JP2015031842A - Radiation-sensitive resin composition, cured film, method for forming the same and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition which sufficiently satisfies general characteristics required for a radiation-sensitive resin composition such as radiosensitivity, has excellent storage stability and can reduce adhesive failures of a cured film, and further to provide a cured film formed from the radiation-sensitive resin composition and a method for forming the same, and a display element provided with the cured film.SOLUTION: There is provided a radiation-sensitive resin composition which comprises: a polymer component containing a first structural unit having an acid-dissociable group and a second structural unit having a crosslinkable group; a nonionic photoacid generator having a sulfonyl group; and an ionic compound represented by the following formula (1). In the following formula (1), Ris a hydrogen atom or a monovalent organic group; -Ais -N-SO-R, -COO, -Oor -SO; Ris a linear, branched or cyclic monovalent hydrocarbon group; and Xis an onium cation.

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 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 2001-354822 A). In recent years, various radiation-sensitive compositions have been proposed.

  As an example, Japanese Patent Application Laid-Open No. 2004-4669 aims to form a cured film for a display element with higher sensitivity than a positive radiation sensitive resin composition using an acid generator such as naphthoquinonediazide. Positive chemical amplification materials have been proposed. 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 cleaved by the action of an acid and is insoluble or hardly soluble in an aqueous alkali solution, but is soluble in an aqueous alkali solution by cleaving the protecting group by the action of an acid. Become. JP 2004-264623 A and JP 2008-304902 A disclose a positive radiation-sensitive composition containing an acid generator and a resin having an acetal structure and / or a ketal structure and an epoxy group. Proposed.

  However, when these radiation-sensitive resin compositions are used, particularly when a positive chemical amplification material is used, the acid generated during exposure is neutralized by the basic substance in the atmosphere during the holding time until the heating step. May cause inactivation or acid diffusion to unexposed areas. When such acid deactivation or diffusion occurs, there arises a problem that the adhesion between the substrate and the cured film is lowered (see JP-A-6-266100).

  Placement after exposure frequently occurs in the manufacturing process when a large-sized glass substrate is used. Therefore, there is a demand for a radiation-sensitive resin composition that can reduce the influence of leaving after exposure and can stably form a pattern.

  In order to reduce the influence by the leaving after exposure, it is conceivable to reduce the diffusion of the acid to the unexposed area. In order to suppress the diffusion of the acid, it is effective to add a basic substance. However, when an amine compound is used as the basic substance, the curing reaction of the resin in the composition is promoted, so there is a concern that the storage stability of the radiation-sensitive resin composition is lowered.

  As described above, it is difficult to suppress both the decrease in the adhesion of the cured film due to acid diffusion and the like and the storage stability of the radiation-sensitive resin composition. On the other hand, since radiation sensitive resin compositions require general characteristics such as radiation sensitivity, it is necessary to consider so as to satisfy the above general characteristics even when improving the adhesion and storage stability of a cured film. There is.

JP 2001-354822 A JP 2004-4669 A JP 2004-264623 A JP 2008-304902 A See JP-A-6-266100

  The present invention has been made based on the above circumstances, and is excellent in general characteristics and storage stability required for a radiation-sensitive resin composition such as radiation sensitivity, and reduced inadhesiveness of a cured film. An object of the present invention is to provide a radiation-sensitive resin composition capable of achieving the above. Another object of the present invention is to 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.

（式（１）中、Ｒ^１は、水素原子又は１価の有機基である。−Ａ⁻は、−Ｎ⁻−ＳＯ_２−Ｒ^Ａ、−ＣＯＯ⁻、−Ｏ⁻又は−ＳＯ_３ ⁻である。Ｒ^Ａは、炭素数１〜１０の直鎖状若しくは分岐状の１価の炭化水素基又は炭素数３〜２０の環状の１価の炭化水素基である。但し、Ｒ^Ａの炭化水素基が有する水素原子の一部又は全部はフッ素原子で置換されていてもよい。Ｘ^＋は、オニウムカチオンである。） The invention made in order to solve the above problems includes a first structural unit having an acid dissociable group (hereinafter also referred to as “structural unit (I)”) and a second structural unit having a crosslinkable group (hereinafter referred to as “structure”). A polymer component (hereinafter also referred to as “[A] polymer component”) containing a unit (II) ”, a nonionic photoacid generator having a sulfonyl group (hereinafter referred to as“ [B] nonionic light ”). It is also a radiation-sensitive resin composition containing an acid generator ”and an ionic compound represented by the following formula (1) (hereinafter also referred to as“ [C] ionic compound ”).

(In the formula (1), ^{R 1} is a hydrogen atom or a monovalent organic group-A ^{-. _{Is, -N - -SO 2 -R A,}} -COO -, -O - or -SO ₃ ^- in R ^A is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms or a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, provided that R ^{A is} a hydrocarbon. (Part or all of the hydrogen atoms contained in the group may be substituted with fluorine atoms. X ⁺ is an onium cation.)

  Another invention made | formed in order to solve the said subject is a display element provided with the cured film formed from the said radiation sensitive resin composition, and the said 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, a step of irradiating at least a part of the coating film, a step of developing the coating film irradiated with radiation, and a development process. A method for forming a cured film including a step of heating a coating film, wherein the radiation-sensitive resin composition is used for forming the coating film.

  INDUSTRIAL APPLICABILITY The present invention can provide a radiation-sensitive resin composition that sufficiently satisfies general characteristics such as radiation sensitivity and is excellent in storage stability and can reduce poor adhesion of a cured film. 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. Accordingly, 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 a manufacturing process of a liquid crystal display device or the like.

<Radiation sensitive resin composition>
The radiation sensitive resin composition of the present invention contains [A] a polymer component, [B] a nonionic photoacid generator, and [C] an ionic compound. Moreover, the said radiation sensitive resin composition may contain [D] antioxidant etc. as a suitable component. Furthermore, the said radiation sensitive resin composition may contain another arbitrary component in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.

<[A] Polymer component>
[A] The polymer component includes a structural unit (I) having an acid dissociable group and a structural unit (II) having a crosslinkable group. This [A] polymer component may contain the structural unit (I) and the structural unit (II) one by one, or may contain two or more of one or both of the structural units. [A] The polymer component may contain (1) one type of polymer molecule A having both the structural unit (I) and the structural unit (II), and (2) has the structural unit (I). The polymer molecule B1 and the polymer molecule B2 having the structural unit (II) may be included, and (3) the polymer molecule A and the polymer molecule B1 and / or the heavy molecule. The combined molecule B2 may be included. Moreover, the [A] polymer component may contain other structural units in the range which does not impair the effect of this invention.

  The radiation-sensitive resin composition is excellent in radiation sensitivity because the polymer component [A] has the structural unit (I) and the structural unit (II), and has an unexposed portion after the development process and after the post-baking process. The film thickness change can be suppressed.

[Structural unit (I)]
The structural unit (I) has an acid dissociable group. This acid dissociable group acts as a protecting group for protecting a carboxyl 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 structural unit (I), thereby achieving high radiation sensitivity and improving the stability of the pattern shape obtained by development or the like. Become.

  As the structural unit (I) containing an acid dissociable group, a structural unit represented by the following formula (2) or the following formula (3) is preferable.

In formula (2), R ⁷ is a hydrogen atom or a methyl group. R ⁸ is a linear or branched alkyl group having 1 to 12 carbon atoms. R ⁹ is a linear or branched alkyl group having 1 to 12 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.

Examples of the linear alkyl group having 1 to 12 carbon atoms represented by R ⁸ and R ⁹ include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- A hexyl group, n-octyl group, etc. are mentioned. As a C1-C12 branched alkyl group represented by said R < ⁸ > and R < ⁹ >, i-propyl group, i-butyl group, t-butyl group, neopentyl group etc. are mentioned, for example.

Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ⁹ include:
A monocyclic cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group, an ethylcyclohexyl group;
A monocyclic cycloalkenyl group such as a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclodecenyl group, a cyclopentadienyl group, a cyclohexadienyl group, a cyclooctadienyl group, a cyclodecadienyl group;
Bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, 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 (2) include structural units represented by the following formulas (2-1) to (2-10).

In the above formula (2-1) ~ (2-10), ^{R 7} has the same meaning as ^{R 7} in the formula (2).

  Examples of the monomer that gives the structural unit represented by the above formula (2) include 1-ethoxyethyl methacrylate, 1-butoxyethyl methacrylate, 1- (tricyclodecanyloxy) ethyl methacrylate, and methacrylic acid. 1- (pentacyclopentadecanylmethyloxy) ethyl, 1- (pentacyclopentadecanyloxy) ethyl methacrylate, 1- (tetracyclododecanylmethyloxy) ethyl methacrylate, 1- (adamantyloxy) ethyl methacrylate Etc.

In said formula (3), R < ¹⁰ > is a hydrogen atom or a methyl group. R ^{11 to} R ¹⁷ are a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms. f is 1 or 2. If f is 2, between the two R ¹⁶ together and the two R ¹⁷ may be different even in the same.

