KR20130120391A - Radiation-sensitive composition, interlayer insulating film for display element, and formation method for same - Google Patents

Abstract

The purpose of the present invention is to provide a radiation sensitive composition capable of forming an interlayer dielectric for a display device having excellent sensitivity, surface hardness, solvent resistance, heat resistance and voltage conservation rate, an interlayer dielectric for a display device manufactured by using the same and a manufacturing method for the same. The present invention is the radiation sensitive composition comprising polymers having a structure unit (I) comprising an acid-dissociable group, a structure unit (II) including a polymerizable group and a structure unit (III) represented by an equation (1), and a radiation sensitive acid generator.

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation-sensitive composition, an interlayer insulating film for a display device, and a method for forming the same.

The present invention relates to a radiation-sensitive composition, an interlayer insulating film for a display element and a method of forming the same.

In the display element, an interlayer insulating film for a display element is formed for the purpose of insulating between wires arranged in a generally layered form. As a material for forming a display element interlayer insulating film, a number of steps for obtaining a necessary pattern shape are few, and a radiation resistance resin composition is widely used because a highly planarity is required for the obtained interlayer insulating film for a display element. Such a radiation sensitive resin composition is required to have good sensitivity, and the surface insulating interlayer for a display element is required to have excellent surface hardness, solvent resistance, heat resistance, voltage preservation ratio and the like in addition to the above flatness.

As such a radiation-sensitive resin composition, a composition containing a crosslinking agent, an acid generator, and an alkali-soluble resin is known (see Japanese Patent Application Laid-Open No. 2004-4669). The alkali-soluble resin is a resin having a protecting group (a group which is insoluble or hardly soluble in an aqueous alkali solution and capable of being dissociated by the action of an acid) and which becomes soluble or readily soluble in an aqueous alkaline solution after dissociation of the protecting group It says. As another radiation-sensitive resin composition, a radiation-sensitive resin composition containing an acetal structure or a resin containing a ketal structure and an epoxy group and an acid generator has been proposed (see JP-A-2004-264623).

However, in the above conventional radiation-sensitive resin composition, since the radiation sensitivity is insufficient, there is a problem that a fine and elaborate pattern can not be easily formed.

Japanese Laid-Open Patent Publication No. 2004-4669 Japanese Patent Application Laid-Open No. 2004-264623

The object of the present invention is to provide a radiation-sensitive composition capable of forming a display element interlayer insulating film having a higher sensitivity, a surface hardness, a solvent resistance, a heat resistance and a voltage holding ratio, An interlayer insulating film for a display element formed using the same, and a method of forming the same.

According to an aspect of the present invention,

(A) a polymer having a structural unit (I) containing an acid-dissociable group, a structural unit (II) containing a polymerizable group and a structural unit (III) represented by the following formula (1) ), And

[B] a radiation-sensitive composition containing a radiation-sensitive acid generator:

(Wherein R ¹ is a hydrogen atom or a methyl group; R ² is an alkyl group, an alkenyl group, an alkynyl group or an acyloxyalkyl group having 6 to 30 carbon atoms or a crosslinked cyclic hydrocarbon group having 4 to 30 carbon atoms; , A part of the hydrogen atoms of the alkyl group, alkenyl group, alkynyl group, acyloxyalkyl group and crosslinked cyclic hydrocarbon group may be substituted with a hydroxyl group or a carboxyl group).

Since the radiation sensitive composition has a structural unit (III) in which the polymer [A] includes a group represented by R ² , flexibility before curing is enhanced, diffusion of the acid generated during exposure is promoted, Can be improved. In addition, the radiation sensitive composition of the present invention is a radiation sensitive composition which has a structural unit (II) containing a polymerizable group, so that a cured film such as an interlayer insulating film for a display device having sufficient surface hardness, solvent resistance, heat resistance, .

The radiation sensitive composition preferably further contains a compound having a molecular weight of 1,000 or less (hereinafter also referred to as " [C] compound ") containing at least one [C] (meth) acryloyl group. The radiation sensitive composition further contains a [C] compound to form a cured film having improved surface hardness, solvent resistance, heat resistance and voltage holding ratio.

The acid-cleavable group in the structural unit (I) is preferably represented by the following formula (2)

　　

(In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, with the proviso that some of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group, R ³ and R ⁴ are not both hydrogen atoms; R ⁵ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, an aryl group or a group represented by -M (R ⁶ ) ₃ ; and; M is Si, Ge or Sn, and; R ⁶ is alkyl group; however, a part or all of the hydrogen atoms having the alkyl group of the R ⁵ alkyl group, an alicyclic hydrocarbon group, an aralkyl group and an aryl group and R ⁶ a is R ³ and R ⁵ may be bonded to each other, and a carbon atom to which R ³ is bonded and an oxygen atom to which R ⁵ is bonded may form a cyclic ether structure).

The acid-cleavable group represented by the formula (2) has a structure which is easily dissociated by the action of an acid generated from the [B] radiation-sensitive acid generator. Therefore, by containing the polymer [A] containing such an acid-cleavable group, the sensitivity of the radiation sensitive composition can be further improved, and a fine and elaborate pattern can be easily formed.

The polymerizable group in the structural unit (II) is preferably an epoxy group. When the polymer [A] contains an epoxy group as a polymerizable group, a cured film such as an interlayer insulating film for a display element formed from the radiation sensitive composition can further improve surface hardness, solvent resistance, heat resistance and voltage holding ratio. Here, the epoxy group is a concept including an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

The content of the structural unit (III) in the polymer [A] is preferably 3% by mass or more and 50% by mass or less. By thus setting the content ratio of the structural unit (III) in the polymer [A] within the above range, diffusion of the acid is further promoted and the sensitivity can be further improved.

The [C] compound is preferably a compound having a skeleton derived from a diol structure having 2 to 12 carbon atoms, a skeleton derived from trimethylolpropane, a skeleton derived from pentaerythritol, or a skeleton derived from dipentaerythritol. By containing the specific compound as the [C] compound, the surface hardness, solvent resistance, heat resistance, and voltage holding ratio of the cured film such as an interlayer insulating film for a display element to be formed can be further improved.

The content of the [C] compound is preferably 1% by mass or more and 50% by mass or less in terms of solid content. By setting the content of the [C] compound within the above range, the radiation sensitive composition can have excellent surface hardness, solvent resistance, heat resistance and voltage holding ratio of the cured film such as an interlayer insulating film for a display element to be formed.

The radiation sensitive composition is suitable as a material for forming an interlayer insulating film for a display element. Further, the present invention suitably includes an interlayer insulating film for a display element formed of the radiation sensitive composition.

In the method of forming an interlayer insulating film for a display element of the present invention,

(1) a step of forming a coating film on a substrate using the radiation sensitive composition,

(2) a step of irradiating at least a part of the coating film with radiation,

(3) a step of developing the coating film irradiated with the radiation, and

(4) heating the developed coating film.

According to this forming method, an interlayer insulating film for a display element having excellent surface hardness, solvent resistance, heat resistance and voltage holding ratio can be formed. Further, by using the radiation sensitive composition having excellent sensitivity, it is possible to easily form an interlayer insulating film for a display element having a fine and elaborate pattern. Therefore, the formed interlayer insulating film for a display element can be suitably used for a display element such as a liquid crystal display element or an organic EL display element.

The term " radiation " of the " radiation-sensitive composition " in the present specification is a concept including visible rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle rays and the like.

INDUSTRIAL APPLICABILITY As described above, the radiation sensitive composition of the present invention can form an interlayer insulating film for a display element having a fine and precise pattern easily because of its excellent sensitivity. Further, the radiation sensitive composition of the present invention can form an interlayer insulating film for a display element having excellent surface hardness, solvent resistance, heat resistance and voltage holding ratio. Therefore, the radiation sensitive composition is suitable as a material for forming an interlayer insulating film for a display element such as a liquid crystal display element, an organic EL display element, or the like.

(Mode for carrying out the invention)

<Radiation-sensitive composition>

The radiation sensitive composition of the present invention contains the [A] polymer and the [B] radiation-sensitive acid generator as essential components, and contains the [C] compound as a suitable component. The radiation sensitive composition may contain other optional components as long as the effect of the present invention is not impaired. Hereinafter, each component will be described in detail.

<[A] Polymer>

The polymer [A] is a polymer having a structural unit (I) containing an acid-dissociable group, a structural unit (II) containing a polymerizable group and a structural unit (III) represented by the above formula (1). Further, the [A] polymer may contain other structural units within the scope of not impairing the effect of the present invention. The polymer [A] may have two or more kinds of structural units. Hereinafter, each structural unit will be described in detail.

[Structural unit (I)]

The structural unit (I) is a structural unit containing an acid-dissociable group. The acid-cleavable group is dissociated by the action of an acid generated from the [B] radiation-sensitive acid generator during exposure to generate a polar group, so that the polymer [A] which is insoluble or poorly soluble in an aqueous alkali solution is soluble in an aqueous alkali solution do. The radiation sensitive composition of the present invention can have good sensitivity by having the [A] polymer have such a structural unit (I).

