JP6318957B2 - Radiation sensitive resin composition, cured film, method for forming the same, and display element - Google Patents

Description

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

  A display element such as a thin film transistor type liquid crystal display element or an organic electroluminescence element (organic EL element) generally has an insulating film such as an interlayer insulating film or a planarizing film. Such an insulating film is generally formed using a radiation-sensitive composition. As such a radiation-sensitive composition, a positive-type radiation-sensitive resin composition using an acid generator such as naphthoquinonediazide has been used from the viewpoint of patterning performance (see JP-A-2001-354822). In recent years, various radiation-sensitive compositions have been proposed.

  As an example, there has been proposed a positive chemical amplification material intended to form a cured film for a display element with higher sensitivity than the positive radiation sensitive resin composition using an acid generator such as naphthoquinonediazide. (See JP 2004-4669 A). This positive chemical amplification material contains a cross-linking agent, an acid generator, and an acid dissociable resin. The acid dissociable resin has a protecting group that can be dissociated by the action of an acid and is insoluble or hardly soluble in an aqueous alkali solution, but becomes soluble in an aqueous alkali solution by the dissociation of the protecting group by the action of an acid. . Further, a positive radiation sensitive composition containing an acetal structure and / or a ketal structure and a resin having an epoxy group and an acid generator has also been proposed (Japanese Patent Application Laid-Open Nos. 2004-264623 and 2011-215596). Gazette and JP-A-2008-304902).

  In these radiation-sensitive resin compositions, in addition to high radiation sensitivity, storage stability that does not change the viscosity even when stored for a long period of time is required. Further, a cured film formed from these radiation-sensitive resin compositions has Chemical resistance that is difficult to swell with a developer or the like is required. Furthermore, the pattern formed from this cured film was that the pattern was sufficiently adhered to the substrate after development and difficult to peel off, that the cured film had sufficient transparency, and that the pattern was placed after exposure. However, it is also required that the pattern is sufficiently adhered to the substrate and difficult to peel off.

  However, the above-mentioned conventional radiation-sensitive resin composition does not sufficiently satisfy these requirements.

JP 2001-354822 A JP 2004-4669 A JP 2004-264623 A JP 2011-215596 A JP 2008-304902 A

  The present invention has been made based on the above circumstances, and is excellent in radiation sensitivity and storage stability, chemical resistance, pattern adhesion after development, pattern adhesion after exposure, and transparency. An object of the present invention is to provide a radiation-sensitive resin composition capable of forming a cured film excellent in heat resistance, a cured film formed from the radiation-sensitive resin composition, a method for forming the cured film, and a display element including the cured film.

（式（１）中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、炭素数１から２０のアルキル基、脂環式炭化水素基、アリール基、これらの基が有する水素原子の一部又は全部が置換基で置換された基、又は−ＳｉＲ^Ａ _３である。Ｒ^Ａは、炭素数１から１０のアルキル基である。Ｒ^４は、単結合又は炭素数１から１２の２価の有機基である。）

（式（２）中、Ｒ^５は、炭素数１から２０のアルキル基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の一部又は全部が置換基で置換された基である。） The invention made in order to solve the above-mentioned problems includes: [A] a first structural unit having a group represented by the following formula (1) and a second structural unit having a crosslinkable group in the same or different polymers; And a radiation sensitive acid generator containing at least one compound selected from a compound having an oxime sulfonate group represented by the following formula (2) and an N-sulfonyloxyimide compound: It is a radiation sensitive resin composition.

(In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a hydrogen contained in these groups. A group in which some or all of the atoms are substituted with a substituent, or -SiR ^A _3. R ^A is an alkyl group having 1 to 10 carbon atoms, R ⁴ is a single bond or 1 to 12 carbon atoms. Divalent organic group.)

(In Formula (2), R ⁵ is an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a part or all of hydrogen atoms of these groups are substituted with a substituent. Group.)

  Another invention made to solve the above problems is a cured film formed from the radiation-sensitive resin composition.

  The method for forming a cured film of the present invention includes the step of forming a coating film on a substrate using the radiation-sensitive resin composition, the step of irradiating at least a part of the coating film, and the coating applied with radiation. A step of developing the film, and a step of heating the developed coating film.

  The present invention further includes a display element including the cured film.

  Here, the “alicyclic hydrocarbon group” means a hydrocarbon group containing only an alicyclic structure as a ring structure and not containing an aromatic ring structure, and includes a monocyclic alicyclic hydrocarbon group and a polycyclic hydrocarbon group. Includes both alicyclic hydrocarbon groups. However, it is not necessary to be composed only of the alicyclic structure, and a part thereof may include a chain structure. “Organic group” refers to a group containing at least one carbon atom.

  The radiation-sensitive resin composition of the present invention includes [A] a first structural unit having a group represented by the following formula (1) and a second structural unit having a crosslinkable group in the same or different polymers. A polymer component containing, and [B] a radiation sensitive acid generator containing at least one compound selected from a compound having an oxime sulfonate group represented by the following formula (2) and an N-sulfonyloxyimide compound. Therefore, a cured film having excellent radiation sensitivity and storage stability, chemical resistance, pattern adhesion after development, pattern adhesion after exposure and exposure, and transparency can be formed. The present invention can further provide a cured film formed from the radiation-sensitive resin composition, a method for forming the cured film, and a display element including the cured film. Therefore, the radiation-sensitive resin composition, the cured film and the method for forming the cured film, and the display element can be suitably used for manufacturing processes such as liquid crystal display devices, organic EL elements, and organic EL lighting.

<Radiation sensitive resin composition>
The radiation sensitive resin composition of the present invention includes [A] a first structural unit having a group represented by the following formula (1) and a second structural unit having a crosslinkable group in the same or different polymers. At least selected from a compound having an oxime sulfonate group represented by the following formula (2) and an N-sulfonyloxyimide compound (hereinafter also referred to as “[A] polymer component”). By containing a radiation-sensitive acid generator containing one compound (hereinafter also referred to as “[B] radiation-sensitive acid generator”), it has excellent radiation sensitivity and storage stability, chemical resistance, and after development. It is possible to form a cured film having excellent pattern adhesion and pattern adhesion after exposure. The reason why the radiation-sensitive resin composition exhibits the above-described effect by having the above-described configuration is not necessarily clear, but can be inferred as follows, for example. That is, when the [A] polymer component includes the first structural unit and the second structural unit, a structure in which silicon atoms are dispersed in the cured film is formed. As a result, it is considered that the chemical resistance of the cured film is improved, and the storage stability of the radiation-sensitive resin composition is improved by the presence of the silicon atom. In addition, it is considered that the above structure makes it difficult for a developer or the like to penetrate between the cured film and the substrate, and as a result, the pattern adhesion is improved.