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms represented by R ^{11 to} R ¹⁷ include the linear or branched alkyl group having 1 to 12 carbon atoms of R ⁸ and R ^{9 in} the above formula (2). The same thing as a branched alkyl group is mentioned.

  Examples of the structural unit represented by the above formula (3) include structural units represented by the following formulas (3-1) to (3-5).

In the above formula (3-1) ~ ^{(3-5), R 10} has the same meaning as ^{R 10} in formula (3).

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

  The content of the structural unit (I) is preferably 0.1 mol% or more and 80 mol% or less, more preferably 1 mol% or more and 60 mol% or less with respect to all the structural units constituting the [A] polymer component. preferable. By setting the content of the structural unit (I) within the above range, it is possible to achieve high radiation sensitivity and effectively improve the stability of the pattern shape obtained by development or the like.

[Structural unit (II)]
The structural unit (II) contains a crosslinkable group. The cured film formed from the radiation-sensitive resin composition has [A] polymer components having a structural unit (II) containing a crosslinkable group, so that the polymers constituting the [A] polymer components or [A] The strength can be increased by crosslinking the polymer constituting the polymer component with the [D] antioxidant 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 (1,2-epoxy structure), an oxetanyl group (1,3- Epoxy structure), alkoxymethyl group, formyl group, acetyl group, dialkylaminomethyl group, dimethylolaminomethyl group and the like.

  The crosslinkable group is preferably a (meth) acryloyl group, an oxiranyl group, or 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 structural unit (II) include structural units represented by the following formula.

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

As the monomer that gives the structural unit (II), 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, More preferred are 3-methacryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate.

  The content of the structural unit (II) is preferably 0.1 mol% or more and 80 mol% or less, more preferably 1 mol% or more and 60 mol% or less with respect to all the structural units constituting the [A] polymer component. preferable. By making content of structural unit (II) into the said range, the intensity | strength of the cured film formed from the said radiation sensitive resin composition can be raised effectively.

[Other structural units]
[A] The polymer component may have other structural units other than the structural unit (I) and the structural unit (II) as long as the effects of the present invention are not impaired.

  Examples of monomers that give other structural units include unsaturated monocarboxylic acids, (meth) acrylic acid esters having a hydroxyl group, (meth) acrylic acid chain alkyl esters, (meth) acrylic acid cyclic alkyl esters, ( Examples include unsaturated compounds having a meth) acrylic acid aryl ester, an unsaturated aromatic compound, a conjugated diene, a tetrahydrofuran skeleton and the like.

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

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

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

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

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

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

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

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

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

  As content of another structural unit, Preferably it is 5 mol%-30 mol% with respect to all the structural units, More preferably, it is 10 mol%-25 mol%. By setting the content of other structural units to 5 mol% to 30 mol%, a radiation-sensitive resin composition that optimizes solubility in an aqueous alkali solution and is excellent in radiation sensitivity can be obtained.

<[A] Polymer component synthesis method>
[A] The polymer component can be produced, for example, by polymerizing a monomer corresponding to 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 in the polymerization reaction of the polymer component include the solvents exemplified in the section of preparation of the radiation-sensitive resin composition described later.

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

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

[A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and preferably 3.0 × 10 ³ or more. 5.0 × 10 ⁴ or less is more preferable, and 5.0 × 10 ³ or more and 2.0 × 10 ⁴ or less is more preferable. [A] By making Mw of a polymer component into the said range, the sensitivity and alkali developability of the said radiation sensitive resin composition can be improved.

[A] The number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer component is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and 3.0 × 10 ³ or more and 5.0 × 10 ^4. The following is more preferable, and 5.0 × 10 ³ or more and 2.0 × 10 ⁴ or less is more preferable. [A] By making Mn of a polymer into the said range, the cure reactivity at the time of hardening of the coating film of the said radiation sensitive resin composition can be improved.

  [A] The molecular weight distribution (Mw / Mn) of the polymer component is preferably 3.0 or less, and more preferably 2.6 or less. [A] By making Mw / Mn of a polymer component 3.0 or less, the developability of the obtained cured film can be improved.

<[B] Nonionic photoacid generator>
[B] The nonionic photoacid generator is a compound that generates an acid upon irradiation with radiation. As the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. This [B] nonionic photoacid generator is nonionic having a sulfonyl group (—SO ₂ —), and is different from ionic photoacid generators represented by onium salts and the like.

  The said radiation sensitive resin composition can exhibit a radiation sensitive characteristic by having a [B] nonionic photo-acid generator, and can have favorable radiation sensitivity.

  In the radiation sensitive resin composition, the content of the [B] nonionic photoacid generator is incorporated as a part of the polymer constituting the [A] polymer component even in the form of a compound as described below. It may be in the form of a photoacid generating group or in both forms.

  Examples of the [B] nonionic photoacid generator include oxime sulfonate compounds and sulfonic acid derivative compounds. [B] Nonionic photoacid generators may be used alone or in combination of two or more.

[Oxime sulfonate compound]
An oxime sulfonate compound is a compound having an oxime sulfonate group. As the oxime sulfonate compound, a compound represented by the following formula (7) is preferable.

In the above formula (7), R ³¹ is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent.

The alkyl group represented by R ³¹ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl- Examples thereof include alicyclic groups including a bridged alicyclic group such as a 2-oxonorbornyl group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptylfluoropropyl group, and the like.

The alicyclic hydrocarbon group represented by R ³¹ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms. The alicyclic hydrocarbon group having 4 to 12 carbon atoms may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. .

The aryl group represented by R ³¹ is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group. The aryl group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

  Examples of the compound containing an oxime sulfonate group represented by the above formula (7) include oxime sulfonate compounds represented by the following formulas (7-1) to (7-3).

In the above formula (7-1) ~ ^{(7-3), R 31} has the same meaning as ^{R 31} in the formula (7). The formula (7-1) and formula ^{(7-2), R 32} represents an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms.

In the above formula (7-3), ^{Y 4} is an alkyl group, an alkoxy group, or a halogen atom. j is an integer of 0-3. However, when j is 2 or 3, the plurality of Y ⁴ may be the same or different.

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

  Examples of the oxime sulfonate compound represented by the above formula (7-3) include compounds represented by the following formulas (7-3-1) to (7-3-5).

  The compounds represented by the above formulas (7-3-1) to (7-3-5) are (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, 5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5- p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile and 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, which are commercially available. .

[Sulfonic acid derivative compound]
A sulfonic acid derivative compound is a compound having a sulfonyl group. As the sulfonic acid derivative compound, a compound represented by the following formula (4) is preferable.

In the formula ^{(4), R 18} and ^R 21 ^{to R 23} is a hydrogen atom.

One of R ¹⁹ and R ²⁰ is a linear or branched alkoxy group having 4 to 18 carbon atoms, and a methylene group at any position not adjacent to the oxygen atom of the alkoxy group is substituted with a —C (═O) — group. A group interrupted by an —O—C (═O) — bond or —OC (═O) —NH— bond from the side closer to the naphthalene ring, a straight chain having 4 to 18 carbon atoms Or a branched alkylthio group, a group in which a methylene group at any position not adjacent to the sulfur atom of this alkylthio group is substituted with a —C (═O) — group, and the above alkylthio group is —O—C from the side closer to the naphthalene ring It is a group interrupted by a (═O) — bond or —OC (═O) —NH— bond, or a group represented by the following formula (5). However, a part or all of the hydrogen atoms of the alkoxy group and alkylthio group of R ¹⁹ and R ²⁰ may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. The other of R ¹⁹ and R ²⁰ is a hydrogen atom.

In the above formula ^{(5), R 25} is a hydrocarbon group having 1 to 12 carbon atoms. R ²⁶ is an alkanediyl group having 1 to 4 carbon atoms. R ²⁷ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group or heterocyclic group having 3 to 10 carbon atoms. Y ¹ is an oxygen atom or a sulfur atom. Y ² is a single bond or an alkanediyl group having 1 to 4 carbon atoms. g is an integer of 0-5.

R ²⁴ in the above formula (4) is a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, a halogen atom A linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted at least one of an atom and an alicyclic hydrocarbon group, and 3 to 18 carbon atoms which may be substituted with a halogen atom A monovalent alicyclic hydrocarbon group, a halogen atom, and an aryl group having 6 to 20 carbon atoms which may be substituted at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, a halogen atom and 1 to carbon atoms An arylalkyl group having 7 to 20 carbon atoms which may be substituted on at least one of 18 alkylthio groups, an alkylaryl having 7 to 20 carbon atoms which may be substituted with a halogen atom Group, an aryl group having 7 to 20 carbon atoms substituted with an acyl group, a 10-camphoryl group, or a group represented by the following formula (6).

The formula (6), ^{Y 3} is a single bond or an alkanediyl group having 1 to 4 carbon atoms.

R ²⁸ is an alkanediyl group having 2 to 6 carbon atoms, a halogenated alkanediyl group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms.

