TWI668512B - Sensitive radiation linear resin composition, pattern manufacturing method, transparent insulating film, and display device - Google Patents

Abstract

An object of the present invention is to provide a radiation sensitive linear resin composition excellent in adhesion to a substrate and optical lithography characteristics, a pattern manufacturing method using the above-mentioned sensitive radiation linear resin composition, and a composition using the above-mentioned radiation sensitive linear resin composition. A transparent insulating film and a display device including the transparent insulating film.

The solution is a sensitive radiation linear resin composition of the present invention: a monomer comprising at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, the above element The oxide, the compound of the above-mentioned element, the salt of the above element, and one or more selected from the group consisting of the alloy of the above-mentioned elements, and a filler having an average particle diameter of 200 nm or less, an alkali-soluble resin, and a polyfunctional compound Monomer, and photopolymerization initiator. The above polyfunctional monomer is preferably a polyfunctional monomer having 5 or more functional groups. Further, the content of the polyfunctional monomer is preferably 25 to 55 parts by mass based on 100 parts by mass of the alkali-soluble resin.

Description

Sensitive radiation linear resin composition, pattern manufacturing method, transparent insulating film, and display device

The present invention relates to a radiation sensitive linear resin composition, a pattern manufacturing method using the above sensitive radiation linear resin composition, a transparent insulating film obtained by using the above sensitive radiation linear resin composition, and a display having the above transparent insulating film Device.

In recent years, in the field of manufacturing electronic components such as semiconductor elements and liquid crystal display devices, as the progress of microfabrication progresses, the negative resist composition used therein generally requires high resolution, high sensitivity, and good shape. The formation of the resist pattern, the high residual film rate after the etching treatment, and the like. For example, in a thin film transistor (TFT) device used as a driving element of a liquid crystal display element, the transparent electrode circuit is transparently guided by an indium tin oxide film substrate (hereinafter also referred to as "ITO film substrate"). A resist pattern is formed on the film substrate, and the resist pattern is used as a mask to form a transparent conductive film substrate.

As a negative resist composition used for the formation of a transparent electrode circuit, it has been proposed to blend a bisphenol compound with a phenol novolac resin. A negative resist composition comprising a negative resist composition composed of chloromethylated polystyrene or polyvinylphenol and an aromatic diazide compound (Patent Document 1), and a thermosetting resin and A negative-resistance composition (Patent Document 2) which is a photo-acid generator which can absorb an actinic ray having an actinic ray in the wavelength range of 210 to 299 nm (Patent Document 2).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 62-8777

[Patent Document 2] Japanese Laid-Open Patent Publication No. 62-164045

In particular, in the etching of the transparent conductive film substrate, for the purpose of eliminating the steps, etc., the negative resist composition also requires adhesion to the substrate or before the hardening (post-baking) of the negative resist composition. Excellent light micro-image characteristics, etc., can form a good pattern. However, the conventional negative-type resist composition used for etching the transparent conductive film substrate is insufficient in adhesion to the substrate or optical lithography characteristics.

The present invention has been made in view of the above circumstances, and provides a photosensitive radiation linear resin composition excellent in adhesion to a substrate and optical lithography characteristics, a pattern manufacturing method using the above-mentioned sensitive radiation linear resin composition, and use. A transparent insulating film obtained by the above-mentioned sensitive radiation linear resin composition and a display device including the above transparent insulating film are used.

The inventors of the present invention have found that a filler containing a specific metal element, an oxide of the above element, and the like having a mean particle diameter of 200 nm or less and a polyfunctional monomer can be blended in the radiation sensitive linear resin composition. The above problems are solved, and the present invention is finally completed.

A first aspect of the present invention is a radiation sensitive linear resin composition comprising: a monomer comprising at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, One or more selected from the group consisting of the oxide of the element, the compound of the above-mentioned element, the salt of the above element, and the alloy of the above-mentioned element, and the filler having an average particle diameter of 200 nm or less, an alkali-soluble resin, and the like A functional monomer, and a photopolymerization initiator.

A second aspect of the present invention is a pattern manufacturing method comprising: a photosensitive radiation linear resin composition film forming step of forming a radiation sensitive linear resin composition film using the above-mentioned sensitive radiation linear resin composition; and the above-mentioned sensitive radiation linear resin An exposure step of selectively exposing the film position; and a developing step of developing the exposed photosensitive radiation linear resin composition film.

A third aspect of the present invention is a transparent insulating film obtained by using the above-mentioned radiation-sensitive linear resin composition.

A fourth aspect of the invention is a display device comprising the transparent insulating film.

According to the present invention, it is possible to provide a sensitive radiation linear resin composition excellent in adhesion to a substrate and photo lithography characteristics, a pattern manufacturing method using the above-mentioned sensitive radiation linear resin composition, and a composition using the above-mentioned radiation sensitive linear resin composition. A transparent insulating film and a display device including the transparent insulating film.

Sensitive radiation linear resin composition≫

The sensitive radiation linear resin composition of the present invention (hereinafter also referred to simply as "sensitive radiation linear resin composition") includes a group selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta. One or more selected from the group consisting of a monomer of at least one element, an oxide of the above element, a compounded compound of the above element, a salt of the above element, and an alloy of the above element, and an average particle diameter of 200 nm The following fillers (hereinafter also referred to as "(A) fillers"), alkali-soluble resins (hereinafter also referred to as "(B) alkali-soluble resins"), and polyfunctional monomers (hereinafter also referred to as "(C) polyfunctional monomers "), and a photopolymerization initiator (hereinafter also referred to as "(D) photopolymerization initiator"). The sensitive radiation linear resin composition of the present invention contains (A) a filler and (C) a polyfunctional monomer, and is excellent in adhesion to a substrate and photo lithography characteristics particularly before curing (post-baking). Therefore, by using the sensitive radiation linear resin composition of the present invention, it is easy to form a good film before the hardening (post-baking) of the above-mentioned radiation sensitive linear resin composition. The pattern is easy to delete the steps in the etching of the transparent conductive film substrate. As a result, for example, a display device such as a liquid crystal panel can be efficiently manufactured.

The sensitive radiation linear resin composition of the present invention is preferably a film which can be formed by using a sample having a thickness of 2 μm and having a transmittance of light having a wavelength of 400 nm of 90% or more. In the transparent film containing the (A) filler, the shorter the wavelength of light, the higher the absorption. Therefore, the transmittance of the transparent insulating film formed using the sensitive radiation linear resin composition is 90% or more at a wavelength of 400 nm, and the transparent insulating film has high transparency in the visible light wavelength region. For this reason, the transmittance of light at a wavelength of 400 nm is used as an index of transparency of the transparent insulating film.

Hereinafter, each component contained in the sensitive radiation linear resin composition will be described.