  Moreover, since the said radiation sensitive resin composition has the said structure, while being able to improve a radiation sensitivity, the cured film excellent in transparency can be formed. Although it is not necessarily clear why the radiation-sensitive resin composition is used, the radiation sensitivity is improved because the radiation sensitive acid generator contains the specific compound. It is considered that the strength of the generated acid is moderately adjusted, and as a result, it is possible to suppress the residue of the substance that causes a decrease in the transmittance of the cured film.

  The group represented by the following formula (1) is preferably an acid dissociable group. In general, when an acid dissociable group containing an acetal group is used, it is known that the acid dissociable group containing an acetal group is dissociated into a compound having a vinyl bond. When such a compound having a vinyl bond remains in the film in a large amount, the transmittance of the cured film decreases. However, when the group represented by the following formula (1) is used as an acid-dissociable group, the compound having a vinyl group remaining in the cured film is reduced, so that a decrease in transmittance can be further suppressed. It becomes.

  Further, the radiation-sensitive resin composition of the present invention may contain a compound having [C] antioxidant and [D] cyclic ether group as suitable components, and within a range not impairing the effects of the present invention, Other optional components may be contained. Hereinafter, each component will be described in detail.

<[A] Polymer component>
[A] The polymer component includes a first structural unit having a group represented by the following formula (1) and a second structural unit having a crosslinkable group in the same or different polymers.

  [A] The polymer component has other structural units such as a structural unit having an acid dissociable group (hereinafter also referred to as “third structural unit”) in addition to the first structural unit and the second structural unit. It may be. [A] The polymer component may have two or more of each structural unit.

[First structural unit]
The first structural unit has a group represented by the following formula (1).

In the above formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or hydrogen contained in these groups. A group in which some or all of the atoms are substituted with a substituent, or —SiR ^A ₃ . R ^A is an alkyl group having 1 to 10 carbon atoms. R ⁴ is a single bond or a divalent organic group having 1 to 12 carbon atoms. When the group represented by the formula (1) is an acid dissociable group, R ¹ , R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, and R ⁴ is a single bond. It is preferable that

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ³ include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group and an n-butyl group; Examples thereof include branched alkyl groups such as propyl group, i-butyl group, sec-butyl group and t-butyl group. As said alkyl group, a C1-C10 alkyl group is preferable.

Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ¹ , R ² and R ³ include monocyclic alicyclic hydrocarbon groups such as cyclopentyl group and cyclohexyl group; adamantyl group and norbornyl group And polycyclic alicyclic hydrocarbon groups such as a tetracyclodecanyl group.

Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ , R ² and R ³ include a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4,6-trimethylphenyl group and a naphthyl group. As said aryl group, a C6-C10 aryl group is preferable.

  Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a nitro group, and a cyano group.

Examples of the divalent organic group having 1 to 12 carbon atoms represented by R ⁴ include a divalent hydrocarbon group, a group containing a hetero atom-containing group between carbon and carbon of the hydrocarbon group, and these groups. And a group in which part or all of the hydrogen atoms are substituted with a substituent.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

Examples of the divalent chain hydrocarbon group include:
Alkanediyl groups such as methanediyl, ethanediyl, propanediyl, butanediyl;
Alkenediyl groups such as ethenediyl group, propenediyl group, butenediyl group;
Examples include alkynediyl groups such as ethynediyl group, propynediyl group, and butynediyl group.

Examples of the divalent alicyclic hydrocarbon group include:
Monocyclic cycloalkanediyl groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group;
Monocyclic cycloalkenediyl groups such as cyclopropenediyl group and cyclobutenediyl group;
A polycyclic cycloalkanediyl group such as a norbornanediyl group, an adamantanediyl group, a tricyclodecanediyl group, a tetracyclododecanediyl group;
Examples thereof include polycyclic cycloalkenediyl groups such as norbornenediyl group and tricyclodecenediyl group.

Examples of the divalent aromatic hydrocarbon group include:
Arenediyl groups such as benzenediyl group, toluenediyl group, xylenediyl group, naphthalenediyl group;
Examples thereof include arenediyl (cyclo) alkanediyl groups such as benzenediylmethanediyl group and naphthalenediylcyclohexanediyl group.

  The hetero atom-containing group refers to a group having a divalent or higher valent hetero atom in the structure. The hetero atom-containing group may have one hetero atom or two or more hetero atoms.

  The diatomic or higher hetero atom of the hetero atom-containing group is not particularly limited as long as it is a hetero atom having a divalent or higher valence. For example, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, phosphorus An atom, a boron atom, etc. are mentioned.

Examples of the heteroatom-containing group include:
Groups consisting only of heteroatoms such as —SO—, —SO ₂ —, —SO ₂ O—, —SO ₃ —;
-CO-, -COO-, -COS-, -CONH-, -OCOO-, -OCOS-, -OCONH-, -SCONH-, -SCSNH-, -SCSS-, etc. Group and the like.

As said substituent, the group similar to what was illustrated in said R < ¹ >, R < ² > and R < ³ >, etc. are mentioned, for example.

  Examples of the group represented by the above formula (1) include trimethylsilyl group, t-butyldimethylsilyl group, diethylisopropylsilyl group, triisopropylsilyl group, dimethylhexylsilyl group, t-butyldiphenylsilyl group, and dimethylphenylsilyl group. , Triphenylsilyl group, tris (trimethylsilyl) silyl group, 2- (trimethylsilyl) ethyl group, (2-phenyl-2-trimethylsilyl) ethyl group, 2- (trimethylsilyl) ethoxymethyl group, [2- (trimethylsilyl) ethyl] A sulfonyl group, 2- (trimethylsilyl) ethoxycarbonyl group, etc. are mentioned.

  Among these, a trimethylsilyl group, a triethylsilyl group, an isopropylsilyl group, and a t-butyldimethylsilyl group are preferable.

  In addition, examples of the first structural unit include those represented by the following formula.

In the above formula, R ⁶ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[Second structural unit]
The second structural unit includes a crosslinkable group. The cured film formed from the radiation-sensitive resin composition has a second structural unit containing a crosslinkable group in the [A] polymer component, so that the polymers constituting the [A] polymer component or [ A] Strength can be increased by crosslinking between a polymer constituting the polymer component and a compound [D] having a cyclic ether group, which will be described later.

  Examples of the crosslinkable group include a group containing a polymerizable carbon-carbon double bond, a group containing a polymerizable carbon-carbon triple bond, an oxiranyl group, an oxetanyl group, an alkoxymethyl group, a formyl group, an acetyl group, and a dialkylamino. A methyl group, a dimethylolaminomethyl group, etc. are mentioned.

  The crosslinkable group is preferably at least one selected from the group consisting of a (meth) acryloyl group, an oxiranyl group, and an oxetanyl group. Thereby, the intensity | strength of the cured film formed from the said radiation sensitive resin composition can be raised more.

  Examples of the second structural unit include a structural unit represented by the following formula.

In the above formula, R ⁷ is a hydrogen atom or a methyl group.