R ²⁹ is a single bond, an alkanediyl group having 2 to 6 carbon atoms, a halogenated alkanediyl group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms. .

R ³⁰ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms. , An aryl group having 6 to 20 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms. One of h and i is 1 and the other is 0 or 1.

Examples of the linear or branched alkoxy group having 4 to 18 carbon atoms represented by R ¹⁹ or R ²⁰ in the above formula (4) include a butyloxy group, a second butyloxy group, a third butyloxy group, and isobutyl. Oxy group, amyloxy group, isoamyloxy group, third amyloxy group, hexyloxy group, heptyloxy group, isoheptyloxy group, third heptyloxy group, octyloxy group, isooctyloxy group, third octyloxy group, 2 -Ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, etc. It is done.

Examples of the linear or branched alkylthio group having 4 to 18 carbon atoms represented by R ¹⁹ or R ²⁰ include, for example, a butylthio group, a second butylthio group, a third butylthio group, an isobutylthio group, an amylthio group, Isoamylthio group, tertiary amylthio group, hexylthio group, heptylthio group, isoheptylthio group, tertiary heptylthio group, octylthio group, isooctylthio group, tertiary octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, undecylthio group , Dodecylthio group, tridecylthio group, tetradecylthio group, pentadecylthio group, hexadecylthio group, heptadecylthio group, octadecylthio group and the like.

  Examples of the group in which the methylene group not adjacent to the oxygen atom of the alkoxy group having 4 to 18 carbon atoms in the above formula (4) is substituted with —C (═O) — group include 2-ketobutyl-1-oxy Group, 2-ketopentyl 1-oxy group, 2-ketohexyl-1-oxy group, 2-ketoheptyl-1-oxy group, 2-ketooctyl-1-oxy group, 3-ketobutyl-1-oxy group, 4-ketoamyl- 1-oxy group, 5-ketohexyl-1-oxy group, 6-ketoheptyl-1-oxy group, 7-ketooctyl-1-oxy group, 3-methyl-2-ketopentane-4-oxy group, 2-keto-pentane Examples include -4-oxy group, 2-methyl-2-ketopentane-4-oxy group, 3-ketoheptane-5-oxy group, 2-adamantanone-5-oxy group and the like.

  Examples of the group in which the methylene group not adjacent to the sulfur atom of the alkylthio group having 4 to 18 carbon atoms in the above formula (4) is substituted with —C (═O) — group include, for example, 2-ketobutyl-1-thio Group, 2-ketopentyl 1-thio, 2-ketohexyl-1-thio group, 2-ketoheptyl-1-thio group, 2-ketooctyl-1-thio group, 3-ketobutyl-1-thio group, 4-ketoamyl-1 -Thio group, 5-ketohexyl-1-thio group, 6-ketoheptyl-1-thio group, 7-ketooctyl-1-thio group, 3-methyl-2-ketopentane-4-thio group, 2-keto-pentane- 4-thio group, 2-methyl-2-ketopentane-4-thio group, 3-ketoheptane-5-thio group and the like can be mentioned.

A group interrupted by an —O—C (═O) — bond or —OC (═O) —NH— bond from the side closer to the naphthalene ring in the alkoxy group having 4 to 18 carbon atoms in the above formula (4), And a group interrupted by an —O—C (═O) — bond or —OC (═O) —NH— bond from the side closer to the naphthalene ring in the above-mentioned alkylthio group having 4 to 18 carbon atoms is —Y ⁵ — ^{R f -O-C (= O} ) -R g or ^-Y 5 ^-R f OC is ^{(= O) -NH-R g} . Y ⁵ is an oxygen atom or a sulfur atom. R ^f and R ^g are groups capable of forming R ¹⁹ and R ²⁰ in the above formula (4). R ^f is a linear or branched alkylene group. This alkylene group may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. R ^g is a linear or branched alkyl group. This alkyl group may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. The total number of carbon atoms in R ^f and ^{R g} is 4 to 18.

  The alkoxy group and the alkylthio group may be substituted with a halogen atom, an alicyclic hydrocarbon group, or a heterocyclic group.

  Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.

  The alicyclic hydrocarbon group and the heterocyclic group may be present in a form substituted with the methylene group in the alkoxy group or the alkylthio group, and are substituted with the proton of the methylene group in the alkoxy group or the alkylthio group. Or may be present at the terminal in the alkoxy group or alkylthio group. The alkoxy group and the alkylthio group also include a group formed by directly bonding a carbon atom constituting the ring structure of an alicyclic hydrocarbon group or a heterocyclic group and an oxygen atom or a sulfur atom.

  Examples of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, And groups derived from bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, adamantane, and the like.

  Examples of the heterocyclic group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine , Isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, pyringin, indolizine, indole, indazole, purine, quinolidine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline Quinazoline, cinnoline, pteridine, acridine, perimidine, phenanthroline, carbazole, carboline, Enazine, anti-lysine, thiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofuroxane, naphthimidazole, benzotriazole, tetraazaindene, present in the above heterocyclic compounds And a group derived from a saturated heterocyclic (tetrahydrofuran ring) compound hydrogenated to an unsaturated bond or a conjugated bond.

  Examples of the alkoxy group substituted with the alicyclic hydrocarbon group include a cyclopentyloxy group, a methylcyclopentyloxy group, a cyclohexyloxy group, a fluorocyclohexyloxy group, a chlorocyclohexyloxy group, a cyclohexylmethyloxy group, and a methylcyclohexyloxy group. , Norbornyloxy group, ethylcyclohexyloxy group, cyclohexylethyloxy group, dimethylcyclohexyloxy group, methylcyclohexylmethyloxy group, norbornylmethyloxy group, trimethylcyclohexyloxy group, 1-cyclohexylbutyloxy group, adamantyloxy group , Menthyloxy group, n-butylcyclohexyloxy group, tertiary butylcyclohexyloxy group, bornyloxy group, isobornyloxy group, decahydro Futyloxy group, dicyclopentadienoxy group, 1-cyclohexylpentyloxy group, methyladamantyloxy group, adamantanemethyloxy group, 4-amylcyclohexyloxy group, cyclohexylcyclohexyloxy group, adamantylethyloxy group, dimethyladamantyloxy group, etc. Is mentioned.

  Examples of the alkoxy group substituted by the heterocyclic group include a tetrahydrofuranyloxy group, a furfuryloxy group, a tetrahydrofurfuryloxy group, a tetrahydropyranyloxy group, a butyrolactyloxy group, a butyrolactylmethyloxy group, An indoleoxy group may be mentioned.

  Examples of the alkylthio group substituted with the alicyclic hydrocarbon group include a cyclopentylthio group, a cyclohexylthio group, a cyclohexylmethylthio group, a norbornylthio group, and an isonorbornylthio group.

  Examples of the alkylthio group substituted with the heterocyclic group include a furfurylthio group and a tetrahydrofurfurylthio group.

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented by R ²⁵ in the above formula (5) include aliphatic hydrocarbon groups such as alkanediyl group, alkenediyl group, alkynediyl group, and cycloalkanediyl. And an alicyclic hydrocarbon group such as a group, and a group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded. Specific examples of the hydrocarbon group having 1 to 12 carbon atoms include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butylene group, butane-1,3- Diyl group, butane-2,3-diyl group, butane-1,2-diyl group, pentylene group, hexylene group, cyclohexylene group, cyclohexylenemethyl group, heptylene group, octylene group, cyclohexyleneethyl group, methylenecyclohexyl Examples include a silylenemethyl group, a nonylene group, a decylene group, an adamantylene group, a norbornylene group, an isonorbornylene group, a dodecylene group, and an undecylene group.

Examples of the alkanediyl group having 1 to 4 carbon atoms represented by R ²⁶ and Y ² in the formula (5) include a methylene group, an ethylene group, a propane-1,3-diyl group, and propane-1,2. -Diyl group, butylene group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group and the like can be mentioned.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R ²⁷ in the above formula (5) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second group. Examples include a butyl group, a tertiary butyl group, and an isobutyl group.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ²⁷ in the above formula (5) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, Cyclooctyl group, cyclodecyl group, bicyclo [2.1.1] hexyl group, bicyclo [2.2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group And an adamantyl group.

Examples of the monovalent heterocyclic group having 3 to 10 carbon atoms represented by R ²⁷ in the above formula (5) include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, and oxazole. , Isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, pyrinidine , Indolizine, indole, indazole, purine, quinolidine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, perimi Gin, phenanthroline, carbazole, carboline, phenazine, antilysine, thiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofuroxan, naphthimidazole, benzotriazole, tetraazaindene And monovalent groups obtained by removing a hydrogen atom from an unsaturated bond or a saturated heterocyclic (tetrahydrofuran ring) compound hydrogenated to a conjugated bond, which is present in the heterocyclic compound.

Examples of the unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by R ²⁴ in the above formula (4) include an alkenyl group, an alkyl group, an alicyclic hydrocarbon group, and a methylene group in the alkyl group. A group substituted with a cyclic hydrocarbon group, a group where a hydrogen atom of a methylene group in an alkyl group is substituted with an alicyclic hydrocarbon group, or a group where an alicyclic hydrocarbon is present at the terminal of the alkyl group, etc. Can be mentioned.

