KR20090104841A - Composition for forming planarization insulating film for liquid crystal display element and method for producing planarization insulating film for liquid crystal display element - Google Patents

Abstract

Disclosed is a composition which enables to form a planarization insulating film for liquid crystal display elements, which film has photosensitivity, excellent transparency and excellent heat resistance. Also disclosed is a method for producing a planarization insulating film for liquid crystal display elements. Specifically disclosed is a composition for forming a planarization insulating film for liquid crystal display elements, which contains a resin (A) containing a constituent unit (a1) represented by the general formula (a1-1) (wherein R1 represents a single bond or a straight or branched chain alkylene group, R101 represents an alkyl group, and n1 represents an integer of 0-4), and a sensitizer (B).

Description

COMPOSITION FOR FORMING PLANARIZATION INSULATING FILM FOR LIQUID CRYSTAL DISPLAY ELEMENT AND METHOD FOR PRODUCING PLANARIZATION INSULATING FILM FOR LIQUID CRYSTAL DISPLAY ELEMENT

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

This application claims priority based on Japanese Patent Application No. 2007-023510 for which it applied to Japan Patent Office on February 1, 2007, and uses the content here.

Background Art Conventionally, in electronic components such as liquid crystal display devices, integrated circuit devices and solid-state imaging devices, protective films for preventing deterioration and damage, and interlayer insulating films for insulating electrodes, wirings, and the like have been formed.

In the case of an integrated circuit element, for example, a multilayer wiring of an LSI (large scale integrated circuit element) is formed by alternately forming and processing a metal wiring for passing electricity and an interlayer insulating film for electrically insulating 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 layer such as ITO (indium tin oxide) on a transparent substrate such as a glass substrate on which a polarizing plate is formed. And forming a TFT, covering with an interlayer insulating film to form a back plate (liquid crystal array substrate), and forming a pattern of a black matrix layer and a color filter layer on a transparent substrate such as a glass substrate on which a polarizing plate is formed, if necessary, Furthermore, transparent conductive circuit layers, such as ITO, are formed one by one, and it is set as a top plate (counter substrate), and this liquid crystal array board | substrate and an opposing board | substrate are made to oppose through a spacer, and a liquid crystal is sealed between both boards.

An example of a liquid crystal array substrate is shown in FIG. 1 and FIG. FIG. 1: is a schematic top view which shows one of the pixel area | region of the liquid crystal array substrate 1, and FIG. 2 is a cross-sectional partial enlarged view at the position A-A 'in FIG.

The liquid crystal array substrate 1 generally includes a plurality of gate lines 3 formed 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. It consists of the transparent pixel electrode 5 formed in each (pixel area), and the TFT 6 arrange | positioned at each pixel electrode 5, respectively.

The TFT 6 is composed of a gate 7 formed on the transparent substrate 2, and an amorphous silicon layer 9 formed above the insulating film (gate insulating film) 8. The gate line 3 and the gate 7 are connected via the gate electrode 10. In addition, the source line 4 and the amorphous silicon layer 9 are connected via the source electrode. The amorphous silicon layer 9 and the pixel electrode 5 are connected via the drain electrode 11.

Moreover, on the transparent substrate 2, the transparent interlayer insulation film 12 which covers the TFT 6, the source line 4, the gate electrode 10, and the drain electrode 11 is formed. The interlayer insulating film 12 is formed on the highly insulating interlayer insulating film 13 directly covering the TFT 6, the source line 4, the gate electrode 10, and the drain electrode 11 and the interlayer insulating film 13. And an interlayer insulating film (flattening insulating film) 14 formed to planarize the surface irregularities resulting from the TFT 6 and the like.

By forming the planarization insulating film, the distance between the pixel electrode and the TFT in the longitudinal cross-sectional direction can be sufficiently secured, so that the pixel electrode can be formed over the entire area surrounded by the source line and the gate line, and the effective pixel range is increased. As a result, the aperture ratio of the liquid crystal display element is improved, contributing to power saving and improvement in luminance. In addition, by improving the surface flatness of the liquid crystal array substrate, unevenness of the liquid crystal portion can be reduced, and there is an advantage that the image quality is improved.

At present, in the manufacture of liquid crystal display elements, acrylic resins are mainly used for interlayer insulation film forming materials because of their excellent transparency.

Moreover, as a material used for formation of an interlayer insulation film, the photosensitive material is preferable at the point which is excellent in the workability at the time of forming a pixel electrode etc. For example, in manufacture of the liquid crystal array substrate shown in FIG. 2, in order to partially connect TFT and pixel electrode, it is necessary to form a hole in an interlayer insulation film, The process can be easily performed by using a photosensitive material. Can be.

For example, Patent Documents 1 to 2 describe photosensitive resin compositions containing acrylic alkali-soluble resins and photosensitizers as materials for forming an interlayer insulating film.

Patent Document 1: Japanese Patent Application Laid-Open No. 10-153854

Patent Document 2: Japanese Unexamined Patent Publication No. 2006-259083

Disclosure of Invention

Problems to be Solved by the Invention

However, the present situation has overwhelmingly little photosensitive property in the interlayer insulation film formation material proposed so far.

Moreover, in the liquid crystal display element, although the process at high temperature may be performed at the time of manufacture of a liquid crystal display element, high heat resistance is needed, but the said photosensitive resin composition does not have sufficient heat resistance. For example, although an interlayer insulating film having heat resistance close to 400 ° C. can be formed, such as an SOG (spin on glass) thin film, such a material conventionally does not have photosensitivity. In the case of using a material having no photosensitivity, a multi-step such as forming a resist film over the insulating film, patterning the resist film to form a resist pattern, etching the resist pattern as a mask, and then peeling off the resist is necessary. In view of this, there is a disadvantage in terms of throughput cost.

Moreover, especially in the use of a planarization insulating film, since the film thickness needs to be thickened to some extent, transparency is very important and transparency improvement is further requested | required.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a composition capable of forming a flattening insulating film for liquid crystal display elements having photosensitivity and having excellent transparency and heat resistance, and a method for producing a flattening insulating film for liquid crystal display elements. do.

Means to solve the problem

In order to achieve the above object, the present invention adopts the following configuration.

That is, the 1st aspect (aspect) of this invention contains resin (A) and photosensitive agent (B) containing structural unit (a1) represented by the following general formula (a1-1), For liquid crystal display elements characterized by the above-mentioned. It is a composition for planarization insulating film formation.

[Formula 1]

[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].

According to a second aspect of the present invention, a step of forming a resin film using the composition for forming a planarization insulating film for liquid crystal display elements of the first aspect on the support, a step of exposing the resin film, and developing the resin film to develop a pattern It is a manufacturing method of the planarization insulating film for liquid crystal display elements containing the process of forming and the process of baking the said pattern.

In this specification and a claim, a "structural unit" means the monomeric unit (monomer unit) which comprises resin (polymer, a copolymer).

"Alkyl group" shall include a linear, branched and cyclic monovalent saturated hydrocarbon group unless otherwise specified.

"Alkylene group" shall include a divalent saturated hydrocarbon group of straight, branched and cyclic unless otherwise specified.

"Lower alkyl group" represents an alkyl group having 1 to 5 carbon atoms.

"Exposure" is taken as the concept containing the irradiation of the whole radiation.

Effects of the Invention

According to this invention, the composition which can form the planarization insulating film for liquid crystal display elements which has photosensitivity, and has the outstanding transparency and heat resistance, and the manufacturing method of the planarization insulating film for liquid crystal display elements can be provided.

1 is a schematic top view showing one of pixel areas of a liquid crystal array substrate constituting a liquid crystal display element.

FIG. 2 is a partially enlarged view of a cross section at position A-A 'in FIG. 1. FIG.

* Description of the sign *

One… 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 insulation film,

13... Interlayer insulation film,

14... Planarization insulating film.