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

  [A] The upper limit of the content ratio of the second structural unit with respect to all the structural units constituting the polymer component is preferably 80 mol%, more preferably 60 mol%. On the other hand, as a minimum of the above-mentioned content rate, 0.1 mol% is preferred and 1 mol% is more preferred. By making the content rate of a 2nd structural unit into the said range, the intensity | strength of the cured film formed can be raised effectively.

[Third structural unit]
The third structural unit has an acid dissociable group. This acid-dissociable group acts as a protecting group for protecting a carboxy group, a phenolic hydroxyl group and the like in the polymer. A polymer having such a protective group is usually insoluble or hardly soluble in an alkaline aqueous solution. Since this protecting group is an acid-dissociable group, this polymer becomes soluble in an alkaline aqueous solution when the protecting group is cleaved by the action of an acid.

  In the radiation-sensitive resin composition, the [A] polymer component has the third structural unit, whereby the radiation sensitivity is further improved, and the stability of the pattern shape obtained by development or the like is further improved.

  As the third structural unit containing an acid dissociable group, a structural unit represented by the following formula (3) or the following formula (4) is preferable.

In formula (3), R ⁸ is a hydrogen atom or a methyl group. R ⁹ and R ¹⁰ are each independently a hydrogen atom, a monovalent chain hydrocarbon group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms, or 4 to 20 carbon atoms. These are monovalent alicyclic hydrocarbon groups.

In formula (4), R ¹¹ is a hydrogen atom or a methyl group. R ^{12 to} R ¹⁸ are each independently a hydrogen atom or a monovalent chain hydrocarbon group having 1 to 12 carbon atoms. n is 1 or 2. When n is 2, the plurality of R ¹⁷ and R ¹⁸ may be the same or different.

Examples of the monovalent chain hydrocarbon group having 1 to 12 carbon atoms represented by R ⁹ and R ¹⁰ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, Examples include linear alkyl groups such as n-hexyl group and n-octyl group; branched alkyl groups such as i-propyl group, i-butyl group, t-butyl group and neopentyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms represented by R ⁹ and R ¹⁰ include a phenyl group and a naphthyl group.

Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ⁹ and R ¹⁰ include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, Monocyclic cycloalkyl groups such as methylcyclohexyl and ethylcyclohexyl groups; cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl Monocyclic cycloalkenyl groups such as an enyl group and cyclodecadiene; a bicyclo [2.2.2] octyl group, a tricyclo [5.2.1.0 ^2,6 ] decyl group, a tetracyclo [6.2.1. 1 ^3,6 . 0 ^2,7 ] dodecyl group, norbornyl group, a polycyclic cycloalkyl group such as adamantyl group and the like.

  Examples of the structural unit represented by the above formula (3) include structural units represented by the following formulas (3-1) to (3-10).

In the above formula (3-1) ~ (3-10), ^{R 8} is as defined in the above formula (3).

  Examples of the monomer that gives the structural unit represented by the formula (3) of the third structural unit include 1-ethoxyethyl methacrylate, 1-butoxyethyl methacrylate, 1- (tricyclodecanyloxy) methacrylate. Ethyl, 1- (pentacyclopentadecanylmethyloxy) ethyl methacrylate, 1- (pentacyclopentadecanyloxy) ethyl methacrylate, 1- (tetracyclododecanylmethyloxy) ethyl methacrylate, 1- (methacrylate Adamantyloxy) ethyl and the like.

In the above formula (4), examples of the monovalent chain hydrocarbon group having 1 to 12 carbon atoms represented by R ^{12 to} R ¹⁸ include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Linear alkyl groups such as i-propyl group, i-butyl group, sec-butyl group, t-butyl group and the like; linear alkenyl groups such as ethenyl group and n-propenyl group Group; branched alkenyl groups such as i-propenyl group and i-butenyl group.

  Examples of the structural unit represented by the above formula (4) include structural units represented by the following formulas (4-1) to (4-5).

In the above formulas (4-1) to (4-5), R ¹¹ has the same meaning as the above formula (4).

  As the monomer that gives the structural unit represented by the above formula (4), tetrahydro-2H-pyran-2-yl methacrylate that gives the structural unit represented by the above formula (4-3) is preferable.

  [A] The upper limit of the content ratio of the third structural unit with respect to all the structural units constituting the polymer component is preferably 80 mol%, more preferably 60 mol%, further preferably 40 mol%. On the other hand, as a minimum of the above-mentioned content rate, 0.1 mol% is preferred, 1 mol% is more preferred, and 10 mol% is still more preferred.

[Other structural units]
[A] The polymer component may have other structural units other than the first to third structural units as long as the effects of the present invention are not impaired.

  Other monomers that give structural units include, for example, unsaturated carboxylic acids and anhydrides thereof, (meth) acrylic acid esters having a hydroxyl group, (meth) acrylic acid chain alkyl esters, and (meth) acrylic acid alicyclic rings. Examples thereof include unsaturated esters having a formula ester, (meth) acrylic acid aryl ester, unsaturated aromatic compound, N-substituted maleimide, conjugated diene, tetrahydrofuran skeleton and the like.

As unsaturated carboxylic acid and its anhydride, for example,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid, or anhydrides thereof;
Mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, mono 2- (methacryloyloxy) ethyl hexahydrophthalate mono [ (Meth) acryloyloxyalkyl] ester;
mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate;
5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2. 1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, Unsaturation having a carboxyl group such as 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride Examples thereof include polycyclic compounds or anhydrides thereof.

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

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

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

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

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

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like.

  Examples of the N-substituted maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-tolylmaleimide, N-naphthylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-benzylmaleimide and the like.

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

  Examples of the unsaturated compound having a tetrahydrofuran skeleton include 3-tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like. It is done.

  [A] The upper limit of the content of other structural units with respect to all structural units constituting the polymer component is preferably 50 mol%, more preferably 30 mol%, and even more preferably 25 mol%. On the other hand, as a minimum of the above-mentioned content rate, 5 mol% is preferred and 10 mol% is more preferred. By setting the content ratio of other structural units in the above range, a radiation-sensitive resin composition that optimizes solubility in an alkaline aqueous solution and is superior in radiation sensitivity can be obtained.

<[A] Polymer component synthesis method>
[A] The polymer component can be produced, for example, by polymerizing a monomer corresponding to a predetermined structural unit in a suitable solvent using a radical polymerization initiator. For example, a method of dropping a solution containing a monomer and a radical initiator into a reaction solvent or a solution containing the monomer to cause a polymerization reaction, a solution containing the monomer, and a solution containing the radical initiator Separately, a method of dropping a reaction solvent or a monomer-containing solution into a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator, It is preferable to synthesize by a method such as a method of dropping it into a reaction solvent or a solution containing a monomer to cause a polymerization reaction.

  [A] Examples of the solvent used for the polymerization reaction of the polymer component include the same solvents as those exemplified in the section “<Preparation of radiation-sensitive resin composition>” described later.

