cyanide, α- ( 2-Chlorobenzenesulfonyloxyimino) 4-methoxybenzylcyanide, α- (benzenesulfonyloxyimino) -thien-2-ylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -benzylcyanide, α-[(p-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- (tosyloxyimino) -4-thienyl cyanide, α- (methylsulfonyloxyimino) -1-cyclo Pentenyl acetonitrile, α- (methylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -1-cycloheptenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclooctene Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile, α- (ethylsulfonyloxyimino) -ethylacetonitrile, α- (propyl Sulfonyloxyimino) -propylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α- (cyclohexylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- ( Ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclope N-tenyl acetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile , Α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (trifluoro Methylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p- Butoxy phenylacetonitrile, alpha-(propylsulfonyl oxyimino)-p-methylphenyl acetonitrile, alpha-like (methylsulfonyloxyimino)-p-bromophenyl acetonitrile.
Further, an oxime sulfonate-based acid generator disclosed in JP-A-9-208554 (paragraphs [0012] to [0014] [chemical formula 18] to [chemical formula 19]), WO2004 / 074242A2 (pages 65 to 85). The oxime sulfonate acid generators disclosed in Examples 1 to 40) of No. 1 can also be suitably used.
Moreover, the following can be illustrated as a suitable thing.

  Of the above exemplified compounds, the following four compounds are preferred.

Among diazomethane acid generators, specific examples of bisalkyl or bisarylsulfonyldiazomethanes include bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, Examples include bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, and the like.
Further, diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552, and JP-A-11-035573 can also be suitably used.
Examples of poly (bissulfonyl) diazomethanes include 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane and 1,4-bis (phenylsulfonyldiazo) disclosed in JP-A-11-322707. Methylsulfonyl) butane, 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (phenylsulfonyldiazomethylsulfonyl) decane, 1,2-bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane, 1,3 -Bis (cyclohexylsulfonyldiazomethylsulfonyl) propane, 1,6-bis (cyclohexylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyldiazomethylsulfonyl) decane, etc. Door can be.

(C) As a component, these may be used individually by 1 type and may be used in combination of 2 or more type.
Among the above, the oxime sulfonate acid generator is excellent in transparency, has high performance as an acid generator, and has good solubility in an organic solvent. In addition, the liquid crystal display element is preferable because there is no infiltration of halogen atoms or the like into the liquid crystal adjacent to the planarization insulating film, and the liquid crystal is hardly deteriorated.
The content of the component (C) in the composition for forming a planarizing insulating film for a liquid crystal display element of the present invention is preferably 1 to 10 parts by mass and more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the component (A). preferable. When it is at least the lower limit of the above range, the effect of blending the component (C) is sufficiently obtained, and when it is at most the upper limit, a uniform solution is obtained when the composition is dissolved in an organic solvent. It is preferable because the storage stability is good.

The composition for forming a planarization insulating film for a liquid crystal display element of the present invention further contains a crosslinking agent (D) (hereinafter referred to as “component (D)”) as an optional component as long as the effects of the present invention are not impaired. May be. By containing the component (D), the heat resistance is further improved.
The component (D) is preferably a component capable of forming a crosslinked structure in the component (A) or in the component (D) by the action of heat and / or ultraviolet rays.
Examples of the component (D) include compounds having an epoxy group and / or an oxetane group. Specific examples include various epoxy resins and copolymers of polymerizable unsaturated compounds including epoxy group-containing polymerizable unsaturated compounds.

  Examples of the epoxy resin include those described in JP-A-8-262709. Preferably, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, glycidyl methacrylate ) Polymerized resins and the like can be mentioned. Among these, bisphenol A type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin and the like are preferable.

