KR20170077053A - Radiation-sensitive resin composition, cured film, method for forming the cured film, and display device - Google Patents

Abstract

A radiation-sensitive resin composition having a good radiation sensitivity, a small amount of change in the film thickness of an unexposed portion, and a high refractive index, excellent in transparency, insulation, and corrosion resistance can be obtained, a cured film formed of the composition, A method of forming the cured film, and a display element having the cured film.
(Solution) The invention made to solve the above problems is achieved by a radiation-sensitive resin composition containing a polymer, a radiation-sensitive acid generator and a compound having two or more groups represented by formula (1).

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation-sensitive resin composition, a cured film, a method of forming the same, and a display device,

The present invention relates to a radiation-sensitive resin composition, a cured film, a method of forming the same, and a display device.

The display element is provided with a cured film such as an interlayer insulating film, a spacer, a protective film or the like which insulates wiring arranged in layers. A cured film such as an interlayer insulating film is required to have insulating properties (low dielectric constant), corrosion resistance (which can suppress corrosion of wiring provided on a coated substrate) and the like.

On the other hand, as a material for forming an interlayer insulating film or the like, a radiation-sensitive resin composition is widely used. The radiation sensitive resin composition is required to have good sensitivity to radiation, and the like.

Examples of such a radiation-sensitive resin composition include a composition containing a resin dissociated by an acid and being soluble in an aqueous alkali solution, a crosslinking agent and an acid generator, a resin having an acetal structure or a ketal structure and an epoxy group, (Japanese Unexamined Patent Application Publication No. 2004-4669 and Japanese Unexamined Patent Publication No. 2004-264623).

In the case of attempting to form a cured film of a display element by using the above conventional radiation-sensitive resin composition, the amount of decrease in the film thickness of the non-exposed portion in the heating step after development is large and the flatness of the cured film is impaired, There is a problem that a deviation occurs. There is also room for improvement in the radiation sensitivity and the like.

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

The present invention has been made based on the above-described circumstances, and its object is to provide a cured film having good radiation sensitivity, a small amount of change in the film thickness of the unexposed portion, a high refractive index and excellent transparency, A cured film formed from the composition, a method of forming the cured film, and a display element having the cured film.

(A) polymer, a radiation-sensitive acid generator (hereinafter also referred to as " [B] acid generator ") and a compound represented by the following formula ) (Hereinafter, also referred to as a " compound [C] ") having at least two groups in one molecule.

(In the formula (1), Z represents a sulfur atom or a nitrogen atom, X represents a divalent hydrocarbon group having 2 or more carbon atoms, Y represents an organic group including an acid dissociable group or an acid dissociable group, )

Another invention made to solve the above problems is a cured film formed from the radiation sensitive resin composition. The method may further comprise a step of forming a coating film on the substrate, a step of irradiating at least a part of the coating film with radiation, a step of developing the coating film irradiated with the radiation, and a step of heating the developed coating film, A method of forming a cured film using the radiation sensitive resin composition and a display element having the cured film are also included in the present invention.

The method of forming a radiation sensitive resin composition and a cured film according to the present invention can exhibit excellent transparency, insulation and corrosion resistance with a high refractive index, a good radiation sensitivity, a small amount of change in the film thickness of the unexposed portion, . Further, the cured film of the present invention can exhibit excellent insulating properties and corrosion resistance, and can be suitably used for display devices.

Fig. 1 is a photograph showing a state in which there is no wiring corrosion in the corrosion prevention evaluation of the embodiment. Fig.
Fig. 2 is a photograph showing a state of wiring corrosion.

<Radiation-Resistant Resin Composition>

The radiation sensitive resin composition contains the [A] polymer, the [B] acid generator, and the [C] compound. The radiation sensitive resin composition may further contain, as other optional components, an antioxidant and the like.

The radiation sensitive resin composition is used for forming a cured film for a display element. Further, the radiation-sensitive resin composition is usually used for forming a positive pattern using an alkali developing solution. In the radiation sensitive resin composition, an acid is generated from the acid generator [B] in the exposed portion by exposure at the time of pattern formation, and the acid dissociable group of the [C] compound is dissociated by the acid. As a result, the difference in solubility between the exposed portion and the non-exposed portion in the developing solution increases, and good radiation sensitivity is exhibited. Further, as described above, since the [C] compound having a low molecular weight as compared with the [A] polymer has an acid-dissociable group, a change in solubility in a developer is less than that of a radiation- It becomes remarkable. Further, the cured film [A] is cured by heating after exposure, the cured film having a small change in film thickness, a low dielectric constant, and excellent corrosion resistance can be obtained. Since the [C] compound contains a sulfur atom, the refractive index of the cured film can be improved. Each component will be described below.

<[A] Polymer>

The polymer [A] is a component which becomes a main material of the obtained cured film. As the polymer [A], conventionally known polymers contained in the radiation-sensitive resin composition may be used alone or in combination of two or more. As the [A] polymer, it is preferable to use a polymer having no acid dissociable group. By using a polymer having no acid dissociable group, the film thickness variation can be made smaller.

The polymer [A] is suitably used, usually having suitable solubility in an alkali developing solution and curing property by heating. Examples of the polymer (A) include polymers selected from the group consisting of (A-1) an acrylic resin having a carboxyl group, (A-2) a polyimide or polyimide precursor, (A- 3) polysiloxane and And at least one polymer selected from the group consisting of at least one polymer selected from the group consisting of: By using these polymers, the amount of change in the film thickness can be further reduced, and the insulating property and the corrosion prevention property can be further improved. Further, since the polymer [A] is one of these polymers, the radiation-sensitive resin composition suitably functions as a positive radiation-sensitive resin composition using an alkali developing solution.

((A-1) an acrylic resin having a carboxyl group)

(A-1) The acrylic resin having a carboxy group has alkali solubility by a carboxy group. (A-1) The acrylic resin having a carboxy group preferably has a structural unit having a carboxy group and a structural unit having a polymerizable group. In this case, the solubility (alkali developability) and curability of the alkali developing solution can be excellently exerted.

The structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group. When the acrylic resin having a carboxy group contains the above specific structural unit, a stronger cured film can be formed.

Examples of the structural unit having a (meth) acryloyloxy group include a method in which (meth) acrylic acid is reacted with an epoxy group in a polymer, a method in which a (meth) acrylic acid ester having an epoxy group is reacted with a carboxyl group in the polymer, A method of reacting a (meth) acrylic acid ester having an isocyanate group, a method of reacting a (meth) acrylic acid hydroxy ester to an acid anhydride moiety in the polymer, and the like. Among these, a method of reacting a (meth) acrylic acid ester having an epoxy group in a carboxy group in the polymer is preferred.

The acrylic resin comprising a structural unit having a carboxy group and a structural unit having an epoxy group as a polymerizable group is obtained by reacting (a1) at least one member selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Hereinafter also referred to as "(a1) compound") and (a2) epoxy group-containing unsaturated compound (hereinafter also referred to as "(a2) compound"). (a3) a hydroxyl group-containing unsaturated compound giving a hydroxyl group-containing structural unit (hereinafter also referred to as &quot; (a3) compound &quot;) may be further added to form a copolymer. In the production of an acrylic resin having a carboxy group, structural units other than the structural units derived from the compounds (a4) to (a3) other than the above-mentioned (a1) , May be further added to form a copolymer. Next, each of the compounds (a1) to (a4) will be described in detail.

((a1) compound)

Examples of the compound (a1) include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an anhydride of an unsaturated dicarboxylic acid.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid and crotonic acid.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like.

Examples of the anhydrides of the unsaturated dicarboxylic acids include anhydrides of the compounds exemplified as the unsaturated dicarboxylic acids.

Of these compounds (a1), acrylic acid, methacrylic acid, and maleic anhydride are more preferable in terms of copolymerization reactivity, solubility in an aqueous alkali solution, and availability. These (a1) compounds may be used alone or in combination of two or more.

The lower limit of the use ratio of the compound (a1) is preferably 5% by mass, more preferably 10% by mass based on the total amount of the monomers forming the acrylic resin having the carboxyl group (A-1). On the other hand, the upper limit is preferably 30% by mass, more preferably 25% by mass. By setting the ratio of the compound (a1) to be within this range, it is possible to optimize the solubility of the acrylic resin having a carboxyl group in an aqueous alkali solution and to form a film having excellent radiation sensitivity.

((a2) compound)

(a2) is an epoxy group-containing unsaturated compound having a radical polymerizing property. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure) and 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl group.

Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate , 6,7-epoxyheptyl acrylate, 6,7-epoxyhexyl methacrylate,? -Ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p Vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexyl acrylate, and the like. Of these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 6,7-epoxyhexyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- Vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl acrylate, and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate are preferable because of the copolymerization reactivity And solvent resistance of an insulating film and the like.

Examples of the unsaturated compound having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- Acrylic acid esters such as ethyl oxetane, 3- (2-acryloyloxyethyl) -3-ethyl oxetane and 3- (2-acryloyloxyethyl) -2-phenyloxetane;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- , 2-difluorooxetane and the like, and the like.

