JP6764636B2 - Radiation-sensitive resin composition, pattern manufacturing method, transparent insulating film, and display device - Google Patents

Description

The present invention comprises a radiation-sensitive resin composition, a pattern manufacturing method using the radiation-sensitive resin composition, a transparent insulating film obtained by using the radiation-sensitive resin composition, and a display device including the transparent insulating film. Regarding.

In recent years, microfabrication has progressed in the field of manufacturing electronic components such as semiconductor elements and liquid crystal display elements, and negative resist compositions used there generally have high resolution, sensitivity, and a resist pattern having a good profile shape. The formation of the film, the high residual film ratio after the etching process, and the like are required. For example, in a thin film transistor (TFT) element used as a driving element of a liquid crystal display element, the transparent electrode circuit is a resist on a transparent conductive film substrate such as an indium tin oxide film substrate (hereinafter, also referred to as “ITO film substrate”). It is formed by forming a pattern and etching a transparent conductive film substrate using the resist pattern as a mask.

As a negative resist composition used for forming a transparent electrode circuit, conventionally, a negative resist composition in which a bisazide compound is mixed with a phenol novolac resin, or a negative composed of chloromethylated polystyrene or polyvinylphenol and an aromatic bisazide compound. A negative resist composition (Patent Document 1), a negative resist composition composed of a thermosetting resin and a halogenated organic compound that absorbs chemical rays in the wavelength range of 210 to 299 nm as a photoacid generator (Patent Document 2), etc. Has been proposed.

Special Publication No. 62-8777 Japanese Unexamined Patent Publication No. 62-164045

In particular, in the etching of a transparent conductive film substrate, for the purpose of reducing the number of steps, the negative resist composition is provided with a negative resist composition so that a good pattern is formed even before curing (post-baking) of the negative resist composition. There is an increasing demand for excellent adhesion to a substrate, photolithography characteristics, and the like. However, the conventional negative resist composition used for etching a transparent conductive film substrate has insufficient adhesion to the substrate, photolithography characteristics, and the like.

The present invention has been made in view of the above circumstances, and is a radiation-sensitive resin composition having excellent adhesion to a substrate and photolithographic properties, a pattern manufacturing method using the radiation-sensitive resin composition, and the above feeling. An object of the present invention is to provide a transparent insulating film obtained by using a radioactive resin composition and a display device provided with the transparent insulating film.

The present inventors have described the above by blending a filler containing a specific metal element, an oxide of the above element, and the like and having an average particle size of 200 nm or less and a polyfunctional monomer into a radiation-sensitive resin composition. We have found that the problem can be solved and have completed the present invention.

A first aspect of the present invention is a simple substance of at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, an oxide of the element, and a chelate of the element. Photopolymerization of a filler containing one or more selected from the group consisting of a compound, a salt of the above element, and an alloy of the above element and having an average particle size of 200 nm or less, an alkali-soluble resin, a polyfunctional monomer, and initiation of photopolymerization. It is a radiation-sensitive resin composition containing an agent.

A second aspect of the present invention is a step of forming a radiation-sensitive resin composition film using the radiation-sensitive resin composition and positioning the radiation-sensitive resin composition film. It is a pattern manufacturing method including an exposure step of selectively exposing and a developing step of developing the exposed radiation-sensitive resin composition film.
A third aspect of the present invention is a transparent insulating film obtained by using the above-mentioned radiation-sensitive resin composition.
A fourth aspect of the present invention is a display device provided with the transparent insulating film.

According to the present invention, it can be obtained by using a radiation-sensitive resin composition having excellent adhesion to a substrate and photolithographic properties, a pattern manufacturing method using the radiation-sensitive resin composition, and the radiation-sensitive resin composition. A transparent insulating film and a display device provided with the transparent insulating film can be provided.

≪Radiation-sensitive resin composition≫
The radiation-sensitive resin composition according to the present invention (hereinafter, also simply referred to as “radiation-sensitive resin composition”) is selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta. Contains at least one selected from the group consisting of a single element of at least one element, an oxide of the element, a chelate compound of the element, a salt of the element, and an alloy of the element, and has an average particle size of 200 nm or less. (Hereinafter, also referred to as “(A) filler”), an alkali-soluble resin (hereinafter, also referred to as “(B) alkali-soluble resin”), and a polyfunctional monomer (hereinafter, “(C)). It also contains a "polyfunctional monomer") and a photopolymerization initiator (hereinafter, also referred to as "(D) photopolymerization initiator"). The radiation-sensitive resin composition according to the present invention contains (A) a filler and (C) a polyfunctional monomer, so that it has good adhesion to a substrate and photolithography characteristics even before curing (post-baking). Excellent. Therefore, by using the radiation-sensitive resin composition according to the present invention, a good pattern can be easily formed even before the curing (post-baking) of the radiation-sensitive resin composition, and the step in etching the transparent conductive film substrate can be performed. Easy to reduce. As a result, for example, a display device such as a liquid crystal panel can be efficiently manufactured.

The radiation-sensitive resin composition according to the present invention is preferably capable of forming a film having a light transmittance of 90% or more at a wavelength of 400 nm when measurement is performed using a sample having a thickness of 2 μm. (A) In a transparent film containing a filler, the shorter the wavelength of light, the greater the absorption tends to be. Therefore, if the transmittance of the transparent insulating film formed by using the radiation-sensitive resin composition is 90% or more at a wavelength of 400 nm, the transparent insulating film has sufficiently high transparency in the wavelength range of visible light. .. For this reason, the transmittance of light at a wavelength of 400 nm is used as an index of the transparency of the transparent insulating film.
Hereinafter, each component contained in the radiation-sensitive resin composition will be described.

[(A) Filler]
The filler (A) is a simple substance of at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, an oxide of the element, and a chelate compound of the element. It contains one or more selected from the group consisting of salts of the above elements and alloys of the above elements, and has an average particle size of 200 nm or less. The above elements have a high electron density. Therefore, the elemental substance of the element, the oxide of the element, the chelate compound of the element, the salt of the element, and the alloy of the element have high dielectric constants. Further, a simple substance of the element, an oxide of the element, a chelate compound of the element, a salt of the element, and an alloy of the element constitute a film in a film formed by using a radiation-sensitive resin composition. It is difficult to block the transmission of visible light when it is dispersed in the matrix. Therefore, the transparent insulating film formed by using the radiation-sensitive resin composition containing the above-mentioned filler (A) tends to have a high dielectric constant and excellent transparency. Each of the elemental substance, the oxide of the element, the chelate compound of the element, the salt of the element, and the alloy of the element can be used alone or in combination of two or more.

The valence of the element contained in the oxide of the element is not particularly limited.
In the chelate compound of the above element, examples of the ligand forming a chelate with the above element include pyridine, triphenylphosphine, carbon monoxide, ethylenediamine, bipyridine, catechol, ethylenediaminetetraacetic acid (EDTA) and the like.

