KR20150016087A - Radiation-sensitive resin composition, cured film, method for forming the same, and display element - Google Patents

Abstract

Provided is a radiation-sensitive resin composition, wherein general properties, such as radiation sensitivity, required for a radiation-sensitive resin composition can be sufficiently satisfied, and storing stability is excellent at the same time, so that defective adhesion of a hardening film can be reduced. Moreover, the present invention provides a hardening film produced using the radiation-sensitive resin composition, a method for producing the same, and a display device equipped with the hardening film. The radiation-sensitive resin composition of the present invention contains: a polymer component including a first structure unit having an acid dissociation group and a second structure unit having a cross-linking group; a non-ionic photoacid generating agent having a sulfonyl group; and an ionic compound represented by Formula (1). In Formula (1), R^1 is a hydrogen atom or a univalent organic group. -A^- is -N^--SO^2-R^A, -COO^-, -O^-, or -SO_3^-. R^A is a straight-chain, branched-chain, or cyclic univalent hydrocarbon group. X^+ is an onium cation.

Description

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

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

Display elements such as a thin film transistor type liquid crystal display element and an organic electroluminescence element generally have 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 radiation-sensitive resin composition using an acid generator such as naphthoquinone diazide has been used from the viewpoint of patterning performance (see Japanese Patent Application Laid-Open No. 2001-354822) Branched radiation sensitive compositions have been proposed.

For example, Japanese Patent Laid-Open No. 2004-4669 discloses a positive-type radiation sensitive resin composition for forming a cured film for a display element with a sensitivity higher than that of a positive radiation sensitive resin composition using an acid generator such as naphthoquinone diazide Type chemically amplified materials have been proposed. This positive chemical amplification material contains a crosslinking agent, an acid generator, and an acid dissociable resin. The acid dissociable resin has a protecting group which can be cleaved by the action of an acid and is insoluble or hardly soluble in an aqueous alkaline solution. However, the protecting group is cleaved by the action of an acid, Availability. In JP-A-2004-264623 and JP-A-2008-304902, a positive radiation-sensitive composition containing an acid generator, a resin having an acetal structure and / or a ketal structure and an epoxy group is proposed have.

However, in the case of using these radiation-sensitive resin compositions, particularly in the case of using a positive type chemically amplified material, the acid generated in the exposure is neutralized in a basic substance in the atmosphere during the period of time left until the heating step, Or the acid may diffuse into the unexposed portion. If such an acid is inactivated or diffused, the adhesion between the substrate and the cured film deteriorates (see JP-A-6-266100).

When a glass substrate of a large size is used, the exposure after exposure often occurs in the manufacturing process. For this reason, a radiation-sensitive resin composition capable of stably forming a pattern by reducing the influence of exposure after exposure has been desired.

It is conceivable to reduce the diffusion of the acid to the unexposed portion in order to reduce the influence of the exposure after exposure. In order to suppress the diffusion of 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, and therefore, there is a concern that the storage stability of the radiation-sensitive resin composition may be deteriorated.

As described above, it is difficult to both suppress the deterioration of the adhesion of the cured film due to the diffusion of acid and the like and the storage stability of the radiation-sensitive resin composition. On the other hand, since the radiation-sensitive resin composition requires general characteristics such as radiation sensitivity, it is necessary to consider the above general characteristics in order to improve the adhesiveness and storage stability of the cured film.

Japanese Patent Application Laid-Open No. 2001-354822 Japanese Laid-Open Patent Publication No. 2004-4669 Japanese Patent Application Laid-Open No. 2004-264623 Japanese Patent Application Laid-Open No. 2008-304902 Japanese Patent Application Laid-Open No. 6-266100

The present invention has been accomplished on the basis of the above-described circumstances, and it is an object of the present invention to provide a radiation-sensitive resin composition which is excellent in general characteristics and storage stability required for a radiation-sensitive resin composition such as radiation sensitivity and capable of reducing poor adhesion of a cured film And to provide the above objects. Another object of the present invention is to provide a cured film formed from the radiation sensitive resin composition, a method of forming the same, and a display device including the cured film.

(Hereinafter referred to as " structural unit (II) ") having a crosslinkable group and a second structural unit (hereinafter referred to as " structural unit (Hereinafter, also referred to as a "[B] nonionic photoacid generator") having a sulfonyl group (hereinafter, also referred to as a " , And an ionic compound represented by the following formula (1) (hereinafter also referred to as " [C] ionic compound "))

(Formula (1) of, R ¹ is a hydrogen atom or a monovalent organic group, and; -A ^{- _{is, -N - -SO 2 -R A,}} -COO -, -O - or -SO ₃ ^-, and; R ^A is a linear or branched monovalent hydrocarbon group of 1 to 10 carbon atoms or a monovalent monovalent hydrocarbon group of 3 to 20 carbon atoms, provided that a part or all of the hydrogen atoms of the hydrocarbon group of R ^A are substituted with fluorine atoms And X ^< ^{+ &} gt ^; is an onium cation).

Another invention made to solve the above problems is a display element comprising a cured film formed of the radiation sensitive resin composition and the cured film.

The method of forming a cured film of 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 with radiation, a step of developing the coating film irradiated with the radiation, and a step of heating the developed coating film Wherein the radiation-sensitive resin composition is used for forming the coating film.

The present invention can provide a radiation-sensitive resin composition that satisfactorily satisfies general characteristics such as radiation sensitivity and is excellent in storage stability and can reduce the poor adhesion property of the cured film. The present invention can also provide a cured film formed of the radiation sensitive resin composition, a method for forming the same, and a display element provided with the cured film. Accordingly, the radiation sensitive resin composition, the cured film, the method of forming the same, and the display element can be suitably used for a manufacturing process of a liquid crystal display device or the like.

(Mode for carrying out the invention)

<Radiation-Resistant Resin Composition>

The radiation sensitive resin composition of the present invention contains a polymer component [A], a nonionic photoacid generator [B] and an ionic compound [C]. Further, the radiation sensitive resin composition may contain [D] antioxidant as a suitable component. The radiation sensitive resin composition may contain other optional components as long as the effect of the present invention is not impaired. Each component will be described in detail below.

&Lt; [A] Polymer Component &gt;

[A] The polymer component includes a structural unit (I) having an acid dissociable group and a structural unit (II) having a crosslinkable group. The polymer component [A] may contain one structural unit (I) and one structural unit (II), and may contain two or more structural units either or both. The polymer component [A] may include (1) one kind of polymer molecule A having both of the structural unit (I) and the structural unit (II), (2) the polymer molecule B1 having the structural unit And polymer molecule B2 having the structural unit (II), and (3) the polymer molecule A and the polymer molecule B1 and / or the polymer molecule B2. The polymer component [A] may contain other structural units within the range not to impair the effects of the present invention.

The radiation sensitive resin composition is excellent in radiation sensitivity because the polymer component has the structural unit (I) and the structural unit (II), and at the same time, the radiation sensitive resin composition is excellent in radiation sensitivity and the film thickness of the unexposed portion after the post- The 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 the carboxyl group, the phenolic hydroxyl group and the like in the polymer. The polymer having such a protecting group is usually insoluble or sparingly soluble in an aqueous alkali solution. In this polymer, since the protecting group is an acid-dissociable group, the protecting group is cleaved by the action of an acid to become soluble in an aqueous alkali solution.

In the radiation sensitive resin composition of the present invention, the polymer component has the structural unit (I) so that a high radiation sensitivity can be attained and the stability of the pattern shape obtained by development or the like can be improved.

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

In the 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 linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms such as a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, Tyl group and the like. Examples of the branched alkyl group having 1 to 12 carbon atoms represented by R ⁸ and R ⁹ include an i-propyl group, an i-butyl group, a t-butyl group and a neopentyl group.