Among these compounds (a2), glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable. These (a2) compounds may be used alone or in combination of two or more.

The lower limit of the use ratio of the compound (a2) is preferably 5% by mass, more preferably 10% by mass, based on the total monomer forming the acrylic resin having the carboxyl group (A-1). On the other hand, the upper limit is preferably 60% by mass, more preferably 50% by mass. By setting the use ratio of the compound (a2) within this range, a cured film having excellent curability can be formed.

((a3) compound)

Examples of the compound (a3) include a (meth) acrylic acid ester having a hydroxyl group, a (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.

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

Examples of the methacrylic acid ester having a hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6- Hydroxyhexyl and the like.

Examples of the acrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate. Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate, 4-hydroxyphenyl methacrylate and the like.

Examples of the hydroxystyrene include o-hydroxystyrene, p-hydroxystyrene, and? -Methyl-p-hydroxystyrene. These (A3) compounds may be used alone or in combination of two or more.

The lower limit of the amount of the compound (a3) used is preferably 1% by mass, more preferably 5% by mass based on the total amount of all the monomers forming the acrylic resin having a carboxyl group (A-1). On the other hand, the upper limit is preferably 30% by mass, more preferably 25% by mass. By optimizing the solubility of the compound (a3) in the alkaline aqueous solution, it is possible to optimize the solubility of the compound in the alkali aqueous solution.

((a4) compound)

The compound (a4) is not particularly limited as long as it is an unsaturated compound other than the compounds (a1) to (a3). Examples of the compound (a4) include methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid chain alkyl esters, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, Unsaturated compounds having a conjugated diene compound, a mid-compound, an unsaturated aromatic compound, a conjugated diene, a tetrahydrofuran skeleton and the like, and other unsaturated compounds.

Examples of the methacrylic acid straight chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, Isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

Examples of the methacrylic acid cyclic alkyl esters include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, methacrylic tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate, and the like.

Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, Stearyl acrylate, and the like.

Examples of the acrylic acid cyclic alkyl esters include acrylic acid cyclohexyl, acrylic acid 2-methylcyclohexyl, acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, acrylic acid tricyclo [5.2.1.0 ^2,6 ] 8-yloxyethyl, isobonyl acrylate, and the like.

Examples of the methacrylic acid aryl esters include phenyl methacrylate and benzyl methacrylate.

Examples of the acrylic acid aryl esters include phenyl acrylate and benzyl acrylate.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate and diethyl itaconate.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide Maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide Propionate, N- (9-acridinyl) maleimide, and the like.

Examples of the unsaturated aromatic compound include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and the like.

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

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran- 2-one.

Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these compounds, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, unsaturated aromatic compound and acrylic acid cyclic alkyl ester are preferable. Among these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan- , p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide and tetrahydrofurfuryl methacrylate are preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution. These (a4) compounds may be used alone or in combination of two or more.

The use ratio of the compound (a4) is preferably 10% by mass or more and 80% by mass or less based on the total amount of all the monomers forming the acrylic resin having the carboxyl group (A-1).

The lower limit value of the polystyrene reduced weight average molecular weight (Mw) of the acrylic resin having a carboxy group is preferably 1,000, more preferably 3,000. On the other hand, the upper limit value is preferably 15,000, more preferably 10,000. By setting Mw to the lower limit value or more, the film forming property of the radiation sensitive resin composition can be improved. On the other hand, lowering the Mw below the upper limit value can prevent deterioration of the developability of the radiation sensitive resin composition.

((A-2) polyimide or polyimide precursor)

(A-2) The polyimide or polyimide precursor is not particularly limited, but is preferably polyamide acid (polyamic acid) or polyamide acid ester which is a polyimide precursor. As the polyimide precursor, there can be mentioned a polymer having a structural unit represented by the following formula (M-1) as a main structure. The polymer having the main structural unit represented by the formula (M-1) can be a polymer having an imide ring, an oxazole ring or other cyclic structure by heating or a suitable catalyst. By having a cyclic structure, heat resistance and solvent resistance are remarkably improved. Here, the main structure means that the structural unit thereof has 50 mol% or more of the total structural units. The structural unit represented by the formula (M-1) is preferably contained in an amount of 70 mol% or more, more preferably 90 mol% or more.

In the formula (M-1), R ^1c represents a (2 + p + m) organic group having 2 or more carbon atoms. Examples of the organic group include a substituted or unsubstituted hydrocarbon group and the like. R ^1c is a structure derived from a polyvalent carboxylic acid. Examples of the polyvalent carboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid and bis (carboxyphenyl) propane, aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and adipic acid, Trimellitic acid, trimellitic acid, trimellitic acid, trimellitic acid, trimellitic acid, and trimesic acid; pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylether tetracarboxylic acid, diphenylsulfone tetracarboxylic acid, Aromatic tetracarboxylic acids such as dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester, butane tetracarboxylic acid, cyclopentanetetracarboxylic acid (2,3,5-tricarboxycyclopentyl acetic acid, etc.) Aliphatic tetracarboxylic acids, ester compounds in which the hydrogen atoms of these carboxy groups are substituted with methyl groups or ethyl groups, and acid anhydrides. In addition, acid such as hydroxyphthalic acid and hydroxy trimellitic acid having a hydroxyl group can be used. Two or more of these acids may be used. From the viewpoint of solubility and photosensitivity to an alkali developing solution, it is preferable that the above structural unit contains a residue of an acid having a hydroxyl group in an amount of 50 mol% or more. R ^1c preferably has an aromatic ring in view of heat resistance and is preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.

In the formula (M-1), R ^2c represents a (2 + q + r) organic group having 2 or more carbon atoms. Examples of the organic group include a substituted or unsubstituted hydrocarbon group or a group in which a substituted or unsubstituted hydrocarbon group is bonded by an oxygen atom (ether group). R ^2c is a structure derived from a diamine. It is preferable that R ^2c has an aromatic ring in view of heat resistance. Examples of the diamine include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) Aminophenoxyphenyl) sulfone, bis (amino-hydroxy-phenyl) hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, di (3-amino-4-hydroxyphenyl) hexafluoropropane, compounds obtained by substituting the hydrogen of these aromatic rings with an alkyl group or a halogen atom, aliphatic Cyclohexyldiamine, methylenebiscyclohexylamine, hexamethylenediamine, and the like.

In the formula (M-1), R ^3c and R ^4c each independently represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms. Examples of the organic group include a substituted or unsubstituted aliphatic or aromatic hydrocarbon group. From the viewpoints of solubility in an alkali developing solution and solution stability of the resulting radiation-sensitive resin composition, it is preferable that 10 mol% or more and 90 mol% or less of R ^3c and R ^4c are hydrogen. It is more preferable that R ^3c and R ^4c each contain at least one monovalent hydrocarbon group of 1 to 16 carbon atoms, and the others are hydrogen atoms.

In the formula (M-1), p and q are each independently an integer of 0 to 4, and p + q> 0 is preferable. M and r are each independently an integer of 0 to 2, and 1 and 2 are preferable. n ² is 10 or more and 100000 or less. If n ² is less than 10, the solubility of the polymer in an alkali developing solution becomes too high, and the contrast between the exposed portion and the non-exposed portion can not be obtained, and a desired pattern can not be formed. On the other hand, if n ² is larger than 100000, the solubility of the polymer in an alkali developing solution becomes too small, and the exposed portion is not dissolved and a desired pattern can not be formed. From the viewpoint of solubility of the polymer in an alkali developing solution and the like, the upper limit of n ² is preferably 1000, more preferably 100. From the viewpoint of solubility and elongation improvement, the lower limit of n ² is preferably 20.

((A-3) polysiloxane)

(A-3) The polysiloxane is not particularly limited as long as it is a polymer having a siloxane bond, but a hydrolysis-condensation product of a hydrolyzable silane compound is preferable.

The term "hydrolyzable silane compound" generally refers to a silane compound that hydrolyzes to produce a silanol group or a siloxane condensate by heating in a temperature range of room temperature (about 25 ° C.) to 100 ° C. in the presence of an excess of water, Refers to a compound having a decomposer. Further, in the radiation-sensitive resin composition, the hydrolyzable group of some or all of the molecules of the partially hydrolyzable silane compound remains in the form of an unmolyzed hydrolysis and condensation with other hydrolyzable silane compounds, There may be.

The term "hydrolysis-condensation product" means a hydrolysis-condensation product in which some silanol groups of the hydrolyzed silane compound are condensed.

As the hydrolyzable silane compound, there may be mentioned a compound represented by the following formula (S-1) (hereinafter also referred to as "(S1) compound").

In the formula (S-1), R ^1d is an alkyl group having 1 to 6 carbon atoms. R ^2d is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, a 3,4- q ¹ is an integer of 0 to 20; n ³ is an integer of 0 to 3; Provided that when R ^1d and R ^2d are plural, plural R ^1d and R ^2d each independently satisfy the above definition.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^1d include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Of these, methyl and ethyl are preferable from the viewpoint of ease of hydrolysis.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^2d include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec- Methylbutyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, . The number of carbon atoms of the alkyl group having 1 to 20 carbon atoms is preferably 1 to 10, more preferably 1 to 3.

