KR20170136653A - Radiation sensitive composition and pattern forming method - Google Patents

Abstract

A radiation-sensitive composition which is excellent in sensitivity, storage stability, coating property, developability, and safety and can form a pattern in which the generation of foreign matter is suppressed by exposure and development, and a method for producing a pattern using the same.
The radiation sensitive composition according to the present invention contains a compound represented by the following general formula (1). Wherein, R ¹ is a hydrogen atom or a hydroxyl group, R ² and R ³ are, independently represents a hydrogen atom or an alkyl group of C ₁ ~ C _3, R ⁴ and R ⁵ are, independently, C ₁ ~ C ₃ alkyl group.

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation sensitive composition,

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

In the production of integrated circuits, color filters, liquid crystal devices and the like, microfabrication is required, but in order to satisfy this demand, a radiation-sensitive composition has been conventionally used. Generally, the radiation sensitive composition has a positive type and a negative type, and usually, any of them is dissolved in a solvent and used in a solution state.

The radiation sensitive composition is applied onto a substrate such as a silicon substrate or a glass substrate by a known coating method such as a spin coat, a roller coat, a slit coat, or an ink jet, and then prebaked to form a radiation sensitive composition film. Exposure is performed by a particle beam of ultraviolet rays, deep ultraviolet rays, X-rays, electron beams, or the like depending on the photosensitive wavelength range of the afterimage radiation composition, and then dry etching is performed as required to form a desired pattern.

As the solvent used in the radiation-sensitive composition, various ones have been conventionally used and are selected and used in consideration of solubility, coating ability, sensitivity, developability, pattern characteristics to be formed, and the like. For example, ethylene glycol monoethyl ether acetate has been known as a solvent excellent in properties such as solubility, coating properties, and radiation-sensitive composition film forming characteristics. Recently, however, there has been pointed out the problem of safety against human body, There is a demand for a solvent which is excellent in resin solubility and initiator solubility and has improved performance such as film forming property of a radiation-sensitive composition.

As a solution therefor, propylene glycol monomethyl ether acetate or the like has been proposed as a solvent instead of ethylene glycol monoethyl ether acetate (for example, Patent Document 1).

Japanese Patent Publication No. 3-1659

However, the conventional radiation-sensitive compositions using these solvents, which are considered to have higher safety than ethylene glycol monoethyl ether acetate, are insufficient in sensitivity, storage stability, coating ability, or developability, There is a problem that foreign matter is likely to be generated in a pattern obtained by exposure and development.

The present invention has been made in view of the above circumstances and has an object of providing a photosensitive composition which is excellent in sensitivity, storage stability, coating property, developability and safety, and capable of forming a pattern in which the generation of foreign matter is suppressed by exposure and development It is another object of the present invention to provide a radiation-sensitive composition and a method for producing a pattern using the same.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, they have found out what can solve the above problems by using a specific organic solvent, and have completed the present invention. Specifically, the present invention provides the following.

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

[Chemical Formula 1]

(Wherein R ¹ represents a hydrogen atom or a hydroxyl group, R ² and R ³ independently represent a hydrogen atom or a C ₁ -C ₃ alkyl group, R ⁴ and R ⁵ independently represent C ₁ To C < ₃ >).

A second aspect of the present invention is a method for manufacturing a radiation sensitive composition, comprising the steps of: forming a radiation sensitive composition film on a substrate, the radiation sensitive composition film comprising the radiation sensitive composition; an exposure process for selectively exposing the radiation sensitive composition film; And a developing step of developing the film of the radiation sensitive composition.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a radiation-sensitive composition which is excellent in sensitivity, storage stability, coating property, developability, and safety and can form a pattern in which the generation of foreign matter is suppressed by exposure and development, Can be provided.

&Quot; Radiation-sensitive composition "

The radiation sensitive composition according to the present invention contains at least the compound represented by the above general formula (1). The compound represented by the above general formula (1) is used as a solvent in the radiation-sensitive composition according to the present invention. The radiation sensitive composition according to the present invention may contain only the compound represented by the general formula (1) as a solvent, and may contain an organic solvent other than the compound represented by the general formula (1) (hereinafter also referred to as " other organic solvent " ) May be further contained. That is, the radiation sensitive composition according to the present invention contains the compound represented by the above general formula (1) as at least one kind of solvent. The compound represented by the above general formula (1) is a component other than a solvent (hereinafter referred to as " base component ") in the form of a mixed solvent with other organic solvents in the radiation sensitive composition according to the present invention. ) Is used as a solvent for dissolving and / or dispersing. Since the radiation sensitive composition according to the present invention contains the compound represented by the above general formula (1), it is excellent in sensitivity, storage stability, coatability, developability and safety, and suppresses generation of foreign matter by exposure and development Can be formed. The radiation sensitive composition according to the present invention can be suitably used for the production of, for example, a black matrix, a color filter, a black photo spacer, an integrated circuit, a liquid crystal device and the like.

[Compound represented by the general formula (1)

The compound represented by the general formula (1) is a solvent capable of satisfactorily dissolving and / or dispersing a base component contained in the radiation-sensitive composition, and can be widely used in the radiation sensitive composition in general. In particular, when the radiation sensitive composition comprises a oxime-based photopolymerization initiator, the compound represented by the general formula (1) has good solubility of the oxime-based photopolymerization initiator. The compounds represented by the above general formula (1) may be used alone or in combination of two or more.