Examples of the monovalent alicyclic hydrocarbon group having ⁴ to 20 carbon atoms represented by R ⁹ include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group , Ethylcyclohexyl group, and other monocyclic cycloalkyl groups;

Cyclic cyclic groups such as cyclopentenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl and cyclodecadienyl; An alkenyl group; A bicyclic [2.2.2] octyl group, a tricyclo [5.2.1.0 ^2,6 ] decyl group, a tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecyl group, a norbornyl group and an adamantyl group A polycyclic cycloalkyl group and the like.

Examples of the structural unit represented by the formula (2) include structural units represented by the following formulas (2-1) to (2-10).

In the formulas (2-1) to (2-10), R ⁷ has the same meaning as R ⁷ in the formula (2).

Examples of the monomer giving the structural unit represented by the formula (2) include 1-ethoxyethyl methacrylate, 1-butoxyethyl methacrylate, 1- (tricyclodecanyloxy) ethyl methacrylate , Ethyl methacrylate, 1- (pentacyclopentadecanylmethyloxy) ethyl methacrylate, 1- (pentacyclopentadecanyloxy) ethyl methacrylate, 1- (tetracyclododecanylmethyloxy) ethyl methacrylate, And acid 1- (adamantyloxy) ethyl.

In the formula (3), R ¹⁰ is a hydrogen atom or a methyl group. R ¹¹ to R ¹⁷ are each a hydrogen atom or a straight or branched alkyl group having 1 to 12 carbon atoms. f is 1 or 2; When f is 2, two R ^{16 s} and two R ^{17 s} may be the same or different.

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms represented by R ¹¹ to R ¹⁷ include the same groups as the linear or branched alkyl group having 1 to 12 carbon atoms represented by R ⁸ and R ⁹ in the formula (2) .

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

In the formulas (3-1) to (3-5), R ¹⁰ has the same meaning as R ¹⁰ in the formula (3).

As the monomer giving 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 from 0.1 mol% to 80 mol%, and more preferably from 1 mol% to 60 mol%, based on the total structural units constituting the polymer component [A]. By setting the content of the structural unit (I) in the above range, high radiation sensitivity can be attained, and the stability of the pattern shape obtained by development or the like can be effectively improved.

[Structural unit (II)]

The structural unit (II) contains a crosslinkable group. The cured film formed from the radiation sensitive resin composition of the present invention is a cured film formed from the radiation sensitive resin composition in which the polymer component has a structural unit (II) containing a crosslinkable group, whereby the polymer constituting the polymer component [A] or the polymer component Can be strengthened by cross-linking with a [D] antioxidant to be described later.

Examples of the crosslinkable group include a group containing a polymerizable carbon-carbon double bond, a group containing a polymerizable carbon-carbon triple bond, an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), alkoxymethyl group, formyl group, acetyl group, dialkylaminomethyl group, dimethylolaminomethyl group and the like.

As the crosslinkable group, a (meth) acryloyl group, an oxiranyl group or an oxetanyl group is preferable. Thus, the strength of the cured film formed from the radiation sensitive resin composition can be further increased.

Examples of the structural unit (II) include structural units represented by the following formulas.

Wherein R ^E is a hydrogen atom or a methyl group.

As the monomer giving the structural unit (II), a monomer including a (meth) acryloyl group, an oxiranyl group and an oxetanyl group is preferable, a monomer containing an oxiranyl group and an oxetanyl group is more preferable, 3-methacryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate, More preferable.

The content of the structural unit (II) is preferably from 0.1 mol% to 80 mol%, more preferably from 1 mol% to 60 mol%, based on the total structural units constituting the polymer component [A]. When the content of the structural unit (II) is within the above range, the strength of the cured film formed from the radiation sensitive resin composition can be effectively increased.

[Other structural units]

The polymer component [A] may have other structural units other than the structural unit (I) and the structural unit (II) within the range that does not impair the effect of the present invention.

Examples of the monomer giving 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, (meth) acrylic acid aryl esters , An unsaturated aromatic compound, a conjugated diene, and an unsaturated compound having a tetrahydrofuran skeleton.

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. The anhydrides of the unsaturated dicarboxylic acids include, for example, anhydrides of the compounds exemplified as the dicarboxylic acids. Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl ], Hexahydrophthalic acid mono 2- (methacryloyloxy) ethyl, and the like. Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals include ω-carboxypolycaprolactone mono (meth) acrylate and the like. Examples of the unsaturated polycyclic compound having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] And the like.

Among them, a monocarbonic acid and an anhydride of a dicarboxylic acid are preferable, and (meth) acrylic acid and maleic anhydride are more preferable from the viewpoint of solubility and availability of an aqueous alkaline solution and copolymerization reactivity.

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, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate and the like.

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

Examples of the (meth) acrylic acid cyclic alkyl esters include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-methacrylic acid, Tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl, methacrylic acid isoboronyl, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane -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 esters include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.

Examples of the unsaturated aromatic compound include styrene,? -Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-tolyl maleimide, N-naphthyl maleimide, N-ethyl maleimide, N-hexyl maleimide and N-benzyl maleimide.

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

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

The content of the other structural units is preferably from 5 mol% to 30 mol%, more preferably from 10 mol% to 25 mol%, based on the total structural units. By setting the content ratio of the other structural units to 5 to 30 mol%, a radiation-sensitive resin composition having excellent solubility in an alkali aqueous solution and excellent radiation sensitivity can be obtained.

<Method of synthesizing polymer component [A]

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

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

As the polymerization initiator to be used in the polymerization reaction, those known as radical polymerization initiators can be used, and examples thereof include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azo Azo compounds such as bisisobutyronitrile, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis (methyl 2-methylpropionate); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; Hydrogen peroxide and the like.

In the polymerization reaction of the polymer component [A], a molecular weight modifier may be used to adjust the molecular weight. Examples of the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like.

The polystyrene-reduced weight average molecular weight (Mw) of the polymer [A] by the gel permeation chromatography (GPC) is preferably 2.0 x 10 ³ or more and 1.0 x 10 ⁵ or less, more preferably 3.0 x 10 ³ or more and 5.0 x 10 ⁴ or less And more preferably 5.0 x 10 ³ or more and 2.0 x 10 ⁴ or less. By setting the Mw of the polymer component [A] within the above range, the sensitivity and alkali developability of the radiation sensitive resin composition can be increased.

The polystyrene reduced number average molecular weight (Mn) of the polymer component [A] by GPC is preferably 2.0 x 10 ³ or more and 1.0 x 10 ⁵ or less, more preferably 3.0 x 10 ³ or more and 5.0 x 10 ⁴ or less, More preferably not less than 10 ^{3 and not} more than 2.0 × 10 ⁴ . By setting the Mn of the polymer [A] within the above range, the curing reactivity at the time of curing the coating film of the radiation sensitive resin composition can be improved.

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

<[B] Nonionic photoacid generator>

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

 The radiation-sensitive resin composition of the present invention can exhibit the radiation sensitivity characteristic and can have a good radiation sensitivity by containing the [B] nonionic photo-acid generator.

The form of the [B] nonionic photoacid generator in the radiation-sensitive resin composition may be a form of a compound described later, or a form of a photoacid generator embedded as a part of the polymer constituting the polymer component [A] , Or both of them may be used.

Examples of the [B] nonionic photoacid generator include oxime sulfonate compounds, sulfonic acid derivative compounds, and the like. The [B] nonionic photoacid generator may be used singly or in combination of two or more.

[Oxime sulfonate compound]

The 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 formula (7), R ³¹ represents an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, A group in which a part or all of the hydrogen atoms contained in the formula hydrocarbon group and the aryl group is 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 straight or branched alkyl group having 1 to 12 carbon atoms may be substituted by a substituent, and examples of the substituent include an alkoxy group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxononorbornyl group and the like And a cycloaliphatic group including a polycyclic alicyclic group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptyl fluoropropyl group.

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

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

In the formulas (7-1) to (7-3), R ³¹ has the same meaning as R ³¹ in the formula (7). In the formulas (7-1) and (7-2), R ³² is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms.