The structural unit (I) is not particularly limited as long as it is a structural unit containing an acid-cleavable group, but it is preferably a structural unit containing an acid-cleavable group represented by the formula (2) from the viewpoint that it is easily dissociated by an acid. In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group. Provided that some or all of hydrogen atoms contained in these alkyl groups, alicyclic hydrocarbon groups or aryl groups may be substituted. R ³ and R ⁴ are not both hydrogen atoms. R ⁵ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, an aryl group or a group represented by -M (R ⁶ _{) 3} . M is Si, Ge or Sn. R ⁶ is an alkyl group. However, some or all of the hydrogen atoms having the alkyl group of the R ⁵ group, an alicyclic hydrocarbon group, an aralkyl group and an aryl group and R ⁶ a may be substituted. R ³ and R ⁵ may be connected to form a cyclic ether structure.

Examples of the alicyclic hydrocarbon group represented by R ³ and R ⁴ include an alicyclic hydrocarbon group having 3 to 20 carbon atoms. The alicyclic hydrocarbon group having 3 to 20 carbon atoms may be a polycyclic ring. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a boronyl group, a norbornyl group and an adamantyl group .

Examples of the aryl group represented by R ³ and R ⁴ include an aryl group having 6 to 14 carbon atoms. The aryl group having 6 to 14 carbon atoms may be monocyclic or monocyclic, or may be a condensed ring. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the substituent for the optionally substituted alkyl, alicyclic hydrocarbon and aryl group represented by R ³ and R ⁴ include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, an alicyclic hydrocarbon group ( Cyclohexyl group, cycloheptyl group, cyclooctyl group, boronyl group, norbornyl group and adamantyl group), an aryl group (e.g., phenyl group, naphthyl group and the like), alkoxy An alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a n-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group and an octyloxy group) (For example, an acyl group having 2 to 20 carbon atoms such as acetyl, propionyl, butyryl and i-butyryl), an acyloxy group (for example, an acetoxy group, , t-butyryloxy group, t-amyloxy group, etc. An alkoxycarbonyl group (e.g., an alkoxycarbonyl group having 2 to 20 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and propoxycarbonyl group), a haloalkyl group (e.g., methyl group, ethyl group, n A straight chain alkyl group such as propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a butyl group, a t-butyl group, a neopentyl group, A group in which a part or all of hydrogen atoms of an alicyclic hydrocarbon group such as a tyl group is substituted with a halogen atom, etc.), a hydroxyalkyl group (e.g., a hydroxymethyl group), and the like.

For alkyl groups, alicyclic hydrocarbon groups, aryl represented by the above R ^5, can be applied to the description of each of the groups represented by the above R ³ and R ^4. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group and an n-propyl group. Examples of the aralkyl group represented by R ⁵ include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

As the alkyl group represented by R ⁶ in the group represented by -M (R ⁶ ) ₃ of R ⁵ , the description of the alkyl group represented by R ³ and R ⁴ can be applied.

The cyclic ether structure which may be formed by combining R ³ and R ⁵ with each other is preferably a cyclic ether structure having a reduced number of 3 to 20, more preferably a cyclic ether structure having a reduced number of 5 to 8, more preferably a tetrahydrofuran and tetrahydrofuran Piranha is more preferable.

The group represented by the formula (2) includes, for example, groups represented by the following formulas.

Examples of the monomer giving the structural unit (I) include monomers such as 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1- Methoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1- (2-chloroethoxy) ethyl methacrylate, 1- (2-ethylhexyloxy) Propyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, Methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-t-butoxyethyl acrylate, 1- (2-chloroethoxy) Cyclohexyloxyethyl acrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1- Di (1- (trimethylsilanyloxy) ethoxy) carbonyl) -2-norbornene, 5,6-di (1-cyclohexyloxy) ethoxy) carbonyl) -2-norbornene, 5,6-di (1-methoxyethoxycarbonyl) (Benzyloxy) ethoxycarbonyl) -2-norbornene, p or m-1-ethoxyethoxystyrene p or m-1-methoxyethoxystyrene, p or m-1-n-butoxyethoxystyrene, p or m-1-isobutoxyethoxystyrene, p or m- P or m-1- (2-chloroethoxy) ethoxystyrene, p or m-1- (2-ethylhexyloxy) ethoxystyrene, p or m- P or m-1-cyclohexyloxyethoxystyrene, p or m-1- (2-cyclohexylethoxy) ethoxystyrene, p or m-1-benzyloxyethoxystyrene .

As the monomer giving the structural unit (I), a structural unit containing an acid-dissociable group represented by the formula (2) is preferable, and 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate , 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate and 1-cyclohexyloxyethyl methacrylate are more preferable, and 2-tetrahydropyranyl methacrylate is more preferable.

The content of the structural unit (I) in the polymer [A] is not particularly limited as long as the effect of the present invention is exhibited, but the content of the structural unit (I) in the polymer [A] Or less, more preferably 10 mass% or more and 70 mass% or less, and still more preferably 15 mass% or more and 65 mass% or less.

[Structural unit (II)]

The structural unit (II) is a structural unit containing a polymerizable group. By having the polymer [A] having the structural unit (II), the interlayer insulating film for a display element formed of the radiation sensitive composition can have better surface hardness, heat resistance, solvent resistance and voltage holding ratio.

The structural unit (II) is not particularly limited as long as it is a structural unit containing a polymerizable group, but the structural unit (II-1) and the structural unit (II-2) containing an epoxy group and a . Hereinafter, the epoxy group-containing structural unit and the (meth) acryloyl group-containing structural unit will be described in detail.

[Epoxy group-containing structural unit (II-1)]

The epoxy group-containing structural unit (II-1) is not particularly limited as long as it is a structural unit having an epoxy group in its structural unit. Examples of the epoxy group-containing monomer which imparts the structural unit (II-1) include, for example,

(Meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3-methyl-3,4-epoxybutyl acrylate, 3-ethyl- , 6-epoxyhexyl methacrylate, 5-methyl-5,6-epoxyhexyl methacrylate, 5-ethyl-5,6-epoxyhexyl methacrylate, 6,7-epoxyhexyl methacrylate, methacrylic acid, 4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylpropyl methacrylate, 3,4-epoxycyclohexyl methacrylate, Cyclohexylbutyl methacrylate, 3,4-epoxycyclohexylhexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl acrylate, 3,4-epoxycyclohexylpropyl acrylate, acrylic acid 3,4 (Meth) acrylic compounds containing an oxiranyl group such as epoxy cyclohexylbutyl and 3,4-epoxycyclohexylhexyl acrylate;

o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -methyl-o-vinyl benzyl glycidyl ether,? -methyl- Vinyl benzyl glycidyl ethers such as diester,? -Methyl-p-vinylbenzyl glycidyl ether;

vinylphenyl glycidyl ethers such as o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether and p-vinylphenyl glycidyl ether;

3-acryloyloxymethyl-3-ethyloxetane, 3-acryloyloxymethyl-3-phenyloxane, 3-acryloyloxymethyl- Cetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -3-methyloxetane, 3- Cetyl, 3-methacryloyloxymethyloxetane, 3-methacryloyloxymethyl-3-methyloxetane, 3-methacryloxypropyltrimethoxysilane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- 3-methyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) Acryloyloxymethyl-2-ethyloxetane, 2-acryloyloxymethyl-2-phenyloxetane, 2-acryloyloxymethyl-2-methyloxetane, 2- 2- (2- Acryloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl) -2-methyloxetane, 2- 2-methacryloyloxymethyl-2-methyloxymethyl-2-methyloxetane, 2-methacryloyloxymethyl-2- (2-methacryloyloxyethyl) oxetane, 2- (2-methacryloyloxyethyl) -2-methyloctane, 2- (Meta) acrylic compounds containing an oxetanyl group such as cetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane and 2- (2-methacryloyloxyethyl) And the like.

Among the above-mentioned epoxy group-containing monomers, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3- 3-methyloxetane, 3-methacryloyloxymethyl-3-ethyloxetane are preferable from the viewpoint of copolymerization reactivity with other monomers and developability of the radiation-sensitive composition. These monomers may be used alone or in combination of two or more.

[(Meth) acryloyl group-containing structural unit (II-2)]

The (meth) acryloyl group-containing structural unit (II-2) is not particularly limited as long as it is a structural unit having a (meth) acryloyloxy group as a polymerizable group.

As a method for introducing the structural unit (II-2) into the polymer [A], for example, a polymer of a monomer containing an unsaturated compound having at least one hydroxyl group in one molecule (hereinafter also referred to as "[A1] A method of reacting an unsaturated isocyanate compound with an unsaturated isocyanate compound.

Examples of the monomer used in the synthesis of the [A1] polymer include (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid dihydroxyalkyl ester, (meth) acrylic acid (6-hydroxyhexanoyloxy) have.

Examples of the (meth) acrylic acid hydroxyalkyl ester include (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester and (meth) acrylic acid 4-hydroxybutyl ester. have. Examples of the dihydroxyalkyl (meth) acrylate ester include (meth) acrylic acid 2,3-dihydroxypropyl ester, (meth) acrylic acid 1,3-dihydroxypropyl ester, (meth) - dihydroxybutyl ester, and the like. Examples of the (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl esters include 2- (6-hydroxyhexanoyloxy) ethyl (meth) acrylate, 3- Hexanoyloxy) propyl ester, and the like.