In the in the general formula (1), the alkyl group of R ² or R ³ C alkyl group of ₁ ~ C ₃ shown by a, and R ^4, or C ₁ ~ C ₃ represented by R ⁵ is a methyl group, an ethyl group, a propyl group , And isopropyl group.

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

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

(2)

Among the compounds represented by the above general formula (1), preferred examples are the compounds 1 to 4 used in the examples, and the compound 1, that is, the compound represented by the following formula (E1) is particularly preferable. The compound represented by the following formula (E1) is not designated as a highly toxic substance (SVHC) and is low in toxicity, so that the safety is particularly high.

(3)

In the radiation sensitive composition according to the present invention, the content of the solvent is preferably such that the solid concentration of the radiation sensitive composition is from 1 to 50 mass%, more preferably from 5 to 30 mass%. In the solvent contained in the radiation sensitive composition according to the present invention, the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0, More preferably 100: 0. When the content of the solvent and the mass ratio of the compound represented by the general formula (1) to the other organic solvent are in the above ranges, the resulting radiation sensitive composition tends to have excellent sensitivity, storage stability, coatability, developability and safety , The pattern formed by exposure and development of the radiation sensitive composition tends to be inhibited from the generation of foreign matter. Other organic solvents will be described later.

≪ Example of radiation sensitive composition >

The radiation sensitive composition according to the present invention may be either a negative type or a positive type. As the negative-tone radiation-sensitive composition, a negative-tone radiation-sensitive composition containing a compound represented by the general formula (1) and an alkali-soluble resin; A radiation-sensitive polyimide precursor composition containing a photosensitive component such as a compound represented by the general formula (1), a polyamic acid, a photo-base generator, and a photo-acid generator; A radiation-sensitive polybenzoxazole precursor composition containing a photosensitive component such as a compound represented by the general formula (1), a polybenzoxazole precursor, a photo-base generator, and a photo-acid generator; And a radiation-sensitive SOG (spin-on glass) composition containing the compound represented by the above general formula (1). As the positive-tone radiation-sensitive composition, a positive-tone radiation-sensitive composition containing the compound represented by the general formula (1), an alkali-soluble resin, and a quinonediazide group-containing compound; A radiation sensitive polyimide composition containing a photosensitive component such as a compound represented by the general formula (1), a polyimide resin, a photo base generator, and a photo acid generator; A chemically amplified positive radiation-sensitive composition containing a resin represented by the above general formula (1), a resin having an increased solubility in alkali by the action of an acid and a photoacid generator, and the like. The negative radiation-sensitive composition (hereinafter referred to as " negative-tone radiation-sensitive composition 1 ") containing the compound represented by the general formula (1) and an alkali- A radiation-sensitive polyimide precursor composition (hereinafter referred to as " negative radiation-sensitive composition 2 ") containing a photosensitive component such as a compound represented by the general formula (1) and a polyamic acid and a photo- ), A radiation-sensitive polybenzoxazole precursor composition containing a photosensitive component such as a compound represented by the general formula (1), a polybenzoxazole precursor, a photo-base generator, and a photo-acid generator (hereinafter, (Hereinafter, referred to as "radiation-sensitive composition 3"), and a positive-type radiation-sensitive resin composition containing a compound represented by the above general formula (1), an alkali-soluble resin and a quinonediazide- The detailed description of the radiation-sensitive composition (hereinafter referred to as "positive-tone radiation-sensitive composition 1").

≪ Negative radiation sensitive composition 1 >

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

[Compound represented by the general formula (1)

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

[Alkali-soluble resin]

The alkali-soluble resin is a resin film having a thickness of 1 占 퐉 formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass% and immersed in a KOH aqueous solution with a concentration of 0.05 mass% Means that the film has a thickness of not less than 0.01 탆.

The alkali-soluble resin is not particularly limited as long as it is the above-described alkali-soluble resin, and conventionally known alkali-soluble resins can be used. The alkali-soluble resins may 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. The resin having (A1) cardo structure is not particularly limited, and conventionally known resins can be used. Among them, a resin represented by the following formula (a-1) is preferable.

[Chemical Formula 4]

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

[Chemical Formula 5]

In the formula (a2), R ^a1 is, each independently represents a hydrocarbon group, or a halogen atom, a hydrogen atom, a carbon number of 1 ~ 6, R ^a2 are each independently a hydrogen atom or a methyl group, W is ^a , A single bond or a group represented by the following formula (a-3).

[Chemical Formula 6]

In the formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, methylendomethylenetetrahydrophthalic anhydride, anhydrous chlorodic acid, Phthalic acid, and anhydrous glutaric acid.

In the above formula (a-1), Z ^a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, and biphenyl ether tetracarboxylic acid dianhydride.

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

The mass average molecular weight of the resin having (A1) cardo structure is preferably 1000 to 40000, and more preferably 2000 to 30,000. Within the above range, sufficient heat resistance and film strength can be obtained while obtaining good developing properties. In the present specification, the mass average molecular weight refers to a value calculated by polystyrene conversion measured by gel permeation chromatography (GPC).

Another example of the preferable alkali-soluble resin is (A2) epoxy resin. (A2) The epoxy resin is not particularly limited, and conventionally known epoxy resins may be used, and those having no ethylenic unsaturated group may be used, and those having an ethylenic unsaturated group may also be used.

