JP2017197655A - Radiation-sensitive resin composition, cured film, method for forming cured film, and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition which can exhibit positive type and negative type action mechanisms for each member and step to be applied in one radiation-sensitive resin composition, and to provide a method for forming an interlayer insulating film suitable as a cured film for display element which provides a cured film formed so as to sufficiently satisfy general characteristics such as excellent chemical resistance and transmissivity, can form the cured film by the positive type and negative type action mechanisms with one exposure even when a multi-gradation gradation mask is used.SOLUTION: There are a radiation-sensitive resin composition for display element which contains [A] a compound having a plurality of groups represented by formula (1) in the molecule and [B] a radiation-sensitive acid generating body; and a method for forming an interlayer insulating film using the radiation-sensitive resin composition for display element and a multi-gradation gradation mask.SELECTED DRAWING: None

Description

  The present invention relates to a radiation-sensitive resin composition, a cured film, a method for forming a cured film, and a display element.

  Generally, a cured film such as an interlayer insulating film, a spacer, a protective film, and a color filter coloring pattern is used for a display element such as a liquid crystal display element. The cured film such as the interlayer insulating film is required to have high hardness, low dielectric constant, high voltage holding ratio, and the like. As a material for forming such a cured film, a radiation-sensitive resin composition is widely used because the number of steps for forming a pattern is small and a high surface hardness is obtained.

As a radiation-sensitive resin composition for forming a cured film, one containing a copolymer containing a carboxy group and an epoxy group is known (see JP-A-2001-354822). In this radiation sensitive resin composition, it is comprised so that a cured film with high surface hardness can be obtained when a carboxy group and an epoxy group react. There are two types of such radiation-sensitive resin compositions, a positive-type radiation-sensitive resin composition and a negative-type radiation-sensitive resin composition, which are properly used depending on the member, process, etc. to be applied.
If a single radiation-sensitive resin composition can properly use a positive type and a negative type for each applied member and process, it is desirable from the viewpoint of the manufacturing process of liquid crystal panels and the like and reduction of materials used.
In addition, a technique using a multi-tone mask such as a half-tone mask or a gray-tone mask in photolithography, which has been used for miniaturization of wirings in the manufacture of semiconductor elements recently, has been used for manufacturing liquid crystal display elements. It has come to be used (refer Unexamined-Japanese-Patent No. 2013-243121). By using a multi-tone mask in photolithography, exposure energy can be controlled, and film thicknesses having different thicknesses can be formed at the same time, thereby shortening the manufacturing process and associated costs (for example, special characteristics). (See Japanese Unexamined Patent Publication No. 2015-7704).

  Therefore, if a cured film can be formed by a positive exposure mechanism and a negative exposure mechanism by a single exposure by controlling exposure energy using a multi-tone mask, the process can be reduced and the materials used in the manufacturing process of display elements, etc. Desirable from the viewpoint of reduction.

JP 2001-354822 A JP 2013-243121 A Japanese Patent Laying-Open No. 2015-007704

The present invention has been made on the basis of the circumstances as described above, and its purpose is to provide a positive-type and negative-type working mechanism for each applied member and process in one radiation-sensitive resin composition. It is to provide a radiation sensitive resin composition that can be shown.
The resulting cured film can form a cured film that can sufficiently satisfy general characteristics such as excellent chemical resistance and transmittance, and if a multi-tone mask is used, a positive type and a negative type can be obtained with a single exposure. It is an object to provide a method for forming an interlayer insulating film that can form a cured film by an action mechanism and is suitable as a cured film for a display element.
The exposure technique using the multi-tone mask is considered to be applied to the formation of a resist pattern in semiconductor manufacturing. The resist pattern applied there is removed by etching or the like in the semiconductor manufacturing process.
The cured film of the present invention is not removed by etching, but remains in the device as it is, and its insulating properties and the like must be maintained over a long period according to the life of the device. Therefore, the use purpose and material design of the radiation-sensitive resin composition suitable for the multi-tone mask in the resist pattern for semiconductor manufacture are greatly different.
The present invention has been made on the basis of the above circumstances, and by using a multi-tone mask, a cured film can be formed with a positive type and a negative type by an action mechanism in one exposure. It is to provide a method for forming an interlayer insulating film suitable as a cured film for a display element.

  The invention made to solve the above-mentioned problems is achieved by the following radiation-sensitive composition for display elements.

[A] Compound having a plurality of groups represented by the following formula (1) in the molecule
[B] A radiation-sensitive composition for display elements comprising a radiation-sensitive acid generator.