Among these monomers, from the viewpoint of copolymerization reactivity and reactivity with an isocyanate compound, acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester, methacrylic acid 2-hydroxyethyl ester, Methacrylic acid 3-hydroxypropyl ester, methacrylic acid 4-hydroxybutyl ester, acrylic acid 2,3-dihydroxypropyl ester, and methacrylic acid 2,3-dihydroxypropyl ester are preferable. These monomers may be used alone or in combination of two or more.

The polymer [A1] thus obtained may be added to the synthesis of the polymer [A] while remaining the polymerization reaction solution, and the polymer [A1] may be provided for the synthesis of the polymer [A] after the polymer is once separated from the solution.

Examples of the unsaturated isocyanate compound include an isocyanate group-containing derivative of (meth) acrylic acid. Examples of the unsaturated isocyanate compound include 2- (meth) acryloyloxyethyl isocyanate, 4- (meth) acryloyloxybutyl isocyanate, 2- (2-isocyanatoethoxy) - (bis (meth) acryloyloxymethyl) ethyl isocyanate and the like. The unsaturated isocyanate compounds may be used alone or in combination of two or more.

Examples of commercially available products of unsaturated isocyanate compounds include Karenz AOI (manufactured by Showa Denko K.K.) and 2-methacryloyloxyethyl isocyanate as a commercially available product of 2-acryloyloxyethyl isocyanate, (Trade name, manufactured by Showa Denko K.K.) and 2- (2-isocyanatoethoxy) ethyl methacrylate as a commercially available product of KARENS MOI-EG (manufactured by Showa Denko K.K.) and 1,1- (bisacryloyloxymethyl) ethyl isocyanate And a car lens BEI (manufactured by Showa Denko K.K.).

Of these unsaturated isocyanate compounds, from the viewpoint of reactivity with the [A1] polymer, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4- methacryloyloxybutyl isocyanate or methacrylic acid 2 - (2-isocyanatoethoxy) ethyl, and 1,1- (bisacryloyloxymethyl) ethyl isocyanate are preferable.

The reaction of the [A1] polymer with the unsaturated isocyanate compound can be carried out by reacting the unsaturated isocyanate compound with a solution of the polymer [A1], preferably containing a polymerization inhibitor, in the presence of a suitable catalyst, Can be carried out.

Examples of the catalyst include di-n-butyl tin dilaurate (IV) and the like. Examples of the polymerization inhibitor include p-methoxyphenol and the like.

As another method for introducing the structural unit (II-1) into the polymer [A], for example, a polymer of a monomer containing an unsaturated compound having at least one carboxyl group in one molecule (hereinafter also referred to as "[A2] polymer" ) Is reacted with a compound having a vinyl ether group and a (meth) acryloyloxy group.

As a method for synthesizing the polymer [A2], for example, a method of polymerizing a carboxyl group-containing monomer may be mentioned from the viewpoint of obtaining a material and easy synthesis.

Examples of the monomer used in the synthesis of the polymer [A2] include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic acid monoester and itaconic acid monoester. Of these, (meth) acrylic acid is preferable.

Examples of the compound having a vinyl ether group and a (meth) acryloyloxy group include compounds represented by the following formula (3).

In the above formula (3), R ⁷ is a hydrogen atom or a methyl group. R ⁸ is a divalent linking group. R ⁹ is a hydrogen atom or a monovalent organic group.

Examples of the divalent linking group represented by R ⁸ include a linear, branched or cyclic alkylene group having 2 to 18 carbon atoms, an alkoxyalkylene group having 2 to 20 carbon atoms, a halogenated alkylene group having 2 to 8 carbon atoms, a terminal hydroxyl group , A polypropylene glycol skeleton excluding a terminal hydroxyl group, a polybutylene glycol skeleton excluding a terminal hydroxyl group, and an aryl group. Examples of the monovalent organic group represented by R ⁹ include linear, branched or cyclic alkyl groups of 1 to 10 carbon atoms, aromatic groups of 6 to 11 carbon atoms which may be substituted, and the like.

Examples of the compound having a vinyl ether group and a (meth) acryloyloxy group represented by the formula (3) include 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, (Meth) acrylate, 1-methyl-2-vinyloxyethyl, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl 2-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclo 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethyl (meth) acrylate Vinyloxymethylphenylmethyl (meth) acrylate, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl Acrylic acid 2- (vinyloxyethoxy) isopropyl, (meth) acrylic acid 2 (vinyloxyethoxy) propyl (meth) acrylate, 2- Acrylate such as 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (Methoxy) isopropoxy) ethyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) ethyl, 2- (vinyloxyisopropoxyisopropoxy) (Vinyl oxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, (Meth) acrylate such as 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxypropoxy) (Meth) acrylic acid 2- (vinyloxyethoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyisoprop (Meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxy) (Meth) acrylic acid 2- (isopropenyloxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxy) 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl acrylate, polyethylene glycol monovinyl ether (meth) acrylate, (Meth) acrylic acid polypropylene glycol monovinyl ether, and the like. The compounds having these vinyl ether groups and (meth) acryloyloxy groups may be used alone or in combination of two or more.

Among these compounds having a vinyl ether group and a (meth) acryloyloxy group, the compound represented by the formula (3) is preferable, and 2- (vinyloxyethoxy) ethyl (meth) acrylate is more preferable. Examples of commercially available products of 2- (vinyloxyethoxy) ethyl (meth) acrylate include VEEA as 2- (vinyloxyethoxy) ethyl acrylate and VEEM as 2- (vinyloxyethoxy) ethyl methacrylate Manufactured by Nippon Shokubai Co., Ltd.).

The addition reaction of the polymer [A2] with the compound having a vinyl ether group and a (meth) acryloyloxy group is not particularly limited, and can be carried out by adding it to the reaction system. In the addition reaction, since the [A2] polymer itself serves as a catalyst, the reaction can be carried out in the absence of a catalyst, but it is also possible to use a catalyst in combination.

As another method for introducing the structural unit (II-2) into the polymer [A], there can be mentioned a method of copolymerizing with the monomer giving the structural unit (I) or the like using a polyfunctional (meth) acrylate as a monomer And the like.

Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, triethylene glycol di (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) (Meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylol propane tri (meth) acrylate, ethylene oxide modified trimethylol propane (Meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neo (Meth) acrylic acid adduct of bisphenol A diglycidyl ether, 1,4-butanediol di (meth) acrylate, hexanediol di (meth) acrylate, bisphenol A diglycidyl ether, Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa Caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (metha) acrylate, caprolactone modified dipentaerythritol hexa (Meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, (Meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, and phenol novolac polyglycidyl ether of (meth) acrylate, tylene oxide modified hydrogenated bisphenol A di (meth) acrylate, propylene oxide modified hydrogenated bisphenol A di Methacrylate, and the like. These monomers may be used alone or in combination of two or more.

Examples of commercially available products of polyfunctional (meth) acrylate include SA1002 (manufactured by Mitsubishi Chemical), Viscoat 195, Copper 230, Copper 260, Copper 215, Copper 310, Copper 214HP, Copper 295, 300, copper 360, copper GPT, copper 400, copper 700, copper 540, copper 3000, copper 3700 (manufactured by Osaka Yuki Kagakuko Co., Ltd.), Kayarad R-526 copper HDDA copper NPGDA copper TPGDA, copper MANDA, copper R-551, copper R-712, copper R-604, copper R-684, copper PET-30, copper GPO-303, copper TMPTA, copper THE-330, copper DPHA, copper DPHA-2H , DPHA-2C, DPHA-2I, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475 , T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R-011, R-300 and R-205 (Manufactured by Nippon Kayaku), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M-309 and M -310, Dong M-315, Dong M-325, Dong M-400, Dong M-6200, Dong M-6400 (manufactured by Toagosei Co., Ltd.) (Light Acrylate) BP-4EA, BP-4PA, BP-2EA, BP-2PA, Copper DCP-A (manufactured by Kyoei Shakagaku Corporation), New Frontier BPE- SP-1506, SP-1507, SP-1509, SP-1507, and SP- SP-4010, SP-4060, VR-77 (manufactured by Showa Kobunshi Co., Ltd.), and NK Ester A-BPE-4 (manufactured by Shin Nakamura Kagakukogyo Co., Ltd.).

Among these polyfunctional (meth) acrylates, a compound having at least two (meth) acryloyloxy groups in the molecule and a compound having at least three (meth) acryloyloxy groups in the molecule are preferable. As the compound having two or more (meth) acryloyloxy groups in the molecule, diethylene glycol di (meth) acrylate is more preferable. Examples of the compound having three or more (meth) acryloyloxy groups in the molecule include a tri (meth) acrylate compound, a tetra (meth) acrylate compound, a penta (meth) acrylate compound, a hexa And the like. Of these compounds having three or more (meth) acryloyloxy groups, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) Pentaerythritol penta (meth) acrylate, and ditrimethylol propane tetra (meth) acrylate are preferable.

As the structural unit (II), those having two or more (meth) acryloyloxy groups are preferable. By having the structural unit (II) contain two or more (meth) acryloyloxy groups, it is possible to realize better sensitivity and to form an interlayer insulating film for a display element having excellent surface hardness and heat resistance.

The content of the structural unit (II) in the polymer [A] is not particularly limited as long as the desired effect of the present invention is exhibited. The content of the structural unit (II) in the polymer [A] , More preferably from 7% by mass to 55% by mass, and particularly preferably from 10% by mass to 50% by mass.