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

Examples of the unsaturated carboxylic acid 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; Anhydrides of these dicarboxylic acids; And the like. Of these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the resin to be obtained, ease of obtaining water, and the like. These unsaturated carboxylic acids may be used alone or in combination of two or more.

In the present specification, "(meth) acrylic acid" means both of acrylic acid and methacrylic acid.

The proportion of the constituent unit derived from unsaturated carboxylic acid (constituent unit having a carboxyl group) in the resin (A2-1) is preferably 5 to 29% by mass, more preferably 10 to 25% by mass. Within the above range, the developability of the negative-tone radiation-sensitive composition 1 can be made appropriate.

The epoxy group-containing unsaturated compound may have no alicyclic epoxy group, may have an alicyclic epoxy group, and more preferably have an alicyclic epoxy group.

Examples of the epoxy group-containing unsaturated compound having no alicyclic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) (Meth) acrylic acid epoxy alkyl esters such as epoxy heptyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate; ? -alkylacrylic acid epoxyalkyl esters such as glycidyl? -ethyl acrylate, glycidyl? -n-propyl acrylate, glycidyl? -n-butyl acrylate, and 6,7-epoxyheptyl? -ethylacrylate; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; And the like. Of these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o -Vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether are preferable.

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

Specifically, examples of the epoxy group-containing unsaturated compound having an alicyclic epoxy group include compounds represented by the following formulas (a4-1) to (a4-16). Among them, a compound represented by the following formulas (a4-1) to (a4-6) is preferable in order to make the developability of the negative-tone radiation-sensitive composition 1 appropriate, and the following formulas (a4-1) to 4) is more preferable.

(7)

[Chemical Formula 8]

[Chemical Formula 9]

Wherein R ^a3 is a hydrogen atom or a methyl group, R ^a4 is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a5 is a divalent hydrocarbon group having 1 to 10 carbon atoms, n is 0 to 10 Represents an integer. As R ^a4 , a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group is preferable. Examples of R ^a5 include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH ₂ -Ph-CH ₂ - And Ph represents a phenylene group).

These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

The proportion of the constituent unit derived from an epoxy group-containing unsaturated compound (constituent 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 thickness to the above range, it becomes easy to form a pattern of a good shape.

It is preferable that the resin (A2-1) is further copolymerized with an unsaturated alicyclic compound.

The alicyclic group of the alicyclic group-containing unsaturated compound may be singly or in combination. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the alicyclic group of the heterocyclic ring include adamantyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group and tetracyclododecyl group.

Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the following formulas (a5-1) to (a5-8). Among these, compounds represented by the following formulas (a5-3) to (a5-8) are preferable, and the following formulas (a5-3) and (a5- 4) is more preferable.

[Chemical formula 10]

(11)

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. In the formula, R ^a6 represents a hydrogen atom or a methyl group; As R ^a7 , a single bond, a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group and a hexamethylene group is preferable. As R ^a8 , for example, methyl group and ethyl group are preferable.

The proportion of the constituent unit 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.

Further, the resin (A2-1) may be obtained by further copolymerizing a compound other than the above. Examples of such other compounds include (meth) acrylate esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters and styrenes. These compounds may be used alone or in combination of two or more.

Examples of the (meth) acrylic esters include linear (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate and t- Or branched alkyl (meth) acrylates; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Furfuryl (meth) acrylate; And the like.

Examples of the (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (Meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide and N-hydroxyethyl-N-methyl (meth) acrylamide.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; Allyloxyethanol; And the like.

Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chlorethyl vinyl ether, 1-methyl-2,2- Vinyl ethers such as vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl Alkyl vinyl ethers such as ethers; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; And the like.

The vinyl esters include vinyl butyrate, vinyl isobutylate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloracetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate , Vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl-beta-phenylbutylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Examples of the styrenes include styrene; And examples thereof include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, , And acetoxymethylstyrene; Alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; But are not limited to, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo- Styrene, and 4-fluoro-3-trifluoromethylstyrene; And the like.

The mass average molecular weight of the resin (A2-1) is preferably from 2,000 to 50,000, and more preferably from 5,000 to 30,000. Within the above range, there is a tendency to balance the film forming ability and developability of the negative-tone radiation-sensitive composition 1.

Examples of the epoxy resin having an ethylenic unsaturated group include resins (A2-2) obtained by reacting a carboxyl group of a resin obtained by at least polymerization of an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound with an epoxy group of an epoxy group-containing unsaturated compound, (A2-3) obtained by reacting an epoxy group of a resin obtained by at least polymerization of an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound with a carboxyl group of an unsaturated carboxylic acid can be used.

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

The proportion of the constituent unit derived from unsaturated carboxylic acid (constituent unit having a carboxyl group) in the resin (A2-2) or (A2-3) is preferably 5 to 60 mass%, more preferably 10 to 40 mass% Is more preferable. Within the above range, the developability of the negative-tone radiation-sensitive composition 1 can be made appropriate.

The proportion of the constituent unit derived from an epoxy group-containing unsaturated compound (constituent unit having an epoxy group) in the resin (A2-2) or (A2-3) is preferably 5 to 90% by mass, more preferably 15 to 75% % Is more preferable. By setting the thickness to the above range, it becomes easy to form a pattern of a good shape.