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or one or more hydrogen atoms in the phenyl group having 1 to 12 carbon atoms. An alkyl group, a group substituted with one or more groups selected from an alkoxyl group having 1 to 12 carbon atoms, R ¹ and R ² may form a ring having 3 or more carbon atoms, and * is a bonding position. Is shown.)
2. The display element according to claim 1, wherein the resin composition for forming a cured film used in the method for forming the cured film for display element is a polymer in which the compound [A] has a structural unit represented by the following formula (2). Achieved with a radiation sensitive composition.

(In formula (2), R ¹ and R ² have the same meanings as in formula (1). R ³ represents a hydrogen atom or a methyl group. X represents a single bond or a divalent organic group.)
Furthermore, the formation method of the interlayer insulation film including the process of the following (1) to (4).
(1) The process of forming a coating film on a base material with the radiation sensitive composition for display elements as described in any one of Claims 1-5.
(2) Step (3) for exposing the coating film obtained in (1) through a multi-tone mask (3) Step for developing the film obtained in (2) (4) Obtained in step (3) Heating the membrane

This invention is providing the radiation sensitive resin composition which can show a positive type and a negative type action mechanism for every member and process applied with one type of radiation sensitive resin composition.
The resulting cured film can form a cured film that can sufficiently satisfy general characteristics such as excellent chemical resistance and transmittance, and if a multi-tone mask is used, a positive type and a negative type can be obtained with a single exposure. It is an object to provide a method for forming an interlayer insulating film that can form a cured film by an action mechanism and is suitable as a cured film for a display element.

The present invention is described in detail below.
<Radiation-sensitive resin composition for display element>
The radiation-sensitive resin composition for display elements according to an embodiment of the present invention includes: [A] a compound having a plurality of groups represented by the following formula (1) in the molecule (hereinafter also referred to as [A] component), [ B] A radiation-sensitive composition for display elements comprising a radiation-sensitive acid generator (hereinafter also referred to as [B] component).
<[A] Compound>
The compound [A] is a compound having a plurality of groups represented by the following formula (1) in the molecule.

In the above formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or one or more hydrogen atoms in the phenyl group having 1 to 12 carbon atoms. A group substituted with one or more groups selected from an alkyl group and an alkoxyl group having 1 to 12 carbon atoms. R ¹ and R ² may form a ring having 3 or more carbon atoms. * Indicates a bonding position.
Specific examples of R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, phenyl Groups and the like. Examples of the group in which one or more hydrogen atoms in the phenyl group are substituted with one or more groups selected from an alkyl group having 1 to 12 carbon atoms and an alkoxyl group having 1 to 12 carbon atoms include a tolyl group and a xylyl group. , P-methoxyphenyl group, p-ethoxyphenyl group and the like.
The group represented by the following formula (1) is, for example, a partial structure of a glucofuranose derivative as shown in the following figure, and by reacting a hydroxyl group of the glucofuranose derivative with a compound having a polymerizable group such as a methacryloyl group, A monomer having a group represented by the formula (1) can be synthesized.

  Further, for example, a compound having two or more groups represented by the formula (1) in one molecule is obtained by reacting a compound having a plurality of carboxyl groups in one molecule with a glucofuranose derivative having a hydroxyl group.

The group represented by the formula (1) exhibits a positive behavior when exposed in the presence of an acid generator, and the exposed portion of the film is removed through a development step. Although the detailed reaction mechanism of such behavior is not clear, as shown in the following formula, the hydroxyl protecting group is eliminated in the presence of an acid, so that a plurality of hydroxyl groups are generated in the molecule. It is presumed that the affinity to the developer increases and shows a positive behavior.

  Further, when the exposure amount is increased and exposure is performed, this time, a negative-type behavior is exhibited, and even if the post-exposure film is developed, it is not removed and a cured film is formed. Although the detailed reaction mechanism of such behavior is not clear, as shown in the following formula, the hydroxyl group from which the protecting group has been removed in the presence of an acid undergoes a dehydration reaction to cause cross-linking between molecules. It is inferred to show the behavior of the mold.

The group represented by the above formula (1) can synthesize a monomer by, for example, reacting a hydroxyl group of a glucofuranose derivative with a compound having a polymerizable group such as a methacryloyl group.

  By polymerizing such a monomer, a polymer having a structural unit represented by the following formula (2) is obtained.

(In formula (2), R ¹ and R ² have the same meanings as in formula (1). R ³ represents a hydrogen atom or a methyl group. X represents a single bond or a divalent organic group.)
X represents a single bond or a divalent organic group. Examples of the divalent organic group include dicarboxylic acids such as succinic acid, maleic acid, and phthalic acid or anhydrides thereof such as 2-hydroxyethyl (meth) acrylic acid. And the like, and the like. Examples of such monomers include the following compounds.