Best Mode for Carrying Out the Invention

`` Composition for forming a planarization insulating film for liquid crystal display element ''

The planarization insulation film formation composition for liquid crystal display elements of this invention is resin (A) (henceforth (A) component) containing the structural unit (a1) represented by the said General formula (a1-1), and the photosensitive agent (B) (Hereinafter, referred to as component (B)).

The resin film formed using such a composition is alkali insoluble by presence of (B) component before exposure. When exposing to this resin film, the structure of (B) component changes and alkali solubility will increase. 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 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)

(A) component has a structural unit (a1) represented by general formula (a1-1).

In general formula (a1-1), when R <^1> is a single bond, a benzene ring is couple | bonded directly with the silicon atom.

The alkylene group of R ¹ is preferably 1 to 5 carbon atoms.

Examples of the linear alkylene group include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and the like.

Examples of the branched alkylene group include methylethylene group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 1,1-dimethylethylene group and 1-methyl Butane-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 And a, 2-dimethylpropane-1,3-diyl group.

As R ^{1, a} linear alkylene group is preferable, and a methylene group or an ethylene group is particularly preferable.

In formula (a1-1), although the bonding position of the hydroxyl group in a benzene ring is not specifically limited, 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 the R ^101" means that a part or all of the hydrogen atoms bonded to the carbon atom of the benzene ring which is 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, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group and neo Pentyl group etc. are mentioned. Industrially, a methyl group or an ethyl group is preferable.

n1 is an integer of 0-4, 0 or 1 is preferable and 0 is especially preferable.

A structural unit (a1) may be used individually by 1 type, or may use 2 or more types together.

It is preferable that it is 10 mol% or more with respect to the total of all the structural units which comprise (A) component, and, as for the ratio of a structural unit (a1) in (A) component, 25 mol% or more is more preferable, and 30 mol% The above is more preferable. When it is 10 mol% or more, alkali solubility after exposure improves and a favorable pattern can be formed. Although an upper limit in particular is not restrict | limited, 80 mol% or less is preferable and 75 mol% or less is the most preferable.

(A1) A component may contain structural units other than a structural unit (a1). As structural units other than a structural unit (a1), the structural unit (a2)-(a5) etc. which are shown below are mentioned, for example.

`` Composition Unit (a2) ''

It is preferable that (A) component further contains the structural unit (a2) represented by the following general formula (a2-1). Thereby, alkali dissolution suppression effect improves and it is not necessary to add a large amount of (B) component.

[Formula 2]

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

As an aromatic hydrocarbon group of R <^2> , group which removed one hydrogen atom from the aromatic ring which may or may not have a substituent is mentioned, for example.

As an aromatic ring, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc. are mentioned, for example.

As a substituent which an aromatic ring may have, the thing similar to what was illustrated as a substituent which the benzene ring in Formula (a1-1) may have is mentioned.

As an aromatic hydrocarbon group of R <^2> , a phenyl group or a phenanthryl group is especially preferable.

The alkyl group of R ² may be any of linear, branched, and cyclic.

As a linear alkyl group, it is preferable that it is C1-C5, and C1-C3 is more preferable.

The branched alkyl group preferably has 3 to 5 carbon atoms, for example, 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, etc. are mentioned.

As a cyclic alkyl group, it is preferable that carbon number (number of the carbon which comprises a ring) of a basic ring is 3-10, and a cyclopentyl group or a cyclohexyl group is more preferable. The cyclic alkyl group may have a substituent bonded to a basic ring, and examples of the substituent include the same as those described for R ¹⁰¹ in formula (a1-1).

As an alkyl group of R <^2> , a linear C3-C5 alkyl group is especially preferable.

A structural unit (a2) may be used individually by 1 type, or may use 2 or more types together.

It is preferable that it is the range of 5-80 mol% with respect to the total of all the structural units which comprise (A) component, and, as for the ratio of a structural unit (a2) in (A) component, 10-75 mol% is more preferable. , 20-70 mol% is more preferable. If it is more than the lower limit of the said range, the effect by containing a structural unit (a2) is fully acquired, and if it is below an upper limit, the balance with another structural unit is favorable.

Structural Unit (a3)

It is preferable that (A) component contains the following structural unit (a3) in addition to a structural unit (a1) or structural unit (a1) and (a2). Structural unit (a3) is a preferable structural unit in adjusting the balance of alkali solubility.

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

[Formula 3]

[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 to 4 Represents an integer of].

As R <^3> , the same thing as R <^1> in Formula (a1-1) is mentioned.

Examples of R ⁴ include the same linear alkyl groups and branched alkyl groups as the alkyl groups of R ² in formula (a2-1).

Examples of R ¹⁰³ and n 3 in General Formula (a3-1) include the same as those described for R ¹⁰¹ and n 1 in General Formula (a1-1).

A structural unit (a3) may be used individually by 1 type, or may use 2 or more types together.

When it contains a structural unit (a3), 5-50 mol% is preferable and, as for the ratio of the structural unit (a3) in (A) component with respect to the total of all the structural units which comprise (A) component, 30 mol% is more preferable.

`` Composition Unit (a4) ''

It is preferable that (A) component contains the following structural unit (a4) in addition to structural unit (a1), structural unit (a1) and (a2), or structural unit (a1), (a2) and (a3). . Structural unit (a4) is a preferable structural unit in adjusting the balance of alkali solubility.

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

[Formula 4]

[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 to 4 Represents an integer of].

As R <^5> , the same thing as R <^1> in Formula (a1-1) is mentioned.

Examples of R ⁶ include the same linear alkyl groups and branched alkyl groups as the alkyl groups of R ² in formula (a2-1).

As R <^104> , n4 in general formula (a4-1), the same thing as R <^101> , n1 in said general formula (a1-1) is mentioned, respectively.

A structural unit (a4) may be used individually by 1 type, or may use 2 or more types together.

When it contains a structural unit (a4), 5-50 mol% is preferable and, as for the ratio of the structural unit (a4) in (A) component with respect to the total of all the structural units which comprise (A) component, 30 mol% is more preferable.

Structural unit (a5)

The component (A) is composed of structural units (a1), structural units (a1) and (a2), structural units (a1), (a2) and (a3), or structural units (a1), (a2), (a3) and In addition to (a4), it is preferable to contain the following structural unit (a5). Structural unit (a5) is a preferable structural unit in adjusting the balance of alkali solubility.

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

[Formula 5]

[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 to 4 Represents an integer of].

As R <^7> , the same thing as R <^1> in Formula (a1-1) is mentioned.

Examples of R ⁸ include the same linear alkyl groups and branched alkyl groups as the alkyl groups of R ² in formula (a2-1).

General formula (a5-1) in R ^105, R ¹⁰¹ n5 roneun can be given, the same and each of n1 in the formula (a1-1).

A structural unit (a5) may be used individually by 1 type, or may use 2 or more types together.

When it contains a structural unit (a5), 5-50 mol% is preferable and, as for the ratio of the structural unit (a5) in (A) component with respect to the total of all the structural units which comprise (A) component, 30 mol% is more preferable.

The mass average molecular weight (Mw) of the component (A) (polystyrene conversion by gel permeation chromatography (hereinafter sometimes abbreviated as GPC), which is the same below) is not particularly limited, but is preferably 2000 to 15000, 2500-10000 are more preferable. By setting it as this range, the solubility with respect to the 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 a pattern shape become favorable.

The component (A) can be produced, for example, by the method described in Patent No. 2567984 (Japanese Patent Application Laid-open No. Hei 04-130324).

<(B) component>

The component (B) is not particularly limited as long as it is generally used as a photosensitive agent in the positive resist composition.

In the present invention, as the component (B), a compound (quinonediazide group-containing compound) having a naphthoquinone diazide group is preferable.

As a quinone diazide group containing compound, the naphthoquinone diazide sulfonic-acid compound and the ester compound of a phenol compound are mentioned, for example.

Examples of the naphthoquinone diazide sulfonic acid compound include naphthoquinone-1,2-diazide-5-sulfonic acid or naphthoquinone-1,2-diazide-4-sulfonic acid.

