TWI637936B - Radiation-sensitive composition and pattern manufacturing method - Google Patents

Abstract

The invention provides a radiation-sensitive composition and a method for manufacturing a pattern using the radiation-sensitive composition. The radiation-sensitive composition is excellent in sensitivity, storage stability, coatability, developability, and safety, and through exposure And development can form a pattern by suppressing the generation of foreign matter.

The radiation-sensitive composition of the present invention contains a compound represented by the following general formula (1). In the formula, R ¹ represents a hydrogen atom or a hydroxyl group, R ² and R ³ independently represent a hydrogen atom or a C ₁ to C ₃ alkyl group, and R ⁴ and R ⁵ independently represent a C ₁ to C ₃ alkyl group.

Description

Radiation-sensitive composition and pattern manufacturing method

The present invention relates to a radiation-sensitive composition and a pattern manufacturing method using the radiation-sensitive composition.

When manufacturing integrated circuits, color filters, liquid crystal elements, etc., microfabrication is required. However, in order to meet this requirement, radiation-sensitive compositions have been used so far. Generally speaking, there are positive and negative types in the radiation-sensitive composition. Generally, any of these is dissolved in a solvent and used in a solution state.

The radiation-sensitive composition is applied to a substrate such as a silicon substrate or a glass substrate by a conventional coating method such as a spin coating method, a roll coating method, a slit coating method, or an inkjet method. Pre-bake to form a radiation-sensitive composition film, and then, according to the photosensitive wavelength region of the radiation-sensitive composition, exposure is performed by particle beams such as ultraviolet, far ultraviolet, X-ray, and electron beam, and development is performed. If necessary, dry etching is performed to form a desired pattern.

The solvents used in the radiation-sensitive composition have hitherto been used in various solvents, and they are selected and used in consideration of solubility, coatability, sensitivity, developability, and characteristics of formed patterns. For example, ethylene glycol monoethyl ether acetate is known as a solvent having excellent properties such as solubility, coating properties, and film-forming properties of a radiation-sensitive composition film. In recent years, the problem of its safety to the human body has been Means However, there is a growing demand for a solvent that has improved safety, high resin solubility, excellent initiator solubility, and improved radiation-sensitive composition film formation properties.

As a solution to these problems, propylene glycol monomethyl ether acetate and the like have been proposed as solvents for replacing ethylene glycol monoethyl ether acetate (for example, Patent Document 1).

[Prior technical literature] (Patent Literature)

Patent Document 1: Japanese Patent Publication No. 3-1659

However, although these solvents are considered to be more safe than ethylene glycol monoethyl ether acetate, conventional radiation-sensitive compositions using these solvents have sensitivity, storage stability, coatability, or development There is a problem that the properties are insufficient, or a pattern obtained by exposing and developing such a radiation-sensitive composition has a problem that foreign matter is liable to occur.

The present invention has been developed in view of the circumstances as described above, and an object thereof is to provide a radiation-sensitive composition and a method for producing a pattern using the radiation-sensitive composition, and the sensitivity, storage stability, and coatability of the radiation-sensitive composition. It has excellent developability and safety, and can form a pattern by suppressing the generation of foreign matter by exposure and development.

The present inventors have repeatedly researched in order to solve the above problems As a result, it was found that by using a specific organic solvent, the above problems can be solved, and the present invention was completed. Specifically, the present invention provides the following technical means.

A first aspect of the present invention is a radiation-sensitive composition containing a compound represented by the following general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a hydroxyl group, R ² and R ³ independently represent a hydrogen atom or a C ₁ to C ₃ alkyl group, and R ⁴ and R ⁵ independently represent a C ₁ to C ₃ alkyl group).

A second aspect of the present invention is a pattern manufacturing method, which includes the following steps: a radiation-sensitive composition film forming step of forming a radiation-sensitive composition film composed of the radiation-sensitive composition on a substrate; An exposure step that selectively exposes the position of the radiation-sensitive composition film; and a development step that develops the exposed radiation-sensitive composition film.

According to the present invention, it is possible to provide a radiation-sensitive composition and a pattern manufacturing method using the radiation-sensitive composition. The radiation-sensitive composition is excellent in sensitivity, storage stability, coatability, developability, and safety, and By exposing and developing, it is possible to form a pattern in which the generation of foreign matter is suppressed.

[Best Mode for Carrying Out the Invention]

《Radiation Sensitive Composition》

The radiation-sensitive composition of the present invention contains at least a compound represented by the general formula (1). The compound represented by the general formula (1) is used as a solvent in the radiation-sensitive composition of the present invention. The radiation-sensitive composition of the present invention may contain only the compound represented by the general formula (1) as a solvent, or may further contain an organic solvent other than the compound represented by the general formula (1) (hereinafter also referred to as " Other organic solvents "). In other words, the radiation-sensitive composition of the present invention contains at least one of the compounds represented by the general formula (1) as a solvent. The compound represented by the general formula (1) in the radiation-sensitive composition of the present invention is in the form of a mixed solvent alone or mixed with other organic solvents. As a component other than the solvent (hereinafter referred to as "Base material component") is used as a solvent for dissolving and / or dispersing. Since the radiation-sensitive composition of the present invention contains the compound represented by the general formula (1) described above, it has excellent sensitivity, storage stability, coatability, developability, and safety, and can be formed by exposure and development. A pattern that suppresses foreign objects. The radiation-sensitive composition of the present invention can be preferably used for manufacturing, for example, a black matrix, a color filter, a black light spacer, an integrated circuit, a liquid crystal element, and the like.

[Compound represented by Formula (1)]

The compound represented by the general formula (1) is a solvent capable of well dissolving and / or dispersing the base material component contained in the radiation-sensitive composition, and can be widely used in general radiation-sensitive compositions. Among them, when the radiation-sensitive composition contains an oxime-based photopolymerization initiator, the compound represented by the general formula (1) has good solubility to the oxime-based photopolymerization initiator. Represented by the above general formula (1) A compound can be used individually or in combination of 2 or more types.

The above general formula (1), C in FIG. ⁴ or R ⁵ R ² R C, or ³ shown in the ₁ ~ C ₃ alkyl group, and R ₁ ~ C ₃ alkyl group includes, for example: methyl, Ethyl, propyl, isopropyl.

R ² , R ³ , R ⁴ and R ⁵ are preferably independently methyl or ethyl.

Specific examples of the compound represented by the general formula (1) include compounds represented by the following formulae.

Among the compounds represented by the general formula (1), preferred specific examples include the compounds 1 to 4 used in the examples. The compound 1 is particularly preferably the compound represented by the following formula (E1). The compound represented by the following formula (E1) is particularly safe because it is a compound that is not designated as a highly toxic substance (SVHC) and has low toxicity.

In the radiation-sensitive composition of the present invention, the content of the solvent is preferably such that the solid content concentration of the radiation-sensitive composition becomes 1 to 50% by mass, and the solid content concentration of the radiation-sensitive composition becomes 5 to An amount of 30% by mass is preferable. In addition, in the solvent contained in the radiation-sensitive composition of the present invention, the mass ratio of the compound represented by the general formula (1) to other organic solvents is preferably 5:95 to 100: 0, and 20:80. ~ 100: 0 is better. By setting the content of the solvent and the mass ratio of the compound represented by the general formula (1) to other organic solvents to the above ranges, the sensitivity, storage stability, coatability, and stability of the obtained radiation-sensitive composition can be easily made. It has excellent developability and safety, and it is easy to form a pattern in which the generation of a foreign substance is suppressed by exposing and developing the radiation-sensitive composition. The other organic solvents are described later.

<Example of radiation-sensitive composition>

The radiation-sensitive composition of the present invention may be any of a negative type and a positive type. Examples of the negative radiation-sensitive composition include: a negative radiation-sensitive composition containing the compound represented by the general formula (1) and an alkali-soluble resin; and a compound containing the compound represented by the general formula (1) and polyamide. Radiation-sensitive polyimide precursor composition of an acid, and a photosensitive component such as a photobase generator, a photoacid generator, and the like; containing a compound represented by the general formula (1), polybenzo Photosensitive polybenzoxazole precursors, and photosensitive components such as photobase generators and photoacid generators A azole precursor composition; a radiation-sensitive spin-on-glass (SOG) composition containing a compound represented by the general formula (1); and the like. Examples of the positive-type radiation-sensitive composition include a positive-type radiation-sensitive composition containing the compound represented by the general formula (1), an alkali-soluble resin, and a quinonediazide-containing compound; and containing the general formula (1). A radiation-sensitive polyfluorene imine composition comprising a compound, a polyimide resin, and a photosensitive component such as a photobase generator and a photoacid generator; the compound comprising the compound represented by the general formula (1), Chemically amplified positive radiation-sensitive compositions such as resins and photoacid generators whose solubility is increased by the action of acids. Hereinafter, the following composition among these radiation-sensitive compositions: a negative radiation-sensitive composition (hereinafter referred to as "negative radiation-sensitive radiation") containing a compound represented by the above-mentioned general formula (1) and an alkali-soluble resin will be described in detail. Sexual composition 1 "); a radiation-sensitive polyimide precursor composition containing photosensitive compounds such as the compound represented by the general formula (1), a polyamic acid, a photobase generator, and a photoacid generator (Hereinafter referred to as "negative radiation-sensitive composition 2"); containing a compound represented by the above general formula (1), polybenzo Radiation-sensitive polybenzo with photosensitive ingredients such as azole precursors, photobase generators, and photoacid generators An azole precursor composition (hereinafter referred to as "negative radiation-sensitive composition 3"); and a positive-type sensation containing the compound represented by the above-mentioned general formula (1), an alkali-soluble resin, and a quinonediazide-containing compound Radiation composition (hereinafter referred to as "positive radiation-sensitive composition 1").

<Negative radiation-sensitive composition 1>

The negative radiation-sensitive composition 1 contains the compound represented by the general formula (1) and an alkali-soluble resin, and more specifically contains the compound represented by the general formula (1), an alkali-soluble resin, and a photopolymerizable monomer. And photopolymerization initiator.

[Compound represented by Formula (1)]

The compound represented by the general formula (1) can be used in a radiation-sensitive composition. Compounds exemplified in the general description. The compound represented by the general formula (1) can be used alone or in combination of two or more kinds.

[Alkali soluble resin]

The so-called alkali-soluble resin refers to a resin which is formed by a resin solution (solvent: propylene glycol monomethyl ether acetate) with a resin concentration of 20% by mass to form a resin film with a thickness of 1 μm on a substrate, and the concentration is 0.05. When immersed in a mass% KOH aqueous solution for 1 minute, the film thickness was dissolved by 0.01 μm or more.

The alkali-soluble resin is not particularly limited as long as it is a resin that exhibits the above-mentioned alkali-solubility, and a conventional alkali-soluble resin can be used. The alkali-soluble resin can be used alone or in combination of two or more.

An example of a preferable alkali-soluble resin is (A1) a resin having a cardo structure. (A1) The resin having a carbazole structure is not particularly limited, and a conventional resin can be used. Among them, a resin represented by the following formula (a-1) is preferred.

In the formula (a-1), X ^a represents ^{a group} represented by the following formula (a-2).

In the above formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^a2 each independently represents a hydrogen atom or a methyl group, and W ^a represents a single bond or the following A group represented by formula (a-3).

In the above formula (a-1), Y ^a represents ^a residue remaining after the acid anhydride group (-CO-O-CO-) is removed from the dicarboxylic anhydride. Examples of the dicarboxylic anhydride include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylmethylenetetrahydro Phthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.

In the formula (a-1), Z ^a represents ^a residue remaining after removing two acid anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.

In the formula (a-1), m represents an integer of 0 to 20.

(A1) The mass average molecular weight of the resin having a cardo structure is preferably 1,000 to 40,000, and more preferably 2,000 to 30,000. By setting the mass average molecular weight to the above range, it is possible to obtain good developability while obtaining sufficient heat resistance and film strength. In this specification, the term “mass average molecular weight” refers to a value measured in terms of polystyrene by gel permeation chromatography (GPC).

In addition, other examples of preferred alkali-soluble resins include (A2) epoxy resins. (A2) The epoxy resin is not particularly limited, and a conventional epoxy resin can be used, and it may be an epoxy resin having no ethylenically unsaturated group or an epoxy resin having an ethylenically unsaturated group.

As the epoxy resin having no ethylenically unsaturated group, for example, a resin (A2-1) obtained by copolymerizing at least an unsaturated carboxylic acid and an unsaturated compound containing an epoxy group can be used.

Examples of unsaturated carboxylic acids include: monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; these dicarboxylic acids Anhydride. Among these, (meth) acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, and availability. These unsaturated carboxylic acids can be used individually or in combination of 2 or more types.

In addition, in this specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid.

The proportion of the structural unit derived from the unsaturated carboxylic acid (that is, the structural unit having a carboxyl group) in the resin (A2-1) is preferably 5 to 29% by mass, and more preferably 10 to 25% by mass. By setting the ratio to the above range, it is possible to obtain a developability of a moderate negative radiation-sensitive composition 1.

The epoxy-containing unsaturated compound may be an epoxy-containing unsaturated compound having no alicyclic epoxy group, or an epoxy-containing unsaturated compound having an alicyclic epoxy group, so as to have an aliphatic Cyclic epoxy-based unsaturated compounds are preferred.

Epoxy-containing unsaturated compounds without alicyclic epoxy groups, Examples include: glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, (meth) acrylic acid, 7-epoxyheptyl, 3,4-epoxycyclohexyl (meth) acrylate, and other epoxy alkyl (meth) acrylates; propylene oxide α-ethyl acrylate, α-n-propyl Α-alkylacrylic epoxy alkyl esters such as propylene acrylate, α-n-butyl propylene acrylate, α-ethylhexyl 6,7-epoxyheptyl; o-vinylbenzyl ring Glycidyl ethers such as oxypropyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. From the viewpoints of copolymerization reactivity, strength of the resin after curing, etc., among these, (meth) acrylic acid propylene oxide, (meth) acrylic acid 2-methyl propylene oxide, and (meth) acrylic acid 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred.

The alicyclic group of the epoxy-containing unsaturated compound having an alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. In addition, examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

Specific examples of the alicyclic group of the epoxy-containing unsaturated compound having an alicyclic epoxy group include compounds represented by the following formulae (a4-1) to (a4-16). In order to obtain a moderate developability of the negative radiation-sensitive composition 1, among these, compounds represented by the following formulae (a4-1) to (a4-6) are preferred, and the following formulae (a4-1) to The compound represented by (a4-4) is preferred.

In the above formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a3 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. R ^{a4 is} preferably a linear or branched alkylene group, for example: methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentamethylene, hexamethylene . R ^{a5 is} preferably, for example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexyl, -CH ₂ -Ph-CH _2- (Ph stands for phenylene).

These unsaturated compounds containing an epoxy group can be used individually or in combination of 2 or more types.

Derived from the constituent units of unsaturated compounds containing epoxy groups (i.e. The proportion of the structural unit having an epoxy group) in the resin (A2-1) is preferably 5 to 90% by mass, and more preferably 15 to 75% by mass. By setting the ratio to the above range, it is easy to form a pattern with a good shape.

The resin (A2-1) is preferably one obtained by copolymerizing an alicyclic group-containing unsaturated compound.

The alicyclic group of the alicyclic group-containing unsaturated compound may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. In addition, examples of the polycyclic alicyclic group include adamantyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl.

Specific examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulae (a5-1) to (a5-8). In order to obtain a moderate developability of the negative radiation-sensitive composition 1, among these, compounds represented by the following formulae (a5-3) to (a5-8) are preferred, and the following formulae (a5-3), The compound represented by (a5-4) is preferred.

In the above formula, R ^a6 represents a hydrogen atom or a methyl group, R ^a7 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a8 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^{a7 is} preferably a single bond, linear or branched alkylene, for example: methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentamethylene, hexamethylene Methylene. R ^{a8 is} preferably, for example, methyl or ethyl.

The proportion of the constituent units derived from the alicyclic group-containing unsaturated compound in the resin (A2-1) is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass.

The resin (A2-1) may be one obtained by copolymerizing another compound other than the above. Examples of such other compounds include: (meth) acrylates, (meth) acrylamides, allyl compounds, Vinyl ethers, vinyl esters, styrenes, etc. These compounds can be used alone or in combination of two or more.

Examples of (meth) acrylic acid esters are: (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and tertiary (meth) acrylate Linear or branched alkyl (meth) acrylates such as octyl ester; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxyethyl ester, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate, and the like.

Examples of (meth) acrylamide are (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dioxane (Meth) acrylamide, N, N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (Meth) acrylamide and the like.

Examples of allyl compounds include: allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, ethyl醯 Allyl acetate and allyl lactate; allyloxyethanol and so on.

Examples of vinyl ethers include: hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl 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, Alkyl vinyl ethers such as dimethylamino ethyl vinyl ether, diethylamino ethyl vinyl ether, butylamino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; Vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl Vinyl aryl ethers such as ethers and vinyl anthryl ethers.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, trimethyl vinyl acetate, vinyl hexanoate, vinyl chloroacetate, Vinyl chloroacetate, vinyl methoxyacetate, vinyl butoxylate, phenyl vinyl acetate, ethyl acetate, vinyl lactate, β-phenyl butyrate, vinyl benzoate, willow Acid vinyl ester, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthalate and the like.

Examples of styrenes include: styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexyl Alkanes such as styrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, and ethoxymethylstyrene Styrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3 -Halostyrene such as trifluoromethylstyrene.

The mass average molecular weight of the resin (A2-1) is preferably 2,000 to 50,000, and more preferably 5,000 to 30,000. By setting the mass average molecular weight to the above range, there is a tendency that a balance between the film-forming ability and the developability of the negative-type radiation-sensitive composition 1 can be easily obtained.

On the other hand, as the epoxy resin having an ethylenically unsaturated group, for example, resin (A2-2) can be used, which is at least an unsaturated carboxylic acid and an epoxy group-containing resin. After the unsaturated compound is polymerized to obtain a resin, a carboxyl group of the resin is reacted with an epoxy group-containing unsaturated compound to obtain a resin; or a resin (A2-3), which is at least an unsaturated carboxylic acid and After the epoxy-containing unsaturated compound is polymerized to obtain a resin, the epoxy group of the resin is reacted with a carboxyl group of an unsaturated carboxylic acid to obtain a resin.

Examples of the unsaturated carboxylic acid and the epoxy-containing unsaturated compound include the compounds exemplified for the resin (A2-1). Therefore, the resin obtained by polymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound can be exemplified by the above-mentioned resin (A2-1).

The proportion of the constituent units derived from the unsaturated carboxylic acid (the constituent unit having a carboxyl group) in the resins (A2-2) and (A2-3) is preferably 5 to 60% by mass, and 10 to 40% by mass. % Is better. By setting the ratio to the above range, it is possible to obtain a developability of a moderate negative radiation-sensitive composition 1.

In addition, the proportion of the structural unit (a structural unit having an epoxy group) derived from an unsaturated compound containing an epoxy group in the resins (A2-2) and (A2-3) is 5 to 90% by mass. Preferably, 15 to 75% by mass is preferred. By setting the ratio to the above range, it is easy to form a pattern with a good shape.

The mass average molecular weight of the resins (A2-2) and (A2-3) is preferably 2,000 to 50,000, and more preferably 5,000 to 30,000. By setting the mass average molecular weight to the above range, there is a tendency that a balance between the film-forming ability and the developability of the negative-type radiation-sensitive composition 1 can be easily obtained.

In addition to the above, (A2) epoxy resin can also use epoxy (meth) acrylate resin, etc. This epoxy (meth) acrylate resin is made by epoxy group of epoxy resin and (meth) acrylic acid Obtained from the reaction, the epoxy resin is: bisphenol A Type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol novolac type epoxy resin, triphenol methane type epoxy resin, multicomponent Poly (glycidyl carboxylic acid), poly (glycidyl) polyhydric alcohol, amine epoxy resin, dihydroxybenzene epoxy resin, etc.

The content of the alkali-soluble resin relative to the solid content of the negative radiation-sensitive composition 1 is preferably 5 to 90% by mass, and more preferably 10 to 85% by mass. By setting the content of the alkali-soluble resin to the above-mentioned range, there is a tendency that a balance between the film-forming ability and the developability of the negative radiation-sensitive composition 1 can be easily obtained.

[Photopolymerizable monomer]

The photopolymerizable monomer is not particularly limited, and conventionally known monofunctional monomers and polyfunctional monomers can be used. The photopolymerizable monomer can be used alone or in combination of two or more.

Examples of the monofunctional monomer include: (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (meth) acryl Ammonium amine, 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-acrylamide 2-methylpropanesulfonic acid, tertiary butyl acrylamidosulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl ester, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (formyl) Base) 2-phenoxy-2-hydroxypropyl acrylate, 2- (meth) acryloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, (meth) acrylic acid Tetrahydrofurfuryl ester, (A (Meth) acrylate, dimethylamine acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate Esters, semi- (meth) acrylates of phthalic acid derivatives, etc. These monofunctional monomers can be used alone or in combination of two or more.

On the other hand, the polyfunctional monomer may be, for example, 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, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (methyl) ) Acrylate, trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 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) acryloxyethoxyphenylethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, (meth) acrylic acid 2-hydroxy-3- (meth) acrylic acid oxypropyl ester, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl Ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane ) (Meth) acrylate (i.e. toluene diisocyanate), reactant of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis Polyfunctional monomers such as (meth) acrylamide, (meth) acrylamide methylene ether, polycondensates of polyhydric alcohols and N-methylol (meth) acrylamide, or triacrylamide Hexahydrotris (triacrylformal) and so on. These polyfunctional monomers can be used alone or in combination of two or more.

The content of the photopolymerizable monomer relative to the solid content of the negative radiation-sensitive composition 1 is preferably 1 to 45% by mass, and more preferably 5 to 40% by mass. By setting the content of the photopolymerizable monomer to the above range, it tends to be easy to achieve a balance between sensitivity, developability, and resolution.