[(A) filler]

(A) The filler material includes a monomer selected from at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, an oxide of the above element, and a combination of the above elements. One or more selected from the group consisting of a compound, a salt of the above element, and an alloy of the above elements, and having an average particle diameter of 200 nm or less. The above elements have a high electron density. Therefore, the monomer of the above element, the oxide of the above element, the compounded compound of the above element, the salt of the above element, and the alloy of the above element have a high dielectric constant. Further, in the film formed using the sensitive radiation linear resin composition, the monomer of the above element, the oxide of the above element, the compounding compound of the above element, the salt of the above element, and the alloy of the above element are dispersed in the constituent film. In the state of the matrix, it is difficult to hinder the penetration of visible light. Therefore, the transparent insulating film formed using the radiation sensitive linear resin composition containing the above-mentioned (A) filler has a high dielectric constant and is excellent in transparency. Each of the monomer of the above element, the oxide of the above element, the compounding compound of the above element, the salt of the above element, and the alloy of the above element may be used alone or in combination of two or more.

The valence of the above elements contained in the oxide of the above element is not particularly limited.

In the conjugated compound of the above element, examples of the ligand capable of forming a condensate with the above element include pyridine, triphenylphosphine, carbon monoxide, ethylenediamine, bipyridine, catechol, and ethylenediamine. Acetic 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 examples of the salt include a halide, a sulfate, a nitrate, a phosphate, an acetate, a formate, a propionate, and a benzoate. The valence of the above elements constituting the salt is not particularly limited.

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

The monomer of the above element, the oxide of the above element, the compounding compound of the above element, the salt of the above element, and the alloy of the above element are preferably formed transparently based on the composition in the composition or the linear resin composition using the sensitive radiation. The film excellent in properties is preferably an oxide. Preferred examples of the oxide of the above element 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 .

(A) The shape of the filler is not particularly limited. The average particle diameter of the filler (A) is 200 nm or less, preferably 150 nm or less, more preferably 100 nm or less. (A) When the average particle diameter of the filler is 200 nm or less, the filler (A) is less likely to precipitate in the dispersion, and a photosensitive radiation linear resin composition in a liquid form is easily obtained. Further, the lower limit of the average particle diameter of the filler (A) is not particularly limited, but is preferably 40 nm or more, and more preferably 45 nm or more. (A) When the lower limit of the average particle diameter of the filler is 40 nm or more, the surface of the filler (A) is more easily applied, and the film obtained by using the radiation-sensitive linear resin composition is less likely to have a lower dielectric constant and leakage current. It is not easy to produce, and (A) the filler is not easy to aggregate.

Further, in the present specification, the average particle diameter means a volume average particle diameter measured by dynamic light scattering measurement (DLS).

The content of the (A) filler in the sensitive radiation linear resin composition is not particularly limited insofar as it does not impair the object of the present invention. The content of the (A) filler in the sensitive radiation linear resin composition is typically 7.5 to 15 parts by mass, based on 100 parts by mass of the total of (B) the alkali-soluble resin and the (C) polyfunctional monomer. More preferably 8 to 12 parts by mass. When the (A) filler having such a range is blended with the sensitive radiation linear resin composition, it is easy to obtain a radiation sensitive linear resin composition excellent in adhesion to the substrate and photo lithography.

[(B) alkali soluble resin]

In the present specification, the alkali-soluble resin means a film obtained by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass. A resin film having a thickness of 1 μm was formed on a substrate, and was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter also referred to as TMAH) for 1 minute to dissolve 0.01 μm or more. The sensitive radiation linear resin composition of the present invention contains the (B) alkali-soluble resin, and after coating the above-mentioned radiation-sensitive linear resin composition as a substrate for forming a film of the radiation-sensitive linear resin composition, the coating is applied. The film is subjected to selective exposure and development using an alkali developing solution such as an aqueous solution of tetramethylammonium hydroxide to form a patterned film of the radiation sensitive linear resin composition. (B) The alkali-soluble resin may be used alone or in combination of two or more.

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

The (B) alkali-soluble resin is preferably a polymer having a monomer having an ethylenically unsaturated double bond, because it is excellent in film formability, and it is easy to adjust the properties of the resin by selection of a monomer. Examples of the monomer having an ethylenically unsaturated double bond include (meth)acrylic acid; (meth)acrylic acid ester; (meth)acrylic acid decylamine; crotonic acid; maleic acid, fumaric acid, and citraconic acid. , zhongkang acid, itaconic acid, anhydrides of such dicarboxylic acids; allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allylic stearate Allyl compounds such as esters, allyl benzoate, allyl acetate, allyl lactate, and allyloxyethanol; hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether Ethylhexyl vinyl ether, Methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl ethylene 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 tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, And vinyl ethers such as vinyl decyl ether; vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl Chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butyrate acetate, vinyl phenyl acetate, ethylene vinyl acetate, vinyl lactate, vinyl butyrate - β- Vinyl esters such as phenyl ester, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate; styrene, A Styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene , benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ethoxymethyl styrene, methoxy styrene, 4-methoxy-3 -methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, Styrene or styrene derivatives such as fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; 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-ten Olefins such as octaene and 1-icosene.

From the viewpoint of alkali solubility and transparency, as the (B) alkali-soluble resin contained in the sensitive radiation linear resin composition, a polymer having a monomer having an ethylenically unsaturated double bond, that is, a polymer containing an unsaturated carboxylic acid is derived. The unit of resin.

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

Among the polymers of the monomer having an ethylenically unsaturated double bond which is a polymer of one or more monomers selected from the monomers exemplified above, it is preferably selected from (meth)acrylic acid and (meth) A polymer of one or more monomers of acrylate, polyethylene, polypropylene, polystyrene, or the like. Among these, a polymer having one or more monomers selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid ester is preferable because of a good balance of mechanical properties such as transparency, film forming property, and hardness. Hereinafter, a polymer of one or more monomers selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid ester will be described. The (meth) acrylate used for the preparation of the polymer of one or more monomers selected from the group consisting of (meth)acrylic acid and (meth) acrylate is not particularly limited as long as the object of the present invention is not impaired, and may be It is appropriately selected from the (meth) acrylate.

Preferred examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and amyl (meth)acrylate, (methyl). a linear or branched alkyl (meth)acrylate such as trioctyl acrylate; chloroethyl (meth)acrylate; 2,2-dimethylhydroxypropyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, decyl (meth)acrylate; having an epoxy group ( Methyl) acrylate; (meth) acrylate having a group having an alicyclic skeleton. Details of the (meth) acrylate having a group having an epoxy group and the (meth) acrylate having a group having an alicyclic skeleton will be described later.

Among the polymers of one or more kinds of monomers selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid, the adhesion of the film of the radiation sensitive linear resin composition formed by using the sensitive radiation linear resin composition to the substrate Or, in terms of excellent mechanical strength, a resin containing a unit derived from a (meth) acrylate having an epoxy group is preferable.

The (meth) acrylate having a group having an epoxy group may be a (meth) acrylate having a group having a chain aliphatic epoxy group, or may have an alicyclic epoxy group as described later. Base (meth) acrylate.

The (meth) acrylate having an epoxy group may also contain an aromatic group. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of the (meth) acrylate having an aromatic group and having a group having an epoxy group include 4-glycidoxyphenyl (meth)acrylate and 3-cyclo(meth)acrylate. Oxypropoxyphenyl ester, 2-glycidoxyphenyl (meth)acrylate, 4-glycidoxyphenyl methyl (meth)acrylate, 3-glycidoxy (meth)acrylate Phenyl phenyl methyl ester, and 2-glycidoxyphenyl methyl (meth) acrylate.