Examples of the fluorinated alkyl group having 1 to 20 carbon atoms include a trifluoromethyl group, a tetrafluoroethyl group, and a heptafluoropropyl group.

The compound (S-1) wherein n ³ is 1 is a silane compound having one non-hydrolyzable group and three hydrolyzable groups. Examples of the silane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriethoxysilane, but are not limited to, i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, naphtyltrimethoxysilane, phenyltriethoxysilane, naphthyltriethoxysilane, 3-isocyanopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3- -Isocyanopropyltriethoxysilane o-tolyltrimethoxysilane, m-tolyltrimethoxysilane, p-tolyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-methacryloxyethyltri Methoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxy 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 2-acryloxyethyltrimethoxysilane, 2-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, - methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, And trialkoxysilane compounds such as trifluoro butyltrimethoxysilane and 3- (trimethoxysilyl) propylsuccinic anhydride.

The compound (S-1) wherein n ³ is 2 is a silane compound having two non-hydrolyzable groups and two hydrolyzable groups. Examples of the silane compound include 3-methacryloxypropylmethyldimethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Aminopropylmethyldimethoxysilane,? -Isocyanatepropylmethyldimethoxysilane, and the like. .

The compound (S-1) wherein n ³ is 3 is a silane compound having three non-hydrolyzable groups and one hydrolyzable group. Examples of the silane compound include 3-methacryloxypropyldimethylmethoxysilane,? -Glycidoxypropyldimethylmethoxysilane,? -Aminopropyldimethylmethoxysilane,? -Isocyanatepropyldimethylmethoxysilane, and the like. .

The (S-1) compound wherein n ³ is 0 is a silane compound having four hydrolysable groups. Examples of the silane compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra-n-propoxysilane and tetra-i-propoxysilane.

(Synthesis of polysiloxane (hydrolysis and condensation))

The polysiloxane is usually heated in the temperature range of room temperature (about 25 ° C) to 100 ° C under the coexistence of a solvent and a catalyst as necessary in the coexistence of excess water, and a silane obtained by hydrolysis of the hydrolyzable silane compound It can be synthesized by condensing the play.

Examples of the solvent for the hydrolysis and condensation reaction 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 propionate, aromatic hydrocarbons, ketones, and other esters. These solvents may be used alone or in combination of two or more. As the catalyst for the hydrolysis and condensation reaction, an acid catalyst, a base catalyst and an alkoxide are preferable.

The lower limit of the polystyrene reduced weight average molecular weight (Mw) of the polysiloxane such as hydrolysis condensate is preferably 500, more preferably 1,000. On the other hand, the upper limit value is preferably 15,000, more preferably 10,000. By setting the Mw of the polysiloxane to the lower limit value or more, the film-forming property of the radiation-sensitive resin composition can be improved. On the other hand, by lowering the Mw of the polysiloxane to the upper limit value or less, deterioration of the developability of the radiation sensitive resin composition can be prevented.

((A-4) aromatic polyether)

(A-4) An aromatic polyether refers to a polymer having a structure in which an aromatic ring is linked by an ether bond (oxygen atom). The aromatic polyether preferably has a structural unit represented by the following formula (T-1), a structural unit represented by the following formula (T-2), or a combination thereof.

In the formula (T-1), R ^1e to R ^4e each independently represent a monovalent organic group having 1 to 12 carbon atoms. a to d are each independently an integer of 0 to 4;

In the formula (T-2), the definitions of R ^1e to R ^4e and a to d are the same as those of the formula (T-1). Y is a single bond, -SO ₂ - or -C (= O) -. R ^5e and R ^6e are each independently a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group. e and f are each independently an integer of 0 to 4; m1 is 0 or 1; However, m1 is when 0, R ^6e is not a cyano group.

Examples of the monovalent organic group having 1 to 12 carbon atoms represented by R ^1e to R ^4e in the formulas (T-1) and (T-2) include aliphatic or aromatic hydrocarbon groups, alkoxy groups and carboxy groups.

As the aromatic polyether (A-4), it is also preferable to have a structural unit represented by the following formula (T-3), a structural unit represented by the following formula (T-4)

In the formula (T-3), R ^7e and R ^8e each independently represent a monovalent organic group having 1 to 12 carbon atoms. Z represents a single bond, -O-, -S-, -SO ₂ -,> C═O, -CONH-, -COO-, a divalent hydrocarbon group of 1 to 12 carbon atoms, or a divalent At least a part of the hydrogen atoms of the hydrocarbon group is a group substituted with at least one member selected from the group consisting of a carboxy group, a hydroxyl group, a sulfo group and a fluorine atom. g and h are each independently an integer of 0 to 4; n is 0 or 1;

Examples of the monovalent organic group having 1 to 12 carbon atoms represented by R ^7e and R ^8e include an aliphatic or aromatic hydrocarbon group, an alkoxy group and a carboxy group.

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented by Z include a methane di- yl group, an ethane-1,1-diyl group, a propane-2,2-diyl group, And an alkanediyl group such as a 2,2-diyl group, an alkenediyl group, an areenediyl group, and the like.

The formula (T-4) of, R ^5e, R ^6e, Y, m1, e and f, R ^5e, R ^6e, Y, m1, e and f in each independently, the above formula (T-2) and The same meaning. ^{R 7e, R 8e, Z,} n, g and h are, each independently, the same as defined the above formula (T-3) in the ^{R 7e, R 8e, Z,} n, g and h.

The lower limit of the polystyrene reduced weight average molecular weight (Mw) of the aromatic polyether is preferably 3,000, more preferably 5,000. On the other hand, the upper limit value is preferably 20,000, more preferably 15,000. By setting Mw to the lower limit value or more, the film forming property of the radiation sensitive resin composition can be improved. On the other hand, lowering the Mw below the upper limit value can prevent deterioration of the developability of the radiation sensitive resin composition.

<[B] acid generator>

[B] The acid generator is a compound which generates an acid upon irradiation with radiation. As the radiation, visible rays, ultraviolet rays, deep ultraviolet rays, electron rays (charged particle rays), X rays and the like can be used. The acid generator [B] is not particularly limited as long as it generates an acid (for example, carbonic acid, sulfonic acid, etc.) upon irradiation with radiation. The acid generator [B] may be in the form of an acid generator, which will be described later, or may be in the form of a photo acid generator combined as a part of the polymer, or both of them.

Examples of the radiation-sensitive acid generator include oxime sulfonate compounds, onium salts, N-sulfonyloxyimide (sulfonimide compounds), halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, , Quinone diazide compounds, and the like. Among them, an oxime sulfonate compound and N-sulfonyloxyimide are preferable, and an oxime sulfonate compound is more preferable.

(Oxime sulfonate compound)

As the oxime sulfonate compound, a compound containing a group represented by the following formula (5) or (6) is preferable.

(In the formulas (5) and (6), R ¹⁴ or R ¹⁵ each represent an alkyl group, an alicyclic hydrocarbon group, an aryl group or a group in which at least a part of the hydrogen atoms of these groups are substituted with a substituent, Lt; / RTI &gt;

Examples of the alkyl group represented by R ¹⁴ or R ¹⁵ in the formulas (5) and (6) include a methyl group, an ethyl group, a n-propyl group, an i- Or a linear or branched alkyl group having 1 to 10 carbon atoms. Examples of the alicyclic hydrocarbon group represented by R ¹⁴ or R ¹⁵ include a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl group and cyclohexyl group. Examples of the aryl group represented by R ¹⁴ or R ¹⁵ include an aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group and a naphthyl group. Examples of the substituent which the alkyl group, alicyclic hydrocarbon group or aryl group may have include a halogen atom, an alkoxy group having 1 to 10 carbon atoms, an alicyclic group (such as a bridged group such as a 7,7-dimethyl-2-oxonorbornyl group, Preferably a bicycloalkyl group including an alicyclic group), and the like.

Examples of the oxime sulfonate group-containing compound represented by the above formula (5) include compounds represented by the following formulas (3-i) to (3-v), respectively.

(3-i) [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2- methylphenyl) acetonitrile] (3-iii) [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile] -Methylphenyl) acetonitrile], compound (3-iv) [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) v) [2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile] is commercially available.

Examples of the compound containing an oxime sulfonate group represented by the above formula (5) include N-sulfonyloxyimide (sulfonimide compound).

Examples of the N-sulfonyloxyimide (sulfonimide compound) include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4- N- (trifluoromethylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- Amide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, trifluoromethanesulfonic acid-1,8-naphthalimide and the like .

The radiation-sensitive acid generators may be used singly or in combination of two or more. The lower limit of the content of the radiation-sensitive acid generator in the radiation sensitive resin composition is preferably 0.1 part by mass, more preferably 1 part by mass, per 100 parts by mass of the polymer [A]. On the other hand, the upper limit is preferably 10 parts by mass, more preferably 5 parts by mass. When the content of the radiation sensitive acid generator is within the above range, the radiation sensitivity can be optimized, and the transparency of the resulting cured film becomes suitable.