[Photopolymerization initiator]

The photopolymerization initiator is not particularly limited, and a conventional photopolymerization initiator can be used. The photopolymerization initiator can be used alone or in combination of two or more kinds.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethyl (Oxy) 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, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzene Formamidinediphenylphosphine oxide, 4-benzamido-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-di Ethyl methylaminobenzoate, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzene Methyl β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime (1-phenyl- 1,2-propanedione-2- (o-ethoxycarbonyl) oxime), methyl o-benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone , 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methyl Ghithione, 2 -Isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzamidine Peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzo 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- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone , 2-chlorobenzophenone, 4,4'-bis (dimethylamino) benzophenone (also known as Michler's ketone), 4,4'-bis (diethylamino) di Benzophenone (i.e. ethyl Michler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzil, 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-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tertiary-butylacetophenone, p-dimethylaminoacetophenone, p-tertiary Butyl trichloroacetophenone, p-tertiary butyl Dichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone ( dibenzosuberone), 4-dimethylaminoamyl benzoate, 9-phenylacridine, 1,7-bis (9-acridyl) heptane, 1,5-bis (9-acryl) Pyridyl) pentane, 1,3-bis (9-acridyl) propane, p-methoxytri , 2,4,6-ginseng (trichloromethyl) -s-tri , 2-methyl-4,6-bis (trichloromethyl) -s-tri , 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (4-Diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-tri , 2,4-bis (trichloromethyl) -6- (3-bromo-4-methoxy) phenyl-s-tri , 2,4-bis (trichloromethyl) -6- (2-bromo-4-methoxy) phenyl-s-tri , 2,4-bis (trichloromethyl) -6- (3-bromo-4-methoxy) styrylphenyl-s-tri , 2,4-bis (trichloromethyl) -6- (2-bromo-4-methoxy) styrylphenyl-s-tri ; "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade name, made by BASF); "NCI-831" (trade name, made by ADEKA), etc. These photopolymerization initiators can be used alone or in combination of two or more.

From the viewpoint of sensitivity, it is particularly preferable to use an oxime-based photopolymerization initiator among these.

Preferred examples of the oxime-based photopolymerization initiator include a photopolymerization initiator represented by the following formula (c-1).

In the formula (c-1), R ^c1 represents a heterocyclic group which may have a substituent, a fused ring aromatic group, or an aromatic group. Rc2 to Rc4 each independently represent a monovalent organic group.

The heterocyclic group in R ^c1 may be, for example, a heterocyclic group of 5 or more members, preferably a heterocyclic group of 5 or 6 members. The heterocyclic group contains a nitrogen atom, a sulfur atom, and an oxygen atom. At least 1 atom. Examples of heterocyclic groups include: nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl, and pyrazolyl; pyridyl, pyridyl (Pyrazinyl), pyrimidinyl, 6-membered cyclic groups such as pyridazinyl; nitrogen-containing sulfur-containing groups such as thiazolyl and isothiazolyl; Oxazolyl, iso Nitrogen and oxygen-containing groups such as oxazolyl; sulfur-containing groups such as thienyl and thiopyranyl; oxygen-containing groups such as furyl and piperanyl. Among these, it is preferable to contain one nitrogen atom or sulfur atom. This heterocyclic ring may contain a fused ring. Examples of the heterocyclic group containing a fused ring include benzothienyl and the like.

Examples of the fused ring aromatic group in R ^c1 include naphthyl, anthracenyl, and phenanthryl. Examples of the aromatic group in R ^c1 include a phenyl group.

The heterocyclic group, fused ring aromatic group, or aromatic group may have a substituent. In particular, when R ^c1 is an aromatic group, it is preferable to have a substituent. Examples of such a substituent include -NO ₂ , -CN, -SO ₂ R ^c5 , -COR ^c5 , -NR ^c6 R ^c7 , -R ^c8 , -OR ^c8 , -OR ^c9 -OR ^c10, and the like.

R ^c5 each independently represents an alkyl group, which may be substituted by a halogen atom or separated by an ether bond, a thioether bond, or an ester bond. The alkyl group in R ^c5 is preferably 1 to 5 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, and isobutyl.

R ^c6 and R ^c7 each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, which may be replaced by a halogen atom. In these, the alkylene part of the alkyl group and the alkoxy group may also be ether bonded. , Thioether bond or ester bond. R ^c6 and R ^c7 may be bonded to form a ring structure. The alkyl or alkoxy group in R ^c6 and R ^c7 is preferably 1 to 5 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and methoxy groups. , Ethoxy, propoxy, etc.

Examples of the ring structure that R ^c6 and R ^c7 can be bonded to include a heterocyclic ring. This heterocyclic ring may be, for example, a heterocyclic ring having 5 or more members, preferably a heterocyclic ring having 5 to 7 members, which contains at least a nitrogen atom. This heterocyclic ring may contain a fused ring. Examples of the heterocyclic ring include a piperidine ring, a morpholine ring, and a thiomorpholine ring. Among these, a morpholine ring is preferred.

R ^c8 represents an alkyl group in which some or all of the hydrogen atoms are replaced by a halogen atom. The alkyl group in R ^c8 is preferably 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, and isobutyl.

R ^c9 and R ^c10 each independently represent an alkyl group, and these may be substituted by a halogen atom or separated by an ether bond, a thioether bond, or an ester bond. The preferred number of carbons and specific examples are the same as those of R ^c1 described above.

Among these, preferable examples of R ^c1 include, for example, pyrrolyl, pyridyl, thienyl, piperanyl, benzothienyl, naphthyl, and phenyl having a substituent.

In the formula (c-1), R ^c2 represents a monovalent organic group. This organic group is preferably a group represented by -R ^c11 , -OR ^c11 , -COR ^c11 , -SR ^c11 , -NR ^c11 R ^c12 . R ^c11 and R ^c12 each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these may be substituted with a halogen atom, an alkyl group, or a heterocyclic group. And the alkylene part of the aralkyl group can also be separated by unsaturated bonds, ether bonds, thioether bonds, and ester bonds. In addition, R ^c11 and R ^c12 may be bonded to form a ring structure together with a nitrogen atom.

The alkyl group in R ^c11 and R ^c12 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, and secondary Amyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, secondary octyl, tertiary octyl, n-nonyl, isononyl, n-decyl, isodecyl, etc. Chained or branched base. In addition, this alkyl group may have a substituent. Examples of the alkyl group having a substituent include methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, and methoxypropyl.

The alkenyl group in R ^c11 and R ^c12 is preferably an alkenyl group having 1 to 20 carbon atoms, and more preferably an alkenyl group having 1 to 5 carbon atoms. Examples of the alkenyl group include linear or branched groups such as vinyl, allyl, butenyl, ethenyl, and propenyl. In addition, this alkenyl group may have a substituent. Examples of the alkenyl group having a substituent include, for example, 2- (benzo Azole-2-yl) vinyl and the like.

The aryl group in R ^c11 and R ^c12 is preferably an aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 10 carbon atoms is more preferred. Examples of the aryl group include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl and the like.

The aralkyl group in R ^c11 and R ^c12 is preferably an aralkyl group having 7 to 20 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms is more preferred. Examples of the aralkyl group include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenethyl, and phenylvinyl.

Examples of the heterocyclic group in R ^c11 and R ^c12 include: a heterocyclic group having a 5-membered ring or more, preferably a heterocyclic group having a 5-7 member ring, and the heterocyclic group contains a nitrogen atom, a sulfur atom, and an oxygen atom At least 1 atom. The heterocyclic group may include a fused ring. Examples of the heterocyclic group include pyrrolyl, pyridyl, pyrimidinyl, furyl, thienyl, and the like.

In these R ^c11 and R ^c12 , the alkylene part of the alkyl group and the aralkyl group may be separated by unsaturated bonds, ether bonds, thioether bonds, and ester bonds.

In addition, the ring structure that R ^c11 and R ^c12 can be bonded to each other ^includes , for example, a heterocyclic ring. This heterocyclic ring may be, for example, a heterocyclic ring having 5 or more members, preferably a heterocyclic ring having 5 to 7 members, which contains at least a nitrogen atom. This heterocyclic ring may contain a fused ring. Examples of the heterocyclic ring include a piperidine ring, a morpholine ring, and a thiomorpholine ring.

Of these, R ^{c2 is most} preferably methyl, ethyl, propyl, or phenyl.

In the formula (c-1), R ^c3 represents a monovalent organic group. This organic group is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a group represented by the following formula (c-2), or a heterocyclic group which may have a substituent. Better. Examples of the substituent include the same ones as those in the case of R ^c1 described above. Examples of the aryl group having 6 to 12 carbon atoms include phenyl, naphthyl, anthracenyl, and phenanthryl.

-R ^c13 -R ^c14    (c-2)

In the formula (c-2), R ^c13 represents an alkylene group having 1 to 5 carbon atoms which can be separated by an oxygen atom. Examples of such alkylene groups include: methylene, ethylidene, n-propylidene, i-propylidene, i-butylidene, i-butylidene, i-butylidene, i-pentyl, i-pentyl, i-butyl Linear or branched groups such as pentapentyl. Of these, R ^c13 is most preferably isopropyl.

In the formula (c-2), R ^c14 represents a monovalent organic group represented by -NR ^c15 R ^c16 (R ^c15 and R ^c16 each independently represent a monovalent organic group). From the viewpoint of improving the solubility of the photopolymerization initiator, it is preferable that the structure of R ^c14 in such an organic group is a structure represented by the following formula (c-3).

In the formula (c-3), R ^c17 and R ^c18 each independently represent an alkyl group having 1 to 5 carbon atoms. Examples of such an alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, secondary Amyl, tertiary amyl and so on. Of these, R ^c17 and R ^{c18 are most} preferably methyl.

The heterocyclic group in R ^c3 may be, for example, a heterocyclic group of 5 or more members, preferably a heterocyclic group of 5 or 6 members. The heterocyclic group contains a nitrogen atom, a sulfur atom, and an oxygen atom. At least 1 atom. Examples of heterocyclic groups include: nitrogen-containing 5-membered ring groups such as pyrrolyl, imidazolyl, and pyrazolyl; pyridyl, pyridyl Base, pyrimidinyl, Nitrogen-containing 6-membered cyclic groups such as radicals; nitrogen-containing sulfur-containing groups such as thiazolyl and isothiazolyl; Oxazolyl, iso Nitrogen and oxygen-containing groups such as oxazolyl; sulfur-containing groups such as thienyl and thioranyl; oxygen-containing groups such as furanyl and piperanyl. Among these, it is preferable to contain one nitrogen atom or sulfur atom. This heterocyclic ring may contain a fused ring. Examples of the heterocyclic group containing a fused ring include benzothienyl and the like.

The heterocyclic group may have a substituent. Examples of the substituent include the same ones as those in the case of R ^c1 described above.

In the formula (c-1), R ^c4 represents a monovalent organic group. Among them, an alkyl group having 1 to 5 carbon atoms is preferred. Examples of such an alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, secondary Amyl, tertiary amyl and so on. Of these, R ^{c4 is most} preferably methyl.

In addition, as another preferable example of the oxime-based photopolymerization initiator, for example, a photopolymerization initiator represented by the following formula (c-4) proposed in Japanese Patent Application Laid-Open No. 2010-15025.

In the formula (c-4), R ^c21 and R ^c22 each independently represent R ^c31 , OR ^c31 , COR ^c31 , SR ^c31 , CONR ^c32 R ^c33 , or CN.

R ^c31 , R ^c32 and R ^c33 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an alkyl group having 2 to 20 carbon atoms Heterocyclyl. The hydrogen atoms of alkyl, aryl, aralkyl and heterocyclic groups may be further substituted by OR ^c41 , COR ^c41 , SR ^c41 , NR ^c42 R ^c43 , CONR ^c42 R ^c43 , -NR ^c42 -OR ^c43 , -NCOR ^c42 -OCOR ^c43 , -C (= N-OR ^c41 ) -R ^c42 , -C (= N-OCOR ^c41 ) -R ^c42 , CN, halogen atom, -CR ^c41 = CR ^c42 R ^c43 , -CO -CR ^c41 = CR ^c42 R ^c43 , a carboxyl group, or an epoxy group. R ^c41 , R ^c42, and R ^c43 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an alkyl group having 2 to 20 carbon atoms Heterocyclyl.

R ^m31 , R ^c32 , R ^c33 , R ^c41 , R ^c42, and R ^c43 . The methylene group of the alkylene part of the substituent may be unsaturated, ether, thioether, ester, or thioester. The amine bond or amine ester bond is separated 1 to 5 times. The alkyl portion of the substituent may have a branch or a cyclic alkyl group. The alkyl terminal of the substituent may be an unsaturated bond. R ^c32 and R ^c33 and R ^c42 and R ^c43 may be bonded to form a ring structure, respectively.

In the above formula (c-4), R ^c23 and R ^c24 each independently represent R ^c31 , OR ^c31 , COR ^c31 , SR ^c31 , CONR ^c32 R ^c33 , NR ^c31 COR ^c32 , OCOR ^c31 , COOR ^c31 , SCOR ^c31 , OCSR ^c31 , COSR ^c31 , CSOR ^c31 , CN, a halogen atom, or a hydroxyl group. a and b each independently represent an integer of 0 to 4.

R ^c23 may be bonded to one carbon atom of an adjacent benzene ring via -X ^{c 2} -to form a ring structure, and R ^c23 and R ^c24 may be bonded to form a ring structure.

In the formula (c-4), X ^c1 represents a single bond or CO.

In the formula (c-4), X ^c2 represents an oxygen atom, a sulfur atom, a selenium atom, CR ^c51 R ^c52 , CO, NR ^c53 , or PR ^c54 . R ^c51 , R ^c52 , R ^c53, and R ^c54 each independently represent R ^c31 , OR ^c31 , COR ^c31 , SR ^c31 , CONR ^c32 R ^c33 , or CN. R ^c51 , R ^c53, and R ^c54 may independently form a ring structure together with any adjacent benzene ring.

In the formula (c-4), the alkyl group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42, and R ^c43 may be, for example, methyl, ethyl, n-propyl, isopropyl, or n- Butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, secondary pentyl, tertiary pentyl and the like.

In the formula (c-4), the aryl groups in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42, and R ^c43 include, for example, phenyl, tolyl, xylyl, ethylphenyl, and chloro Phenyl, naphthyl, anthracenyl, phenanthryl and the like.

In the formula (c-4), the aralkyl groups in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42, and R ^c43 include, for example, benzyl, chlorobenzyl, and α-methylbenzene. Methyl, α, α-dimethylbenzyl, phenethyl, phenylvinyl and the like.

In the above formula (c-4), the heterocyclic groups in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42, and R ^c43 are preferably, for example, pyridyl, pyrimidinyl, furyl, thienyl, Tetrahydrofuranyl, dioxolanyl, benzo Azol-2-yl, tetrahydropiperanyl, pyrrolidinyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, Oxazolyl, iso Oxazidinyl, piperidinyl, piperidine 5 to 7-membered ring groups such as methyl, morpholinyl and the like.

In the above formula (c-4), R ^c32 and R ^c33 can be bonded to form a ring, R ^c42 and R ^c43 can be bonded to form a ring, and R ^c23 can be formed together with an adjacent benzene ring. Examples of the ring include a 5- to 7-membered ring such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring.

Furthermore, when X ^c2 is NR ^c53 and R ^{c23 is} bonded to one carbon atom of an adjacent benzene ring to form a 5-membered ring structure with X ^b2 , the photopolymerization initiator will have a carbazole skeleton.

In the above formula (c-4), it may be used to replace the halogen atoms of R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 , and the halogen atoms of R ^c24 and R ^c25 . For example: a fluorine atom , Chlorine atom, bromine atom, iodine atom.

The methylene group in the alkylene part of the substituent may be separated by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, a amide bond, or an amine ester bond 1 to 5 times. At this time, the bonding base used for separation may be one or more bases. When the base can be used for continuous separation, two or more bases may be continuously separated. The alkyl portion of the substituent may have a branched chain or a cyclic alkyl group, and the alkyl terminal of the substituent may be an unsaturated bond.

Moreover, as another more preferable example of an oxime-type photoinitiator, the oxime ester compound represented by following formula (2) is mentioned, for example.

(In the formula, R ^d1 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen atom, a nitro group, and a cyano group, i is an integer of 0 to 4, j is 0 or 1, and R is ^d2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent, and R ^d3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

In the formula (2), when R ^d1 is a monovalent organic group, R ^{d1 is} not particularly limited as long as it is within a range that does not hinder the object of the present invention, and can be appropriately selected from various organic groups. When R ^d1 is an organic group, preferred examples include alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic fluorenyl, alkoxycarbonyl, saturated aliphatic fluorenyl, and may have Substituent phenyl, phenoxy which may have a substituent, benzamidine which may have a substituent, phenoxycarbonyl which may have a substituent, benzamyloxy which may have a substituent, Phenylalkyl, naphthyl that may have a substituent, naphthyloxy that may have a substituent, naphthylmethyl that may have a substituent, naphthyloxycarbonyl that may have a substituent, naphthylmethyloxy that may have a substituent Group, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group substituted with one or two organic groups, morpholin-1-yl, and piperidine -1-yl, etc. When i is an integer of 2 to 4, R ^d1 may be the same or different. In addition, the carbon number of the substituent does not include the carbon number of the substituent which the substituent further has.

When R ^d1 is an alkyl group, its carbon number is preferably from 1 to 20, and more preferably from 1 to 6. In addition, when R ^d1 is an alkyl group, it may be linear or branched. When R ^d1 is an alkyl group, specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, Isoamyl, secondary pentyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, secondary octyl, tertiary octyl, n-nonyl, isononyl, n-decyl , And isodecyl. In addition, when R ^d1 is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl Oxyethyl, and methoxypropyl.

When R ^d1 is an alkoxy group, its carbon number is preferably from 1 to 20, and more preferably from 1 to 6. In addition, when R ^d1 is an alkoxy group, it may be linear or branched. When R ^d1 is an alkoxy group, specific examples include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secondary butoxy, and Butyloxy, n-pentyloxy, isopentyloxy, secondary pentyloxy, tertiary pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, secondary octyloxy Group, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. In addition, when R ^d1 is an alkoxy group, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include, for example, methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy , Propoxyethoxyethoxy, and methoxypropoxy.

When R ^d1 is a cycloalkyl group or a cycloalkoxy group, its carbon number is preferably from 3 to 10, and more preferably from 3 to 6. When R ^d1 is a cycloalkyl group, specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. When R ^d1 is a cycloalkoxy group, specific examples include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

When R ^d1 is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyl group, its carbon number is preferably 2-20, and more preferably 2-7. When R ^d1 is a saturated aliphatic fluorenyl group, specific examples may include: ethyl fluorenyl, propionyl, n-butylfluorenyl, 2-methylpropylfluorenyl, n-pentylfluorenyl, and 2,2-dimethylpropanyl N-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecanyl N-pentadecanyl, and n-hexadecylfluorenyl. When R ^d1 is a saturated aliphatic fluorenyloxy group, specific examples include ethoxyl, propionyloxy, n-butyridyloxy, 2-methylpropionyloxy, n-pentyloxy, 2 , 2-dimethylpropoxyl, n-hexamethyleneoxy, n-heptylfluorenyloxy, n-octylfluorenyloxy, n-nonylfluorenyloxy, n-decylfluorenyloxy, n-undecylfluorenyloxy, n-decyl Dialkylfluorenyloxy, n-tridecylfluorenyloxy, n-tetradecanylfluorenyloxy, n-pentadecanylfluorenyloxy, and n-hexadecylfluorenyloxy.

When R ^d1 is an alkoxycarbonyl group, its carbon number is preferably 2-20, and more preferably 2-7. When R ^d1 is an alkoxycarbonyl group, specific examples may include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, secondary butoxycarbonyl, and Primary butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, secondary pentyloxycarbonyl, tertiary pentyloxycarbonyl, n-hexanoylcarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, secondary octyloxy Carbonyl, tertiary octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.

When R ^d1 is a phenylalkyl group, its carbon number is preferably 7-20, and more preferably 7-10. In addition, when R ^d1 is a naphthylalkyl group, its carbon number is preferably 11-20, and more preferably 11-14. When R ^d1 is a phenylalkyl group, specific examples include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. When R ^d1 is a naphthylalkyl group, specific examples include α-naphthylmethyl, β-naphthylmethyl, 2- (α-naphthyl) ethyl, and 2- (β-naphthyl) ethyl. Base etc. When R ^d1 is phenylalkyl or naphthylalkyl, R ^d1 may further have a substituent on phenyl or naphthyl.

When R ^d1 is a heterocyclic group, the heterocyclic group is: a single ring of 5 or 6 members in total of N, S, and O; or a heterocyclic ring formed by condensing such single rings Or a heterocyclic group obtained by condensing such a monocyclic ring with a benzene ring. When the heterocyclic group is a fused ring, it is a fused ring having a ring number of 3 or less. Examples of the heterocyclic ring constituting such a heterocyclic group include furan, thiophene, pyrrole, Azole, iso Azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine , Pyrimidine, da , Benzofuran, benzothiophene, indole, isoindole, indole (indolizine), benzimidazole, benzotriazole, benzo Azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthaloline (phthalazine), cinnoline, and quinoline Quinoxaline and the like. When R ^d1 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^d1 is an amine group substituted with one or two organic groups, preferred examples of the organic group include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon number 2 to 20 saturated aliphatic fluorenyl groups, phenyl groups which may have substituents, benzamidine groups which may have substituents, phenylalkyl groups which may have 7 to 20 carbon atoms, and naphthalenes which may have substituents A naphthylmethyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbons which may have a substituent, a heterocyclic group, and the like. Specific examples of these preferable organic groups are the same as those of R ^d1 . Specific examples of the amino group substituted by one or two organic groups include: methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, and n-butylamino , Di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, aniline, naphthylamine, acetamidoamine, propylamidine Amine, n-Butylamino, n-pentamidine, n-hexamidine, n-heptazone, n-octylamine, n-decylamidine, benzamidine, α-naphthylamidine And β-naphthylamino group.