As said phenolic compound, For example, Polyhydroxy benzophenone compounds, such as 2,3, 4- trihydroxy benzophenone and 2,3,4,4'- tetrahydroxy benzophenone;

Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxy Phenylmethane, 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-hydroxyphenylmethane, 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-hour Clohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl Trisphenol-type compounds such as -4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane;

2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol Linear trinuclear 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- Hydroxy-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 Linear tetranuclear phenol compounds such as -3- (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-hydroxy Hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4 Linear polyphenol compounds such as linear 5-nuclear body phenol compounds such as -methyl phenol;

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-trihydroxy Phenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxy-3 ', 5'-dimethylphenyl) propane and the like Bisphenol type compounds;

1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl Multinuclear branched phenolic compounds such as isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;

Condensation type phenol compounds, such as 1, 1-bis (4-hydroxyphenyl) cyclohexane, etc. are mentioned.

The esterified product of the naphthoquinone diazide sulfonic acid compound and the phenolic compound is, for example, the phenol compound and naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazide-4 -Sulfonyl chloride can be manufactured by condensing in presence of alkali, such as a triethanolamine, an alkali carbonate, and an alkali hydrogen carbonate, in dioxane etc. suitable solvent, and esterifying a part or all of hydroxyl groups.

It is preferable that esterification rate is 40 to 100%, and, as for the said esterified product, it is more preferable that it is 50 to 100%. Esterification rate can be calculated | required as [(number of esterified hydroxyl group) / (total number of hydroxyl groups (of phenolic compound) before esterification)] x100.

Moreover, other quinonediazide group containing compound of that excepting the above can also be used.

As another quinone diazide group containing compound, Orthoquinone diazides, such as an ortho benzoquinone diazide, an ortho naphthoquinone diazide, an ortho anthraquinone diazide, for example, the nuclear substitution derivative (for example, an ortho naphthoquinone) Diazide sulfonic acid esters, etc.); orthoquinone diazide sulfonyl chloride and a compound having a hydroxyl group or an amino group (for example, phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, Pyrogalol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethylether, gallic acid, a reaction product of esterified or etherified gallic acid, aniline, p-aminodiphenylamine, etc., with some hydroxyl groups; have.

These may be used independently and may be used in combination of 2 or more type.

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.

[Formula 6]

[Wherein, R ¹¹ to R ²⁰ 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; R ²² to R ²⁵ each independently represent 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 (b-2) Or a terminal represented by R ^{21 and} a terminal of Q ¹ may be bonded to each other to form an alkylene group having 2 to 5 carbon atoms; a and b represent an integer of 1 to 3; d and e represent 0 to 3 Provided that when a, b, d or e represents 3, R ¹³ , R ¹⁶ , R ¹⁸ or R ²⁰ are absent, respectively; h and i represent an integer such that h + i = 0 to 3; ]

[Formula 7]

[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].

As a halogen atom in R <^11> -R <^20> , R <^26> and R <^27> , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

The alkyl group in R ¹¹ to R ²⁷ may be any one of a linear, branched, and cyclic type, particularly preferably a methyl group or a cyclohexyl group.

The R ²¹ end, and combines the ends of Q ¹ when forming an alkylene group having a carbon number of 2 ~ 5, Q ¹ and R ²¹ and, by a carbon atom between Q ¹ and R ²¹ form rings having 3 to 6 carbon atoms An alkyl group is formed.

As for the compounding quantity of (B) 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 the most desirable. If it is more than the lower limit of the said range, a sensitivity, resolution, etc. will improve, and if it is below an upper limit, transparency, insulation, low dielectric constant, etc. of the film obtained will improve.

<Acid generator (C)>

The composition for forming a planarization insulating film for a liquid crystal display device of the present invention further includes an acid generator (C) which generates an acid by irradiation (exposure) of radiation as an optional component within a range that does not impair the effects of the present invention. Or C) component). By containing (C) component, a sensitivity, resolution, etc. improve.

It does not specifically limit as (C) component, The thing currently proposed as an acid generator for chemically amplified resist can be used. As such acid generators, onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyl diazomethanes, and poly (bissulfonyl) diazos Various kinds of diazomethane-based acid generators such as methane, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators and disulfone-based acid generators are known.

As an onium salt type acid generator, the acid generator represented by following General formula (c-0) is mentioned, for example.

[Formula 8]

[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, a straight chain or a branched chain; Is an alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group; R ⁵³ is an aryl group which may have a substituent; u ”is an integer of 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.

As said linear or branched alkyl group, it is preferable that it is C1-C10, It is more preferable that it is C1-C8, It is most preferable that it is C1-C4.

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.

As said linear or branched fluorinated alkyl group, it is preferable that it is C1-C10, It is more preferable that it is C1-C8, It is most preferable that it is C1-C4.

The cyclic fluorinated alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.

Further, the fluorination rate (number ratio of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) of the fluorinated alkyl group is preferably 10 to 100%, more preferably 50 to 100%, and especially all of the hydrogen atoms Substitution with a fluorine atom is preferable because the strength of the acid becomes stronger.

As R ⁵¹ , it is most preferable that it is a linear alkyl group or a linear fluorinated alkyl group.

R ⁵² is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group.

In R ⁵² , a halogen atom includes a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, and the like, and a fluorine atom is preferable.

In R ⁵² , the alkyl group is linear or branched, and the carbon number is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.

In R ⁵² , a halogenated alkyl group is a group in which some or all of the hydrogen atoms in the alkyl group are replaced with halogen atoms. The alkyl group here is the same as the "alkyl group" in R ⁵² described above. Examples of the halogen atom to be substituted include the same ones described for the "halogen atom". In a halogenated alkyl group, it is preferable that 50-100% of the total number of hydrogen atoms is substituted by the halogen atom, and it is more preferable that all are substituted.

In R ⁵² , the alkoxy group is linear or branched, and the carbon number is preferably 1 to 5, particularly 1 to 4, and more preferably 1 to 3.

Among these, as R ⁵² , a hydrogen atom is preferable.

R ⁵³ is an aryl group which may have a substituent, and the naphthyl group, phenyl group, anthryl group, etc. may be mentioned as a structure of the basic ring (maternal ring) which removed the substituent, The effect of this invention, ArF excimer laser, etc. exposure. Preference is given to the phenyl group in terms of light absorption.

As a substituent, a hydroxyl group, a lower alkyl group (it is a linear or branched chain type, the preferable carbon number is 1-5, especially a methyl group is preferable), etc. are mentioned.

As for the aryl group of R ⁵³ , it is more preferable not to have a substituent.

u ”is an integer of 1-3, It is preferable that it is 2 or 3, It is preferable that it is 3 especially.

 The following are mentioned as a preferable thing of the acid generator represented by general formula (c-0).

[Formula 9]

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

[Formula 10]

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

R <^1>'-R<^3>' respectively independently represents an aryl group or an alkyl group in a formula (c-1). At least 1 of R <^1>'-R<^3>' represents an aryl group. R ¹ "~ R ^3" is an aryl group of 2 or more is preferable, in which all of R ¹ "~ R ^3" is most preferably an aryl group.

There is no restriction | limiting in particular as an aryl group of R <^1>'-R< ³ >', For example, as a C6-C20 aryl group, one or all of the hydrogen atoms are substituted by the alkyl group, the alkoxy group, the halogen atom, etc. in this aryl group There may or may not be. As an aryl group, a C6-C10 aryl group is preferable at the point which can be synthesize | combined cheaply. Specifically, a phenyl group and a naphthyl group are mentioned, for example.

As an alkyl group which the hydrogen atom of the said aryl group may be substituted, the C1-C5 alkyl group is preferable, and it is most preferable that they are a methyl group, an ethyl group, a propyl group, n-butyl group, and a tert- butyl group.

As an alkoxy group which the hydrogen atom of the said aryl group may substitute, the C1-C5 alkoxy group is preferable and a methoxy group and an ethoxy group are the most preferable.

As a halogen atom in which the hydrogen atom of the said aryl group may be substituted, it is preferable that it is a fluorine atom.