&Lt; Compound [C] >

The [C] compound is a compound having two or more groups represented by the following formula (1) in one molecule. For example, in the case where Z in the formula (1) is a sulfur atom, as shown in the following diagrams, an acetylation reaction of a compound having an unsaturated double bond in which a carboxyl group is protected with an acetal group and a compound having a plurality of thiol groups in a molecule , And a compound containing two or more of these groups in one molecule is a [C] compound (a synthesis example of a compound (C-1)). Since such a compound contains a plurality of sulfur atoms in one molecule, the refractive index of the resulting cured film can be improved, and the transmittance can be improved in that the sulfur change of the film can be prevented.

For example, when Z in the formula (1) is a nitrogen atom, the compound [C] can be obtained by acetalizing a compound having a plurality of nitrogen atoms and a carboxyl group in one molecule.

In the formula (1), Z represents a sulfur atom or a nitrogen atom, X represents a divalent hydrocarbon group having 2 or more carbon atoms, and Y represents an organic group having an acid dissociable group or an acid dissociable group. * Indicates the binding position. These compounds may be used alone or in combination with each other.

The acid dissociable group in the organic group having an acid dissociable group or an acid dissociable group means a group capable of substituting a hydrogen atom such as a carboxy group or a phenolic hydroxyl group and dissociating by the action of an acid. An organic group refers to a group containing at least one carbon atom. In the acid dissociable group represented by Y, a carboxy group and phenolic hydroxyl group are generated by dissociation of the acid dissociable group.

Examples of the acid dissociable group represented by Y include groups represented by the following formulas (2), (3) and (4). When the organic group represented by Y includes an acid dissociable group having such a structure, the acid dissociable group may be dissociated by heating. Accordingly, the [C] compound containing such a group promotes the pattern formation in the developing step of the coated film formed from the radiation-sensitive resin composition after the exposure step.

In formula (2), R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrogen atom of a hydrocarbon group having 1 to 30 carbon atoms in the presence of a hydroxyl group, (Provided that R ¹ and R ² are not hydrogen atoms together). R ³ is an ether group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, or a group in which a part of hydrogen atoms contained in a hydrocarbon group having 1 to 30 carbon atoms is substituted with a hydroxyl group, a halogen atom or a cyano group. In the formula (3), R ⁴ to R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group of 1 to 12 carbon atoms. n is an integer of 1 or 2; In the formula (4), R &lt; ¹¹ &gt; To R ¹³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or an ether group having 1 to 12 carbon atoms. * Indicates the binding position.

Examples of the hydrocarbon group having 1 to 30 carbon atoms include a linear and branched alkyl group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 30 carbon atoms.

Examples of the linear and branched alkyl groups include linear, branched and cyclic alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, , and n-octadecyl; branched alkyl groups such as i-propyl, i-butyl, t-butyl, neopentyl, 2-hexyl and 3-hexyl groups .

Examples of the ether group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a t-butoxy group.

The alicyclic hydrocarbon group may be either a monocyclic or a polycyclic group, and examples thereof 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.

The aromatic hydrocarbon group may be a monocyclic ring, a monocyclic ring-linked structure, a condensed ring, or a structure in which an aromatic ring and an aliphatic hydrocarbon group are connected to each other. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a tolyl group, and a benzyl group.

As R &lt; ^{1 &} gt ;, a hydrogen atom is preferable. As R ² , a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable.

The R ³ is preferably a hydrocarbon group having 1 to 30 carbon atoms (an alkoxy group having 1 to 30 carbon atoms) containing an oxygen atom at the bond terminal of the bond, a straight chain and branched alkoxy group having 1 to 20 carbon atoms, More preferably a cycloalkoxy group having 1 to 20 carbon atoms, more preferably a linear and branched alkoxy group having 1 to 8 carbon atoms and a cycloalkoxy group having 3 to 8 carbon atoms.

Specific examples of the formula (2) include, for example, groups represented by the following (2-1) to (2-6). * Indicates the binding position.

Specific examples of the formula (3) include, for example, the groups shown in the following (3-1) to (3-4). * Indicates the binding position.

Specific examples of the formula (4) include, for example, the groups shown in the following (4-1) to (4-6). * Indicates the binding position.

An organic group having an acid dissociable group is represented by the following formula (7).

(Wherein W represents a divalent organic group, Y1 represents an acid dissociable group, and has the same meaning as in the formula (2), the formula (3) and the formula (4) )

As the divalent organic group represented by W, for example, at least one hydrogen atom of an alkylene group having 2 to 40 carbon atoms, a phenylene group, a naphthylene group, a divalent alicyclic group, and an alkylene group having 2 to 40 carbon atoms is substituted with a hydroxyl group, , A cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an acyl group having 1 to 12 carbon atoms, and an alkylene group having 2 to 40 carbon atoms may be substituted with a phenylene group, Bond, urethane bond or urea bond.

Specific examples of such an organic group having an acid-dissociable group include groups represented by the following (7-1) and (7-2). * Indicates the binding position.

In the formula (1), X represents a divalent hydrocarbon group having 2 or more carbon atoms. At least one hydrogen atom in the alkylene group having 2 to 40 carbon atoms, the phenylene group, the naphthylene group, the bivalent alicyclic group and the alkylene group having 2 to 40 carbon atoms is substituted with a hydroxyl group, a halogen atom, an amino group, a cyano group, An alkoxyl group having 1 to 12 carbon atoms, an acyl group having 1 to 12 carbon atoms, or an alkylene group having 2 to 40 carbon atoms may be interrupted by a phenylene group, an ester bond, an ether bond, an amide bond, a urethane bond or a urea bond .

The alkylene group having 2 to 40 carbon atoms is a group represented by the following formula (8): wherein R ^a is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and b is an integer of 1 to 39. * Indicates the binding position.

Specific examples of such [C] compounds include, for example, compounds represented by (C-1) to (C-9).

The lower limit of the content of the [C] compound in the radiation-sensitive resin composition is preferably 5 parts by mass, more preferably 10 parts by mass, further preferably 15 parts by mass, per 100 parts by mass of the polymer [A]. On the other hand, the upper limit is preferably 200 parts by mass, more preferably 100 parts by mass, still more preferably 40 parts by mass. By setting the content of the [C] compound within this range, it is possible to improve the patterning performance by increasing the difference in solubility between the irradiated portion of the radiation and the non-irradiated portion of the aqueous alkaline solution as the developer, for example.

In addition, since such a compound contains a plurality of sulfur atoms in one molecule, the refractive index of the resulting cured film can be improved, and the transmittance can be improved in that the change in sulfur of the film can be prevented.

&Lt; Other optional components >

The radiation sensitive resin composition may contain, if necessary, additives such as antioxidants, polyfunctional acrylates, surfactants, adhesion aids, inorganic oxide particles, compounds having a cyclic ether group, Solvents and other optional components. The other optional components may be used singly or in combination of two or more.

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and an amine-based antioxidant, but a phenol-based antioxidant is particularly preferable. The antioxidants may be used alone or in combination of two or more. The content of the antioxidant is preferably 0.1 part by mass to 10 parts by mass, particularly preferably 0.2 parts by mass to 5 parts by mass, relative to 100 parts by mass of the total amount of the polymer component [A] contained in the radiation sensitive resin composition of the present embodiment Mass part. When used in this range, the heat resistance of the interlayer insulating film formed of the radiation sensitive resin composition can be further improved.

As the antioxidant, an antioxidant described in Japanese Laid-Open Patent Publication No. 2011-227106 can be used.

The polyfunctional acrylate is preferably 100 parts by mass or less, more preferably 0.1 parts by mass or more and 80 parts by mass or less, more preferably 0.5 parts by mass or more and 50 parts by mass or less, and most preferably 1 part by mass or less, relative to 100 parts by mass of the polymer component [A] And not more than 25 parts by mass. When used in this range, the heat resistance and solvent resistance of the interlayer insulating film formed of the radiation sensitive resin composition can be further improved.

As polyfunctional acrylates, polyfunctional acrylates described in JP-A-2005-227525 can be used.

The surfactant is a component for enhancing the film-forming property of the radiation-sensitive resin composition. By containing the surfactant, the above-mentioned cell-free resin composition can improve the surface smoothness of the coating film, and as a result, it is possible to further improve the uniformity of the film thickness of the infrared shielding film formed of the above radiation- sensitive resin composition.

The adhesion aid is a component that improves the adhesion between the film formation object such as a substrate and the infrared ray shielding film. The adhesion aid is particularly useful for improving the adhesion between the inorganic substrate and the infrared shielding film.

As the adhesion aid, a functional silane coupling agent is preferred.

As the inorganic oxide particles, inorganic oxide particles which are oxides containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium can be used . The inorganic oxide particles described in JP-A-2011-128385 can be used.

&Lt; Compound having cyclic ether group >

The compound having a cyclic ether group is a compound having a cyclic ether group and different from the polymer having the polymer component [A]. The radiation sensitive resin composition contains a compound having a cyclic ether group, thereby promoting crosslinking of the polymer component and the like by the thermal reactivity of the compound having a cyclic ether group, and the infrared shielding film formed of the radiation sensitive resin composition The hardness of the radiation-sensitive resin composition can be further increased, and the radiation sensitivity of the radiation-sensitive resin composition can be increased.