When the phenyl, naphthyl, and heterocyclic group contained in R ^d1 further has a substituent, the substituent may be, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 2 carbon atoms. ~ 7 saturated aliphatic fluorenyl groups, alkoxycarbonyl groups with 2 to 7 carbon atoms, saturated aliphatic fluorenyl groups with 2 to 7 carbon atoms, monoalkylamine groups with 1 to 6 carbon alkyl groups, and carbon numbers 1 to 6 alkyl dialkylamino, morpholin-1-yl, piperidine -1-yl, halogen atom, nitro, and cyano. When the phenyl, naphthyl, and heterocyclic group contained in R ^d1 further has a substituent, the number of the substituent is not limited as long as it does not hinder the object of the present invention, and preferably 1 to 4 . When the phenyl, naphthyl, and heterocyclic group contained in R ^d1 has a plurality of substituents, the plurality of substituents may be the same or different.

In terms of chemical stability, low steric hindrance, easy synthesis of oxime ester compounds, and high solubility in solvents, R ^d1 includes nitro groups, alkyl groups having 1 to 6 carbon atoms, and carbon atoms having 1 to 6 carbon atoms. A group selected from the group consisting of an alkoxy group and a saturated aliphatic fluorene group having 2 to 7 carbon atoms is preferred. A nitro group or an alkyl group having 1 to 6 carbon atoms is preferred, and a nitro group or methyl group is particularly preferred. .

When R ^d1 are bonded to the phenyl group position of the bond between the phenyl and the main skeleton of the oxime ester compound to a junction of the bond, the position is set to 2 methyl groups, R ^d1 and phenyl bonded The position is preferably 4 or 5 digits, and more preferably 5 digits. In addition, i is preferably an integer of 0 to 3, preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ^d2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. When R ^d2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^d2 , the substituent of the phenyl group or the carbazolyl group is not particularly limited as long as it is within a range that does not hinder the object of the present invention. Examples of preferred substituents which may be present on the carbon atom of phenyl or carbazolyl include, for example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 3 to 10 carbon atoms. Cycloalkyl, cycloalkoxy having 3 to 10 carbons, saturated aliphatic fluorenyl having 2 to 20 carbons, alkoxycarbonyl having 2 to 20 carbons, saturated aliphatic fluorenyl having 2 to 20 carbons, 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 benzamidine group which may have a substituent, a phenoxycarbonyl group which may have a substituent, Benzamyloxy, phenylalkyl having 7 to 20 carbon atoms which may have a substituent, naphthyl optionally having a substituent, naphthyloxy having a substituent, naphthylmethyl which may have a substituent, may be Naphthyloxycarbonyl group having a substituent, naphthylmethyloxy group which may have a substituent, naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, heterocyclic group which may have a substituent, hetero Cyclic carbonyl, amine, amine substituted with 1 or 2 organic groups, morpholin-1-yl, piperidine -1-yl, halogen atom, nitro, and cyano.

When R ^d2 is a carbazolyl group, examples of preferred substituents which may be present on the nitrogen atom of the carbazolyl group include, for example, 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, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzamidine group which may have a substituent, a phenoxycarbonyl group which may have a substituent, may A phenylalkyl group having 7 to 20 carbon atoms of a substituent, 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 11 which may have a substituent A naphthylalkyl group of ~ 20, 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 preferable, an alkyl group having 1 to 6 carbon atoms is preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the phenyl or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic fluorenyloxy group, and a benzene which may have a substituent. An alkyl group, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and an amine group substituted with one or two organic groups are the same as those of R ^d1 .

In R ^d2 , when a phenyl group, a naphthyl group, and a heterocyclic group included in a substituent group having a phenyl group or a carbazolyl group further have a substituent group, examples of the substituent group include, for example, an alkyl group having 1 to 6 carbon atoms. Alkoxy groups having 1 to 6 carbon atoms; saturated aliphatic fluorenyl groups having 2 to 7 carbon atoms; alkoxycarbonyl groups having 2 to 7 carbon atoms; saturated aliphatic fluorenyl groups having 2 to 7 carbon atoms; phenyl group; Naphthyl; benzamyl; naphthyl; naphthyl; 1 to 6 carbon alkyl, morpholin-1-yl, piperidine A benzamidine group substituted with a selected group from the group consisting of a -1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; and an alkyl group having 1 to 6 carbon atoms Alkylamino; morpholin-1-yl; piperidine -1-yl; halogen atom; nitro; cyano. When a phenyl group, a naphthyl group, and a heterocyclic group included in a substituent group included in a phenyl group or a carbazolyl group further have a substituent group, the number of the substituent groups is within a range that does not hinder the object of the present invention. There is no limitation, preferably 1 to 4. When a phenyl group, a naphthyl group and a heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

From the viewpoint of excellent sensitivity of the negative radiation-sensitive composition 1, R ^d2 is preferably a group represented by the following formula (3) or (4), and more preferably a group represented by the following formula (3) A group represented by the following formula (3) and A is S is particularly preferred.

(In the formula, R ^d4 represents a group selected from the group consisting of a monovalent organic group, an amine group, a halogen atom, a nitro group, and a cyano group, A is S or O, and k is an integer of 0 to 4).

(In the formula, R ^d5 and R ^d6 are monovalent organic groups, and may be the same or different.)

When R ^d4 in the formula (3) is an organic group, it can be selected from various organic groups as long as it is within a range that does not hinder the object of the present invention. When R ^d4 in the formula (3) is an organic group, preferred examples include: an alkyl group having 1 to 6 carbons; an alkoxy group having 1 to 6 carbons; a saturated aliphatic fluorenyl group having 2 to 7 carbons ; Alkoxycarbonyl groups with 2 to 7 carbons; Saturated aliphatic fluorenyl groups with 2 to 7 carbons; phenyl; naphthyl; benzamidine; naphthylmethyl; Base, morpholin-1-yl, piperazine A benzamidine group substituted with a selected group from the group consisting of a -1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; and an alkyl group having 1 to 6 carbon atoms Alkylamino; morpholin-1-yl; piperidine -1-yl; halogen atom; nitro; cyano.

^Among R ^d4 , preferred are: benzamidine; naphthylmethyl; alkyl from 1 to 6 carbon atoms, morpholin-1-yl, piperidine Benzamidine substituted by a selected group from the group consisting of -1-yl and phenyl; nitro, more preferably: benzamidine, naphthylmethyl, 2-methylphenylcarbonyl, 4- (Pipe 1-yl) phenylcarbonyl, 4- (phenyl) phenylcarbonyl.

In the above formula (3), k is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When k is 1, the bonding position of R ^d4, is preferred with respect to the bonded phenyl and R ^d4 atoms bonded to the A key for the bonding position.

R ^d5 in the above formula (4) can be selected from various organic groups as long as it does not inhibit the object of the present invention. Preferred examples of R ^d5 include, for example, 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 alkoxycarbonyl group having 2 to 20 carbon atoms. , A phenyl group which may have a substituent, a benzamidine group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms, and a naphthalene which may have a substituent A naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a substituent which may have a substituent Heterocyclic carbonyl and the like.

R ^d5 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group.

R ^d6 in the formula (4) can be selected from various organic groups as long as it is within a range that does not hinder the object of the present invention. Specific examples of a preferable group of R ^d6 include, for example, 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 ^d6 , among these groups, a phenyl group which may have a substituent is preferred, and a 2-methylphenyl group is particularly preferred.

When the phenyl, naphthyl, and heterocyclic group contained in R ^d4 , R ^d5, or R ^d6 further has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbons, and an alkyl group having 1 to 6 carbons Oxygen, saturated aliphatic fluorenyl group with 2 to 7 carbons, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic fluorenyl group with 2 to 7 carbon atoms, monoalkane having an alkyl group with 1 to 6 carbon atoms Amine groups, dialkylamino groups having 1 to 6 carbon atoms, morpholin-1-yl, piperidine -1-yl, halogen atom, nitro, and cyano. When the phenyl, naphthyl, and heterocyclic group contained in R ^d4 , R ^d5, or R ^d6 further has a substituent, the number of the substituent is not limited as long as it does not hinder the object of the present invention, 1 ~ 4 is preferred. When the phenyl, naphthyl, and heterocyclic group contained in R ^d4 , R ^d5, or R ^d6 has a plurality of substituents, the plurality of substituents may be the same or different.

R ^d3 in formula (2) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^d3 is preferably methyl or ethyl, and more preferably methyl. When R ^d3 is a methyl group, the sensitivity of the photopolymerization initiator composed of the compound represented by the formula (2) is particularly excellent.

When j is 0, the oxime ester compound represented by the formula (2) can be synthesized according to the following scheme 1, for example. Specifically, a halogenated carbonyl compound represented by the following formula (d1-2) can be used to perform a fluorenyl group on an aromatic compound represented by the following formula (d1-1) by a Friedel-Crafts reaction. To obtain a ketone compound represented by the following formula (d1-3), and oxidize the obtained ketone compound (d1-3) with a hydroxylamine to obtain the following formula (d1-4) Then, the oxime compound of formula (d1-4) and the acid anhydride ((R ^d3 CO) ₂ O) represented by the following formula (d1-5) or the following formula (d1-6) The sulfonium halide (R ^d3 COHal, Hal is a halogen atom) is reacted to obtain an oxime ester compound represented by the following formula (d1-7). In the following formula (d1-2), Hal is a halogen atom, and the following formulas (d1-1), (d1-2), (d1-3), (d1-4), and (d1-7) Here, R ^d1 , R ^d2 , R ^d3 and i are the same as those described in the formula (2).

When j is 1, the oxime ester compound represented by formula (2) can be synthesized according to the following scheme 2, for example. Specifically, in the presence of hydrochloric acid, a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (d2-2) and the following formula (d2-1) can be used. The ketone oxime compound represented by the following formula (d2-3) is reacted to obtain a ketoxime compound represented by the following formula (d2-3). The acid anhydride ((R ^d3 CO) ₂ O) shown, or the halogen halide (R ^d3 COHal, Hal being a halogen atom) represented by the following formula (d2-5) is reacted to obtain the following formula (d2-6) The oxime ester compound shown. Furthermore, in the following formulae (d2-1), (d2-3), (d2-4), (d2-5), and (d2-6), R ^d1 , R ^d2 , R ^d3, and i, and The same applies to the expression (2).

<Process 2>

In addition, when the oxime ester compound represented by the formula (2) is when j is 1, R ^d1 is a methyl group, and R ^d1 is bonded to a para position with respect to a methyl group bonded to a benzene ring bonded to R ^d1 It can also be synthesized by, for example, oximizing and amidating the compound represented by the following formula (d2-7) in the same manner as in Scheme 1. In the following formula (d2-7), R ^d2 is the same as that described in formula (2).

Among the oxime ester compounds represented by the formula (2), particularly preferred compounds include compounds of the following formula.

Other preferable examples of the oxime-based photopolymerization initiator include "IRGACURE OXE01" (trade name, manufactured by BASF).

The content of the photopolymerization initiator relative to the solid content of the negative radiation-sensitive composition 1 is preferably 0.3 to 20% by mass, and more preferably 0.5 to 15% by mass. By setting the content of the photopolymerization initiator to the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved to suppress hardening defects.

[Colorant]

The negative radiation-sensitive composition 1 may contain a colorant. The negative radiation-sensitive composition 1 can be preferably used for, for example, forming a color filter of a liquid crystal display by containing a colorant. In addition, the negative-type radiation-sensitive composition 1 can be suitably used, for example, for forming a black matrix of a color filter and forming a black light spacer by containing a light-shielding agent as a colorant. The colorant can be used alone or in combination of two or more.

The colorant is not particularly limited, and it is preferable to use, for example, a compound classified as a pigment in the Color Index (CI; issued by The Society of Dyers and Colourists). Specifically, it is labeled as follows Color index (CI) numbered compounds.

CIPigment Yellow 1 (hereinafter also referred to as "CIPigment Yellow", and only the number is described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61 , 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120 , 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185; CIPigment Orange 1 (hereinafter, also "CIPigment Orange "and only the number), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73 ; CIPigment Violet 1 (hereinafter also referred to as "CIPigment Violet", and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; CIPigment Red 1 (below , Which is also "CIPigment Red", and only the number is described), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21 , 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52 : 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90 : 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174 , 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226 , 227, 228, 240, 242, 24 3, 245, 254, 255, 264, 265; CIPigment Blue 1 (hereinafter also referred to as "CIPigment Blue", and only the number is recorded), 2, 15, 15: 3, 15: 4, 15: 6, 16 , 22, 60, 64, 66; CIPigment Green 7, CIPigment Green 36, CIPigment Green 37; CIPigment Brown 23, CIPigment Brown 25, CIPigment Brown 26, CIPigment Brown 28; C.I.Pigment Black 1, C.I.Pigment Black 7.

When the colorant is used as a light-shielding agent, a black pigment is preferably used as the light-shielding agent. Black pigments, whether organic or inorganic, include carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides, Various pigments such as metal sulfate and metal carbonate. Among these, it is preferable to use carbon black having a high light-shielding property.

As the carbon black, conventional carbon blacks such as groove black, furnace black, thermal carbon black, and lamp black can be used, and it is preferable to use groove black having excellent light shielding properties. Alternatively, resin-coated carbon black can be used.

Resin-coated carbon black has lower conductivity than carbon black without resin. Therefore, when it is used as a black matrix of a liquid crystal display, it is possible to produce a low-power display with low current leakage and high reliability.

In addition, in order to adjust the hue of carbon black, the above-mentioned organic pigment may be appropriately added as an auxiliary pigment.

In addition, when a pigment is used as a colorant, a pigment and a dye may be used in combination. Examples of dyes that can be used with pigments include xanthene dyes, cyanine dyes, azo dyes, anthraquinone dyes, and (dioxazine) -based dyes, triphenylmethane-based dyes, and the like.

Further, in order to uniformly disperse the colorant in the radiation-sensitive resin composition (radiation-sensitive composition), a dispersant may be further used. Such a dispersant is preferably a polymer dispersant of polyethyleneimine-based, urethane resin-based, or acrylic resin-based. In particular, when carbon black is used as the colorant, an acrylic resin-based dispersant is preferably used as the dispersant.

In addition, inorganic pigments and organic pigments can be used separately. It can be used in combination. When used in combination, it is better to use an organic pigment in the range of 10 to 80 parts by mass relative to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment, and to use the organic pigment in the range of 20 to 40 parts by mass. Better.

Relative to the solid content of the negative radiation-sensitive composition 1, the content of the colorant is preferably 5 to 90% by mass, and more preferably 10 to 80% by mass.

[Other organic solvents (organic solvents other than the compound represented by the general formula (1))]

The negative radiation-sensitive composition 1 may contain other organic solvents. Other organic solvents can be used alone or in combination of two or more. Other organic solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethyl 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 (Poly) alkanediol monoalkyl ethers such as tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, (Poly) alkanediol monoalkyl groups such as ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like Ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2 -Heptanone Ketones such as 3-heptanone; Alkyl lactates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, propane 3-methyl-3-methoxybutyl acid, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, propionic acid N-butyl ester, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl酯 Ethyl esters such as ethyl acetate and ethyl 2-ketobutyrate; aromatic hydrocarbons such as toluene and xylene.

The content of the solvent in the negative radiation-sensitive composition 1 is preferably such that the solid content concentration of the negative radiation-sensitive composition 1 becomes 1 to 50% by mass, and the solid content of the negative radiation-sensitive composition 1 The concentration is preferably 5 to 30% by mass. In addition, in the solvent contained in the negative radiation-sensitive composition 1, the mass ratio of the compound represented by the general formula (1) to other organic solvents is preferably 5:95 to 100: 0, and 20:80. ~ 100: 0 is better. By setting the content of the solvent and the mass ratio of the compound represented by the general formula (1) to other organic solvents to the above ranges, the sensitivity, storage stability, and coatability of the negative radiation-sensitive composition 1 can be easily made. It has excellent developability and safety, and it is easy to form a pattern by suppressing the generation of foreign matter by exposing and developing the negative radiation-sensitive composition 1.

[Other ingredients]

The negative radiation-sensitive composition 1 may contain various additives as required. Examples of the additives include sensitizers, hardening accelerators, fillers, adhesion promoters, antioxidants, anticoagulants, thermal polymerization inhibitors, defoamers, and surfactants.

<Negative radiation-sensitive composition 2>

The negative radiation sensitive composition 2 is a radiation sensitive polyimide precursor composition containing a compound represented by the general formula (1), a polyamic acid, and a photosensitive component.

[Compound represented by Formula (1)]

As the compound represented by the general formula (1), the compounds exemplified in the general description of the radiation-sensitive composition can be used. The compound represented by the general formula (1) can be used alone or in combination of two or more kinds.

[Polyamic acid]

In the present invention, the polyamic acid is not particularly limited as long as it is obtained by reacting a tetracarboxylic dianhydride with a diamine, and it can be used among polyamines known to date as precursors of polyimide resins. Choose appropriately. Polyamic acid can be used individually or in mixture of 2 or more types.

Preferred polyamidic acid is, for example, a polyamidic acid represented by the following formula (11).

(In the formula, R ^1A is a tetravalent organic group, R ^2A is a divalent organic group, and n is a repeating number of a structural unit shown in parentheses).

In formula (11), R ^1A is a tetravalent organic group, and R ^2A is a divalent organic group. The carbon number of these organic groups is preferably 2 to 50, and more preferably 2 to 30. R ^1A and R ^2A may each be an aliphatic group, an aromatic group, or a combination of these structures. R ^1A and R ^2A may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to a carbon atom and a hydrogen atom. When R ^1A and R ^2A contain an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, nitrogen atom, or sulfur atom may be selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N = N-, -CH = N-, -COO-, -O-, -CO-, -SO-, -SO _2- , -S-, and -SS- The form of the selected base is contained in R ^1A and R ^2A , preferably It is contained in R ^1A and R ^2A in a form selected from -O-, -CO-, -SO-, -SO _2- , -S-, and -SS-.

The polyamidoimide resin represented by the above formula (12) can be obtained by ring-closing the polyamidate represented by the above formula (11) with heat or a catalyst.

(In the formula, R ^1A and R ^2A are synonymous with those described in formula (11), and n is the number of repeating units shown in parentheses).

The polyamic acid represented by the formula (11) can be obtained by reacting a tetracarboxylic dianhydride and a diamine in a solvent. The tetracarboxylic dianhydride and diamine, which are synthetic raw materials of polyamic acid, are not particularly limited as long as they can form a polyamino acid by reacting an acid anhydride group with a diamine.

The amount of tetracarboxylic dianhydride and diamine used in synthesizing polyphosphoric acid is not particularly limited. It is better to use 0.50 to 1.50 mol of diamine relative to 1 mol of tetracarboxylic dianhydride, and to use 0.60 to 1.30. A mol of diamine is preferred, and 0.70 to 1.20 mol of diamine is particularly preferred.

The tetracarboxylic dianhydride can be appropriately selected from tetracarboxylic dianhydrides which have been used as synthetic raw materials of polyamic acid. Tetracarboxylic dianhydride, may be aromatic The tetracarboxylic dianhydride or the aliphatic tetracarboxylic dianhydride is preferably an aromatic tetracarboxylic dianhydride from the viewpoint of the heat resistance of the obtained polyimide resin. Tetracarboxylic dianhydride can be used in combination of 2 or more types.

Preferred specific examples of the aromatic tetracarboxylic dianhydride include, for example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4 '-Biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, and 3,3 ', 4 , 4'-diphenylphosphonium tetracarboxylic dianhydride and the like. Among these, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferred from the viewpoints of price and availability.

When synthesizing polyamic acid, tetracarboxylic dianhydride and dicarboxylic anhydride can be used in combination. If these carboxylic anhydrides are used in combination, the characteristics of the polyfluorene imide resin obtained may be better. Examples of the dicarboxylic anhydride include: maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylmethylenetetrahydrophthalic anhydride Dicarboxylic anhydride, chlorobridged anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, cis 4-cyclohexene-1,2-dicarboxylic anhydride, and the like.

The diamine can be appropriately selected from diamines which have been used as synthetic raw materials of polyamic acid. The diamine may be an aromatic diamine or an aliphatic diamine. From the viewpoint of the heat resistance of the obtained polyimide resin, an aromatic diamine is preferred. Diamine can be used in combination of two or more kinds.

Preferred specific examples of the aromatic diamine include, for example, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, and 4,4'- Diamino-2,2'-bis (trifluoromethyl) biphenyl, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, 4,4'- Diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis (4-aminobenzene Oxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4 '-(4-aminophenoxy ) Biphenyl, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2-bis [4- (4 -Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) fluorene , 9,9-bis (4-amino-3-methylphenyl) fluorene, and 4,4 '-[1,4-phenylenebis (1-methylethyl-1,1-diyl) ] Diphenylamine and the like. Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferred from the viewpoints of price, availability, and the like.

The reaction of tetracarboxylic dianhydride and diamine is usually carried out in an organic solvent. The organic solvent used when the tetracarboxylic dianhydride reacts with a diamine is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride and diamine and does not react with the tetracarboxylic dianhydride and diamine. The organic solvent can be used alone or in combination of two or more.

Examples of organic solvents used in the reaction of tetracarboxylic dianhydride with diamine include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diamine Ethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylcaprolactam, and N, N, N ', N'-Tetramethyl Nitrogen-containing polar solvents such as urea; β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone-based polar solvents Dimethyl sulfene; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, two Ethers such as dioxane, tetrahydrofuran, methylcellulose acetate, and ethylcellulose acetate.

From the perspective of the solubility of the resulting polyamic acid and polyimide resin, Among these organic solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide , N, N-diethylformamide, N-methylcaprolactam, and N, N, N ', N'-tetramethylurea and other nitrogen-containing polar solvents are preferred.

[Photosensitive component]

The photosensitive component is not particularly limited, and examples thereof include compounds (A) such as a photobase generator and a photoacid generator, which decompose by the action of light to generate at least one of an alkali and an acid. The photosensitive component can be used individually or in mixture of 2 or more types.

By exposing the negative-type radiation-sensitive composition 2 containing the compound (A), the compound (A) in the negative-type radiation-sensitive composition 2 is decomposed to generate at least one of an alkali and an acid. The alkali or acid produced in this way acts as a sulfonium imidization catalyst and promotes the ring closure of the polyfluorene acid in the negative radiation-sensitive composition 2.