The salt of the above element may be a salt of an inorganic acid or a salt of an organic acid. Preferred salts include halides, sulfates, nitrates, phosphates, acetates, formates, propionates, benzoates and the like. The valence of the above elements constituting the salt is not particularly limited.

The combination of metals (elements) contained in the alloy of the above elements is not particularly limited. Further, the mixing ratio of a plurality of metals (elements) contained in the alloy is not particularly limited.

Among the simple substances of the above elements, the oxides of the above elements, the chelate compounds of the above elements, the salts of the above elements, and the alloys of the above elements, the stability in the composition and the radiation-sensitive resin composition are used. Oxides are preferable because they can easily form a film having excellent transparency. Suitable specific examples of oxides of the above elements include La ₂ O ₃ , CeO ₂ , Nd ₂ O ₃ , Gd ₂ O ₃ , Ho ₂ O ₃ , Lu ₂ O ₃ , HfO ₂ , and Ta ₂ O _5. Can be mentioned.

(A) The shape of the filler is not particularly limited. The average particle size of the filler (A) is 200 nm or less, preferably 150 nm or less, and more preferably 100 nm or less. When the average particle size of the (A) filler is 200 nm or less, the (A) filler is less likely to precipitate in the dispersion, and it is easy to obtain a radiation-sensitive resin composition in a liquid form. The lower limit of the average particle size of the filler (A) is not particularly limited, and is preferably 40 nm or more, more preferably 45 nm or more. When the lower limit of the average particle size of the (A) filler is 40 nm or more, the surface of the (A) filler is easily coated, and the dielectric constant of the film obtained by using the radiation-sensitive resin composition is lowered. It is difficult, leakage current is unlikely to occur, and (A) the filler is difficult to aggregate.
In addition, in this specification, the average particle diameter means the volume average particle diameter measured by the dynamic light scattering measurement method (DLS).

The content of the filler (A) in the radiation-sensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. The content of (A) filler in the radiation-sensitive resin composition is typically 7.5 to 15 based on 100 parts by mass of the total of (B) alkali-soluble resin and (C) polyfunctional monomer. It is preferably parts by mass, more preferably 8 to 12 parts by mass. When the filler (A) in such an amount is blended with the radiation-sensitive resin composition, it is easy to obtain a radiation-sensitive resin composition having excellent adhesion to a substrate and photolithography characteristics.

[(B) Alkali-soluble resin]
In the present specification, the alkali-soluble resin means a resin film having a thickness of 1 μm formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and a tetra of 2.38% by mass. Methylammonium hydroxide (hereinafter, also referred to as TMAH) means a solvent that dissolves in 0.01 μm or more when immersed in an aqueous solution for 1 minute. Since the radiation-sensitive resin composition according to the present invention contains (B) an alkali-soluble resin, after the above-mentioned radiation-sensitive resin composition is applied to the base material on which the radiation-sensitive resin composition film is formed. A patterned radiation-sensitive resin composition film can be formed by selectively exposing the coating film and developing it with an alkaline developing solution such as an aqueous solution of tetramethylammonium hydroxide. .. (B) The alkali-soluble resin can be used alone or in combination of two or more.

The alkali-soluble resin (B) is not particularly limited, and examples thereof include novolak resin, polyhydroxystyrene resin, and acrylic resin. The content of the alkali-soluble resin (B) in the solid content of the radiation-sensitive resin composition is preferably 20 to 99% by mass, more preferably 30 to 80% by mass, and even more preferably 40 to 70% by mass.

(B) As the alkali-soluble resin, a polymer of a monomer having an ethylenically unsaturated double bond is used because it has excellent film-forming properties and the characteristics of the resin can be easily adjusted by selecting a monomer. preferable. Examples of the monomer having an ethylenically unsaturated double bond include (meth) allylic acid; (meth) allylic acid ester; (meth) allylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, and mesaconic acid. Itaconic acid, an anhydride of these dicarboxylic acids; such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyloxyethanol. Allyl compounds; hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl trill ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, And vinyl ethers such as vinyl anthranyl ether; vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinylmethoxyacetate, vinyl butoxyacetate, Vinyl esters such as vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate; styrene, Methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, Methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyle , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethyl. Styrene or styrene derivatives such as styrene; ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4 -Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

In terms of alkali solubility and transparency, the alkali-soluble resin (B) to be contained in the radiation-sensitive resin composition is a polymer of a monomer having an ethylenically unsaturated double bond and is an unsaturated carboxylic acid. A resin containing a unit derived from is preferable.

Examples of unsaturated carboxylic acids include (meth) acrylic acid; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids. The amount of the unit derived from the unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has the desired alkali solubility. .. The amount of the unit derived from the unsaturated carboxylic acid in the (B) alkali-soluble resin is preferably 5 to 25% by mass, more preferably 8 to 16% by mass, based on the total amount of the (B) alkali-soluble resin.

Among the polymers of monomers having an ethylenically unsaturated double bond, which are polymers of one or more types of monomers selected from the monomers exemplified above, (meth) acrylic acid and (meth) acrylic acid and (meth) ) A polymer of one or more monomers selected from acrylic acid esters, polyethylene, polypropylene, polystyrene and the like are preferable. Among these, one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester have a good balance of mechanical properties such as transparency, film-forming property, and hardness. Polymers are preferred. Hereinafter, a polymer of one or more types of monomers selected from (meth) acrylic acid and (meth) acrylic acid ester will be described.

The (meth) acrylic acid ester used in the preparation of a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester is particularly suitable as long as it does not impair the object of the present invention. It is not limited, and is appropriately selected from known (meth) acrylic acid esters.

Preferable examples of the (meth) acrylic acid ester are linear or linear such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate and the like. Branched chain alkyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) Examples thereof include acrylates, furfuryl (meth) acrylates; (meth) acrylic acid esters having a group having an epoxy group; and (meth) acrylic acid esters having a group having an alicyclic skeleton. Details of the (meth) acrylic acid ester having a group having an epoxy group and the (meth) acrylic acid ester having a group having an alicyclic skeleton will be described later.

Among the polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, the radiation-sensitive resin composition film formed by using the radiation-sensitive resin composition A resin containing a unit derived from a (meth) acrylic acid ester having a group having an epoxy group is preferable from the viewpoint of excellent adhesion to a base material and mechanical strength.

The (meth) acrylic acid ester having a group having an epoxy group is a group having an alicyclic epoxy group as described later, even if it is a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group. It may be a (meth) acrylic acid ester having.

The (meth) acrylic acid ester having a group having an epoxy group may contain an aromatic group. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of (meth) acrylic acid esters having an aromatic group and a group having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyl. Examples thereof include oxyphenyl (meth) acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, and 2-glycidyloxyphenylmethyl (meth) acrylate.