There is no restriction | limiting in particular as an alkyl group of R <^1>'-R< ³ >, For example, a C1-C10 linear, branched, or cyclic alkyl group etc. are mentioned. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, decanyl group, etc. are mentioned. have. It is preferable that it is C1-C5 from the point which is excellent in resolution. Among these, a methyl group is preferable at the point which is excellent in resolution and can be synthesize | combined in low cost.

Among them, R ¹ ″ to R ³ ″ are each most preferably a phenyl group or a naphthyl group.

R ⁴ ″ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.

As said linear or branched alkyl group, it is preferable that it is C1-C10, It is more preferable that it is C1-C8, It is most preferable that it is C1-C4.

As said cyclic alkyl group, it is preferable that it is C4-C15 as a cyclic group represented by said R <^1>', It is more preferable that it is C4-C10, It is most preferable that it is C6-C10.

As said linear or branched fluorinated alkyl group, it is preferable that it is C1-C10, It is more preferable that it is C1-C8, It is most preferable that it is C1-C4.

The cyclic fluorinated alkyl group preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.

In addition, the fluorination rate (ratio of fluorine atoms in the alkyl group) of the fluorinated alkyl group is preferably 10 to 100%, more preferably 50 to 100%, and in particular, all of the hydrogen atoms are substituted with fluorine atoms to give strong acid strength. It is preferable as it is.

R ⁴ ″ is most preferably a linear or cyclic alkyl group or a linear or cyclic fluorinated alkyl group.

In formula (c-2), R <^5>'and R <^6>"respectively independently represent an aryl group or an alkyl group. At least one of R ⁵ ″ and R ⁶ ″ represents an aryl group. It is preferable that all of R ⁵ ″ and R ⁶ ″ are aryl groups.

Examples of the aryl group for R ⁵ ″ and R ⁶ ″ include the same aryl groups as R ¹ ″ to R ³ ″.

Examples of the alkyl group of R ⁵ ″ and R ⁶ ″ include the same alkyl groups as those of R ¹ ″ to R ³ ″.

Of these, R ⁵ ″ and R ⁶ ″ are all most preferably a phenyl group.

Examples of R ⁴ ″ in formula (c-2) include the same ones as R ⁴ ″ in formula (c-1).

Specific examples of the onium salt-based acid generator represented by formula (c-1) or (c-2) include trifluoromethanesulfonate or nonafluorobutanesulfonate of diphenyliodonium, and bis (4-tert-butyl Trifluoromethanesulfonate or nonafluorobutanesulfonate of phenyl) iodonium, trifluoromethanesulfonate of triphenylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, tri ( Trifluoromethanesulfonate of 4-methylphenyl) sulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethanesulfonate of dimethyl (4-hydroxynaphthyl) sulfonium, its Heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, heptafluoropropanesulfonate or nonaple thereof Fluorobutanesulfonate, trifluoromethanesulfonate of diphenylmonomethylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethane of (4-methylphenyl) diphenylsulfonium Sulfonates, heptafluoropropanesulfonates or nonafluorobutanesulfonates thereof, trifluoromethanesulfonates of (4-methoxyphenyl) diphenylsulfonium, heptafluoropropanesulfonates or nonafluoro thereof Butanesulfonate, trifluoromethanesulfonate of tri (4-tert-butyl) phenylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, diphenyl (1- (4-methoxy) Trifluoromethanesulfonate of naphthyl) sulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethanesulfo of di (1-naphthyl) phenylsulfonium Sites may heptafluoropropanesulfonate include butane sulfonate such as propane sulfonate or a nonafluoro. Moreover, the onium salt in which the anion part of these onium salt was substituted by methanesulfonate, n-propanesulfonate, n-butanesulfonate, and n-octanesulfonate can also be used.

Moreover, in the said general formula (c-1) or (c-2), the onium salt type acid generator substituted with the anion part represented by the following general formula (c-3) or (c-4) can also be used. (The cation part is the same as (c-1) or (c-2).).

[Formula 11]

[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 an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; ].

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, and most preferably 3 carbon atoms.

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 1 to 7 carbon atoms, more preferably. It is C1-C3.

The smaller the carbon number of the alkylene group of X ”or the carbon number of the alkyl group of Y”, Z ”is, the smaller the reason is, for example, the solubility in the resist solvent is good within the range of the carbon number.

Moreover, in the alkylene group of X ”or the alkyl group of Y”, Z ”, the more the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and the transparency to high energy light or electron beam of 200 nm or less It is preferable because it improves. The proportion of the fluorine atoms in the alkylene group or the alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably, a perfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms. Or a perfluoroalkyl group.

In this specification, an oxime sulfonate-type acid generator is a compound which has at least 1 group represented by following General formula (C-1), and has a characteristic which generate | occur | produces an acid by irradiation of a radiation. Since such an oxime sulfonate-type acid generator is used abundantly for the chemically amplified resist composition, it can select arbitrarily and can use it.

[Formula 12]

(In formula (C-1), R <^31> , R <^32> represents an organic group each independently.).

The organic group of R ³¹ and R ³² is a group containing a carbon atom, and atoms other than the carbon atom (for example, hydrogen atom, oxygen atom, nitrogen atom, sulfur atom, halogen atom (fluorine atom, chlorine atom, etc.)) You may have it.

As an organic group of R <^31> , a linear, branched or cyclic alkyl group or an 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 one part or all of the hydrogen atoms of an alkyl group or an aryl group are substituted by the substituent.

The alkyl group of R ³¹ is preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, and most preferably 1 to 4 carbon atoms. Do. Particularly preferred as the alkyl group is a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group). In addition, the partially halogenated alkyl group means the alkyl group in which a part of hydrogen atoms were substituted by the halogen atom, and the fully halogenated alkyl group means the alkyl group in which all the hydrogen atoms were substituted by the halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.

The aryl group as the organic group of R ³¹ is preferably 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. Particularly preferred aryl groups are partially or completely halogenated aryl groups. In addition, the partially halogenated aryl group means the aryl group in which a part of hydrogen atoms are substituted by the halogen atom, and the fully halogenated aryl group means the aryl group in which all the hydrogen atoms were substituted by the halogen atom.

Especially as R <^31> , a C1-C4 alkyl group or a C1-C4 fluorinated alkyl group which does not have a substituent is preferable.

As an organic group of R <^32> , a linear, branched or cyclic alkyl group, an aryl group, or a cyano group is preferable. As an alkyl group and an aryl group of R <^32>, the thing similar to the alkyl group and aryl group which were illustrated by said R <^31> is mentioned.

Especially as R <^32> , a cyano group, a C1-C8 alkyl group which does not have a substituent, or a C1-C8 fluorinated alkyl group is preferable.

As a more preferable thing as an oxime sulfonate-type acid generator, the compound represented by the following general formula (C-2) or (C-3) is mentioned.

[Formula 13]

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

[Formula 14]

[In formula (C-3), R ³⁶ is a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁷ is a divalent or trivalent aromatic hydrocarbon group. R ³⁸ is an alkyl group or halogenated alkyl group having no substituent. p ”is 2 or 3].

In the general formula (C-2), the alkyl group or halogenated alkyl group having no substituent of R ³³ is preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms. . As a halogen atom in a halogenated alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

As R ³³ , a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.

The fluorinated alkyl group in R ³³ is preferably 50% or more fluorinated, and more preferably 70% or more, and still more preferably 90% or more fluorinated.

The aryl group for R ³⁴ is a group in which one hydrogen atom is removed from a ring of an aromatic hydrocarbon 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 the carbon atoms constituting the ring of these groups is substituted with a hetero atom 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 substituents, such as a C1-C10 alkyl group, a halogenated alkyl group, and an alkoxy group. The alkyl group or halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. As a halogen atom in a halogenated alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. Moreover, it is preferable that this halogenated alkyl group is a fluorinated alkyl group.

The alkyl group or halogenated alkyl group having no substituent of R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms. As a halogen atom in a halogenated alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

As R ^{35, a} halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.