The mass average molecular weights of the resins (A2-2) and (A2-3) are preferably from 2,000 to 50,000, and more preferably from 5,000 to 30,000. Within the above range, there is a tendency to balance the film forming ability and developability of the negative-tone radiation-sensitive composition 1.

Examples of the (A2) epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol or cresol novolak epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, (Meth) acrylate obtained by reacting an epoxy group of an epoxy resin such as polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, amine epoxy resin or dihydroxybenzene type epoxy resin with (meth) acrylic acid, Resin or the like may be used.

The content of the alkali-soluble resin is preferably 5 to 90% by mass, more preferably 10 to 85% by mass, based on the solid content of the negative-tone radiation-sensitive composition 1. Within the above range, there is a tendency to balance the film forming ability and developability of the negative-tone radiation-sensitive composition 1.

[Photopolymerizable monomer]

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

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl 2-phenoxy-2-hydroxypropyl (meth) (Meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate and half . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin (meth) acrylate, trimethylolpropane tri (meth) (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (Meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene di (Meth) acrylamide, (meth) acrylamide methylene ether, a condensation product of a polyhydric alcohol and N-methylol (meth) acrylamide, and the like, as well as a reaction product of isocyanate and 2-hydroxyethylMeona furnace, and the like can be triacrylate formal. These polyfunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable monomer is preferably 1 to 45% by mass, more preferably 5 to 40% by mass, based on the solid content of the negative-tone radiation sensitive composition 1. When the concentration is in the above range, a balance between sensitivity, developability and resolution tends to be easily obtained.

[Photopolymerization initiator]

The photopolymerization initiator is not particularly limited, and conventionally known photopolymerization initiators can be used. The photopolymerization initiators may be used alone or in combination of two or more.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- 2-methylpropane-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl- Dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino- Benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, Oxanthanone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4- But are not limited to, propoxytitanium oxide, propoxytitanium oxide, propoxytitanium oxide, propoxytoxanthanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, Anthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidal, 2- mercaptobenzooxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole (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'-bisdimethylamino Benzophenone (i.e., Michler's ketone), 4,4'-bisdiethylaminobenzophenone (i.e., ethyl Michler's ketone), 4,4'-dichlorobenzo Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin isobutyl ether, Benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p- Butyl dichloroacetophenone, p-tert-butyldichloroacetophenone,?,? -Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2- (9-acridinyl) heptane, 1,5-bis- (9-methoxybenzyl) heptane, isopropyl thioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, -Acryidinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -4,6-bis ( (Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6 (Trichloromethyl) -s-triazine, 2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis 4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) Bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4- methoxy) (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis- trichloromethyl-6- Ajin, "IRGACURE OXE02", "IRGACU (Trade name, manufactured by BASF) and "NCI-831" (trade name, manufactured by ADEKA) can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

Among them, it is particularly preferable to use a oxime-based photopolymerization initiator in terms of sensitivity.

A preferable example of the oxime-based photopolymerization initiator is a photopolymerization initiator represented by the following formula (c-1).

[Chemical Formula 12]

In the formula (c-1), R ^c1 represents a heterocyclic group, a condensed ring aromatic group or an aromatic group which may have a substituent. R ^c2 to R ^c4 each independently represent a monovalent organic group.

The heterocyclic group in R ^c1 includes a heterocyclic group having 5 or more rings, preferably a 5-membered ring or a 6-membered ring including at least one atom of a nitrogen atom, a sulfur atom and an oxygen atom. Examples of the heterocyclic group include a nitrogen-containing five-membered ring group such as a pyrrolyl group, an imidazolyl group, and a pyrazolyl group; A nitrogen-containing 6-membered ring group such as a pyridyl group, a pyrazinyl group, a pyrimidyl group, and a pyridazinyl group; A nitrogen-containing heterocyclic group such as a thiazolyl group or an isothiazolyl group; A nitrogen-containing oxygen group such as an oxazolyl group and an isoxazolyl group; Thienyl group, and thiopyranyl group; An impurity group such as a furyl group and a pyranyl group; And the like. Among them, it is preferable to include one nitrogen atom or sulfur atom. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group and the like.

^Examples of the condensed ring aromatic group in R ^c1 include a naphthyl group, an anthryl group, and a phenanthryl group. As the aromatic group in R ^c1 , a phenyl group can be exemplified.

The heterocyclic group, the condensed ring aromatic group, or the aromatic group may have a substituent. Particularly, when R ^c1 is an aromatic group, it preferably has 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 with a halogen atom, or may be interrupted by an ether bond, a thioether bond or an ester bond. The alkyl group in R ^c5 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group.

R ^c6 and R ^c7 each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, which may be substituted with a halogen atom, and the alkylene moiety of the alkyl group and the alkoxy group may be an ether bond, a thioether bond, As shown in Fig. R ^c6 and R ^c7 may combine to form a ring structure. The alkyl group or alkoxy group in R ^c6 and R ^c7 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, And a width period.

The ring structure that R ^c6 and R ^c7 can combine to form may be a heterocyclic ring. As the heterocyclic ring, there can be mentioned a heterocyclic ring of at least 5 atomic ring including nitrogen atom, preferably 5 to 7 atomic ring. The heterocyclic ring may contain a condensed ring. Examples of heterocyclic rings include piperidine rings, morpholine rings, thiomorpholine rings and the like. Among them, a morpholine ring is preferable.