When the negative-type radiation-sensitive composition 2 containing the compound (A) is exposed, the compound (A) is decomposed in the exposure portion to generate at least one of an alkali and an acid. The alkali or acid generated in this way can promote the ring closure of the polyamic acid in the negative radiation-sensitive composition 2 and prevent the exposed portion from being dissolved in the developing solution. On the other hand, since the unexposed portion can be dissolved in the developing solution, it can be removed by being dissolved in the developing solution. Therefore, by selectively exposing the negative-type radiation-sensitive composition 2, a desired pattern can be formed.

Examples of the compound (A) include: a compound (A-1) which is decomposed by the action of light to produce an imidazole compound; and an oxime compound (A-2). The compounds (A-1) and (A-2) will be described below.

(Compound (A-1) which is decomposed by the action of light to produce an imidazole compound)

The imidazole compound produced by the compound (A-1) acts as a basic amidine imidization catalyst and promotes the ring closure of the polyamidate in the negative radiation-sensitive composition 2. The imidazole compound produced by the compound (A-1) may be an imidazole or a compound in which a part or all of hydrogen atoms bonded to a carbon atom in the imidazole are substituted with a substituent, and the imidazole compound represented by the following formula (3) Better.

(Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silane group, a silanol group, a nitro group, a nitroso group, and a sulfonato group. , Phosphino, phosphinyl, phosphonato, or organic).

Examples of the organic group represented by R ¹ , R ² or R ³ include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain heteroatoms. The organic group may be any of linear, branched, and cyclic. This organic group is usually monovalent, but when the cyclic structure is formed, the organic group can be divalent or more.

R ¹ and R ² may be bonded to form a cyclic structure, or may include a hetero atom bond. Examples of the cyclic structure include heterocycloalkyl, heteroaryl, and the like, or fused rings.

When the organic group represented by R ¹ , R ² or R ³ contains a hetero atom, examples of the hetero atom include an oxygen atom, a nitrogen atom, and a silicon atom. Specific examples of the bond including a hetero atom include, for example, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, a amide bond, an amine ester bond, and an imine bond (-N = C (-R) -Or-C (= NR)-(where R represents a hydrogen atom or an organic group, the same applies hereinafter), a carbonic acid bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like. Among them, from the viewpoint of the heat resistance of the imidazole compound, ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amido bonds, amine ester bonds, imine bonds, carbonic acid bonds, and sulfonyl bonds The sulfinyl bond is preferred.

A hydrogen atom contained in a group other than the organic group represented by R ¹ , R ^2, or R ³ may be substituted with a hydrocarbon group. This hydrocarbon group may be any of linear, branched, and cyclic.

R ¹ , R ² and R ³ each independently preferably represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom, A hydrogen atom is preferred. R ¹ , R ^2, or R ³ are all hydrogen atoms, that is, imidazole, and since they have a simple structure with little steric hindrance, they can easily act as polyimide catalysts as polyimide.

The compound (A-1) is not particularly limited as long as it can decompose by the action of light to produce an imidazole compound, and it is preferred that the compound (A-1) can produce an imidazole compound represented by the formula (3). So far, compounds prepared in the photosensitive composition that generate amines due to the action of light are replaced with the skeleton derived from the imidazole compound by replacing the skeleton derived from the amine generated upon exposure, preferably from the above. The skeleton of the imidazole compound represented by the formula (3) can be used as a compound (A-1).

As a preferable compound (A-1), the compound represented by a following formula (4) is mentioned, for example.

(Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silane group, a silanol group, a nitro group, a nitroso group, a phosphine group, and a sulfonate group. , Phosphinyl, phosphonate, or organic groups; R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silane group, a silanol group, a nitro group, or a nitroso group , Sulfino, sulfo, sulfo, phosphono, phosphinyl, phosphono, phosphonate, or organic groups; R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silane group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphine group, and a phosphinyl group Fluorenyl, phosphonate, phosphonate, amine, ammonio, or organic groups; R ⁶ , R ⁷ , R ⁸ , R ^9, and R ¹⁰ can be bonded to form a ring Like structure, may also include heteroatom bonding).

In Formula (4), R ¹ , R ² and R ³ are the same as those described in Formula (3).

Examples of the organic group represented by R ⁴ or R ⁵ in formula (4) include those exemplified for R ¹ , R ^2, and R ³ . This organic group may contain a hetero atom similarly to the case of R ¹ , R ² and R ³ . The organic group may be any of linear, branched, and cyclic.

R ⁴ and R ^{5 are} preferably each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, Aryloxyalkyl group having 7 to 16 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkyl group having 2 to 11 carbon atoms having cyano group, alkyl group having 1 to 10 carbon atoms having hydroxyl group, and carbon number 1 Alkoxy group of 10 to 10, fluorenyl group of 2 to 11 carbon, alkylthio group of 1 to 10 carbon, fluorenyl group of 1 to 10 carbon, ester group of 2 to 11 carbon (-COOR or -OCOR (However, R represents a hydrocarbon group)), an aryl group having 6 to 20 carbon atoms, a benzyl group, a cyano group, and a methylthio group substituted with an electron-withdrawing group and / or an electron-withdrawing group. More preferably, both R ⁴ and R ⁵ are hydrogen atoms, or R ⁴ is a methyl group and R ⁵ is a hydrogen atom.

Examples of the organic group represented by R ⁶ , R ⁷ , R ⁸ , R ^9, and R ¹⁰ in formula (4) include R ¹ , R ^2, and R ³ . This organic group may contain a hetero atom similarly to the case of R ¹ and R ² . The organic group may be any of linear, branched, and cyclic.

R ⁶ , R ⁷ , R ⁸ , R ^9, and R ¹⁰ may be bonded by two or more of them to form a cyclic structure, and may also include a hetero atom bond. Examples of the cyclic structure include heterocycloalkyl, heteroaryl, and the like, and may be a fused ring. For example: R ⁶ , R ⁷ , R ⁸ , R ^9, and R ^{10 may} be bonded together, and the atoms of the benzene ring bonded by R ⁶ , R ⁷ , R ⁸ , R ^9, and R ¹⁰ may be shared. To form fused rings such as naphthalene, anthracene, phenanthrene, and indene.

R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 are} preferably each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, and 4 to 13 carbon atoms. Cycloalkenyl, aryloxyalkyl having 7 to 16 carbons, aralkyl having 7 to 20 carbons, alkyl having 2 to 11 carbons and alkane having 1 to 10 carbons Group, alkoxy group having 1 to 10 carbon atoms, fluorenyl group having 2 to 11 carbon atoms, alkylthio group having 1 to 10 carbon atoms, fluorenyl group having 1 to 10 carbon atoms, ester group having 2 to 11 carbon atoms, 6-20 carbon aryl groups, 6-20 carbon aryl groups substituted with electron-withdrawing group and / or electron-withdrawing group, benzyl, cyano, methyl Sulfur, nitro.

In addition, R ⁶ , R ⁷ , R ⁸ , R ^9, and R ¹⁰ , from the viewpoint of making the absorption wavelength a long wavelength, these two or more are bonded to form fused rings such as naphthalene, anthracene, phenanthrene, indene, and the like. The situation is also good.

Among the compounds represented by the formula (4), a compound represented by the following formula (5) is preferred.

(In the formula, R ¹ , R ² and R ³ are synonymous with those described in formulas (3) and (4); R ⁴ to R ⁹ are synonymous with those described in formula (4); R ¹¹ represents a hydrogen atom or organic R ⁶ and R ^{7 are} not hydroxyl groups; R ⁶ , R ⁷ , R ⁸ and R ⁹ may be bonded by two or more of them to form a cyclic structure, and may also include a hetero atom bond).

Since the compound represented by formula (5) has a substituent -OR ¹¹ , it has excellent solubility in an organic solvent.

In formula (5), when R ¹¹ is an organic group, examples of the organic group include those exemplified for R ¹ , R ^2, and R ³ . This organic group may contain heteroatoms. The organic group may be any of linear, branched, and cyclic. R ^{11 is} preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.

As a preferable compound (A-1), the compound represented by a following formula (6) is mentioned, for example.

(Wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silane group, a silanol group, a nitro group, a nitroso group, a phosphine group, and a sulfonate group. , Phosphinyl fluorenyl, phosphonate, or organic; R ¹² represents a hydrocarbon group which may be substituted).

In the formula (6), R ¹ , R ² and R ³ are the same as those described in the formula (3).

In formula (6), R ¹² may be, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms which may be substituted. The aralkyl group having 7 to 20 carbon atoms which can be substituted is preferably an aralkyl group having 7 to 20 carbon atoms which can be substituted. When the above aryl or aralkyl group is substituted, examples of the substituent include a halogen atom, a nitro group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

The compound represented by the formula (6) can be synthesized by the following reaction: the reaction of an imidazole compound represented by the formula (3) with a chloroformate represented by the following formula (7); The reaction of the imidazole compound with a dicarbonate represented by the following formula (8); or the reaction of a carbonyl diimidazole compound represented by the following formula (9) with an alcohol represented by the following formula (10).

(In formulae (7) to (10), R ¹ , R ^2, and R ³ are synonymous with those described in formula (3); R ¹² is synonymous with those described in formula (6)).

Specific examples of compounds particularly preferred as the compound (A-1) are listed below.

(Oxime compound (A-2))

The oxime compound (A-2) is decomposed by light to generate at least one of a base and an acid. The alkali or the acid generated by the decomposition of the compound (A-2) can promote the ring closure of the polyamino acid in the negative radiation-sensitive composition 2.

A preferable compound (A-2) is, for example, a compound represented by the following formula (D1): 组合。 The compound.

(In the formula, R ^d1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aryl group having a substituent group, or a carbazolyl group which may have a substituent, and R ^d2 is a fat group having 1 to 10 carbon atoms. Group hydrocarbon group or aryl group which may have a substituent, R ^d3 is a hydrogen atom or a group represented by -CO-R ^d5 , R ^d5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aromatic group which may have a substituent Base, p is 0 or 1).

When R ^d1 in the formula (D1) is an aryl group which may have a substituent, examples of the aryl group which may have a substituent include, for example, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and Anthracenyl having a substituent, and phenanthryl which may have a substituent. Among these groups, a phenyl group which may have a substituent and a naphthyl group which may have a substituent are preferable, and a phenyl group which may have a substituent is more preferable.

When the aryl group has a substituent, the number of the substituents bonded to the aryl group is not particularly limited. When the aryl group has a plurality of substituents, the plurality of substituents may be the same or different. The kind of the substituent which the aryl group may have is not particularly limited as long as it is within a range that does not hinder the object of the present invention. Preferred examples of the substituent include an organic group, an amine group, a halogen atom, a nitro group, and a cyano group.

When the substituent is an organic group, the kind of the organic group is not particularly limited as long as it does not hinder the object of the present invention, and can be appropriately selected from various organic groups. Preferred examples of the 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 fluorenyl group, and a phenyl group which may have a substituent. , A phenoxy group which may have a substituent, a benzamidine group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzophenoxy group which may have a substituent, a phenylalkyl group which may have a substituent, Naphthyl group which may have a substituent, naphthyloxy group which may have a substituent, naphthylmethyl group which may have a substituent, naphthyloxycarbonyl group which may have a substituent, naphthylmethyloxy group which may have a substituent, may have a substituent Naphthylalkyl, heterocyclic groups which may have substituents, amino groups substituted with one or two organic groups, morpholin-1-yl, and piperidine -1-yl, etc. The carbon number of the substituent does not include the carbon number of the substituent which the substituent further has.

When the organic group is an alkyl group, its carbon number is preferably from 1 to 20, and more preferably from 1 to 6. When the organic group is an alkyl group, it may be linear or branched. When the organic group is an alkyl group, specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, Isoamyl, secondary pentyl, tertiary pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, secondary octyl, tertiary octyl, n-nonyl, isononyl, n-decyl , And isodecyl. In addition, when the organic group is an alkyl group, the alkyl group may include an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl Oxyethyl, and methoxypropyl.

When the organic group is an alkoxy group, its carbon number is preferably 1-20, and 1 ~ 6 is better. In addition, when the organic group is an alkoxy group, it may be linear or branched. When the organic group is an alkoxy group, specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secondary butoxy, and Butyloxy, n-pentyloxy, isopentyloxy, secondary pentyloxy, tertiary pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, secondary octyloxy Group, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. In addition, when the organic group is an alkoxy group, the alkoxy group may include an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include, for example, methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy , Propoxyethoxyethoxy, and methoxypropoxy.

When the organic group is a cycloalkyl group or a cycloalkoxy group, its carbon number is preferably 3 to 10, and more preferably 3 to 6. When the organic group is a cycloalkyl group, specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. When the organic group is a cycloalkoxy group, specific examples include cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy.

When the organic group is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyl group, its carbon number is preferably 2-20, and more preferably 2-7. When the organic group is a saturated aliphatic fluorenyl group, specific examples may include: ethyl fluorenyl, propyl fluorenyl, n-butyl fluorenyl, 2-methyl propyl fluorenyl, n-pentyl fluorenyl, 2,2-dimethylpropyl fluorenyl N-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecanyl N-pentadecanyl, and n-hexadecylfluorenyl. When the organic group is a saturated aliphatic fluorenyloxy group, specific examples include ethoxyl, propylfluorenyl, n-butylfluorenyl, and 2-methyl Propyloxy, n-pentyloxy, 2,2-dimethylpropoxy, n-hexamethyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy , N-undecylfluorenyloxy, n-dodecylfluorenyloxy, n-tridecylfluorenyloxy, n-tetradecanylfluorenyloxy, n-pentadecanylfluorenyloxy, and n-hexadecylfluorenyloxy Wait.

When the organic group is an alkoxycarbonyl group, its carbon number is preferably 2-20, and more preferably 2-7. When the organic group is an alkoxycarbonyl group, specific examples include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, secondary butoxycarbonyl, and Primary butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, secondary pentyloxycarbonyl, tertiary pentyloxycarbonyl, n-hexanoylcarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, secondary octyloxy Carbonyl, tertiary octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyloxycarbonyl.

When the organic group is a phenylalkyl group, its carbon number is preferably 7-20, and more preferably 7-10. In addition, when the organic group is a naphthylalkyl group, its carbon number is preferably 11-20, and more preferably 11-14. When the organic group is a phenylalkyl group, specific examples include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl. When the organic group is a naphthylalkyl group, specific examples include α-naphthylmethyl, β-naphthylmethyl, 2- (α-naphthyl) ethyl, and 2- (β-naphthyl) ethyl. Base etc. When the organic group is a phenylalkyl or naphthylalkyl group, the organic group may further have a substituent on the phenyl or naphthyl group.

When the organic group is a heterocyclic group, the heterocyclic group is: a monocyclic ring containing 5 or 6 members of one or more N, S, O; or a heterocyclic group in which such monocyclic rings are condensed with each other, or Such a heterocyclic group obtained by condensing a monocyclic ring with a benzene ring. When the heterocyclic group is a fused ring, it is a fused ring having a ring number of 3 or less. Examples of the heterocyclic ring constituting such a heterocyclic group include furan, thiophene, pyrrole, Azole, iso Azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine , Pyrimidine, da , Benzofuran, benzothiophene, indole, isoindole, ind , Benzimidazole, benzotriazole, benzo Azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalate Quinoline Porphyrin, etc. When the organic group is a heterocyclic group, the heterocyclic group may further have a substituent.

When the organic group is an amine group substituted with one or two organic groups, preferred examples of the organic group bonded to a nitrogen atom include, for example, an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 3 to 10 carbon atoms. A cycloalkyl group, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzamidine group which may have a substituent, a phenylalkyl group which may have 7 to 20 carbon atoms, A naphthyl group which may have a substituent, a naphthylmethyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group, and the like. Specific examples of these preferable organic groups are the same as the specific examples of the organic group which the aryl group may have as a substituent when R ^d1 is an aryl group which may have a substituent. Specific examples of the amino group substituted by one or two organic groups include: methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine , N-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamine, n-nonylamino, n-decylamino, aniline, naphthylamine, acetamidine Amino, propanamido, n-butyrimidine, n-pentamidine, n-hexamidine, n-heptamidinyl, n-octylamino, n-decamidine, benzamidine, α -Naphthyridine, and β-naphthyridine; and the like.

When R ^d1 is an aryl group which may have a substituent, when a phenyl group, a naphthyl group, and a heterocyclic group included in the organic group as a substituent group bonded to the aryl group further have a substituent, the substituent may be, for example, : Alkyl group with 1 to 6 carbons, alkoxy group with 1 to 6 carbons, saturated aliphatic fluorenyl group with 2 to 7 carbons, alkoxycarbonyl group with 2 to 7 carbons, and saturated fat with 2 to 7 carbons Group alkoxy groups, monoalkylamino groups having 1 to 6 carbon alkyl groups, dialkylamino groups having 1 to 6 carbon alkyl groups, morpholin-1-yl, piperidine -1-yl, halogen atom, nitro, and cyano.

When R ^d1 is an aryl group which may have a substituent, when a phenyl group, a naphthyl group, and a heterocyclic group included in the organic group as a substituent group bonded to the aryl group further have a substituent group, the number of the substituent group As long as it is within the range that does not hinder the object of the present invention, it is not limited, and 1 to 4 is preferred. When R ^d1 is an aryl group which may have a substituent, when a phenyl group, a naphthyl group, and a heterocyclic group included in the organic group as a substituent group bonded to the aryl group have a plurality of substituents, a plurality of substituents Can be the same or different.

When R ^d1 is an aryl group which may have a substituent, it is easy to synthesize the compound represented by the formula (D1) and the solvent of the compound represented by the formula (D1) from the stability of the chemical properties of the substituent and less steric hindrance. From the viewpoint of higher solubility, the substituents of the aryl group include nitro, alkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, and saturated aliphatic fluorenyl having 2 to 7 carbons. The group selected from the group is preferably a nitro group or an alkyl group having 1 to 6 carbon atoms, and a nitro group or a methyl group is particularly preferable.

When R ^d1 is an aryl group which may have a substituent, R ^d1 preferably has the following formula (D1-1).

In the formula (D1-1), R ^d4 is a group selected from the group consisting of an organic group, an amine group, a halogen atom, a nitro group, and a cyano group, and q is an integer of 0 to 4).

When R ^d4 is an organic group, a preferable example of the organic group is the same as an example of an organic group which the aryl group may have as a substituent when R ^d1 is an aryl group which may have a substituent.

When R ^d4 are bonded to the phenyl group position of the bond between the phenyl and the main skeleton of the junction bond of the oxime compound a set, the set position of methyl 2, R ^d4 and bonded to the phenyl The position is preferably 4 or 5 positions, and more preferably 5 positions. In addition, q is preferably an integer of 0 to 3, preferably an integer of 0 to 2, and particularly preferably 0 or 1.

In the formula (D1), when R ^d1 is an aliphatic hydrocarbon group which may have a substituent, its carbon number is 1 to 10. The carbon number does not include the carbon number of the substituent. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 9, and more preferably 1 to 8. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or a hydrocarbon group having an unsaturated bond. The structure of the aliphatic hydrocarbon group may be a linear, branched, cyclic, or a combination of these structures, and a linear one is preferred.

In the above formula (D1), when R ^d1 is a linear aliphatic hydrocarbon group, preferred examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl. Base, n-octyl, n-nonyl, and n-decyl.

When R ^d1 is a cyclic aliphatic hydrocarbon group, preferred examples include cyclopentyl and cyclohexyl.

When R ^d1 is a combination of a linear aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group, preferred examples include cyclohexylmethyl, cyclopentylmethyl, 2-cyclohexylethyl, 2-cyclopentylethyl, 3-cyclohexyl-n-propyl, and 3-cyclopentyl-n-propyl. Among these groups, 2-cyclohexylethyl and 2-cyclopentylethyl are preferred.

When R ^d1 is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may have a substituent, and examples thereof include a hydroxyl group, a halogen atom, a cyano group, an alkoxy group having 1 to 10 carbon atoms, and an alkylthio group having 1 to 10 carbon atoms. , An aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, a saturated aliphatic fluorenyl group having 2 to 10 carbon atoms, an arylcarbonyl group which may have a substituent, an amine group, An amine group substituted with one or two alkyl groups having 1 to 6 carbon atoms, and an amine group substituted with an aryl group which may have one or two substituents. The carbon number of these substituents is not included in the carbon number of the aliphatic hydrocarbon group.

When the substituent of the aliphatic hydrocarbon group is an aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, an arylcarbonyl group which may have a substituent, and Or an amine group substituted with an aryl group of two substituents, the aryl group contained in these groups may be, for example, phenyl, naphthyl, anthracenyl, and phenanthryl, and phenyl and naphthyl are preferred Of these, phenyl is preferred.

When the substituent of the aliphatic hydrocarbon group is an aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, an arylcarbonyl group which may have a substituent, and Or an amine group substituted with an aryl group of two substituents, the aryl group contained in these groups may have a substituent, for example, a hydroxyl group, a halogen atom, a cyano group, a nitro group, and a carbon number of 1 to 6 Alkyl, alkoxy having 1 to 6 carbons, and saturated aliphatic fluorenyl having 2 to 7 carbons.

When R ^d1 is an aliphatic hydrocarbon group, specific examples of the above-mentioned substituents described in the substituents that the aliphatic hydrocarbon group may have are within the carbon number range described above, and when R ^d1 is an aryl group, The aryl group may have the same substituent.

When R ^d1 is a carbazolyl group which may have a substituent, the kind of the substituent is not particularly limited as long as it is within a range that does not hinder the object of the present invention. Examples of preferred substituents that may be present on the carbazolyl carbon atom include, for example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. , 3 to 10 carbon alkoxy groups, 2 to 20 saturated aliphatic fluorenyl groups, 2 to 20 carbon alkoxycarbonyl groups, 2 to 20 saturated aliphatic fluorenyl groups, and may have substitutions Phenyl, phenoxy which may have a substituent, phenylthio which may have a substituent, phenylcarbonyl which may have a substituent, benzamidine which may have a substituent, phenoxycarbonyl which may have a substituent, A benzamyloxy 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 naphthyloxy group which may have a substituent, a naphthalene which may have a substituent A carbonyl group, a naphthylmethyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthylmethyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, may have Heterocyclic group of substituent, heterocyclic carbonyl group which may have substituent, amine group, amine group substituted by 1 or 2 organic groups, morpholin-1-yl, piperidine -1-yl, halogen atom, nitro, and cyano.