In the formula (7-3), Y ⁴ is an alkyl group, an alkoxy group or a halogen atom. j is an integer of 0 to 3; Provided that a plurality of Y ⁴ when j is 2 or 3 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 compound represented by the above formulas (7-3-1) to (7-3-5) is preferably (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen- ) 2- (4-methoxyphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen- Methoxyphenyl) acetonitrile, which is commercially available.

[Sulfonic acid derivative compound]

The 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 are hydrogen atoms.

One of R ¹⁹ and R ²⁰ is a straight chain or branched chain alkoxy group having 4 to 18 carbon atoms, a group in which 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 -OC (= O) - bond or -OC (= O) -NH- bond from the side nearest to the naphthalene ring, a straight or branched alkylthio group having 4 to 18 carbon atoms, (= O) - or -OC (= O) - group from the side nearer to the naphthalene ring, a group in which the methylene group at any arbitrary position not adjacent to the sulfur atom of the alkylthio group is substituted with a -C NH-bond, or a group represented by the following formula (5). Provided that a part or all of the hydrogen atoms of the alkoxy group and the alkylthio group of R ¹⁹ and R ²⁰ may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. And the other of R ¹⁹ and R ²⁰ is a hydrogen atom.

In the above formula (5), R ²⁵ is a hydrocarbon group of 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 having 3 to 10 carbon atoms or a heterocyclic group. 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 to 5;

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

In 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 represents 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, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, A halogenated aryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms. h and i have one of 1 and 0 or 1, respectively.

Examples of the linear or branched alkoxy group having 4 to 18 carbon atoms represented by R ¹⁹ or R ²⁰ in the formula (4) include a butyloxy group, a sec-butyloxy group, a tert-butyloxy group, An isoamyloxy group, a tertiary amyloxy group, a hexyloxy group, a heptyloxy group, an isoheptyloxy group, a tertiary heptyloxy group, an octyloxy group, an isooctyloxy group, a tertiary octyloxy group, Heptadecyloxy group, heptadecyloxy group, octadecyl group, octadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyl group, heptadecyloxy group, And the period of time when the painting is finished.

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 sec-butylthio group, a sec-butylthio group, an isobutylthio group, An isoamylthio group, a tert-amylthio group, a tert-amylthio group, a tert-amylthio group, a tert-butylthio group, Dodecylthio group, dodecylthio group, tridecylthio group, tetradecylthio group, pentadecylthio group, hexadecylthio group, heptadecylthio group, octadecylthio group, and the like are preferable .

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 formula (4) is substituted with a -C (= O) - group include a 2-ketobutyl- A 2-ketoheptyl-1-oxy group, a 2-ketooxyl-1-oxy group, a 3-ketobutyl- , A 4-ketoamyl-1-oxy group, a 5-ketohexyl-1-oxy group, a 6-ketoheptyl- 4-oxo group, 3-ketoheptan-5-oxy group, 2-adamantanone-5-ox Time and so on.

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 formula (4) is substituted with a -C (= O) - group include, for example, 2-ketobutyl- , 2-ketoheptyl-1-thio group, 2-ketoheptyl-1-thio group, 3-ketobutyl- 1-thio group, 3-methyl-2-keto, 4-ketoamyl-1-thio group, 5-ketohexyl- Pentan-4-thio group, 2-keto-pentane-4-thio group, 2-methyl-2-keto-pentane-4-thio group and 3-ketoheptan-5-thio group.

The group in which the alkoxy group having 4 to 18 carbon atoms in the formula (4) is interrupted by a -OC (= O) - bond or -OC (= O) -NH- bond from the side closer to the naphthalene ring, (= O) -R ^g or -Y ⁵ -R ^f -OC (= O) -R ^g wherein the alkylthio group of the alkylthio group of the alkylthio group in the naphthalene ring is interrupted by a -OC (= O) -Y ⁵ -R ^f OC (= 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 formula (4). R ^f is a linear or branched alkylene group. The 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. The alkyl group may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom. The total carbon number of 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, and iodine.

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

Examples of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, Bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, groups derived from 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, isooxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, iso The compounds of the present invention can be used in combination with thiochroman, indoline, isoindoline, pyridine, indolizine, indole, indazole, purine, quinolizine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, The present invention relates to the use of a compound selected from the group consisting of thiadiazole, thiadiazine, acridine, perimidine, phenanthroline, carbazole, carbolin, phenadine, antithyridine, thiadiazole, oxadiazole, triazine, triazole, tetrazole, , Benzothiazole, benzothiadiazole, benzofuroxan, naphtoimidazole, benzotriazole, tetraazindene, the above An unsaturated bond or a conjugated bond present in the heterocyclic compound and the like can be mentioned groups derived from a saturated heterocyclic ring the hydrogenation (tetrahydrofuran ring, etc.) compounds.

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, Cyclohexyloxy group, methylcyclohexyloxy group, norbornylmethyloxy group, trimethylcyclohexyloxy group, 1-methylcyclohexyloxy group, norbornyloxy group, ethylcyclohexyloxy group, cyclohexylethyloxy group, dimethylcyclohexyloxy group, -Cyclohexylbutyloxy group, adamantyloxy group, menthyloxy group, n-butylcyclohexyloxy group, tert-butylcyclohexyloxy group, boronyloxy group, isobornyloxy group, decahydronaphthyloxy group, Cyclohexylmethyloxy group, dienoxy group, 1-cyclohexylpentyloxy group, methyladamantyloxy group, adamantanemethyloxy group, 4-amylcyclohexyloxy group, cyclohexyl Cyclohexyloxy group, adamantylethyloxy group, and dimethyladamantyloxy group.

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 , And indoleoxy group.

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 by the heterocyclic group include a furfurylthio group, a tetrahydrofurfurylthio group, and the like.

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented by R ²⁵ in the formula (5) include aliphatic hydrocarbon groups such as alkanediyl groups, alkenediyl groups and alkynediyl groups, alicyclic hydrocarbon groups such as cycloalkanediyl groups, A hydrocarbon group, a group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded, and the like. Specific examples of the hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butylene group, A cyclohexylene group, a cyclohexylmethylene group, a cyclohexylene group, a cyclohexylene group, an octylene group, a cyclohexyleneethylene group, a methylene cyclohexylene methyl 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, a propane-1,2- , Butylene group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group and the like.

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

Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ²⁷ in the formula (5) 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, a bicyclo [2.2.1] heptyl group, a bicyclo [3.2.1] octyl group, a bicyclo [2.2.2] octyl group, .

Examples of the monovalent heterocyclic group having 3 to 10 carbon atoms represented by R ²⁷ in the formula (5) include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, Wherein the substituents are selected from the group consisting of oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, Indolin, indoline, indoline, indoline, indazole, purine, quinolizine, isoquinoline, quinoline, naphthyridine, But are not limited to, pyridine, pyrimidine, pyrazine, pyrimidine, pyrazine, pyrazine, pyrazine, pyrazine, pyrazine, pyrazine, pyrazine, Triazine, triazole, tetrazole, benzoimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofuroxan, naphtho A monovalent group excluding a hydrogen atom from an unsaturated bond present in the above heterocyclic compound or a saturated heterocyclic ring (such as a tetrahydrofuran ring) added by hydrogenation to a conjugated bond, etc. have.

Examples of the unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms in R ²⁴ in the formula (4) include an alkenyl group, an alkyl group, an alicyclic hydrocarbon group, a group in which the methylene group in the alkyl group is substituted with an alicyclic hydrocarbon group, A group in which the hydrogen atom of the methylene group is substituted with an alicyclic hydrocarbon group or a group in which an alicyclic hydrocarbon exists at the terminal of the alkyl group.

Examples of the alkenyl group include an allyl group and a 2-methyl-2-propenyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, , A hexyl group, a heptyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a 3-heptyl group, an octyl group, an isooxyl group, a 3-octyl group, A nonyl group, an isononyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. 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, Cyclo [2.2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group and adamantyl group.