Examples of (meth) acrylic acid esters having a group having a chain aliphatic epoxy group include ester groups (-O-CO) such as epoxyalkyl (meth) acrylates and epoxyalkyloxyalkyl (meth) acrylates. Examples thereof include a (meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to an oxy group (−O−) in −). The chain aliphatic epoxy group contained in such a (meth) acrylic acid ester may contain one or more oxy groups (-O-) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

Specific examples of the (meth) acrylic acid ester having a group having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6. , Epoxyalkyl (meth) acrylates such as 7-epoxyheptyl (meth) acrylates; 2-glycidyloxyethyl (meth) acrylates, 3-glycidyloxy-n-propyl (meth) acrylates, 4-glycidyloxy-n-butyl ( Examples thereof include epoxyalkyloxyalkyl (meth) acrylates such as meth) acrylates, 5-glycidyloxy-n-hexyl (meth) acrylates, and 6-glycidyloxy-n-hexyl (meth) acrylates.

An epoxy group in a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, which comprises a unit derived from a (meth) acrylic acid ester having a group having an epoxy group. The content of the unit derived from the (meth) acrylic acid ester having a group having a group is preferably 1 to 95% by mass, more preferably 30 to 70% by mass, based on the weight of the resin.

Further, among the polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, it is easy to form a film having excellent transparency by using the radiation-sensitive resin composition. Therefore, a resin containing a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton is also preferable.

In a (meth) acrylic acid ester having a group having an alicyclic skeleton, the group having an alicyclic skeleton is a group having an alicyclic epoxy group even if it has a group having an alicyclic hydrocarbon group. You may. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like.

Among the (meth) acrylic acid esters having a group having an alicyclic skeleton, the (meth) acrylic acid ester having a group having an alicyclic hydrocarbon group is, for example, the following formulas (b2-1) to (b2-). Examples thereof include the compounds represented by 8). Among these, the compounds represented by the following formulas (b2-3) to (b2-8) are preferable, and the compounds represented by the following formulas (b2-3) or (b2-4) are more preferable.

In the above formula, R ^b1 represents a hydrogen atom or a methyl group, R ^b2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^b3 represents a hydrogen atom or 1 to 5 carbon atoms. Indicates the alkyl group of. As R ^b2 , a single bond, linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group is preferable. As R ^b3 , a methyl group and an ethyl group are preferable.

Among the (meth) acrylic acid esters having a group having an alicyclic skeleton, specific examples of the (meth) acrylic acid ester having a group having an alicyclic epoxy group include the following formulas (b3-1) to ( Examples thereof include the compounds represented by b3-16). Among these, in order to make the developability of the film-forming resin composition appropriate, the compounds represented by the following formulas (b3-1) to (b3-6) are preferable, and the following formula (b3-1) is preferable. )-(B3-4) are more preferable.

In the above formula, R ^b4 represents a hydrogen atom or a methyl group, R ^b5 represents a divalent aliphatic saturated hydrocarbon group having 1 to ⁶ carbon atoms, and R ^b6 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Indicates a group, where n represents an integer from 0 to 10. As R ^b5 , a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. Examples of R ^b6 include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, and -CH ₂ -Ph-CH _2- (Ph). Indicates a phenylene group) is preferred.

A resin in which a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester contains a unit derived from (meth) acrylic acid ester having a group having an alicyclic skeleton. In the case of, the amount of the unit derived from the (meth) acrylic acid ester having a group having an alicyclic skeleton in the resin is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and 30 to 70%. Even more preferably by mass%.

In addition, a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, which comprises a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton. Among them, a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group is preferable. Such a resin has excellent adhesion to a base material on which a transparent insulating film is formed. Further, when such a resin is used, it is possible to cause a self-reaction between the carboxyl group contained in the resin and the alicyclic epoxy group. Therefore, when a radiation-sensitive resin composition containing such a resin is used, it is formed by causing a self-reaction between a carboxyl group and an alicyclic epoxy group by using a method of heating a film or the like. It is possible to improve mechanical properties such as the hardness of the film.

In a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group, a unit derived from (meth) acrylic acid in the resin. The amount of the above is preferably 1 to 95% by mass, more preferably 10 to 50% by mass. In a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group, a group having an alicyclic epoxy group in the resin is used. The amount of the unit derived from the (meth) acrylic acid ester contained is preferably 1 to 95% by mass, more preferably 30 to 70% by mass.

Selected from (meth) acrylic acid and (meth) acrylic acid esters, which include units derived from (meth) acrylic acid and units derived from (meth) acrylic acid esters having a group having an alicyclic epoxy group. Among the polymers of one or more kinds of monomers, a unit derived from (meth) acrylic acid, a unit derived from (meth) acrylic acid ester having a group having a chain aliphatic epoxy group, and a fat A resin containing a unit derived from a (meth) acrylic acid ester having a group having a cyclic epoxy group and a unit derived from styrene or a styrene derivative is preferable.

A (meth) acrylic acid ester having a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group, and a group having an alicyclic epoxy group. In a resin containing a unit derived from styrene or a unit derived from a styrene derivative, the amount of the unit derived from (meth) acrylic acid in the resin is preferably 1 to 95% by mass, preferably 10 to 50% by mass. Is more preferable.

A (meth) acrylic acid ester having a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group, and a group having an alicyclic epoxy group. In a resin containing a unit derived from styrene or a unit derived from a styrene derivative, the amount of the unit derived from a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group in the resin is 1. It is preferably ~ 95% by mass, more preferably 10 to 70% by mass.

A (meth) acrylic acid ester having a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group, and a group having an alicyclic epoxy group. In a resin containing a unit derived from styrene or a unit derived from a styrene derivative, the amount of the unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group in the resin is 1 to 1. 95% by mass is preferable, and 30 to 70% by mass is more preferable.

A (meth) acrylic acid ester having a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group, and a group having an alicyclic epoxy group. In a resin containing a unit derived from styrene or a unit derived from a styrene derivative, the amount of the unit derived from styrene or a styrene derivative in the resin is preferably 1 to 95% by mass, preferably 10 to 70% by mass. More preferable.

The mass average molecular weight of the alkali-soluble resin is preferably 1000 to 40,000, more preferably 2000 to 30,000. Within the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability. In the present specification, the mass average molecular weight means a value in terms of polystyrene measured by gel permeation chromatography (GPC).

In addition, in this specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid. Also, "(meth) acrylate" means both acrylate and methacrylate. Further, as used herein, the term "(meth) acryloyl" means both acryloyl and methacryloyl. In addition, "(meth) acrylamide" means both acrylamide and methacrylamide.

[(C) Polyfunctional Monomer]
Since the radiation-sensitive resin composition according to the present invention contains (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, it is radiation-sensitive and radiation-sensitive. After applying the radiation-sensitive resin composition to the base material on which the sex resin composition film is to be formed, selective exposure and an aqueous solution of tetramethylammonium hydroxide are applied to the radiation-sensitive resin composition film. By developing with an alkaline developing solution such as the above, it can be used to produce a pattern made of the above-mentioned radiation-sensitive resin composition film. The polyfunctional monomer (C) can be used alone or in combination of two or more.