Examples of the epoxy group-containing polymerizable unsaturated compound include compounds having a vinyl group and an epoxy group. Specific examples include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, Methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, N- [4- (2 , 3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, N- [4- (2,3-epoxypropoxy) -3,5-dimethylphenylpropyl] acrylamide, acrylic acid-β-methylglycidyl, methacrylic acid -Β-methylglycidyl, o-vinylbenzyl glycidyl ether, m-vinyl Nji glycidyl ether, such as p- vinylbenzyl glycidyl ether.
In the above-mentioned “polymerizable unsaturated compound copolymer containing an epoxy group-containing polymerizable unsaturated compound”, the polymerizable unsaturated compound used together with the epoxy group-containing polymerizable unsaturated compound has a polymerizable unsaturated bond. And compounds having no epoxy group, specifically, for example, acrylic acid, methacrylic acid, acrylic esters, acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, Examples thereof include vinyl esters, styrenes, and croton esters. Among these, acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters are preferable, acrylic acid and methacrylic acid are particularly preferable, and methacrylic acid is more preferable.
In the polymerizable unsaturated compound used in the copolymer, the proportion of the epoxy group-containing polymerizable unsaturated compound is 5 to 90 mol%, preferably 50 to 85 mol%.

Moreover, as (C) component, what has an alicyclic epoxy group is preferable, and the copolymer of the polymerizable unsaturated compound containing an alicyclic epoxy group containing polymerizable unsaturated compound is especially preferable. The alicyclic epoxy group is a group formed by bonding —O— to two adjacent carbon atoms among the carbon atoms constituting the ring of the aliphatic cyclic group to form a ring. As for carbon number of the alicyclic group of an alicyclic epoxy group, about 5-10 are preferable.
Examples of the alicyclic epoxy group-containing polymerizable unsaturated compound include compounds represented by general formulas (2) to (32) described in JP-A-8-262709.

Moreover, as (D) component, the crosslinking agent generally used for the resist composition other than the above can be used. Examples of the crosslinking agent include 2,3-dihydroxy-5-hydroxymethylnorbornane, 2-hydroxy-5,6-bis (hydroxymethyl) norbornane, cyclohexanedimethanol, 3,4,8 (or 9) -trihydroxy. Aliphatic cyclic having hydroxyl group or hydroxyalkyl group or both such as tricyclodecane, 2-methyl-2-adamantanol, 1,4-dioxane-2,3-diol, 1,3,5-trihydroxycyclohexane A hydrocarbon or its oxygen-containing derivative is mentioned.
In addition, amino group-containing compounds such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, propylene urea, glycoluril are reacted with formaldehyde or formaldehyde and lower alcohol, and the hydrogen atom of the amino group is hydroxymethyl group or lower alkoxymethyl. And a compound substituted with a group. Of these, those using melamine are melamine crosslinking agents, those using urea are urea crosslinking agents, those using alkylene ureas such as ethylene urea and propylene urea are alkylene urea crosslinking agents, and glycoluril is used. This was called a glycoluril-based crosslinking agent.

Melamine-based crosslinking agents include compounds in which melamine and formaldehyde are reacted to replace the amino group hydrogen atom with a hydroxymethyl group, and melamine, formaldehyde and lower alcohol are reacted to convert the amino group hydrogen atom into a lower alkoxy group. Examples include compounds substituted with a methyl group. Specific examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like, among which hexamethoxymethyl melamine is preferable.
Urea-based crosslinking agents include compounds in which urea and formaldehyde are reacted to replace amino group hydrogen atoms with hydroxymethyl groups, and urea, formaldehyde and lower alcohols are reacted to convert amino group hydrogen atoms into lower alkoxy groups. Examples include compounds substituted with a methyl group. Specific examples include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea, etc. Among them, bismethoxymethylurea is preferable.
Examples of the alkylene urea cross-linking agent include compounds obtained by condensation reaction of alkylene urea and formalin, and by reacting this product with a lower alcohol. Specific examples include, for example, mono and / or dihydroxymethylated ethylene urea, mono and / or dimethoxymethylated ethylene urea, mono and / or diethoxymethylated ethylene urea, mono and / or dipropoxymethylated ethylene urea, mono And / or ethylene urea-based cross-linking agents such as dibutoxymethylated ethylene urea; mono and / or dihydroxymethylated propylene urea, mono and / or dimethoxymethylated propylene urea, mono and / or diethoxymethylated propylene urea, mono and Propylene urea crosslinkers such as / or dipropoxymethylated propylene urea, mono and / or dibutoxymethylated propylene urea; 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone, 1, 3-di (methoxymethyl) -4,5-dimethyl Like and carboxymethyl-2-imidazolidinone.
Examples of the glycoluril-based crosslinking agent include glycoluril derivatives in which the N position is substituted with one or both of a hydroxyalkyl group and an alkoxyalkyl group having 1 to 4 carbon atoms. Such a glycoluril derivative can be obtained by a condensation reaction between glycoluril and formalin and by reacting this product with a lower alcohol. Specific examples include, for example, mono, di, tri and / or tetrahydroxymethylated glycoluril, mono, di, tri and / or tetramethoxymethylated glycoluril, mono, di, tri and / or tetraethoxymethylated glycoluril. Mono, di, tri and / or tetrapropoxymethylated glycoluril, mono, di, tri and / or tetrabutoxymethylated glycoluril, and the like.