Examples of the (meth) acrylate having a group having a chain aliphatic epoxy group include, for example, epoxyalkyl (meth)acrylate and epoxyalkyloxyalkyl (meth)acrylate. The (meth) acrylate in which an oxy group (-O-) in an ester group (-O-CO-) such as an ester is bonded with a chain aliphatic epoxy group. The chain aliphatic epoxy group of such a (meth) acrylate may contain 1 or a plurality of oxy groups (-O-) in the chain. The carbon number 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) acrylate having a group having a chain aliphatic epoxy group include glycidyl (meth)acrylate and 2-methylglycidyl (meth)acrylate. (meth)acrylic acid alkyl (meth)acrylate, such as 3,4-butyl butyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate; 2-glycidyl (meth)acrylate Oxyethyl ester, 3-glycidoxypropyl n-propyl (meth)acrylate, 4-glycidoxy n-butyl (meth)acrylate, 5-epoxypropoxy (meth)acrylate Ester, 6-glycidoxy-n-hexyl ester of (meth)acrylic acid, etc. Base) acrylic acid alkyl alkoxyalkyl ester.

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

Further, among the polymers of one or more kinds of monomers selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid ester, it is preferred to use a radiation-sensitive linear resin composition to easily form a film having excellent transparency. A resin comprising a unit derived from a (meth) acrylate having a group of an alicyclic skeleton.

In the (meth) acrylate having a group having an alicyclic skeleton, the group having an alicyclic skeleton may be a group having an alicyclic hydrocarbon group or a group having an alicyclic epoxy group. 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. Further, examples of the polycyclic alicyclic group include a thiol group, an isodecyl group, a tricyclic fluorenyl group, a tricyclic fluorenyl group, and a tetracyclic decyl group.

Among the (meth) acrylates having a group having an alicyclic skeleton, examples of the (meth) acrylate having a group having an alicyclic hydrocarbon group include the following formulas (b2-1) to (b2-8). ) the compound shown. Among these, a compound represented by the following formula (b2-3) to (b2-8) is preferred, and a compound represented by the following formula (b2-3) or (b2-4) is more preferred.

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 an alkyl group having 1 to 5 carbon atoms. R ^{b2 is} preferably a single bond, a linear chain, or a branched alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an ethyl group, an ethyl group, a pentyl group, and a stretching group. Heji. As R ^b3 , a methyl group or an ethyl group is preferred.

Among the (meth) acrylates having a group having an alicyclic skeleton, specific examples of the (meth) acrylate having a group having an alicyclic epoxy group include, for example, the following formula (b3-1) ~(b3-16) compound. Among these, it is a resin composition for forming a moderate film. The developing property is preferably a compound represented by the following formulas (b3-1) to (b3-6), more preferably a compound represented by the following formulas (b3-1) to (b3-4).

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, R ^b6 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. R ^{b5 is} preferably a linear or branched alkylene group such as a methyl group, an ethyl group, a propyl group, a butyl group, an ethyl group, a pentyl group or a hexyl group. R ^{b6 is} preferably, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an ethyl group, an ethyl group, a pentyl group, a phenyl group, a phenyl group, a cyclohexyl group, or a CH ₂ -Ph- CH ₂ - (Ph represents a phenyl group).

When selected from (meth)acrylic acid and (meth) acrylate When the polymer of one or more kinds of monomers is a resin containing a unit derived from a (meth) acrylate having a group having an alicyclic skeleton, a group having a group having an alicyclic skeleton in the resin (methyl group) The amount of the unit derived from the acrylate is preferably from 5 to 95% by mass, more preferably from 10 to 90% by mass, still more preferably from 30 to 70% by mass.

Further, among the polymers of one or more monomers selected from the group consisting of (meth)acrylic acid and (meth)acrylic acid esters having a unit derived from a (meth) acrylate having an alicyclic skeleton, A resin comprising a unit derived from (meth)acrylic acid and a unit derived from a (meth) acrylate having a group having an alicyclic epoxy group is preferred. Such a resin is excellent in adhesion to a substrate on which a transparent insulating film is formed. Moreover, when such a resin is used, the carboxyl group contained in the resin and the self-reaction with the alicyclic epoxy group can occur. Therefore, when a sensitive radiation linear resin composition containing such a resin is used, the hardness of the formed film can be improved by causing a carboxyl group to be reacted with an alicyclic epoxy group by a method such as heating the film. Mechanical properties.

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

a unit derived from (meth)acrylic acid, and a unit derived from a (meth) acrylate having a group having an alicyclic epoxy group, selected from (meth)acrylic acid and (meth) acrylate Among the polymers of the above monomers, preferred are units derived from (meth)acrylic acid, units derived from (meth)acrylate having a chain aliphatic epoxy group, and having a fat. A unit derived from a (meth) acrylate of a cyclopentyloxy group, or a resin derived from a unit derived from styrene or a styrene derivative.

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

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

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

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

The mass average molecular weight of the alkali-soluble resin is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. By taking the above range, good development performance can be obtained, and sufficient heat resistance and film strength can be obtained. Further, in the present specification, the mass average molecular weight means a value converted into polystyrene as measured by gel permeation chromatography (GPC).

Further, in the present specification, "(meth)acrylic acid" means both acrylic acid and methacrylic acid. Moreover, "(meth)acrylate" means both an acrylate and a methacrylate. Further, in the present specification, the term "(meth)acryloyl) means both an acryloyl group and a methacryloyl group. Further, "(meth)acrylamide" means both acrylamide and methacrylamide.

[(C) polyfunctional monomer]

The sensitive radiation linear resin composition of the present invention can contain (B) alkali a soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, and therefore, can be applied to a substrate for a substrate having a linearity of sensitivity radiation and forming a film of a radiation sensitive linear resin composition. After irradiating the linear resin composition, the above-mentioned sensitive radiation linear resin composition film is selectively exposed, and developed through an alkali developing solution such as an aqueous solution of tetramethylammonium hydroxide to produce a linear resin composition composed of the above-mentioned sensitive radiation. The pattern formed by the film. (C) The polyfunctional monomer can be used individually or in combination of 2 or more types.