When R ^d1 is a carbazolyl group which may have a substituent, examples of preferred substituents which may be present on the nitrogen atom of the carbazolyl group may include, for example, an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 3 to 10 carbon atoms. A cycloalkyl group, a saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzamidine group which may have a substituent, Phenoxycarbonyl, phenylalkyl having 7 to 20 carbons which may have a substituent, naphthyl which may have a substituent, naphthylmethyl group which may have a substituent, naphthyloxycarbonyl group which may have a substituent, may have a substituent A naphthylalkyl group having 11 to 20 carbon atoms, 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 preferable, an alkyl group having 1 to 6 carbon atoms is preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic fluorenyl group, and a substituent A phenylalkyl group, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, and an amine group substituted with one or two organic groups, and when R ^d1 is a In the case of an aryl group, examples of the substituent which the aryl group has are the same.

In R ^d1 , when a phenyl group, a naphthyl group, and a heterocyclic group included in the substituent group of the carbazolyl group further have a substituent group, examples of the substituent group include, for example, an alkyl group having 1 to 6 carbon atoms; carbon Alkoxy groups of 1 to 6; saturated aliphatic fluorenyl groups of 2 to 7 carbons; alkoxycarbonyl groups of 2 to 7 carbons; saturated aliphatic fluorenyl groups of 2 to 7 carbons; phenyl; naphthyl; Benzamidine; naphthylmethyl; alkyl from 1 to 6 carbon atoms, morpholin-1-yl, piperidine A benzamidine group substituted with a selected group from the group consisting of a -1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; and an alkyl group having 1 to 6 carbon atoms Alkylamino; morpholin-1-yl; piperidine -1-yl; halogen; nitro; cyano. When a phenyl group, a naphthyl group, and a heterocyclic group included in the substituents of the carbazolyl group further have a substituent, the number of the substituents is not limited as long as it does not hinder the object of the present invention, 1 ~ 4 is preferred. When a phenyl group, a naphthyl group and a heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aryl group which may have a substituent.

When R ^d2 is an aliphatic hydrocarbon group, the carbon number of the aliphatic hydrocarbon group and the carbon number of the aliphatic hydrocarbon group are preferably 1 to 6, and more preferably 1. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or a hydrocarbon group having an unsaturated bond. The structure of the aliphatic hydrocarbon group may be a linear, branched, cyclic, or a combination of these structures, and a linear one is preferred.

When R ^d2 is a linear aliphatic hydrocarbon group, preferred examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Nonyl and n-decyl. Of these, methyl is particularly preferred.

When R ^d2 is an aryl group which may have a substituent, examples may include: a phenyl group which may have a substituent, a naphthyl group which may have a substituent, an anthracene group which may have a substituent, and a phenanthryl group which may have a substituent . Among these groups, a phenyl group which may have a substituent and a naphthyl group which may have a substituent are preferable, and a phenyl group which may have a substituent is more preferable.

In R ^d2 , the substituent of the aryl group is not particularly limited as long as it is within a range that does not hinder the object of the present invention. Examples of preferable substituents which may be contained on the carbon atom of the aryl group include, for example, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, Cycloalkoxy group having 3 to 10 carbon atoms, saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, and may have a substituent Phenyl, phenoxy which may have a substituent, phenylthio which may have a substituent, benzamidine which may have a substituent, phenoxycarbonyl which may have a substituent, benzamyloxy which may have a substituent 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, naphthylmethyloxy which may have a substituent, naphthylalkyl having 11 to 20 carbon atoms which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amine Group, amine group substituted with 1 or 2 organic groups, morpholin-1-yl, piperidine -1-yl, halogen atom, nitro, and cyano.

Specific examples of the substituent which the aryl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic fluorenyl group, and a substituent which may have a substituent. Phenylalkyl, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, and amine group substituted with one or two organic groups, and when R ^d1 is an aromatic group which may have a substituent Examples of the substituent which the aryl group has at the same time are the same.

In R ^d2 , when a phenyl group, a naphthyl group, and a heterocyclic group included in the substituent group of the aryl group further have a substituent group, examples of the substituent group include, for example, an alkyl group having 1 to 6 carbon atoms; a carbon number 1 to 6 alkoxy groups; saturated aliphatic fluorenyl groups with 2 to 7 carbons; alkoxycarbonyl groups with 2 to 7 carbons; saturated aliphatic fluorenyl groups with 2 to 7 carbons; phenyl; naphthyl; benzene Formamyl; naphthylmethyl; methyl; alkyl from 1 to 6 carbon atoms; morpholin-1-yl; A benzamidine group substituted with a selected group from the group consisting of a -1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; and an alkyl group having 1 to 6 carbon atoms Alkylamino; morpholin-1-yl; piperidine -1-yl; halogen atom; nitro; cyano. When a phenyl group, a naphthyl group, and a heterocyclic group included in a substituent group having an aryl group further have a substituent group, the number of the substituent group is not limited as long as it does not hinder the object of the present invention. 1 ~ 4 is better. When a phenyl group, a naphthyl group and a heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^d3 in formula (D1) is a hydrogen atom or a group represented by -CO-R ^{d5, and} in the group represented by -CO-R ^d5 , R ^d5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or An aryl group which may have a substituent. When R ^d5 is an aryl group which may have a substituent, the aryl group may have the same substituents as when the aforementioned R ^d1 is an aryl group which may have a substituent. When R ^d5 is an aryl group which may have a substituent, the aryl group may have two or more kinds of substituents. In this case, the substituents of the aryl group may be the same or different. R ^{d5 is} preferably a hydrogen atom, an ethylfluorenyl group, a propionyl group, and a benzamyl group, and more preferably a hydrogen atom, an ethylamyl group, and a benzamyl group.

In the compound represented by the formula (D1), from the viewpoint of the base production efficiency or the acid production efficiency of the compound, R ^d1 in the formula (D1) is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent or may have A compound having an aryl group as a substituent and R ^d2 is a group represented by the following formula (D1-2), or a compound where R ^d1 in the formula (D1) is a group represented by the following formula (D1-3) From the viewpoint of obtaining a resin with suppressed coloration and high transparency, R ^d1 in the formula (D1) is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent or an aryl group which may have a substituent, and A compound in which R ^d2 is a group represented by the following formula (D1-2) is preferred.

(In the formula (D1-2), R ^d6 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen atom, a nitro group, and a cyano group, A is S or O, and r is 0 to Integer of 4).

When R ^d6 in the formula (D1-2) is an organic group, it can be selected from various organic groups as long as it is within a range that does not hinder the object of the present invention. When R ^d6 in the formula (D1-2) is an organic group, preferred examples include: an alkyl group having 1 to 6 carbons; an alkoxy group having 1 to 6 carbons; a saturated aliphatic having 2 to 7 carbons Fluorenyl; alkoxycarbonyl with 2 to 7 carbons; saturated aliphatic fluorenyl with 2 to 7 carbons; phenyl; naphthyl; benzamyl; naphthylmethyl; Alkyl, morpholin-1-yl, piperidine A benzamidine group substituted with a selected group from the group consisting of a -1-yl group and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; and an alkyl group having 1 to 6 carbon atoms Alkylamino; morpholin-1-yl; piperidine -1-yl; halogen atom; nitro; cyano.

In R ^d6 , preferred are: benzamidine; naphthylmethyl; via alkyl having 1 to 6 carbon atoms, morpholin-1-yl, piperidine Benzamidine substituted by a selected group from the group consisting of -1-yl and phenyl; nitro, more preferably: benzamidine, naphthylmethyl, 2-methylphenylcarbonyl, 4- (Pipe 1-yl) phenylcarbonyl, 4- (phenyl) phenylcarbonyl.

In addition, in the formula (D1-2), r is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When r is 1, the bonding position of R ^d6, preferably with respect to the R ^d6 are bonded to an oxygen atom or a phenyl group bonded to the sulfur atom is bonded to the bond position.

In formula (D1-2), A is preferably S.

When the phenyl, naphthyl, and heterocyclic group contained in R ^d6 further has a substituent, the substituent may be, for example, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 2 carbon atoms. ~ 7 saturated aliphatic fluorenyl groups, alkoxycarbonyl groups with 2 to 7 carbon atoms, saturated aliphatic fluorenyl groups with 2 to 7 carbon atoms, monoalkylamine groups with 1 to 6 carbon alkyl groups, and carbon numbers 1 to 6 alkyl dialkylamino, morpholin-1-yl, piperidine -1-yl, halogen atom, nitro, and cyano. When the phenyl, naphthyl, and heterocyclic group contained in R ^d6 further has a substituent, the number of the substituent is not limited as long as it does not hinder the object of the present invention, and preferably 1 to 4 . When the phenyl group, naphthyl group and heterocyclic group contained in R ^d6 have a plurality of substituents, the plurality of substituents may be the same or different.

(In the formula (D1-3), R ^d7 and R ^d8 are each a monovalent organic group, and s is 0 or 1).

(R ^d7 in formula (D1-3) can be selected from various organic groups as long as it does not hinder the object of the present invention. Preferred examples of R ^d7 include, for example, alkane having 1 to 20 carbon atoms. Group, cycloalkyl group having 3 to 10 carbon atoms, saturated aliphatic fluorenyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, phenyl group which may have a substituent, and benzamidine which may have a substituent Group, phenoxycarbonyl group which may have a substituent, phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, naphthyl group which may have a substituent, naphthylmethyl group which may have a substituent, and A naphthyloxycarbonyl group, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, and the like.

R ^d7 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group.

(R ^d8 in formula (D1-3) is not particularly limited as long as it does not hinder the object of the present invention, and can be selected from various organic groups. Specific examples of preferred groups for R ^d8 include, for example, : 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, a heterocyclic group which may have a substituent, etc. As R ^d8 , these groups may be substituted A phenyl group and a naphthyl group which may have a substituent are preferred, and a 2-methylphenyl group and a naphthyl group are particularly preferred.

When the phenyl, naphthyl, and heterocyclic group contained in R ^d7 or R ^d8 further has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic fluorenyl group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, Dialkylamino groups with 1 to 6 carbon atoms, morpholin-1-yl, piperidine -1-yl, halogen, nitro, and cyano. When the phenyl, naphthyl, and heterocyclic group contained in R ^d7 or R ^d8 further has a substituent, the number of the substituent is not limited as long as it does not hinder the object of the present invention, and ranges from 1 to 4 is better. When the phenyl group, naphthyl group and heterocyclic group contained in R ^d7 or R ^d8 have a plurality of substituents, the plurality of substituents may be the same or different.

The compound represented by formula (D1) can be synthesized according to the following scheme 1 when p is 0, R ^d2 is an aryl group which may have a substituent, and R ^d3 is a hydrogen atom. Specifically, the halogenated carbonyl compound represented by the following formula (1-2) can be used to fluorinate the aromatic compound represented by the following formula (1-1) by a Huf-Kwa reaction to obtain the following: The ketone compound represented by the formula (1-3) is described, and the obtained ketone compound (1-3) is oximatized with a hydroxylamine to obtain an oxime compound represented by the following formula (1-4). In the following formula (1-2), Hal is a halogen atom, and in the following formulae (1-1), (1-2), (1-3), and (1-4), R ^d1 and R ^d2 is the same as that described in the formula (D1).

The compound represented by formula (D1) can be synthesized according to the following scheme 2 when p is 0, R ^d2 is an aryl group which may have a substituent, and R ^d3 is a group represented by -CO-R ^d5 . Specifically, the oxime compound of the formula (1-4) obtained by the method described in the above scheme 1 and the acid anhydride ((R ^d5 CO) ₂ O) represented by the following formula (1-5) can be used, or The phosphonium halide (R ^d5 COHal, Hal being a halogen atom) represented by the following formula (1-6) is reacted to obtain an oxime ester compound represented by the following formula (1-7). In addition, in the following formulae (1-4), (1-5), (1-6), and (1-7), R ^d1 , R ^d2, and R ^d5 are the same as those described in formula (D1) .

In the compound represented by formula (D1), when p is 0, R ^d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ^d3 is a hydrogen atom, the method described in Scheme 1 can be used to treat the compound by hydroxylamine. The ketone compound represented by R ^d2 -CO-R ^{d1 is oximatized} and obtained as a compound represented by R ^d2 -C (= N-OH) -R ^d1 .

In addition, when p is 0, R ^d2 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R ^d3 is a group represented by -CO-R ^d5 , the compound represented by formula (D1) can be described in Scheme 2 In the method, the oxime compound represented by R ^d2 -C (= N-OH) -R ^d1 is amidated, and the compound represented by R ^d2 -C (= NO-CO-R ^d5 ) -R ^d1 is Form of acquisition.

When p is 1 and R ^d3 is a hydrogen atom, the compound represented by the formula (D1) can be synthesized according to the following scheme 3, for example. Specifically, a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (2-2) and the following formula (2-1) can be made in the presence of hydrochloric acid. The ketone compound is reacted to obtain a ketoxime compound represented by the following formula (2-3). In the following formulae (d2-1) and (d2-3), R ^d1 and R ^d2 are the same as those described in the formula (D1).

The compound represented by formula (D1) can be synthesized according to the following scheme 4 when p is 1, and R ^d3 is a group represented by -CO-R ^d5 . Specifically, the oxime compound of formula (2-3) obtained by the method described in the above scheme 3 and the acid anhydride ((R ^d5 CO) ₂ O) represented by the following formula (2-4) can be used, or The phosphonium halide (R ^d5 COHal, where Hal is a halogen atom) represented by the following formula (2-5) is reacted to obtain an oxime ester compound represented by the following formula (2-6). In addition, in the following formulae (2-3), (2-4), (2-5), and (2-6), R ^d1 , R ^d2, and R ^d5 are the same as those described in the formula (D1) .

Among the oxime compounds represented by the formula (D1), particularly preferred compounds include compounds of the following formula.

As the oxime compound (A-2), an oxime compound other than the oxime compound represented by the formula (D1) can be used. As the other oxime compound, the oxime-based photopolymerization initiator described in the negative radiation-sensitive composition 1 can be used.

The content of the photosensitive component in the negative radiation-sensitive composition 2 is not particularly limited as long as it is within a range that does not hinder the object of the present invention. In the negative radiation-sensitive composition 2, the content of the photosensitive component is preferably 1 to 50 parts by mass, and more preferably 1 to 30 parts by mass, with respect to 100 parts by mass of the polyamic acid.

[Other organic solvents (organic solvents other than the compound represented by the general formula (1))]

The negative radiation-sensitive composition 2 may contain other organic solvents. Other organic solvents can be used alone or in combination of two or more. As other organic solvents, the organic solvents exemplified in the negative radiation-sensitive composition 1 can be used.

The content of the solvent in the negative radiation-sensitive composition 2 is preferably such that the solid content concentration of the negative radiation-sensitive composition 2 becomes 1 to 50% by mass, and the solid content of the negative radiation-sensitive composition 2 The concentration is preferably an amount of 5 to 40% by mass. In addition, in the solvent contained in the negative radiation-sensitive composition 2, the mass ratio of the compound represented by the general formula (1) to other organic solvents is preferably 5:95 to 100: 0, and 20:80. ~ 100: 0 is better. By setting the content of the solvent and the mass ratio of the compound represented by the general formula (1) to other organic solvents to the above ranges, the sensitivity, storage stability, and coatability of the negative radiation-sensitive composition 2 can be easily made. It has excellent developability and safety, and it is easy to form a pattern with suppressed foreign matter by exposing and developing the negative radiation-sensitive composition 2.

[Other ingredients]

The negative radiation-sensitive composition 2 may contain various additives as required. Examples of the additives include sensitizers, hardening accelerators, fillers, adhesion promoters, antioxidants, anticoagulants, thermal polymerization inhibitors, defoamers, and surfactants.

<Negative radiation-sensitive composition 3>

The negative radiation-sensitive composition 3 contains a compound represented by the general formula (1) and polybenzo Azole precursors and photosensitive polyphenylene oxides A azole precursor composition.

[Compound represented by Formula (1)]

As the compound represented by the general formula (1), the compounds exemplified in the general description of the radiation-sensitive composition can be used. The compound represented by the general formula (1) can be used alone or in combination of two or more kinds.

[Polybenzo Azole precursor]

Polybenzo The azole precursor can be used alone or in combination of two or more. Polybenzo The raw materials for the synthesis of azole precursors are: aromatic diamine diols, and dicarbonyl compounds with specific structures. Hereinafter, the aromatic diamine diol and the dicarbonyl compound will be described.

(Aromatic diamine glycol)

In the present invention, a compound represented by the following formula (21) is used as the aromatic diamine diol. The aromatic diamine diol may be used singly or in combination of two or more kinds.

(In the formula, R ^a1 is a tetravalent organic group containing one or more aromatic rings. Regarding the combination of the two groups of amine groups and hydroxyl groups contained in the aromatic diamine diol represented by formula (21), each combination is In the above, the amine group and the hydroxyl group are bonded to two adjacent carbon atoms on the aromatic ring contained in R ^a1 ).

In the formula (21), R ^a1 is a tetravalent organic group containing one or more aromatic rings, and its carbon number is preferably 6 to 50, and more preferably 6 to 30. R ^a1 may be an aromatic group or a group in which two or more aromatic groups are bonded through: an aliphatic hydrocarbon group and a halogenated aliphatic hydrocarbon group; or a hetero atom including an oxygen atom, a sulfur atom, and a nitrogen atom. Atomic bond. The bonding of heteroatoms including oxygen atom, sulfur atom and nitrogen atom contained in R ^a1 can be exemplified by: -CONH-, -NH-, -N = N-, -CH = N-, -COO-, -O-, -CO-, -SO-, -SO _2- , -S-, and -SS-, etc., and -O-, -CO-, -SO-, -SO _2- , -S-, and -SS- is better.

The aromatic ring contained in R ^a1 may be an aromatic heterocyclic ring. The aromatic ring bonded to the amine group and the hydroxyl group in R ^a1 is preferably a benzene ring. When the ring bonded to an amine group and a hydroxyl group in R ^a1 is a condensed ring including two or more rings, the ring bonded to an amine group and a hydroxyl group in the condensed ring is preferably a benzene ring.

Preferable examples of R ^a1 include a group represented by any one of the following formulae (1-1) to (1-9).

(In the formula (1-1), X ¹ is an alkylene group having 1 to 10 carbon atoms, a fluoroalkylene group having 1 to 10 carbon atoms, -O-, -S-, -SO-, -SO ₂ One selected from the group consisting of-, -CO-, -COO-, -CONH-, and single bond; in formulas (1-2) to (1-5), Y ¹ may be the same or different, respectively, as One selected from the group consisting of -CH _2- , -O-, -S-, -SO-, -SO _2- , -CO- and a single bond).

The group represented by any one of the formulae (1-1) to (1-9) may have one or a plurality of substituents on the aromatic ring. Preferred examples of the substituent include a fluorine atom, An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and a fluoroalkoxy group having 1 to 6 carbon atoms are preferred. When the substituent is a fluoroalkyl group or a fluoroalkoxy group, a perfluoroalkyl group or a perfluoroalkoxy group is preferred.