(D) component can be used 1 type or in mixture of 2 or more types.
(D) As for the compounding quantity of a component, 5-100 mass parts is preferable with respect to 100 mass parts of (A) component, and 10-50 mass parts is more preferable. By setting it within this range, the effect of improving heat resistance is further improved.

The composition for forming a flattening insulating film for a liquid crystal display device of the present invention is a surfactant, sensitizer, antifoaming agent, ultraviolet absorber, storage stabilizer, additional additive, as long as the effects of the present invention are not impaired. Various additives such as a resin, a plasticizer, a stabilizer, and a contrast improver may be added.
The surfactant may be a conventionally known surfactant, and examples thereof include anionic, cationic, and nonionic compounds. Specific examples include X-70-090 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.).
As the sensitizer, those used in conventionally known positive resists can be used. For example, a compound having a phenolic hydroxyl group having a molecular weight of 1000 or less can be used.
As an antifoamer, a conventionally well-known thing may be used and a silicone type and a fluorine-type compound are mentioned.

The composition for forming a planarization insulating film for a liquid crystal display element of the present invention can be produced by dissolving the above components in an organic solvent (hereinafter referred to as (S) component).
As the component (S), any component can be used as long as it dissolves each component to be used to form a uniform solution. It can be selected and used.
Specific examples include, for example, lactones such as γ-butyrolactone;
Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone;
Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol;
Compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, monomethyl ether, monoethyl ether, monopropyl of the polyhydric alcohols or the compound having an ester bond Derivatives of polyhydric alcohols such as ethers, monoalkyl ethers such as monobutyl ether or compounds having an ether bond such as monophenyl ether [in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) Is preferred];
Cyclic ethers such as dioxane and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate;
Aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. be able to.
These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
Of these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and EL are preferable.
Moreover, the mixed solvent which mixed PGMEA and the polar solvent is preferable. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be within the range.
More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7-7: 3.
In addition, as the component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
The amount of the component (S) used is not particularly limited, and is a concentration that can be applied on the support and is appropriately set according to the coating film thickness. Usually, the solid content concentration in the composition is 10 to 10. It is used so that it may become in the range of 50 mass%, Preferably 15-35 mass%.

≪Method for manufacturing planarization insulating film for liquid crystal display element≫
The method for producing a planarization insulating film for a liquid crystal display element according to the present invention includes a step of forming a resin film on a support using the composition for forming a planarization insulating film for a liquid crystal display element, and exposing the resin film. A step of developing the resin film to form a pattern, and a step of baking the pattern.

Hereinafter, an embodiment of a method for producing a planarization insulating film for a liquid crystal display element according to the present invention will be described by taking the liquid crystal array substrate 1 shown in FIGS.
First, a support is prepared. In the present embodiment, as a support, a plurality of gate lines 3 formed in parallel on the transparent substrate 2, a plurality of source lines 4 orthogonal to the gate lines 3, and a plurality of regions surrounded by them A TFT 6 provided in each (pixel region) and an interlayer insulating film 13 directly covering them are used.
The TFT 6 includes a gate 7 formed on the transparent substrate 2 and an amorphous silicon layer 9 provided above the gate 7 via an insulating film (gate insulating film) 8. The gate line 3 and the gate 7 are connected via a gate electrode 10. The source line 4 and the amorphous silicon layer 9 are connected via a source electrode. The amorphous silicon layer 9 and the pixel electrode 5 are connected via the drain electrode 11.
The step of forming the gate line 3, the source line 4, the TFT 6, and the interlayer insulating film 13 on the transparent substrate 2 can be performed by a conventionally known method.
Note that since the planarization insulating film for a liquid crystal display element formed according to the present invention has an insulating property, the interlayer insulating film 13 is not necessarily provided.