The content ratio of the monomers (a-1) to (a-12) represented by the above formula is 0.1 mol% or more and 80 mol with respect to all structural units constituting the [A] polymer component. % Or less, more preferably 1 mol% or more and 60 mol% or less, still more preferably 10 mol% or more and 40 mol% or less. By setting it as the said range, the behavior of a positive type and a negative type can be shown.
[A] A polymer component has other structural units other than the structural unit shown by Formula (2) in the range which does not impair the effect of this invention.
Examples of monomers that give other structural units include unsaturated monocarboxylic acids, (meth) acrylic acid esters having a hydroxyl group, (meth) acrylic acid chain alkyl esters, (meth) acrylic acid cyclic alkyl esters, ( A meta) acrylic acid aryl ester, an unsaturated aromatic compound, a conjugated diene, an unsaturated compound having a tetrahydrofuran skeleton, or a compound represented by the following formula (3).

(In formula (3), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents an epoxy group, a 3,4-epoxycyclohexyl group, the following formula (3-1), the following formula (3-2) or X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, Y ¹ is a single bond, oxygen, or a group selected from the group of groups represented by the following formula (3-3). An atom, a sulfur atom or an imino group, wherein in formula (3-3), R ¹³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and * represents a bonding site.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like. As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example. Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include, for example, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], hexane. And mono- (methacryloyloxy) ethyl hydrophthalate. Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends include ω-carboxypolycaprolactone mono (meth) acrylate.
Examples of unsaturated polycyclic compounds having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1]. Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5- Carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2. 2.1] hept-2-ene anhydride and the like.

  Of these, monocarboxylic acid and dicarboxylic acid anhydrides are preferred, and (meth) acrylic acid and maleic anhydride are more preferred from the viewpoints of copolymerization reactivity, solubility in alkaline aqueous solutions, and availability.

  Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, and methacrylate. Examples include 2-hydroxyethyl acid, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, and the like.

  Examples of the (meth) acrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, N-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Examples include isodecyl, n-lauryl acrylate, tridecyl acrylate, and n-stearyl acrylate.

Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclo [5 methacrylate]. .2.1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate , Tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl acrylate, isobornyl acrylate and the like.

  Examples of the (meth) acrylic acid aryl ester include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-tolyl. Maleimide, N-naphthylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-benzylmaleimide and the like can be mentioned.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.
The structural unit represented by the above formula (3) is preferably a structural unit represented by the following formula.

In the above formula, R ²⁹ is a hydrogen atom or a methyl group.

As the compound giving such a structural unit, a monomer containing a (meth) acryloyl group, oxiranyl group or oxetanyl group is preferred, a monomer containing an oxiranyl group or oxetanyl group is more preferred, glycidyl methacrylate, 3- More preferred are methacryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate.

As a content rate of another structural unit, Preferably it is 5 mol%-30 mol% with respect to all the structural units, More preferably, it is 10 mol%-25 mol%. By setting the content of other structural units to 5 mol% to 30 mol%, a radiation sensitive resin composition that optimizes solubility in an aqueous alkali solution and is excellent in radiation sensitivity can be obtained.
<[A] Polymer component synthesis method>
[A] The polymer component can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator. For example, a method of dropping a solution containing a monomer and a radical initiator into a reaction solvent or a solution containing the monomer to cause a polymerization reaction, a solution containing the monomer, and a solution containing the radical initiator Separately, a method of dropping a reaction solvent or a monomer-containing solution into a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator, It is preferable to synthesize by a method such as a method of dropping it into a reaction solvent or a solution containing a monomer to cause a polymerization reaction.

  [A] Examples of the solvent used in the polymerization reaction of the polymer component include the solvents exemplified in the section of preparation of the radiation-sensitive resin composition described later.

  As the polymerization initiator used in the polymerization reaction, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis ( 2,4-Dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), azo compounds such as 2,2′-azobis (methyl 2-methylpropionate); benzoyl Organic peroxides such as peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; hydrogen peroxide and the like.

  [A] In the polymerization reaction of the polymer component, a molecular weight modifier may be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; Examples thereof include xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene and α-methylstyrene dimer.

[A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and preferably 5.0 × 10 ³ or more. 5.0 × 10 ⁴ or less is more preferable. [A] By making Mw of a polymer component into the said range, the sensitivity and alkali developability of the said radiation sensitive resin composition can be improved.

[A] The number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer component is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and 5.0 × 10 ³ or more and 5.0 × 10 ^4. The following is more preferable. [A] By making Mn of a polymer into the said range, the cure reactivity at the time of hardening of the coating film of the said radiation sensitive resin composition can be improved.