As the (C) polyfunctional monomer, those having an ethylenically unsaturated group can be preferably used. Examples of the (C) polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di( Methyl) acrylate, polypropylene glycol di(meth) acrylate, butane diol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 1,6-hexanediol di(methyl) ) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, neopentyl alcohol di (meth) acrylate, neopentyl alcohol tri (meth) acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, 2,2-bis(4-(methyl) Propylene oxime diethoxy phenyl) propane, 2,2-bis(4-(methyl) propylene oxypolyethoxy phenyl) propane, 2-hydroxy-3-(methyl) propylene oxy propylene (meth) acrylate, ethylene glycol diepoxy propyl ether di (meth) acrylate, diethylene glycol diepoxy propyl ether di (meth) acrylate, phthalic acid diepoxy Propyl ester di(meth)acrylate, glycerol triacrylate, glycerol polyepoxypropyl ether poly( Methyl) acrylate, urethane (meth) acrylate Reaction of ester (i.e., toluene diisocyanate), trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate with 2-hydroxyethyl (meth)acrylate, methylene bis(methyl) propylene oxime Amine, (meth) acrylamide, methylene ether, condensate of polyol and N-methylol (meth) acrylamide, tripropylene hexahydrotriazine, 2, 4, 6-trilateral Oxy hexahydro-1,3,5-triazine-1,3,5-paraxyl alcohol triacrylate, and 2,4,6-trisethoxy hexahydro-1,3,5-triazine-1 3,5-parameter ethanol diacrylate, ginseng ((meth) propylene oxiranyl) isocyanurate, trimethylolpropane EO modified tri(meth) acrylate, and the like. Among them, a 5-functional or higher polyfunctional monomer such as diheptaerythritol pentaacrylate or dipentaerythritol hexaacrylate is preferred because of the adhesion to the substrate.

The content of the (C) polyfunctional monomer is preferably 25 to 55 parts by mass, more preferably 30 to 50 parts by mass, per 100 parts by mass of the (B) alkali-soluble resin. When the content of the (C) polyfunctional monomer in the linear radiation-sensitive resin composition is in the above range, it is easy to obtain a radiation-sensitive linear resin composition excellent in adhesion to a substrate and optical lithography.

[(D) Photopolymerization initiator]

As the (D) photopolymerization initiator to be used together with the (C) polyfunctional monomer, various photopolymerization initiators which have been used as the polymerization initiator for the (C) polyfunctional monomer can be used. (D) The photopolymerization initiator may be used alone or in combination of two or more.

Specific examples of the suitable (D) photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropane - 1-ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-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)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl Propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone, 1-[9-ethyl-6 -(2-Methylbenzylidene)-9H-carbazol-3-yl], 1-(o-ethylindenyl), 2,4,6-trimethylbenzimidyldiphenylphosphine oxide , 4-benzylidene-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate , 4-dimethylaminobenzoic acid butyl ester, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isopentylbenzoic acid, benzyl-β-methoxy Ethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) fluorene, methyl o-tolyl benzoate, 2, 4-diethylthiazinone, 2-chlorothiazepinone, 2,4-dimethylthiaxanthone 1-Chloro-4-propoxythiazinone, thiazepine, 2-chlorothiazepine, 2,4-diethylthiazepine, 2-methylthiazepine, 2-isopropylsulfide Rhodium, 2-ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl hydrazine, azobisisobutyronitrile, benzammonium peroxide, hydrogen peroxide Cumene oxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2- (o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(neighbor Oxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole Dimer, diphenyl Ketone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (ie, miconesone), 4,4'-bisdiethylaminobenzophenone (ie ethyl Miclotone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, diphenylethylenedione, benzoin, benzoin methyl ether, benzoin Ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylamino Propiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl acetophenone, p-dimethylaminoacetophenone, p-tertiary butyl trichloroacetophenone, p-tertiary butyl Chloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthiaxanone, 2-isopropylthioxanthone, dibenzocycloheptane Ketone, pentyl-4-dimethylaminobenzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridine Pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-paraxyl (trichloromethyl) symmetrical triazine, 2-methyl-4 ,6-bis(trichloromethyl)symmetric triazine, 2-[2-(5-methylfuran-2- ) vinyl]-4,6-bis(trichloromethyl)symmetric triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl) symmetric triazine 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)symmetric triazine, 2-[2-(3,4- Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)symmetric triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) symmetry Triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)symmetric triazine, 2-(4-n-butoxyphenyl)-4,6-bis ( Trichloromethyl)symmetric triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl symmetric triazine, 2,4-bis-trichloromethyl- 6-(2-bromo-4-methoxy)phenyl symmetric triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy Styrylphenyl symmetric triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl symmetrical triazine, "IRGACURE OXE02", IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade name: BASF), "NCI-831" (trade name: ADEKA). Among these, a lanthanide photopolymerization initiator is particularly preferred in terms of sensitivity.

Further, in addition to the above, the oxime ester compound represented by the following formula (E1) or the oxime ester compound represented by the following formula (E2) may be suitably used as the (D) photopolymerization initiator.

(R ^E11 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, a is an integer of 0 to 4, b is 0 or 1, and R ^E12 is a substitutable a phenyl group or a carbazolyl group which may have a substituent, and R ^E13 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

(d is an integer from 1 to 5, e is an integer from 1 to 8, f is an integer from 0 to (d+3), and R ^E21 is an alkyl group having from 1 to 11 carbon atoms which may have a substituent, or may have a substitution Based on the aryl group, R ^E22 is of the following formula (E21)~(E23): Any one of the substituents shown, R ^E23 is an alkyl group having 1 to 11 carbon atoms, R ^E24 is an aryl group which may have a substituent, and R ^E25 is a hydrogen atom, and an alkyl group having 1 to 10 carbon atoms which may have a substituent Or an aryl group, R ^E26 is an aryl group which may have a substituent).

In the example of the above-mentioned (D) photopolymerization initiator, the oxime ester compound represented by the following formula (E1) or the following formula (E2) is preferred from the viewpoint of easy to use the linear composition of the radiation sensitive linear resin composition. The oxime ester compound shown. Hereinafter, the oxime ester compound represented by the formula (E1) and the formula (E2) The oxime ester compounds are shown in order.

(an oxime ester compound represented by formula (E1))

Hereinafter, an oxime ester compound represented by the following formula (E1) which is suitable as the (D) photopolymerization initiator will be described.

(R ^E11 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, a is an integer of 0 to 4, b is 0 or 1, and R ^E12 is a substitutable a phenyl group or a carbazolyl group which may have a substituent, and R ^E13 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the above formula (E1), when R ^E11 is a monovalent organic group, R ^E11 is not particularly limited as long as it does not impair the object of the present invention, and can be appropriately selected from various organic groups. Preferable examples of the case where R ^E11 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic decyloxy group, and may have a phenyl group of a substituent, a phenoxy group which may have a substituent, a benzyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyl group which may have a substituent, may have a substituent a phenylalkyl group, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylmethoxycarbonyl group which may have a substituent A naphthyl group which may have a substituent, a heterocyclic group which may have a substituent, an amine group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. When a is an integer from 2 to 4, R ^E11 may be the same or different. Further, the carbon number of the substituent does not include the carbon number of the substituent which the substituent further has.

When R ^E11 is an alkyl group, the carbon number thereof is preferably from 1 to 20, more preferably from 1 to 6. Further, when R ^E11 is an alkyl group, it may be a straight chain or a branched chain. Specific examples of the case where R ^E11 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tert-butyl group, n-pentyl group, Isoamyl, secondary pentyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, secondary octyl, tertiary octyl, n-decyl, isodecyl, n-decyl , and different bases, etc. Further, when R ^E11 is an alkyl group, the alkyl group may have an ether bond (-O-) in its 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, and a propoxy group B. Oxyethyl, methoxypropyl and the like.