The fluorinated alkyl group in R ³⁵ is preferably fluorinated at least 50% of the hydrogen atoms of the alkyl group, more preferably at least 70%, even more preferably at least 90%, because the strength of the acid generated is increased. . Most preferably, it is a fully fluorinated alkyl group in which the hydrogen atom is 100% fluorine substituted.

In said general formula (C-3), the alkyl group or halogenated alkyl group which does not have a substituent of R <^36> is the same as the alkyl group or halogenated alkyl group which does not have a substituent of said R <^33> .

Examples of the divalent or trivalent aromatic hydrocarbon group of R ^{37 include} a group in which one or two hydrogen atoms are further removed from the aryl group of R ³⁴ .

Examples of the alkyl group or halogenated alkyl group having no substituent of R ³⁸ include the same alkyl group or halogenated alkyl group having no substituent of R ³⁵ described above.

p ”is preferably 2.

-(p-톨루엔술포닐옥시이미노)-벤질시아니드,

-(p-클로로벤젠술포닐옥시이미노)-벤질시아니드,

-(4-니트로벤젠술포닐옥시이미노)-벤질시아니드,

-(4-니트로-2-트리플루오로메틸벤젠술포닐옥시이미노)-벤질시아니드,

-(벤젠술포닐옥시이미노)-4-클로로벤질시아니드,

-(벤젠술포닐옥시이미노)-2,4-디클로로벤질시아니드,

-(벤젠술포닐옥시이미노)-2,6-디클로로벤질시아니드,

-(벤젠술포닐옥시이미노)-4-메톡시벤질시아니드,

-(2-클로로벤젠술포닐옥시이미노)-4-메톡시벤질시아니드,

-(벤젠술포닐옥시이미노)-티엔-2-일아세토니트릴,

-(4-도데실벤젠술포닐옥시이미노)-벤질시아니드,

-[(p-톨루엔술포닐옥시이미노)-4-메톡시페닐]아세토니트릴,

-[(도데실벤젠술포닐옥시이미노)-4-메톡시페닐]아세토니트릴,

-(토실옥시이미노)-4-티에닐시아니드,

-(메틸술포닐옥시이미노)-1-시클로펜테닐아세토니트릴,

-(메틸술포닐옥시이미노)-1-시클로헥세닐아세토니트릴,

-(메틸술포닐옥시이미노)-1-시클로헵테닐아세토니트릴,

-(메틸술포닐옥시이미노)-1-시클로옥테닐아세토니트릴,

-(트리 플루오로메틸술포닐옥시이미노)-1-시클로펜테닐아세토니트릴,

-(트리플루오로메틸술포닐옥시이미노)-시클로헥실아세토니트릴,

-(에틸술포닐옥시이미노)-에틸아세토니트릴,

-(프로필술포닐옥시이미노)-프로필아세토니트릴,

-(시클로헥실술포닐옥시이미노)-시클로펜틸아세토니트릴,

-(시클로헥실술포닐옥시이미노)-시클로헥실아세토니트릴,

-(시클로헥실술포닐옥시이미노)-1-시클로펜테닐아세토니트릴,

-(에틸술포닐옥시이미노)-1-시클로펜테닐아세토니트릴,

-(이소프로필술포닐옥시이미노)-1-시클로펜테닐아세토니트릴,

-(n-부틸술포닐옥시이미노)-1-시클로펜테닐아세토니트릴,

-(에틸술포닐옥시이미노)-1-시클로헥세닐아세토니트릴,

-(이소프로필술포닐옥시이미노)-1-시클로헥세닐아세토니트릴,

-(n-부틸술포닐옥시이미노)-1-시클로헥세닐아세토니트릴,

-(메틸술포닐옥시이미노)-페닐아세토니트릴,

-(메틸술포닐옥시이미노)-p-메톡시페닐아세토니트릴,

-(트리플루오로메틸술포닐옥시이미노)-페닐아세토니트릴,

-(트리플루오로메틸술포닐옥시이미노)-p-메톡시페닐아세토니트릴,

-(에틸술포닐옥시이미노)-p-메톡시페닐아세토니트릴,

-(프로필술포닐옥시이미노)-p-메틸페닐아세토니트릴,

-(메틸술포닐옥시이미노)-p-브로모페닐아세토니트릴 등을 들 수 있다.As a specific example of an oxime sulfonate-type acid generator

-(p-toluenesulfonyloxyimino) -benzylcyanide,

-(p-chlorobenzenesulfonyloxyimino) -benzylcyanide,

-(4-nitrobenzenesulfonyloxyimino) -benzylcyanide,

-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -benzylcyanide,

-(Benzenesulfonyloxyimino) -4-chlorobenzylcyanide,

-(Benzenesulfonyloxyimino) -2,4-dichlorobenzylcyanide,

-(Benzenesulfonyloxyimino) -2,6-dichlorobenzylcyanide,

-(Benzenesulfonyloxyimino) -4-methoxybenzylcyanide,

-(2-chlorobenzenesulfonyloxyimino) -4-methoxybenzylcyanide,

-(Benzenesulfonyloxyimino) -thien-2-ylacetonitrile,

-(4-dodecylbenzenesulfonyloxyimino) -benzyl cyanide,

-[(p-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile,

-[(Dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile,

-(Tosyloxyimino) -4-thienyl cyanides,

-(Methylsulfonyloxyimino) -1-cyclopentenylacetonitrile,

-(Methylsulfonyloxyimino) -1-cyclohexenylacetonitrile,

-(Methylsulfonyloxyimino) -1-cycloheptenylacetonitrile,

-(Methylsulfonyloxyimino) -1-cyclooctenylacetonitrile,

-(Trifluoromethylsulfonyloxyimino) -1-cyclopentenylacetonitrile,

-(Trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile,

-(Ethylsulfonyloxyimino) -ethylacetonitrile,

-(Propylsulfonyloxyimino) -propylacetonitrile,

-(Cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile,

-(Cyclohexylsulfonyloxyimino) -cyclohexyl acetonitrile,

-(Cyclohexylsulfonyloxyimino) -1-cyclopentenylacetonitrile,

-(Ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile,

-(Isopropylsulfonyloxyimino) -1-cyclopentenylacetonitrile,

-(n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile,

-(Ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile,

-(Isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile,

-(n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile,

-(Methylsulfonyloxyimino) -phenylacetonitrile,

-(Methylsulfonyloxyimino) -p-methoxyphenylacetonitrile,

-(Trifluoromethylsulfonyloxyimino) -phenylacetonitrile,

-(Trifluoromethylsulfonyloxyimino) -p-methoxyphenylacetonitrile,

-(Ethylsulfonyloxyimino) -p-methoxyphenylacetonitrile,

-(Propylsulfonyloxyimino) -p-methylphenylacetonitrile,

-(Methylsulfonyloxyimino) -p-bromophenylacetonitrile etc. are mentioned.

Moreover, the oxime sulfonate-type acid generator disclosed by Unexamined-Japanese-Patent No. 9-208554 (Patent [0012]-[0014]-[Formula 18]-[Formula 19], WO2004 / 074242A2 (65- The oxime sulfonate acid generator disclosed in Examples 1 to 40 on page 85 can also be preferably used.

Moreover, the following can be illustrated as a preferable thing.

[Formula 15]

Moreover, the following four compounds are also preferable.

[Formula 16]

Specific examples of bisalkyl or bisarylsulfonyldiazomethanes in the diazomethane-based acid generator include bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and bis ( 1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, etc. are mentioned.

Moreover, the diazomethane-type acid generator disclosed in Unexamined-Japanese-Patent No. 11-035551, Unexamined-Japanese-Patent No. 11-035552, and Unexamined-Japanese-Patent No. 11-035573 can also be used preferably.

Moreover, as poly (bissulfonyl) diazomethanes, 1, 3-bis (phenylsulfonyl diazommethyl sulfonyl) propane, 1, which is disclosed by Unexamined-Japanese-Patent No. 11-322707, for example, 4-bis (phenylsulfonyldiazomethylsulfonyl) 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 (cyclohexyl sulfonyl diazommethyl sulfonyl) decane, etc. are mentioned.