Next, a resin film is formed on the support. The resin film can be formed, for example, by applying the composition for forming a planarizing insulating film for liquid crystal display elements of the present invention on the surface of a support with a spinner, roll coater, spray, or the like and drying. The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at a temperature of 80 ° C. to 150 ° C. for 60 seconds to 120 seconds, (2) a method of leaving at room temperature for several hours to several days, ( 3) Any method of removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours may be used.
The film thickness of the resin film is not particularly limited and may be set as appropriate. Usually, the thickness from the upper end part of a support body to the upper surface (flattened surface) of the said resin film is formed with the film thickness used as 1-10 micrometers.

Next, the resin film is selectively irradiated (exposed) with radiation such as visible light, ultraviolet light, or excimer laser light.
In the present invention, at the time of exposure, the molecular structure of the component (B) changes in the portion irradiated with radiation, and the solubility in an aqueous alkali solution increases. Therefore, in the next step, when the resin film is developed with a developer (alkaline aqueous solution), the portion of the resin film solubilized by exposure is selectively dissolved and removed, and a pattern faithful to the mask is formed.
The exposure conditions are not particularly limited. Depending on the light source and method used for exposure, the exposure region, exposure time, exposure intensity, and the like can be selected as appropriate.
The exposure light source is not particularly limited, and g-line (436 nm), h-line (405 nm), i-line (365 nm), KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet) ), EB (electron beam), X-ray, soft X-ray or the like. In the present invention, g-line (436 nm), h-line (405 nm) or i-line (365 nm) is particularly preferable, and g-line or i-line is more preferable.
After exposure, post-exposure baking (PEB) may be performed at a temperature of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 90 seconds.

  Next, the resin film after exposure is subjected to an alkali developer, for example, an organic alkali aqueous solution such as 0.1 to 10% by mass tetramethylammonium hydroxide aqueous solution, or sodium hydroxide, potassium hydroxide, sodium metasilicate, sodium phosphate, etc. Development processing is performed using an inorganic alkali aqueous solution. Thereby, a hole penetrating the resin film is formed in the resin film.

In the present invention, it is preferable to perform an ultraviolet curing process on the pattern after development and before firing the resin film. Thereby, the heat resistance of the pattern is improved, deformation of the pattern during firing can be suppressed, and a highly accurate pattern can be obtained. The reason why such an effect can be obtained is not certain, but it is presumed that the component (B) functions as a crosslinking agent and forms a bridge between molecules of the component (A).
The ultraviolet curing treatment can be performed using a known method. For example, it can be carried out by irradiating the entire pattern with ultraviolet rays using a known ultraviolet irradiation device (for example, DeepUVProcessor lamp L-800FS manufactured by Nippon Battery Co., Ltd., excimer light irradiation device SCG01 manufactured by USHIO INC.).
For the ultraviolet irradiation, it is preferable to use a light source that mainly outputs ultraviolet light having a wavelength of 400 nm or less, particularly ultraviolet light having a wavelength of 150 to 300 nm. Examples of such a light source include a lamp L-800FS (main wavelength: 254 nm, 185 nm) manufactured by Nippon Battery Co., Ltd., a lamp UEM50L-172A / x4 (main wavelength: 172 nm) manufactured by USHIO INC., And the like.
Ultraviolet is preferably irradiated at an irradiation amount of about 500~20000mJ / cm ^2, about 1000~15000mJ / cm ² is more preferable. The amount of irradiation can be controlled by the intensity of the irradiated ultraviolet rays and the irradiation time.
In addition, when irradiating with ultraviolet rays, it is desirable to suppress rapid irradiation and temperature increase due to irradiation so as not to cause wrinkles on the pattern surface of the irradiation portion.