As the compound having a cyclic ether group, a compound having two or more epoxy groups (oxiranyl group, oxetanyl group) in the molecule is preferable. As the compound having an epoxy group as the compound having a cyclic ether group, the compounds described in JP-A No. 2011-257537 can be used.

Among them, the compound having a cyclic ether group is preferably a compound having at least two oxetanyl groups in the molecule, and the isophthalic acid bis [(3-ethyloxetan-3-yl) methyl], 1,4-bis [ Epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1- EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.)) is more preferable.

The content of the cyclic ether group-containing compound is preferably 150 parts by mass or less, more preferably 0.5 parts by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less, based on 100 parts by mass of the polymer component [A] And more preferably 10 parts by mass or more and 25 parts by mass or less. By setting the content of the compound having a cyclic ether group within the above range, the hardness of the infrared shielding film formed of the radiation sensitive resin composition can be further increased.

As the acid diffusion controlling agent, it can be arbitrarily selected from those used as the chemically amplified resist. The radiation-sensitive resin composition contains an acid diffusion control agent, so that the diffusion length of the acid generated from the radiation-sensitive acid generator can be appropriately controlled by exposure, and the pattern developing property can be improved. As the acid diffusion controlling agent, the acid diffusion controlling agent disclosed in Japanese Patent Laid-Open Publication No. 2011-232632 can be used.

The content of the acid diffusion control agent is preferably 2 parts by mass or less, more preferably 0.001 parts by mass or more and 1 part by mass or less, more preferably 0.005 parts by mass or more and 0.2 parts by mass or less, based on 100 parts by mass of the polymer component [A] . When the content of the acid diffusion control agent is within the above range, the pattern developing property is further improved.

&Lt; Preparation method of radiation-sensitive resin composition >

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

<Solvent>

The solvent is suitably used so that the other components in the radiation-sensitive resin composition are uniformly dissolved or dispersed and do not react with the other components. Examples of such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates , Aromatic hydrocarbons, ketones, and other esters. As the solvent, a solvent described in JP-A-2011-232632 can be used.

<Cured film>

The cured film is formed of the radiation sensitive resin composition. Since the cured film is formed of the radiation sensitive resin composition, the cured film is excellent in insulation and corrosion resistance. Such a cured film having such characteristics can be used for, for example, a bank (partition wall) for defining an area for forming an interlayer insulating film, a planarizing film, and a light emitting layer of a display device, a spacer, a protective film, . The method of forming the cured film is not particularly limited, but it is preferable to apply the following method of forming a cured film.

&Lt; Method of forming a cured film &

The method of forming the cured film includes a step of forming a coating film on a substrate (hereinafter also referred to as a &quot; coating film formation step &quot;) using the radiation sensitive resin composition, a step of irradiating at least a part of the coating film with radiation (Hereinafter also referred to as a &quot; developing step &quot;) and a step of heating the developed coating film (hereinafter also referred to as &quot; heating step &quot; .

According to this forming method, a cured film excellent in radiation sensitivity and small in film thickness change amount in the non-visible portion and excellent in insulating property and corrosion prevention property can be obtained.

(Coating film forming step)

In this step, the radiation-sensitive resin composition is applied to a substrate to form a coating film. When the radiation sensitive resin composition contains a solvent, it is preferable to remove the solvent by pre-baking the coated 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, cyclic olefin, and hydrogenated products thereof. The conditions for the prebaking are usually 70 deg. C or more and 120 deg. C or less, and 1 minute or more and 10 minutes or less, depending on the kind of each component and the mixing ratio.

(Irradiation process)

In this step, at least a part of the coating film is exposed to radiation. When exposure is performed, exposure is usually performed through a photomask having a predetermined pattern. Examples of the radiation used for exposure include electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, and gamma ray, electron beams, and subordinate electron beams such as alpha rays. As the radiation, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable. The upper limit of the exposure dose is preferably 20,000 J / m 2, more preferably 10,000 J / m 2. On the other hand, the lower limit of the exposure dose may be, for example, 1 J / m 2, preferably 500 J / m 2, and more preferably 1,500 J / m 2. The exposure dose is a value obtained by measuring the intensity of the radiation at a wavelength of 365 nm by a light meter ("OAI model 356" manufactured by OAI Optical Associates).

(Developing step)

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 developer used in this 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. As the developer, an organic solvent such as a ketone-based organic solvent or an alcohol-based organic solvent may be used.

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 obtaining suitable developability.

Examples of the developing method include a puddle method, a dipping method, a swing dipping method, a shower method, and the like. The developing time varies depending on the composition of the radiation sensitive resin composition, but is usually from 10 seconds to 180 seconds.

Following this developing treatment, for example, water washing is carried out for 30 seconds to 90 seconds, followed by air drying with compressed air or compressed nitrogen, for example, to form a desired pattern.

(Heating process)

In this step, the developed coating film is heated. For the heating, the patterned thin film is heated by using a heating device such as a hot plate or oven to accelerate the curing reaction of the [A] polymer, thereby forming a cured film. The heating temperature is, for example, 120 DEG C or more and 250 DEG C or less. The heating time varies depending on the type of the heating apparatus, but is, for example, 5 minutes to 30 minutes or less for a hot plate and 30 minutes or more to 90 minutes or less for 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 a desired cured film can be formed on the surface of the substrate.

<Display element>

The display element is provided with the cured film. Examples of the display element include a liquid crystal display element and an organic EL display element.

The liquid crystal display element is constituted by, for example, a liquid crystal cell, a polarizing plate or the like. This liquid crystal display element is excellent in long-term reliability because the liquid crystal display element is provided with the cured film excellent in insulation property and corrosion prevention property.

A method of manufacturing a liquid crystal display element will be exemplified below. First, a pair (two pieces) of transparent substrates having a transparent conductive film (electrode) on one surface are prepared. An interlayer insulating film as a cured film, a spacer, a protective film, and the like are formed on the transparent conductive film of this substrate by the method described in the above &quot; Method of forming a cured film &quot; Then, an alignment film having liquid crystal alignability is formed on the substrate on which these cured films are formed. These substrates are arranged opposite to each other with a certain gap (cell gap) so that the liquid crystal aligning directions of the respective alignment films are orthogonal or antiparallel, with the side on which the alignment film is formed inside. Subsequently, the liquid crystal is filled in the cell gap defined by the surface (alignment film) and the spacer of the substrate, and the filling hole is sealed to constitute the liquid crystal cell. Then, a polarizing plate is bonded to both outer surfaces of the liquid crystal cell to obtain a liquid crystal display element.

On the other hand, in the organic electroluminescence element, the cured film formed of the radiation sensitive resin composition can be used as a planarizing film formed on the TFT element, a partition wall defining the light emitting portion, and the like.

[Example]

Hereinafter, the present invention will be described concretely based on examples, but the present invention is not limited to these examples. The weight average molecular weight (Mw) of the polymer component [A] was measured by the following method.

[Weight average molecular weight (Mw)]

Was measured by gel permeation chromatography (GPC) under the following conditions.

Device: "GPC-101" of Showa major

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

¹ H-NMR (analyzer: "ECX400P" Japan Electronics Corporation), ¹³ C-NMR (analyzing device: Japan Electronics Corporation "ECX400P"), FT-IR (analysis apparatus: Nicolet's "Nexus470") and thermal decomposition gas chromatography The structure of the polymer and the content of the structural units of the polymer ((JPS330) (Py), Agilent's GC6890A (GC) and Agilent's 5973Inert Content ratio).

<Synthesis Example of [A] Polymer>

[Synthesis Example 1] Synthesis of polymer (A-1)

A cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were charged. Subsequently, 13 parts by mass of methacrylic acid, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of? -Methyl-p-hydroxystyrene, 12 parts by mass of tetrahydrofurfuryl methacrylate, 15 parts by mass of N-cyclohexylmaleimide 15 And 10 parts by mass of n-lauryl methacrylate were charged, and after replacing with nitrogen, the temperature of the solution was raised to 70 占 폚 while stirring slowly, and the polymerization was carried out at this temperature for 5 hours. Thus, a polymer solution containing a polymer (A-1) as an acrylic resin having an (A-1) carboxy group as an alkali-soluble resin was obtained. The solid concentration of the polymer solution was 31.9 mass%, the polymer (A-1) had an Mw of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3.

[Synthesis Example 2] Synthesis of polymer (A-2)

After adding 80 parts by mass of propylene glycol monoethyl ether acetate as a polymerization solvent to the reaction vessel, the diamine compound and the tetracarboxylic acid derivative tetracarboxylic acid dianhydride were added to a polymerization solvent / RTI &gt; As the diamine compound, 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) was used, and after dissolving the 2,3,4,5-tetraacetic acid dianhydride, Carboxycyclopentyl acetic acid dianhydride (TCA) and 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester (TMHQ) in the presence of tetracarboxylic acid dianhydride And a composition of TCA: TMHQ = 95: 5 (molar ratio). Then, 90 parts by mol of tetracarboxylic acid dianhydride was added to 100 parts by mol of the total amount of the diamine compound. Thereafter, the mixture was reacted at 60 DEG C for 3 hours. Thus, about 100 g of a solution containing a polyimide (A-2) having a solution viscosity of 20 mPa · s at a solid concentration of 20 mass% and a polymer (A-2) as a polyamic acid as a polyimide precursor was obtained.