As (C) 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-based acid generator has excellent transparency, high performance as an acid generator, and good solubility in an organic solvent. Moreover, in a liquid crystal display element, since there is no infiltration of a halogen atom etc. with respect to the liquid crystal adjacent to a planarization insulating film, it is preferable to deteriorate a liquid crystal.

1-10 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (C) component in the composition for flattening insulation film formation for liquid crystal display elements of this invention, 2-5 mass parts is more preferable. If it is more than the lower limit of the said range, the effect by mix | blending (C) component is fully acquired, and if it is below an upper limit, since a uniform solution will be obtained when dissolving the said composition in the organic solvent, storage stability will become favorable, and it is preferable. .

The composition for planarization insulating film formation for liquid crystal display elements of this invention may contain a crosslinking agent (D) (henceforth (D) component) as an arbitrary component in the range which does not impair the effect of this invention. By containing (D) component, heat resistance further improves.

As (D) component, it is preferable that it is a component which can form a crosslinked structure in (A) component or in the said (D) component by action of a heat and / or an ultraviolet-ray.

As (D) component, the compound which has an epoxy group and / or an oxetane group is mentioned, for example. Specifically, the copolymer etc. of the polymerizable unsaturated compound containing various epoxy resins and an epoxy-group containing polymerizable unsaturated compound are mentioned, for example.

As an epoxy resin, the thing of Unexamined-Japanese-Patent No. 8-262709 is mentioned, for example. 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, glycidylamine type epoxy resin, heterocyclic type epoxy resin And resins (co) polymerized with glycidyl methacrylate. Among these, bisphenol A type epoxy resins, cresol novolac type epoxy resins, glycidyl ester type epoxy resins, and the like are preferable.

-에틸아크릴산글리시딜,

-n-프로필아크릴산글리시딜,

-n-부틸아크릴산글리시딜, 아크릴산-3,4-에폭시부틸, 메타크릴산-3,4-에폭시부틸, 아크릴산-6,7-에폭시헵틸, 메타크릴산-6,7-에폭시헵틸,

-에틸아크릴산-6,7-에폭시헵틸, N-[4-(2,3-에폭시프로폭시)-3,5-디메틸벤질]아크릴아미드, N-[4-(2,3-에폭시프로폭시)-3,5-디메틸페닐프로필]아크릴아미드, 아크릴산-β-메틸글리시딜, 메타크릴산-β-메틸글리시딜, o-비닐벤질글리시딜에테르, m-비닐벤질글리시딜에테르, p-비닐벤질글리시딜에테르 등을 들 수 있다.As an epoxy group containing polymerizable unsaturated compound, the compound which has a vinyl group and an epoxy group is mentioned, for example. Specific examples include glycidyl acrylate, glycidyl methacrylate,

-Glycidyl ethyl acrylate,

-n-propyl acrylate glycidyl,

-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl,

-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-beta -methyl glycidyl, methacrylic acid-beta -methyl glycidyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

In the "copolymer of a polymerizable unsaturated compound containing an epoxy group-containing polymerizable unsaturated compound", the polymerizable unsaturated compound used together with an epoxy group-containing polymerizable unsaturated compound has a polymerizable unsaturated bond and does not have an epoxy group. Examples of the compound include, for example, acrylic acid, methacrylic acid, acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrene. 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 said "polymerizable unsaturated compound used for a copolymer", the ratio of an epoxy group containing polymeric unsaturated compound is 5-90 mol%, Preferably it is 50-85 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. An alicyclic epoxy group is group which -O- couples to two adjacent carbon atoms of the carbon atom which comprises the alicyclic cyclic group, and forms ring. As for carbon number of the alicyclic group of an alicyclic epoxy group, about 5-10 are preferable.

As an alicyclic epoxy group containing polymeric unsaturated compound, the compound represented by General formula (2)-(32) of Unexamined-Japanese-Patent No. 8-262709 is mentioned, for example.

Moreover, as (D) component, the crosslinking agent generally used for the resist composition can be used other than the above. As the crosslinking agent, for example, 2,3-dihydroxy-5-hydroxymethylnorbornane, 2-hydroxy-5,6-bis (hydroxymethyl) norbornane, cyclohexanedi methanol, 3, 4,8 (or 9) -trihydroxytricyclodecane, 2-methyl-2-adamantanol, 1,4-dioxane-2,3-diol, 1,3,5-trihydroxycyclohexane, etc. And an aliphatic cyclic hydrocarbon having an hydroxyl group or a hydroxyalkyl group or both thereof, or an oxygen derivative thereof.

Moreover, formaldehyde or formaldehyde and a lower alcohol are made to react with amino-group containing compounds, such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, propylene urea, and glycoluril, and a hydrogen atom of the amino group is made into a hydroxymethyl group or The compound substituted by the lower alkoxy methyl group is mentioned. Among them, those using melamine, those using melamine-based crosslinking agents and urea, those using alkylene ureas such as urea-based crosslinking agents, ethylene urea, and propylene urea are referred to as glycoluril-based crosslinking agents.

As a melamine type crosslinking agent, the compound which made melamine react with formaldehyde, substituted the hydrogen atom of the amino group by the hydroxymethyl group, the compound which reacted the melamine, formaldehyde, and lower alcohol, and substituted the hydrogen atom of the amino group with the lower alkoxymethyl group, etc. Can be mentioned. Specifically, hexamethoxy methyl melamine, hexaethoxy methyl melamine, hexapropoxy methyl melamine, hexabutoxy butyl melamine, etc. are mentioned, Especially, hexamethoxy methyl melamine is preferable.

As a urea-type crosslinking agent, the compound which made urea react with formaldehyde, substituted the hydrogen atom of the amino group by the hydroxymethyl group, the compound which made the urea, formaldehyde, and lower alcohol react, and substituted the hydrogen atom of the amino group with the lower alkoxymethyl group etc. Can be mentioned. Specifically, bismethoxy methyl urea, bisethoxy methyl urea, bispropoxy methyl urea, bisbutoxy methyl urea, etc. are mentioned, Especially, bismethoxy methyl urea is preferable.

As an alkylene urea type crosslinking agent, the compound obtained by condensation reaction of alkylene urea and formaldehyde, and making this product react with lower alcohol is mentioned. Specific examples include mono or dihydroxymethylated ethyleneurea, mono or dimethoxymethylated ethyleneurea, mono or diethoxymethylated ethyleneurea, mono or dipropoxymethylated ethyleneurea, mono or dibutoxymethylated ethyleneurea, and the like. Ethyleneurea-based crosslinking agents; propyleneurea such as mono or dihydroxymethylated propyleneurea, mono or dimethoxymethylated propyleneurea, mono or diethoxymethylated propyleneurea, mono or dipropoxymethylated propyleneurea, mono or dibutoxymethylated propyleneurea System crosslinking agent; 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone, 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imida Zolidinone etc. are mentioned.

Examples of the glycoluril 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 glycoluril derivatives can be obtained by condensation reaction between glycoluril and formaldehyde and by reacting this product with a lower alcohol. Specific examples include mono, di, tri or tetrahydroxymethylated glycoluril, mono, di, tri or tetramethoxymethylated glycoluril, mono, di, tri or tetraethoxymethylated glycoluril, mono, di, Tri or tetrapropoxymethylated glycoluril, mono, di, tri or tetrabutoxymethylated glycoluril and the like.

(D) component can be used 1 type or in mixture of 2 or more types.

5-100 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for the compounding quantity of (D) component, 10-50 mass parts is more preferable. By setting it as this range, the heat resistance improvement effect will become more favorable.

The composition for forming a planarization insulating film for a liquid crystal display device of the present invention includes a surfactant, a sensitizer, an antifoaming agent, an ultraviolet absorber, a storage stabilizer, an additional resin, a plasticizer, a stabilizer, a contrast enhancer, and the like without affecting the effect of the present invention. Various additives of may be added.