You may post-bake after an ultraviolet curing process and before baking. Although this post-baking process is not necessarily required, heat resistance is further improved by performing post-baking. Further, the adhesion between the pattern and the support is improved by the post-baking treatment.
As post-baking process, the heat processing for about 1 to 10 minutes are preferable at the temperature of 150-230 degreeC.
In addition, since the heat resistance of the pattern is improved by the ultraviolet curing treatment, there is no concern that pattern deformation will occur in the post-baking process.

Next, the pattern (resin film) is fired. Thereby, a film (planarization insulating film 14) containing SiO ₂ as a main component is formed. Since the planarization insulating film 14 has SiO ₂ as a main component, it has very high transparency to visible light. Moreover, it has the insulation (for example, the insulation in the range whose dielectric constant in 1 MHz is 3.5-5) required for the planarization insulating film.
The firing temperature is preferably 250 to 450 ° C, more preferably 300 to 400 ° C. These are preferably fired in a nitrogen atmosphere. Within this range, the higher the firing temperature, the better the transparency and insulation of the resulting planarized insulating film.
Although the firing time varies depending on the firing temperature, it is usually preferably 10 to 60 minutes and more preferably 15 to 30 minutes.

In the support on which the planarization insulating film is formed, the pixel electrode 5 that fills the holes formed in the planarization insulating film 14 and covers a part of the surface of the planarization insulating film 14 is formed. Thus, the liquid crystal array substrate 1 is obtained.
A liquid crystal display element is obtained by arranging the liquid crystal array substrate 1 and the counter substrate obtained as described above to face each other and sandwiching the liquid crystal therebetween.

The composition for forming a planarization insulating film for a liquid crystal display element of the present invention has photosensitivity. Therefore, in the formation of a planarization insulating film for a liquid crystal display element, there is a great merit in terms of throughput and cost.
Moreover, the planarization insulating film for liquid crystal display elements formed by using the composition for forming a planarization insulating film for liquid crystal display elements of the present invention through a process such as baking is excellent in heat resistance, for example, 250 to 450. Even when exposed to high temperatures such as ° C., deformation and deterioration of properties such as insulation hardly occur. Moreover, since the planarization insulating film is basically composed of silica, it has a very high visible light transmittance and excellent transparency.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.
[Examples 1-7, Comparative Examples 1-2]
Each component shown in Table 1 was mixed to prepare a resin composition.

Each abbreviation in Table 1 indicates the following. Moreover, the numerical value in [] shows a compounding quantity (mass part).
(A) -1: a resin having Mw = 8500 represented by the following chemical formula (A) -1 [wherein x1: y1 = 30: 70 (molar ratio)].
(A) -2: A resin having Mw = 2800 represented by the following chemical formula (A) -2 [wherein x2: y2 = 28: 72 (molar ratio)].
(A) -3: A resin having Mw = 3000 represented by the following chemical formula (A) -3 [wherein x3: y3 = 70: 30 (molar ratio)].
(A) -4: A resin having Mw = 3600 represented by the following chemical formula (A) -4 [wherein x4: y4 = 70: 30 (molar ratio)].
(A) -5: Resin with Mw = 6000 represented by the following chemical formula (A) -5.
(B) -1 to (B) -3: Chemical formulas (B) -1 to (B) -3 shown below, respectively, wherein D represents a naphthoquinone-1,2-diazidosulfonyl group. ] The compound represented by this.

The following evaluation was performed about the obtained resin composition.
<Photosensitive evaluation and heat resistance evaluation>
The resin composition was applied on the surface of a silicon substrate by a spin coating method, and heat treatment (soft baking) at 120 ° C. for 90 seconds was performed on a hot plate to form a resin film having a thickness of 1.0 μm. .
Next, the resin film is exposed through a mask with an exposure machine (manufactured by Nikon Corporation, product name: NSR-2005i10D, NA = 0.57), and then 150 ° C. for 90 seconds on a hot plate. Heat treatment (PEB) was performed. After PEB, development processing was performed for 20 seconds using an aqueous tetramethylammonium hydroxide (TMAH) solution having a concentration of 2.38% by mass, and rinsed with pure water. Next, UV irradiation by UV curing treatment (high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd., product name: Deep UV Processor lamp L-800FS, main wavelength 254, 185 nm; irradiation amount: 2700 mJ / cm ² ) on the resin film. And baking at 150 ° C. for 90 seconds).