  Examples of the alkenyl group include allyl group and 2-methyl-2-propenyl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, second butyl group, third butyl group, isobutyl group, amyl group, isoamyl group, third amyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, third heptyl group, octyl group, isooctyl group, third octyl group, 2-ethylhexyl group, nonyl group, Examples include isononyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a bicyclo [2.1.1] hexyl group, and a bicyclo [2 2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group, adamantyl group and the like.

  As a halogen atom which substitutes the said C1-C18 aliphatic hydrocarbon group, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom etc. are mentioned, for example. Examples of the alkylthio group having 1 to 18 carbon atoms that replaces the aliphatic hydrocarbon group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a second butylthio group, a third butylthio group, and an isobutylthio group. Group, amylthio group, isoamylthio group, third amylthio group, hexylthio group, heptylthio group, isoheptylthio group, third heptylthio group, octylthio group, isooctylthio group, third octylthio group, 2-ethylhexylthio group, nonylthio group, Examples include a decylthio group, an undecylthio group, a dodecylthio group, a tridecylthio group, a tetradecylthio group, a pentadecylthio group, a hexadecylthio group, a heptadecylthio group, and an octadecylthio group.

  Examples of the C1-C18 aliphatic hydrocarbon group substituted with a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a heptafluoropropyl group, and a 3-bromo group. Propyl group, nonafluorobutyl group, tridecafluorohexyl group, heptadecafluorooctyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoropropyl group, 1,1 , 2,2-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, norbornyl-1,1-difluoroethyl group, norbornyltetra And halogenated alkyl groups such as a fluoroethyl group and an adamantane-1,1,2,2-tetrafluoropropyl group. Examples of the C1-C18 aliphatic hydrocarbon substituted with an alkylthio group include a 2-methylthioethyl group, a 4-methylthiobutyl group, a 4-butylthioethyl group, and the like. Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with an -18 alkylthio group include a 1,1,2,2-tetrafluoro-3-methylthiopropyl group.

Examples of the unsubstituted linear or branched alkyl group having 1 to 18 carbon atoms for R ²⁴ in the above formula (4) include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n -Pentyl group, n-hexyl group, n-octyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group and the like.

  Examples of the halogen atom for substituting the alkyl group having 1 to 18 carbon atoms include those similar to the halogen atom for substituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms. Examples of the alicyclic hydrocarbon group that replaces the alkyl group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, and bicyclo [2.2. .1] groups derived from heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, adamantane, and the like.

Examples of the unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms in R ²⁴ in the above formula (4) include:
A monocyclic cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group, an ethylcyclohexyl group;
Monocyclic cycloalkenyl groups such as cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl, cyclodecadiene;
Bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] decyl group, 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.

  As a halogen atom which substitutes the said C3-C18 alicyclic hydrocarbon group, the same thing as the halogen atom which substitutes a C1-C18 aliphatic hydrocarbon group is mentioned.

The unsubstituted aryl group having 6 to 20 carbon atoms in R ²⁴ in the formula (4), for example, a phenyl group, a naphthyl group, 4-vinylphenyl group, and biphenyl group.

  As the halogen atom and the alkylthio group having 1 to 18 carbon atoms for substituting the aryl group having 6 to 20 carbon atoms, the halogen atom and the alkyl group having 1 to 18 carbon atoms for substituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms. The same thing as an alkylthio group is mentioned.

  Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group, a 2,4-bis (trifluoromethyl) phenyl group, and a bromoethylphenyl group. Groups and the like. Examples of the aryl group having 6 to 20 carbon atoms substituted with an alkylthio group having 1 to 18 carbon atoms include, for example, 4-methylthiophenyl group, 4-butylthiophenyl group, 4-octylthiophenyl group, 4-dodecylthiophenyl group Groups and the like. Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom and an alkylthio group having 1 to 18 carbon atoms include, for example, 1,2,5,6-tetrafluoro-4-methylthiophenyl group, 1,2,5. , 6-tetrafluoro-4-butylthiophenyl group, 1,2,5,6-tetrafluoro-4-dodecylthiophenyl group, and the like.

Examples of the unsubstituted arylalkyl group having 7 to 20 carbon atoms for R ²⁴ in the above formula (4) include benzyl group, phenethyl group, 2-phenylpropan-2-yl group, diphenylmethyl group, and triphenylmethyl. Group, styryl group, cinnamyl group and the like.

  As a halogen atom and C1-C18 alkylthio group which substitutes the said C7-20 arylalkyl group, a halogen atom which substitutes the said C1-C18 aliphatic hydrocarbon group, and C1-C18 The same thing as the alkylthio group of is mentioned.

  Examples of the arylalkyl group substituted with a halogen atom include a pentafluorophenylmethyl group, a phenyldifluoromethyl group, a 2-phenyl-tetrafluoroethyl group, a 2- (pentafluorophenyl) ethyl group, and the like. Examples of the arylalkyl group having 7 to 20 carbon atoms substituted with an alkylthio group having 1 to 18 carbon atoms include a p-methylthiobenzyl group. Examples of the arylalkyl group substituted with a halogen atom and an alkylthio group having 1 to 18 carbon atoms include a 2,3,5,6-tetrafluoro-4-methylthiophenylethyl group.

Examples of the unsubstituted alkylaryl group having 7 to 20 carbon atoms in R ²⁴ in the above formula (4) include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and a 3-isopropylphenyl group. 4-isopropylphenyl group, 4-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-octylphenyl group, 4- (2- Ethylhexyl) phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethyl Phenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl group, 2, 4-di-tertiary pentylphenyl group, 2,5-di-tertiary amylphenyl group, 2,5-di-tertiary octylphenyl group, cyclohexylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6 -A trimethylphenyl group, 2,4,6-triisopropylphenyl group, etc. are mentioned.

Examples of the unsubstituted aryl group having 7 to 20 carbon atoms in R ²⁴ in the above formula (4) include a naphthyl group and a biphenyl group.

  Examples of the acyl group that substitutes for the aryl group having 7 to 20 carbon atoms include a methanoyl group, an ethanoyl group, a propanoyl group, a benzoyl group, and a propenoyl group.

  Examples of the aryl group having 7 to 20 carbon atoms substituted with an acyl group include an acetylphenyl group, an acetylnaphthyl group, a benzoylphenyl group, a 1-anthraquinolyl group, and a 2-anthraquinolyl group.

10-camphorsulfonic yl group represented by R ²⁴ in the formula (4) are those represented by the following formula.

Examples of the alkanediyl group having 1 to 4 carbon atoms represented by Y ³ in the above formula (6) include a methylene group, an ethylene group, a propane-1,3-diyl group, and a propane-1,2-diyl group. , Butylene group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group, and the like.

Examples of the alkanediyl group having 2 to 6 carbon atoms represented by R ²⁸ or R ²⁹ in the above formula (6) include, for example, at least one hydrogen atom in the alkanediyl group having 2 to 6 carbon atoms is a halogen atom. And a group substituted with. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the alkanediyl group having 2 to 6 carbon atoms include a tetrafluoroethylene group, a 1,1-difluoroethylene group, a 1-fluoroethylene group, a 1,2-difluoroethylene group, and a hexafluoropropane 1,3-diyl. Group, 1,1,2,2-tetrafluoropropane-1,3-diyl group, 1,1,2,2-tetrafluoropentane-1,5-diyl group and the like.

Examples of the halogenated alkanediyl group having 2 to 6 carbon atoms represented by R ²⁸ or R ²⁹ in the above formula (6) include, for example, a tetrafluoroethylene group, a 1,1-difluoroethylene group, and a 1-fluoroethylene group. 1,2-difluoroethylene group, hexafluoropropane 1,3-diyl group, 1,1,2,2-tetrafluoropropane-1,3-diyl group, 1,1,2,2-tetrafluoropentane- 1,5-diyl group and the like can be mentioned.

Examples of the arylene group having 6 to 20 carbon atoms represented by R ²⁸ or R ²⁹ in the above formula (6) include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,5-dimethyl-1,4-phenylene group, 4,4′-biphenylene group, diphenylmethane-4,4′-diyl group, 2,2-diphenylpropane-4,4′-diyl group, naphthalene-1, 2-diyl group, naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl, naphthalene -1,8-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group and the like.

In the halogenated arylene group having 6 to 20 carbon atoms represented by R ²⁸ or R ²⁹ in the above formula (6), at least one hydrogen atom in the arylene group having 6 to 20 carbon atoms is substituted with a halogen atom. Group, for example, tetrafluorophenylene group and the like.

Examples of the linear or branched alkyl group having 1 to 18 carbon atoms represented by R ³⁰ in the above formula (6) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second group. Butyl, tertiary butyl, isobutyl, amyl, isoamyl, tertiary amyl, hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl 3rd heptyl group, octyl group, isooctyl group, 3rd octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, An octadecyl group etc. are mentioned.