Examples of the halogen atom substituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom. Examples of the alkylthio group having 1 to 18 carbon atoms for substituting the aliphatic hydrocarbon group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a sec-butylthio group, Isoamylthio group, heptylthio group, heptylthio group, heptylthio group, heptylthio group, heptylthio group, octylthio group, isooctylthio group, isoamylthio group, A heptyldecylthio group, a heptadecylthio group, a heptadecylthio group, a heptadecylthio group, a heptadecylthio group, a heptadecylthio group, a heptadecylthio group, a heptadecylthio group, a heptadecylthio group, Tetradecylthio, octadecylthio, and the like.

Examples of the C1-18 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, a 3-bromopropyl A nonafluorobutyl group, a nonafluorobutyl group, a tridecafluorohexyl group, a heptadecafluorooctyl group, a 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 1,1-difluoropropyl Group, a 1,1,2,2-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a norbornyl-1, A halogenated alkyl group such as a 1-difluoroethyl group, a norbornyltetrafluoroethyl group, an adamantane-1,1,2,2-tetrafluoropropyl group, etc., and an alkylthio group-substituted C1-18 Methylthioethyl group, 4-methylthiobutyl group and 4-butylthioethyl group, and examples of the aliphatic hydrocarbon include a halogen atom and an alkyl group having 1 to 18 carbon atoms Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with a keto group include 1,1,2,2-tetrafluoro-3-methylthiopropyl group and the like.

Examples of the unsubstituted straight or branched alkyl group having 1 to 18 carbon atoms in R ²⁴ in the formula (4) include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, -Hexyl group, n-octyl group, i-propyl group, i-butyl group, t-butyl group and neopentyl group.

Examples of the halogen atom for substituting the alkyl group having 1 to 18 carbon atoms include the same halogen atoms as those for substituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms. Examples of the alicyclic hydrocarbon group substituting the alkyl group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2. 1] 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 for R ²⁴ in the formula (4) include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A monocyclic cycloalkyl group such as an acyl group, a methylcyclohexyl group and an ethylcyclohexyl group;

Monocyclic cycloalkanes such as cyclopentenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl and cyclodecadiene; Nil group;

A bicyclic [2.2.2] octyl group, a tricyclo [5.2.1.0 ^2,6 ] decyl group, a tetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] dodecyl group, a norbornyl group and an adamantyl group A polycyclic cycloalkyl group and the like.

Examples of the halogen atom for substituting the alicyclic hydrocarbon group having 3 to 18 carbon atoms include the same halogen atoms as those for substituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms.

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

Examples of the halogen atom and the alkylthio group having 1 to 18 carbon atoms substituting the aryl group having 6 to 20 carbon atoms include the same groups as the halogen atom and the alkylthio group having 1 to 18 carbon atoms substituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms .

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, . Examples of the aryl group having 6 to 20 carbon atoms substituted with an alkylthio group having 1 to 18 carbon atoms include a 4-methylthiophenyl group, a 4-butylthiophenyl group, a 4-octylthiophenyl group, a 4-dodecylthiophenyl group, . 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 1,2,5,6-tetrafluoro-4-methylthiophenyl group, 6-tetrafluoro-4-butylthiophenyl group, and 1,2,5,6-tetrafluoro-4-dodecylthiophenyl group.

Examples of the unsubstituted arylalkyl group having 7 to 20 carbon atoms in R ²⁴ in the formula (4) include a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a diphenylmethyl group, Reel, thinning, and the like.

Examples of the halogen atom and the alkylthio group having 1 to 18 carbon atoms substituting the arylalkyl group having 7 to 20 carbon atoms include the same groups as the halogen atom and the alkylthio group having 1 to 18 carbon atoms which substitute the aliphatic hydrocarbon group having 1 to 18 carbon atoms have.

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

Examples of the unsubstituted alkylaryl group having 7 to 20 carbon atoms in R ²⁴ in the formula (4) include a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, (2-ethylhexyl) phenyl group, 2-ethylhexylphenyl group, 2-ethylhexylphenyl group, 2-ethylhexylphenyl group, 2-ethylhexylphenyl group, 3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5- Di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-butylphenyl, 2,5-dibenzylphenyl, 2,5-dibenzylphenyl, 4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group, and the like.

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

Examples of the acyl group for substituting 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.

The 10-camphor rex represented by R ²⁴ in the formula (4) is represented by the following formula.

Examples of the alkanediyl group having 1 to 4 carbon atoms represented by Y ³ in the formula (6) include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl 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 formula (6) include groups in which at least one hydrogen atom in the alkanediyl group having 2 to 6 carbon atoms is substituted with a halogen atom . 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 tetrafluoroethylene group, 1,1-difluoroethylene group, 1-fluoroethylene group, 1,2-difluoroethylene group, hexafluoroethylene group, 1,3-diyl group, 1,1,2,2-tetrafluoropropane-1,3-diyl group, 1,1,2,2-tetrafluoropentane-1,5-diyl group, etc. .

Examples of the halogenated alkanediyl group having 2 to 6 carbon atoms represented by R ²⁸ or R ²⁹ in the formula (6) include a tetrafluoroethylene group, a 1,1-difluoroethylene group, 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.

Examples of the arylene group having 6 to 20 carbon atoms represented by R ²⁸ or R ²⁹ in the 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- A naphthalene-1, 3-diyl group, a naphthalene-1, 4-diyl group, a naphthalene-1,5-diyl group, a naphthalene-1,6-diyl group, A naphthalene-1,8-diyl group, a naphthalene-2,3-diyl group, a naphthalene-2,6-diyl group, and a naphthalene-2,7-diyl group.

As the halogenated arylene group having 6 to 20 carbon atoms represented by R ²⁸ or R ²⁹ in the formula (6), groups in which at least one hydrogen atom in the arylene group having 6 to 20 carbon atoms is substituted with a halogen atom, such as tetrafluoro And a phenylene group.

Examples of the linear or branched alkyl group having 1 to 18 carbon atoms represented by R ³⁰ in the formula (6) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a butyl group, A heptyl group, a heptyl group, a 3-heptyl group, an isoheptyl group, a 3-heptyl group, an isobutyl group, an amyl group, an isoamyl group, a tertiary amyl group, a hexyl group, A heptadecyl group, a hexadecyl group, a heptadecyl group, a heptadecyl group, a hexadecyl group, a heptadecyl group, a heptadecyl group, a heptadecyl group, a heptadecyl group, Acyl group, octadecyl group and the like.

Examples of the linear or branched halogenated alkyl group having 1 to 18 carbon atoms in the formula (6) include groups in which at least one hydrogen atom in the alkyl group having 1 to 18 carbon atoms is substituted with a halogen atom. 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, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, heptadecafluorooctyl group, A 2,2,2-trifluoroethyl group, a 1,1-difluoroethyl group, a 1,1-difluoropropyl group, a 1,1,2,2-tetrafluoropropyl group, a 3,3,3- A trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, and a 1,1,2,2-tetrafluorotetradecyl group.

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

R ²⁴ in the formula (6) As the halogenated aryl group and the arylalkyl group, having a carbon number of 7 to 20 of the halogenated aryl group, a 7 to 20 carbon atoms of the aryl group, 6 to 20 carbon atoms of 6 to 20 carbon atoms in the formula (4) And the like.

The content of the [B] nonionic photoacid generator is preferably 0.1 part by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, per 100 parts by mass of the polymer component [A]. When the content of the [B] nonionic photoacid generator is within the above range, the radiation sensitivity of the radiation sensitive resin composition can be optimized, and a cured film having a high surface hardness can be formed while maintaining transparency.

<[C] ionic compound>

The [C] ionic compound is an ionic compound of an onium salt 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 ^- a. R ^A is a linear or branched monovalent hydrocarbon group of 1 to 10 carbon atoms or a monovalent monovalent hydrocarbon group of 3 to 20 carbon atoms. Provided that some or all of the hydrogen atoms contained in the hydrocarbon group of R ^A may be substituted with a fluorine atom. X ^{&lt; + &} gt ^; is an onium cation.

The radiation-sensitive resin composition contains the [C] ionic compound, and thereby the acid-strength adjusting function in the exposed portion, the high acid capturing function in the unexposed portion, and the inactivating function of the acid capturing function in the exposed portion So that the lithography performance can be effectively improved.