When R ^E11 is an alkoxy group, the carbon number thereof is preferably from 1 to 20, more preferably from 1 to 6. Further, when R ^E11 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ^E11 is an alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a secondary butoxy group, and the like. Butoxy, n-pentyloxy, isopentyloxy, secondary pentyloxy, tertiary pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, secondary octyloxy a group, a tertiary octyloxy group, a n-decyloxy group, an isodecyloxy group, a n-decyloxy group, an isodecyloxy group, and the like. Further, when R ^E11 is an alkoxy group, the alkoxy group may also have an ether bond (-O-) in its carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, and an ethoxyethoxyethoxy group. , propoxyethoxyethoxy, and methoxypropoxy.

When R ^E11 is a cycloalkyl group or a cycloalkoxy group, the carbon number thereof is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the case where R ^E11 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the case where R ^E11 is a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^E11 is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, the carbon number thereof is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of the case where R ^E11 is a saturated aliphatic fluorenyl group include an ethyl fluorenyl group, a propyl fluorenyl group, a n-butyl fluorenyl group, a 2-methyl propyl fluorenyl group, a n-pentamethylene group, and a 2,2-dimethyl propyl hydrazine group. Base, positive hexyl group, n-heptyl sulfhydryl group, n-octyl sulfhydryl group, n-decyl group, n-decyl group, positive eleventh fluorenyl group, positive zirconium group, positive thirteenth fluorenyl group, positive fourteenth fluorenyl group, positive ten Wuyiji, and Zhengliujiji, etc. Specific examples of the case where R ^E11 is a saturated aliphatic decyloxy group include an ethyl ethoxy group, a propenyloxy group, a n-butenyloxy group, a 2-methylpropenyloxy group, a n-pentyloxy group, and 2 ,2-dimethylpropoxycarbonyl, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-decyloxy, n-xyl Alkoxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecanoyloxy and the like.

When R ^E11 is an alkoxycarbonyl group, the carbon number thereof is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of the case where R ^E11 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, a secondary butoxycarbonyl group, and the like. Butyroxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, secondary pentyloxycarbonyl, tertiary pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, secondary octyloxy A carbonyl group, a tertiary octyloxycarbonyl group, a n-decyloxycarbonyl group, an isoindoleoxycarbonyl group, a n-decyloxycarbonyl group, an isoindoleoxycarbonyl group or the like.

When R ^E11 is a phenylalkyl group, the carbon number thereof is preferably from 7 to 20, more preferably from 7 to 10. Further, when R ^E11 is a naphthyl group, the carbon number thereof is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of the case where R ^E11 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 R ^E11 is a naphthyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. When R ^E11 is a phenylalkyl group or a naphthylalkyl group, R ^E11 may further have a substituent on the phenyl group or the naphthyl group.

When R ^E11 is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing one or more of N, S, O, or the monocyclic ring or the monocyclic ring is condensed with a benzene ring. a heterocyclic group. When the heterocyclic group is a condensed ring, the number of rings is up to three. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine. , pyridazine, benzofuran, benzothiophene, anthracene, isoindole, pyridazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, iso Quinoline, quinazoline, pyridazine, porphyrin, and quinoxaline. When R ^E11 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^E11 is an amine group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon number of 2 to 20 a saturated aliphatic fluorenyl group, a phenyl group which may have a substituent, a benzyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, A naphthylmethyl group having a substituent, a naphthyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclic group. Specific examples of such preferred organic groups are the same as R ^E11 . Specific examples of the amine group substituted with 1 or 2 organic groups include a methylamino group, an ethylamino group, a diethylamino group, a n-propylamino group, a di-n-propylamino group, an isopropylamine group, a n-butylamino group, Di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-nonylamino, anilino, naphthylamino, ethamamine, propionamide Base, n-butylammonium, n-pentamethyleneamine, n-hexylamine, n-heptylamino, n-octylamine, n-nonylamino, benzamidine, α-naphthylamino And β-naphthylaminoamine and the like.

Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^E11 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number of 2 a saturated aliphatic fluorenyl group of ~7, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic decyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, having a carbon number a dialkylamino group of a 1 to 6 alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^E11 further have a substituent, the number of the substituents is not limited, and is preferably from 1 to 4, without impairing the object of the present invention. When the phenyl, naphthyl, and heterocyclic groups contained in R ^E11 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^E11 , it is preferably a nitro group, an alkyl group having 1 to 6 carbon atoms, or a carbon number based on chemical stability, less steric hindrance, easy synthesis of an oxime ester compound, or high solubility in a solvent. a group selected from the group consisting of alkoxy groups of 1 to 6 and saturated aliphatic fluorenyl groups having 2 to 7 carbon atoms, more preferably a nitro group or an alkyl group having 1 to 6 carbon atoms, particularly preferably a nitro group. Or methyl.

To R ^E11 bonded to the phenyl position, if the key for R ^E11 knot phenyl, phenyl disposed at a position bonded with the main skeleton of the oxime ester compound is 1, the position provided methyl 2 Preferably, it is 4 bits or 5 bits, and more preferably 5 bits. Further, a is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0 or 1.

R ^E12 is a phenyl group which may have a substituent, or an oxazolyl group which may have a substituent. Further, when R ^E12 is a carbazole group which may have a substituent, the nitrogen atom on the oxazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^E12 , the substituent of the phenyl group or the carbazolyl group is not particularly limited insofar as it does not impair the object of the present invention. Examples of preferred substituents which the phenyl group or the 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 a carbon number of 3 to 10. a cycloalkyl group, a cycloalkyloxy group having 3 to 10 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms. 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 benzyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, may have a substituent a benzepoxy group, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylmethyl group which may have a substituent, A naphthyloxycarbonyl group which may have a substituent, a naphthylmethoxy group which may have a substituent, a naphthyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a heterocyclic ring which may have a substituent A carbonyl group, an amine group, an amine group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, and a cyano group.

When R ^E12 is a carbazolyl group, examples of preferred substituents which 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. a saturated aliphatic fluorenyl group of 2 to 20, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzamyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and may have a phenylalkyl group having 7 to 20 carbon atoms, a naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, and a carbon number which may have a substituent of 11 to 20 A naphthyl group, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred, and ethyl is particularly preferred.

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 fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic fluorenyloxy group. The phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, the heterocyclic group which may have a substituent, and the amine group substituted by one or two organic groups are the same as R ^E11 .

In R ^E12 , examples of the substituent when the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent include carbon numbers 1 to 6. Alkyl group; alkoxy group having 1 to 6 carbon atoms; saturated aliphatic fluorenyl group having 2 to 7 carbon atoms; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic fluorenyloxy group having 2 to 7 carbon atoms; Naphthyl; benzhydryl; naphthylmethyl; a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; Substituted benzhydryl group; monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholin-1-yl; piperazin-1-yl Halogen; nitro; cyano. When the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, the number of the substituents is not particularly limited insofar as it does not hinder the object of the present invention, and is preferably 1~4. When the phenyl, naphthyl, and heterocyclic groups have a plurality of substituents, the plurality of substituents may be the same or different.