[A] The molecular weight distribution (Mw / Mn) of the polymer component is preferably 3.0 or less, and more preferably 2.6 or less. [A] By making Mw / Mn of a polymer component 3.0 or less, the developability of the obtained cured film can be improved.
<[B] Radiation sensitive acid generator>
[B] The radiation-sensitive acid generator is a compound that generates an acid upon irradiation with radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. When the radiation-sensitive resin composition contains [B] a radiation-sensitive acid generator, the radiation-sensitive resin composition can exhibit radiation-sensitive characteristics and can have good sensitivity. . [B] The radiation sensitive acid generator is contained in the radiation sensitive resin composition in the form of a radiation sensitive acid generator (hereinafter referred to as “[B] radiation sensitive acid generator” as appropriate). Or the form of a photoacid generating group incorporated as a part of the polymer constituting the polymer component, or both of these forms.

[B] Examples of the radiation-sensitive acid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds. An oxime sulfonate compound and a sulfonimide compound are particularly preferable. In addition, you may use these [B] radiation sensitive acid generators individually or in combination of 2 or more types.
[Oxime sulfonate compound]
As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (4) is preferable.

In the above formula (4), R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent. * Indicates a bonding position.

The alkyl group represented by R ¹⁴ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl- Examples thereof include alicyclic groups containing a bridged alicyclic group such as a 2-oxonorbornyl group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptylfluoropropyl group.

The alicyclic hydrocarbon group represented by R ¹⁴ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms. The alicyclic hydrocarbon group having 4 to 12 carbon atoms may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. .

The aryl group represented by R ¹⁴ is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group. The aryl group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.
Specific examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-yl). Ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2- Examples include ylidene)-(2-methylphenyl) acetonitrile, 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, and the like, which are commercially available.
Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2- Trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenyl) Sulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) Diphenyl maleimides, 4-methylphenyl-sulfonyloxy) diphenyl maleimide, and the like.

  Examples of the onium salt described above include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and benzylsulfonium salt.

As the onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoro Phosphate is more preferred, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate is more preferred.

  Preferable examples of the sulfonic acid ester compound described above include haloalkyl sulfonic acid esters, and more preferable examples include N-hydroxynaphthalimide-trifluoromethane sulfonic acid ester.

  Examples of the quinonediazide compound described above include a condensation of a phenolic compound or an alcoholic compound (hereinafter also referred to as “mother nucleus”) with 1,2-naphthoquinonediazidesulfonic acid halide or 1,2-naphthoquinonediazidesulfonic acid amide. Can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei other than the mother nucleus.

  Among these, as the mother nucleus, 2,3,4,4′-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 ′-[1- [4- [ 1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

  The 1,2-naphthoquinonediazide sulfonic acid halide is preferably 1,2-naphthoquinonediazidesulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid. Chloride is more preferred, and 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

  In the condensation reaction of the above-described phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinone diazide sulfonic acid halide corresponding to a range of not less than 85% and not more than 85% by mole, that is, 30% to 85% by mole, preferably 50% to 70% by mole. In addition, the said condensation reaction can be implemented by a well-known method.

  [B] By using the above-mentioned compound as the radiation-sensitive acid generator, the radiation-sensitive resin composition of the present embodiment containing the compound can improve sensitivity and solubility. [B] The content of the radiation sensitive acid generator is preferably 0.1 part by mass to 50 parts by mass and more preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the polymer [A]. [B] By setting the content of the radiation-sensitive acid generator within the above range, the sensitivity of the radiation-sensitive fat composition of the present embodiment is optimized, and a cured film having excellent patternability and high surface hardness is obtained. Can be formed.

<Other optional components>
The radiation-sensitive resin composition is a compound having an antioxidant, a polyfunctional acrylate, a surfactant, an adhesion aid, inorganic oxide particles, and a cyclic ether group as necessary, as long as the effects of the present invention are not impaired. In addition, other optional components such as an acid diffusion controller and a solvent may be contained. Other optional components may be used alone or in combination of two or more.
Examples of the antioxidant include phenolic antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like, and phenolic antioxidants are particularly preferable. Antioxidants can be used alone or in combination of two or more. The content of the antioxidant is preferably 0.1 parts by mass to 10 parts by mass, particularly preferably 100 parts by mass in total of the [A] polymer component contained in the radiation-sensitive resin composition of the present embodiment. Is 0.2 to 5 parts by mass. By using in this range, the heat resistance of the interlayer insulation film formed from this radiation sensitive resin composition can be improved more.
As the antioxidant, an antioxidant described in JP 2011-227106 A can be used.
The polyfunctional acrylate is 100 parts by mass or less with respect to 100 parts by mass of the [A] polymer component, preferably 0.1 parts by mass or more and 80 parts by mass or less, more preferably 0.5 parts by mass or more and 50 parts by mass or less. 1 to 25 parts by mass is more preferable. By using in this range, the heat resistance and solvent resistance of the interlayer insulation film formed from this radiation sensitive resin composition can be improved more.
As the polyfunctional acrylate, polyfunctional acrylates described in JP-A-2005-227525 can be used.