  As the linear or branched alkyl halide group having 1 to 18 carbon atoms in the above formula (6), for example, at least one hydrogen atom in the alkyl group having 1 to 18 carbon atoms is substituted with a halogen atom. Group. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the halogenated alkyl group having 1 to 18 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a tridecafluorohexyl group, a heptadecafluorooctyl group, 2, 2,2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoropropyl group, 1,1,2,2-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 2 , 2,3,3,3-pentafluoropropyl group, 1,1,2,2-tetrafluorotetradecyl group and the like.

  Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms in the above formula (6) include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, bicyclo [ 2.1.1] hexyl group, bicyclo [2.2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group, adamantyl group and the like.

As the aryl group having 6 to 20 carbon atoms, the halogenated aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the halogenated arylalkyl group having 7 to 20 carbon atoms in the above formula (6) Is the same as R ²⁴ in the above formula (4).

  [B] As content of a nonionic photo-acid generator, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] polymer components, and 1 mass part-5 mass parts are more. preferable. [B] By setting the content of the nonionic photoacid generator in the above range, the radiation sensitivity of the radiation-sensitive resin composition can be optimized, and a cured film having high surface hardness can be formed while maintaining transparency. .

<[C] ionic compound>
[C] The ionic compound is an ionic compound of an onium salt represented by the following formula (1).

In the above formula (1), R ¹ is a hydrogen atom or a monovalent organic group. -A ^{- _{is, -N - -SO 2 -R A,}} -COO -, -O - or -SO ₃ ^- is. R ^A is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms or a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms. However, a part or all of the hydrogen atoms contained in the hydrocarbon group of ^RA may be substituted with fluorine atoms. X ⁺ is an onium cation.

  The radiation-sensitive resin composition contains the [C] ionic compound, thereby deactivating the acid strength adjusting function in the exposed area, the high acid capturing function in the unexposed area, and the acid capturing function in the exposed area. The lithography performance can be effectively improved by exhibiting an advanced acid diffusion control function.

Moreover, the said radiation sensitive resin composition increases the dispersibility of the [C] ionic compound in the coating film formed from the said radiation sensitive resin composition because X ^<+> is an onium cation, The said The diffusion of the acid generated from the [B] nonionic photoacid generator in the coating film is controlled with higher accuracy. In addition, by setting the pKa of the acid generated from the [C] ionic compound to a value larger than the pKa of the acid generated from the [B] nonionic photoacid generator, the [B] nonionic photoacid generator It becomes possible to control the diffusion of the generated acid. As a result, the adhesiveness etc. of the pattern formed from the said radiation sensitive resin composition can be improved more.

Examples of the monovalent organic group represented by R ¹ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 7 to 30 carbon atoms. An aralkyl group, a heterocyclic group having 3 to 30 carbon atoms, one or more of these groups, and -O-, -CO-, -S-, -CS-, or -NH- Groups and the like. In R ¹ , the atom bonded to A ⁻ is preferably a carbon atom, and this carbon atom is an acid generated from the [C] ionic compound than an acid generated from the [B] nonionic photoacid generator. In order to make it relatively weak, it is preferable not to have an electron-withdrawing group (atom).

Examples of the linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ^A include a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of the cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms represented by R ^A include a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.

  In the alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group, part or all of the hydrogen atoms may be substituted. Examples of the substituent in this case include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.

The onium cation represented by X ⁺ is preferably a sulfonium cation or an iodonium cation, more preferably a sulfonium cation represented by the following formula (1-1) or an iodonium cation represented by the formula (1-2).

In formulas (1-1) and (1-2), R ^{2 to} R ⁶ are a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, —S—R ^B , —OSO ₂ —R ^C , or it is a -SO ₂ -R ^D. R ^B is an alkyl group or an aryl group. R ^C and R ^D are each independently an alkyl group, a cycloalkyl group, an alkoxy group or an aryl group. ^{However, R 2 ~R 6, R B} , an alkyl group of R ^C and R ^D, a cycloalkyl group, a part or all of the hydrogen atom of the alkoxy group and the aryl group may be substituted. a, b, c, d and e are each independently an integer of 0 to 5;

The halogen atom represented by R ² to R ^6, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group represented by R ^{2 to} R ⁶ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

The cycloalkyl group represented by R ^{2 to} R ⁶ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

The alkoxy group represented by R ^{2 to} R ⁶ is preferably an alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

The alkyl group represented by R ^B is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

The aryl group represented by R ^B, preferably an aryl group having 6 to 20 carbon atoms, for example, a phenyl group, a naphthyl group, and the like.

Examples of the alkyl group, cycloalkyl group and alkoxy group represented by R ^C and R ^D include the same alkyl groups, cycloalkyl groups and alkoxy groups as those described above for R ^{2 to} R ⁴ . The aryl group represented by R ^C and R ^D is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

Examples of the group that substitutes for the alkyl group, cycloalkyl group, alkoxy group, and aryl group of R ^{2 to} R ⁶ and R ^{B to} R ^D include a hydroxyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Is mentioned.

  Examples of the sulfonium cation include cations represented by the following formulas (1-1-1) to (1-1-14).

  Examples of the iodonium cation include cations represented by the following formulas (1-2-1) to (1-2-3).

  As the onium cation, a sulfonium cation is preferable, and cations represented by the above formulas (1-1-1) and (1-1-10) are more preferable.

  Preferable [C] ionic compound includes a compound represented by the following formula.

  In the radiation sensitive resin composition, two or more [C] ionic compounds can be used in combination. [C] The content of the ionic compound is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the polymer component [A]. Preferably they are 0.1 mass part-2 mass parts. [C] If the content of the ionic compound is less than 0.01 parts by mass, the acid diffusion control function may not be sufficiently exhibited. On the other hand, when the content of the [C] ionic compound exceeds 10 parts by mass, the radiation sensitivity of the resulting radiation-sensitive resin composition may be significantly reduced.

<[D] Antioxidant>
[D] The antioxidant is a component that suppresses the breakage of the bond of the polymer molecule by capturing radicals generated by exposure or heating or by decomposing a peroxide generated by oxidation.

  When the radiation-sensitive resin composition contains [D] antioxidant, the degradation degradation of polymer molecules in the cured film formed by the radiation-sensitive resin composition is suppressed, and for example, light resistance Etc. can be improved. In addition, you may use [D] antioxidant individually or in combination of 2 or more types.

  [D] Examples of the antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, and a compound having a thioether structure. Among these, as [D] antioxidant, what has a hindered phenol structure is preferable. [D] When the antioxidant has a hindered phenol structure, the degradation degradation of the polymer molecules in the cured film can be further suppressed.

  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.

  Examples of commercially available compounds having the hindered phenol structure include, for example, ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80. AO-330 (above, ADEKA), Sumilizer GM, GS, MDP-S, BBM-S, WX-R, GA-80 (above, Sumitomo Chemical), IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 1525L, 245, 259, 3114, 565, IRGAMOD295 (above, Ciba Japan), Yoshinox BHT, BB, 2246G, 425, 250, 930, SS, TT, 917, 314 (above, API Corporation) Shon Co., Ltd.), and the like.

  [D] As an antioxidant, among 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.

  [D] The content of the antioxidant is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the polymer component [A]. preferable. [D] By making content of antioxidant into the said range, the cracking degradation of a cured film can be suppressed effectively.

<Other optional components>
The said radiation sensitive resin composition may contain other arbitrary components as needed in the range which does not impair the effect of this invention in addition to said [A]-[D] component. Examples of other optional components include [E] polyfunctional (meth) acrylate, [F] photo radical polymerization initiator, [G] surfactant, and [H] adhesion assistant. Other optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

<[E] polyfunctional (meth) acrylate>
[E] The polyfunctional (meth) acrylate can enhance the curability of the radiation-sensitive composition. The [E] polyfunctional (meth) acrylate is not particularly limited as long as it is a compound having two or more (meth) acryloyl groups. For example, an aliphatic polyhydroxy compound and (meth) acrylic acid The polyfunctional (meth) acrylate obtained by reacting, the polyfunctional (meth) acrylate modified with caprolactone, the polyfunctional (meth) acrylate modified with alkylene oxide, the (meth) acrylate having a hydroxyl group and the polyfunctional isocyanate are reacted. And a polyfunctional urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with an acid anhydride, and the like.

  Examples of the aliphatic polyhydroxy compound include trivalent or more divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. And aliphatic polyhydroxy compounds.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dihydrate. And methacrylate.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate.

  Examples of the acid anhydride include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic acid. And dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955.

  Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include, for example, ethylene oxide of bisphenol A and / or propylene oxide-modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide-modified tri (meth) acrylate. , Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of trimethylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) of pentaerythritol ) Ethylene oxide and / or propylene oxide modified penta (meth) acrylate of acrylate and dipentaerythritol Over DOO, ethylene oxide dipentaerythritol and / or propylene oxide-modified hexa (meth) acrylate.