In addition, the radiation-sensitive resin composition is an ionic cation of X ^{&lt; + &} gt ;, whereby the dispersibility of the [C] ionic compound in the coating film formed of the radiation- sensitive resin composition becomes higher, B] The diffusion of the acid generated from the nonionic photoacid generator is controlled with higher precision. Further, 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 diffusion of the acid generated from the [B] nonionic photo- It becomes possible to control it. As a result, the adhesion of the pattern formed of the radiation sensitive resin composition can be further improved.

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, an aralkyl group having 7 to 30 carbon atoms, an aralkyl group having 3 to 30 carbon atoms And a group obtained by combining at least one of these groups with -O-, -CO-, -S-, -CS-, or -NH-. In R ¹ , it is preferable that the atom bonding to A ^- is a carbon atom, and the carbon atom is an acid which is generated from the [C] ionic compound relative to the acid generated from the [B] nonionic photoacid generator In order to make it weak, it is preferable not to have an electron attractive 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 and an adamantyl group.

The alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group may be substituted with a part or all of hydrogen atoms. 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 ^&lt; ⁺ &gt; 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) .

Formula (1-1) and (1-2) of, R ² ~R ⁶ is a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy _{^{group, -SR B, -OSO 2 -R C}} , or -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, some or all of the hydrogen atoms of the alkyl group, cycloalkyl group, alkoxy group and aryl group of R ² to R ⁶ , R ^B , R ^C and R ^D may be substituted. a, b, c, d and e are each independently an integer of 0 to 5;

Examples of the halogen atom represented by R ² to R ⁶ include 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 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 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 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 substituting 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, an alkoxycarbonyloxy group, .

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 a cation represented by the formulas (1-1-1) and (1-1-10) is more preferable.

Preferred examples of the [C] ionic compound include the compounds represented by the following formulas.

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

<[D] Antioxidant>

[D] The antioxidant is a component that inhibits cleavage of polymer molecules due to trapping of radicals generated by exposure or heating, or decomposition of peroxides formed by oxidation.

When the radiation-sensitive resin composition contains [D] an antioxidant, the deterioration in clearing of the polymer molecules in the cured film formed by the radiation-sensitive resin composition is suppressed and, for example, have. Further, the [D] antioxidant may be used alone or in combination of two or more.

[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, [D] antioxidants preferably have a hindered phenol structure. [D] Since the antioxidant has a hindered phenol structure, it is possible to further suppress deterioration in clearing of the polymer molecules in the cured film.

Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5- Hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert- , 5 ', 5'-hexa-tert-butyl-a, a', a'- (mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis 3- [5- (tert- butyl-4-hydroxy-m- tolyl) propionate , Hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine- 3H, 5H) -thione and 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine 2-ylamine) .

Examples of commercially available products of the compound having a hindered phenol structure include ADEKASTAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, AO-330 (above, ADEKA), sumilizerGM, copper GS, copper MDP-S, copper BBM-S copper WX-R copper GA- ), IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 565, IRGAMOD295 YOSHINOX BHT, Dong BB, Dong 2246G, Dong 425, Dong 250, Dong 930, Dong SS, Dong TT, Dong 917, Dong 314 (API Corporation).

Among the compounds having a hindered phenol structure, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3 , 5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate are more preferable.

The content of [D] antioxidant is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the polymer component [A]. By setting the content of [D] antioxidant within the above range, deterioration in cleanness of the cured film can be effectively suppressed.

&Lt; Other optional components &gt;

The radiation sensitive resin composition may contain, in addition to the above components [A] to [D], other arbitrary components as necessary insofar as the effect of the present invention is not impaired. Examples of other arbitrary components include [E] a polyfunctional (meth) acrylate, an [F] optical radical polymerization initiator, a [G] surfactant, and a [H] adhesion aid. The 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>

The [E] polyfunctional (meth) acrylate can increase 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, and for example, it can be obtained by reacting an aliphatic polyhydroxy compound with (meth) A polyfunctional (meth) acrylate obtained by reacting a (meth) acrylate having a hydroxy group with a polyfunctional (meth) acrylate, a caprolactone modified polyfunctional (meth) acrylate, an alkylene oxide- Urethane (meth) acrylate, and a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

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

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 dimethacrylate.

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

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

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 ethylene oxide and / or propylene oxide-modified di (meth) acrylate of bisphenol A, ethylene oxide and / or propylene oxide- Tri (meth) acrylate of trimethylolpropane, 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 (Meth) acrylate of dipentaerythritol, ethylene oxide and / or propylene oxide modified penta (meth) acrylate of dipentaerythritol, ethylene oxide and / or propylene oxide modified hexa (meta) acrylate of dipentaerythritol, ) Acrylate, and the like.

Among these polyfunctional (meth) acrylates, a polyfunctional (meth) acrylate obtained by reacting a trifunctional or higher aliphatic polyhydroxy compound with (meth) acrylic acid, a caprolactone modified polyfunctional (meth) acrylate, a polyfunctional urethane (Meth) acrylate, and a polyfunctional (meth) acrylate having a carboxyl group are preferable. Among the polyfunctional (meth) acrylates obtained by reacting tri- or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, di Among the polyfunctional (meth) acrylates having a carboxyl group, pentaerythritol hexaacrylate is preferably a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride Compound is particularly preferable in view of good alkali developability.

[E] The polyfunctional (meth) acrylate may be used alone or in combination of two or more.

The content of the [E] compound is preferably 1 part by mass to 100 parts by mass, more preferably 5 parts by mass to 50 parts by mass, per 100 parts by mass of the polymer component [A]. When the content of the [E] compound is within the above range, the hardness of the cured film can be further increased and the radiation sensitivity of the radiation sensitive resin composition can be further increased.

&Lt; [F] Photo radical polymerization initiator &gt;

The [F] photoradical polymerization initiator generates radicals capable of initiating polymerization of the [E] polyfunctional (meth) acrylate by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam, .

[F] Examples of the photoradical polymerization initiator include thioazanone compounds, acetophenone compounds, nonimidazole compounds, triazine compounds, O-acyloxime compounds, benzoin compounds, benzophenone compounds, -Diketone compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds and the like.

[F] The photo radical polymerization initiators may be used alone or in combination of two or more. As the [F] photoradical polymerization initiator, a thioazane-based compound, an acetophenone-based compound, a nonimidazole-based compound, a triazine-based compound, or an O-acyloxime-based compound is preferable.

Specific examples of the thioazane-based compound in the [F] photoradical polymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, Dichlorotothiazane, 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-morpholinopropane- 1- (4-morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Examples of the nonimidazole 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 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

When a non-imidazole-based compound is used as the [F] photoradical polymerization initiator, it is preferable to use a hydrogen donor in combination because it can improve the radiation sensitivity. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole 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. The hydrogen donors may be used alone or in combination of two or more. From the viewpoint of improving the radiation sensitivity, it is preferable to use at least one mercaptan-based hydrogen donor and at least one amine-based hydrogen donor in combination.

Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4 (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) - 4,6-bis (trichloromethyl) -s-triazine, and the like.

Examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime) 1- [9-ethyl-6- (2-methyl-4- (2-methylbenzoyl) -9H-carbazol- 1- [9-ethyl-6- (2-methyl-4- (2-methyl- 2-dimethyl-1,3-dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -, 1- (O-acetyloxime).

The content of the [F] photoradical polymerization initiator is preferably 0.01 part by mass to 120 parts by mass, more preferably 1 part by mass to 100 parts by mass, per 100 parts by mass of the [E] polyfunctional (meth) acrylate. If the content of the [F] photoradical polymerization initiator is too small, there is a possibility that the curing by exposure can not be sufficiently obtained. On the other hand, if the content of the [F] photoradical polymerization initiator is too large, the pattern tends to be easily removed from the substrate at the time of development.