Specific examples of the compound represented by the formula (21) include 2,4-diamino-1,5-benzenediol, 2,5-diamino-1,4-benzenediol, 2, 5-diamino-3-fluoro-1,4-benzenediol, 2,5-diamino-3,6-difluoro-1,4-benzenediol, 2,6-diamino-1 1,5-dihydroxynaphthalene, 1,5-diamino-2,6-dihydroxynaphthalene, 2,6-diamino-3,7-dihydroxynaphthalene, 1,6-diamino-2,5 -Dihydroxynaphthalene, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, 2,3'-diamine -3,2'-dihydroxybiphenyl, 3,4'-diamino-4,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-6, 6'-bis (trifluoromethyl) biphenyl, 3,3'-diamino-4,4'-dihydroxy-6,6'-bis (trifluoromethyl) biphenyl, 2,3'- Diamino-3,2'-dihydroxy-6,6'-bis (trifluoromethyl) biphenyl, 3,4'-diamino-4,3'-dihydroxy-6,6'-di (Trifluoromethyl) biphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-bis (trifluoromethyl) biphenyl, 3,3'-diamino- 4,4'-dihydroxy-5,5'-bis (trifluoromethyl) biphenyl, 2,3'-diamino-3,2'-dihydroxy-5,5'-bis (trifluoromethyl) Group) biphenyl, 3,4'-diamino-4,3'-dihydroxy-5, 5'-bis (trifluoromethyl) biphenyl, bis (4-amino-3-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) methane, 3,4'-diamine -4,3'-dihydroxydiphenylmethane, bis (4-amino-3-hydroxy-6-trifluoromethyl) methane, bis (3-amino-4-hydroxy-6-trifluoromethyl) Methyl), methane, 3,4'-diamino-4,3'-dihydroxy-6,6'-bis (trifluoromethyl) diphenylmethane, bis (4-amino-3-hydroxyphenyl) ) Difluoromethane, bis (3-amino-4-hydroxyphenyl) difluoromethane, 3,4'-diamino-4,3'-dihydroxydiphenyldifluoromethane, bis (4-amine Methyl-3-hydroxy-6-trifluoromethylphenyl) difluoromethane, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) difluoromethane, 3,4'-diamine -4,3'-dihydroxy-6,6'-bis (tri Fluoromethyl) diphenyldifluoromethane, bis (4-amino-3-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) ether, 3,4'-diamino- 4,3'-dihydroxydiphenyl ether, bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) ether, bis (3-amino-4-hydroxy-6-trifluoromethyl) Phenyl) ether, 3,4'-diamino-4,3'-dihydroxy-6,6'-bis (trifluoromethyl) diphenyl ether, bis (4-amino-3-hydroxy Phenyl) ketone, bis (3-amino-4-hydroxyphenyl) ketone, 3,4'-diamino-4,3'-dihydroxydiphenyl ketone, bis (4-amino-3- Hydroxy-6-trifluoromethyl) ketone, bis (3-amino-4-hydroxy-6-trifluoromethyl) ketone, 3,4'-diamino-4,3'-dihydroxy-6, 6'-bis (trifluoromethyl) diphenyl ketone, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl ) Propane, 2- (3-amino-4-hydroxyphenyl) -2- (4'-amino-3'-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxy -6-trifluoromethylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) propane, 2- (3-amino-4-hydroxy- 6-trifluoromethylphenyl) -2- (4'-amino-3'-hydroxy-6'-trifluoromethylphenyl) propane, 2,2-bis (3-amino-4-hydroxy -5-trifluoromethyl Phenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (3-Amino-4-hydroxyphenyl) -2- (4'-amino-3'-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-6- Trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy -6-trifluoromethylphenyl) -2- (4'-amino-3'-hydroxy-6'-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino- 4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) fluorene, bis (3-amino-4-hydroxyphenyl) fluorene, 3,4 '-Diamino-4,3'-dihydroxydiphenylfluorene, bis (4-amino-3-hydroxy-6-trifluoromethyl) fluorene, bis (3-amino-4-hydroxy-6 -Trifluoromethyl) fluorene, 3,4'-diamino-4,3'-dihydroxy-6,6'-bis (trifluoromethyl) diphenylfluorene, bis (4-amino-3) -Hydroxyphenyl) sulfide, bis (3-amino-4-hydroxyphenyl) sulfide, 3,4'-diamino-4,3'- Dihydroxydiphenyl sulfide, bis (4-amino-3-hydroxy-6-trifluoromethyl) sulfide, bis (3-amino-4-hydroxy-6-trifluoromethyl) sulfide, 3,4'-diamino-4,3'-dihydroxy-6,6'-bis (trifluoromethyl) diphenyl sulfide, 4-amino-3-hydroxyphenylbenzoic acid 4-amine 3-Amino-3-hydroxyphenyl ester, 3-Amino-4-hydroxyphenylbenzoic acid 3-Amino-4-hydroxyphenyl ester, 4-Amino-3-hydroxyphenylbenzoic acid 3-Amino-4- Hydroxyphenyl ester, 3-amino-4-hydroxyphenylbenzoic acid 4-amino-3-hydroxyphenyl ester, N- (4-amino-3-hydroxyphenyl) 4-amino-3-hydroxybenzene Benzamidine, N- (3-amino-4-hydroxyphenyl) 3-amino-4-hydroxyphenylbenzamide, N- (3-amino-4-hydroxyphenyl) 4 -Amino-3-hydroxyphenylbenzamide, N- (4-amino-3-hydroxyphenyl) 3-amino-4-hydroxyphenylbenzamide, 2,4'-bis ( 4-amino-3-hydroxyphenoxy) biphenyl, 2,4'-bis (3-amino-4-hydroxyphenoxy) biphenyl, 4,4'-bis (4-amino-3 -Hydroxyphenoxy) biphenyl, 4,4'-bis (3-amino-4-hydroxyphenoxy) biphenyl, bis [4- (4-amino-3-hydroxyphenoxy) phenyl ] Ether, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] ether, 2,4'-bis (4-amino-3-hydroxybenzene (Oxy) benzophenone, 2,4'-bis (3-amino-4-hydroxyphenoxy) benzophenone, 4,4'-bis (4-amino-3-hydroxyphenoxy) ) Benzophenone, 4,4'-bis (3-amino-4-hydroxyphenoxy) benzophenone, 2,4'-bis (4-amino-3-hydroxyphenoxy) Fluorobiphenyl, 2,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 4,4'-bis (4-amino-3-hydroxyphenoxy) octafluorobiphenyl Benzene, 4,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 2,4'-bis (4-amino-3-hydroxyphenoxy) octafluorobiphenyl Ketone, 2,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobenzophenone, 4,4'-bis (4-amino-3-hydroxyphenoxy) octafluorodione Benzophenone, 4,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobenzophenone, 2,2-bis [4- (4-amino-3-hydroxyphenoxy ) Phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-hydroxybenzene (Oxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) Phenyl] hexafluoropropane, 2,8-diamino-3,7-dihydroxydibenzofuran, 2,8-diamino-3,7-dihydroxyfluorene, 2,6-diamino- 3,7-dihydroxyxanthene (2,6-diamino-3,7-dihydroxyxanthene), 9,9-bis (4-amino-3-hydroxyphenyl) fluorene, and 9,9-bis (3- Amino-4-hydroxyphenyl) fluorene.

From the formation of polybenzo with excellent transparency From the viewpoint of an azole resin, among these, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferred.

(Dicarbonyl compound)

Polybenzo The synthetic raw material of the azole precursor is the aromatic diamine diol described above and a dicarbonyl compound represented by the following formula (22). By condensing the aromatic diamine diol with a dicarbonyl compound represented by the following formula (22), polybenzo can be obtained. Azole precursor.

(In the formula, R ^a2 is a divalent organic group, and A represents a hydrogen atom or a halogen atom.)

R ^a2 in formula (22) may be an aromatic group, an aliphatic group, or a combination of an aromatic group and an aliphatic group. Polybenzo From the standpoint of good heat resistance, mechanical properties, and chemical resistance of the azole resin, R ^{a2 is} preferably an aromatic group and / or a group containing an alicyclic group. The aromatic group in R ^a2 may be an aromatic hydrocarbon group or an aromatic heterocyclic group.

R ^a2 may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to a carbon atom and a hydrogen atom. When R ^a2 contains an oxygen atom, a nitrogen atom or a sulfur atom, the oxygen atom, nitrogen atom or sulfur atom may be selected from a divalent nitrogen-containing heterocyclic group, -CONH-, -NH-, -N = N-, -CH = The form of the base selected from N-, -COO-, -O-, -CO-, -SO-, -SO _2- , -S-, and -SS- is included in R ^a2 , preferably as- The form of the base selected from O-, -CO-, -SO-, -SO _2- , -S-, and -SS- is included in R ^a2 .

In the formula (22), one of the two As may be a hydrogen atom and the other is a halogen atom, but it is preferable that both of the As are hydrogen atoms or that both of the As are halogen atoms. When A is a halogen atom, A is preferably a chlorine atom, a bromine atom, and an iodine atom, and more preferably a chlorine atom.

When two dialdehyde compounds each of which A is a hydrogen atom are used as the dicarbonyl compound represented by the formula (22), a polybenzo compound represented by the following formula (10) can be produced. Azole intermediates.

(In the formula, R ^a1 and R ^a2 are the same as those described in formula (21) and formula (22), and n is the number of repetitions of the unit represented by formula (10)).

When two dicarboxylic acid halides each of which A is a halogen atom are used as the dicarbonyl compound represented by the formula (22), a polybenzo compound represented by the following formula (20) can be produced. Azole intermediates.

(In the formula, R ^a1 and R ^a2 are the same as those described in formulas (21) and (22), and n is the number of repeating units represented by formula (20)).

In the following, two compounds which are preferable as dicarbonyl compounds Aldehyde compounds and dicarboxylic acid halides.

‧Dialdehyde compound

As polybenzo The dialdehyde compound used as the raw material of the azole precursor is a compound represented by the following formula (2-1). A dialdehyde compound may be used individually by 1 type, and may be used in combination of 2 or more type.

(In the formula, R ^a2 is the same as that described in formula (22)).

Examples of the preferable aromatic group or aromatic ring-containing group of R ^a2 in formula (2-1) include the following groups.

(In the above formula, X ² is an alkylene group having 1 to 10 carbon atoms, a fluoroalkylene group having 1 to 10 carbon atoms, -O-, -S-, -SO-, -SO _2- , -CO One selected from the group consisting of-, -COO-, -CONH-, and single bond; when X ² is plural, the plural X ² may be the same or different; Y ² may be the same or different, respectively, as One selected from the group consisting of -CH _2- , -O-, -S-, -SO-, -SO _2- , -CO-, and single bond; p and q are 0 to 3 respectively Integer).

Examples of the preferable alicyclic group or alicyclic group containing R ^a2 in the formula (2-1) include the following groups.

(In the above formula, X ² is an alkylene group having 1 to 10 carbon atoms, a fluoroalkylene group having 1 to 10 carbon atoms, -O-, -S-, -SO-, -SO _2- , -CO One selected from the group consisting of-, -COO-, -CONH-, and single bond; when X ² is plural, the plural X ² may be the same or different; Y ² may be the same or different, respectively, as One selected from the group consisting of -CH _2- , -O-, -S-, -SO-, -SO _2- , -CO-, and a single bond; Z is derived from -CH _2- , One selected from the group consisting of -CH ₂ CH ₂ -and -CH = CH-; p is an integer from 0 to 3).

As an aromatic ring or an alicyclic ring included in the above-mentioned preferable R ^a2 group, the ring may have one or a plurality of substituents. Preferred examples of the substituent include a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, and a fluoroalkoxy group having 1 to 6 carbon atoms. Better. When the substituent is a fluoroalkyl group or a fluoroalkoxy group, a perfluoroalkyl group or a perfluoroalkoxy group is preferred.

When the dialdehyde compound represented by the formula (2-1) is an aromatic dialdehyde, preferred examples thereof include benzaldehyde, pyridinedialdehyde, and pyridine. Diformaldehydes, Pyrimidine Dialdehydes, Naphthalenedialdehydes, Biphenyl Dialdehydes, Diphenyl Ethers Dialdehydes, Diphenylstilbene Dialdehydes, Diphenyl Sulfide Distilbaldehydes, Bis (methylamido) Phenoxy) benzenes, [1,4-phenylenebis (1-methylethylene)] bisbenzaldehydes, 2,2-bis [4- (methylamidophenoxy) phenyl] Propanes, bis [4- (methylaminophenoxy) phenyl] thioethers, bis [4- (methylaminophenoxy) phenyl] fluorenes, and europium-containing formaldehyde.

Specific examples of phthalaldehydes include, for example, orthophthalaldehyde, isophthalaldehyde, terephthalaldehyde, 3-fluorophthalaldehyde, 4-fluorophthalaldehyde, 2-fluorophthalaldehyde, 4-fluoroisophthalaldehyde, 5-fluoroisophthalaldehyde, 2-fluoroterephthalaldehyde, 3-trifluoromethylphthalaldehyde, 4-trifluoromethylphthalaldehyde, 2-trifluoro Methyl isophthalaldehyde, 4-trifluoromethyl isophthalaldehyde, 5-trifluoromethyl isophthalaldehyde, 2-trifluoromethyl terephthalaldehyde, 3,4,5,6-tetrafluoro O-phthalaldehyde, 2,4,5,6-tetrafluoroisophthalaldehyde, and 2,3,5,6-tetrafluoroterephthalaldehyde.

Specific examples of the pyridine dicarbaldehydes include pyridine-2,3-dicarbaldehyde, pyridine-3,4-dicarbaldehyde, and pyridine-3,5-dicarbaldehyde.

Pyridine Specific examples of diformaldehydes include: -2,3-formaldehyde, pyridine -2,5-formaldehyde, and pyridine -2,6-formaldehyde.

Specific examples of the pyrimidine dicarbaldehydes include, for example, pyrimidine-2,4-dicarbaldehyde, pyrimidine-4,5-dicarbaldehyde, and pyrimidine-4,6-dicarbaldehyde.

Specific examples of naphthalene dialdehydes include naphthalene-1,5-dialdehyde, naphthalene-1,6-dialdehyde, naphthalene-2,6-dialdehyde, naphthalene-3,7-dialdehyde, 2,3 , 4,6,7,8-hexafluoronaphthalene-1,5-dicarbaldehyde, 2,3,4,5,6,8-hexafluoronaphthalene-1,6-dicarbaldehyde, 1,3,4,5 , 7,8-hexafluoronaphthalene-2,6-dicarbaldehyde, 1-trifluoromethylnaphthalene-2,6-dicarbaldehyde, 1,5-bis (trifluoro (Methyl) naphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene-3,7-dialdehyde, 1,5-bis (trifluoromethyl) naphthalene-3,7-dialdehyde, 1-tri Fluoromethyl-2,4,5,6,8-pentafluoronaphthalene-3,7-dicarbaldehyde, 1-bis (trifluoromethyl) methoxy-2,4,5,6,8-pentafluoro Naphthalene-3,7-dicarbaldehyde, 1,5-bis (trifluoromethyl) -2,4,6,8-tetrafluoronaphthalene-3,7-dicarbaldehyde, and 1,5-bis [bis (tri (tri Fluoromethyl) methoxy] -2,4,6,8-tetrafluoronaphthalene-3,7-dicarbaldehyde and the like.

Specific examples of biphenyl dialdehydes include biphenyl-2,2'-dialdehyde, biphenyl-2,4'-dialdehyde, biphenyl-3,3'-dialdehyde, biphenyl-4, 4'-formaldehyde, 6,6'-difluorobiphenyl-3,4'-formaldehyde, 6,6'-difluorobiphenyl-2,4'-formaldehyde, 6,6'-difluoride Benzene-3,3'-formaldehyde, 6,6'-difluorobiphenyl-3,4'-formaldehyde, 6,6'-difluorobiphenyl-4,4'-formaldehyde, 6,6 ' -Bis (trifluoromethyl) biphenyl-2,2'-dicarbaldehyde, 6,6'-bis (trifluoromethyl) biphenyl-2,4'-dicarbaldehyde, 6,6'-bis (tri Fluoromethyl) biphenyl-3,3'-dicarbaldehyde, 6,6'-bis (trifluoromethyl) biphenyl-3,4'-dicarbaldehyde, and 6,6'-bis (trifluoromethyl) ) Biphenyl-4,4'-formaldehyde.

Specific examples of diphenyl ether dialdehydes include diphenyl ether-2,4'-dicarbaldehyde, diphenyl ether-3,3'-dicarbaldehyde, and diphenyl ether-3,4'- Diformaldehyde, and diphenyl ether-4,4'-dicarbaldehyde.

Specific examples of the diphenylsulfonium dialdehydes include diphenylsulfonium-3,3'-dicarbaldehyde, diphenylsulfonium-3,4'-dicarbaldehyde, and diphenylsulfonium-4,4 ' -Diformaldehyde, etc.

Specific examples of the diphenyl sulfide diformaldehydes include diphenyl sulfide-3,3'-dicarbaldehyde, diphenyl sulfide-3,4'-dicarbaldehyde, and diphenyl sulfide- 4,4'-formaldehyde and so on.

Specific examples of diphenyl ketone dicarbaldehydes include diphenyl ketone-3,3'-dicarbaldehyde, diphenyl ketone-3,4'-dicarbaldehyde, and diphenyl ketone-4,4 ' -Second Aldehydes, etc.

Specific examples of the bis (formamylphenoxy) benzenes include benzene 1,3-bis (3-formamylphenoxy) benzene, and 1,4-bis (3-formamylphenoxy) ) Benzene, and 1,4-bis (4-methylfluorenylphenoxy) benzene.

Specific examples of [1,4-phenylenebis (1-methylethylene)] bisbenzaldehydes include 3,3 '-[1,4-phenylenebis (1-methylethylene) (Ethyl)] bisbenzaldehyde, 3,4 '-[1,4-phenylene bis (1-methylethylene)] bisbenzaldehyde, and 4,4'-[1,4-phenylene Bis (1-methylethylene)] bisbenzaldehyde and the like.

Specific examples of 2,2-bis [4- (methylamidophenoxy) phenyl] propanes include 2,2-bis [4- (2-methylamidophenoxy) phenyl] propane , 2,2-bis [4- (3-methylfluorenylphenoxy) phenyl] propane, 2,2-bis [4- (4-methylfluorenylphenoxy) phenyl] propane, 2,2 -Bis [4- (3-methylfluorenylphenoxy) phenyl] hexafluoropropane, and 2,2-bis [4- (4-methylfluorenylphenoxy) phenyl] hexafluoropropane and the like.

Specific examples of the bis [4- (methylaminophenoxy) phenyl] thioethers include bis [4- (3-methylaminophenoxy) phenyl] thioether, and bis [4- (4-methylfluorenylphenoxy) phenyl] sulfide and the like.

Specific examples of the bis [4- (methylfluorenylphenoxy) phenyl] fluorenes include bis [4- (3-methylfluorenylphenoxy) phenyl] fluorene, and bis [4- (4 -Methylaminophenoxy) phenyl] fluorene and the like.

Specific examples of fluorene-containing formaldehyde include, for example, fluorene-2,6-dialdehyde, fluorene-2,7-dialdehyde, dibenzofuran-3,7-dialdehyde, 9,9-bis (4-formaldehyde) Fluorenylphenyl) fluorene, 9,9-bis (3-methylfluorenylphenyl) fluorene, and 9- (3-methylfluorenylphenyl) -9- (4'-methylmethylphenyl) fluorene, etc. .

In addition, diphenylalkanedialdehyde or diphenylfluoroalkanedi represented by the following formula Aldehydes can also be preferably used as aromatic dialdehyde compounds.

Furthermore, a compound having a fluorene imine bond represented by the following formula can also be suitably used as an aromatic dialdehyde compound.

When the dicarbonyl compound represented by the formula (2-1) is an alicyclic dialdehyde containing an alicyclic group, preferred examples thereof include cyclohexane-1,4-dialdehyde, and cyclohexane- 1,3-dicarboxaldehyde, bicyclo [2.2.1] heptane-2,5-dicarbaldehyde, bicyclo [2.2.2] octane-2,5-dicarbaldehyde, bicyclo [2.2.2] oct-7-ene -2,5-dicarbaldehyde, bicyclo [2.2.1] heptane-2,3-dicarbaldehyde, bicyclo [2.2.1] hept-5-ene-2,3-dicarbaldehyde, tricyclo [5.2.1.0 ^{2 , 6} ] decane-3,4-dicarbaldehyde, tricyclo [5.2.1.0 ^2,6 ] dec-4-ene-8,9-dicarbaldehyde, perhydronaphthalene-2,3-dialdehyde, perhydronaphthalene -1,4-Dicarbaldehyde, Perhydronaphthalene-1,6-Dicarbaldehyde, Perhydro-1,4-Methylnaphthalene-2,3-Dicarbaldehyde, Perhydro-1,4-Methylnaphthalene-2, 7-Dicarbaldehyde, Perhydro-1,4-Methylnaphthalene-7,8-Dicarbaldehyde, Perhydro-1,4: 5,8-Dimethylnaphthalene-2,3-Dicarbaldehyde, Perhydro-1 , 4: 5,8-dimethyl bridgenaphthalene-2,7-dicarbaldehyde, perhydro-1,4: 5,8: 9,10-trimethyl bridge anthracene-2,3-dicarbaldehyde, bicyclohexane- 4,4'-dicarbaldehyde, dicyclohexyl ether-3,4'-dicarbaldehyde, dicyclohexylmethane-3,3'-dicarbaldehyde, dicyclohexylmethane-3,4'-dicarbaldehyde, dicyclohexyl Methane-4,4'-dicarbaldehyde, dicyclohexyldifluoromethane-3,3'-dicarbaldehyde, dicyclohexyldi Methane-3,4'-dicarbaldehyde, dicyclohexyldifluoromethane-4,4'-dicarbaldehyde, dicyclohexylfluorene-3,3'-dicarbaldehyde, dicyclohexylfluorene-3,4'-dicarbaldehyde , Dicyclohexylfluorene-4,4'-dicarbaldehyde, dicyclohexylsulfide-3,3'-dicarbaldehyde, dicyclohexylsulfide-3,4'-dicarbaldehyde, dicyclohexylsulfide-4, 4'-Dicarbaldehyde, Dicyclohexyl Ketone-3,3'-Dicarbaldehyde, Dicyclohexyl Ketone-3,4'-Dicarbaldehyde, Dicyclohexyl Ketone-4,4'-Dicarbaldehyde, 2,2-Bis (3-formamylcyclohexyl) propane, 2,2-bis (4-formamylcyclohexyl) propane, 2,2-bis (3-formamylcyclohexyl) hexafluoropropane, 2,2-bis (4-formamylcyclohexyl) hexafluoropropane, 1,3-bis (3-formamylcyclohexyl) benzene, 1,4-bis (3-formamylcyclohexyl) benzene, 1,4-bis (4-formamylcyclohexyl) benzene, 3,3 '-[1,4-cyclohexylbis (1-methylethylene)] bicyclohexanecarboxaldehyde, 3,4'-[1,4- Cyclohexylbis (1-methylethylene)] bicyclohexanecarboxaldehyde, 4,4 '-[1,4-cyclohexylbis (1-methylethylene)] bicyclohexanecarboxaldehyde, 2, 2-bis [4- (3-methylfluorenylcyclohexyl) cyclohexyl] propane, 2,2-bis [4- (4-methylfluorenylcyclohexyl) cyclohexyl] propane, 2,2-bis [4- (3-formamylcyclohexyl) cyclohexyl] hexafluoropropane 2,2-bis [4- (4-methylfluorenylphenoxy) cyclohexyl] hexafluoropropane, bis [4- (3-methylfluorenylcyclohexyloxy) cyclohexyl] sulfide, bis [4- (4-formamylcyclohexyloxy) cyclohexyl] sulfide, bis [4- (3-formamylcyclohexyloxy) cyclohexyl] fluorene, bis [4- (4-formamylcyclohexyloxy) Group) cyclohexyl] fluorene, 2,2'-bicyclo [2.2.1] heptane-5,6'-dicarbaldehyde, 2,2'-bicyclo [2.2.1] heptane-6,6'-dicarbaldehyde , And 1,3-dimethylformamide fund adamantane and the like.

Easy to synthesize and obtain, and easy to obtain polybenzo with excellent heat resistance and mechanical properties In terms of azole resins, among the dialdehyde compounds described above, isophthalaldehyde is preferred.

‧Dicarboxylic acid halide

As polybenzo The dicarboxylic acid halide used as the raw material of the azole precursor is a compound represented by the following formula (2-2). The dicarboxyphosphonium halide may be used singly or in combination of two or more kinds.

(In the formula, R ^a2 is the same as that described in formula (22), and Hal is a halogen atom).

In the formula (2-2), Hal is preferably a chlorine atom, a bromine atom, and an iodine atom, and more preferably a chlorine atom.

As a preferable compound of the compound represented by the formula (2-2), for example, a compound obtained by substituting two aldehyde groups of the compound described in the above-mentioned preferred examples of dialdehyde compounds with halocarbonyl groups The halocarbonyl group is preferably a chlorocarbonyl group.

Easy to synthesize and obtain, and easy to obtain polybenzo with excellent heat resistance and mechanical properties In terms of azole resins, among the dicarboxylic acid halides described above, p-xylylene chloride is preferred.