  Among these polyfunctional (meth) acrylates, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone Polyfunctional urethane (meth) acrylate and polyfunctional (meth) acrylate having a carboxyl group are preferred. Among polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, di Among the polyfunctional (meth) acrylates in which pentaerythritol hexaacrylate is a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, dipentaerythritol pentaacrylate and succinic anhydride are reacted. The compound obtained in this way is particularly preferred from the viewpoint of good alkali developability.

  [E] Polyfunctional (meth) acrylates may be used alone or in admixture of two or more.

  [E] The content of the compound is preferably 1 part by mass to 100 parts by mass and more preferably 5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the polymer component [A]. [E] By making content of a compound into the said range, while being able to raise the hardness of a cured film more, the radiation sensitivity of the said radiation sensitive resin composition can be raised more.

<[F] Photoradical polymerization initiator>
[F] The radical photopolymerization initiator generates a radical capable of initiating polymerization of the [E] polyfunctional (meth) acrylate by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like. A compound.

  [F] Photoradical polymerization initiators include, for example, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, benzoin compounds, benzophenone compounds, α-diketone compounds , Polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like.

  [F] The radical photopolymerization initiator may be used alone or in combination of two or more. [F] The photo radical polymerization initiator is preferably a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, or an O-acyloxime compound.

  [F] Among photoradical polymerization initiators, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis ( 2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, Examples include 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a [F] radical photopolymerization initiator, it is preferable to use a hydrogen donor together at the point which can improve a radiation sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And amine-based hydrogen donors. The hydrogen donor may be used alone or in combination of two or more. From the viewpoint of improving the radiation sensitivity, it is preferable to use one or more mercaptan hydrogen donors in combination with one or more amine hydrogen donors.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5 -Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n- butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

  Examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, and 1- [9-ethyl-6. -(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) ) Methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  [F] The content of the radical photopolymerization initiator is preferably 0.01 parts by mass to 120 parts by mass and more preferably 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the [E] polyfunctional (meth) acrylate. preferable. [F] If the content of the photoradical polymerization initiator is too small, curing by exposure may not be sufficiently obtained. On the other hand, if the content of the [F] radical photopolymerization initiator is too large, the pattern tends to fall off the substrate during development.

<[G] Surfactant>
[G] Surfactant is a component that enhances the film-forming property of the radiation-sensitive resin composition. [G] Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. The said radiation sensitive resin composition can improve the surface smoothness of a coating film by containing [G] surfactant, As a result, the film thickness uniformity of a cured film can be improved more.

  As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable. For example, 1,1,2,2-tetrafluoro n-octyl (1,1,2,2-tetrafluoro n-propyl) ether, 1,1,2,2-tetrafluoro n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2, , 2,3,3-hexafluoro n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro n-butyl) ether, hexapropylene glycol di (1,1,2,2,3) , 3-Hexafluoron-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoron-butyl) ether , Sodium perfluoro n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylpolyoxyethylene ether Perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester, and the like.

  Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (above, BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, and F471. F476 (above, Dainippon Ink & Chemicals, Inc.), Florard FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M), Surflon S-112, S-113 S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Asahi Glass Co., Ltd.), F-Top EF301, EF303, EF352 (Shin-Akita Kasei Co., Ltd.), Footent FT-100, FT-1 0, FT-140A, FT-150, FT-250, FT-251, FT-300, FT-310, FT-400S, FTX-218, FT-251 (above, Neos Manufactured) and the like.

  Examples of commercially available silicone surfactants include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, and SZ-6032. SF-8428, DC-57, DC-190, DC-190, SH 8400 FLUID (above, Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF -4452 (above, GE Toshiba Silicone), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) and the like.

  [G] As content of surfactant, [A] 0.01 mass part-2 mass parts are preferable with respect to 100 mass parts of polymer components, and 0.05 mass part-1 mass part or less are more preferable. . [G] By setting the content of the surfactant in the above range, the film thickness uniformity of the coating film can be further improved.

<[H] Adhesion aid>
[H] The adhesion assistant is a component that improves the adhesion between a cured film and an inorganic substance serving as a substrate, for example, a silicone compound such as silicone, silicone oxide, or silicon nitride, or a metal such as gold, copper, or aluminum. [H] The adhesion assistant is preferably a functional silane coupling agent. As said functional silane coupling agent, the silane coupling agent etc. which have reactive substituents, such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group (preferably oxiranyl group), a thiol group, etc. are mentioned, for example.

  Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycidoxy. Examples include propyltrimethoxysilane, 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.

  [H] The content of the adhesion assistant is preferably 0.5 parts by mass to 20 parts by mass and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the polymer component [A]. [H] By making the content of the adhesion assistant in the above range, the adhesion between the cured film and the substrate is further improved.

<Method for preparing radiation-sensitive resin composition>
The said radiation sensitive resin composition mixes a [A] polymer, a [B] nonionic photoacid generator, a [C] ionic compound, a suitable component as needed, and other arbitrary components with a solvent. Prepared in a dissolved or dispersed state. For example, the said radiation sensitive resin composition can be prepared by mixing each component in a predetermined ratio in a solvent.

  As the solvent, a solvent in which each component is uniformly dissolved or dispersed and does not react with each component is preferably used. Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, and aromatics. Examples include hydrocarbons, ketones, and other esters.

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

  Examples of the ethers include tetrahydrofuran.

  Examples of the glycol ether include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

  Examples of the ethylene glycol alkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and the like.

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

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

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

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

  Examples of the aromatic hydrocarbons include toluene and xylene.

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

  Examples of the other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and ethyl 2-hydroxy-2-methylpropionate. , Methyl hydroxyacetate, ethyl hydroxyacetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropion Acid butyl, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, , Methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxy Ethyl propionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, -Butyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3- Examples include propyl propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

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

<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 of the present invention includes a step of forming a coating film on a substrate (hereinafter also referred to as “step (1)”), a step of irradiating at least a part of the coating film (hereinafter referred to as “step”). (Also referred to as “(2)”), a step of developing the coating film irradiated with radiation (hereinafter also referred to as “step (3)”), and a step of heating the developed coating film (hereinafter referred to as “step (4)”). ”).

[Step (1)]
In this step, the radiation-sensitive resin composition is used and applied onto a substrate to form a coating film. Preferably, the solvent is removed by prebaking the coated surface.

  Examples of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and a hydrogenated product thereof. As prebaking conditions, although it changes also with kinds, compounding ratios, etc. of each component, it can be set as 70 degreeC-120 degreeC, about 1 minute-10 minutes.

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

[Step (3)]
In this step, the coating film irradiated with the radiation is developed. By developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern. As the developer used in this development 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, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. It is done.

  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. The concentration of alkali in the aqueous alkali solution is preferably 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. 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 about 10 seconds to 180 seconds. Subsequent to such development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

[Step (4)]
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 about 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device, but is, for example, about 5 to 30 minutes for a hot plate and about 30 to 90 minutes for an oven. Moreover, the step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the desired cured film can be formed on the surface of the substrate. The thickness of the cured film is preferably 0.1 μm to 8 μm, and more preferably 0.1 μm to 6 μm.

  According to the method for forming a cured film, a cured film having high pattern shape stability can be formed. Further, since the amount of change in the film thickness of the unexposed portion can be suppressed, the production process margin can be improved as a result, and the yield can be improved. Furthermore, a cured film having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development and heating utilizing photosensitivity.

<Curing film>
The cured film of the present invention is formed from the radiation sensitive resin composition. Since the said cured film is formed from the said radiation sensitive resin composition, it is excellent in a radiation sensitivity and adhesiveness. Since the cured film has the above properties, it is suitable as, for example, an interlayer insulating film of a display element, a spacer, a protective film, a color filter coloring pattern, or the like. In addition, although it does not specifically limit as a formation method of the said cured film, It is preferable to use the formation method of the said cured film mentioned above.

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

  As a method for manufacturing the 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. Using an object, an interlayer insulating film, a spacer, a protective film, or both are formed according to the method for forming a cured film described above. 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. Then, the display element of the present invention is bonded to both outer surfaces of the liquid crystal cell such that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. can get.

  As another method for manufacturing a 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, the 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 manufacturing method of each 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, the H film itself The polarizing plate which consists of, etc. are mentioned.

  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 material that separates the light emitting sites, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The measuring method of the weight average molecular weight (Mw) of the polymer synthesize | combined below is shown below.

[Weight average molecular weight (Mw)]
The weight average molecular weight (Mw) was 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>
[Synthesis Example 1] (Synthesis of polymer (A-1))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by weight of methacrylic acid, 50 parts by weight of 1-butoxyethyl methacrylate, 40 parts by weight of 3-methacryloyloxymethyl-3-ethyloxetane and 10 parts by weight of hydroxyethyl methacrylate were substituted with nitrogen, and then gently stirred. I started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1). The polymer (A-1) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.6 mass%.

[Synthesis Example 2] (Synthesis of polymer (A-2))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by weight of methacrylic acid, 40 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of styrene were charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-2) was 9,500. Moreover, the solid content concentration of the polymer solution obtained here was 31.6 mass%.