[Structural unit (III)]

The structural unit (III) is a structural unit represented by the above formula (1). The polymer [A] has the structural unit (III), and when the R ² in the formula (1) is an alkyl group, an alkenyl group, an alkynyl group or an acyloxyalkyl group having 6 to 30 carbon atoms, rigidity of the polymer main chain skeleton And the glass transition point can be lowered. When R ² is a crosslinked cyclic hydrocarbon group, it is possible to reduce entanglement between molecular chains. As described above, since the flexibility of the polymer [A] is high before curing, the radiation-sensitive composition can promote the diffusion of the acid generated during exposure and further improve the sensitivity.

In the above formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is an alkyl, alkenyl, alkynyl or acyloxyalkyl group having 6 to 30 carbon atoms or a bridged cyclic hydrocarbon group having 4 to 30 carbon atoms. However, a part of the hydrogen atoms of the alkyl group, alkenyl group, alkynyl group, acyloxyalkyl group and crosslinked cyclic hydrocarbon group may be substituted with a hydroxyl group or a carboxyl group.

The group represented by R ² is not an acid-dissociable group, and the structural unit (III) is a structural unit other than the structural unit (I).

Examples of the alkyl group having 6 to 30 carbon atoms represented by R ² include a linear or branched alkyl group having 6 to 30 carbon atoms. Specific examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, , A dodecyl group, a hexadecyl group, a stearyl group, and a behenyl group. Among these, an alkyl group having 6 to 20 carbon atoms is preferable, an alkyl group having 10 to 20 carbon atoms is more preferable, and a dodecyl group, a hexadecyl group and a stearyl group are more preferable.

Examples of the alkenyl group having 6 to 30 carbon atoms represented by R ² include a hexenyl group, a heptenyl group, an octenyl group, a decenyl group, an undecenyl group, a dodecenyl group and a hexadecenyl group.

Examples of the alkynyl group having 6 to 30 carbon atoms represented by R ² include a hexynyl group, a heptynyl group, an octynyl group, a decynyl group, an undecynyl group, a dodecynyl group, and a hexadecynyl group.

The acyloxyalkyl group having 6 to 30 carbon atoms represented by R ² includes, for example, a lauroyloxyethyl group, a lauroyloxypropyl group, a stearoyloxyethyl group, a stearoyloxypropyl group, an oleoyloxyethyl group, And an oxypropyl group. Further, groups in which the glycidyl group is modified with an oleic acid or a soybean oil fatty acid are also included.

Examples of the bridged cyclic hydrocarbon group having ⁴ to 30 carbon atoms represented by R ² include a norbornanyl group (bicyclo [5.1.0] heptyl group), an norpyranyl group (bicyclo [3.1.0] heptyl group) (Bicyclic [2.2.1] heptyl group), adamantyl group, bicyclo [2.2.2] octyl group, bicyclo [3.2.1] octyl group, tricyclo [2.2.1.0 ^2,6 ] heptyl group , Tricyclo [5.2.1.0 ^2,6 ] decanyl, tricyclo [5.3.1.1 ^2,6 ] dodecyl, tricyclo [4.4.1.1 ^1,5 ] dodecyl, caranyl, . Of these, a crosslinked cyclic hydrocarbon group having 6 to 20 carbon atoms is preferable, and an adamantyl group and a tricyclo [5.2.1.0 ^2,6 ] decanyl group are more preferable.

The bridged cyclic hydrocarbon group having ⁴ to 30 carbon atoms represented by R ² may further include rings condensed with rings including the ring exemplified above. Examples of the group in which the rings are condensed include a condensed ring group such as a norbornane ring and a condensed polycyclic group such as a monocyclic or decahydronaphthalene ring such as a cycloheptane ring or a cyclohexane ring, A group represented by the following formula, and the like.

Examples of the monomer giving the structural unit (III) include hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl , A dodecyl (meth) acrylate, hexadecyl methacrylate, stearyl methacrylate, behenyl methacrylate, a compound obtained by modifying glycidyl methacrylate with oleic acid or modified with soybean oil fatty acid, or Monomers containing an acyloxyalkyl group;

(Meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, adamantyl (meth) acrylate, bicyclo [2.2.2] octyl (Meth) acrylic acid tricyclo [2.2.1.0 ^2,6 ] heptyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decanyl, (meth) acrylic acid tricyclo [5.3. 1.1 ^2,6] dodecyl (meth) acrylate, tricyclo [4.4.1.1 ^1,5] dodecyl (meth) acrylate, color carbonyl, (meth) acrylic acid Pina carbonyl, (meth) acrylic acid having a carbon number such as isobornyl 4 to A monomer containing a crosslinked cyclic hydrocarbon group of 30 carbon atoms, and the like. Of these, dodecyl methacrylate, adamantyl methacrylate, and stearyl methacrylate are preferable.

The content of the structural unit (III) in the polymer [A] is preferably from 3 mol% to 50 mol%, more preferably from 5 mol% to 50 mol%, still more preferably from 10 mol% to 25 mol% More preferable. By setting the content of the structural unit (III) within the above range, the radiation-sensitive composition can further promote the diffusion of acid, thereby further improving the sensitivity.

[Other structural units]

The polymer [A] may have other structural units in addition to the structural unit (I), the structural unit (II) and the structural unit (III) within the range not impairing the effect of the present invention. Examples of the monomer giving another structural unit include a monomer having a carboxyl group or a derivative thereof, a monomer having a hydroxyl group, and other monomers. It is to be noted that these other structural units do not include the structural units contained in the structural units (I) to (III).

Examples of the monomer having the carboxyl group or derivative thereof include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethyl hexa Monocarboxylic acids such as hydrophthalic acid and 2-methacryloyloxyethylhexahydrophthalic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And the acid anhydrides of the above-mentioned dicarboxylic acids.

Examples of the monomer having a hydroxyl group include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxymethylcyclohexylmethyl acrylate; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, 4- And hydroxyalkyl methacrylate such as hydroxymethyl-cyclohexylmethyl. From the viewpoint of the heat resistance of the resulting interlayer insulating film for a display element, among the monomers having a hydroxyl group, it is preferable to use at least one monomer selected from the group consisting of 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxymethyl-cyclohexylmethyl acrylate, 4-hydroxymethyl-cyclohexylmethyl methacrylate are preferred.

As other monomers, for example,

Alkyl acrylates such as methyl acrylate and i-propyl acrylate;

Methyl methacrylate such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate;

2-methylcyclohexyl acrylate, acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl , Acrylic acid alicyclic alkyls such as isobornyl acrylate;

2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] Decane-8-yloxy) ethyl methacrylate, isobornyl methacrylate and the like;

Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate, or aralkyl of acrylic acid;

Aralkyl of methacrylic acid such as phenyl methacrylate or benzyl methacrylate, or aralkyl of methacrylic acid;

Dialkyl dicarboxylates such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Unsaturated heterocyclic 5-membered methacrylic acid esters or unsaturated heterocyclic 6-membered methacrylic acid containing 1 oxygen atom such as tetrahydrofuranyl methacrylate, tetrahydrofuryl methacrylate, and tetrahydropyran-2-methyl methacrylate;

4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl- , 4-methacryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl- Unsaturated heterocyclic 5-membered cyclic methacrylic acid containing two oxygen atoms such as methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane;

4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2,2-dimethyl- 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxy Methyl-2-cyclopentyl-1,3-dioxolane, 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4- acryloyloxyethyl- Ethyl-1,3-dioxolane, 4-acryloyloxypropyl-2-methyl-2-ethyl- Unsaturated heterocyclic 5-membered acrylic acid containing two oxygen atoms such as 1,3-dioxolane;

Vinyl aromatic compounds such as styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and 4-isopropenylphenol;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- N-substituted maleimides such as 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

Conjugated diene-based compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;

And unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.

Among these monomers, styrene, 4-isopropenylphenol, methacrylic tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, methacrylic acid tetrahydrofurfuryl, 1,3-butadiene, 4- Acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, benzyl methacrylate, the above carboxyl group or a derivative thereof From the viewpoints of copolymerization reactivity with a monomer, a monomer having a hydroxyl group, and developability of the radiation-sensitive composition.

The polystyrene-reduced weight average molecular weight (Mw) of the polymer [A] by gel permeation chromatography (GPC) is preferably 2.0 x 10 ^{3 to} 1.0 x 10 ⁵ , more preferably 5.0 x 10 ^{3 to} 5.0 x 10 ⁴ to be. By setting the Mw of the polymer [A] within the above-specified range, the sensitivity and alkali developability of the radiation sensitive composition can be increased.

The polystyrene reduced number average molecular weight (Mn) of the polymer [A] by GPC is preferably 2.0 x 10 ^{3 to} 1.0 x 10 ⁵ , more preferably 5.0 x 10 ^{3 to} 5.0 x 10 ⁴ . By setting the Mn of the polymer [A] to the above-specified range, the curing reactivity at the time of curing the coating film of the radiation sensitive composition can be improved.

The molecular weight distribution (Mw / Mn) of the polymer [A] is preferably 3.0 or less, more preferably 2.6 or less. When the Mw / Mn of the polymer [A] is 3.0 or less, the alkaline developability of the obtained interlayer insulating film for a display device can be enhanced.

Mw and Mn were measured by GPC under the following conditions.