As the polyfunctional monomer (C), a monomer having an ethylenically unsaturated group can be preferably used. Examples of the polyfunctional monomer (C) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and butylene. Glycoldi (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylpropantri (meth) acrylate, glycerindi (meth) acrylate, pentaerythritol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloyloxydi) Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), Reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, etc. and 2-vidroxyethyl (meth) acrylate, condensate of methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol (meth) acrylamide. , Triacrylic formal, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol triacrylate, and 2,4,6-trioxohexahydro-1,3 , 5-Triazine-1,3,5-Trisethanoldiacrylate, Tris ((meth) acryloyloxyethyl) isocyanurate, Trimethylolpropane EO-modified tri (meth) acrylate and the like. Among them, a polyfunctional monomer having five or more functionalities such as dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is preferable from the viewpoint of adhesion to a base material.

The content of the polyfunctional monomer (C) is preferably 25 to 55 parts by mass, more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the (B) alkali-soluble resin. By setting the content of the (C) polyfunctional monomer in the radiation-sensitive resin composition within the above range, it is easy to obtain a radiation-sensitive resin composition having excellent adhesion to a substrate and photolithography characteristics.

[(D) Photopolymerization Initiator]
As the (D) photopolymerization initiator used together with the (C) polyfunctional monomer, various photopolymerization initiators conventionally used as the polymerization initiator for the (C) polyfunctional monomer can be used. (D) The photopolymerization initiator can be used alone or in combination of two or more.

Specific examples of a suitable (D) photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 1- [4- (2-hydroxyethoxy). Phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)- 2-Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4-( Methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, etanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, 4-benzoyl-4'-methyldimethylsulfide, 4 -Dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamylbenzoate Acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propandion-2- (o-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 2,4-diethylthioxanthone, 2 -Chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2- Ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumempa oxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2 -Mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-) Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Body, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4'-bisdiethylaminobenzophenone (ie, ethylmihi) Larsketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin Butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloro Acetphenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9-phenylaclydin, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6- Tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6- Bis (trichloromethyl) -s-triazine, 2- [2- (fran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2) -Methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine , 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2 , 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine , 2,4-Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl -S-Triazine, "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade name: BASF), "NCI-831" (trade name: ADEKA), etc. Can be mentioned. Among these, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity.

In addition to the above, an oxime ester compound represented by the following formula (E1) and an oxime ester compound represented by the following formula (E2) are also preferably used as the (D) photopolymerization initiator.

（Ｒ^Ｅ１１は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ａは０〜４の整数であり、ｂは０又は１であり、Ｒ^Ｅ１２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、Ｒ^Ｅ１３は、水素原子、又は炭素数１〜６のアルキル基である。）

( ^RE11 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, a is an integer of 0 to 4, and b is 0 or 1. , ^RE12 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent, and ^RE13 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

（ｄは１〜５の整数であり、ｅは１〜８の整数であり、ｆは０〜（ｄ＋３）の整数であり、Ｒ^Ｅ２１は、置換基を有してもよい炭素数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、Ｒ^Ｅ２２は下記式（Ｅ２１）〜（Ｅ２３）：

で表される置換基のいずれかであり、Ｒ^Ｅ２３は炭素数１〜１１のアルキル基であり、Ｒ^Ｅ２４は置換基を有してもよいアリール基であり、Ｒ^Ｅ２５は水素原子、置換基を有してもよい炭素数１〜１０のアルキル基、又はアリール基であり、Ｒ^Ｅ２６は置換基を有してもよいアリール基である。）

(D is an integer of 1 to 5, e is an integer of 1 to 8, f is an integer of 0 to (d + 3), and ^RE21 has 1 to 11 carbon atoms which may have a substituent. It is an alkyl group or an aryl group which may have a substituent, and ^RE22 is represented by the following formulas (E21) to (E23):

In is either of substituents ^{represented, R E23} is an alkyl group of 1 to 11 carbon ^{atoms, R E24} is an aryl group which may have a ^{substituent, R E25} is a hydrogen atom, a substituent It is an alkyl group or an aryl group having 1 to 10 carbon atoms which may have a substituent, and ^RE26 is an aryl group which may have a substituent. )

Among the above examples of the photopolymerization initiator (D), since it is easy to produce a pattern using the radiation-sensitive resin composition, the oxime ester compound represented by the following formula (E1) or the following formula (E2) The oxime ester compound represented by) is preferable. Hereinafter, the oxime ester compound represented by the formula (E1) and the oxime ester compound represented by the formula (E2) will be described in order.

（Ｒ^Ｅ１１は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ａは０〜４の整数であり、ｂは０又は１であり、Ｒ^Ｅ１２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、Ｒ^Ｅ１３は、水素原子、又は炭素数１〜６のアルキル基である。） (Oxime ester compound represented by the formula (E1))
Hereinafter, the oxime ester compound represented by the following formula (E1), which is suitable as the (D) photopolymerization initiator, will be described.

( ^RE11 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, a is an integer of 0 to 4, and b is 0 or 1. , ^RE12 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent, and ^RE13 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the above formula (E1), when ^RE11 is a monovalent organic group, ^RE11 is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of the case where ^RE11 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group and a substituent. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a benzoyloxy which may have a substituent. A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent. A naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, 1, or 2 Examples thereof include an amino group substituted with the organic group of, a morpholin-1-yl group, a piperazine-1-yl group and the like. When a is an integer of 2 to 4, ^{RE 11} may be the same or different. Further, the carbon number of the substituent does not include the carbon number of the substituent further possessed by the substituent.

When ^RE11 is an alkyl group, the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 6. When ^RE11 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where ^RE11 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, Examples thereof include an n-decyl group and an isodecyl group. Further, when ^RE11 is an alkyl group, the alkyl group may contain an ether bond (−O−) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When ^RE11 is an alkoxy group, its carbon number is preferably 1 to 20, and more preferably 1 to 6. When ^RE11 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where ^RE11 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, and n. -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxyl group , Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like. Further, when ^RE11 is an alkoxy group, the alkoxy group may contain an ether bond (−O−) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

When ^RE11 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms thereof is preferably 3 to 10 and more preferably 3 to 6. Specific examples of the case where ^RE11 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Specific examples of the case where ^RE11 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group and the like.

When ^RE11 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms thereof is preferably 2 to 20, more preferably 2 to 7. Specific examples of the case where ^RE11 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and n. -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where ^RE11 is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, 2, 2-Dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like can be mentioned.

When ^RE11 is an alkoxycarbonyl group, it preferably has 2 to 20 carbon atoms, more preferably 2 to 7 carbon atoms. Specific examples of the case where ^RE11 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

When ^RE11 is a phenylalkyl group, it preferably has 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. When ^RE11 is a naphthylalkyl group, the number of carbon atoms thereof is preferably 11 to 20, more preferably 11 to 14. Specific examples of the case where ^RE11 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where ^RE11 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl group. .. When ^RE11 is a phenylalkyl group or a naphthylalkyl group, ^RE11 may further have a substituent on the phenyl group or naphthyl group.