In the case of R ^E12 , the sensitivity of the linear radiation-sensitive resin composition is more excellent, preferably a group represented by the following formula (E11) or (E12), more preferably a group represented by the following formula (E11). Preferably, it is a group represented by the following formula (E11), and A is a group of S.

(R ^E14 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, and A is S or O, and c is an integer of 0 to 4).

(R ^E15 and R ^E16 are each a monovalent organic group).

When R ^E14 in the formula (E11) is an organic group, it can be selected from various organic groups without departing from the object of the present invention. Preferred examples of the formula (E11) in which R ^E14 is an organic group include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms. ; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic methoxy group having 2 to 7 carbon atoms; phenyl; naphthyl group; benzamyl group; naphthylmethyl group; alkyl group having 1 to 6 carbon atoms; a benzylamino group substituted with a group selected from the group consisting of morpholin-1-yl, piperazin-1-yl, and phenyl; monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; having carbon a dialkylamino group of an alkyl group of 1 to 6; morpholin-1-yl; piperazin-1-yl; halogen; nitro; cyano.

Among R ^E14 , a benzamidine group; a naphthylmethyl group; a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; Substituted benzhydryl; nitro, more preferably benzinyl; naphthylmethyl; 2-tolylcarbonyl; 4-(piperazin-1-yl)phenylcarbonyl; 4-(phenyl ) phenylcarbonyl.

Further, in the formula (E11), c is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0 or 1. When c is 1, the bonding position of R ^E14 is preferably para-position with respect to the bond where the phenyl group bonded to R ^E14 is bonded to the sulfur atom.

R ^E15 in the formula (E12) can be selected from various organic groups without departing from the object of the present invention. Preferred examples of R ^E15 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, and an alkoxy group having 2 to 20 carbon atoms. a carbonyl group, a phenyl group which may have a substituent, a benzhydryl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, may have a substituent A naphthyl group, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and may have a substitution A heterocyclic carbonyl group or the like.

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

R ^E16 in the formula (E12) is not particularly limited ^insofar as it does not impair the object of the present invention, and may be selected from various organic groups. Specific examples of the preferred group of R ^E16 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 heterocyclic group which may have a substituent. As R ^E16 , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

^Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^E14 , R ^E15 or R ^E16 further have a substituent include an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to 6. Alkoxy group, saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic decyloxy group having 2 to 7 carbon atoms, and alkyl group having 1 to 6 carbon atoms An alkylamino group, 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, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^E14 , R ^E15 or R ^E16 further have a substituent, the number of substituents is not in the range of the object of the present invention, and is preferably from 1 to 4. When the phenyl, naphthyl, and heterocyclic groups contained in R ^E14 , R ^E15 , or R ^E16 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^E13 in the formula (E1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R ^E13 , a methyl group or an ethyl group is preferred, and a methyl group is more preferred. When R ^E13 is a methyl group, the photopolymerization initiator composed of the compound represented by the formula (E1) is particularly excellent in sensitivity.

When the oxime ester compound represented by the formula (E1) is 0, for example, it can be synthesized according to the following route diagram 1. Specifically, the aromatic compound represented by the following formula (E1-1) can be deuterated by a fu-exaggeration reaction using a halocarbonyl compound represented by the following formula (E1-2) to give the following formula (E1- 3) The ketone compound shown, and the obtained ketone compound (E1-3) is deuterated by hydroxylamine to obtain a hydrazine compound represented by the following formula (E1-4), and secondly, a hydrazine compound of the formula (E1-4) And reacting with an acid anhydride ((R ^E13 CO) ₂ O) represented by the following formula (E1-5) or a hydrazine halide (R ^E13 COHal, Hal is a halogen) represented by the following formula (E1-6), An oxime ester compound represented by the following formula (E1-7). Further, in the following formula (E1-2), Hal is a halogen, and in the following formulae (E1-1), (E1-2), (E1-3), (E1-4), and (E1-7), R ^E11 , R ^E12 , R ^E13 , and a are the same as equation (E1).

<Path Figure 1>

The oxime ester compound represented by the formula (E1), when b is 1, can be synthesized, for example, according to the following scheme. Specifically, a ketone compound represented by the following formula (E2-1) can be used in the presence of hydrochloric acid with a nitrite represented by the following formula (E2-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms). The reaction is carried out to obtain a ketoxime compound represented by the following formula (E2-3), and secondly, a ketoxime compound represented by the following formula (E2-3) and an acid anhydride represented by the following formula (E2-4) are obtained (( R ^E13 CO) ₂ O), or a hydrazine halide (R ^E13 COHal, Hal is a halogen) represented by the following formula (E2-5), gives an oxime ester compound represented by the following formula (E2-6). Further, in the following formulae (E2-1), (E2-3), (E2-4), (E2-5), and (E2-6), R ^E11 , R ^E12 , R ^E13 , and a (E1) is the same.

<Path Figure 2>

Moreover, from the formula (E1) of the oxime ester compound shown, when b is 1, R ^E11 is methyl, and with respect to R ^E11 methyl bonded to the benzene ring of the knot, R ^E11 bonded to the para position In other words, for example, the compound represented by the following formula (E2-7) can be deuterated and synthesized in the same manner as in the scheme of FIG. Further, in the following formula (E2-7), the R ^E12 system is the same as the formula (E1).

As a particularly preferable compound among the oxime ester compounds represented by the formula (E1), a compound of the following formula can be mentioned.

(an oxime ester compound represented by 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 from 1 to 5, e is an integer from 1 to 8, f is an integer from 0 to (d+3), and R ^E21 is an alkyl group having from 1 to 11 carbon atoms which may have a substituent, or may have a substitution Based on the aryl group, R ^E22 is of the following formula (E21)~(E23): Any one of the substituents shown, R ^E23 is an alkyl group having 1 to 11 carbon atoms, R ^E24 is an aryl group which may have a substituent, and R ^E25 is a hydrogen atom, and an alkyl group having 1 to 10 carbon atoms which may have a substituent Or an aryl group, R ^E26 is an aryl group which may have a substituent).

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

The substituent which may be possessed when R ^E21 is an alkyl group is preferably a phenyl group, a naphthyl group or the like. Further, the substituent which may be ^contained when R ^E21 is an aryl group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom or the like.

In the above formula (E2), as R ^E21 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a phenyl group, a benzyl group, a tolyl group, a naphthyl group or the like is preferable, and among these, More preferably, it is a methyl group or a phenyl group.

In the above formula (E2), examples of R ^{E23 include a} methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a phenyl group and the like, and among these, a methyl group is more preferable.

In the above formulae (E21) and (E22), the substituent which may be contained in the aryl group of R ^E24 may, for example, be an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. Good. In the above formulae (E21) and (E22), the substituent which may be contained when R ^E25 is an alkyl group is preferably an alkoxy group having 1 to 5 carbon atoms, a phenyl group or a naphthyl group.

In the above formulae (E21) and (E22), as R ^E24 , a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, and 3 are preferable. -ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethyl Phenyl, naphthyl, 2-methoxy-1-naphthyl, 9-fluorenyl and the like.