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

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

  [A] The upper limit of polystyrene-equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the polymer is preferably 100,000, more preferably 50,000. On the other hand, the lower limit of Mw is preferably 2,000, and more preferably 5,000. [A] By making Mw of a polymer component into the said range, the radiation sensitivity and developability of the said radiation sensitive resin composition can be improved more.

  [A] The upper limit of the number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer component is preferably 100,000, more preferably 50,000. On the other hand, the lower limit of Mn is preferably 2,000, and more preferably 5,000. [A] By making Mn of a polymer into the said range, the cure reactivity at the time of hardening of the coating film of the said radiation sensitive resin composition can be improved.

  [A] The upper limit of the molecular weight distribution (Mw / Mn) of the polymer component is preferably 3, and more preferably 2.6. [A] By making Mw / Mn of a polymer component below the above upper limit, the sensitivity of the obtained cured film can be further increased.

<[B] Radiation sensitive acid generator>
[B] The radiation-sensitive acid generator is a compound that generates an acid upon irradiation with radiation, and is at least selected from a compound containing an oxime sulfonate group represented by the following formula (2) and an N-sulfonyloxyimide compound. One of them can be used, and examples of the radiation include visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. When the radiation-sensitive resin composition contains [B] a radiation-sensitive acid generator, the radiation-sensitive resin composition can exhibit radiation-sensitive characteristics and has good radiation sensitivity. it can. As the containing form of the [B] radiation sensitive acid generator in the radiation sensitive resin composition, as described later, even in the form of a compound (hereinafter, referred to as “[B] radiation sensitive acid generator” as appropriate) [A] Either a form incorporated as a part of the polymer constituting the polymer component or the like, or both forms thereof may be used. These [B] radiation sensitive acid generators may be used alone or in combination of two or more.

  [B] Radiation sensitive acid generator includes oxime sulfonate compound containing oxime sulfonate group, N-sulfonyloxyimide compound, onium salt, halogen-containing compound, diazomethane compound, sulfone compound, sulfonate ester compound, carboxylate ester You may contain a compound etc.

[Oxime sulfonate compound]
An oxime sulfonate compound is a compound containing an oxime sulfonate group represented by the following formula (2).

In Formula (2), R ⁵ represents an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group or an alkyl group, a monovalent alicyclic hydrocarbon group, a part or all of the hydrogen atoms of the aryl group. It is a group substituted with a substituent.

The alkyl group represented by R ^5, preferably a linear or branched alkyl group having 1 to 12 carbon atoms.

The monovalent alicyclic hydrocarbon group represented by R ⁵ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms.

The aryl group represented by R ⁵ is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group.

  As said substituent, a C1-C5 alkyl group, an alkoxy group, an oxo group, a halogen atom etc. are mentioned, for example.

  Examples of the compound containing a group represented by the above formula (2) include oxime sulfonate compounds represented by the following formulas (2-1) to (2-3).

In the above formulas (2-1) to (2-3), R ¹⁹ has the same definition as R ^{5 in the} above formula (2).
In the above formulas (2-1) and (2-2), R ²⁰ is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms.
In formula (2-3), X is an alkyl group, an alkoxy group, or a halogen atom. i is an integer of 0-3. However, when i is 2 or 3, a plurality of X may be the same or different.

  The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

  Examples of the oxime sulfonate compound represented by the above (2-3) include compounds represented by the following formulas (2-4) to (2-8).

  The compounds represented by the above formulas (2-4) to (2-8) are (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile and (5-octyl), respectively. Sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p -Toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, 4-methylphenylsulfonyloxyimino -Α- (4-methoxyphenyl) acetoni Is Lil, available as a commercial product.

[N-sulfonyloxyimide compound]
Examples of the N-sulfonyloxyimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoro). Methylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) ) Phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) Diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) ) Diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1]. ] Hept-5-ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro) Butanesulfonyloxy) bicyclo [2. .1] Hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphor Sulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 -Methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) Xyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-fluoro Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimi N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2 2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3 -Dicarboximide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (camphorsulfonyloxy) naphthalimide, N- (4-methylphenylsulfonyloxy) naphthalimide, N- (phenylsulfonyloxy) naphthalimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthalimide, N- (4-F Orophenylsulfonyloxy) naphthalimide, N- (pentafluoroethylsulfonyloxy) naphthalimide, N- (heptafluoropropylsulfonyloxy) naphthalimide, N- (nonafluorobutylsulfonyloxy) naphthalimide, N- (ethylsulfonyloxy) ) Naphthalimide, N- (propylsulfonyloxy) naphthalimide, N- (butylsulfonyloxy) naphthalimide, N- (pentylsulfonyloxy) naphthalimide, N- (hexylsulfonyloxy) naphthalimide, N- (heptylsulfonyloxy) ) Naphthalimide, N- (octylsulfonyloxy) naphthalimide, N- (nonylsulfonyloxy) naphthalimide and the like.

  As the onium salt, the halogen-containing compound, the diazomethane compound, the sulfone compound, the sulfonic acid ester compound, the carboxylic acid ester compound, and the like described above, the compounds described in JP2011-232632A can be used.

  [B] As the radiation-sensitive acid generator, compounds represented by the above formulas (2-4) to (2-8) among the oxime sulfonate compounds represented by the above formula (2) are preferable. It is also preferable to include an N-sulfonyloxyimide compound.

  The said radiation sensitive resin composition can improve radiation sensitivity by using the compound illustrated as a [B] radiation sensitive acid generator.

  [A] The upper limit of the content of the [B] radiation-sensitive acid generator with respect to 100 parts by mass of the polymer component is preferably 10 parts by mass, and more preferably 5 parts by mass. On the other hand, as a minimum of the above-mentioned content, 0.1 mass part is preferred and 1 mass part is more preferred. [B] By setting the content of the radiation-sensitive acid generator within the above range, the sensitivity of the radiation-sensitive resin composition can be optimized, and a cured film having high surface hardness can be formed while maintaining transparency.

<Other optional components>
In addition to the above [A] component and [B] component, the radiation sensitive resin composition contains [C] antioxidant and [D] cyclic ether group as necessary within the range not impairing the effects of the present invention. And other optional components such as [E] acid diffusion controller, [F] surfactant, [G] adhesion aid, and [H] solvent. Other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

<[C] Antioxidant>
[C] Antioxidant is a component that suppresses the breakage of the bond of polymer molecules by capturing radicals generated by exposure or heating, or by decomposing a peroxide generated by oxidation.

  By containing the [C] antioxidant, the radiation-sensitive resin composition suppresses the degradation degradation of the polymer molecules in the cured film formed from the radiation-sensitive resin composition, and the light resistance, etc. Can be improved.

  [C] Examples of the antioxidant include compounds having a hindered phenol structure, compounds having a hindered amine structure, compounds having an alkyl phosphite structure, compounds having a thioether structure, and the like. These [C] antioxidants may be used alone or in combination of two or more.

  Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-dithione). -Tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-tert-butyl-4- Hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1, 6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide) 3,3 ′, 3 ′, 5 ′, 5′-hexa-tert-butyl-a, a ′, a ′-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (Octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) Propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6- Xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio)- 1,3 5-triazin-2-ylamine) phenol, and the like.

As a commercial item of the compound having the hindered phenol structure, for example,
"ADK STAB AO-20", "ADK STAB AO-30", "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-70", "ADK STAB AO-80", " ADK STAB AO-330 "(above, ADEKA);
“Sumilizer GM”, “sumilizer GS”, “sumilizer MDP-S”, “sumilizer BBM-S”, “sumilizer WX-R”, “sumilizer GA-80” (above, Sumitomo Chemical);
"IRGANOX1010", "IRGANOX1035", "IRGANOX1076", "IRGANOX1098", "IRGANOX1135", "IRGANOX1330", "IRGANOX1726", "IRGANOX1425WL", "IRGANOX1520L", "IRGANOX245", "IRGANOX245", "IRGANOX245", "IRGANOX245", "IRGANOX245" “IRGAMOD295” (Ciba Japan)
“Yoshinox BHT”, “Yoshinox BB”, “Yoshinox 2246G”, “Yoshinox 425”, “Yoshinox 250”, “Yoshinox 930”, “Yoshinox SS”, “Yoshinox TT”, “Yoshinox 917”, “Yoshinox 314” ( As above, API Corporation) and the like can be mentioned.

  In these, as [C] antioxidant, it is preferable to have a hindered phenol structure. [C] When the antioxidant has a hindered phenol structure, the degradation degradation of the polymer molecules in the cured film formed from the radiation-sensitive resin composition can be further suppressed. Among the compounds having a hindered phenol structure, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-tert-butyl- 4-Hydroxybenzyl) -isocyanurate is more preferred.

  [A] As an upper limit of content of [C] antioxidant with respect to 100 mass parts of polymer components, 15 mass parts is preferred, 10 mass parts is more preferred, and 5 mass parts is still more preferred. On the other hand, as a minimum of the above-mentioned content, 0.1 mass part is preferred and 0.2 mass part is more preferred. [C] By making content of antioxidant into the said range, the cracking degradation of the cured film formed from the said radiation sensitive resin composition can be suppressed more effectively.

<[D] Compound having cyclic ether group>
[D] A compound having a cyclic ether group (hereinafter also referred to as “[D] compound”) is a compound having a cyclic ether group and different from the polymer of the [A] polymer component. The radiation-sensitive resin composition contains the [D] compound, thereby promoting the crosslinking of the [A] polymer component and the like by the thermal reactivity of the [D] compound, and formed from the radiation-sensitive resin composition. The hardness of the cured film can be increased, and the radiation sensitivity of the radiation-sensitive resin composition can be further increased.

  [D] As the compound, a compound having two or more epoxy groups (oxiranyl group, oxetanyl group) in the molecule is preferable.

Examples of the [D] compound having two or more oxiranyl groups in the molecule include:
Bisphenol type diglycidyl ethers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ethers;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Aliphatic polyglycidyl ethers;
Examples include epoxidized soybean oil and epoxidized linseed oil. These [D] compounds may be used alone or in combination of two or more.

As a commercial item of a [D] compound which has two or more oxiranyl groups in a molecule, for example,
As the bisphenol A type epoxy resin, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1003”, “Epicoat 1004”, “Epicoat 1007”, “Epicoat 1009”, “Epicoat 1010”, “Epicoat 828” (above, Japan) Epoxy resin)
As bisphenol F type epoxy resin, “Epicoat 807” (Japan Epoxy Resin Co., Ltd.) and the like;
Examples of phenol novolac type epoxy resins include “Epicoat 152”, “Epicoat 154”, “Epicoat 157S65” (Japan Epoxy Resin Co., Ltd.), “EPPN201”, “EPPN202” (Japan Nippon Kayaku Co., Ltd.) and the like;
Examples of cresol novolac type epoxy resins include “EOCN102”, “EOCN103S”, “EOCN104S”, “EOCN1020”, “EOCN1025”, “EOCN1027” (Nippon Kayaku Co., Ltd.), Epicort 180S75 (Japan Epoxy Resin), etc .;
As the polyphenol type epoxy resin, “Epicoat 1032H60”, “Epicoat XY-4000” (Japan Epoxy Resin Co., Ltd.) and the like;
Cycloaliphatic epoxy resins include “CY-175”, “CY-177”, “CY-179”, “Araldite CY-182”, “Araldite 192”, “Araldite 184” (above, Ciba Specialty Chemicals) ), “ERL-4234”, “ERL-4299”, “ERL-4221”, “ERL-4206” (above U.C.C.), “Shaudyne 509” (Showa Denko), “Epicron 200” ”,“ Epicron 400 ”(above, Dainippon Ink Co., Ltd.),“ Epicoat 871 ”,“ Epicoat 872 ”(above, Japan Epoxy Resin Co., Ltd.),“ ED-5661 ”,“ ED-5562 ”(above, Celanese Coating) Etc.);
Examples of the aliphatic polyglycidyl ether include “Epolite 100MF” (Kyoeisha Chemical Co.), “Epiol TMP” (Nippon Yushi Co., Ltd.) and the like.

  [D] compounds having two or more oxetanyl groups in the molecule include, for example, bis [(3-ethyloxetane-3-yl) methyl] isophthalate, 1,4-bis [(3-ethyloxetane-3 -Yl) methoxymethyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [1-ethyl- (3-oxetanyl) methyl] ether (also known as bis (3-ethyl) -3-oxetanylmethyl) ether), 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-[1,3- (2-methylenyl) propanediylbis (oxymethylene)] bis -(3-ethyloxetane), 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetani Methoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3-oxetanylmethyl) ) Ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ) Ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, xylenebisoxetane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3) − Xetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether Dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ) Ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3) -Oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3- Ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, and the like.

  Among these, the [D] compound is preferably a compound having two or more oxetanyl groups in the molecule, such as bis [(3-ethyloxetane-3-yl) methyl] isophthalate, 1,4-bis [ (3-Ethyloxetane-3-yl) methoxymethyl] benzene is more preferred.

  [A] The upper limit of the content of the [D] compound with respect to 100 parts by mass of the polymer component is preferably 150 parts by mass, more preferably 100 parts by mass, further preferably 50 parts by mass, and particularly preferably 25 parts by mass. On the other hand, as a minimum of the above-mentioned content, 0.5 mass part is preferred, 1 mass part is more preferred, and 10 mass parts is still more preferred. [D] By making content of a compound into the said range, the hardness of the cured film formed from the said radiation sensitive resin composition can be raised more.

<[E] acid diffusion controller>
[E] The acid diffusion control agent can be arbitrarily selected from those used in chemically amplified resists. The radiation-sensitive resin composition can appropriately control the diffusion length of the acid generated from the [B] radiation-sensitive acid generator by exposure by containing the [E] acid diffusion controller. Developability can be improved.

  [E] As the acid diffusion control agent, for example, an acid diffusion control agent described in JP2011-232632A can be used.