When ^RE11 is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or the monocycles are fused together, or the monocycle and the benzene ring are condensed. It is a heterocyclyl group. When the heterocyclyl group is a condensed ring, the number of rings is up to 3. Examples of the heterocycle constituting such a heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiaziazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Examples thereof include isoindole, indolidin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When ^RE11 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When ^RE11 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 to 2 carbon atoms. A saturated aliphatic acyl group of 20, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 to 20 carbon atoms, and a substituent. Examples thereof include a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Specific examples of these suitable organic groups are the same as for ^RE11 . Specific examples of the amino group substituted with the organic group 1 or 2 include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, an isopropylamino group and an n-. Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naftylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples thereof include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, a β-naphthoylamino group and the like.

When the phenyl group, naphthyl group, and heterocyclyl group contained in ^RE11 further have a substituent, the substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 2 carbon atoms. 7 saturated aliphatic acyl group, 2-7 carbon number alkoxycarbonyl group, 2-7 carbon number saturated aliphatic acyloxy group, 1 to 6 carbon number alkyl group monoalkylamino group, 1 to 6 carbon number carbon number Examples thereof include a dialkylamino group having an alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, a cyano group and the like. When the phenyl group, naphthyl group, and heterocyclyl group contained in ^RE11 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. Included in R ^E11, a phenyl group, a naphthyl group, and the heterocyclyl group, when having a plurality of substituents, the plurality of substituents may be different and the same.

Among ^RE11 , it has a nitro group and 1 carbon number because it is chemically stable, has few steric obstacles, is easy to synthesize an oxime ester compound, and has high solubility in a solvent. A group selected from the group consisting of an alkyl group having ~ 6 to, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, and a nitro group or an alkyl having 1 to 6 carbon atoms is preferable. More preferably, a nitro group or a methyl group is particularly preferable.

Position R ^E11 is attached to the phenyl group, the phenyl group R ^E11 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group The 4th or 5th position is preferable, and the 5th position is more preferable. Further, a is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

^RE12 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. Also, when R ^E12 is a good carbazolyl group which may have a substituent, a nitrogen atom on carbazolyl groups may be substituted with an alkyl group having 1 to 6 carbon atoms.

In ^RE12 , the substituent contained in the phenyl group or the carbazolyl group is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 to 10 carbon atoms. Cycloalkyl group, cycloalkoxy group with 3 to 10 carbon atoms, saturated aliphatic acyl group with 2 to 20 carbon atoms, alkoxycarbonyl group with 2 to 20 carbon atoms, saturated aliphatic acyloxy group with 2 to 20 carbon atoms, substituent It may have a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, and a substituent. It has a phenoxycarbonyl group, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent and has 7 to 20 carbon atoms, a naphthyl group which may have a substituent, and a substituent. It may have a naphthoxy group, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, or a substituent. A good naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, or an amino group substituted with an organic group of 1, or 2. , Morphorin-1-yl group, and piperazine-1-yl group, halogen, nitro group, cyano group and the like.

When ^RE12 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon. Saturated aliphatic acyl group of several 2 to 20, alkoxycarbonyl group of 2 to 20 carbons, phenyl group which may have a substituent, benzoyl group which may have a substituent, and may have a substituent. It has a good phenoxycarbonyl group, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent. May have a naphthoxycarbonyl group, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, etc. Can be mentioned. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the phenyl group or the carbazolyl group may have are an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. For a phenylalkyl group which may have a group, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and an amino group substituted with one or two organic groups. , ^RE11 is the same.

In ^RE12 , an alkyl group having 1 to 6 carbon atoms is an example of a substituent when the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent; An alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl Group; naphthoyl group; benzoyl group substituted with a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group; a benzoyl group having 1 to 1 carbon atoms. Examples thereof include a monoalkylamino group having an alkyl group of 6; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; a morpholin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1 to 4 are preferable. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Among ^RE12, the group represented by the following formula (E11) or (E12) is preferable, and the group represented by the following formula (E11) is more preferable, because the radiation-sensitive resin composition is excellent in sensitivity. , A group represented by the following formula (E12), in which A is S, is particularly preferable.

（Ｒ^Ｅ１４は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｃは、０〜４の整数である。）

( ^RE14 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, A is S or O, and c is an integer of 0 to 4. is there.)

（Ｒ^Ｅ１５及びＲ^Ｅ１６は、それぞれ、１価の有機基である。）

( ^RE15 and ^RE16 are monovalent organic groups, respectively.)

If R ^E14 in Formula (E11) is an organic radical, within a range that does not impair the object of the present invention can be selected from various organic groups. A preferred example of the case where ^RE14 is an organic group in the formula (E11) is an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, A benzoyl group substituted with a group selected from the group consisting of a piperazin-1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms. Dialkylamino group; morpholin-1-yl group; piperazin-1-yl group; halogen; nitro group; cyano group.

In ^RE14 , it was substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group. Benzoyl group; nitro group is preferable, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferable.

Further, in the formula (E11), n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. when n is 1, the binding position of R ^E14, to the bond to the phenyl group R ^E14 is attached is bound to a sulfur atom, it is preferably in the para position.

R ^E15 in formula (E12), to the extent that does not impair the object of the present invention can be selected from various organic groups. Preferable examples of ^RE15 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and an alkoxycarbonyl group having 2 to 20 carbon atoms. A phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a phenylalkyl having 7 to 20 carbon atoms which may have a substituent. A group, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and 11 to 20 carbon atoms which may have a substituent. Examples thereof include a naphthylalkyl group, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among the R ^E15, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, an ethyl group is particularly preferred.

R ^E16 in Formula (E12) is not particularly limited within a range not inhibiting the object of the present invention can be selected from various organic groups. Specific examples of a group suitable as ^RE16 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. A good heterocyclyl group is mentioned. As R ^E16, more preferably a phenyl group which may have a substituent Among these groups, a 2-methylphenyl group are particularly preferred.

When the phenyl group, naphthyl group, and heterocyclyl group contained in ^RE14 , ^RE15 , or ^RE16 have further substituents, the substituents include an alkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms. Monoalkylamino having an alkoxy group, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Examples thereof include a group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in ^RE14 , ^RE15 , or ^RE16 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1 to 4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in ^RE14 , ^RE15 , or ^RE16 has a plurality of substituents, the plurality of substituents may be the same or different.

^RE13 in the formula (E1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As ^RE13 , a methyl group or an ethyl group is preferable, and a methyl group is more preferable. When ^RE13 is a methyl group, the photopolymerization initiator composed of the compound represented by the formula (E1) is particularly excellent in sensitivity.