R ^c8 represents an alkyl group in which a part or all of the hydrogen atoms may be substituted with a halogen atom. The alkyl group in R ^c8 preferably has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^c9 and R ^c10 each independently represent an alkyl group, which may be substituted with a halogen atom, or may be interrupted by an ether bond, a thioether bond or an ester bond. The preferred number of carbon atoms and the specific examples thereof are the same as those of R ^c1 .

Among these, preferred examples of R ^c1 include a pyrrolyl group, a pyridyl group, a thienyl group, a thiopyraryl group, a benzothienyl group, a naphthyl group, and a phenyl group having a substituent group.

In the above formula (c-1), R ^c2 represents a monovalent organic group. The organic group is preferably a group represented by -R ^c11 , -OR ^c11 , -COR ^c11 , -SR ^c11 or -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, which may be substituted with a halogen atom, an alkyl group or a heterocyclic group, The lene moiety may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. R ^c11 and R ^c12 may combine with each other to form a ring structure together with the nitrogen atom.

The alkyl group for R ^c11 and R ^c12 preferably has 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- , n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, And straight-chain or branched-chain groups such as an actual group. The alkyl group may have a substituent. Examples of the substituent group include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

The alkenyl group for R ^c11 and R ^c12 preferably has 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the alkenyl group include a linear or branched chain group such as a vinyl group, an allyl group, a butenyl group, an ethenyl group, and a propynyl group. The alkenyl group may have a substituent. Examples of the group having a substituent include a 2- (benzoxazol-2-yl) ethenyl group and the like.

The aryl group for R ^c11 and R ^c12 preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

The aralkyl group in ^Rc11 and ^Rc12 preferably has 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include benzyl group,? -Methylbenzyl group,?,? - dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

The heterocyclic group for R ^c11 and R ^c12 includes a heterocyclic group having 5 or more atoms, preferably 5 to 7 atoms, including at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom . The heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include a pyrrolyl group, a pyridyl group, a pyrimidyl group, a furyl group, and a thienyl group.

In these R ^c11 and R ^c12 , the alkyl group and the alkylene moiety of the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond.

As the ring structure that R ^c11 and R ^c12 can combine to form, there can be mentioned a heterocyclic ring. As the heterocyclic ring, there can be mentioned a heterocyclic ring of at least 5 atomic ring including nitrogen atom, preferably 5 to 7 atomic ring. The heterocyclic ring may contain a condensed ring. Examples of heterocyclic rings include piperidine rings, morpholine rings, thiomorpholine rings and the like.

Among them, R ^c2 is most preferably a methyl group, an ethyl group, a propyl group or a phenyl group.

In the above formula (c-1), R ^c3 represents a monovalent organic group. The organic group is preferably 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 optionally having a substituent. Examples of the substituent include the same groups as in the case of R ^c1 . Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

[Chemical Formula 13]

In the formula (c-2), R ^c13 represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Examples of such alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, n-pentylene, Chain or branched-chain groups of the above-mentioned groups. Among them, R ^c13 is most preferably an isopropylene group.

The formula (c-2) of, R ^c14 represents a monovalent organic group represented by -NR ^c15 R ^c16 (R ^c15 and R ^c16 are each independently a monovalent organic group). Among such organic ^groups , it is ^{preferable that} the structure of R ^c14 is represented by the following formula (c-3) in that the solubility of the photopolymerization initiator can be improved.

[Chemical Formula 14]

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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- A tert-pentyl group, and the like. Among them, R ^c17 and R ^c18 are most preferably a methyl group.

The heterocyclic group in R ^c3 includes a heterocyclic group having 5 or more rings, preferably a 5-membered ring or a 6-membered ring, which contains at least one atom of a nitrogen atom, a sulfur atom and an oxygen atom. Examples of the heterocyclic group include a nitrogen-containing five-membered ring group such as a pyrrolyl group, an imidazolyl group, and a pyrazolyl group; A nitrogen-containing 6-membered ring group such as a pyridyl group, a pyrazinyl group, a pyrimidyl group, and a pyridazinyl group; A nitrogen-containing heterocyclic group such as a thiazolyl group or an isothiazolyl group; A nitrogen-containing oxygen group such as an oxazolyl group and an isoxazolyl group; Thienyl group, and thiopyranyl group; An impurity group such as a furyl group and a pyranyl group; And the like. Among them, it is preferable to include one nitrogen atom or sulfur atom. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group and the like.

The heterocyclic group may have a substituent. Examples of the substituent include the same groups as in the case of R ^c1 .

In the above formula (c-1), R ^c4 represents a monovalent organic group. Among them, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- A tert-pentyl group, and the like. Among them, R ^c4 is most preferably a methyl group.

Another preferred example of the oxime-based photopolymerization initiator is a photopolymerization initiator represented by the following formula (c-4) proposed in JP-A-2010-15025.

[Chemical Formula 15]

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 arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms . Alkyl group, an aryl group, an arylalkyl group, and a hydrogen atom of the heterocyclic ring group is added to ^c41 OR, COR ^{c41, c41} SR, NR ^c42 R ^c43, CONR ^c42 R ^c43, -NR ^c42 -OR ^{c43, c42} -NCOR -OCOR ^{c43, -C (= N-OR} c41) -R c42, -C (= N-OCOR c41) -R c42, CN, halogen atom, -CR = CR ^{c41 c42} R ^c43, -CO-CR = CR ^{c41 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 arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms .

Wherein R ^c31, R ^c32, R ^c33, R ^c41, R ^c42, and the group is a methylene of the alkylene part of the substituents in R ^c43, an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond , Or an urethane bond, the alkyl moiety of the substituent may be branched or cyclic, the alkyl terminus of the substituent may be an unsaturated bond, and R ^c32 and R ^c33 , And R ^c42 and R ^c43 may combine with each other to form a ring structure.

R ^c23 and R ^c24 are each independently selected from the group consisting of 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 is, -X ^c2 - may form a ring structure of benzene to the first coupling and one of the carbon atoms of the ring are adjacent via the sun combined R ^c23 and R ^c24 may 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 cyclic structure together with any adjacent benzene ring.

Examples of the alkyl group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 in the above formula (c-4) include methyl group, ethyl group, n- An isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group and a tert-pentyl group.

Examples of the aryl group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 in the above formula (c-4) include phenyl group, tolyl group, xylyl group, ethylphenyl group, chlorophenyl group, naphthyl group , Anthryl group, phenanthrenyl group and the like.

Examples of the arylalkyl group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 in the above formula (c-4) include a benzyl group, a chlorobenzyl group, an? -dimethylbenzyl group, a phenylethyl group, and a phenylethenyl group.

In the formula (c-4), heterocyclic groups in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 include ^pyridyl , ^pyrimidyl , furyl, thienyl, A thiazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, an isoxazolyl group, an isoxazolyl group, an isoxazolyl group, , A piperidyl group, a piperazyl group, and a morpholinyl group.

A ring which R ^c32 and R ^c33 may bond together to form a ring, a ring which R ^c42 and R ^c43 can form by bonding, and R ^c23 may be formed together with the 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.

When X ^c2 is NR ^c53 and R ^c23 is bonded to one of the carbon atoms of the adjacent benzene ring to form a 5-membered ring structure together with X ^c2 , the photopolymerization initiator has a carbazole skeleton.

As the halogen atom which may be substituted for R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 in the above formula (c-4), and the halogen atom for R ^c24 and R ^c25 , A chlorine atom, a bromine atom, and an iodine atom.

The methylene group of the alkylene moiety of the substituent may be interrupted one to five times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond. In this case, the couplers to be interrupted may be one kind or two or more kinds of groups, and two or more kinds of groups may be continuously stopped when they are groups which can be continuously interrupted. The alkyl moiety of the substituent may be branched or cyclic alkyl, and the alkyl terminus of the substituent may be an unsaturated bond.

Another preferable example of the oxime-based photopolymerization initiator is an oxime ester compound represented by the following formula (2).

[Chemical Formula 16]

( ^Wherein R ^d1 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen atom, a nitro group, and a cyano group, i is an integer of 0 to 4, j is 0 or 1, R ^d2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent and ^Rd3 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 within a range that does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferred examples of R ^{d1 in the} case where R ^d1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyl group which may have a substituent A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, 1 Or an amino group substituted with an organic group of 2, a morpholin-1-yl group, and a piperazin-1-yl group. When i is an integer of 2 to 4, R ^d1 may be the same or different. The carbon number of the substituent does not include the carbon number of the substituent further having a substituent.

When R ^d1 is an alkyl group, the carbon number thereof is preferably from 1 to 20, more preferably from 1 to 6. When R ^d1 is an alkyl group, it may be a linear chain or a branched chain. Specific examples of when R ^d1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- N-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl, and isodecyl. When R ^d1 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^d1 is an alkoxy group, the number of carbon atoms thereof is preferably from 1 to 20, more preferably from 1 to 6. When R ^d1 is an alkoxy group, it may be a linear chain or a branched chain. Specific examples of when R ^d1 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, An n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a n-hexyloxy group, Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^d1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group, and And a methoxypropyloxy group.

When R ^d1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms thereof is preferably from 3 to 10, more preferably from 3 to 6. Concrete examples of the case where R ^d1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Concrete examples of the case where R ^d1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^d1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms thereof is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of when R ^d1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, Heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-pentadecanoyl group, and n-hexadecanoyl group. Concrete examples of the case where R ^d1 is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2- N-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy , n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^d1 is an alkoxycarbonyl group, the number of carbon atoms thereof is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of when R ^d1 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyloxycarbonyl, tert An n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, , a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ^d1 is a phenylalkyl group, the number of carbon atoms thereof is preferably 7 to 20, more preferably 7 to 10. When R ^d1 is a naphthylalkyl group, the number of carbon atoms thereof is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of the case where R ^d1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^d1 is a naphthylalkyl group include? -Naphthylmethyl group,? -Naphthylmethyl group, 2- (? -Naphthyl) ethyl group and 2- (? -Naphthyl) ethyl group . When R ^d1 is a phenylalkyl group or a naphthylalkyl group, R ^d1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^d1 is a heterocyclyl group, the heterocyclyl group may be a 5- or 6-membered monocyclic ring having a total number of N, S, and O of 1 or more, or a heterocyclic ring containing such a monocyclic ring and a benzene ring-condensed hetero Cyclohexyl group. When the heterocyclyl group is a condensed ring, the number of rings is 3 or less. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Benzoimidazole, benzothiazole, benzothiazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, isoindoline, quinazoline, Phthalazine, cinnolin, and quinoxaline. When R ^d1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^d1 is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, , A benzoyl 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 naphthoyl group which may have a substituent, A naphthylalkyl group having 1 to 20 carbon atoms, and a heterocyclyl group. Specific examples of these preferred organic ^groups are the same as R ^d1 . Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- An n-butylamino group, an n-pentylamino group, an n-hexylamino group, an n-heptylamino group, an n-octylamino group, N-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, .