[Synthesis Example 3] Synthesis of polymer (A-3)

20 parts by mass of propylene glycol monomethyl ether was charged into a container equipped with a stirrer, and then 70 parts by mass of methyltrimethoxysilane and 30 parts by mass of tolyltrimethoxysilane were charged. The solution was heated did. After the solution temperature reached 60 占 폚, 0.15 parts by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged and heated to 75 占 폚 and maintained for 4 hours. Further, methanol was removed by ion exchange water and hydrolysis and condensation by this dissolution while maintaining the solution temperature at 40 占 폚 while maintaining this temperature. Thus, a polymer (A-3) as the polysiloxane (A-3) which is an alkali-soluble resin was obtained. The polymer (A-3) had an Mw of 6,000 and a molecular weight distribution (Mw / Mn) of 2.3.

[Synthesis Example 4] Synthesis of polymer (A-4)

1.7 parts by mass of 2,6-difluorobenzonitrile as a monomer, 0.5 parts by mass of 2,2-bis (4-hydroxyphenyl) propane, and 4.5 parts by mass of 5,5 , 0.5 parts by mass of bis (4-hydroxyphenyl) hexanoic acid and 2.2 parts by mass of potassium carbonate as a base, 100 parts by mass of N, N-dimethylacetoamide and 25 parts by mass of toluene were added as a solvent. Vacuum suction and nitrogen substitution were repeated to remove water in the system. Thereafter, while the reaction system was under nitrogen pressure, the temperature of the solution was raised to 130 캜 while stirring slowly, and the temperature was maintained for 4 hours to polymerize. Thus, a solution containing a polymer (A-4) as an aromatic polyether (A-4) which is an alkali-soluble resin was obtained. An ion-exchange resin was added to the obtained polymer solution, which was then stirred for 4 hours and filtered. The polymer solution was filtered, the solid was washed with N, N-dimethylacetoamide, the solution was recovered, and the obtained solution was reprecipitated with water to obtain the desired resin. The polymer (A-4) had an Mw of 12,000 and a molecular weight distribution (Mw / Mn) of 2.5.

[Synthesis Example 5] Synthesis of polymer (A-5)

A cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were charged. Subsequently, 13 parts by mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate, 57 parts by mass of methacrylic acid (3-ethyloxetan-3-yl) and 10 parts by mass of N-cyclohexylmaleimide were charged, After the substitution, the temperature of the solution was raised to 70 캜 while being slowly stirred, and the temperature was maintained for 5 hours to polymerize. Thus, a polymer solution containing a polymer (A-5) as an acrylic resin having an (A-1) carboxy group as an alkali-soluble resin was obtained. The solid content concentration of the polymer solution was 32.2% by mass, the polymer (A-5) had an Mw of 11,000 and a molecular weight distribution (Mw / Mn) of 2.4.

[Synthesis Example 6] Synthesis of polymer (A-6)

A cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were charged. Subsequently, 10 parts by mass of methacrylic acid, 5 parts by mass of acrylic acid, 10 parts by mass of styrene, 30 parts by mass of benzyl methacrylate, and 45 parts by mass of n-butyl methacrylate were charged, and after nitrogen substitution, The temperature was raised to 70 캜, and this temperature was maintained for 5 hours to polymerize. Thus, a polymer solution containing a polymer (A-6) as an acrylic resin having an (A-1) carboxy group as an alkali-soluble resin was obtained. The solid concentration of the polymer solution was 31.5% by mass, the polymer (A-6) had an Mw of 12,000 and a molecular weight distribution (Mw / Mn) of 2.4.

[Comparative Synthesis Example 1] Synthesis of Comparative Polymer (a-1) of Polymer [A]

7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were fed into a flask equipped with a condenser and a stirrer. Subsequently, 40 parts by mass of 1-ethoxyethyl methacrylate, 10 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, and 3 parts by mass of -methylstyrene dimer After the reaction mixture was purged with nitrogen, stirring was started slowly. 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 comparative polymer (a-1). The solid polymer concentration of the polymer solution was 31.8 mass%, the weight average molecular weight (Mw) of the comparative polymer (a-1) was 9,000, and the molecular weight distribution (Mw / Mn) was 2.3.

<Synthesis of [C] compound>

[Synthesis Example 7] Synthesis of Compound (C-1)

To a reaction vessel equipped with a stirrer were added 10 parts by mass of methacrylic acid (Sigma Aldrich), 8.2 parts by mass of 3,4-dihydrofuran (Sigma Aldrich), p-toluenesulfonic acid monohydrate (Sigma Aldrich Corp. ), And 20 parts by mass of tetrahydrofuran were placed, followed by stirring at room temperature for 2 hours. 5 parts by mass of sodium hydrogencarbonate was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated to obtain 17 parts by mass of tetrahydrofuran-2-methacrylate as a colorless liquid. To the reaction vessel equipped with another stirrer, 17 parts by mass of the obtained tetrahydrofuran-2-methacrylate-2-yl, 13.6 parts by mass of 4,4'-thiobisbenzenethiol (Sigma Aldrich Co.) ) And 100 parts by mass of tetrahydrofuran (manufactured by Sigma-Aldrich Co.), and the mixture was stirred at room temperature for 3 hours. After the obtained reaction product was washed with water, the unreacted material was distilled off under reduced pressure to obtain the intended compound (C-1) having an acid-dissociable group in a yield of 80%. ¹ H-NMR (300 MHz, CDCl 3) of Compound (C-1) was 隆 1.25 (6H, d), 隆 1.85-2.11 (8H, m), 隆 2.82-3.09 (2H, t),? 7.22 (2H, d),? 7.42 (2H, d).

[Synthesis Example 8] Synthesis of Compound (C-2)

To a reaction vessel equipped with a stirrer, 30 parts by mass of M-5400 (East Asia Synthesis), 8.2 parts by mass of ethyl vinyl ether (Sigma Aldrich), 0.02 parts by mass of p-toluenesulfonic acid monohydrate (Sigma Aldrich) And 20 parts by mass of tetrahydrofuran, and the mixture was stirred at room temperature for 2 hours. To the reaction mixture, 5 parts by mass of sodium hydrogencarbonate was added and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated to obtain 36 parts by mass of phthalic acid (1-ethoxyethyl) 2- (acryloyloxy) Water. 30 parts by mass of the obtained phthalic acid (1-ethoxyethyl) 2- (acryloyloxy) ethyl, 7.6 parts by mass of 1,4-benzene dimethanethiol (Sigma Aldrich) 62 parts by mass of potassium carbonate (Sigma-Aldrich) and 80 parts by mass of tetrahydrofuran (Sigma-Aldrich) were added and stirred at room temperature for 3 hours. After the obtained reaction product was washed with water, the unreacted material was distilled off under reduced pressure to obtain the intended compound (C-2) having an acid-dissociable group in a yield of 80%. ^The structure was identified with ¹ H-NMR (300 MHz, CDCL 3).

[Synthesis Example 9] Synthesis of Compound (C-3)

10 parts by mass of methacrylic acid (Sigma Aldrich Co.), 9.8 parts by mass of 3,4-dihydro-2H-pyran (Sigma-Aldrich Co.), and p-toluenesulfonic acid monohydrate Manufactured by Sigma-Aldrich), and 20 parts by mass of tetrahydrofuran, and the mixture was stirred at room temperature for 2 hours. 5 parts by mass of sodium hydrogencarbonate was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated to obtain 18 parts by mass of tetrahydro-2H-pyran-2-ylmethacrylate as a colorless liquid. 17 parts by mass of the resulting tetrahydro-2H-pyran-2-ylmethacrylate obtained, 9.6 parts by mass of TS-G (Shikoku Chemical), 34 parts by mass of potassium carbonate (Sigma Aldrich Co.) And 50 parts by mass of tetrahydrofuran (manufactured by Sigma-Aldrich Co.) were added, and the mixture was stirred at room temperature for 3 hours. After the obtained reaction product was washed with water, the unreacted material was distilled off under reduced pressure to obtain the desired compound (C-3) having an acid-dissociable group in a yield of 92%. ^The structure was identified by ¹ H-NMR (300 MHz, CDCL 3).