  [A] The upper limit of the content of the [E] acid diffusion controller relative to 100 parts by mass of the polymer component is preferably 2 parts by mass, more preferably 1 part by mass, and even more preferably 0.2 parts by mass. On the other hand, as a minimum of the above-mentioned content, 0.001 mass part is preferred and 0.005 mass part is more preferred. [E] By making content of an acid diffusion control agent into the said range, pattern developability improves more.

<[F] Surfactant>
[F] Surfactant is a component which improves the film-forming property of the said radiation sensitive resin composition. The said radiation sensitive resin composition can improve the surface smoothness of a coating film by containing [F] surfactant, As a result, the film thickness of the cured film formed from the said radiation sensitive resin composition Uniformity can be further improved.

  Examples of [F] surfactants include fluorine-based surfactants and silicone-based surfactants. These [F] surfactants may be used alone or in combination of two or more. [F] As the surfactant, for example, surfactants described in JP 2011-18024 A can be used.

  [A] The upper limit of the content of the [F] surfactant relative to 100 parts by mass of the polymer component is preferably 3 parts by mass, more preferably 2 parts by mass, and even more preferably 1 part by mass. On the other hand, as a minimum of the above-mentioned content, 0.01 mass part is preferred and 0.05 mass part is more preferred. [F] By making content of surfactant into the said range, the film thickness uniformity of the coating film formed can be improved more.

<[G] Adhesion aid>
[G] Adhesion aid is a component that improves the adhesion between a film-forming object such as a substrate and a cured film. [G] The adhesion aid is particularly useful for improving the adhesion between the inorganic substrate and the cured film. Examples of the inorganic substance include silicon compounds such as silicon, silicon oxide, and silicon nitride, and metals such as gold, copper, and aluminum.

  [G] As the adhesion assistant, a functional silane coupling agent is preferable. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group. These [G] adhesion assistants may be used alone or in combination of two or more.

  Examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycidoxypropyl. Examples include trimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Among these, as the functional silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane is preferred.

  [A] The upper limit of the content of the [G] adhesion assistant with respect to 100 parts by mass of the polymer component is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 10 parts by mass. On the other hand, as a minimum of the above-mentioned content, 0.5 mass part is preferred and 1 mass part is more preferred. [G] By setting the content of the adhesion assistant in the above range, the adhesion between the formed cured film and the substrate is further improved.

<[H] solvent>
[H] As the solvent, a solvent that uniformly dissolves or disperses other components in the radiation-sensitive resin composition and does not react with the other components is preferably used. Examples of such [H] solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ether pros. Pionate, aromatic hydrocarbons, ketones, other esters and the like can be mentioned. [H] As the solvent, the solvents described in JP2011-232632 can be used.

<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition is dissolved or mixed by, for example, mixing [A] a polymer component and [B] a radiation-sensitive acid generator, if necessary, a suitable component and other optional components in a [H] solvent. Prepared in a dispersed state.

<Curing film>
The cured film of the present invention is formed from the radiation sensitive resin composition. Since the cured film is formed from the radiation-sensitive resin composition, the cured film is excellent in radiation sensitivity, chemical resistance, transparency, pattern adhesion after development, and pattern adhesion after exposure. The cured film having such characteristics is, for example, an interlayer insulating film, a planarization film, a bank (partition wall) that defines a region for forming a light emitting layer, a spacer, a protective film, a color, for an electronic device such as a display element. It can be used for coloring patterns for filters. In addition, although it does not specifically limit as a formation method of the said cured film, It is preferable to apply the formation method of the cured film demonstrated below.

<Method for forming cured film>
The said radiation sensitive resin composition can be used suitably for formation of a cured film.

  The method for forming a cured film according to the present invention includes a step of forming a coating film on a substrate using the radiation-sensitive resin composition (hereinafter also referred to as “coating film forming step”), and at least a part of the coating film. A step of irradiating radiation (hereinafter also referred to as “irradiation step”), a step of developing a coating film irradiated with radiation (hereinafter also referred to as “development step”), and a step of heating the developed coating film (hereinafter referred to as “irradiation step”) , Also referred to as “heating step”).

  According to the method of forming the cured film, a cured film excellent in radiation sensitivity, chemical resistance, transparency, pattern adhesion after development, and pattern adhesion after exposure can be easily formed.

[Coating film forming process]
In this step, the radiation-sensitive resin composition is used and applied onto a substrate to form a coating film. When the said radiation sensitive resin composition contains a solvent, it is preferable to remove a solvent by prebaking an application surface.

  Examples of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof. The pre-baking conditions are usually 70 ° C. or higher and 120 ° C. or lower and 1 minute or longer and 10 minutes or shorter, although it varies depending on the type of each component, the mixing ratio, and the like.

[Irradiation process]
In this step, at least a part of the coating film is irradiated with radiation and exposed. When exposing, it exposes normally through the photomask which has a predetermined pattern. The radiation used for exposure is preferably radiation having a wavelength in the range of 190 nm or more and 450 nm or less, and more preferably radiation containing ultraviolet light of 365 nm. As an upper limit of the exposure amount, 6,000 J / m ² is preferable, and 1,800 J / m ² is more preferable. On the other hand, the lower limit of the exposure dose is preferably ^{500J / m 2, 1,500J / m} 2 is more preferable. This exposure amount is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (“OAI model 356” manufactured by OAI Optical Associates).

[Development process]
In this step, the coating film irradiated with radiation is developed. By developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern.

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

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

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

  Following such development processing, for example, after washing with running water for 30 seconds to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

  It is preferable that the film thickness change rate of the film thickness after development with respect to the film thickness of the coating film before development is 90% or more. According to the formation method using the radiation-sensitive resin composition, since the amount of change in the film thickness of the unexposed part with respect to the development time can be suppressed, the film thickness after development can be set in the above range.

[Heating process]
In this step, the developed coating film is heated. For heating, the patterned thin film is heated using a heating device such as a hot plate or an oven, whereby the curing reaction of the polymer component [A] can be promoted to form a cured film. As heating temperature, it is 120 to 250 degreeC, for example. The heating time varies depending on the type of heating device, but is, for example, 5 minutes to 30 minutes for a hot plate and 30 minutes to 90 minutes for an oven. Moreover, the step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the desired cured film can be formed on the surface of the substrate. The upper limit of the thickness of the cured film is preferably 8 μm, and more preferably 6 μm. On the other hand, the lower limit of the film thickness is preferably 0.1 μm.

<Display element>
The electronic device of the present invention includes 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 composed of, for example, a liquid crystal cell, a polarizing plate, and the like. Since the liquid crystal display element includes the cured film, the liquid crystal display element is excellent in reliability such as heat resistance.

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

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

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

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

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

[Weight average molecular weight (Mw)]
It measured by gel permeation chromatography (GPC) under the following conditions.
Equipment: “GPC-101” from Showa Denko
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[A] Synthesis of polymer component>
[A] The compounds used for the synthesis of the polymer component are shown below.