Examples of the substituent in the case where the phenyl group, naphthyl group and heterocyclyl group further have substituents included in R ^d1 include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic group having 2 to 7 carbon atoms An alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, A piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^d1 further have a substituent, the number of the substituent is not limited within the range not impairing the object of the present invention, but is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^d1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the R ^d1 , there are a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the like. An alkoxy group, and a saturated aliphatic acyl group having 2 to 7 carbon atoms are preferred, and a nitro group or alkyl having 1 to 6 carbon atoms is more preferable, and a nitro group or a methyl group is particularly preferable.

The R ^d1 is a position coupled to a phenyl group, R ^d1 is the bonding position of the phenyl group and the oxime ester compound week combination the position of the hand in the first position, and a methyl group of a skeleton of for the phenyl group in the case of a two-position, the 4 Position or the 5 position is preferable, and the 5 position is more preferable. I is preferably an integer of 0 to 3, more 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.

The substituent of the phenyl group or the carbazolyl group in R ^d2 is not particularly limited within the range not hindering the object of the present invention. Examples of preferable substituents which the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy 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 naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a substituent A naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, An amino group, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.

When R ^d2 is a carbazolyl group, examples of preferred substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl 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 benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent A naphthoyl group which may have a substituent, a naphthoylcarbonyl group which may have a substituent, a naphthylalkyl group having a carbon number of 11 to 20 which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent And a heterocyclylcarbonyl group. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the phenyl group or carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, A naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and an amino group substituted by 1 or 2 organic groups are the same as R ^d1 .

Examples of the substituent in the case where the phenyl group, naphthyl group and heterocyclyl group contained in the substituent of the phenyl group or carbazolyl group in R ^d2 further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; A halogen atom; A nitro group; And cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent possessed by the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited within the range not hindering the object of the present invention, 4 is preferable. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

Among the R ^d2 , a group represented by the following formula (3) or (4) is preferable, a group represented by the following formula (3) is more preferable, and a compound represented by the following formula ), And a group in which A is S is particularly preferable.

[Chemical Formula 17]

( ^Wherein R ^d4 is a group selected from the group consisting of a monovalent organic group, an amino 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)

[Chemical Formula 18]

(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 a variety of organic groups within the range not hindering the object of the present invention. In the formula (3), when R ^d4 is an organic group, preferred examples thereof include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; A halogen atom; A nitro group; And cyano group.

Among R ^d4 , a benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A nitro group is preferable, a benzoyl group; A naphthoyl group; A 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; And a 4- (phenyl) phenylcarbonyl group is more preferable.

In the 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 binding position of R ^d4 are, for binding hand is a phenyl group which is bonded to R ^d4 combined with the atoms A, preferably in the para position.

R ^d5 in the expression (4) can be selected from various organic devices within a range not hindering the object of the present invention. Preferable examples of R ^d5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, , A phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyl group which may have a substituent A naphthylalkyl group having a carbon number of 11 to 20 which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

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

R ^d6 in the formula (4) is not particularly limited within a range that does not impair the object of the present invention, and can be selected from various organic devices. Specific examples of the group represented by R ^d6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. As R ^d6 , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

The substituent in the case where the phenyl group, the naphthyl group, and the heterocyclyl group have additional substituents included in R ^d4 , R ^d5 , or R ^d6 includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkyl group having an alkyl group having 1 to 6 carbon atoms An amino group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^d4 , R ^d5 , or R ^d6 further have a substituent, the number of the substituent is not limited to the extent that the object of the present invention is not impaired, 1 to 4 is preferable. When a phenyl group, a naphthyl group, and a heterocyclyl group contained in R ^d4 , R ^d5 , or R ^d6 have a plurality of substituents, the plurality of substituents may be the same or different.

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

The oxime ester compound represented by the formula (2) can be synthesized, for example, according to the following scheme 1 when j is 0. Specifically, an aromatic compound represented by the following formula (d1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (d1-2) To obtain an oxime compound represented by the formula (d1-4) in which the obtained ketone compound (d1-3) is oxycinized by hydroxylamine, and then the oxime compound of the formula (d1-4) reacting an acid anhydride represented by the formula ^{(d1-5) ((R d3 CO} ) 2 O), or acid halide (R ^d3 COHal, Hal is a halogen atom.) represented by the following formula (d1-6), the following formula (d1-7) can be obtained. (D1-2), (d1-3), (d1-4), and (d1-7) shown below in the formula (d1-2) R ^d1 , R ^d2 , R ^d3 , and i are the same as in the formula (2).

<Scheme 1>

[Chemical Formula 19]

The oxime ester compound represented by the formula (2) can be synthesized, for example, according to the following scheme 2 when j is 1. Specifically, a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (d2-2) is reacted with a ketone compound represented by the following formula (d2-1) formula (d2-3) to Kane toksim obtain a compound, an acid anhydride _{^{((R d3 CO) 2 O}} ) is then represented by the following formula (d2-3) toksim compound with the following formula (d2-4) Ke shown by indicating, Or an acid halide (R ^d3 COHal, Hal is a halogen atom) represented by the following formula (d2-5) can be reacted to obtain an oxime ester compound represented by the following formula (d2-6). R ^d1 , R ^d2 , R ^d3 , and i in the following formulas (d2-1), (d2-3), (d2-4), (d2-5), and (2).