In the above formulae (E21) and (E22), examples of R ^{E25 include a} hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group. A group, a n-pentyl group, a n-hexyl group, a phenyl group, a 3-methylbutyl group, a 3-methoxybutyl group and the like are preferable, and among them, an ethyl group is more preferable.

In the above formula (E23), the aryl group of R ^E26 may have a substituent, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or the like is preferable. As R ^E26 , a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group can be illustrated. , 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, naphthyl, p-terphenyl A base, a p-methoxyphenyl group or the like is preferred, and among these, a phenyl group is more preferred.

As a particularly preferable specific example of the oxime ester compound represented by the formula (E2), a compound of the following formula can be exemplified as a preferred one.

The content of the (D) photopolymerization initiator in the sensitive radiation linear resin composition, relative to the solid content of the radiation sensitive linear resin composition It is 100 parts by mass, preferably 0.1 to 50 parts by mass, more preferably 0.5 to 10 parts by mass. By using (D) a photopolymerization initiator in an amount within the above range, the radiation sensitive linear resin composition can be sufficiently hardened by radiation, and a sensitive radiation linear resin composition can be used to produce a good pattern.

[(S) organic solvent]

The touch sensitive linear resin composition may also contain (S) an organic solvent (hereinafter also referred to as "(S) component") for improvement in coating properties or viscosity adjustment. The (S) component may be used alone or in combination of two or more.

Specific examples of the (S) organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl ether. Diethylene glycol monoethyl ether, 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. Olefin diol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, (poly)olefin diol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether Other ethers such as diethylene glycol diethyl ether or tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; 2-hydroxypropionic acid , 2-hydroxy ethyl lactate and the like; esters of 2-hydroxy-2-methylpropane Ethyl acetate, 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 propionate - methoxybutyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, butyrate B Ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2- Other esters such as ethyl oxybutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethyl A guanamine such as acetamide. Among these, an olefin diol monoalkyl ether, an olefin diol monoalkyl ether acetate, the above other ethers, an alkyl lactate, and the other esters described above are more preferred. An olefin diol monoalkyl ether acetate, the other ethers described above, and the other esters described above.

The content of the (S) component in the sensitive radiation linear resin composition is not particularly limited. The content of the (S) component in the sensitive radiation linear resin composition can be applied to the substrate which is the object of forming the film of the radiation sensitive linear resin composition within the range of the radiation sensitive linear resin composition, and the coating film thickness is appropriate. set up. The solid content concentration of the sensitive radiation linear resin composition is typically from 1 to 50% by mass, more preferably from 5 to 30% by mass, still more preferably from 5 to 15% by mass.

[other ingredients]

Various additives may be added to the sensitive radiation linear resin composition as needed. Specifically, a monofunctional monomer, a sensitizer, a crosslinking agent, an antioxidant, a UV absorber, an antifoaming agent, a adhesion enhancer, a surfactant, a thermal polymerization inhibitor, etc. are illustrated. Any one of the additives can be used widely known. The amount of the additive to be used is not particularly limited insofar as it does not impair the object of the present invention, and may be appropriately determined depending on the kind of the additive. The additive may be used alone or in combination of two or more.

As the monofunctional monomer, those having an ethylenically unsaturated group can be preferably used. Examples of the monofunctional compound include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (meth) propylene. Indoleamine, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) 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-propenylamine 2-methylpropanesulfonic acid, tertiary butyl propylene sulfonamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-(meth) acrylate Ethylhexyl ester, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (methyl) ) 2-phenoxy-2-hydroxypropyl acrylate, 2-(methyl) propylene oxime-2-hydroxypropyl phthalate, glycerol mono(meth) acrylate, tetrahydrogen (meth) acrylate Anthracene ester, dimethylamine (meth)acrylate, glycidyl (meth)acrylate, (methyl) Acid 2,2,2-trifluoroethyl acrylate, (meth) acrylic acid 2,2,3,3-tetrafluoropropyl ester, a half (meth) acrylate of a phthalic acid derivative, or the like. Examples of the antifoaming agent include a polyfluorene-based compound and a fluorine-based compound. As the adhesion enhancer, a conventionally known decane coupling agent can be mentioned. Examples of the surfactant include compounds such as anionic, cationic, and nonionic. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether, and the like.

Method for producing sensitized radiation linear resin composition≫

The method for producing the sensitive radiation linear resin composition is not particularly limited. The radiation sensitive linear resin composition can be produced by uniformly mixing the components described above by a known mixing device. When the sensitive radiation linear resin composition is a solid or a high-viscosity gel at room temperature, the components may be mixed by a melt kneading apparatus such as a kneader or a two-roll mill and a three-roll mill.

≪ pattern manufacturing method≫

The pattern manufacturing method of the present invention comprises: a film forming step of a radiation sensitive linear resin composition for forming a film of a radiation sensitive linear resin composition using the sensitive radiation linear resin composition of the present invention; and selecting a film position of the above sensitive radiation linear resin composition An exposure step of performing exposure; and a developing step of developing the exposed photosensitive radiation linear resin composition film.

In the sensitive radiation linear resin composition film forming step, the radiation sensitive linear resin composition film is preferably formed on the substrate. The base material may, for example, be a transparent conductive film substrate such as an ITO film substrate. Forming a film of the radiation sensitive linear resin composition in the film formation step of the sensitive radiation linear resin composition The method is not particularly limited. When the sensitive radiation linear resin composition is a solid or high viscosity gel, for example, after a predetermined amount of the sensitive radiation linear resin composition is supplied onto the substrate, the surface is heated appropriately with a linear radiation sensitive resin composition. A method of pressing is performed to form a film of a sensitive radiation linear resin composition. When the sensitive radiation linear resin composition is a liquid, for example, a contact transfer type coating device using a roll coater, a reverse coater, a bar coater, a slit coater, or the like, or A method of a non-contact type coating device such as a spin coater (rotary coating device) or a curtain coater to form a film of a radiation sensitive linear resin composition.

In the exposure step, the film position of the sensitive radiation linear resin composition can be selectively exposed, for example, by exposure to a mask or the like. The exposure system is irradiated with radiation of ArF excimer laser, KrF excimer laser, F ₂ excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X-ray, or the like. The amount of exposure varies depending on the composition of the sensitive radiation linear resin composition, and is, for example, 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 employed. Specific examples of the developing liquid include organic substances such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

As described above, the pattern can be manufactured. The sensitive radiation linear resin composition of the present invention is excellent in light lithography characteristics, and is easy to make the pattern made of the sensitive radiation linear resin composition more excellent in rectangularity. Further, the pattern has excellent adhesion. Thus, the above pattern is formed on the ITO film base When the transparent conductive film substrate is etched with an etching solution of oxalic acid or the like on the transparent conductive film substrate such as a board, the transparent conductive film can be effectively suppressed by the etching liquid. The case where the substrate is peeled off.