The oxime ester compound represented by the formula (E1) can be synthesized, for example, according to the following scheme 1 when b is 0. Specifically, an aromatic compound represented by the following formula (E1-1) is acylated by a Friedercrafts reaction using a halocarbonyl compound represented by the following formula (E1-2), and the following formula is used. A ketone compound represented by (E1-3) was obtained, and the obtained ketone compound (E1-3) was oximeized with hydroxylamine to obtain an oxime compound represented by the following formula (E1-4), and then the formula was obtained. oxime compound of (E1-4), an acid anhydride represented by the following formula ^{(E1-5) ((R E13 CO} ) 2 O), or an acid halide represented by the following formula (E1-6) (R ^E13 COHal and Hal are halogens.) To obtain an oxime ester compound represented by the following formula (E1-7). In the following formula (E1-2), H is a halogen, and in the following formulas (E1-1), (E1-2), (E1-3), (E1-4), and (E1-7). , R ^E11 , R ^E12 , R ^E13 , and a are the same as in the formula (E1).

<Scheme 1>

The oxime ester compound represented by the formula (E1) can be synthesized, for example, according to the following scheme 2 when b is 1. Specifically, the ketone compound represented by the following formula (E2-1) has a nitrite ester represented by the following formula (E2-2) in the presence of hydrochloric acid (RONO and R have 1 to 6 carbon atoms). The alkyl group) is reacted to obtain a ketooxime compound represented by the following formula (E2-3), and then the ketooxime compound represented by the following formula (E2-3) is combined with the following formula (E2-4). acid anhydride represented _{^{((R E13 CO) 2 O}} ), or the following formula acid halide represented by (E2-5) with ^(R E13 COHal, Hal is a halogen.) is reacted with the following formula (E2 An oxime ester compound represented by -6) can be obtained. Incidentally, the following formula (E2-1), (E2-3), (E2-4), in (E2-5), and ^{(E2-6), R E11, R} E12, R E13, and a has the formula It is the same as (E1).

<Scheme 2>

Further, the oxime ester compound represented by the formula (E1) is, b is ^1, and ^{R E11} is a methyl ^group, with respect to methyl groups attached to the benzene ring ^{to which R E11} are ^{attached, R E11} para In the case of binding to the position, for example, the compound represented by the following formula (E2-7) can be synthesized by oximeization and acylation in the same manner as in Scheme 1. In Formula ^{(E2-7), R E12} is the same as formula (E1).

Among the oxime ester compounds represented by the formula (E1), particularly suitable compounds include compounds of the following formula.

（ｄは１〜５の整数であり、ｅは１〜８の整数であり、ｆは０〜（ｄ＋３）の整数であり、Ｒ^Ｅ２１は、置換基を有してもよい炭素数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、Ｒ^Ｅ２２は下記式（Ｅ２１）〜（Ｅ２３）：

で表される置換基のいずれかであり、Ｒ^Ｅ２３は炭素数１〜１１のアルキル基であり、Ｒ^Ｅ２４は置換基を有してもよいアリール基であり、Ｒ^Ｅ２５は水素原子、置換基を有してもよい炭素数１〜１０のアルキル基、又はアリール基であり、Ｒ^Ｅ２６は置換基を有してもよいアリール基である。） (Oxime ester compound represented by the formula (E2))
Hereinafter, the oxime ester compound represented by the following formula (E2), which is suitable as the (D) photopolymerization initiator, will be described.

(D is an integer of 1 to 5, e is an integer of 1 to 8, f is an integer of 0 to (d + 3), and ^RE21 has 1 to 11 carbon atoms which may have a substituent. It is an alkyl group or an aryl group which may have a substituent, and ^RE22 is represented by the following formulas (E21) to (E23):

In is either of substituents ^{represented, R E23} is an alkyl group of 1 to 11 carbon ^{atoms, R E24} is an aryl group which may have a ^{substituent, R E25} is a hydrogen atom, a substituent It is an alkyl group or an aryl group having 1 to 10 carbon atoms which may have a substituent, and ^RE26 is an aryl group which may have a substituent. )

In the above formula (E2), d is preferably 1 to 3, more preferably 1 or 2. e is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2.

As the substituent which may be possessed when ^RE21 is an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. Further, as the substituent which may be possessed when ^RE21 is an aryl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom and the like are preferably exemplified.

In the above formula (E2), as ^RE21 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like are preferably exemplified, and among these, methyl A group or a phenyl group is more preferable.

In the above formula (E2), as ^RE23 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a phenyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

In the above formulas (E21) and (E22), ^examples of the substituent that the aryl group of ^RE24 may have include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom and the like. Preferably exemplified. In the above formulas (E21) and (E22), an alkoxy group having 1 to 5 carbon atoms, a phenyl group, a naphthyl group and the like are preferably exemplified as the substituent which may be possessed when ^RE25 is an alkyl group. ..

In the above formulas (E21) and (E22), ^RE24 includes a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, and 4 -Ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, naphthyl group, 2-methoxy-1-naphthyl group, 9 -Anthracenyl group and the like are preferable.

In the above formulas (E21) and (E22), ^RE25 includes a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-Pentyl, n-hexyl group, phenyl group, 3-methylbutyl group, 3-methoxybutyl group and the like are preferably exemplified, and among these, the ethyl group is more preferable.

In the above formula (E23), examples of the substituent that the aryl group of ^RE26 may have are preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom and the like. .. The ^RE26 includes phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, and 2,3-dimethylphenyl. Groups, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, naphthyl group, p-tert-butylphenyl group, p-methoxyphenyl group and the like are preferably exemplified and used. Of these, a phenyl group is more preferable.

As a particularly preferable specific example among the oxime ester compounds represented by the formula (E2), the compound of the following formula can be preferably exemplified.

The content of the (D) photopolymerization initiator in the radiation-sensitive resin composition is preferably 0.1 to 50 parts by mass, preferably 0.5 parts by mass, based on 100 parts by mass of the total solid content of the radiation-sensitive resin composition. More preferably, 10 parts by mass. By using the (D) photopolymerization initiator in an amount within the above range, the radiation-sensitive resin composition can be sufficiently cured by radiation, and a good pattern can be produced by using the radiation-sensitive resin composition. be able to.

[(S) Organic solvent]
The radiation-sensitive resin composition may contain (S) an organic solvent (hereinafter, also referred to as “(S) component”) in order to improve coatability and adjust viscosity. The component (S) can be used alone or in combination of two or more.

Specific examples of the organic solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono. -N-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono- n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (Poly) alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, etc. (Poly) alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; 2- Lactate alkyl esters such as methyl hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl -3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate , N-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate and other esters; Aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide; and the like can be mentioned. Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, lactic acid alkyl esters, and other esters described above are preferable, and alkylene glycol monoalkyl ether acetates described above. Other ethers and other esters described above are more preferred.

The content of the component (S) in the radiation-sensitive resin composition is not particularly limited. The content of the component (S) in the radiation-sensitive resin composition is within a range in which the radiation-sensitive resin composition can be applied to the base material on which the radiation-sensitive resin composition film is formed. , It is appropriately set according to the coating film thickness. The solid content concentration of the radiation-sensitive resin composition is typically preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and even more preferably 5 to 15% by mass.