[Synthesis Example 3] (Synthesis of Polymer (A-3))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 40 parts by mass of tetrahydro-2H-pyran-2-yl methacrylate, 40 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, 10 parts by mass of hydroxyethyl methacrylate, and 10 parts by mass of styrene were charged, and then gently replaced with nitrogen. Stirring started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-3). The polymer (A-3) had a polystyrene equivalent weight average molecular weight (Mw) of 11,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.4 mass%.

[Synthesis Example 4] (Synthesis of polymer (a-1))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 50 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 35 parts by weight of benzyl methacrylate, and 15 parts by weight of hydroxyethyl methacrylate were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (a-1). The polymer (a-1) had a weight average molecular weight (Mw) in terms of polystyrene of 10,500. Moreover, the solid content concentration of the polymer solution obtained here was 31.8 mass%.

[Synthesis Example 5] (Synthesis of polymer (a-2))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, after 40 parts by mass of glycidyl methacrylate, 30 parts by mass of styrene, and 30 parts by mass of benzyl methacrylate were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (a-2). The polymer (a-2) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.0 mass%.

<Preparation of radiation-sensitive resin composition>
The radiation sensitive resin composition was prepared to the composition shown in Table 1. [B] Nonionic photoacid generator, [C] ionic compound and [D] antioxidant, [E] polyfunctional (meth) acrylate, and [F] photoradical polymerization initiator in Table 1 are as follows. As shown.

Ｂ−５：下記式（Ｂ−５）で表されるスルホン酸誘導体化合物

Ｂ−６：下記式（Ｂ−６）で表されるスルホン酸誘導体化合物

Ｂ−７：下記式（Ｂ−７）で表されるスルホン酸誘導体化合物

Ｂ−８：下記式（Ｂ−８）で表されるスルホン酸誘導体化合物

Ｂ−９：下記式（Ｂ−９）で表されるスルホン酸誘導体化合物

Ｂ−１０：下記式（Ｂ−１０）で表されるスルホン酸誘導体化合物

Ｂ−１１：下記式（Ｂ−１１）で表されるスルホン酸誘導体化合物

Ｂ−１２：下記式（Ｂ−１２）で表されるスルホン酸誘導体化合物

Ｂ−１３：下記式（Ｂ−１３）で表されるスルホン酸誘導体化合物

Ｂ−１４：下記式（Ｂ−１４）で表されるスルホン酸誘導体化合物

Ｂ−１５：下記式（Ｂ−１５）で表されるスルホン酸誘導体化合物

Ｂ−１６：下記式（Ｂ−１６）で表されるスルホン酸誘導体化合物

[[B] Nonionic photoacid 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: (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile (“CGI-725” from BASF)
B-4: An oxime sulfonate compound represented by the following formula (B-4) ("IRGACURE PAG 203" from BASF)

B-5: A sulfonic acid derivative compound represented by the following formula (B-5)

B-6: A sulfonic acid derivative compound represented by the following formula (B-6)

B-7: A sulfonic acid derivative compound represented by the following formula (B-7)

B-8: A sulfonic acid derivative compound represented by the following formula (B-8)

B-9: A sulfonic acid derivative compound represented by the following formula (B-9)

B-10: A sulfonic acid derivative compound represented by the following formula (B-10)

B-11: A sulfonic acid derivative compound represented by the following formula (B-11)

B-12: A sulfonic acid derivative compound represented by the following formula (B-12)

B-13: A sulfonic acid derivative compound represented by the following formula (B-13)

B-14: A sulfonic acid derivative compound represented by the following formula (B-14)

B-15: A sulfonic acid derivative compound represented by the following formula (B-15)

B-16: A sulfonic acid derivative compound represented by the following formula (B-16)

Ｃ−２：下記式（Ｃ−２）で表されるイオン性化合物

Ｃ−３：下記式（Ｃ−３）で表されるイオン性化合物

[[C] ionic compound]
C-1: an ionic compound represented by the following formula (C-1)

C-2: an ionic compound represented by the following formula (C-2)

C-3: an ionic compound represented by the following formula (C-3)

Ｄ−３：下記式（Ｄ−３）で表されるＡＤＥＫＡ社の「アデカスタブＡＯ−７０」

Ｄ−４：下記式（Ｄ−４）で表されるＡＤＥＫＡ社の「アデカスタブＡＯ−８０」

Ｄ−５：１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン）（ＡＤＥＫＡ製の「アデカスタブＡＯ−３３０」）
Ｄ−６：下記式（Ｄ−６）で表されるＢＡＳＦ社の「ＩＲＧＡＮＯＸ１０９８」

[[D] Antioxidant]
D-1: 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane (“ADEKA STAB AO-30” from ADEKA)
D-2: “ADEKA STAB AO-60” of ADEKA Corporation represented by the following formula (D-2)

D-3: “ADEKA STAB AO-70” of ADEKA Corporation represented by the following formula (D-3)

D-4: “ADEKA STAB AO-80” of ADEKA Corporation represented by the following formula (D-4)

D-5: 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (“ADEKA STAB AO-330” manufactured by ADEKA)
D-6: “IRGANOX 1098” from BASF represented by the following formula (D-6)

[E] Multifunctional (meth) acrylate E-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“KAYARAD DPHA” from Nippon Kayaku Co., Ltd.)
E-2: Succinic acid-modified pentaerythritol triacrylate (“Aronix TO-756” manufactured by Toagosei Co., Ltd.)
E-3: Trimethylolpropane triacrylate E-4: Mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate (“Biscoat 802” from Osaka Organic Chemical Industry Co., Ltd.)
E-5: Succinic acid-modified dipentaerythritol pentaacrylate (“Aronix M-520” manufactured by Toagosei Co., Ltd.)

[[F] Photoradical polymerization initiator]
F-1: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("Irgacure 907" from BASF)
F-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (“Irgacure OXE02” from BASF)
F-3: 2,4-diethylthioxanthone

(Comparative example)
[B] Ionic photoacid generator b-1: triphenylsulfonium trifluoromethanesulfonate

[C] Amine compound c-1: 4-dimethylaminopyridine

[Example 1]
In a polymer solution containing polymer (A-1) (amount corresponding to 100 parts by mass (solid content) of (A-1)), 3 parts by mass of photoacid generator (B-1), and an ionic compound ( C-1) A radiation sensitive resin composition was prepared by mixing 0.2 parts by mass and filtering through a membrane filter having a pore size of 0.2 μm.

[Examples 2 to 15 and Comparative Examples 1 and 2]
A radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that the components having the types and contents shown in Table 1 were used. In addition, "-" in Table 1 indicates that the corresponding component was not blended.

[Example 16]
Polymer solution containing polymer (a-1) (amount corresponding to 50 parts by mass (solid content) of (a-1)) and polymer solution containing polymer (a-2) ((a-2) The amount corresponding to 50 parts by mass (solid content) was mixed to obtain [A] polymer component. In this [A] polymer component, [B] photoacid generator (B-16) 5 parts by mass, [C] ionic compound (C-3) 0.08 parts by mass, [D] antioxidant (D -2) After mixing 0.5 part by mass, 5 parts by mass of [E] photopolyfunctional (meth) acrylate, and 1 part by mass of [F] photoradical polymerization initiator (F-3), the pore diameter is 0.2 μm. The radiation sensitive resin composition was prepared by filtering with a membrane filter.

[Examples 17 to 20 and Comparative Examples 3 and 4]
A radiation-sensitive resin composition was prepared in the same manner as in Example 16 and Comparative Example 3 except that the components having the types and blending amounts shown in Table 1 below were used.

<Evaluation>
Using the radiation-sensitive resin compositions of Examples 1 to 20 and Comparative Examples 1 to 4, evaluation of radiation sensitivity, light resistance, transmittance, pattern adhesion, voltage holding ratio, and storage stability was performed. The evaluation results are shown in Table 2.

[Evaluation of radiation sensitivity]
A radiation sensitive resin composition was applied onto a glass substrate 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. 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. Then, it developed by the piling method for 80 seconds at 25 degreeC with 0.5 mass% tetramethylammonium hydroxide aqueous solution. Next, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the amount of exposure necessary to completely dissolve the 6 μm space pattern was examined. When the exposure value is 500 (J / m ² ) or less, it can be determined that the sensitivity is good.

[Evaluation of light resistance]
A radiation sensitive resin composition was applied onto a silicon substrate 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. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a cured film. Each of the obtained cured films was irradiated with 800,000 J / m ² at an illuminance of 130 mW using a UV irradiation apparatus (“UVX-02516S1JS01” manufactured by Ushio Inc.). It can be said that the light resistance of the cured film is good when the amount of film thickness reduction after irradiation is 3% or less compared to the film thickness before irradiation.
In the evaluation of light resistance, since the patterning of the cured film to be formed is unnecessary, the development process was omitted, and only the coating film forming process, the light resistance test, and the heating process were performed for evaluation.