  Surfactant is a component which improves the film-forming property of the said radiation sensitive resin composition. By containing the surfactant, the radiation sensitive resin composition can improve the surface smoothness of the coating film. As a result, the film thickness uniformity of the cured film formed from the radiation sensitive resin composition can be improved. It can be improved.

The adhesion assistant is a component that improves the adhesion between the film formation target such as a substrate and the cured film. The adhesion assistant is particularly useful for improving the adhesion between the inorganic substrate and the cured film. As the adhesion assistant, a functional silane coupling agent is preferable.
The inorganic oxide particle is an oxide containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium. Can be used. Inorganic oxide particles described in JP2011-128385A can be used.
<Compound having a cyclic ether group>
The compound having a cyclic ether group is a compound having a cyclic ether group and different from the polymer of the [A] polymer component. The radiation-sensitive resin composition contains a compound having a cyclic ether group, thereby promoting cross-linking of the [A] polymer component or the like by the thermal reactivity of the compound having a cyclic ether group, and the radiation-sensitive resin. While the hardness of the cured film formed from a composition can be raised more, the radiation sensitivity of the said radiation sensitive resin composition can be improved.

  The compound having a cyclic ether group is preferably a compound having two or more epoxy groups (oxiranyl group, oxetanyl group) in the molecule. As a compound having an epoxy group as a compound having a cyclic ether group, a compound described in JP 2011-257537 A can be used.

  Among these, the compound having a cyclic ether group is preferably a compound having two or more oxetanyl groups in the molecule, such as bis [(3-ethyloxetane-3-yl) methyl] isophthalate, 1,4- 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene, 2,2-bis (hydroxymethyl) -1-butanol (EHPE3150 ( Daicel Chemical Co., Ltd.)) is more preferable.

  As content of the compound which has a cyclic ether group, it is 150 mass parts or less normally with respect to 100 mass parts of [A] polymer components, 0.5 mass part or more and 100 mass parts or less are preferable, and 1 mass part or more is preferable. 50 mass parts or less are more preferable, and 10 mass parts or more and 25 mass parts or less are still more preferable. The hardness of the cured film formed from the said radiation sensitive resin composition can be raised more by making content of the compound which has a cyclic ether group into the said range.

  The acid diffusion control agent can be arbitrarily selected from those used in chemically amplified resists. By containing the acid diffusion control agent, the radiation sensitive resin composition can appropriately control the diffusion length of the acid generated from the radiation sensitive acid generator by exposure, and the pattern developability can be improved. As the acid diffusion control agent, an acid diffusion control agent described in JP 2011-232632 A can be used.

The content of the acid diffusion controller is usually 2 parts by mass or less, preferably 0.001 part by mass or more and 1 part by mass or less, and 0.005 part by mass or more with respect to 100 parts by mass of the polymer component [A]. 0.2 parts by mass or less is more preferable. Pattern developability improves more by making content of an acid spreading | diffusion controlling agent into the said range.
<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition is dissolved or dispersed by mixing the [A] polymer component and the [B] radiation-sensitive acid generator, a suitable component as necessary, and other optional components in a solvent. Prepared. For example, the said radiation sensitive resin composition can be prepared by mixing each component in a predetermined ratio in a solvent.
<Solvent>
As the solvent, a solvent that uniformly dissolves or disperses other components in the radiation-sensitive resin composition and does not react with the other components is preferably used. Examples of such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, Aromatic hydrocarbons, ketones, other esters and the like can be mentioned. As the solvent, the solvents described in JP2011-232632 can be used.
<Curing film>
The cured film of the present invention is formed from the radiation sensitive resin composition. Since the said cured film is formed from the said radiation sensitive resin composition, it has the outstanding water repellency, the external appearance characteristic of a coating film, and the uniformity of a film thickness. The cured film having such characteristics is, for example, an interlayer insulating film, a planarization film, a bank (partition wall) that defines a region for forming a light emitting layer, a spacer, a protective film, a color, for an electronic device such as a display element. It can be used for coloring patterns for filters. In addition, although it does not specifically limit as a formation method of the said cured film, It is preferable to apply the formation method of the cured film demonstrated below.
<Method for forming interlayer insulating film>
The said radiation sensitive resin composition can be used suitably for formation of a cured film.