[Synthesis Example 10] Synthesis of Compound (C-4)

11.6 parts by mass of methacrylic acid (Sigma Aldrich), butyl vinyl ether (Sigma Aldrich), and 0.02 mass parts of p-toluenesulfonic acid monohydrate (Sigma Aldrich) as a catalyst were added to a reaction vessel equipped with a stirrer And 20 parts by mass of tetrahydrofuran were placed, and the mixture was stirred at room temperature for 2 hours. To the reaction mixture was added 5 parts by mass of sodium hydrogencarbonate, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated to obtain 22 parts by mass of 1-butoxyethyl methacrylate as a colorless liquid. 20 parts by mass of the resulting 1-butoxyethyl methacrylate and 18.8 parts by mass of tris- [(3-mercaptopropionyloxy) -ethyl] -isocyanurate (Sakai Chemical) were added to a reaction vessel equipped with another stirrer , 50 parts by mass of potassium carbonate (Sigma Aldrich) and 70 parts by mass of tetrahydrofuran (Sigma Aldrich) were added, and the mixture was stirred at room temperature for 3 hours. After the obtained reaction product was washed with water, the unreacted material was distilled off under reduced pressure to obtain the intended compound (C-4) having an acid-dissociable group in a yield of 87%. ^The structure was identified by ¹ H-NMR (300 MHz, CDCL 3).

[Synthesis Example 11] Synthesis of Compound (C-5)

30 parts by mass of 6 - ((6- (acryloyloxy) hexanoyl) oxy) hexanoic acid (Sigma Aldrich), 3,4-dihydro-2H-pyran (Sigma Aldrich Toluene sulfonic acid monohydrate (Sigma Aldrich) as a catalyst, and 20 parts by mass of tetrahydrofuran, and the mixture was stirred at room temperature for 2 hours. To the reaction mixture was added 5 parts by mass of sodium hydrogencarbonate and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated to obtain 6- (acryloyloxy) hexanoic acid 6- (1- (cyclohexyloxy) Oxy) -6-oxohexyl (38 parts by mass) as a colorless liquid. 20 parts by mass of the obtained 6- (acryloyloxy) hexanoic acid 6- (1- (cyclohexyloxy) ethoxy) -6-oxohexyl was added to a reaction vessel equipped with another stirrer, 6.4 parts by mass), 16 parts by mass of potassium carbonate (Sigma-Aldrich Co.) and 30 parts by mass of tetrahydrofuran (Sigma Aldrich) were added and stirred at room temperature for 3 hours. After the obtained reaction product was washed with water, the unreacted material was distilled off under reduced pressure to obtain the intended compound (C-5) having an acid-dissociable group in a yield of 90%. ^The structure was identified by ¹ H-NMR (300 MHz, CDCL 3).

[Synthesis Example 12] Synthesis of Compound (C-6)

10 parts by mass of methacrylic acid (Sigma Aldrich), 12.6 parts by mass of chlorotrimethylsilane (Sigma Aldrich), 9.5 parts by mass of 1-methylimidazole (Sigma Aldrich) And 20 parts by mass of tetrahydrofuran were added thereto, followed by stirring at room temperature for 2 hours. To the reaction mixture was added 5 parts by mass of sodium hydrogencarbonate, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and concentrated to obtain 17 parts by mass of trimethylsilyl methacrylate as a colorless liquid. 15 parts by mass of the obtained trimethylsilyl methacrylate, 9.1 parts by mass of TS-G (Shikoku Chemical), 33 parts by mass of potassium carbonate (Sigma Aldrich Co.), and 10 parts by mass of tetrahydrofuran 50 parts by mass was added thereto, followed by stirring at room temperature for 3 hours. The resulting reaction product was washed with water, and the unreacted material was distilled off under reduced pressure to obtain the desired compound (C-6) having an acid-dissociable group in a yield of 80%. ^The structure was identified by ¹ H-NMR (300 MHz, CDCL 3).

[Synthesis Example 13] Synthesis of Compound (C-7)

10 parts by mass of methacrylic acid (Sigma-Aldrich Co.), 9.8 parts by mass of 3,4-dihydro-2H-pyran (Sigma Aldrich Co.), and p-toluenesulfonic acid monohydrate Manufactured by Sigma-Aldrich), and 20 parts by mass of tetrahydrofuran, and the mixture was stirred at room temperature for 2 hours. 5 parts by mass of sodium hydrogencarbonate was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The insoluble matter was filtered and concentrated to obtain 18 parts by mass of tetrahydro-2H-pyran-2-ylmethacrylate as a colorless liquid. 15 parts by mass of the obtained tetrahydro-2H-pyran-2-ylmethacrylate obtained in the above, and 5- (trifluoromethyl) benzene-1,3-diamine (Sigma Aldrich) 60 parts by mass of potassium carbonate (Sigma-Aldrich) and 80 parts by mass of tetrahydrofuran (Sigma Aldrich) were placed in an oil bath at 60 ° C and stirred for 5 hours. The obtained reaction product was returned to room temperature, washed with water, and the unreacted material was distilled off under reduced pressure to obtain the desired compound (C-7) having an acid-dissociable group in a yield of 85%. ^The structure was identified by ¹ H-NMR (300 MHz, CDCL 3).

[Synthesis Example 14] Synthesis of Compound (C-8)

In a reaction vessel equipped with a stirrer, 20 parts by mass of 4-hydroxyphenyl methacrylate (Sigma Aldrich), 8.1 parts by mass of ethyl vinyl ether (Sigma Aldrich), and p-toluenesulfonic acid monohydrate (Sigma Aldrich 0.02 part by mass, and 20 parts by mass of tetrahydrofuran, and the mixture was stirred at room temperature for 2 hours. 5 parts by mass of sodium hydrogencarbonate was added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour, insoluble matter was filtered off and concentrated to obtain 26 parts by mass of 4- (1-ethoxyethoxy) methacrylate as a colorless liquid . 20 parts by mass of the obtained 4- (1-ethoxyethoxy) methacrylate, 7.6 parts by mass of TS-G (Shikoku Chemical), 28 parts by mass of potassium carbonate (Sigma Aldrich) And 40 parts by mass of tetrahydrofuran (manufactured by Sigma-Aldrich Co.) were added, and the mixture was stirred at room temperature for 3 hours. After the obtained reaction product was washed with water, the unreacted material was distilled off under reduced pressure to obtain the desired compound (C-8) having an acid-dissociable group in a yield of 89%. ^The structure was identified by ¹ H-NMR (300 MHz, CDCL 3).

[Synthesis Example 15] Synthesis of Compound (C-9)

To a reaction vessel equipped with a stirrer, 3,3 ', 3 "- (2,4,6-trioxo-1,3,5-triazine-1,3,5-triyl) ), 7.3 parts by mass of 3,4-dihydro-2H-pyran (Sigma Aldrich), 0.02 parts by mass of p-toluenesulfonic acid monohydrate (Sigma Aldrich) as a catalyst, And 20 parts by mass of hydrofuran were added thereto, followed by stirring at room temperature for 3 hours. To the reaction solution, 5 parts by mass of sodium hydrogencarbonate was added, and the mixture was stirred at room temperature for 1 hour. The insoluble matter was filtered and then concentrated. After the reaction product obtained was washed with water, the unreacted material was distilled off under reduced pressure to obtain the desired compound (C-9) having an acid-dissociable group in a yield of 70%. ^The structure was identified by ¹ H-NMR (300 MHz, CDCL 3).

&Lt; Preparation of radiation-sensitive resin composition >

The [B] acid generator and [D] antioxidant used for preparing the radiation sensitive resin compositions of the examples and comparative examples are shown below.

[B] acid generator

B-1: [(5-Propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile] ("IRGACURE PAG 103"

B-2: [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) - (2- methylphenyl) acetonitrile] ("IRGACURE PAG 121"

B-3: Trifluoromethanesulfonic acid-1,8-naphthalimide

B-4: A condensate of 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol)

B-5: PAI-101 manufactured by Midori Chemical Industry Co., Ltd.

B-6: CPI-100P

[D] Antioxidant

D-1: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (Adekastab AO-

D-2: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Adekastab AO-60 from ADEKA)

[E] Crosslinking agent

E-1: phenol novolak type epoxy resin ("JER 157S65" manufactured by Japan Epoxy Resins Co., Ltd.)

E-2: OGSOL PG-100 (manufactured by Osaka Gas Chemical Co., Ltd.)

E-3: ETERNACOLL OXBP (manufactured by Ube Industries, Ltd.)

[F] Thickener

F-1: Anthracure-UVS-1331 (manufactured by Kawasaki Chemical Industry Co., Ltd.)

[G] acid diffusion control agent

G-1: 1,5-Diazabicyclo [4.3.0] -5-nonene (Sigma Aldrich)

G-2: 2-phenylbenzoimidazole (Sigma Aldrich)

&Lt; Preparation of radiation-sensitive resin composition >

[Example 1]

, 3 parts by mass of the acid generator (B-1), 10 parts by mass of the [C] compound (C-1), and 3 parts by mass of the 3-glycidyl ether as the adhesion assistant were added to 100 parts by mass (solid content) And 3 parts by mass of cydyloxypropyltrimethoxysilane were mixed and dissolved in diethylene glycol ethyl methyl ether so as to have a solid content concentration of 30% by mass, followed by filtration through a membrane filter having a pore size of 0.2 탆 to prepare a radiation- did.