≪Transparent insulating film and display device≫

When the sensitive radiation linear resin composition of the present invention is used, a transparent insulating film can be formed by a simple method such as coating, pressing, exposure, or the like as described above. Further, the transparent insulating film thus formed is excellent in transparency and high in dielectric constant, and is suitably used in the production of various types of display devices. The transparent insulating film thus formed is expected to be an alternative material for a transparent insulating film composed of tantalum nitride which is conventionally used in a display device such as a liquid crystal display based on these advantages.

[Examples]

The embodiments of the present invention are described below, but the scope of the present invention is not limited by the embodiments.

<material> [filler]

Filler 1: CeO ₂ , average particle size 100nm

Filler 2: CeO ₂ , average particle size 50 nm

Filler 3: La ₂ O ₃ , average particle diameter 100 nm

Filler 4: TiO ₂ , average particle size 100 nm

Filler 5: BaTiO ₃ , average particle diameter 100 nm

[resin]

Resin 1 to 3: It consists of structural units I to IV shown by the following formula, and the amount of each constituent unit is as shown in Table 1.

[multifunctional monomer]

Polyfunctional monomer 1: 6-functional polyfunctional monomer, dipentaerythritol hexaacrylate

Polyfunctional monomer 2: 3-functional polyfunctional monomer, trimethylolpropane triacrylate

Polyfunctional monomer 3: 3-functional polyfunctional monomer, ginseng Ethyl)isomeric cyanurate

Polyfunctional monomer 4: 3-functional polyfunctional monomer, trimethylolpropane EO modified triacrylate

Polyfunctional monomer 5: 4-functional polyfunctional monomer, neopentyl alcohol tetraacrylate

[Photopolymerization initiator]

Photopolymerization initiator 1: a compound represented by the following formula

[Modulation of sensitive radiation linear resin composition]

The types and amounts of the resins, polyfunctional monomers, photopolymerization initiators, and fillers described in Table 2, and 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, and diethyl ether as solvents The mixed solvent of the diol ethyl methyl ether was uniformly mixed to prepare a radiation sensitive linear resin composition having a solid content of 12% by mass. The composition ratio of the above mixed solvent was determined to be 3-methoxybutyl acetate: propylene glycol monomethyl ether acetate: diethylene glycol ethyl methyl ether = 2:6:2 (mass ratio).

[Assessment of adhesion]

The sensitive radiation linear resin composition was spin-coated on the ITO film substrate. Next, the coating film on the ITO film substrate was dried by heating at 80 ° C for 120 seconds on a hot plate to form a film of the radiation-sensitive linear resin composition 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 linear resin composition film was peeled off from the ITO film substrate was measured. The results are shown in Table 2. Further, as a result of the evaluation of the photolithographic characteristics described below, if the pattern was not formed, the evaluation of the adhesion was not performed.

[Assessment of photolithographic properties]

The sensitive radiation linear resin composition was spin-coated on the ITO film substrate. Next, the coating film on the ITO film substrate was dried by heating at 80 ° C for 120 seconds on a hot plate to form a film of the radiation-sensitive linear resin composition on the ITO film substrate. Then, using a proximity exposure apparatus (product name: TME-150RTO; manufactured by TOPCON Co., Ltd.), the exposure gap was 25 μm, and a negative mask having a hole pattern of 10 μm in diameter was formed, and the exposure amount was set to 20 At the 3rd stage of 30, and 40 mJ/cm ² , the film of the sensitive radiation linear resin composition was exposed. The film of the sensitive radiation linear resin composition after exposure was subjected to development with a 2.38 mass% TMAH aqueous solution at 23 ° C for 100 seconds, and the photo lithography characteristics were evaluated according to the following criteria. The results are shown in Table 2. Further, in each of the examples or the comparative examples, the evaluation results of the light lithography characteristics were the same even when the exposure amounts were different.

×: A pore pattern was formed on the film of the sensitive radiation linear resin composition.

△: A tapered hole pattern was formed on the film of the sensitive radiation linear resin composition.

○: A hole pattern having a good rectangular shape was formed on the film of the sensitive radiation linear resin composition.

◎: A hole pattern having a more rectangular shape is formed on the film of the sensitive radiation linear resin composition.

As is clear from Table 2, the photosensitive ray linear resin composition of the present invention is excellent in adhesion to the substrate and optical lithography characteristics in comparison with the comparative examples 1 and 2. In particular, when the polyfunctional monomer is a polyfunctional monomer having 5 or more functional groups, the content of the polyfunctional monomer is 25 to 55 parts by mass based on 100 parts by mass of the alkali-soluble resin, or the content of the filler relative to the alkali-soluble resin When the total amount of the polyfunctional monomer is 7.5 to 15 parts by mass, the adhesion to the substrate and the optical lithography characteristics are excellent.

Claims (7)

A radiation sensitive linear resin composition comprising: a monomer comprising at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, an oxide of the foregoing element, One or more selected from the group consisting of a compound of the above-mentioned element, a salt of the above-mentioned element, and an alloy of the above-mentioned elements, and a filler having an average particle diameter of 200 nm or less, an alkali-soluble resin, a polyfunctional monomer, and light a polymerization initiator; the aforementioned alkali-soluble resin contains a resin containing a unit derived from a (meth) acrylate having an alicyclic epoxy group. A radiation sensitive linear resin composition comprising: a monomer comprising at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf, and Ta, an oxide of the foregoing element, One or more selected from the group consisting of a compound of the above-mentioned element, a salt of the above-mentioned element, and an alloy of the above-mentioned elements, and a filler having an average particle diameter of 200 nm or less, an alkali-soluble resin, a polyfunctional monomer, and light a polymerization initiator; the photopolymerization initiator includes 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). In the formula (E1), R ^E11 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, a is an integer of 0 to 4, and b is 0 or 1, R ^E12 is a phenyl group which may have a substituent, or an oxazolyl group which may have a substituent, and R ^E13 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In the formula (E2), 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 R ^E21 is an alkyl group having 1 to 11 carbon atoms which may have a substituent Or an aryl group which may have a substituent, and R ^E22 is the following formula (E21) to (E23): Any one of the substituents shown, R ^E23 is an alkyl group having 1 to 11 carbon atoms, R ^E24 is an aryl group which may have a substituent, and R ^E25 is a hydrogen atom, and an alkyl group having 1 to 10 carbon atoms which may have a substituent Or an aryl group, and R ^E26 is an aryl group which may have a substituent. The sensitive radiation linear resin composition of claim 1 or 2, wherein the polyfunctional monomer is a polyfunctional monomer having 5 or more functional groups. The sensitive radiation linear resin composition of claim 1 or 2, wherein the content of the aforementioned polyfunctional monomer is relative to the aforementioned alkali-soluble resin 100 The amount is 25 to 55 parts by mass. A pattern manufacturing method comprising: a photosensitive radiation linear resin composition film forming step of forming a film of a radiation sensitive linear resin composition using the sensitive radiation linear resin composition of claim 1 or 2; An exposure step of selectively exposing the film position; and a developing step of developing the exposed photosensitive radiation linear resin composition film. A transparent insulating film obtained by using the sensitive radiation linear resin composition of claim 1 or 2. A display device comprising the transparent insulating film of claim 6.