  The method for forming an interlayer insulating film of the present invention includes a step of forming a coating film on a substrate using the radiation-sensitive resin composition (hereinafter also referred to as “step (1)”), at least a part of the coating film. A step of irradiating radiation (hereinafter also referred to as “step (2)”), a step of developing a coating film irradiated with radiation (hereinafter also referred to as “step (3)”), and a developed coating film A step of heating (hereinafter also referred to as “step (4)”).

According to the method for forming the interlayer insulating film, an interlayer insulating film having high pattern shape stability can be formed. Further, since the amount of change in the film thickness of the unexposed portion can be suppressed, the production process margin can be improved as a result, and the yield can be improved. Furthermore, an interlayer insulating film having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development and heating utilizing photosensitivity.
[Step (1)]
In this step, the radiation-sensitive resin composition is used and applied onto a substrate to form a coating film. When the said radiation sensitive resin composition contains a solvent, it is preferable to remove a solvent by prebaking an application surface.

Examples of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and a hydrogenated product thereof. The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, but are usually about 70 ° C. to 120 ° C. and about 1 minute to 10 minutes.
[Step (2)]
In this step, at least a part of the coating film is irradiated with radiation and exposed. When exposing, it exposes normally through the photomask which has a predetermined pattern.
A multi-tone mask can be used as the photomask. The multi-tone mask usually includes a gray tone mask and a halftone mask. The gray tone mask makes a slit below the resolution of the exposure machine, and the slit part blocks a part of the light so that intermediate exposure can be realized. On the other hand, the halftone mask uses a “semi-transmissive” film and can perform intermediate exposure. Regardless of which mask is used, three exposure levels of “exposed part”, “intermediate exposed part”, and “unexposed part” can be expressed by one exposure, and films with different thicknesses are formed after development. can do. For this reason, since the production process can be reduced, the production efficiency of the panel can be improved.
As the radiation used for exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable. The exposure amount ^is preferably ^{500J / m 2 ~6,000J / m 2} , 1,500J / m 2 ~1,800J / m 2 is more preferable. This exposure amount is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (“OAI model 356” manufactured by OAI Optical Associates).
[Step (3)]
In this step, the coating film irradiated with radiation is developed. By developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern.

  The developer used in this step is preferably an alkaline aqueous solution. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. It is done. As the developer, an organic solvent such as a ketone organic solvent or an alcohol organic solvent can be used.

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be added to the alkaline aqueous solution. As a density | concentration of the alkali in aqueous alkali solution, from a viewpoint of obtaining suitable developability, 0.1 to 5 mass% is preferable.

  Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, a shower method, and the like. The development time varies depending on the composition of the radiation sensitive resin composition, but is usually about 10 seconds to 180 seconds.

  Subsequent to such development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

It is preferable that the film thickness change rate of the film thickness after development with respect to the film thickness of the coating film before development is 90% or more. As described above, according to the forming method using the radiation-sensitive resin composition, the amount of change in the film thickness of the unexposed portion with respect to the development time can be suppressed, and the film thickness after development is 90% of the film thickness before development. % Or more can be maintained.
[Step (4)]
In this step, the developed coating film is heated. For heating, the patterned thin film is heated by using a heating device such as a hot plate or an oven, whereby the curing reaction of the polymer component [A] can be promoted to form an interlayer insulating film. As heating temperature, it is about 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device, but is, for example, about 5 to 30 minutes for a hot plate and about 30 to 90 minutes for an oven. Moreover, the step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the target interlayer insulating film can be formed on the surface of the substrate. The thickness of the cured film is preferably 0.1 μm to 8 μm, and more preferably 0.1 μm to 6 μm.
<Electronic device>
The electronic device of the present invention includes the interlayer insulating film. The electronic device is, for example, a liquid crystal display element or an organic EL display element.

  The liquid crystal display element is composed of, for example, a liquid crystal cell, a polarizing plate, and the like. Since the liquid crystal display element includes the cured film, the liquid crystal display element has excellent reliability such as heat resistance.

  As a manufacturing method of a liquid crystal display element, first, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition is formed on the transparent conductive film of one of the substrates. In accordance with the method described in the above “<Method for forming cured film>”, an interlayer insulating film, a spacer, a protective film, or both are formed. Next, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. And as an electronic device of the present invention, the polarizing plate is bonded to both outer surfaces of the liquid crystal cell so that the polarization direction thereof coincides with or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. The liquid crystal display element can be obtained.