[Other ingredients]
Various additives may be added to the radiation-sensitive resin composition, if necessary. Specific examples thereof include monofunctional monomers, sensitizers, cross-linking agents, antioxidants, ultraviolet absorbers, defoamers, adhesion enhancers, surfactants, and thermal polymerization inhibitors. As any of the additives, conventionally known ones can be used. The amount of the additive used is not particularly limited as long as it does not impair the object of the present invention, and is appropriately determined according to the type of the additive. Additives can be used alone or in combination of two or more.

As the monofunctional monomer, one having an ethylenically unsaturated group can be preferably used. Examples of the monofunctional compound include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, and N-methylol ( Meta) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-Methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (Meta) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, Glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- Examples thereof include tetrafluoropropyl (meth) acrylate and half (meth) acrylate of a phthalic acid derivative. Examples of the defoaming agent include silicone-based compounds and fluorine-based compounds. Examples of the adhesion enhancer include conventionally known silane coupling agents. Examples of the surfactant include anionic, cationic and nonionic compounds. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether and the like.

<< Manufacturing method of radiation-sensitive resin composition >>
The method for producing the radiation-sensitive resin composition is not particularly limited. The radiation-sensitive resin composition can be produced by uniformly mixing each component described above with a known mixing device. When the radiation-sensitive resin composition is a solid or a highly viscous gel at room temperature, each component is mixed using a kneader or a melt-kneading device such as a double roll and a triple roll. It may be mixed.

≪Pattern manufacturing method≫
The pattern manufacturing method according to the present invention comprises a radiation-sensitive resin composition film forming step of forming a radiation-sensitive resin composition film using the radiation-sensitive resin composition according to the present invention, and the above-mentioned radiation-sensitive resin composition. It includes an exposure step of position-selectively exposing the film and a development step of developing the exposed radiation-sensitive resin composition film.

In the radiation-sensitive resin composition film forming step, the radiation-sensitive resin composition film is preferably formed on the substrate. Examples of the base material include a transparent conductive film substrate such as an ITO film substrate. The method for forming the radiation-sensitive resin composition film in the radiation-sensitive resin composition film forming step is not particularly limited. When the radiation-sensitive resin composition is a solid or a high-viscosity gel, for example, after supplying a predetermined amount of the radiation-sensitive resin composition onto the substrate, the radiation-sensitive resin composition is appropriately heated while being appropriately heated. The radiation-sensitive resin composition film can be formed by the pressing method. When the radiation-sensitive resin composition is a liquid, for example, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, a slit coater, or a non-contact type such as a spinner (rotary coating device) or a curtain flow coater. A radiation-sensitive resin composition film can be formed by a method using a coating device.

In the exposure step, the radiation-sensitive resin composition film can be exposed position-selectively by, for example, a method of exposing through a mask. Exposure, ArF excimer laser, KrF excimer laser, _{F 2} excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beams, X-rays, is carried out by irradiating radiation and soft X-rays. The amount of exposure varies depending on the composition of the radiation-sensitive resin composition, but is preferably about 10 to 600 mJ / cm ² .

In the developing step, the developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

The pattern can be manufactured as described above. Since the radiation-sensitive resin composition according to the present invention is excellent in photolithography characteristics, the pattern produced from this radiation-sensitive resin composition tends to be excellent in rectangularness. In addition, the above pattern has excellent adhesion. Therefore, when the pattern is formed on a transparent conductive film substrate such as an ITO film substrate and the transparent conductive film substrate is etched with an etching solution such as oxalic acid using the pattern as a mask, the pattern becomes transparent with the etching solution. It is possible to effectively suppress peeling from the conductive film substrate.

≪Transparent insulating film and display device≫
When the radiation-sensitive resin composition according to the present invention is used, a transparent insulating film can be formed by a simple method such as coating, pressing, or exposure as described above. Further, since the transparent insulating film thus formed has excellent transparency and a high dielectric constant, it is suitably used when manufacturing various types of display devices. Due to these advantages, the transparent insulating film thus formed is expected as a substitute material for the transparent insulating film made of silicon nitride, which has been conventionally used in display devices such as liquid crystal displays.

Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.

<Material>
[Filler]
Filler 1: CeO ₂ , average particle size 100 nm
Filler 2: CeO ₂ , average particle size 50 nm
Filler 3: La ₂ O ₃ , average particle size 100 nm
Filler 4: TiO ₂ , average particle size 100 nm
Filler 5: BaTIO ₃ , average particle size 100 nm

[resin]
Resins 1 to 3: Resins composed of structural units I to IV represented by the following formulas, and the amount of each structural unit is as shown in Table 1.

[Polyfunctional monomer]
Polyfunctional Monomer 1: 6 Functional Polyfunctional Monomer, Dipentaerythritol Hexaacrylate Polyfunctional Monomer 2: Trifunctional Polyfunctional Monomer, Trimethylol Propanetriacrylate Polyfunctional Monomer 3: Trifunctional Polyfunctional Monomer, Tris (Acryloyloxy) Ethyl) Isocyanurate Polyfunctional Monomer 4: Trifunctional Polyfunctional Monomer, Trimethylol Propane EO Modified Triacrylate Polyfunctional Monomer 5: 4 Functional Polyfunctional Monomer, Pentaerythritol Tetraacrylate

[Photopolymerization initiator]
Photopolymerization Initiator 1: Compound represented by the following formula

[Preparation of radiation-sensitive resin composition]
The types and amounts of resins, polyfunctional monomers, photopolymerization initiators, and fillers shown in Table 2 are uniformly mixed with a mixed solvent of 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, and diethylene glycol ethyl methyl ether. To prepare a radiation-sensitive resin composition having a solid content of 12% by mass. The composition ratio of the mixed solvent was 3-methoxybutyl acetate: propylene glycol monomethyl ether acetate: diethylene glycol ethyl methyl ether = 2: 6: 2 (mass ratio).

[Evaluation of adhesion]
The radiation-sensitive resin composition was spin-coated on the ITO film substrate. Next, the coating film on the ITO film substrate was heated and dried on a hot plate at 80 ° C. for 120 seconds to form a radiation-sensitive resin composition film on the ITO film substrate. The ITO film substrate was immersed in 5% by mass of oxalic acid, and the time until the radiation-sensitive resin composition film was peeled off from the ITO film substrate was measured. The results are shown in Table 2. When the pattern was not formed as a result of the evaluation of the following photolithography characteristics, the adhesion was not evaluated.