<[G] Surfactant>

[G] Surfactant is a component for enhancing the film formability of the radiation sensitive resin composition. Examples of the [G] surfactant include a fluorine-based surfactant and a silicone-based surfactant. By containing the [G] surfactant in the radiation sensitive resin composition, the surface smoothness of the coating film can be improved, and as a result, the uniformity of the film thickness of the cured film can be further improved.

As the fluorine-containing surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least any of the terminal, main chain and side chain is preferable, and 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 , 2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di , 3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, sodium perfluoro n-dodecanesulfonate, 2,2,3,3-hexafluoro-n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, Sodium fluoroalkylcarbonate, diglycerin tetrakis (fluoroalkylpolyoxyethers such as &lt; RTI ID = 0.0 &gt; Fluoroalkylpolyoxyethylene, perfluoroalkylpolyoxyethanol, perfluoroalkylalkoxylate, carbonic acid fluoroalkyl ester, and the like can be used in combination. .

Examples of commercially available products of the above fluorinated surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megaface F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper Fluorad FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), SUPPLOR (Surflon) S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC- 104, SC-105, SC-106 (above, Asahi Glass Co., Ltd.), Eftop EF301, EF303, EF352 (above, Shin Akita Kasei), Ftergent FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FT-300, Copper FT-310, Copper FT-400S, Copper FTX-218, Copper FT-251 , Manufactured by Neos Co., Ltd.).

Examples of commercially available silicone surfactants include Toray silicone DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ TSF-4460, TSF-4446, TSF-4460, TSF-4460, TSF-4432, TSF-4452 (manufactured by GE Toshiba Silicone Co., Ltd.), and organosiloxane polymer KP341 (Shinetsu Kagakuko Co., Ltd.).

The content of the [G] surfactant is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.05 parts by mass to 1 part by mass, per 100 parts by mass of the polymer component [A]. When the content of the [G] surfactant is within the above range, uniformity of film thickness of the coating film can be further improved.

<[H] Adhesion preparation>

[H] The adhesion aid is a component that improves adhesion between an inorganic substance to be a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, or aluminum and the cured film. As the [H] adhesion aid, a functional silane coupling agent is preferred. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane, ? -glycidoxypropyltrimethoxysilane,? -glycidoxypropylalkyldialkoxysilane,? -chloropropyltrialkoxysilane,? -mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) Ethyl trimethoxysilane and the like. Among them, examples of the functional silane coupling agent include? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - methacryloxypropyltrimethoxysilane is preferred.

The content of the [H] adhesion aid is preferably 0.5 parts by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, per 100 parts by mass of the polymer component [A]. [H] When the content of the adhesion aid is within the above range, adhesion between the cured film and the substrate is further improved.

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

The radiation sensitive resin composition of the present invention can be obtained by dissolving or dispersing the [A] polymer, the [B] nonionic photoacid generator, the [C] ionic compound and, if necessary, It is prepared. For example, the radiation-sensitive resin composition can be prepared by mixing the respective components in a predetermined ratio in a solvent.

As the solvent, those which uniformly dissolve or disperse each component and do not react with each component are suitably used. Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates , Aromatic hydrocarbons, ketones, and other esters.

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

The ethers include, for example, tetrahydrofuran.

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

Examples of the ethylene glycol alkyl ether acetate include 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, diethylene glycol ethyl methyl ether and the like .

Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 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, propylene glycol monobutyl ether propionate Nate and so on.

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

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

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

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

&Lt; Method of forming a cured film &

The radiation sensitive resin composition can be suitably used for forming 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 with radiation (Hereinafter also referred to as &quot; step (3) &quot;) for heating the coated film, and a step for heating the developed coated film (hereinafter also referred to as &quot; step (4) &quot;).

[Step (1)]

In the present step, the radiation-sensitive resin composition is applied to a substrate to form a coating film. Preferably, the solvent is removed by prebaking the application surface.

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

[Step (2)]

In this step, at least a part of the formed coating film is exposed to radiation. When exposure is performed, exposure is usually performed through a photomask having a predetermined pattern. As the radiation used for 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 dose is preferably 500 J / m2 to 6,000 J / m2, more preferably 1,500 J / m2 to 1,800 J / m2. The exposure dose is a value obtained by measuring the intensity of the radiation at a wavelength of 365 nm by a light meter ("OAI model 356" manufactured by OAI Optical Associates).

[Step (3)]

In this step, the coated film irradiated with the radiation is developed. By developing the coated film after exposure, unnecessary portions (irradiated portions of radiation) are removed to form a predetermined pattern. As the developing solution used in this developing step, an alkaline aqueous solution is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, .

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

[Step (4)]

In this step, the developed coating film is heated. For the heating, the patterned thin film is heated by using a heating device such as a hot plate or an oven to accelerate the curing reaction of the [A] polymer component to form a cured film. The heating temperature is, for example, about 120 ° C to 250 ° C. The heating time varies depending on the type of the heating apparatus, but is, for example, about 5 minutes to 30 minutes on a hot plate and about 30 minutes to 90 minutes in an oven. Further, a step baking method in which two or more heating steps are performed may be used. In this manner, a patterned thin film corresponding to the intended cured film can be formed on the surface of the substrate. The film thickness of this cured film is preferably from 0.1 mu m to 8 mu m, more preferably from 0.1 mu m to 6 mu m.

According to the method of forming the cured film, a cured film having high pattern stability can be formed. In addition, since the film thickness variation amount of the unexposed portion can be suppressed, the production process margin can be consequently improved, and the yield can be improved. Further, by forming a pattern by exposure, development and heating using photosensitivity, a cured film having a fine and precise pattern can be easily formed.

<Cured film>

The cured film of the present invention is formed from the radiation sensitive resin composition. The cured film is excellent in radiation sensitivity and adhesion because it is formed of the radiation sensitive resin composition. 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 coloring pattern for a color filter, and the like. The method of forming the cured film is not particularly limited, but it is preferable to use the method of forming the cured film described above.

<Display element>

The display element of the present invention comprises the cured film. The display element is constituted by, for example, a liquid crystal cell, a polarizing plate or the like which will be described later. Since the display element is provided with the cured film, the display element is excellent in reliability such as heat resistance.

As a manufacturing method of the display element, a pair (two pieces) of transparent substrates having a transparent conductive film (electrode) on one surface thereof are first prepared, and on the transparent conductive film of one of the substrates, An interlayer insulating film, a spacer, a protective film, or both are formed according to the aforementioned method of forming a cured film by using the resin composition. Then, an alignment film having a liquid crystal aligning ability is formed on the transparent conductive film and the spacer or the protective film of these substrates. These substrates were disposed so as to face each other with a certain gap (cell gap) interposed therebetween so that the liquid crystal alignment directions of the respective alignment films were orthogonal or anti-parallel with the inner surface of the side on which the alignment film was formed, The liquid crystal is filled in the cell gap defined by the spacer, and the filling hole is sealed to constitute the liquid crystal cell. The display device of the present invention is obtained by joining a polarizing plate on both outer surfaces of the liquid crystal cell so that the polarizing direction thereof coincides with or orthogonal to the liquid crystal alignment direction of the alignment film formed on one side of the substrate.

As another manufacturing method of the display element, a pair of transparent substrates having a transparent conductive film, an interlayer insulating film, a protective film or spacer, and an orientation film are prepared in the same manner as the above-mentioned manufacturing method. Thereafter, an ultraviolet curable sealant is applied using a dispenser along the edge of one of the substrates, the liquid crystal is dropped in a minute droplet shape using a liquid crystal dispenser, and the substrates are bonded under vacuum. Then, ultraviolet rays are irradiated to the seal portion using a high-pressure mercury lamp, and both substrates are sealed. Finally, the polarizing plate is bonded to both outer surfaces of the liquid crystal cell to obtain the display element of the present invention.

Examples of the liquid crystal used in the above-described manufacturing method of each display element include a nematic liquid crystal and a smectic liquid crystal. As the polarizing plate used for the outside of the liquid crystal cell, a polarizing plate in which a polarizing film called &quot; H film &quot;, in which iodine is absorbed, in which polyvinyl alcohol is stretched and oriented is sandwiched by a cellulose acetate protective film, .