  As another method for manufacturing a liquid crystal display element, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film, a spacer, or both, and an alignment film are formed are prepared in the same manner as the above manufacturing method. After that, along the edge of one of the substrates, an ultraviolet curable sealant is applied using a dispenser, then the liquid crystal is dropped into a fine droplet using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. Do. Then, both the substrates are sealed by irradiating the sealing agent part with ultraviolet rays using a high-pressure mercury lamp. Finally, a liquid crystal display element as an electronic device of the present invention is obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in the above-described method for manufacturing a liquid crystal display element include nematic liquid crystal and smectic liquid crystal. In addition, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or an H film Examples thereof include a polarizing plate made of itself.

  On the other hand, in the organic electroluminescence element, the cured film formed from the radiation-sensitive resin composition can be used as a planarization film formed on the TFT element, a partition defining a light emitting site, or the like.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In addition, the weight average molecular weight (Mw) of [A] polymer component was measured with the following method.
[Weight average molecular weight (Mw)]
It measured by gel permeation chromatography (GPC) under the following conditions.

Equipment: “GPC-101” from Showa Denko
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodispersed polystyrene Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples. The measuring method of each physical property value is shown below.
<[A] Synthesis of polymer>
[Synthesis Example 1] (Synthesis of polymer (A-1))
A flask equipped with a condenser and a stirrer was charged with 10 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 20 parts by weight of methacrylic acid and 80 parts by weight of (a-1) were charged and purged with nitrogen. Then, while gently stirring, the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours for polymerization. As a result, a polymer solution containing the polymer (A-1) was obtained. The solid content concentration of the polymer solution was 31.5% by mass, the Mw of the polymer (A-1) was 6,000, and the molecular weight distribution (Mw / Mn) was 1.9. In addition, solid content concentration means the ratio of the copolymer mass to the total mass of a polymer solution, and is defined similarly in the following.

[Synthesis Examples 2 to 10] (Synthesis of Polymers (A-2) to (A-11))
The solid content concentration, molecular weight, and molecular weight distribution equivalent to those of the polymer (A-1) were obtained in the same manner as in Synthesis Example 1 except that the components of the types and blending amounts (parts by mass) shown in Table 1 were used. A polymer solution containing the polymers (A-2) to (A-11) was obtained. In Table 1, “-” indicates that the corresponding component was not used.

  Abbreviations of each component described in Table 1 are as follows.

MA: methacrylic acid MMA: methyl methacrylate BMMA: 1-butoxyethyl methacrylate GMA: glycidyl methacrylate NCHM: N-cyclohexylmaleimide IPPH: 4-isopropenylphenol <Preparation of radiation-sensitive resin composition>
[A] polymer, [B] photosensitizer, [C] adhesion assistant and [D] solvent used for the preparation of the radiation sensitive resin compositions of Examples and Comparative Examples are shown below.
[A] Polymers A-1 to A-11: Polymers synthesized in Synthesis Examples 1 to 11 [B] Photosensitizer B-1: [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)- (2-Methylphenyl) acetonitrile] (“IRGACURE PAG 103” manufactured by BASF)
B-2: Condensate of 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) <Radiation sensitive Preparation of functional resin composition>
[Example 1]
With respect to the amount corresponding to 100 parts by mass (solid content) of the polymer (A-10), 20 parts by mass of (A-1), 3 parts by mass of the photosensitive agent (B-1), and 3-glycidyloxy as an adhesion assistant 3 parts by mass of propyltrimethoxysilane is mixed and dissolved in propylene glycol monomethyl ether acetate (PGMEA) as a solvent so that the solid content concentration is 30% by mass, and then filtered through a membrane filter having a pore size of 0.2 μm. A radiation sensitive resin composition was prepared.
[Examples 2 to 12 and Comparative Example 1]
Except having used each component of the kind shown in following Table 2, it operated similarly to Example 1, and prepared the radiation sensitive resin composition of Examples 2-12 and the comparative example 1. FIG. In Table 2, “x” indicates that a negative pattern was not formed.