(Polybenzo (Preparation method of azole precursor)

In the present invention, polybenzo The azole precursor is produced by reacting the aforementioned aromatic diamine diol with a dicarbonyl compound in a solvent in accordance with a conventional method. Hereinafter, a production method when the dicarbonyl compound is a dialdehyde compound, and a production method when the dicarbonyl compound is a dicarboxyfluorene halide will be described as polybenzo. A representative example of a method for producing an azole precursor.

‧Reaction between aromatic diamine diol and dialdehyde compound

The reaction of the aromatic diamine diol and the dialdehyde compound is performed in a solvent. The reaction between the aromatic diamine diol and the dialdehyde compound is a Schiff base formation reaction, and can be performed according to a conventional method. The reaction temperature is not particularly limited, but is usually preferably 20 to 200 ° C, more preferably 20 to 160 ° C, and particularly preferably 100 to 160 ° C.

The reaction of the aromatic diamine diol and the dialdehyde compound can be carried out while adding an entrainer to the solvent while refluxing and dehydrating. The azeotropic agent is not particularly limited, and can be appropriately selected from organic solvents that form an azeotropic mixture with water and form a two-phase system with water at room temperature. Preferable examples of the azeotrope include, for example, isobutyl acetate, allyl acetate, n-propyl propionate, isopropyl propionate, n-butyl propionate, and isobutyl propionate; Ethers such as chloromethyl ether and ethyl isoamyl ether; ketones such as ethylpropyl ketone; aromatic hydrocarbons such as toluene.

The reaction time between the aromatic diamine diol and the dialdehyde compound is not particularly limited, and a typical example is preferably about 2 to 72 hours.

Manufacture of polybenzo In the case of an azole precursor, the amount of the dialdehyde compound used is preferably 0.5 to 1.5 mol, and more preferably 0.7 to 1.3 mol relative to 1 mol of the aromatic diamine diol.

The amount of the solvent used is not particularly limited as long as the reaction between the aromatic diamine diol and the dialdehyde compound can proceed well. Typical examples are: 1 to 40 times the mass of the solvent, and preferably 1.5 to 20 times the mass of the solvent relative to the total mass of the aromatic diamine diol and the mass of the dialdehyde compound.

Reaction of an aromatic diamine diol with a dialdehyde compound to proceed until the resulting polybenzo It is preferable that the number average molecular weight of the azole precursor is 1,000 to 20,000, so as to proceed until the generated polybenzo The number average molecular weight of the azole precursor is preferably 1200 to 5,000.

‧Reaction of Aromatic Diamine Glycol and Dicarboxylic Acid Halide

The reaction between the aromatic diamine diol and the dicarboxylic acid halide is carried out in a solvent. The reaction temperature is not particularly limited, but is usually preferably -20 to 150 ° C, more preferably -10 to 150 ° C, and particularly preferably -5 to 70 ° C. The reaction of an aromatic diamine diol with a dicarboxyphosphonium halide will by-produce hydrogen halides. In order to neutralize such a hydrogen halide, a small amount of the following compounds may be added to the reaction solution: organic bases such as triethylamine, pyridine, and N, N-dimethyl-4-aminopyridine; or sodium hydroxide and hydrogen Alkali metal hydroxides such as potassium oxide.

The reaction time between the aromatic diamine diol and the dicarboxyphosphonium halide is not particularly limited, and a typical example is preferably about 2 to 72 hours.

Manufacture of polybenzo In the case of an azole precursor, the amount of dicarboxylic acid halide used is preferably 0.5 to 1.5 mol, and more preferably 0.7 to 1.3 mol relative to 1 mol of the aromatic diamine diol.

The amount of the solvent used is not particularly limited as long as the reaction between the aromatic diamine diol and the dicarboxylic acid halide can proceed well. Typical examples are: 1 to 40 times the mass of the solvent, and preferably 1.5 to 20 times the mass of the solvent, relative to the total mass of the aromatic diamine diol and the mass of the dicarboxyphosphonium halide.

Reaction of an aromatic diamine diol with a dicarboxyphosphonium halide to proceed until the polybenzo It is preferable that the number average molecular weight of the azole precursor is 1,000 to 20,000, so as to proceed until the generated polybenzo The number average molecular weight of the azole precursor is preferably 1200 to 5,000.

By the method described above, polybenzo A solution of the azole precursor. When the negative radiation-sensitive composition 3 is modulated, polybenzo can be used directly A solution of the azole precursor. It is also possible to use polybenzo A paste or solid of an azole precursor, which is obtained in a manner such that Conversion of azole precursor to polybenzo Low temperature of azole resin from polybenzo At least a portion of the solvent is removed from the azole precursor solution. In addition, it is also possible to adjust the concentration of polybenzo A solution of the azole precursor is used to prepare the negative radiation-sensitive composition 3, and the solid content concentration is a concentration of the polybenzo obtained from the above reaction. The solution of the azole precursor is adjusted by adding an appropriate amount of a solvent or the like.

Examples of the organic solvent used in the reaction between the aromatic diamine diol and the dicarbonyl compound include, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N -Diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N, N, 2-trimethylpropanamide, N-methylcaprolactam Amines, and nitrogen-containing polar solvents such as N, N, N ', N'-tetramethylurea; β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone Lactones, ε-caprolactones, and other lactone-based polar solvents; dimethyl sulfene; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, di Ethers such as alkane, tetrahydrofuran, methylcellulose acetate, and ethylcellulose acetate.

Polybenzo Azole precursor or polybenzo In terms of the solubility of the azole resin, among these organic solvents, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N, N, 2-trimethylpropanamide, N-methylcaprolactam, and N, N, N ', Nitrogen-containing polar solvents such as N'-tetramethylurea are preferred.

[Photosensitive component]

The photosensitive component is not particularly limited. As in the case of the negative radiation-sensitive composition 2, for example, a compound (A) such as a photobase generator and a photoacid generator can be decomposed by light to generate an alkali. And at least one of acids. The photosensitive component can be used individually or in mixture of 2 or more types.

By exposing the negative radiation-sensitive composition 3 containing the compound (A), the compound (A) in the negative radiation-sensitive composition 3 is decomposed to generate at least one of an alkali and an acid. The alkali or acid produced in this way will react with the polybenzo in the negative radiation-sensitive composition 3 Polyazole precursors act to promote polybenzo Conversion of azole precursor to polybenzo Azole resin.

When the negative-type radiation-sensitive composition 3 containing the compound (A) is exposed, the compound (A) is decomposed in the exposure portion to generate at least one of an alkali and an acid. The alkali or acid produced in this way can promote polybenzo Conversion of azole precursor to polybenzo Azole resin so that the exposed portion is not dissolved in the developing solution. On the other hand, since the unexposed portion can be dissolved in the developing solution, it can be removed by being dissolved in the developing solution. Therefore, by selectively exposing the negative radiation-sensitive composition 3, a desired pattern can be formed.

Examples of the compound (A) include the compound (A-1) and the oxime compound (A-2) which decompose by the action of light to generate an imidazole compound, as in the case of the negative radiation-sensitive composition 2. The imidazole compound produced by the compound (A-1) promotes polybenzo in the negative radiation-sensitive composition 3 Conversion of azole precursor to polybenzo Azole resin. In addition, the base or acid generated by the decomposition of the compound (A-2) can promote the polybenzo in the negative radiation-sensitive composition 3 Conversion of azole precursor to polybenzo Azole resin. The detailed description of the compound (A-1) and the compound (A-2) is the same as that in the negative radiation-sensitive composition 2.

The content of the photosensitive component in the negative-type radiation-sensitive composition 3 is not particularly limited as long as it is within a range that does not hinder the object of the present invention. In the negative-type radiation-sensitive composition 3, it is relative to polybenzo The azole precursor is 100 parts by mass, and the content of the photosensitive component is preferably 1 to 50 parts by mass, and more preferably 1 to 30 parts by mass.

[Other organic solvents (organic solvents other than the compound represented by the general formula (1))]

The negative radiation-sensitive composition 3 may contain other organic solvents. Other organic solvents can be used alone or in combination of two or more. As other organic solvents, the organic solvents exemplified in the negative radiation-sensitive composition 1 can be used.

The content of the solvent in the negative radiation-sensitive composition 3 is preferably such that the solid content concentration of the negative radiation-sensitive composition 3 becomes 1 to 50% by mass, and the solid content of the negative radiation-sensitive composition 3 The concentration is preferably an amount of 5 to 40% by mass. In addition, the solubility contained in the negative radiation-sensitive composition 3 Among the agents, the mass ratio of the compound represented by the general formula (1) to other organic solvents is preferably 5:95 to 100: 0, and more preferably 20:80 to 100: 0. By setting the content of the solvent and the mass ratio of the compound represented by the general formula (1) to other organic solvents to the above ranges, the sensitivity, storage stability, and coatability of the negative radiation-sensitive composition 3 can be easily made. It is excellent in developability and safety, and it is easy to form a pattern by suppressing the generation of foreign matter by exposing and developing the negative-type radiation-sensitive composition 3.

[Other ingredients]

The negative radiation-sensitive composition 3 may contain various additives as required. Examples of the additives include sensitizers, hardening accelerators, fillers, adhesion promoters, antioxidants, anticoagulants, thermal polymerization inhibitors, defoamers, and surfactants.

<Positive radiation-sensitive composition 1>

The positive radiation-sensitive composition 1 contains the compound represented by the general formula (1), an alkali-soluble resin, and a quinone-containing diazide-containing compound.

[Compound represented by Formula (1)]

As the compound represented by the general formula (1), the compounds exemplified in the general description of the radiation-sensitive composition can be used. The compound represented by the general formula (1) can be used alone or in combination of two or more kinds.

[Alkali soluble resin]

As the alkali-soluble resin, the alkali-soluble resin exemplified in the negative radiation-sensitive composition 1 can be used.

Relative to the solid content of the positive radiation-sensitive composition 1, the content of the alkali-soluble resin is preferably 5 to 90% by mass, and more preferably 10 to 85% by mass. By setting the content of the alkali-soluble resin to the above range, there is a tendency that the balance between the film-forming ability and the developability of the positive-type radiation-sensitive composition 1 can be easily obtained.

[Quinonediazide-containing compound]

The quinonediazide-containing compound is not particularly limited, and a completely esterified product or a partially esterified product obtained from a compound having one or more phenolic hydroxyl groups and a quinonediazide-containing sulfonic acid is preferred. Such a quinone-containing diazide compound is obtained by: In a suitable solvent such as alkane, a compound having one or more phenolic hydroxyl groups is condensed with a quinonediazidesulfonic acid in the presence of a base such as triethanolamine, an alkali metal carbonate, or an alkali metal carbonate. Fully esterified or partially esterified. The quinone diazide-containing compound can be used alone or in combination of two or more kinds.

Examples of the compound having one or more phenolic hydroxyl groups include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone. Ketones; ginseng (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylbenzene Phenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) 3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4 -Hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxy Phenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3, 4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy- 4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl 4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5 -Cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane and other phenolic compounds; 2,4-bis (3,5-dimethyl-4-hydroxybenzoic acid) Phenyl) -5-hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol and other linear trinuclear phenolic compounds; 1,1-bis [ 3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy-5-methyl Phenylbenzyl) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3, 5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4- Hydroxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- ( 3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzene) (Methyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane Bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [2,5-dimethyl-3- (2-hydroxy-5- Methylbenzyl) -4-hydroxyphenyl] methane and other linear tetranuclear phenolic compounds; 2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl Group] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-Dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol and other linear pentameric phenolic compounds; bis (2 , 3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- (2,3 , 4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'- Dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3'-fluoro -4'- Hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4 '-Hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxy-3', 5'-dimethylphenyl) propane, 4,4'- Bisphenol compounds such as [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylene] bisphenol; 1- [1- (4-hydroxyphenyl ) Isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- Polynuclear branched compounds such as [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene; condensation-type phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane Wait.

Examples of the quinone-containing diazidosulfonic acid include: naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and o-anthraquinone Diazidesulfonic acid, etc.

Relative to the solid content of the positive radiation-sensitive composition 1, the content of the quinonediazide-containing compound is preferably 10 to 95% by mass, and more preferably 15 to 95% by mass. By setting the content of the quinone diazide-containing compound to the above range, the sensitivity of the positive radiation-sensitive composition 1 can be made good.

[Other organic solvents (organic solvents other than the compound represented by the general formula (1))]

The positive radiation-sensitive composition 1 may contain other organic solvents. Other organic solvents can be used alone or in combination of two or more. As other organic solvents, the organic solvents exemplified in the negative radiation-sensitive composition 1 can be used.

The content of the solvent in the positive radiation-sensitive composition 1 is preferably such that the solid content concentration of the positive radiation-sensitive composition 1 becomes 1 to 50% by mass, and the solid content of the positive radiation-sensitive composition 1 The concentration is preferably 5 to 30% by mass. In addition, the solubility contained in the positive radiation-sensitive composition 1 Among the agents, the mass ratio of the compound represented by the general formula (1) to other organic solvents is preferably 5:95 to 100: 0, and more preferably 20:80 to 100: 0. By setting the content of the solvent and the mass ratio of the compound represented by the general formula (1) to other organic solvents to the above ranges, the sensitivity, storage stability, and coatability of the positive radiation-sensitive composition 1 can be easily made. It is excellent in developability and safety, and it is easy to form a pattern with suppressed generation of foreign matter by exposing and developing the positive-type radiation-sensitive composition 1.

[Other polymers]

The positive-type radiation-sensitive composition 1 may contain other polymers. Other polymers can be used alone or in combination of two or more. Other polymers include, for example, the polyamic acid described in the negative radiation-sensitive composition 2 and the polybenzoxide described in the negative radiation-sensitive composition 3 An azole precursor and a polymer having a structure represented by the following general formula (31) as a main component.

A polymer having a structure represented by the following general formula (31) as a main component can be formed into a polymer by heating or an appropriate catalyst, which has a fluorene imine ring, Azole ring, other cyclic structures. Based on polyimide precursors, polyamic acid or polyamic acid esters, polybenzo Polyhydroxyamidine of the azole precursor is preferred. Here, the main component means a structural unit represented by the general formula (31) in which 50 mol% or more of the total structural unit of the polymer is contained. It is preferably 70 mol% or more of the total structural unit containing the polymer, and more preferably 90 mol% or more of the total structural unit containing the polymer.

In the general formula (31), R ¹ and R ² may be the same or different, and represent a divalent to 8-valent organic group having a carbon number of 2 or more. R ³ and R ⁴ may be the same or different, and represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms. l and m represent integers from 0 to 2, and p and q represent integers from 0 to 4. Only p + q> 0.

In the general formula (31), R ¹ represents a divalent to 8-valent organic group having 2 or more carbon atoms, and represents a structural component of an acid. R ¹ is a divalent acid, and examples thereof include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and bis (carboxyphenyl) propane; cyclohexane Aliphatic dicarboxylic acids such as dicarboxylic acid and adipic acid. R ¹ is a trivalent acid, and examples thereof include tricarboxylic acids such as trimellitic acid and trimellitic acid. R ¹ is a tetravalent acid, and examples thereof include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenylphosphonium tetracarboxylic acid; and Aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid; diester compounds in which the hydrogen atoms of two carboxyl groups of these carboxylic acids are replaced with methyl or ethyl groups. In addition, for example, an acid having a hydroxyl group such as hydroxyphthalic acid, hydroxytrimellitic acid, and the like can be mentioned. These acid components can be used in two or more kinds, and preferably contain 1 to 40 mol% of a residue of a tetracarboxylic acid. In addition, from the viewpoint of solubility and photosensitivity to an alkaline developer, it is preferable to contain 50 mol% or more of a residue of an acid having a hydroxyl group.

From the viewpoint of heat resistance, R ¹ preferably has an aromatic ring, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.

In the general formula (31), R ² represents a divalent to 8-valent organic group having 2 or more carbon atoms, and represents a structural component of a diamine. From the viewpoint of heat resistance, R ² preferably has an aromatic ring. Specific examples of the diamine include phenylenediamine, diaminodiphenyl ether, aminephenoxybenzene, diaminodiphenylmethane, diaminodiphenylphosphonium, and bis (trifluoromethyl) ) Benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) fluorene, bis (aminohydroxyphenyl) hexafluoropropane, diaminodihydroxypyrimidine, diamine Dihydroxypyridine, hydroxydiaminopyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid; an alkyl or halogen atom replacing at least a part of these aromatic rings Hydrogenated compounds; aliphatic cyclohexanediamine, methylenebis (cyclohexylamine), hexamethylenediamine. These diamines can be used in two or more kinds, and from the viewpoint of solubility in an alkaline developer, it is preferable to contain 60 mol% or more of residues of a diamine having a hydroxyl group.

R ³ and R ^{4 in the} general formula (31) each independently represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of the solubility of the alkaline developer and the stability of the solution of the positive radiation-sensitive composition 1, 10 to 90 mol% of each of R ³ and R ⁴ is preferably hydrogen. Furthermore, it is preferable that R ³ and R ⁴ each contain at least one or more monovalent hydrocarbon groups having 1 to 16 carbon atoms and the others are hydrogen atoms.

In addition, l and m in the general formula (31) represent the number of carboxyl or ester groups, and each independently represents an integer of 0 to 2. 1 or 2 is preferred. P and q in the general formula (31) each independently represent an integer of 0 to 4, and p + q> 0.

In a polymer having a structure represented by the general formula (31) as a main component, the number of structural units represented by the general formula (31) is preferably in a range of 10 to 100,000, and more preferably in a range of 15 to 1,000. It is better to be in the range of 20 ~ 100.

The number of structural units represented by the general formula (31) is measured by a gel permeation chromatography (GPC) method, a light scattering method, a small-angle X-ray scattering method, and the like. The sub-quantity can be easily calculated. When the molecular weight of the repeating unit is M and the mass average molecular weight of the polymer is Mm, the number of structural units represented by the general formula (31) = Mm / M. The number of structural units represented by the general formula (31) is a value calculated using GPC measurement, which is performed by the simplest polystyrene conversion.

In addition, for example, in order to improve adhesion to a substrate, an aliphatic group having a siloxane structure may be copolymerized within a range that does not reduce heat resistance. Specifically, the diamine component may be, for example, 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisilazane, bis (p-aminophenyl) octamethylpentasiloxane, etc. Copolymers obtained by copolymerization.

The content of other polymers in the positive-type radiation-sensitive composition 1 is not particularly limited as long as it is within a range that does not hinder the object of the present invention. In the positive radiation-sensitive composition 1, the content of other polymers is preferably 1 to 300 parts by mass, and more preferably 1 to 200 parts by mass, with respect to 100 parts by mass of the alkali-soluble resin.

[Other ingredients]

The positive radiation-sensitive composition 1 may contain various additives as required. Examples of the additives include sensitizers, hardening accelerators, fillers, adhesion promoters, antioxidants, anticoagulants, thermal polymerization inhibitors, defoamers, and surfactants.

<Modulation method of radiation-sensitive composition>

The radiation-sensitive composition of the present invention is prepared by mixing the above components with a stirrer. Furthermore, a membrane filter or the like can be used for filtering to make the modulated radiation composition uniform.

《Pattern manufacturing method》

The method for manufacturing a photoresist pattern of the present invention includes the following steps: a radiation-sensitive composition film forming step of forming a radiation-sensitive composition film composed of the radiation-sensitive composition of the present invention on a substrate; Selectively exposing the position of the radiation-sensitive composition film; and a developing step of developing the exposed radiation-sensitive composition film.

First, in the step of forming a radiation-sensitive composition film, for example, a coating device is used to coat the radiation-sensitive composition of the present invention on a substrate, and if necessary, the solvent is removed by drying to form a radiation-sensitive composition. Radial composition film, the coating device is: a roll coater, a reverse coater, a bar coater, and the like; a contact transfer type coating device; or a spinner (rotary coating device), a curtain coating Non-contact coating equipment such as cloth dispensers.

In addition, in the step of forming the radiation-sensitive composition film, the radiation-sensitive composition film (dry film) composed of the radiation-sensitive composition provided on the supporting film can also be adhered to the substrate to A radiation-sensitive composition film is formed on the substrate. The dry film can be formed by applying the radiation-sensitive composition described above to a supporting film by a conventional method and then drying it.

Then, in the exposure step, the radiation-sensitive composition film is irradiated with radiation such as ultraviolet rays and excimer laser light through a mask with a predetermined pattern, and then the position of the radiation-sensitive composition film is selectively exposed. For exposure, for example, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used. The exposure amount also varies depending on the composition of the radiation-sensitive composition, and is preferably about 10 to 600 mJ / cm ² , for example.

Then, in the developing step, the exposed radiation-sensitive composition film is developed with a developing solution to form a predetermined pattern. The developing method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developing solution include organic developing solutions such as monoethanolamine, diethanolamine, and triethanolamine; and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium.

[Example]

The following examples are given to illustrate the present invention in more detail, but the scope of the present invention is not limited by these examples.

<Material>

The detailed description of each component used in an Example and a comparative example is as follows.

‧Alkali soluble resin

Carboxy resin 1: 55% by mass of solid content (solvent: 3-methoxybutyl acetate, mass average molecular weight: 4,000)

Acrylic resin 1: An acrylic resin (mass average molecular weight: 10,000) having a structural unit represented by the following formula, which comprises methacrylic acid (MAA), tricyclodecyl methacrylate (TCDMA), and methacrylic acid. 2,3-Epoxycyclohexyl methyl ester (ECHM) and glycidyl methacrylate (GMA) were mixed with MAA / TCDMA / ECHM / GMA = 15/20/40/25 (mass ratio) and used a conventional method For addition polymerization

Acrylic resin 2: A mixture of benzyl methacrylate (BzMA) and methacrylic acid (MAA) at BzMA / MAA = 80/20 (mass ratio) and addition polymerization by a conventional method to obtain an acrylic resin (Mass average molecular weight 15,000)

‧Photopolymerizable monomer

Photopolymerizable monomer 1: Dipentaerythritol hexaacrylate (DPHA)

‧Photopolymerization initiator

Photopolymerization initiator 1: "NCI-831" (trade name, manufactured by ADEKA)

Photopolymerization initiator 2: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer

Photopolymerization initiator 3: "IRGACURE OXE01" (trade name, manufactured by BASF)

Photopolymerization initiator 4: "IRGACURE OXE02" (trade name, manufactured by BASF)

‧Colorant

Colorant 1: Carbon black "CF Black" (trade name, manufactured by Mikuni Pigment Co., Ltd., solid content 25%, solvent: 3-methoxybutyl acetate)

Colorant 2: A dispersant was used to disperse the black pigment Experimental Black 582 (trade name, manufactured by BASF) using a bead mill by a fixing method to Pigment dispersion liquid (solid content: 15% by mass, solvent: propylene glycol monomethyl ether acetate) prepared so that the average particle diameter of the pigment is 90 to 190 nm

Colorant 3: A dispersant and an acrylic resin 2 (ratio to the solid content of the pigment: 10% by mass) are used together, and R254 (CIPigment Red 254) / Y139 (CIPigment Yellow) is fixed by a bead mill using a fixing method. 139) (mixing mass ratio: 85/15) pigment dispersion liquid (solid content: 18% by mass, solvent: propylene glycol monomethyl ether acetate) prepared so that the average particle diameter of the pigment becomes 90 to 190 nm.