In the organic electroluminescence element, the cured film formed of the radiation sensitive resin composition can be used as a planarizing film formed on the TFT element, a partition wall material for dividing a light emitting portion, and the like.

(Example)

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples. The method for measuring the weight average molecular weight (Mw) of the synthesized polymer will be described below.

[Weight average molecular weight (Mw)]

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions.

Device: "GPC-101" of Showa Denko

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

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

&Lt; Synthesis of polymer component [A]

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

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 10 parts by mass of methacrylic acid, 50 parts by mass of 1-butoxyethyl methacrylate, 40 parts by mass of 3-methacryloyloxymethyl-3-ethyloxetane and 10 parts by mass of hydroxyethyl methacrylate After purging with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained (maintained) for 5 hours to obtain a polymer solution containing the polymer (A-1). The polystyrene reduced weight average molecular weight (Mw) of the polymer (A-1) was 10,000. The solid concentration of the polymer solution obtained here was 31.6 mass%.

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

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 10 parts by mass of methacrylic acid, 40 parts by mass of tetrahydro-2H-pyran-2-yl methacrylate, 40 parts by mass of glycidyl methacrylate, and 10 parts by mass of styrene were charged and replaced with nitrogen. . The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2). The polystyrene reduced weight average molecular weight (Mw) of the polymer (A-2) was 9,500. The solid concentration of the polymer solution obtained here was 31.6 mass%.

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

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. 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 After purging with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 占 폚, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-3). The polystyrene reduced weight average molecular weight (Mw) of the polymer (A-3) was 11,000. The solid concentration of the polymer solution obtained here was 32.4% by mass.

[Synthesis Example 4] (Synthesis of polymer (a-1)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 50 parts by mass of tetrahydro-2H-pyran-2-yl methacrylate, 35 parts by mass of benzyl methacrylate, and 15 parts by mass of hydroxyethyl methacrylate were charged and replaced with nitrogen, followed by gentle agitation. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (a-1). The polystyrene reduced weight average molecular weight (Mw) of the polymer (a-1) was 10,500. The solid concentration of the polymer solution obtained here was 31.8 mass%.

[Synthesis Example 5] (Synthesis of polymer (a-2)

A cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed. Subsequently, 40 parts by mass of glycidyl methacrylate, 30 parts by mass of styrene, and 30 parts by mass of benzyl methacrylate were purged with nitrogen and stirred gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (a-2). The polystyrene reduced weight average molecular weight (Mw) of the polymer (a-2) was 10,000. The solid concentration of the polymer solution obtained here was 32.0% by mass.

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

The radiation-sensitive resin composition was prepared in the composition shown in Table 1. The [B] nonionic photoacid generator, [C] ionic compound and [D] antioxidant, [E] polyfunctional (meth) acrylate and [F] photo radical polymerization initiator shown in Table 1 are as follows .

[[B] nonionic photoacid generator]

(2-methylphenyl) acetonitrile (&quot; IRGACURE PAG 103 &quot; 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"

B-4: An oxime sulfonate compound ("IRGACURE PAG 203" manufactured by BASF) represented by the following formula (B-4)

B-5: A sulfonic acid derivative 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 represented by the following formula (B-7)

B-8: A sulfonic acid derivative 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 represented by the following formula (B-10)

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

B-12: A sulfonic acid derivative 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 represented by the following formula (B-14)

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

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

[[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] antioxidant]

D-1: 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) butane (Adekastab AO-

D-2: Adekastab AO-60 of ADEKA represented by the following formula (D-2)

D-3: Adekastab AO-70 of ADEKA represented by the following formula (D-3)

D-4: Adekastab AO-80 of ADEKA represented by the following formula (D-4)

D-5: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene) (Adekastab AO- )

D-6: "IRGANOX 1098" manufactured by BASF Co., Ltd. represented by the following formula (D-6)

[E] polyfunctional (meth) acrylate

E-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ("KAYARAD DPHA" from Nippon Kayakusha)

E-2: succinic acid-modified pentaerythritol triacrylate ("Aronix TO-756" manufactured by Toagosei Co., Ltd.)

E-3: Trimethylolpropane triacrylate

E-4: A mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate ("Viscoat 802" manufactured by Yuki Kagaku Kogyo Co., Ltd.)

E-5: succinic acid-modified dipentaerythritol pentaacrylate ("ARONIX M-520" manufactured by Toagosei Co., Ltd.)

[[F] Photo radical polymerization initiator]

F-1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907 from BASF)

F-2: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) ("Irgacure OXE02" )

F-3: 2,4-Diethylthioxanthone

(Comparative Example)

[b] Ionic photoacid generator

b-1: Triphenylsulfonium trifluoromethanesulfonate

[c] amine compound

c-1: 4-Dimethylaminopyridine

[Example 1]

3 parts by mass of the photoacid generator (B-1) and 3 parts by mass of the ionic compound (C-1) were added to 100 parts by mass (solid content) of the polymer solution (A- ) Were mixed and filtered through a membrane filter having a pore diameter of 0.2 占 퐉 to prepare a radiation-sensitive resin composition.

[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 of the kind and content shown in Table 1 were used. In Table 1, &quot; - &quot; indicates that the corresponding components are not blended.

[Example 16]

50 parts by mass of a polymer solution ((a-2)) containing the polymer (a-1) and 50 parts by mass (solid content) of the polymer solution (Solid content)) were mixed to obtain a polymer component [A]. 5 parts by mass of the [B] photoacid generator (B-16), 0.08 parts by mass of the [C] ionic compound (C-3), and 0.5 parts by mass of the antioxidant (D-2) , 5 parts by mass of [E] photopolymerizable (meth) acrylate and 1 part by mass of [F] photoradical polymerization initiator (F-3) were mixed and filtered through a membrane filter having a pore size of 0.2 탆 to obtain a radiation- .

[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 of the type and the compounding amount shown in Table 1 were used.

<Evaluation>

The radiation-sensitive resin compositions of Examples 1 to 20 and Comparative Examples 1 to 4 were used to evaluate radiation sensitivity, light resistance, transmittance, pattern adhesion, voltage holding ratio, and storage stability. The evaluation results are shown in Table 2.

[Evaluation of radiation sensitivity]

The radiation-sensitive resin composition was coated on a glass substrate using a spinner, and then baked on a hot plate at 90 占 폚 for 2 minutes to form a coating film having a film thickness of 3.0 占 퐉. Subsequently, a mask having a pattern of a line-and-space (10: 1) of 60 mu m was interposed between the mask and the substrate, using an exposure machine ("MPA-600FA And irradiated with radiation. Thereafter, it was developed with a 0.5 mass% aqueous solution of tetramethylammonium hydroxide at 25 DEG C for 80 seconds by a puddle method. Subsequently, the substrate was subjected to water washing with ultra-pure water for 1 minute, and then dried to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the amount of exposure required to completely dissolve the space pattern of 6 mu m was examined. When the value of the exposure dose is 500 (J / m &lt; 2 &gt;) or less, it can be judged that the sensitivity is good.

[Evaluation of light resistance]

The radiation-sensitive resin composition was coated on a silicon substrate using a spinner, and then baked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. This silicon substrate was heated in a clean oven at 220 DEG 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 with a UV irradiation device (UVX-02516 S1JS01, manufactured by Ushio Inc.). Compared with the film thickness before irradiation, when the film reduction amount of the film thickness after irradiation is 3% or less, it can be said that the light resistance of the cured film is good.

In the evaluation of the light resistance, since the patterning of the cured film to be formed is not necessary, the development step is omitted and evaluation is carried out by performing only the film forming step, the light resistance test and the heating step.