<Evaluation>
A cured film was formed from the radiation-sensitive resin compositions of Examples 1 to 12 and Comparative Example 1, and the radiation sensitivity, insulating properties, and corrosion resistance (wiring corrosion) were evaluated by the methods described below. The evaluation results are shown in Table 2.
[Positive pattern formation Radiation sensitivity]
Using a spinner, a radiation sensitive resin composition was applied on a silicon substrate that had been subjected to HMDS treatment at 60 ° C. for 60 seconds, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Formed. This coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Next, using a developer composed of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was carried out at 25 ° C. for 60 seconds, and then washed with running ultrapure water for 1 minute. At this time, the minimum exposure amount capable of forming a line and space pattern having a width of 10 μm was measured.
[Negative pattern formation]
Using a spinner, a radiation sensitive resin composition was applied on a silicon substrate that had been subjected to HMDS treatment at 60 ° C. for 60 seconds, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Formed. This coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Next, using a developer composed of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was carried out at 25 ° C. for 60 seconds, and then washed with running ultrapure water for 1 minute. At this time, the film thickness of the line part of the line and space pattern having a width of 10 μm was measured.
[Exposure dose dependence of negative pattern film thickness]
The same operation as in [Negative pattern formation] was performed, except that the exposure amount was increased by 10% and decreased by 10% of the exposure amount used in [Negative pattern formation].
When the amount of change in the film thickness of the line and space pattern formed by the increase / decrease of the exposure amount is less than 2%, “◎” is indicated, and when it is 2% or more and less than 10%, “◯” is indicated. In the case of 10% or more, the exposure dose dependency was too large, so that it was regarded as defective.
[Evaluation using halftone mask]
A coating film having an average film thickness of 3.0 μm was formed in the same manner as in the above-mentioned [Formation of positive pattern Radiation sensitivity]. Then, it exposed with the exposure amount of 800 J / m < ² > using the halftone mask. As the halftone mask, a translucent film having a transmittance of 50% was used. Next, using a developer composed of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was carried out at 25 ° C. for 60 seconds, and then washed with running ultrapure water for 1 minute. At this time, when the semi-transmissive portion shows a positive behavior, the film is removed by development, and when the transmissive portion shows a negative behavior, a cured film is formed.
At this time, when the film of the semi-transmissive portion was removed and the remaining film was 1.5 μm or more in the transmissive portion, it was evaluated that a positive pattern and a negative pattern could be formed by one exposure, and “◎” was given. In addition, when the film of the semi-transmissive portion was removed and the remaining film was 1.0 μm or more in the transmissive portion, “◯” was given.
If the semi-permeable portion film was not removed and there was a remaining film, it was judged as defective. The results are shown in Table 2.
[Transmissivity]
Using a spinner, each cured film forming resin composition was applied on a glass substrate, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount was 1,000 J / m ² . Next, this glass substrate was heated on a hot plate at 230 ° C. for 30 minutes to obtain a cured film. The transmittance of the obtained cured film was measured using an ultraviolet-visible spectrophotometer (V-630, manufactured by JASCO Corporation). At this time, the transmittance of light having a wavelength of 400 nm was measured. The results are shown in Table 2.
[chemical resistance]
Using a spinner, each cured film forming resin composition was applied onto a silicon substrate and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount was 1,000 J / m ² . Next, this silicon substrate was heated on a hot plate at 230 ° C. for 30 minutes, and the thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate on which this cured film was formed in N, N-dimethylformamide whose temperature was controlled at 45 ° C. for 20 minutes, the film thickness (t1) of the cured film after the immersion was measured. The film thickness change rate was calculated from the following formula and used as an index of chemical resistance.
Film thickness change rate = {(t1-T1) / T1} × 100 (%)
When the absolute value of this value is less than 5%, the chemical resistance is good (◯), and when it is 5% or more, it can be evaluated as defective. The results are shown in Table 2.

Claims (7)

[A] Compound having a plurality of groups represented by the following formula (1) in the molecule
[B] A radiation-sensitive composition for display elements comprising a radiation-sensitive acid generator.

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or one or more hydrogen atoms in the phenyl group having 1 to 12 carbon atoms. An alkyl group, a group substituted with one or more groups selected from an alkoxyl group having 1 to 12 carbon atoms, R ¹ and R ² may form a ring having 3 or more carbon atoms, and * is a bonding position. Is shown.) The radiation sensitive composition for a display device according to claim 1, wherein the compound [A] is a polymer having a structural unit represented by the following formula (2).
(In formula (2), R ¹ and R ² have the same meanings as in formula (1). R ³ represents a hydrogen atom or a methyl group. X represents a single bond or a divalent organic group.) The radiation sensitive composition for display elements according to claim 1, wherein the polymer is a polymer further containing a structural unit having a crosslinkable group. The display element according to any one of claims 1 to 3, wherein the crosslinkable group is at least one selected from the group consisting of an epoxy group, an alicyclic epoxy group, a (meth) acryloyl group, and a vinyl group. Radiation sensitive composition. Furthermore, the radiation sensitive composition for display elements as described in any one of Claims 1-4 containing the polymer different from a [A] compound. A method for forming an interlayer insulating film including the following steps (1) to (4):
(1) The process of forming a coating film on a base material with the radiation sensitive composition for display elements as described in any one of Claims 1-5.
(2) Step (3) for exposing the coating film obtained in (1) through a multi-tone mask (3) Step for developing the film obtained in (2) (4) Obtained in step (3) Heating the membrane The display element containing the interlayer insulation film formed with the formation method of Claim 6.