[Evaluation of transmittance]
Similar to the light resistance evaluation, a coating film was formed on a silicon substrate using the radiation-sensitive resin composition. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to form a cured film. About this cured film, the transmittance | permeability in wavelength 400nm was measured and evaluated using the spectrophotometer ("150-20 type double beam" of Hitachi, Ltd.). At this time, it can be said that the transparency is poor when the transmittance is less than 90%.

[Evaluation of pattern adhesion]
The adhesion of the pattern was evaluated after exposure. Specifically, first, a radiation sensitive resin composition is applied onto a glass substrate 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. did. Subsequently, 700 (J / m ² ) was passed through a mask having a 10 μm line-and-space (one-to-one) pattern using an exposure machine (“MPA-600FA (ghi line mixing)” manufactured by Canon Inc.). ). Thereafter, it was left in a clean room for 1 hour, and then developed with a 0.5 mass% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 80 seconds. Next, 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 to confirm the presence or absence of pattern peeling. The criteria for determining pattern adhesion are shown below.

When pattern peeling is hardly seen: “○”
When pattern peeling is slightly seen: “△”
When the pattern is peeled off and almost no pattern remains on the substrate: “×”

[Evaluation of voltage holding ratio]
After a SiO ₂ film for preventing elution of sodium ions is formed on the surface, and a soda glass substrate on which an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape, a radiation sensitive composition is spin-coated, and then 90 Pre-baking was performed for 10 minutes in a clean oven at 0 ° C. to form a coating film having a thickness of 2.0 μm. Next, the coating film was exposed at an exposure amount of 500 J / m ² without using a photomask. Thereafter, post-baking was performed at 230 ° C. for 30 minutes to cure the coating film to form a permanent cured film.

  Next, a substrate on which this pixel is formed and a substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 0.8 mm glass beads, and then a cell is formed. A liquid crystal cell was manufactured by injecting “Liquid Crystal MLC6608”). Further, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system (“VHR-1A type” manufactured by Toyo Corporation). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz.

  Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a high risk of causing "burn-in".

[Evaluation of storage stability]
The radiation-sensitive composition solution was left in an oven at 40 ° C. for 1 week, and the viscosity before and after being placed in the oven was measured to determine the rate of change in viscosity (%). At this time, when the viscosity change rate is 5% or less, the storage stability is good, and when it exceeds 5%, the storage stability is poor. The evaluation results are shown in Table 2.

  As is clear from the results in Table 2, Examples 1 to 20 were excellent in radiation sensitivity, light resistance, transmittance, voltage holding ratio, and storage stability. On the other hand, in Comparative Examples 1 to 4, good results were not obtained for radiation sensitivity, light resistance, transmittance, voltage holding ratio, and storage stability.

  INDUSTRIAL APPLICABILITY The present invention can provide a radiation-sensitive composition that sufficiently satisfies general characteristics such as radiation sensitivity, is excellent in storage stability, and can reduce poor adhesion of a cured film. 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. Accordingly, 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 a manufacturing process of a liquid crystal display device or the like.

Claims (10)

A polymer component comprising a first structural unit having an acid-dissociable group and a second structural unit having a crosslinkable group;
A radiation-sensitive resin composition comprising a nonionic photoacid generator having a sulfonyl group and an ionic compound represented by the following formula (1).

(In the formula (1), ^{R 1} is a hydrogen atom or a monovalent organic group-A ^{-. _{Is, -N - -SO 2 -R A,}} -COO -, -O - or -SO ₃ ^- in R ^A is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms or a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, provided that R ^{A is} a hydrocarbon. (Part or all of the hydrogen atoms contained in the group may be substituted with fluorine atoms. X ⁺ is an onium cation.) The radiation sensitive resin composition according to claim 1, wherein X ⁺ in the formula (1) is an onium cation represented by the following formula (1-1) or formula (1-2).

(In formulas (1-1) and (1-2), R ^{2 to} R ⁶ are a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, —S—R ^B , —OSO ₂ —R ^C , or _-SO 2 -R ^D .R ^B is .R ^C and ^{R D} is an alkyl or aryl group are each independently an alkyl group, a cycloalkyl group, an alkoxy group or an aryl group. However , R ^{2 to} R ⁶ , R ^B , R ^C, and R ^D may be partially or wholly substituted on some or all of the hydrogen atoms of the alkyl group, cycloalkyl group, alkoxy group, and aryl group. , D and e are each independently an integer of 0 to 5.)   The radiation sensitive resin composition according to claim 1 or 2, wherein a content of the ionic compound is 0.01 parts by mass or more and 1.00 parts by mass or less with respect to 100 parts by mass of the polymer component. The radiation-sensitive resin composition according to claim 1, wherein the first structural unit is represented by the following formula (2) or the following formula (3).

(In Formula (2), R ⁷ is a hydrogen atom or a methyl group. R ⁸ is a linear or branched alkyl group having 1 to 12 carbon atoms. R ⁹ is a C 1 to 12 carbon atom. A linear or branched alkyl group, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.
In Formula (3), R ¹⁰ is a hydrogen atom or a methyl group. R ^{11 to} R ¹⁷ are a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms. f is 1 or 2. However, if f is 2, between the two R ¹⁶ together and the two R ¹⁷ may be different even in the same. )   The radiation sensitive resin composition according to any one of claims 1 to 4, wherein the crosslinkable group of the second structural unit is a (meth) acryloyl group, an oxiranyl group, or an oxetanyl group. The radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the nonionic photoacid generator is a compound represented by the following formula (4).

(In Formula (4), R ¹⁸ and R ^{21 to} R ²³ are hydrogen atoms. One of R ¹⁹ and R ²⁰ is a linear or branched C 4-18 alkoxy group, this alkoxy group. A group in which a methylene group at any position not adjacent to the oxygen atom is substituted with a -C (= O)-group, and the alkoxy group is closer to the naphthalene ring from the -O-C (= O) -bond or -OC ( ═O) a group interrupted by —NH— bond, a linear or branched alkylthio group having 4 to 18 carbon atoms, or a methylene group at any position not adjacent to the sulfur atom of this alkylthio group is —C (═O) A group substituted with a-group, a group interrupted by an -O-C (= O)-bond or -OC (= O) -NH- bond from the side closer to the naphthalene ring, or the following formula (5 ), Provided that R ¹⁹ and Some or all of the hydrogen atom of the alkoxy group and alkylthio group of R ²⁰ is an alicyclic hydrocarbon group and the other of the heterocyclic may be substituted with group or a halogen atom .R ¹⁹ and R ²⁰ are hydrogen atoms R ²⁴ represents a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, a halogen atom and an alicyclic ring. A linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted on at least one of the formula hydrocarbon groups, or a monovalent having 3 to 18 carbon atoms which may be substituted with a halogen atom. An aryl group having 6 to 20 carbon atoms, a halogen atom and 1 to 18 carbon atoms which may be substituted at least one of an alicyclic hydrocarbon group, a halogen atom and an alkylthio group having 1 to 18 carbon atoms. An arylalkyl group having 7 to 20 carbon atoms which may be substituted, at least one of the alkylthio groups of the above, an alkylaryl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, or an acyl group. (It is a C7-20 aryl group, a 10-camphoryl group, or a group represented by the following formula (6).)

(In Formula (5), R ²⁵ is a divalent hydrocarbon group having 1 to 12 carbon atoms. R ²⁶ is an alkanediyl group having 1 to 4 carbon atoms. R ²⁷ is a hydrogen atom or carbon atom. A linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group or a monovalent heterocyclic group having 3 to 10 carbon atoms, and Y ¹ represents an oxygen atom or a sulfur atom. Y ² is a single bond or an alkanediyl group having 1 to 4 carbon atoms, and g is an integer of 0 to 5.)

(In the formula (6), R ²⁸ represents an alkanediyl group having 2 to 6 carbon atoms, a halogenated alkanediyl group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogen having 6 to 20 carbon atoms. R ²⁹ is a single bond, an alkanediyl group having 2 to 6 carbon atoms, a halogenated alkanediyl group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. R ³⁰ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched halogenated alkyl group having 1 to 18 carbon atoms, or a carbon number of 3 to 3. 12 monovalent alicyclic hydrocarbon groups, aryl groups having 6 to 20 carbon atoms, halogenated aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, or halogens having 7 to 20 carbon atoms An arylalkyl group .Y ³ is .h and i is a single bond or an alkanediyl group having 1 to 4 carbon atoms, one is 1 and the other is 0 or 1.)   The radiation sensitive resin composition according to any one of claims 1 to 6, further comprising an antioxidant.   The cured film formed from the radiation sensitive resin composition of any one of Claims 1-7. A cured film comprising a step of forming a coating film on a substrate, a step of irradiating at least a part of the coating film, a step of developing a coating film irradiated with radiation, and a step of heating the developed coating film A forming method of
A method for forming a cured film, wherein the radiation-sensitive resin composition according to any one of claims 1 to 8 is used for forming the coating film.   A display element provided with the cured film of Claim 8.