[Evaluation of transmittance]

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

[Evaluation of pattern adhesion]

The adhesion of the pattern was evaluated after exposure and exposure. Specifically, first, a radiation-sensitive resin composition was coated on a glass substrate using a spinner, and then pre-baked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 3.0 탆. Subsequently, a mask having a line-and-space (one-to-one) pattern of 10 mu m was interposed using an exposure apparatus (MPA-600FA (ghi line mixing) Exposure was performed. Thereafter, it was allowed to stand in a clean room for one hour, and then developed with a 0.5 mass% aqueous solution of tetramethylammonium hydroxide at 25 DEG C for 80 seconds by a puddle method. Subsequently, the substrate was subjected to water washing with ultra-pure 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 whether or not pattern peeling occurred. Criteria for judging adhesion of the pattern are shown below.

When the pattern peeling is hardly observed: &quot; o &quot;

When the pattern peeling is observed to be slightly: &quot;? &Quot;

When the pattern is peeled off and almost no pattern remains on the substrate: &quot; x &quot;

[Evaluation of Voltage Conservation Rate]

A radiation-sensitive composition is spin-coated on a soda glass substrate on which an SiO ₂ film is formed to prevent dissolution of sodium ions on the surface and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape, In a clean oven for 10 minutes to form a coating film having a film thickness of 2.0 mu m. Subsequently, the coated film was exposed at an exposure amount of 500 J / m &lt; 2 &gt; without interposing a photomask. Thereafter, post baking was performed at 230 캜 for 30 minutes to cure the coating film to form a permanent cured film.

Subsequently, the substrate on which the pixel was formed and the substrate on which the ITO electrode only had been vapor-deposited in a predetermined shape were bonded to each other with a sealing material mixed with glass beads of 0.8 mm to form a cell. Then, a liquid crystal (liquid crystal MLC6608 &quot;) was injected to prepare a liquid crystal cell. Further, the liquid crystal cell was placed in a constant temperature layer at 60 占 폚, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage preservation rate measuring system ("VHR-1A type" manufactured by Toyo Technica Co., Ltd.). At this time, the applied voltage was 5.5 V, and the measurement frequency was 60 Hz.

Here, the voltage holding ratio is a value of (the voltage applied to the liquid crystal cell potential difference after 16.7 milliseconds / 0 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell can not maintain the applied voltage at a predetermined level for 16.7 milliseconds and can not sufficiently orient the liquid crystal. The "burn- There is a high possibility of causing it.

[Evaluation of storage stability]

The solution of the radiation-sensitive composition was allowed to stand in an oven at 40 캜 for 1 week, and the viscosity before and after being placed in an oven was measured to determine the rate of change in viscosity (%). At this time, it can be said that the storage stability is good when the rate of change in viscosity is 5% or less, and the storage stability is inferior when it exceeds 5%. The evaluation results are shown in Table 2.

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

The present invention can provide a radiation-sensitive composition that satisfactorily satisfies general characteristics such as radiation sensitivity and is excellent in storage stability and can reduce the defective adhesion of a cured film. The present invention can also provide a cured film formed of the radiation sensitive resin composition, a method for forming the same, and a display element provided with the cured film. Accordingly, the radiation sensitive resin composition, the cured film, the method of forming the same, 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 non-ionic photoacid generator having a sulfonyl group, and
A radiation-sensitive resin composition containing an ionic compound represented by the following formula (1): &quot;

(Formula (1) of, R ¹ is a hydrogen atom or a monovalent organic group, and; -A ^{- _{is, -N - -SO 2 -R A,}} -COO -, -O - or -SO ₃ ^-, and; R ^A is a linear or branched monovalent hydrocarbon group of 1 to 10 carbon atoms or a monovalent monovalent hydrocarbon group of 3 to 20 carbon atoms, provided that a part or all of the hydrogen atoms of the hydrocarbon group of R ^A are substituted with fluorine atoms And X ^&lt; ^{+ &} gt ^; is an onium cation). The method according to claim 1,
A radiation sensitive resin composition wherein X ⁺ in the formula (1) is an onium cation represented by the following formula (1-1) or (1-2)

(Wherein R ² to R ^{6 each} independently represents a hydroxyl group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, -SR ^B , -OSO ₂ -R ^C , or -SO ₂ ^D is -R; R ^B is an alkyl group or an aryl group; R ^C and R ^D are, each independently, an alkyl group, cycloalkyl group, alkoxy group or aryl group; stage, R ² ~R ^6, R ^B, R A, b, c, d, and e are each independently an integer of 0 to 5) of the hydrogen atoms of the alkyl group, cycloalkyl group, alkoxy group and aryl group of ^C and R ^D may be substituted. The method according to claim 1,
Wherein the content of the ionic compound is 0.01 parts by mass or more and 1.00 parts by mass or less based on 100 parts by mass of the polymer component. The method according to claim 1,
Wherein the first structural unit is represented by the following formula (2) or (3):

(Wherein 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, R ¹⁰ in the formula (3) is a hydrogen atom or a methyl group, and R ¹¹ to R ¹⁷ are each a hydrogen atom or a straight or branched F is 1 or 2, provided that when f is 2, two R ^{16 s} and two R ^{17 s may be the} same or different. 5. The method according to any one of claims 1 to 4,
Wherein the crosslinking group of the second structural unit is a (meth) acryloyl group, an oxiranyl group, or an oxetanyl group. 5. The method according to any one of claims 1 to 4,
Wherein the nonionic photoacid generator is a compound represented by the following formula (4):

(In the formula (4), R ¹⁸ and R ²¹ to R ²³ are each a hydrogen atom; one of R ¹⁹ and R ²⁰ is a linear or branched C 4 -C 18 alkoxy group, (= O) - bond or a -OC (= O) -NH- bond from the side nearest to the naphthalene ring, the group in which the methylene group at any arbitrary non-adjacent position is substituted with a -C A straight or branched alkylthio group having 4 to 18 carbon atoms, a group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with a -C (= O) - group, the alkylthio group is a naphthalene (= O) - bond or -OC (= O) -NH- bond from the near side of the ring, or a group represented by the following formula (5), provided that the alkoxy group of R ¹⁹ and R ²⁰ And some or all of the hydrogen atoms of the alkylthio group may be substituted with an alicyclic hydrocarbon group, a heterocyclic group or a halogen atom, and the other of R ¹⁹ and R ²⁰ R ²⁴ is a monovalent aliphatic hydrocarbon group of 1 to 18 carbon atoms which may be substituted by at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, at least one of a halogen atom and an alicyclic hydrocarbon group A linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted on one side, a monovalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may be substituted with a halogen atom, a halogen atom and an alkylthio group having 1 to 18 carbon atoms An aryl group having 6 to 20 carbon atoms which may be substituted, an arylalkyl group having 7 to 20 carbon atoms which may be substituted by at least one of a halogen atom and an alkylthio group having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group having 7 to 20 carbon atoms An aryl group having 7 to 20 carbon atoms substituted with an acyl group, 10-camphoryl, or a group represented by the following formula (6));

(In the 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, a straight- Or a branched alkyl group or a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms or a monovalent heterocyclic group, 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 to 5;

(In the formula (6), 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, having 2 to 6 carbon atoms in the alkanediyl group, halides of a carbon number of 2 to 6 alkanediyl group, of 6 to 20 carbon atoms an aryl group, or a halogenated arylene group of 6 to 20 carbon atoms, and; R ³⁰ is a straight-chain Or a branched alkyl group having 1 to 18 carbon atoms, a linear or branched halogenated alkyl group having 1 to 18 carbon atoms, a monovalent 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, Y ³ is a single bond or an alkanediyl group having 1 to 4 carbon atoms, h and i are each 1, Is 0 or 1). The radiation sensitive resin composition according to any one of claims 1 to 4, further comprising an antioxidant. A cured film formed from the radiation sensitive resin composition according to any one of claims 1 to 4. A method of forming a cured film including a step of forming a coating film on a substrate, a step of irradiating at least a part of the coating film with radiation, a step of developing the coating film irradiated with the radiation, and a step of heating the developed coating film,
A method for forming a cured film, which comprises using the radiation sensitive resin composition according to any one of claims 1 to 4 in the formation of the coating film. A display element comprising the cured film according to claim 8.