Apparatus: GPC-101 (manufactured by Showa Denko Co., Ltd.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

<Method of synthesizing [A] polymer>

The polymer [A] can be produced, for example, by polymerizing monomers corresponding to predetermined structural units in a suitable solvent using a radical polymerization initiator. For example, a method in which a solution containing a monomer and a radical initiator is added dropwise to a solution containing a reaction solvent or a monomer to carry out a polymerization reaction, a method in which a solution containing a monomer and a solution containing a radical initiator are separately dissolved in a reaction solvent Or a method in which a solution containing a radical initiator is separately added to a solution containing a reaction solvent or a monomer so as to carry out a polymerization reaction And the like.

As the solvent used in the polymerization reaction of the polymer [A], there may be mentioned, for example, the solvents exemplified in the following section for preparing the radiation-sensitive composition.

As the polymerization initiator to be used in the polymerization reaction, those known as radical polymerization initiators can be used, and for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4- Azo compounds such as 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis (methyl 2-methylpropionate); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide.

In the polymerization reaction of the polymer [A], a molecular weight regulator may be used to adjust the molecular weight. Examples of the molecular weight regulator 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; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like.

<[B] Radiation-sensitive acid generator>

[B] The radiation-sensitive acid generator is a compound which generates an acid upon irradiation with radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. When the radiation sensitive composition contains [B] a radiation sensitive acid generator, the radiation sensitive composition can exhibit a positive radiation sensitive property.

[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 carbonic acid ester compounds . These [B] radiation-sensitive acid generators may be used alone or in combination of two or more.

 [Oxime sulfonate compound]

Examples of the oxime sulfonate compound include compounds containing an oxime sulfonate group represented by the following formula (4).

In the formula (4), R ¹⁰ is a linear or branched alkyl group, alicyclic hydrocarbon group or aryl group. However, these groups may be substituted with some or all of the hydrogen atoms.

The linear or branched alkyl group represented by R ¹⁰ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The linear or branched alkyl group having 1 to 10 carbon atoms may be substituted, and examples of the substituent include a caproic ring group such as an alkoxy group having 1 to 10 carbon atoms and a 7,7-dimethyl-2-oxononorbornyl group And the like. The preferable alicyclic group is a bicycloalkyl group. The aryl group represented by R ¹⁰ is preferably an aryl group having ⁶ to ¹¹ carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group may be substituted, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

Examples of the oxime sulfonate group-containing compound represented by the above formula (4) include an oxime sulfonate compound represented by the following formula (5).

In the formula (5), R ¹⁰ has the same meaning as in the formula (4). X is an alkyl group, an alkoxy group, or a halogen atom. r is an integer of 0 to 3; Provided that when plural Xs are present, plural Xs may be the same or different.

The alkyl group which may be represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. As r, 0 or 1 is preferable. In the above formula (5), a compound wherein r is 1, X is a methyl group, and X is an ortho substituted position is preferable.

Examples of the oxime sulfonate compound represented by the formula (5) include compounds represented by the following formulas (5-1) to (5-5), and the like.

The compound (5-1) (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, the compound (5-2) (5-octylsulfonyloxyimino- 5-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, Compound 5-3 (camphorsulfonyloxyimino- , (5-4) (5- p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile and the compound (5-5) (5-octylsulfonyloxy Amino) - (4-methoxyphenyl) acetonitrile is available as a commercial product.

 [Onium salts]

Examples of the onium salts include diphenyl iodonium salts, triphenylsulfonium salts, sulfonium salts, benzothiazonium salts, and tetrahydrothiophenium salts.

Examples of the diphenyl iodonium salt include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroarsenate, diphenyl iodonium tri Diphenyl iodonium trifluoroacetate, diphenyl iodonium-p-toluene sulfonate, diphenyl iodonium butyl tris (2,6-difluorophenyl) borate, 4- Bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p- (4-t-butylphenyl) iodonium camphorsulfonic acid, and the like.

Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium- p-toluenesulfonate, triphenylsulfonium butyltris (2,6-difluorophenyl) borate, and the like.

Examples of the sulfonium salt include an alkylsulfonium salt, a benzylsulfonium salt, a dibenzylsulfonium salt, and a substituted benzylsulfonium salt.

Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenyl (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro 4-acetoxyphenylsulfonium hexafluoroantimonate, and the like.

Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexa 4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro- 4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, and the like.

Examples of dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium Dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3- Methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate and the like.

Examples of the substituted benzylsulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p- 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like can be used. .

Examples of the tetrahydrothiophenium salt include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen- 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- 1- (4-n-butoxy) -naphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2- (norbornan- (5-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoro (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) ethane sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium- -1,1,2,2-tetrafluoroethanesulfonate, and the like.

[Sulfonimide compound]

Examples of the sulfonimide compounds include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (Camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- 2.2.1] hepto-5-ene -2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethanesulfonyloxy ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept- Dicarboxylic imide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2. 1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [ 2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] Amide, N- (2-trifluoromethyl 2,6-dicarboxylic acid imide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept- 2,3-dicarboxylic imide, N (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5- - (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane- 5,6-oxy-2,3-dicarboxylic imide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane- 2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2. 1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyldicarboximide, N- (camphorsulfonyloxy) naphthyldicarboxylimide, N - (4-methylphenyl) (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboxylic imide, N- (4-fluoro-4-fluorophenylsulfonyloxy) (Pentafluoroethylsulfonyloxy) naphthyldicarboxylic imide, N- (heptafluoropropylsulfonyloxy) naphthyldicarboxylimide, N- (nonafluoro (Butylsulfonyloxy) naphthyldicarbamylimide, N- (ethylsulfonyloxy) naphthyldicarboxyimide, N- (propylsulfonyloxy) naphthyldicarboxyimide, N- (Pentylsulfonyloxy) naphthyldicarboxylic imide, N- (hexylsulfonyloxy) naphthyldicarboximide, N- (heptylsulfonyloxy) naphthyldicarboxylic imide, N- Naphthyldicarboxyimide, and N- (nonylsulfonyloxy) naphthyldicarboxylimide.

[Halogen-containing compound]

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound.

[Diazomethane compound]

Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane and the like.

[Sulfone compound]

Examples of the sulfone compound include? -Ketosulfone compounds,? -Sulfonyl sulfone compounds, diaryl sulfone compounds, and the like.

[Sulfonic acid ester compound]

Examples of the sulfonic acid ester compound include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonates, and the like.

[Carbonic acid ester compound]

Examples of the carbonic acid ester compound include carbonic acid o-nitrobenzyl ester and the like.

As the [B] radiation-sensitive acid generator, oxime sulfonate compounds, onium salts and sulfonic acid ester compounds are preferable from the viewpoints of sensitivity and solubility. The oxime sulfonate compound is preferably a compound represented by the above formula (4), more preferably a compound represented by the above formula (5), particularly preferably a compound represented by the above formula (5-1) Do. As the onium salts, tetrahydrothiophenium salts and benzylsulfonium salts are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, benzyl-4-hydroxy Phenylmethylsulfonium hexafluorophosphate is more preferable. As the sulfonic acid ester compound, a haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide trifluoromethanesulfonic acid ester is more preferable.

The content of the [B] radiation-sensitive acid generator in the radiation sensitive composition is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 1 part by mass to 10 parts by mass, per 100 parts by mass of the polymer [A] 5 parts by mass. By setting the content of the [B] radiation-sensitive acid generator to the above-specified range, it is possible to form an interlayer insulating film for a display device having high surface hardness while maintaining transparency by optimizing the sensitivity of the radiation sensitive composition.

&Lt; Compound [C] &gt;

The [C] compound is a compound having a molecular weight of 1,000 or less and containing at least one (meth) acryloyl group. The radiation sensitive composition of the present invention can improve the sensitivity by containing the [C] compound and improve the surface hardness, heat resistance, solvent resistance, voltage maintenance rate, etc. of the cured film such as an interlayer insulating film for a display element to be formed have.

The [C] compound is not particularly limited as long as it is a compound containing at least one (meth) acryloyl group in the molecule. Examples of the compound having one (meth) acryloyl group include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl Acrylate, isobornyl (meth) acrylate, isobornyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol Amide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (Meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl , Tetrahydro (Meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (Meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene (meth) acrylate, polyoxyethylene Acrylate, glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylenediglycol (meth) acrylate and the like. Among these compounds having one (meth) acryloyl group, isobornyl (meth) acrylate, lauryl (meth) acrylate and phenoxyethyl (meth) acrylate are preferable. Examples of these commercial products include Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (manufactured by Toagosei Co., Ltd.), KAYARAD TC- (Manufactured by NIPPON KAYAKU CO., LTD.), Biscott 192, Viscot 220, Viscot 2311HP, Viscot 2000, Viscot 2100, Viscot 2150, Viscot 8F, Viscot 17F Manufactured by Kagaku Kogyo Co., Ltd.).