As surfactant, a conventionally well-known thing may be sufficient, and compounds, such as an anionic type, a cation type, and a nonionic type, are mentioned. Specifically, X-70-090 (product name, the Shin-Etsu Chemical Co., Ltd. product) etc. are mentioned.

As a sensitizer, what is used for the conventionally well-known positive resist can be used. For example, the compound etc. which have phenolic hydroxyl group of molecular weight 1000 or less are mentioned.

As a defoaming agent, a conventionally well-known thing may be sufficient and a silicone type and a fluorine-type compound are mentioned.

The composition for flattening insulation film formation for liquid crystal display elements of this invention can be manufactured by melt | dissolving said each component in the organic solvent (henceforth (S) component).

As (S) component, what is necessary is just to melt | dissolve each component to be used and it can be set as a uniform solution, for example, arbitrary ones or 2 or more types can be suitably selected and used out of what is conventionally known as a resist solvent. .

As a specific example, For example, lactones, such as (gamma) -butyrolactone; Ketones, such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; ethylene glycol, Polyhydric alcohols such as diethylene glycol, propylene glycol and dipropylene glycol; compounds having ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, and the above polyhydric alcohols Or derivatives of polyhydric alcohols such as compounds having ether bonds, such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether and monobutyl ether, or monophenyl ethers of the compounds having the above ester bonds. , Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monomethyl Le (PGME) is preferable; cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxypropionic acid Esters such as ethyl; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phentol, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xyl Aromatic organic solvents, such as ethylene, cymene, and mesitylene, etc. are mentioned.

These organic solvents may be used independently or may be used as 2 or more types of mixed solvents.

Especially, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and EL are preferable.

Moreover, the mixed solvent which mixed PGMEA and a polar solvent is preferable. What is necessary is just to determine the compounding ratio (mass ratio) suitably in consideration of compatibility of PGMEA and a polar solvent, etc., Preferably it is 1: 9-9: 1, More preferably, it is within the range of 2: 8-8: 2. Do.

More specifically, when mix | blending EL as a polar solvent, the mass ratio of PGMEA: EL becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 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.

Moreover, as (S) component, the mixed solvent of at least 1 sort (s) chosen from PGMEA and EL and (gamma) -butyrolactone other than that is also preferable. In this case, as a mixing ratio, the mass ratio of the former and the latter becomes like this. Preferably it is 70: 30-95: 5.

Although the usage-amount of (S) component is not specifically limited, Although it is set suitably according to the coating film thickness in the density | concentration which can be apply | coated on a support body, solid content concentration in a composition is 10-50 mass% normally, Preferably it is 15-35 mass It is used to be in the range of%.

`` Method of manufacturing planarization insulating film for liquid crystal display element ''

The manufacturing method of the planarization insulation film for liquid crystal display elements of this invention is a process of forming a resin film on the support body using the composition for formation of the planarization insulation film for liquid crystal display elements, the process of exposing the said resin film, and developing the said resin film, And forming a pattern and firing the pattern.

EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of the manufacturing method of the planarization insulating film for liquid crystal display elements of this invention is demonstrated, taking the liquid crystal array substrate 1 shown in FIGS.

First prepare the support. In the present embodiment, a plurality of gate lines 3 formed in parallel on the transparent substrate 2 as a support, a plurality of source lines 4 orthogonal to the gate lines 3, and a plurality surrounded by them What consists of the TFT 6 formed in the area | region (pixel area | region) of respectively, and the interlayer insulation film 13 which coat | covers them directly is used.

The TFT 6 is composed of a gate 7 formed on the transparent substrate 2, and an amorphous silicon layer 9 formed above the insulating film (gate insulating film) 8. The gate line 3 and the gate 7 are connected via the gate electrode 10. In addition, the source line 4 and the amorphous silicon layer 9 are connected via the source electrode. The amorphous silicon layer 9 and the pixel electrode 5 are connected via the drain electrode 11.

The process of forming the gate line 3, the source line 4, the TFT 6, and the interlayer insulation film 13 on the transparent substrate 2 can be performed by a conventionally well-known method.

In addition, since the planarization insulating film for liquid crystal display elements formed by this invention has insulating property, the interlayer insulation film 13 does not necessarily need to be formed.

Next, a resin film is formed on the support. A resin film can be formed by apply | coating the composition for flattening insulation film formation for liquid crystal display elements of this invention with a spinner, a roll coater, a spray, etc. to the surface of a support body, for example, and drying it. A drying method is not specifically limited, For example, (1) The method of drying for 60 second-120 second at the temperature of 80 degreeC-150 degreeC on a hotplate, (2) The method of leaving for several hours-several days at room temperature, (3) Any of the methods of removing the solvent in a hot air heater or an infrared heater for several tens of minutes to several hours may be used.

The film thickness of a resin film is not specifically limited, What is necessary is just to set suitably. Usually, the thickness from the upper end part of a support body to the upper surface (flat screen) of the said resin film is formed in the film thickness which becomes 1-10 micrometers.

Next, the resin film is selectively irradiated (exposure) to radiation such as visible light, ultraviolet light, excimer laser light or the like.

In the present invention, at the time of exposure, the molecular structure of the component (B) is changed in the portion irradiated with radiation, so that the solubility in aqueous alkali solution is increased. Therefore, when the said resin film is developed with a developing solution (alkali aqueous solution) in the next process, the part solubilized by exposure of a resin film is selectively dissolved and removed, and the pattern which is faithful to a mask is formed.

Exposure conditions are not specifically limited. An exposure area, exposure time, exposure intensity, etc. can be selected suitably according to the light source and method used for exposure.

The exposure light source is not particularly limited, and g-ray (436 nm), h-ray (405 nm), i-ray (365 nm), KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV ( Vacuum ultraviolet rays), EB (electron beam), X-rays, soft X-rays, and the like. In this invention, especially g line (436 nm), h line (405 nm), or i line (365 nm) are preferable, and g line or i line is more preferable.

After exposure, you may perform post exposure bake (PEB) for 40 to 120 second, Preferably it is 60 to 90 second, on the temperature conditions of 80-150 degreeC.

Next, the resin film after exposure is used as an alkaline developing solution, for example, an organic alkali aqueous solution such as 0.1-10 mass% tetramethylammonium hydroxide aqueous solution or an inorganic alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium metasilicate or sodium phosphate. Development is carried out. Thereby, the hole which penetrates the said resin film is formed in a resin film.

In this invention, after image development, before performing baking of a resin film, it is preferable to implement the process of performing an ultraviolet curing process with respect to the said pattern. Thereby, the heat resistance of the said pattern improves, the deformation | transformation of the pattern at the time of baking can be suppressed, and a high precision pattern is obtained. The reason why such an effect is obtained is not certain, but it is speculated whether the component (B) functions as a crosslinking agent and forms crosslinks between molecules of the component (A).

Ultraviolet curing treatment can be carried out using a known method. For example, by irradiating an ultraviolet-ray to the whole surface of a pattern using a well-known ultraviolet irradiation device (for example, DeepUVProcessor lamp L-800FS manufactured by Nippon Battery Co., Ltd., the excimer light irradiation apparatus SCG01 by Ushio Electric Co., Ltd., etc.). It can be carried out.

As for ultraviolet irradiation, it is preferable to use the light source which mainly outputs the ultraviolet-ray of wavelength 400nm or less, especially the ultraviolet-ray of wavelength 150-300nm. As such a light source, Nippon Battery Co., Ltd. lamp L-800FS (main wavelength: 254 nm, 185 nm), Ushio Electric Co., Ltd. lamp UEM50L-172A / x4 (main wavelength: 172 nm) etc. are mentioned, for example. Can be.

It is preferable to irradiate an ultraviolet-ray at the irradiation amount of about 500-20000 mJ / cm <2>, and about 1000-15000 mJ / cm <2> is more preferable. The irradiation amount can be controlled by the intensity of the ultraviolet rays to be irradiated and the irradiation time.