M-1: Trimethylsilyl methacrylate M-2: Triethylsilyl methacrylate M-3: Glycidyl methacrylate M-4: Triisopropylsilyl methacrylate M-5: T-butyldimethylsilyl methacrylate M-6: Glycidyl acrylate M -7: Styrene M-8: 1-ethoxyethyl methacrylate M-9: 1-butoxyethyl methacrylate M-10: Tetrahydro-2H-pyran-2-yl methacrylate M-11: 3,4-epoxycyclohexylmethyl methacrylate M-12: 2-tetrahydrofuranyl methacrylate M-13: 3-methacryloyloxymethyl-3-ethyloxetane M-14: cyclohexylmaleimide M-15: 2-hydroxyethyl methacrylate M-16: 2-hydroxyethyl methacrylate [ , 4-epoxytricyclo (5.2.1.0 ^{2, 6)} decane-9-yl]
M-17: Methacrylic acid M-18: Benzyl methacrylate M-19: (3-Chloropropanoyl) oxyethyl methacrylate

[Synthesis Example 1] (Synthesis of polymer (A-1))
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl-3-methoxypropionate. The flask was charged with 30 parts by mass of the compound (M-1), 40 parts by mass of the compound (M-3) and 30 parts by mass of the compound (M-7). The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (A-1). The solid content concentration of this polymer solution was 32.5% by mass. The polymer (A-1) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000.

[Synthesis Examples 2 to 14 and Comparative Synthesis Examples 1 and 2]
Except having used the component of the kind and usage-amount shown in following Table 1, it operates similarly to the synthesis example 1, polymer (A-2)-(A-14), (CA-1), and (CA-2). Was prepared. In Table 1, “-” indicates that the corresponding component was not used. In addition, Table 2 shows the Mw and solid content concentration of these polymers.

[Synthesis Example 15]
The same operation as in Synthesis Example 1 was performed using compounds other than glycidyl methacrylate (M-3) among the compounds giving the structural units of Synthesis Example 15 shown in Table 1 below. To 100 parts by mass of the obtained polymer, 1 part by mass of p-methoxyphenol, 3 parts by mass of tetrabutylammonium bromide and 30 parts by mass of glycidyl methacrylate were added to raise the temperature of the solution to 90 ° C. By maintaining this temperature for 9 hours, a polymer (A-15) was obtained. The solid content concentration of this polymer solution was 33.5% by mass. The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-15) was 14,000. The chemical structure as the “second structural unit having a crosslinkable group” contained in the polymer (A-15) corresponds to the following structure. In addition, in the synthesis example 15 of Table 1, the number in the bracket | parenthesis of the usage-amount of M-3 shows the mass part added after superposition | polymerization.

[Synthesis Example 16]
The same operation as in Synthesis Example 1 was performed using components of the types and amounts used shown in Table 1 below. To 100 parts by mass of the obtained polymer, 1 part by mass of p-methoxyphenol and 120 parts by mass of triethylamine were added and stirred for 3 hours while maintaining at 70 ° C. After cooling to room temperature, 200 parts by mass of a saturated aqueous ammonium chloride solution was added and stirred for 30 minutes, and then ethyl acetate was added to separate the layers. After the organic phase was washed with distilled water, the recovered organic phase was concentrated and diluted with methyl 3-methoxypropionate as a [H] solvent to obtain a polymer solution (A-16). The solid content concentration of this polymer solution was 30.8% by mass. The polymer (A-16) had a weight average molecular weight (Mw) in terms of polystyrene of 11,000. The chemical structure as the “second structural unit having a crosslinkable group” contained in the polymer (A-16) corresponds to the following structure.

<Preparation of radiation-sensitive resin composition>
[B] Radiation sensitive acid generator, [C] antioxidant, [D] compound having cyclic ether group, [E] acid diffusion controller and [J] others used for preparation of radiation sensitive resin composition The components of are shown below.

[[B] Radiation sensitive acid generator]
B-1: 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile ("IRGACURE PAG 103" from BASF)
B-2: (5-p-Toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (“IRGACURE PAG 121” from BASF)
B-3: (2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile ("CGI-725" from BASF)
B-4: (5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile ("CGI-1380" from BASF)
B-5: 4-methylphenylsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile (“PAI-101” from Midori Kagaku)
B-6: N- (trifluoromethylsulfonyloxy) naphthalimide

[[C] Antioxidant]
C-1: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (“ADEKA STAB AO-20” from ADEKA)
C-2: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“ADEKA STAB AO-60” manufactured by ADEKA)

[[D] Compound having cyclic ether group]
D-1: Bisphenol A diglycidyl ether

[[E] acid diffusion controller]
E-1: 4-Dimethylaminopyridine E-2: 2-Phenylbenzimidazole

[[J] Other ingredients]
J-1: Dipentaerythritol penta / hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)

[Example 1]
[A] A polymer solution containing (A-1) as a polymer component (amount corresponding to 100 parts by mass (solid content) of (A-1)) is added to (B) as a radiation-sensitive acid generator. B-1) 3 parts by mass, [C] 2 parts by mass of (C-1) as an antioxidant, and [E] 0.1 parts by mass of (E-1) as an acid diffusion controller were mixed, and radiation sensitive. Resin composition (S-1) was prepared.

[Example 2-24 and Comparative Example 1-4]
Except having used the component of the kind and compounding quantity which are shown in following Table 3, it operates like Example 1 and the radiation sensitive resin composition (S-2)-(S-24) and (CS-1)-( CS-4) was prepared. In addition, "-" in Table 3 indicates that the corresponding component was not blended.

<Evaluation>
Using the radiation-sensitive resin compositions of Examples 1 to 24 and Comparative Examples 1 to 4, radiation sensitivity, cured film chemical resistance, cured film transparency, storage stability, pattern adhesion after development, exposure The pattern adhesion after post-laying was evaluated. The evaluation results are shown in Table 4.

[Radiation sensitivity]
After applying the radiation sensitive resin compositions of Examples and Comparative Examples on a silicon substrate using a spinner, pre-baking on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm did. Subsequently, using an exposure machine (Canon's “MPA-600FA” (ghi line mixing)), the exposure amount to the coating film through a mask having a 60 μm line and space (10 to 1) pattern. Was irradiated as a variable. Thereafter, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 80 seconds by a puddle method. Next, running water was washed with ultrapure water for 1 minute and then dried to form a pattern. At this time, the exposure amount required for completely dissolving the 4 μm space pattern was examined. When the exposure value was 80 mJ / cm ² or less, the radiation sensitivity was evaluated as good.