Examples of the compound containing two or more (meth) acryloyl groups include ethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclodecanedimethylenedi (meth) acrylate, tris (Meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide Propane tri (meth) acrylate, propylene oxide (hereinafter referred to as "PO") modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (Meth) acrylic acid adducts of bisphenol A diglycidyl ether, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di Acrylate of bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, and phenol novolac polyglycidyl ether. . Examples of commercially available products of these compounds containing two or more (meth) acryloyl groups include SA1002 (manufactured by Mitsubishi Chemical), Viscot 195, Viscot 230, Viscot 260, Viscot 215, Viscot 310, (Manufactured by Osaka Yuki Kagakuko Kogyo Co., Ltd.), Kaya Co., Ltd. (trade name, manufactured by Sumitomo Bakelite Co., Ltd.) DPDA, DPHA-DP, DPHA, GPDA-303, TMPTA, THE-330, HDDA, NPDA, TPGDA, MANDA, R-551, R-712, R-604, R-684, T-2020, T-2020, D-2040, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, 210, M-220, M-233 (manufactured by Nippon Kayaku), TPA-320, TPA-330, RP-1040, RP-2040, R-011 and R-300 , M-240, M-215, M-305, M-309, M-310, M-315, M-325, M- Light Acrylate BP-4EA, BP-4PA, BP-2EA, BP , New Frontier BPE-4, BR-42M, GX-8345 (manufactured by Daiichi Kyoe Sekiyu Co., Ltd.) and ASF-400 (manufactured by Shin-Tei Kasei Kagaku Co., Ltd.) (Manufactured by Showa Kobunshi Co., Ltd.), NK ester A-BPE-4 (manufactured by Showa Denko KK), SP-1506, SP-1507, SP-1509, VR-77, SP- Ltd.) and the like.

Of these, compounds containing at least two (meth) acryloyl groups in the molecule are preferable, and compounds containing at least three (meth) acryloyl groups in the molecule are more preferable. Examples of the compound containing at least three (meth) acryloyl groups in such molecules include tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, hexa Acrylate compounds and the like.

Of these, the skeleton derived from the diol structure represented by the following formula (6), the skeleton derived from trimethylolpropane represented by the formula (7), and the skeleton derived from the pentaerythritol represented by the formula (8) Or a compound having a skeleton derived from dipentaerythritol represented by the formula (9) is more preferable.

In the above formula (6), n is an integer of 2 to 12.

Examples of such preferred [C] compounds include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethylene oxide modified dipentaerythritol hexaacrylate, propylene oxide modified dipentaerythritol hexaacrylate, epsilon -caprolactone modified dipentaerythritol hexaacrylate , Succinic acid-modified pentaerythritol triacrylate, and the like. Further, in the radiation sensitive composition, the [C] compounds may be used singly or in combination of two or more. The [C] compound is a compound having a molecular weight of 1,000 or less.

The content of the [C] compound in the radiation sensitive composition is preferably 1% by mass or more and 50% by mass or less in terms of solid content, more preferably 1% by mass or more and 30% by mass or less, more preferably 1% % Or less. By setting the content of the [C] compound in the above-described radiation-sensitive composition within the above range, the surface hardness, solvent resistance, heat resistance, and voltage holding ratio of the cured film such as an interlayer insulating film for a display element to be formed can be further improved.

&Lt; Other optional components &gt;

The radiation sensitive composition may contain, in addition to the [A] polymer, the [B] radiation-sensitive acid generator and the [C] compound, a sensitizer, a basic compound, a surfactant, And a compound having a hindered phenol structure, and the like. Each component may be used singly or in combination of two or more kinds. Each component will be described in detail below.

[Increase / decrease]

It is preferable that the radiation sensitive composition further contains a sensitizer as a suitable component. By further containing a sensitizer, the sensitivity of the radiation sensitive composition can be further improved. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer in the electron-excited state comes into contact with the photoacid generator to generate electron transfer, energy transfer, heat generation and the like, whereby the [B] radiation-sensitive acid generator generates a chemical change, .

As the sensitizer, compounds belonging to the following compounds and having an absorption wavelength in the region of 350 nm to 450 nm and the like can be given.

As the sensitizer, for example,

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene and 9,10-dipropyloxyanthracene;

Xanthines such as fluorescein, eosin, erythrosin, rhodamine B and rose bengal;

Xanthones such as xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone and isopropylthioxanthone;

Cyanines such as thiacaboxyan, oxacarbocyanine and the like;

Meloxicans such as meloxican and carbomethicin;

Rhodacyanil;

Oxonol;

Thiazines such as thionine, methylene blue and toluidine blue;

Acridines such as acridine orange, chloroflavin and acriflavine;

Acridine such as acridone, 10-butyl-2-chloroacridone;

Anthraquinones such as anthraquinone;

Scallops such as squalium;

Styryls;

Base styryls such as 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole;

7-hydroxy-4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6.7. 8-ij] quinolizidine-11-one, and the like.

Of these sensitizers, polycyclic aromatic compounds, terpolymers, acridones, styryls, base styryls and coumarins are preferable, polycyclic aromatic compounds and xanthones are more preferable, and 9,10-dibutoxyanthracene, isopropyl Oxantone is particularly preferred.

The content of the sensitizer in the radiation sensitive composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the polymer [A]. By setting the content of the sensitizer to the above range, the sensitivity can be further improved.

[Basic compound]

The basic compound may be selected from those used as a chemically amplified resist, and examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carbonic acid quaternary ammonium salts and the like. By containing a basic compound in the radiation sensitive composition, the diffusion length of the acid generated from the [B] radiation-sensitive acid generator can be appropriately controlled by exposure, and the pattern developing property can be improved.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl- Benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy 4-methyl morpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1, 2-diazabicyclo [4.3.0] -naphthalene, pyrazine, pyridazine, pyridine, pyrrolidine, piperidine, piperazine, morpholine, , 8-diazabicyclo [5.3.0] -7 undecene, and the like.

Examples of quaternary ammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide and tetra-n-hexylammonium hydroxide. .

Examples of the carbonic acid quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate and tetra-n-butylammonium benzoate.

Among these basic compounds, heterocyclic amines are preferable, and 4-dimethylaminopyridine, 4-methylimidazole, and 1,5-diazabicyclo [4,3,0] -5-nonene are more preferable.

The content of the basic compound in the radiation sensitive composition is preferably 0.001 parts by mass to 1 part by mass, more preferably 0.005 parts by mass to 0.2 parts by mass, relative to 100 parts by mass of the polymer [A]. By setting the content of the basic compound within the above-specified range, the pattern developability is further improved.

[Surfactants]

The surfactant can further improve the film formability of the radiation sensitive composition. Examples of the surfactant include fluorine surfactants and silicone surfactants. The surface-smoothness of the coating film can be improved by containing the surfactant in the radiation sensitive composition, and the film thickness uniformity of the resulting interlayer insulating film for a display element can be further improved.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of a terminal, a main chain and a side chain is preferable, and for example, 1,1,2,2-tetrafluoro-n Octyl (n-hexyl) ether, hexaethyleneglycol di (1, 2, 2-tetrafluoro-n-propyl) Hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di Hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro- Hexafluoro-n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro-n-hexafluoro-n-decane, 1,1,2,2,3,3- Dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarbonate, diglycerin tetrakis (fluoroalkyl Polyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carbonic acid fluoroalkyl ester And the like.

Examples of commercially available products of the fluorinated surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megaface F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471, Fluorad FC-170C, FC-171, FC-430 and FC-431 (manufactured by Sumitomo 3M Ltd.), Surflon (manufactured by Dainippon Ink and Chemicals Inc.), Fluorad FC- S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103 and SC-104 SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Epson EF301, EF303 and EF352 (manufactured by Shin-Aichi Kasei K.K.), Ftergent FT-100, (Manufactured by NEOS), FT-140A, FT-150, FT-250, FT-251, FT-300, FT-310, FT-400S, FTX- And the like.

Examples of the silicone surfactants include silicone resins such as Torensilicon DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ- (Manufactured by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 Manufactured by Toshiba Silicon), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The content of the surfactant in the radiation sensitive composition is preferably 0.01 parts by mass or more and 2 parts by mass or less, more preferably 0.05 parts by mass or more and 1 part by mass or less, based on 100 parts by mass of the polymer [A] . By setting the content of the surfactant within the above-specified range, the uniformity of the film thickness of the coating film can be further improved.

[Adhesion preparation]

The adhesion aid can be used to improve the adhesion of an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, and an insulating film. As the adhesion aid, a functional silane coupling agent is preferred. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? - Glycidoxypropyltrimethoxysilane, gamma -glycidoxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl tri Methoxysilane and the like. Of these,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane Lt; / RTI &gt; is preferred.

The content of the adhesion aid in the radiation sensitive composition is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymer [A]. By setting the content of the adhesion promoter within the above-specified range, adhesion between the display element interlayer insulating film and the substrate is further improved.

[Compound having a hindered phenol structure]

A compound having a hindered phenol structure is a component for preventing cleavage of a bond of a compound by a radical or a peroxide. Examples of the compound having a hindered phenol structure include a radical scavenger such as a compound having a hindered amine structure in addition to a compound having a hindered phenol structure.

Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- Di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5- Hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert- 5 ', 5'-hexa-tert-butyl-a, a', a'- (mesitylene-2,4,6-triyl) o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5- Hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Tris [(4-tert-butyl-3-hydroxy-2,6-xyline) methyl] -1,3,5-triazine- 3H, 5H) -thione and 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine 2-ylamine) .

Examples of the compound having a hindered amine structure include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl- Piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octyloxy-2,2,6,6-tetramethyl- - piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl- (1-acyl-2,2,6,6-tetramethyl-4-piperidyl) -2,2-bis (3,5-di-t-butyl) malonate, bis Butyl-4-hydroxybenzyl) -2-butyl maleate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate, 2,2,6,6-tetra Methyl-4-piperidyl methacrylate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- [ Di-t-butyl-4-hydro Ethyl) -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like.