[Evaluation of photolithography characteristics]
The radiation-sensitive resin composition was spin-coated on the ITO film substrate. Next, the coating film on the ITO film substrate was heated and dried on a hot plate at 80 ° C. for 120 seconds to form a radiation-sensitive resin composition film on the ITO film substrate. After that, using a proximity exposure device (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 25 μm, and the exposure amount was set to 20, 30, through a negative mask in which a hole pattern having a diameter of 10 μm was formed. The radiation-sensitive resin composition film was exposed in three steps of 40 mJ / cm ² . The radiation-sensitive resin composition film after exposure was developed with a 2.38 mass% TMAH aqueous solution at 23 ° C. for 100 seconds, and the photolithography characteristics were evaluated according to the following criteria. The results are shown in Table 2. In each Example or each Comparative Example, the result of evaluation of the photolithography characteristics was the same even if the exposure amount was different.
X: No hole pattern was formed on the radiation-sensitive resin composition film.
Δ: A tapered hole pattern was formed on the radiation-sensitive resin composition film.
◯: A hole pattern having good rectangularity was formed on the radiation-sensitive resin composition film.
⊚: A hole pattern having better rectangularity was formed on the radiation-sensitive resin composition film.

＊質量％は、樹脂と多官能モノマーとの合計に対する値である。

* Mass% is a value with respect to the total of the resin and the polyfunctional monomer.

As can be seen from Table 2, the photolithography characteristics were not obtained in Comparative Examples 1 and 2, whereas the radiation-sensitive resin composition according to the present invention is excellent in adhesion to the substrate and photolithography characteristics. In particular, when the polyfunctional monomer is a polyfunctional monomer having 5 or more functionalities, the content of the polyfunctional monomer is 25 to 55 parts by mass with respect to 100 parts by mass of the alkali-soluble resin, or the content of the filler is high. When the total amount is 7.5 to 15 parts by mass with respect to 100 parts by mass of the total of the alkali-soluble resin and the polyfunctional monomer, the adhesion to the substrate and the photolithographic properties are excellent.

Claims (10)

A simple substance of at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, an oxide of the element, a chelate compound of the element, a salt of the element, and the above. A radiation-sensitive resin containing one or more selected from the group consisting of elemental alloys and having an average particle size of 200 nm or less, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. It ’s a composition,
The alkali-soluble resin includes a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group and a unit derived from a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group. Contains resin, including
The photopolymerization initiator is viewed at least Tsuo含selected from the group consisting of an oxime ester compound represented by the following formula (E1), and the oxime ester compound represented by the following formula (E2),
The radiation-sensitive resin composition, wherein the average particle size is a volume average particle size measured by a dynamic light scattering measurement method (DLS) .

( ^RE11 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, a is an integer of 0 to 4, and b is 0 or 1. , ^RE12 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent, and ^RE13 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

(D is an integer of 1 to 5, e is an integer of 1 to 8, f is an integer of 0 to (d + 3), and ^RE21 has 1 to 11 carbon atoms which may have a substituent. It is an alkyl group or an aryl group which may have a substituent, and ^RE22 is represented by the following formulas (E21) to (E23):

In is either of substituents ^{represented, R E23} is an alkyl group of 1 to 11 carbon ^{atoms, R E24} is an aryl group which may have a ^{substituent, R E25} is a hydrogen atom, a substituent It is an alkyl group or an aryl group having 1 to 10 carbon atoms which may have a substituent, and ^RE26 is an aryl group which may have a substituent. ) A simple substance of at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, an oxide of the element, a chelate compound of the element, a salt of the element, and the above. A radiation-sensitive resin containing one or more selected from the group consisting of elemental alloys and having an average particle size of 200 nm or less, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. It ’s a composition,
The alkali-soluble resin includes a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group and a unit derived from a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group. Contains resin, including
The photopolymerization initiator contains an oxime-based photopolymerization initiator (excluding 1,2-octanedione-1- [4- (phenylthio) phenyl-, 2- (o-benzoyloxime)]). See ,
The radiation-sensitive resin composition, wherein the average particle size is a volume average particle size measured by a dynamic light scattering measurement method (DLS) . The radiation-sensitive resin composition according to claim 1 or 2, wherein the polyfunctional monomer is a pentafunctional or higher functional polyfunctional monomer. A simple substance of at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, an oxide of the element, a chelate compound of the element, a salt of the element, and the above. A radiation-sensitive resin containing one or more selected from the group consisting of elemental alloys and having an average particle size of 200 nm or less, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. A composition (excluding a radiation-sensitive resin composition containing a silicon-based compound containing an epoxy group or an amine group).
The alkali-soluble resin contains a resin containing a unit derived from a (meth) acrylic acid ester having an alicyclic skeleton.
Wherein Ri polyfunctional monomer is 5 or more functional polyfunctional monomer der,
The radiation-sensitive resin composition, wherein the average particle size is a volume average particle size measured by a dynamic light scattering measurement method (DLS) . The radiation-sensitive resin composition according to claim 4, wherein the alicyclic skeleton is an alicyclic epoxy group. A simple substance of at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, an oxide of the element, a chelate compound of the element, a salt of the element, and the above. A radiation-sensitive resin containing one or more selected from the group consisting of elemental alloys and having an average particle size of 200 nm or less, an alkali-soluble resin, a polyfunctional monomer, and a photopolymerization initiator. A composition (excluding a radiation-sensitive resin composition containing a silicon-based compound containing an epoxy group or an amine group).
The photopolymerization initiator contains at least one selected from the group consisting of an oxime ester compound represented by the following formula (E1) and an oxime ester compound represented by the following formula (E2).
Wherein Ri polyfunctional monomer is 5 or more functional polyfunctional monomer der,
The radiation-sensitive resin composition, wherein the average particle size is a volume average particle size measured by a dynamic light scattering measurement method (DLS) .

( ^RE11 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, a is an integer of 0 to 4, and b is 0 or 1. , ^RE12 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent, and ^RE13 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

(D is an integer of 1 to 5, e is an integer of 1 to 8, f is an integer of 0 to (d + 3), and ^RE21 has 1 to 11 carbon atoms which may have a substituent. It is an alkyl group or an aryl group which may have a substituent, and ^RE22 is represented by the following formulas (E21) to (E23):

In is either of substituents ^{represented, R E23} is an alkyl group of 1 to 11 carbon ^{atoms, R E24} is an aryl group which may have a ^{substituent, R E25} is a hydrogen atom, a substituent It is an alkyl group or an aryl group having 1 to 10 carbon atoms which may have a substituent, and ^RE26 is an aryl group which may have a substituent. ) The radiation-sensitive resin composition according to any one of claims 1 to 6, wherein the content of the polyfunctional monomer is 25 to 55 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. A radiation-sensitive resin composition film forming step of forming a radiation-sensitive resin composition film using the radiation-sensitive resin composition according to any one of claims 1 to 7.
An exposure step of regioselectively exposing the radiation-sensitive resin composition film, and
A pattern manufacturing method including a developing step of developing the exposed radiation-sensitive resin composition film. A transparent insulating film obtained by using the radiation-sensitive resin composition according to any one of claims 1 to 7. A display device including the transparent insulating film according to claim 9.