In addition, during the irradiation of ultraviolet rays, it is preferable to suppress the temperature rise due to rapid irradiation or irradiation so that wrinkles do not occur on the pattern surface of the irradiation part.

You may perform post-baking after UV hardening process and before baking. Although this post-baking process is not necessarily required, heat resistance improves further by performing post-baking. Moreover, the adhesiveness of a pattern and a support body improves by a postbaking process.

As a post-baking process, the heat processing of about 1 to 10 minutes is 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 fear of pattern deformation occurring in the post-baking process.

Next, baking of the said pattern (resin film) is performed. As a result, a film (flattened insulating film 14) mainly containing SiO ₂ is formed. Since the planarization insulating film 14 has SiO ₂ as a main component, transparency to visible light is very high. Moreover, it has insulation (for example, insulation in the range of 3.5-5 dielectric constant in 1 MHz) required for a planarization insulating film.

250-450 degreeC is preferable and 300-400 degreeC of baking temperature is more preferable. Moreover, it is preferable to bake these in nitrogen atmosphere. Within this range, the higher the firing temperature, the higher the transparency and insulation of the obtained planarization insulating film.

Although baking time changes with baking temperature, 10 to 60 minutes are preferable normally, and 15 to 30 minutes are more preferable.

In the support on which the flattening insulating film is formed, the liquid crystal array substrate 1 is obtained by forming the pixel electrode 5 so that the hole formed in the flattening insulating film 14 is filled and a part of the surface of the flattening insulating film 14 is covered. Lose.

A liquid crystal display element is obtained by arrange | positioning the liquid crystal array substrate 1 and the opposing board | substrate which were obtained as mentioned above and opposing a liquid crystal between them.

The composition for flattening insulation film formation for liquid crystal display elements of this invention has photosensitivity. Therefore, in forming the planarization insulating film for liquid crystal display elements, it has the merit of the throughput cost very.

In addition, the flattening insulating film for liquid crystal display elements formed through a process such as firing using the composition for forming a flattening insulating film for liquid crystal display elements of the present invention is excellent in heat resistance, and is exposed to a high temperature such as, for example, 250 to 450 ° C. Even in this case, deterioration of characteristics such as deformation and insulation hardly occurs. Moreover, since the planarization insulating film consists essentially of silica, the transmittance | permeability of visible light is very high and it is excellent in transparency.

Example

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 and the resin composition was prepared.

Each symbol in Table 1 shows the following, respectively. In addition, the numerical value in [] shows a compounding quantity (mass part), and it shows that "-" in (B) component of the comparative example 1 is a non-mixing.

(A) -1: Resin of Mw = 8500 shown by following General formula (A) -1 [In formula, x1: y1 = 30: 70 (molar ratio)].

(A) -2: Resin of Mw = 2800 represented by following General formula (A) -2 [In formula, x2: y2 = 28: 72 (molar ratio)].

(A) -3: Resin of Mw = 3000 shown by following General formula (A) -3 [wherein, x3: y3 = 70: 30 (molar ratio)].

(A) -4: Resin of Mw = 3600 shown by following General formula (A) -4 [In formula, x4: y4 = 70: 30 (molar ratio)].

(A) -5: Resin of Mw = 6000 represented by following General formula (A) -5.

(B) -1 to (B) -3: compounds represented by the following general formulas (B) -1 to (B) -3, wherein D represents a naphthoquinone-1,2-diazidesulfonyl group .

[Formula 17]

[Formula 18]

The following evaluation was performed about the obtained resin composition.

<Photosensitive evaluation and heat resistance evaluation>

The resin composition was applied onto the surface of a silicon substrate by spin coating, and a heat treatment (soft bake) for 120 ° C. for 90 seconds was performed on a hot plate to form a resin film having a film thickness of 1.0 μm.

Next, the resin film was exposed to light through a mask with an exposure machine (manufactured by Nikon Corporation, product name: NSR-2005i10D, NA = 0.57), and then heat treatment (PEB) for 150 ° C. for 90 seconds was performed on a hot plate. Was carried out. After PEB, the development process was performed for 20 second using the tetramethylammonium hydroxide (TMAH) aqueous solution of 2.38 mass% in concentration, and rinsed with pure water. Next, UV irradiation by the UV curing treatment (high pressure mercury lamp (manufactured by Nippon Battery Co., Ltd., product name: DeepUVProcessor lamp L-800FS, main wavelength 254, 185 nm; irradiation amount: 2700 mJ / cm 2) to the resin film; Baking at 150 ° C. for 90 seconds).

The substrate surface after the said UV curing process was observed with the scanning electron microscope (SEM).

As a result, in the example using the resin composition of Examples 1-7, the line pattern of 1.2 micrometers in line width, and the hole pattern of 2.0 micrometers in diameter were formed on the board | substrate, respectively.

On the other hand, in the example using the resin composition of Comparative Examples 1-2, the pattern could not be formed.

Next, the board | substrate with the said pattern was baked by the high temperature baking process at 400 degreeC for 30 minutes in nitrogen atmosphere in a vertical baking (product name: TOK TS8000MB), and the planarization insulating film was formed.

The surface of the board | substrate after the said high temperature baking process was observed by SEM.

As a result, in the example using the resin composition of Examples 1-7, the pattern (high-precision pattern <dimension change within ± 5%>) of the shape substantially the same as before high temperature bake treatment (after UV curing treatment), respectively Formed.

It was confirmed that the heat resistance of the pattern obtained as described above was high in that a highly accurate pattern could be formed.

Table 2 shows the above result as B which was able to form a high precision pattern and B which was not able to form a pattern.

A flattening insulating film was formed in the same manner as above except that the UV curing treatment was not performed after the resin film formation using the resin composition of Example 1, and observed by SEM.

As a result, the formed pattern was poor in the verticality of the side wall compared with the pattern before the high temperature baking process, for example, the precision was bad, for example, the cross-sectional shape of the line pattern became semicircle shape.

<Insulation evaluation>

In the same manner as in the above pattern formation evaluation, the planarization insulating film was formed, and for the portion where the patterning was not formed, the dielectric constant at 1 MHz and the leakage current value (A / cm 2) at 1 MV / cm were determined by SSM495 (manufactured by SSM). Product name), and the following evaluation criteria evaluated.

The results are shown in Table 2.

[Evaluation criteria of dielectric constant]

A ： 5 or less

B ： 5 or more

[Evaluation Criteria for Leakage Current Value]

A: Less than 1 × 10 ^-7

B ： 1 × 10 ^-7 or more

According to this invention, the composition which can form the planarization insulating film for liquid crystal display elements which has photosensitivity, and has the outstanding transparency and heat resistance, and the manufacturing method of the planarization insulating film for liquid crystal display elements can be provided. Therefore, the present invention is very useful industrially.

Claims (5)

The composition for planarization insulation film formation for liquid crystal display elements containing resin (A) containing the structural unit (a1) represented by the following general formula (a1-1), and a photosensitive agent (B). [Formula 1]

[Wherein, R ¹ represents a single bond or a linear or branched alkylene group; R ¹⁰¹ represents an alkyl group; n1 represents an integer of 0 to 4]. The method of claim 1, The composition for planarization insulating film formation for liquid crystal display elements in which the said resin (A) contains the structural unit (a2) further represented by following General formula (a2-1). [Formula 2]

[Wherein, R ² represents an aromatic hydrocarbon group or an alkyl group]. The method of claim 1, The composition for flattening insulation film formation for liquid crystal display elements whose said photosensitive agent (B) is a compound which has a naphthoquinone diazide group. On the support body, the process of forming a resin film using the composition for flattening insulation film formation for liquid crystal display elements in any one of Claims 1-3, the process of exposing the said resin film, and the said resin film are developed and a pattern is formed. And a step of firing the pattern. The method of claim 4, wherein The manufacturing method of the planarization insulating film for liquid crystal display elements containing the process of performing an ultraviolet curing process with respect to the said pattern before performing the said baking.

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