The content of the compound having a hindered phenol structure in the radiation sensitive composition is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 1.5 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the polymer [A] More preferable. By setting the content of the compound having a hindered phenol structure within the above-specified range, the voltage holding ratio of the display element interlayer insulating film to be formed can be further improved while maintaining the sensitivity of the radiation sensitive composition.

&Lt; Preparation method of radiation sensitive composition &gt;

The radiation sensitive composition is prepared by dissolving or dispersing the [A] polymer, the [B] radiation-sensitive acid generator, the [C] compound and optionally other optional components in a solvent. For example, the respective radiation-sensitive compositions can be prepared by mixing the components in a predetermined ratio in a solvent.

As the solvent, those that do not react with each component by uniformly dissolving or dispersing each component are suitably used. Examples of the solvent 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, Hydrocarbons, ketones, and other esters.

Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

As the ethers, for example, tetrahydrofuran and the like can be mentioned.

As the glycol ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like can be given.

Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like.

Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like.

Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.

Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, and the like. .

Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

Examples of the ketone include methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone.

Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- Hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionate, propyl 3-hydroxypropionate, propyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, Propyl methoxyacetate, propyl methoxy propionate, butyl 2-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, , Butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxyacetate Methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, Ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2- Methoxypropionate, methyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl propoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, Butyl, 3-propoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate.

Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate and butyl methoxyacetate are preferable, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and butyl methoxyacetate are more preferred.

&Lt; Method of forming interlayer insulating film for display element &gt;

The radiation sensitive composition is suitable as a material for forming an interlayer insulating film for a display element. Further, the present invention suitably includes an interlayer insulating film for a display element formed of the radiation sensitive composition.

In the method of forming an interlayer insulating film for a display element of the present invention,

(1) a step of forming a coating film on a substrate (hereinafter also referred to as &quot; step (1) &quot;) using the radiation sensitive composition,

(2) a step of irradiating at least a part of the coating film with radiation (hereinafter also referred to as &quot; step (2) &quot;),

(3) a step of developing the coating film irradiated with the radiation (hereinafter also referred to as &quot; step (3) &quot;),

(4) a step of heating the developed coating film (hereinafter also referred to as &quot; step (4) &quot;).

According to this forming method, an interlayer insulating film for a display element having excellent surface hardness, solvent resistance, heat resistance and voltage holding ratio can be formed. Further, by using the radiation sensitive composition having excellent sensitivity, it is possible to easily form an interlayer insulating film for a display element having a fine and elaborate pattern. Therefore, the formed interlayer insulating film for a display element can be suitably used for a display element such as a liquid crystal display element or an organic EL display element.

[Step (1)]

In this step, the radiation sensitive composition is coated on a substrate to form a coating film. Preferably, the solvent is removed by prebaking the application surface.

Examples of the substrate include glass, quartz, silicon, resin, and the like. Examples of the resin include ring-opening polymers of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide and cyclic olefin, and hydrogenated products thereof. The conditions for the prebaking may vary depending on the kind of each component, the mixing ratio, and the like, but may be about 70 to 120 캜 for about 1 to 10 minutes.

[Step (2)]

In this step, at least a part of the formed coating film is exposed to radiation. When exposure is performed, exposure is usually performed through a photomask having a predetermined pattern. As the radiation used for the exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable. The exposure dose is preferably 500 J / m2 to 6,000 J / m2, preferably 1,500 J / m2 to 1,800 J / m2, as measured by a light meter (OAI model 356, manufactured by OAI Optical Associates) Lt; 2 &gt; is more preferable.

[Step (3)]

In this step, the coated film irradiated with the radiation is developed. By developing the coated film after exposure, unnecessary portions (irradiated portions of radiation) are removed to form a predetermined pattern. As the developing solution used in the developing step, an alkaline aqueous solution is preferable. 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, and the like.

To the aqueous alkali solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. The concentration of the alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of achieving adequate developability. Examples of the developing method include a puddle method, a dipping method, a swing dipping method, a shower method, and the like. The development time varies depending on the composition of the radiation sensitive composition, but is about 10 seconds to 180 seconds. Following this development processing, for example, water washing is carried out for 30 seconds to 90 seconds, and then air is blown with compressed air or compressed nitrogen, for example, to form a desired pattern.

[Step (4)]

In this step, the developed coating film is heated. For the heating, the patterned thin film element is heated by using a heating device such as a hot plate or oven to accelerate the curing reaction of the [A] polymer to obtain a cured product. The heating temperature is, for example, about 120 ° C to 250 ° C. The heating time varies depending on the type of the heating apparatus, but is, for example, about 5 minutes to 30 minutes in a hot plate and 30 minutes to 90 minutes in an oven. Further, a step baking method in which two or more heating steps are performed may be used. In this manner, a patterned thin film corresponding to the target interlayer insulating film for a display element can be formed on the surface of the substrate. The use of the cured film is not limited to the interlayer insulating film for a display element, and can be used as a spacer or a protective film.

The film thickness of the formed interlayer insulating film for a display element is preferably 0.1 mu m to 8 mu m, more preferably 0.1 mu m to 6 mu m, particularly preferably 0.1 mu m to 4 mu m.

(Example)

Hereinafter, the present invention will be described in detail on the basis of examples, but the present invention is not limitedly interpreted based on the description of this example.

<Synthesis of [A] Polymer>

[Synthesis Example 1]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Then, 50 parts by mass of tetrahydropyranyl methacrylate to give the structural unit (I), 35 parts by mass of glycidyl methacrylate to give the structural unit (II), methacrylic acid dodecane 5 parts by mass of methacrylic acid, 10 parts by mass of methacrylic acid giving other structural units and 3 parts by mass of? -Methylstyrene dimer were purged with nitrogen and stirred gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The Mw of the copolymer (A-1) was 9,000. The solid concentration of the polymer solution obtained here was 32.1 mass%.

[Synthesis Example 2]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 50 parts by mass of tetrahydropyranyl methacrylate to give the structural unit (I), 20 parts by mass of glycidyl methacrylate to give the structural unit (II), methacrylic acid diester 20 parts by mass of silane, 10 parts by mass of methacrylic acid giving other structural units and 3 parts by mass of? -Methylstyrene dimer were purged with nitrogen and stirred gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2). The Mw of the copolymer (A-2) was 8,000. The solid concentration of the polymer solution obtained here was 31.5% by mass.

[Synthesis Example 3]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Then, 50 parts by mass of tetrahydropyranyl methacrylate to which the structural unit (I) is added, 20 parts by mass of glycidyl methacrylate to which the structural unit (II) is added, the methacrylic acid 20 parts by mass of til and 10 parts by mass of methacrylic acid giving other structural units and 3 parts by mass of? -Methylstyrene dimer were charged, and after nitrogen substitution, gentle stirring was started. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-3). The Mw of the copolymer (A-3) was 8,500. The solid content concentration of the polymer solution obtained here was 32.5 mass%.

[Synthesis Example 4]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 50 parts by mass of tetrahydropyranyl methacrylate to give the structural unit (I), 20 parts by mass of glycidyl methacrylate to give the structural unit (II), and 0.1 part by mass of methacrylic acid stearate 20 parts by mass of aryl, 10 parts by mass of methacrylic acid imparting other structural units, and 3 parts by mass of? -Methylstyrene dimer were charged, and after nitrogen substitution, stirring was gently started. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-4). The Mw of the copolymer (A-4) was 7,500. The solid concentration of the polymer solution obtained here was 31.0% by mass.

[Synthesis Example 5]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 15 parts by mass of tetrahydropyranyl methacrylate to give the structural unit (I), 10 parts by mass of glycidyl methacrylate to give the structural unit (II), methacrylic acid diester 60 parts by mass of silane, 5 parts by mass of methacrylic acid imparting other structural units and 3 parts by mass of? -Methylstyrene dimer were put into the autoclave and purged with nitrogen, followed by gentle stirring. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-5). The Mw of the copolymer (A-5) was 8,000. The solid concentration of the polymer solution obtained here was 31.5% by mass.

[Synthesis Example 6]

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Then, 55 parts by mass of tetrahydropyranyl methacrylate to give the structural unit (I), 35 parts by mass of glycidyl methacrylate to give the structural unit (II), and 10 parts by mass of methacrylic acid , And 3 parts by mass of? -Methylstyrene dimer were put in a flask, and after the flask was purged with nitrogen, stirring was gently started. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1). The Mw of the copolymer (a-1) was 9,000. The solid concentration of the polymer solution obtained here was 32.1 mass%.

&Lt; Preparation of sensitizing radiation-sensitive composition &gt;

[Example 1]

(B) as a radiation-sensitive acid generator (hereinafter referred to as &quot; component (A)] was added as a polymer [A] to a solution containing 100 parts by mass (solid content) of the copolymer 15 parts by mass of the compound (C-1) as the [C] compound, 0.01 part by mass of the compound (D-1) as the basic compound, and 3 parts by mass of the (E-1) silicone surfactant (SH-8400 FLUID) and 3.0 parts by mass of (F-1)? -Glycidoxypropyltrimethoxysilane as an adhesion aid were mixed and filtered with a membrane filter having a pore diameter of 0.2 占 퐉. To prepare a radiation-curable composition (S-1).