Colorant 4: From G36 (CIPigment Green 36) / Y150 (CIPigment Yellow 150) (mixing mass ratio: 70/30), proceed in the same manner as the coloring agent 3 so that the average particle diameter of the pigment becomes 90 to 190 nm. Pigment dispersion liquid (solid content: 18% by mass, solvent: propylene glycol monomethyl ether acetate)

Colorant 5: From B156 (CIPigment Blue 156) / V23 (CIPigment Violet 23) (mixing mass ratio: 90/10), proceed in the same manner as the coloring agent 3 so that the average particle diameter of the pigment becomes 90 to 190 nm. Pigment dispersion liquid (solid content: 15% by mass, solvent: propylene glycol monomethyl ether acetate)

‧Surface active agent

Surfactant 1: "Glanol 440" (trade name, Kyoeisha Chemical Co., Ltd.)

‧Compounds 1 to 4: Compounds represented by the following formulae (E1) to (E4), respectively

‧Other organic solvents

MBA: 3-methoxybutyl acetate

PGMEA: propylene glycol monomethyl ether acetate

EEP: ethyl 3-ethoxypropionate

EL: ethyl lactate

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

The carbazole resin 1 was synthesized according to the following formulation.

First, in a 500 mL four-necked flask, 235 g of a bisphenol fluorene epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, and 2,6-bis (tertiary butyl) -4-methyl were fed. 100 mg of phenol and 72.0 g of acrylic acid were sprayed into the air at a rate of 25 mL / minute while heating and dissolving at 90 to 100 ° C. Then, while the solution was kept cloudy, the temperature was gradually raised, and the solution was heated to 120 ° C to completely dissolve it. At this time, the solution gradually became transparent and viscous, but continued to be stirred in this state. The acid value was measured during stirring, and heating and stirring were continued until the acid value became 1.0 mgKOH / g. It takes 12 hours until the acid value reaches the target value. Of course Then, it cooled to room temperature, and obtained the colorless transparent and solid bisphenol fluorene type epoxy acrylate represented by the following structural formula (a-4).

Then, to 307.0 g of the above-mentioned bisphenol fluorene type epoxy acrylate, 600 g of 3-methoxybutyl acetate was added and dissolved, and 80.5 g of benzophenone tetracarboxylic dianhydride was mixed therein. And 1 g of tetraethylammonium bromide, the temperature was gradually raised, and the reaction was performed at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed therein, and the reaction was performed at 90 ° C. for 6 hours to obtain a carbaldehyde resin 1. The disappearance of the acid anhydride group was confirmed by infrared (IR) spectrum. This carbole resin 1 corresponds to a compound represented by the aforementioned general formula (a-1).

<Making transparent photoresist>

Mix the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, and the surfactant with the solvent of the composition shown in Table 2 in accordance with the composition and blending amount (unit: part by mass) described in Table 1. A negative-type radiation-sensitive composition having a solid content concentration of 20% by mass was prepared.

[foreign matter]

The negative radiation-sensitive composition was spin-coated on a glass substrate having a thickness of 680 nm × 880 mm × 0.7 mm, and the coating film was dried at 100 ° C. for 120 seconds to form a photosensitive resin layer having a thickness of 1.2 μm. Then, the photosensitive resin layer was exposed at an exposure amount of 100 mJ / cm ² . Then, an aqueous solution containing 0.04% by mass of KOH and 0.1% by mass of the surfactant EMULGEN A60 (manufactured by Kao) was used as a developing solution, and a shower was developed at 23 ° C. for 60 seconds, and then an automatic optical inspection device ( Takano) to calculate foreign objects in the obtained pattern. The results are shown in Table 2.

[Sensitivity]

The negative radiation-sensitive composition was spin-coated on a glass substrate having a thickness of 680 nm × 880 mm × 0.7 mm, and the coating film was dried at 100 ° C. for 120 seconds to form a photosensitive resin layer having a thickness of 1.2 μm. Then, using a mask of a line and a space pattern, the photosensitive resin layer is exposed at various exposure amounts. Then, 0.04% by mass of KOH and 0.1% by mass of a surfactant EMULGEN A60 (manufactured by Kao) were used as a developer, and spray development was performed at 23 ° C. for 60 seconds. The CD (Critical Dimension, critical dimension) of the obtained line pattern is determined as the exposure amount of the CD + 1 μm of the mask, and is evaluated on the basis of the following. The results are shown in Table 2.

○: less than 100mJ / cm ² ; △: 100 ~ 140mJ / cm ² ; ×: more than 140mJ / cm ²

[Precipitate]

After the negative-type radiation-sensitive composition was aged at -5 ° C for 2 weeks, it was spin-coated on a glass substrate of 10 cm square, the number of foreign matters precipitated was counted, and evaluation was performed based on the following criteria. The results are shown in Table 2.

○: 0 to 2; △: 3 to 10; ×: 11 or more

[Viscosity change]

After aging the negative radiation-sensitive composition at 40 ° C for 2 weeks, Measure the viscosity of the negative radiation-sensitive composition, and find the initial viscosity of 5 mPa. The amount of change in s change is evaluated on the basis of the following. The results are shown in Table 2.

○: The variation does not reach 0.5 mPa. s; △: change amount is 0.5 ~ 2mPa. s; ×: The amount of change exceeds 2mPa. s

[Uneven coating]

After the negative radiation-sensitive composition was spin-coated on a glass substrate having a thickness of 680 nm × 880 mm × 0.7 mm, and the coating film was dried at 100 ° C. for 120 seconds, it was visually confirmed whether pinhole unevenness or radiation unevenness occurred. Coating unevenness was evaluated by the following criteria. The results are shown in Table 2.

○: No uneven coating occurred; △: uneven coating occurred locally; ×: uneven coating occurred throughout the entire surface

[Table 2]

As can be seen from Table 2, since the negative radiation-sensitive composition of the example contains the compound represented by the general formula (1), it has excellent sensitivity, storage stability, and coating properties, and can be formed by exposure and development. By suppressing the generation of foreign objects.

On the other hand, the negative radiation-sensitive composition of the comparative example does not contain the compound represented by the general formula (1), and thus has poor sensitivity and storage stability, and also has poor coating properties depending on the solvent used. And / or when more foreign matter is generated in a pattern formed by exposure and development.

<Production of photoresist for black matrix, photoresist for color filter, and photoresist for black photo spacer>

The alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, colorant, and surfactant are shown in Tables 4 to 8 according to the composition and blending amount (unit: part by mass) described in Table 3. Mixed with a solvent (the blending amount of the colorant is converted by the solid content), and a negative-type sensor with a solid content concentration of 18% by mass is prepared. Ray composition.

The obtained negative radiation-sensitive composition was evaluated in the same manner as in the above-mentioned "Production of Transparent Photoresist", and then the foreign matter, sensitivity, viscosity change, and uneven coating were evaluated. The results are shown in Tables 4 to 8.

[Agglutinate]

After the negative radiation-sensitive composition was aged at 40 ° C for 2 weeks, it was spin-coated on a 10 cm square glass substrate, the number of aggregated foreign matter was counted, and evaluation was performed on the basis of the following criteria. The results are shown in Tables 4 to 8.

○: 0 to 2; △: 3 to 10; ×: 11 or more

In the top column of Table 3, BM indicates Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-4, and R indicates Examples 3-1 to 3-7 and Comparative Examples 3-1 to 3-4, G indicates Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-4, B indicates Examples 5-1 to 5-7 and Comparative Examples 5-1 to 5-4, and BPS indicates Examples 6-1 to 6-7 and Comparative Examples 6-1 to 6-4.

[TABLE 6]

[TABLE 8]

As can be seen from Tables 4 to 8, the negative-type radiation-sensitive composition of the examples contains the compound represented by the general formula (1), and has excellent sensitivity, storage stability, and coating properties. It is possible to form a pattern by suppressing the generation of foreign matter.

In contrast, the negative radiation-sensitive composition of the comparative example does not contain the compound represented by the general formula (1), and therefore has poor storage stability, and more foreign substances are generated in the pattern formed by exposure and development. In addition, depending on the solvent used, the coating properties may be poor. In addition, the negative radiation-sensitive composition of the comparative example had poor sensitivity because it contained a light-shielding agent as a colorant.

<Modulation of positive radiation-sensitive composition>

2 g of an esterification reaction product obtained from 1 mol of 2,4,4,4'-tetrahydroxybenzophenone and 3 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride and cresol novolac 8 g of the varnish resin was dissolved in 40 g of the solvent having the composition shown in Table 1 to prepare a positive radiation-sensitive composition. The positive-type radiation-sensitive composition thus obtained was subjected to the following evaluation tests.

[With or without precipitates]

A 0.2 μm membrane filter was used to filter the prepared positive radiation-sensitive composition, and the filtered positive radiation-sensitive composition was allowed to stand at 40 ° C, and the investigation was performed at a time point of 2 months. The presence or absence of precipitates in the positive radiation-sensitive composition. The results are shown in Table 9.

[Sensitivity change]

The sensitivity of the positive radiation-sensitive composition after 3 months was investigated. In other words, the minimum exposure amount (sensitivity) when a positively-modulated positive radiation-sensitive composition is applied to a substrate and dried, and the positive-radiation-sensitive composition after 3 months of modulation After comparing the minimum exposure (sensitivity) when applied to a substrate and drying it, the case where there is no change at all was set to "○", and the case where the sensitivity was decreased was set to "x". The results are shown in Table 9.

[Section shape]

The prepared positive radiation-sensitive composition slit was coated on a glass substrate, and dried on a hot plate at 90 ° C. for 90 seconds to form a photoresist film having a film thickness of 1.3 μm. After using a stepper to expose this photoresist film through a predetermined mask, it was heated at 110 ° C. for 90 seconds on a hot plate, and then, a 2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAH) was used. After development, washing with water, and drying for 30 seconds, the cross-sectional shape of the obtained photoresist pattern was observed, and evaluation was performed based on the following criteria. The results are shown in Table 9. In addition, the undercut refers to a case where the width of the lowermost portion of the photoresist pattern in contact with the glass substrate becomes narrower than the width of the uppermost portion of the photoresist pattern in the cross-section of the photoresist pattern.

○: No undercut occurred at the contact portion between the glass substrate and the photoresist pattern.

×: Undercut occurs at the contact portion between the glass substrate and the photoresist pattern.

[Coated state]

The prepared positive radiation-sensitive composition slit was coated on a glass substrate and dried on a hot plate at 90 ° C for 90 seconds, and then the film thickness was measured, and the case where the coating was uniformly applied on the surface was set to " "Good", and the case where no uniform coating was applied on the surface was set as "bad". The results are shown in Table 9.

As can be seen from Table 9, the positive-type radiation-sensitive composition of the example was excellent in storage stability, developability, and coatability because it contained the compound represented by the general formula (1).

In contrast, the positive radiation-sensitive composition of the comparative example does not contain the compound represented by the general formula (1), and therefore has poor storage stability, developability, and coatability.

<Preparation of Polyamine-containing Negative Radiation Resin Composition>

In a separable 5L capacity flask equipped with a stirrer, a stirring wing, a reflux condenser, and a nitrogen introduction tube, put 654.4 g of tetracarboxylic dianhydride, namely pyromellitic dianhydride (PMDA), and diamine 4, 4'-Diaminodiphenyl ether (ODA) A solvent of 672.8 g and the composition shown in Table 10. Nitrogen was introduced into the flask from a nitrogen introduction tube, and the inside of the flask was set to a nitrogen atmosphere. Then, while stirring the contents of the flask, the tetracarboxylic dianhydride and the diamine were reacted at 50 ° C for 20 hours to obtain a polyamic acid solution. To the obtained polyamic acid solution, 278 g of a photosensitive component "IRGACURE OXE02" (trade name, manufactured by BASF, oxime ester compound) was added and stirred to prepare a negative-type radiation-sensitive resin composition having a solid content of 30% by mass.

About the obtained negative radiation-sensitive resin composition, it carried out similarly to "the manufacture of a transparent photoresist," and then evaluated foreign matter, a viscosity change, and uneven coating. The results are shown in Table 10.

As can be seen from Table 10, the negative-type radiation-sensitive resin composition of the example contains the compound represented by the general formula (1), and has excellent storage stability and coating properties, and can be formed by exposure and development. A pattern that suppresses foreign objects.

In contrast, the negative-type radiation-sensitive resin composition of the comparative example does not contain the compound represented by the general formula (1), and has poor storage stability and coating properties, and has a pattern formed by exposure and development. More foreign bodies are generated.

<Containing polybenzo Modulation of Nazole Precursor Negative Radiation Resin Composition>

In a conical flask equipped with a rotor, 2 mmol of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and a solvent having a composition shown in Table 11 were added. After 1 mL, use a magnetic stirrer to stir the contents of the flask for 5 minutes. Then, 2 mmol of isophthalaldehyde, which is a dicarbonyl compound, was added to the flask, and the contents of the flask were refluxed for 3 hours in a nitrogen atmosphere to perform a reaction. Then, the reaction liquid was dehydrated by distillation under reduced pressure to obtain polybenzo Azole precursor solution.

Polybenzo To the azole precursor solution, 0.5 mmol of a photosensitive component "IRGACURE OXE02" (trade name, manufactured by BASF, oxime ester compound) was added and stirred to prepare a negative-type radiation-sensitive resin composition having a solid content of 30% by mass.

About the obtained negative radiation-sensitive resin composition, it carried out similarly to "the manufacture of a transparent photoresist," and then evaluated foreign matter, a viscosity change, and uneven coating. The results are shown in Table 11.

As can be seen from Table 11, since the negative radiation-sensitive resin composition of the example contains the compound represented by the general formula (1), it has excellent storage stability and coating properties, and can be formed by exposure and development. A pattern that suppresses foreign objects.

In contrast, the negative-type radiation-sensitive resin composition of the comparative example does not contain the compound represented by the general formula (1), and has poor storage stability and coating properties, and has a pattern formed by exposure and development. More foreign bodies are generated.

<Preparation of polyamine-containing positive radiation-sensitive resin composition 1> [Synthesis of hydroxy acid anhydride (a)]

Under a nitrogen gas stream, 18.2 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and 34.2 g (0.3 mol) of allyl epoxypropyl ether were used. Dissolved in 100g of GBL and cooled to -10 ° C. 22.1 g (0.11 mol) of trimellityl chloride dissolved in 50 g of GBL was added dropwise thereto. At this time, the dropping rate was adjusted so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropping, the mixture was stirred at 0 ° C for 5 hours. After concentrating this solution using a rotary evaporator, this solution was poured into 1 L of toluene to obtain a hydroxy-containing acid anhydride (a) represented by the following formula.

[Synthesis of Polymer A]

In a nitrogen gas stream, 4.40 g (0.022 mol) of 4,4'-diaminodiphenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisilazane were made. ) Dissolved in 50 g of NMP. 21.4 g (0.030 mol) of the hydroxy acid anhydride (a) obtained in the above [Synthesis of the hydroxy acid anhydride (a)] was added thereto, and the reaction was performed at 20 ° C for 1 hour, and then, the reaction was performed at 40 ° C. Reaction for 2 hours. Then, 0.65 g (0.006 mol) of 4-aminophenol was added, and it was made to react at 40 degreeC for 45 minutes. Then, it took 10 minutes to drop in a solution obtained by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethyl acetal with 5 g of NMP. After the dropwise addition, the mixture was stirred at 40 ° C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. A 45 ° C. vacuum dryer was used to dry the polymer solids for 80 hours, and a polyfluorene imine precursor, that is, polymer A was obtained. After the mass average molecular weight of the polymer A was measured by GPC, it was confirmed that the number of the structural units represented by the general formula (31) was in the range of 10 to 500.

[Synthesis of Novolac Resin A]

In a nitrogen gas stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g (37% by weight of formaldehyde aqueous solution) (0.93 mol of formaldehyde), and 0.63 g of oxalic acid dihydrate were fed into the flask. (0.005 mol), 264 g of methyl isobutyl ketone, and then immersed in an oil bath, and while the reaction solution was refluxed, a polycondensation reaction was performed for 4 hours. Then, it took 3 hours to raise the temperature of the oil bath. Then, the inside of the flask was decompressed to remove volatiles, and the dissolved resin was cooled to room temperature to obtain a polymer solid of novolac resin A. The mass average molecular weight of the novolak resin A measured by GPC was 4,000.

[Composition of composition]

6 g of polymer A solid, 4 g of novolak resin A, 2 g of quinonediazide compound A shown by the following formula, 6.0 g of HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and BIR- 1 g of PC (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.) and 0.3 g of vinyltrimethoxysilane, and these were dissolved in a solvent having a composition shown in Table 12 to obtain a solid content concentration of 30% by mass. Positive radiation-sensitive resin composition.

About the obtained positive-type radiation-sensitive resin composition, it carried out similarly to "the manufacture of a transparent photoresist," and then evaluated foreign matter, a viscosity change, and uneven coating. The results are shown in Table 12.

[In the above formula, D is H or 1,2-naphthoquinonediazide-5-sulfonyl group, and the average esterification rate of 1,2-naphthoquinonediazide-5-sulfonyl group in D 59.9%; Furthermore, since the number of substitutions and the substitution position of D may vary depending on the molecule, as described above, D is the average ratio of 1,2-naphthoquinonediazide-5-sulfonyl (average Esterification rate (%)); the same applies hereinafter].

As can be seen from Table 12, the positive-type radiation-sensitive resin composition of the example contains the compound represented by the general formula (1), and has excellent storage stability and coating properties, and can be formed by exposure and development. A pattern that suppresses foreign objects.

In contrast, the positive-type radiation-sensitive resin composition of the comparative example does not contain the compound represented by the general formula (1), and has poor storage stability and coating properties, and is formed in a pattern formed by exposure and development. More foreign bodies are generated.

<Preparation of Polyamine-containing Positive Radiation Resin Composition 2>

Measure 6 g of polymer A solid, 4 g of novolac resin A, 2 g of quinonediazide compound B shown by the following formula, and HMOM-TPHAP (trade name, this 6.0 g by Chuju Chemical Industry Co., Ltd., 1 g of BIR-PC (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), 0.3 g of vinyltrimethoxysilane, and these were dissolved in the composition shown in Table 13. In a solvent, a positive-type radiation-sensitive resin composition having a solid content concentration of 30% by mass was obtained. The polymer A and the novolak resin A are those obtained in "Preparation 1 of a polyamine-containing positive-type radiation-sensitive resin composition".

About the obtained positive-type radiation-sensitive resin composition, it carried out similarly to "the manufacture of a transparent photoresist," and then evaluated foreign matter, a viscosity change, and uneven coating. The results are shown in Table 13.

[In the above formula, D is H or 1,2-naphthoquinonediazide-5-sulfonyl group, and the average esterification rate of 1,2-naphthoquinonediazide-5-sulfonyl group in D Is 54.7%].

As can be seen from Table 13, the positive-type radiation-sensitive resin composition of the example contains a compound represented by the above-mentioned general formula (1), and therefore has storage stability and coating properties. It has excellent properties, and can form a pattern by suppressing the generation of foreign matter by exposure and development.

In contrast, the positive-type radiation-sensitive resin composition of the comparative example does not contain the compound represented by the general formula (1), and has poor storage stability and coating properties, and is formed in a pattern formed by exposure and development. More foreign bodies are generated.

Claims (5)

A radiation-sensitive composition containing a compound represented by the following general formula (1): In the formula, R ¹ represents a hydrogen atom, R ² and R ³ independently represent a hydrogen atom or a C ₁ to C ₃ alkyl group, and R ⁴ and R ⁵ independently represent a C ₁ to C ₃ alkyl group; The composition contains at least one of the compound represented by the general formula (1) as a solvent, the compound represented by the general formula (1) is at least one compound represented by each formula below, and the radiation-sensitive composition further With or without an organic solvent other than the compound represented by the general formula (1), the mass ratio of the compound represented by the general formula (1) to the organic solvent is 5:95 to 100: 0, and the radiation-sensitive composition No colorants; The radiation-sensitive composition according to claim 1, wherein the compound represented by the general formula (1) is at least one compound represented by each formula of the following formulae (E1) to (E4): A radiation-sensitive composition comprising a compound represented by the following general formula (1) and a coloring agent: In the formula, R ¹ represents a hydrogen atom, R ² and R ³ independently represent a hydrogen atom or a C ₁ to C ₃ alkyl group, and R ⁴ and R ⁵ independently represent a C ₁ to C ₃ alkyl group; The composition contains at least one of the compound represented by the general formula (1) as a solvent, the compound represented by the general formula (1) is at least one compound represented by each formula below, and the radiation-sensitive composition further With or without organic solvents other than the compound represented by the general formula (1), the mass ratio of the compound represented by the general formula (1) to the organic solvent is 5:95 to 100: 0; The radiation-sensitive composition according to claim 3, wherein the compound represented by the general formula (1) is at least one compound represented by each of the following formulae (E1) to (E3): . A pattern manufacturing method including the following steps: a radiation-sensitive composition film forming step of forming a radiation-sensitive composition composed of the radiation-sensitive composition according to any one of claims 1 to 4 on a substrate A composition film; an exposure step that selectively exposes the position of the radiation-sensitive composition film; and a development step that develops the exposed radiation-sensitive composition film.