The substrate surface after the UV curing treatment was observed with a scanning electron microscope (SEM).
As a result, in the examples using the resin compositions of Examples 1 to 7, a line pattern having a line width of 1.2 μm and a hole pattern having a diameter of 2.0 μm were formed on the substrate, respectively.
On the other hand, in the example using the resin composition of Comparative Examples 1 and 2, a pattern could not be formed.

  Next, the substrate on which the pattern is formed is subjected to a high-temperature baking process at 400 ° C. for 30 minutes in a vertical baking furnace (product name: TOK TS8000MB) in a nitrogen atmosphere to form a planarization insulating film. did.

The substrate surface after the high-temperature baking treatment was observed by SEM.
As a result, in the examples using the resin compositions of Examples 1 to 7, the patterns having almost the same shape as before the high-temperature baking process (after the UV curing process) (high-precision pattern <dimensional change is within ± 5% >) Was formed.
Since a highly accurate pattern was formed, it was confirmed that the heat resistance of the pattern obtained as described above was high.
The results are shown in Table 2 as ◯ when a high-precision pattern was formed and x when a pattern could not be formed.

Further, using the resin composition of Example 1, a planarization insulating film was formed in the same manner as described above except that the UV curing treatment was not performed after the resin film was formed, and observed by SEM.
As a result, the formed pattern was poor in accuracy, for example, the side wall had a lower verticality than the pattern before the high-temperature baking process, and the cross-sectional shape of the line pattern was semicircular, for example.

<Insulation evaluation>
A planarization insulating film is formed in the same manner as in the above pattern formation evaluation, and the dielectric constant at 1 MHz and the leakage current value (A / cm ² ) at 1 MV / cm for the portion where patterning is not formed are SSM Of SSM495 (product name) and evaluated according to the following evaluation criteria.
The results are shown in Table 2.
[Evaluation criteria for dielectric constant]
○: 5 or less ×: More than 5 [Evaluation criteria for leak current value]
○: Less than 1 × 10 ⁻⁷ ×: 1 × 10 ⁻⁷ or more

It is a schematic top view which shows one of the pixel areas of the liquid crystal array substrate which comprises a liquid crystal display element. It is the elements on larger scale of the cross section in the position A-A 'in FIG.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Liquid crystal array substrate, 2 ... Transparent substrate, 3 ... Gate line, 4 ... Source line, 5 ... Pixel electrode, 6 ... TFT, 7 ... Gate, 8 ... Gate insulating film, 9 ... Amorphous silicon layer, 10 ... Gate electrode , 11 ... drain electrode, 12 ... interlayer insulating film, 13 ... interlayer insulating film, 14 ... planarization insulating film.

Claims (5)

A composition for forming a planarizing insulating film for a liquid crystal display element, comprising a resin (A) containing a structural unit (a1) represented by the following general formula (a1-1) and a photosensitizer (B) object.

[Wherein, R ¹ represents a single bond or a linear or branched alkylene group, R ¹⁰¹ represents an alkyl group, and n1 represents an integer of 0 to 4. ] The composition for forming a planarizing insulating film for a liquid crystal display element according to claim 1, wherein the resin (A) further contains a structural unit (a2) represented by the following general formula (a2-1).

[Wherein R ² represents an aromatic hydrocarbon group or an alkyl group. ]   The composition for forming a planarizing insulating film for a liquid crystal display element according to claim 1, wherein the photosensitive agent (B) is a compound having a naphthoquinonediazide group.   The process of forming a resin film on the support body using the composition for planarization insulating film formation for liquid crystal display elements as described in any one of Claims 1-3, the process of exposing the said resin film, The said resin The manufacturing method of the planarization insulating film for liquid crystal display elements including the process of developing a film | membrane and forming a pattern, and the process of baking the said pattern.   The method for producing a planarization insulating film for a liquid crystal display element according to claim 4, comprising a step of subjecting the pattern to an ultraviolet curing treatment before the baking.

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