[Chemical resistance of cured film]
A coating film was formed in the same manner as in the evaluation of the radiation sensitivity, and then the coating film was baked for 30 minutes using an oven heated to 230 ° C. to form a cured film. This cured film was immersed in an N-methylpyrrolidone solvent heated to 40 ° C. for 6 minutes, and the rate of change in film thickness (%) before and after immersion was determined as an index of chemical resistance. When the film thickness change rate is less than 5%, "A", when the film thickness change rate is 5% or more and less than 10%, "B", and when the film thickness change rate is 10% or more and less than 15%, "C" In the case of A or B, the chemical resistance was good, and in the case of C or D, it was evaluated as bad. The film thickness was measured at 25 ° C. using an optical interference type film thickness measuring device (“Lambda Ace VM-1010” manufactured by Dainippon Screen).

[Transparency of cured film]
The transparency of the cured film was evaluated as the transmittance at 400 nm of the cured film. On the glass substrate, the radiation sensitive resin compositions of Examples and Comparative Examples were applied using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. . Then, it baked for 30 minutes using the oven heated at 230 degreeC, and formed the cured film. The transmittance of this film was measured at 25 ° C. using an ultraviolet-visible spectrophotometer (“V-670” manufactured by JASCO Corporation), and used as an index of transparency. The transmittance at 400 nm is A: transmittance of 98% or more, B: transmittance of 95% or more and less than 98%, C: transmittance of 90% or more and less than 95%, D: transmittance of less than 90%, A, B or C In the case of D, the transparency was good, and in the case of D, the transparency was evaluated as bad.

[Storage stability]
The radiation-sensitive resin compositions of Examples and Comparative Examples were left in an oven at 40 ° C. for 1 week, and the viscosity before and after heating was measured to determine the rate of change in viscosity (%), which was used as an index of storage stability. “A” when the viscosity change rate is less than 5%, “B” when the viscosity change rate is 5% or more and less than 10%, “C” when the viscosity change rate is 10% or more and less than 15%, viscosity change The case where the rate was 15% or more was evaluated as “D”. In the case of A, B or C, the storage stability was evaluated as good, and in the case of D, it was evaluated as defective. The viscosity was measured at 25 ° C. using an E-type viscometer (“VISSCONIC ELD.R” manufactured by Toki Sangyo Co., Ltd.).

[Pattern adhesion after development]
After the coating film was formed in the same manner as the evaluation of the radiation sensitivity, the coating film was irradiated with 100 mJ / m ² of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern with a width of 1 to 10 μm. did. Next, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was used for development processing at 25 ° C. for 70 seconds, followed by washing with running ultrapure water for 1 minute. The presence or absence of peeling of the line-and-space pattern having a width of 1 to 10 μm after washing was observed with a microscope to obtain pattern adhesion after development. “A” indicates that the pattern is not peeled off, “B” indicates that the pattern is slightly peeled, “C” indicates that the pattern is partially peeled, and “D” indicates that the entire pattern is peeled off. In the case of B or B, the pattern adhesion after development was evaluated as good, and in the case of C or D, it was evaluated as defective.

[Pattern adhesion after exposure]
After forming a coating film in the same manner as the above-described evaluation of radiation sensitivity, 1-10 μm line and space (one to one) using an exposure machine (“MPA-600FA” (ghi line mixing) manufactured by Canon Inc.) The coating film was exposed with the exposure amount of 100 (mJ / m < ² >) through the mask which has the pattern of this. Subsequently, it was left in a clean room for 1 hour, and developed by a puddle method at 25 ° C. for 70 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Thereafter, running water was washed with ultrapure water for 1 minute, and then dried to form a pattern on the glass substrate. After development, the substrate was observed with an optical microscope, and the presence or absence of pattern peeling was confirmed to determine the pattern adhesion after exposure. “A” when almost no pattern peeling is observed, “B” when pattern peeling up to 5 μm of 1-10 μm line and space (1 to 1) is slightly observed, and 1-10 μm “C” when pattern peeling up to 8 μm in line and space (1 to 1) is observed, pattern peeling up to 10 μm in line and space (1 to 1) of 1 to 10 μm The case where the pattern was removed was designated as “D”, and the case where the pattern was peeled off and almost no pattern remained on the substrate was designated as “E”.

  As is clear from the results in Table 4, the radiation sensitive resin compositions of Examples 1 to 24 are excellent in radiation sensitivity and storage stability, and cured films formed from these radiation sensitive resin compositions are resistant to It was excellent in chemical properties, transparency, pattern adhesion after development, and pattern adhesion after exposure.

  On the other hand, the radiation sensitive resin compositions of Comparative Examples 1 to 4 are inferior in storage stability compared to the radiation sensitive resin compositions of Examples 1 to 24, and these radiation sensitive resin compositions. The cured film formed from is inferior to the cured film formed from the radiation-sensitive resin compositions of Examples 1 to 24 in transparency, pattern adhesion after development, and pattern adhesion after exposure leaving. It was.

  The radiation sensitive resin composition of the present invention is excellent in radiation sensitivity and storage stability, and can form a cured film excellent in chemical resistance, transparency, pattern adhesion after development, and pattern adhesion after exposure. The present invention can further provide a cured film formed from the radiation-sensitive resin composition, a method for forming the cured film, and a display element including the cured film. Therefore, the radiation-sensitive resin composition, the cured film and the method for forming the cured film, and the display element can be suitably used for manufacturing processes such as liquid crystal display devices, organic EL elements, and organic EL lighting.

Claims (8)

[A] A polymer component comprising a first structural unit having an acid dissociable group represented by the following formula (1) and a second structural unit having a crosslinkable group in the same or different polymers, and [B ] as radiation-sensitive acid generator contains at least one compound selected from compounds and N- sulfonyloxy imide compound having an oxime sulfonate group represented by the following formula (2),
[A] A radiation-sensitive resin composition having a polystyrene equivalent weight average molecular weight of 50,000 or less by GPC as a polymer component .

(In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a hydrogen contained in these groups. A group in which some or all of the atoms are substituted with a substituent, or -SiR ^A _3. R ^A is an alkyl group having 1 to 10 carbon atoms, R ⁴ is a single bond or 1 to 12 carbon atoms. Divalent organic group.)

(In Formula (2), R ⁵ is an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a part or all of hydrogen atoms of these groups are substituted with a substituent. Group.) [C] The radiation sensitive resin composition according to claim 1 , further comprising an antioxidant. [C] The radiation-sensitive resin composition according to claim 2 , wherein the antioxidant is a compound having a hindered phenol structure. The radiation-sensitive resin composition according to claim 1, wherein the crosslinkable group is a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, or a combination of two or more thereof. [D] further containing a compound having a cyclic ether group,
The radiation sensitive resin composition according to any one of claims 1 to 4 , wherein the [D] compound is different from the polymer of the [A] polymer component. The cured film formed from the radiation sensitive resin composition of any one of Claims 1-5 . A step of forming a coating film on a substrate using the radiation-sensitive resin composition according to any one of claims 1 to 5 ,
Irradiating at least a part of the coating film with radiation,
A method for forming a cured film, comprising: developing a coating film irradiated with radiation; and heating the developed coating film. A display element provided with the cured film of Claim 6 .