[Examples 2 to 21 and Comparative Examples 1 to 5]

[A] polymer, [B] acid generator, [C] compound, [D] antioxidant, [E] crosslinking agent, [F] sensitizer and [G] acid Sensitive adhesive compositions of Examples 2 to 21 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1, Further, in any of the radiation-sensitive resin compositions, 3 parts by mass of 3-glycidyloxypropyltrimethoxysilane was mixed as an adhesion aid in the same manner as in Example 1. In Table 1 and Table 2, &quot; - &quot; indicates that the corresponding components are not blended.

<Evaluation>

The cured film was formed from the radiation sensitive resin compositions of Examples 1 to 21 and Comparative Examples 1 to 5 and the radiation sensitivity, the residual film ratio, the refractive index, the transmittance, the relative dielectric constant (insulation) and the wiring corrosion Corrosion resistance) was evaluated. The evaluation results of Examples 1 to 21 and Comparative Examples 1 to 5 are shown in Tables 1 and 2.

[Evaluation of radiation sensitivity of radiation sensitive composition]

The radiation-sensitive resin composition was coated on a silicon substrate subjected to HMDS treatment at 60 占 폚 for 60 seconds using a spinner, and then prebaked on a hot plate at 90 占 폚 for 2 minutes to form a coating film having a film thickness of 3.0 占 퐉. This coating film was irradiated with a predetermined amount of ultraviolet light by a mercury lamp through a pattern mask having a line-and-space pattern of width 10 mu m using an MPA-600FA exposure machine manufactured by Canon Inc. Subsequently, development was carried out at 25 DEG C for 60 seconds using a developer consisting of 2.38% by mass aqueous solution of tetramethylammonium hydroxide, followed by water washing with ultrapure water for 1 minute. At this time, the minimum exposure amount capable of forming a line-and-space pattern having a width of 10 mu m was measured. When the measured value is less than 150 mJ / m &lt; 2 &gt;, the sensitivity is good, and when the measured value is not less than 150 mJ / m &

[Evaluation of residual film ratio]

A coating film was formed on the silicon substrate in the same manner as in &quot; Evaluation of radiation sensitivity of the radiation sensitive composition &quot;. Subsequently, a predetermined amount of ultraviolet light was irradiated to the coating film through a mask having a pattern of a line-and-space (one-to-one) of 100 mu m, and then the coating film was irradiated with ultraviolet light of 2.38 mass% in tetramethylammonium hydroxide aqueous solution at 25 DEG C And development processing was performed for 80 seconds. Subsequently, the substrate was washed with ultra-pure water for 1 minute and dried to form a pattern.

After development, the pattern height (T1) was measured by a stylus type film thickness measuring apparatus? -Step (manufactured by KLA Tencor Corporation). Thereafter, the patterned silicon substrate was heated in a clean oven at 220 캜 for 1 hour to obtain a pattern after heat curing. In the same manner, the pattern height t1 after thermosetting was measured. From these measured values, the residual film ratio {(T1-t1) / T1} x 100 [%] was calculated. At this time, it is good when the residual film ratio is 80% or more, and can be evaluated as poor when it is less than 80%.

[Evaluation of dielectric property (relative dielectric constant)] [

Using a spinner, a radiation-sensitive resin composition was coated on an SUS substrate and prebaked on a hot plate at 90 占 폚 for 2 minutes to form a coating film having a film thickness of 3.0 占 퐉. The above coated film was exposed using an exposure machine ("MPA-600FA" manufactured by Canon Inc.) so that the cumulative amount of irradiation was 9,000 J / m 2, and the exposed substrate was heated in a clean oven at 200 ° C for 30 minutes, . Then, a Pt / Pd electrode pattern was formed on the insulating film by a vapor deposition method to prepare a sample for measuring a dielectric constant. Using a electrode (HP16451B, manufactured by Yokogawa Buret Packard Co., Ltd.) and a Precision LCR meter (HP4284A manufactured by Yokogawa Buret Packard Co., Ltd.), a substrate having this electrode pattern was subjected to a CV method To measure the relative dielectric constant. When the relative dielectric constant is 3.7 or less, the insulation property is good, and when it is 3.7 or more, the insulation property is inferior.

[Evaluation of Wiring Corrosion]

Using a spinner, a radiation-sensitive resin composition was coated on a comb-shaped wiring board formed of aluminum, and then baked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. The above coated film was exposed using an exposure machine ("MPA-600FA" manufactured by Canon Inc.) so that the cumulative irradiation amount was 9,000 J / m 2, and the exposed substrate was heated in a clean oven at 200 ° C for 30 minutes, . The wiring board was allowed to stand under a moist heat condition of 65 占 폚 / 90% for 500 hours to conduct a wiring corrosion test. With respect to the substrate after the test, the presence or absence of the wiring corrosion was observed with an optical microscope (see also below), and the wiring corrosion resistance was evaluated based on the following criteria. A: No wiring corrosion, B: Wiring corrosion.

A: No wiring corrosion (see Fig. 1)

B: Wiring corrosion (see Fig. 2)

[Evaluation of refractive index]

Each of the radiation sensitive resin compositions prepared as Examples and Comparative Examples was coated on a glass substrate using a spinner and then prebaked on a hot plate at 90 占 폚 for 2 minutes to form a coating film having a film thickness of 3.0 占 퐉. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 3,000 J / m 2 by a mercury lamp.

Subsequently, this glass substrate was heated on a hot plate at 200 DEG C for 60 minutes. The refractive index of the obtained cured film was measured by "Prism Coupler Model 2010" manufactured by Metricon. The refractive index was measured at three wavelengths of 408 nm, 633 nm, and 828 nm, and the refractive index (nD) at the D line (589 nm) was determined using the Cauchy equation. The refractive indices of the F-line (486 nm) and the C-line (656 nm) were similarly calculated to calculate Abbe's number vD. The refractive index nD was evaluated as "A" when the refractive index was 1.56 or more and "B" when the refractive index was less than 1.56.

[Evaluation of transmittance]

Using the spinner, each resin composition for forming a cured film was applied onto a glass substrate, and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. The obtained coating film was irradiated with ultraviolet rays so that the cumulative amount of irradiation was 1,000 J / m 2 by a mercury lamp. Subsequently, this glass substrate was heated on a hot plate at 200 DEG C for 30 minutes to obtain a cured film. The transmittance of the resulting cured film was measured using an ultraviolet visible spectrophotometer (V-630, manufactured by JASCO Corporation). In this case, the case where the transmittance of light having a wavelength of 400 nm is 90% or more is evaluated as good (good transparency), and the case of less than 90% is evaluated as bad (poor transparency). The results are shown in the table.

In Table 1, "-" indicates that no addition is made.

In Table 2, &quot; - &quot; indicates that no addition was made.

As apparent from the results of Tables 1 and 2, the radiation-sensitive resin compositions and the cured films of Examples 1 to 21 are superior to the radiation-sensitive resin compositions and cured films of Comparative Examples 1 to 5 in radiation sensitivity, And the resulting cured film had a high refractive index and was excellent in transparency, insulation, and corrosion resistance.

Claims (7)

[A] Polymer,
[B] Radiation-sensitive acid generator, and
[C] a compound having two or more groups represented by the following formula (1) in one molecule:
Wherein the radiation-sensitive resin composition comprises:

(In the formula (1), Z represents a sulfur atom or a nitrogen atom, X represents a divalent hydrocarbon group having 2 or more carbon atoms, Y represents an organic group having an acid dissociable group or an acid dissociable group;
* Represents the binding position). The method according to claim 1,
Wherein the acid dissociable group is one group selected from the following formulas (2), (3) and (4):

(In the formula (2), R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms, a cyano group a group substituted with a (where, R ¹ and R ² a is not a hydrogen atom with a); R ³ is a group containing 1 to 30 carbon atoms in the ether group, carbon number of the hydrocarbon group of 1 to 30, or 1 to 30 carbon atoms Is a group in which a part of the hydrogen atoms of the hydrocarbon group is substituted with a hydroxyl group, a halogen atom or a cyano group;
In the formula (3), R ⁴ to R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; n is an integer of 1 or 2;
In the formula (4), R ¹¹ to R ¹³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or an ether group having 1 to 12 carbon atoms;
* Represents the binding position). The method according to claim 1,
Wherein the polymer [A] is an acrylic resin having a carboxyl group, a polyimide or polyimide precursor, a polysiloxane, an aromatic polyether or a combination thereof. The method according to claim 1,
Wherein the radiation-sensitive acid generator [B] is a compound containing a group represented by the following formula (5) or (6)

(In the formulas (5) and (6), R ¹⁴ or R ¹⁵ each represent an alkyl group, an alicyclic hydrocarbon group, an aryl group or a group in which at least a part of the hydrogen atoms of these groups are substituted with a substituent;
* Indicates the binding site). A cured film formed from the radiation sensitive resin composition according to any one of claims 1 to 4. A step of forming a coating film on a substrate,
A step of irradiating at least a part of the coating film with radiation,
A step of developing the coated film irradiated with the radiation,
And a step of heating the developed coating film,
A method for forming a cured film using the radiation sensitive resin composition according to any one of claims 1 to 4 for forming the coating film. A display device comprising the cured film according to claim 5.

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