[Examples 2 to 10 and Comparative Example 1]

(S-2) to (S-10) and (CS-1) were prepared in the same manner as in Example 1 except that the kind and the blending amount of each component were changed as shown in Table 1 , And Examples 2 to 10 and Comparative Example 1, respectively.

Hereinafter, components used for preparing the radiation sensitive compositions of the examples and the comparative examples will be described in detail.

<[B] Radiation-sensitive acid generator>

(B-1): 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

(B-2): N-Hydroxynaphthalimide-trifluoromethanesulfonic acid ester

(2-methylphenyl) acetonitrile (IRGACURE PAG 103, manufactured by Ciba Specialty Chemicals), (B-3): (5-propylsulfonyloxyimino-5H-

&Lt; Compound [C] &gt;

(C-1) a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate

(C-2) ethylene oxide-modified dipentaerythritol hexaacrylate,

(C-3) Trimethylolpropane triacrylate

(C-4) succinic acid-modified pentaerythritol triacrylate

(C-5)? -Caprolactone-modified dipentaerythritol hexaacrylate

(C-6) hexamethylene diacrylate

&Lt; Basic compound &gt;

(D-1) 4-dimethylaminopyridine

<Surfactant>

(E-1) silicone surfactant (TORAY DOW CORNING, SH 8400 FLUID)

<Adhesion preparation>

(F-1)? -Glycidoxypropyltrimethoxysilane

<Evaluation>

The radiation-sensitive compositions of Examples 1 to 10 and Comparative Example 1 were used to evaluate various radiation-sensitive compositions and their various properties as coating films or interlayer insulating films as follows. The results are shown in Table 1.

[Sensitivity (J / m 2)]

Hexamethyldisilazane (HMDS) was applied onto a chromium-deposited glass of 550 x 650 mm and heated at 60 占 폚 for 1 minute (HMDS treatment). Each of the radiation sensitive compositions prepared as described above on the chromium film-formed glass after the HMDS treatment was applied using a slit die coater &quot; TR632105-CL &quot;, the solvent was removed under vacuum by setting the ultimate pressure to 100 Pa, Followed by pre-baking at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. Subsequently, the coating film was irradiated with radiation with varying exposure dose through a mask having a line-and-space (10: 1) pattern of 60 mu m using a Canon MPA-600FA exposure machine, Methyl ammonium hydroxide aqueous solution at 25 占 폚. The development time was 80 seconds. Subsequently, the substrate was subjected to water washing with ultra-pure water for 1 minute, and then dried to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the amount of exposure necessary for completely dissolving the space pattern of 6 mu m was examined. When the value is 300 J / m &lt; 2 &gt; or less, the sensitivity is good.

[Surface hardness]

Similar to the above evaluation of the sensitivity, a coating film was formed on a glass substrate. The glass substrate was heated in a clean oven at 220 占 폚 for 1 hour without exposure, to obtain a cured film. The pencil hardness (surface hardness) of the cured film was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990. When the value is 3H or larger, the surface hardness of the cured film such as an interlayer insulating film is good, and the composition used for forming the cured film has sufficient curability.

[Content Rating (%)]

Similar to the above evaluation of the sensitivity, a coating film was formed on a glass substrate. The glass substrate was heated in a clean oven at 220 占 폚 for 1 hour without exposure, to obtain a cured film. With respect to the substrate having this cured film, the film thickness (T1) of the obtained cured film was measured by a laser microscope (VK-8510, manufactured by KEYENCE CORPORATION). Subsequently, the glass substrate on which the cured film was formed was dipped in dimethylsulfoxide controlled at 70 캜 for 20 minutes, and then the film thickness t 1 of the cured film was measured. From the following equation, (%). &Lt; tb &gt; &lt; TABLE &gt;

Solubility (%) = {(t1-T1) / T1} x 100

When the absolute value of this value was less than 5%, it was judged that the solvent resistance was excellent.

[Voltage Conservation Rate (%)]

Each positive radiation-sensitive composition is spin-coated on a soda glass substrate on which an SiO ₂ film is formed to prevent elution of sodium ions on the surface and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape, Prebaked in a clean oven at 90 占 폚 for 10 minutes to form a coating film having a thickness of 2.0 占 퐉. Subsequently, the coated film was exposed at an exposure amount of 500 J / m &lt; 2 &gt; without interposing a photomask. Thereafter, post-baking was performed at 230 캜 for 30 minutes to cure the coating film. Subsequently, the substrate on which the pixel was formed and the substrate on which the ITO electrode had been deposited in a predetermined shape were bonded to each other with a sealing material mixed with 0.8 mm glass beads, and then a liquid crystal MLC6608 manufactured by Merck Ltd. was injected to prepare a liquid crystal cell . The liquid crystal cell was placed in a thermostatic chamber at 60 캜, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage maintaining rate measuring system (Model VHR-1A, manufactured by Toyo Technica Co., Ltd.). The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. The voltage holding ratio (%) is a value obtained by the following formula.

Voltage Conservation Rate (%) = (Liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds) 占 100

If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell can not maintain the applied voltage at a predetermined level for 16.7 milliseconds and can not sufficiently orient the liquid crystal, Is high.

[Heat resistance (占 폚)]

Similar to the above evaluation of the sensitivity, a coating film was formed on a glass substrate. The glass substrate was heated in a clean oven at 220 占 폚 for 1 hour without exposure, to obtain a cured film. The 5% thermogravimetric reduction temperature of the obtained cured film was measured. For the measurement, TGA was used and the temperature was raised from room temperature to 500 DEG C at 10 DEG C / min under air, and the temperature at which the mass was reduced by 5% was measured. The higher the temperature at which the mass is reduced by 5%, the better the heat resistance can be judged to be.

As is evident from the results of Table 1, Examples 1 to 10 using the radiation sensitive compositions of the present invention exhibited a cured film having good sensitivity and excellent in surface hardness, solvent resistance and heat resistance as compared with the composition of Comparative Example 1 . In addition, the cured films formed from the radiation sensitive compositions of Examples 1 to 10 had a sufficiently high voltage holding ratio.

Since the radiation sensitive composition of the present invention has excellent sensitivity, it is possible to form an interlayer insulating film for a display element having a fine and precise pattern easily. Further, the radiation sensitive composition of the present invention can form an interlayer insulating film for a display element having excellent surface hardness, solvent resistance, heat resistance and voltage holding ratio. Accordingly, the radiation sensitive composition is suitable as a material for forming an interlayer insulating film for a display element such as a liquid crystal display element or an organic EL display element.

Claims (10)

[A] a polymer having a structural unit (I) containing an acid-dissociable group, a structural unit (II) containing a polymerizable group and a structural unit (III) represented by the following formula (1)
[B] Radiation-sensitive acid generator
A radiation-sensitive composition comprising:

(Wherein R ¹ is a hydrogen atom or a methyl group; R ² is an alkyl group, an alkenyl group, an alkynyl group or an acyloxyalkyl group having 6 to 30 carbon atoms or a crosslinked cyclic hydrocarbon group having 4 to 30 carbon atoms; , Part of the hydrogen atoms of the alkyl group, alkenyl group, alkynyl group, acyloxyalkyl group and crosslinked cyclic hydrocarbon group may be substituted with a hydroxyl group or a carboxyl group). The method according to claim 1,
A radiation-sensitive composition further containing a compound having a molecular weight of 1,000 or less and containing at least one [C] (meth) acryloyl group. The method according to claim 1,
Wherein the acid-dissociable group in the structural unit (I) is represented by the following formula (2):

(In the formula (2), R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group or an aryl group, with the proviso that some of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group, R ³ and R ⁴ are not both hydrogen atoms; R ⁵ is an alkyl group, an alicyclic hydrocarbon group, an aralkyl group, an aryl group or a group represented by -M (R ⁶ ) ₃ ; and; M is Si, Ge or Sn, and; R ⁶ is alkyl group; however, a part or all of the hydrogen atoms having the alkyl group of the R ⁵ alkyl group, an alicyclic hydrocarbon group, an aralkyl group and an aryl group and R ⁶ a is R ³ and R ⁵ may be bonded to each other, and a carbon atom to which R ³ is bonded and an oxygen atom to which R ⁵ is bonded may form a cyclic ether structure). The method according to claim 1,
Wherein the polymerizable group in the structural unit (II) is an epoxy group. 5. The method according to any one of claims 1 to 4,
Wherein the content of the structural unit (III) in the polymer [A] is 3% by mass or more and 50% by mass or less. 5. The method according to any one of claims 2 to 4,
Wherein the [C] compound is a compound having a skeleton derived from a diol structure having 2 to 12 carbon atoms, a skeleton derived from trimethylolpropane, a skeleton derived from pentaerythritol, or a skeleton derived from dipentaerythritol. 5. The method according to any one of claims 2 to 4,
Wherein the content of the [C] compound is 1% by mass or more and 50% by mass or less in terms of solid content. 5. The method according to any one of claims 1 to 4,
A radiation-sensitive composition for forming a display element interlayer insulating film. An interlayer insulating film for a display element formed by the radiation sensitive composition according to claim 8. (1) a step of forming a coating film on a substrate by using the radiation sensitive composition of claim 8,
(2) a step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation, and
(4) a step of heating the developed coating film
Of the interlayer insulating film for a display element.