<Scheme 2>

[Chemical Formula 20]

When the oxime ester compound represented by the formula (2) is a compound wherein 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 to which R ^d1 is bonded, The compound represented by the following formula (d2-7) may be synthesized by oximation and acylation in the same manner as scheme 1. In the following formula (d2-7), R ^d2 is the same as in formula (2).

[Chemical Formula 21]

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

[Chemical Formula 22]

Another preferred example of the oxime-based photopolymerization initiator is &quot; IRGACURE OXE01 &quot; (trade name, manufactured by BASF).

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

[coloring agent]

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

The colorant is not particularly limited, but a compound classified as a pigment in a color index (CI, published by The Society of Dyers and Colourists), specifically, a color index (CI) It is preferable to use one with a number.

CI Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the numbers are described below), 3,11,12,13,14,15,16,17,20,24,31,35,55 , 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 ;

CI Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the numbers are described below), 5,13,14,16,17,24,34,36,38,40,43,46,49 , 51, 55, 59, 61, 63, 64, 71, 73;

C. I. Pigment Violet 1 (hereinafter, "C. I. Pigment Violet" is the same and only the numbers are described below), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

CI Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only the numbers are described below), 2,3,4,5,6,7,8,9,10,11,12,14,15 48, 48: 3, 48: 4, 49: 1, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 57: , 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, , 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, , 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

CI Pigment Blue 1 (hereinafter, the same applies to "CI Pigment Blue"), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66 ;

C. I. Pigment Green 7, C. I. Pigment Green 36, C. I. Pigment Green 37;

C. I. Pigment Brown 23, C. I. Pigment Brown 25, C. I. Pigment Brown 26, C. I. Pigment Brown 28;

C. I. Pigment Black 1, C. I. Pigment Black 7.

When a colorant is used as the light shielding agent, it is preferable to use a black pigment as the light shielding agent. Examples of the black pigment include organic pigments such as carbon black, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, complex oxides, metal sulfides, metal sulfates, metal carbonates, Various pigments can be mentioned. Among these, it is preferable to use carbon black having high light shielding properties.

As the carbon black, known carbon black such as channel black, furnace black, thermal black and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

Resin-coated carbon black has a lower conductivity than carbon black without resin coating, so that a low-power-consumption display with low leakage current and high reliability when used as a black matrix of a liquid crystal display can be manufactured.

In order to adjust the color tone of the carbon black, the organic pigment may be appropriately added as an auxiliary pigment.

When a pigment is used as the colorant, a pigment and a dye may be used in combination. Examples of the dyes usable in combination with the pigments include xanthene dyes, cyanine dyes, azo dyes, anthraquinone dyes, dioxazine dyes and triphenylmethane dyes.

In order to uniformly disperse the colorant in the radiation-sensitive resin composition, a dispersant may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of polyethylene imine type, urethane resin type or acrylic resin type. Particularly, when carbon black is used as a coloring agent, it is preferable to use an acrylic resin-based dispersing agent as a dispersing agent.

The inorganic pigments and the organic pigments may be used alone or in combination. When used in combination, the organic pigments are used in an amount of 10 to 80 parts by mass per 100 parts by mass of the total amount of the inorganic pigments and the organic pigments , More preferably from 20 to 40 parts by mass.

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

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

The negative-tone radiation-sensitive composition 1 may contain other organic solvents. Other organic solvents may 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, diethylene glycol monoethyl 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, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono- (Poly) alkylene glycols such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether, Monomethyl ether; (Poly) alkylene ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethoxyacetonate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n- Butyl acetate, isobutyl acetate, isopentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, Other esters such as methyl, ethyl acetoacetate and ethyl 2-oxobutanoate; And aromatic hydrocarbons such as toluene and xylene.

In the negative-tone radiation-sensitive composition 1, the content of the solvent is preferably such that the solid concentration of the negative-tone radiation-sensitive composition 1 is 1 to 50 mass%, more preferably 5 to 30 mass% . In the solvent contained in the negative-tone radiation-sensitive composition 1, the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0, more preferably 20:80 to 100 : 0 is more preferable. By setting the content of the solvent and the mass ratio of the compound represented by the formula (1) to the other organic solvent within the above range, the negative-tone radiation sensitive composition 1 is excellent in sensitivity, storage stability, coatability, developability and safety And the pattern formed by exposure and development of the negative radiation-sensitive composition 1 tends to be inhibited from the generation of foreign matter.

[Other ingredients]

The negative-tone radiation-sensitive composition 1 may contain various additives, if necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, a defoaming agent, and a surfactant.

&Lt; Negative radiation sensitive composition 2 &gt;

The negative-tone 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 the general formula (1)

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

[Polyamic acid]

In the present invention, the polyamic acid is not particularly limited as long as it is obtained by reacting a tetracarboxylic acid dianhydride and a diamine, and is suitably selected from polyamic acid which is conventionally known as a precursor of a polyimide resin. The polyamic acids may be used alone or in combination of two or more.

The preferred polyamic acid is, for example, polyamic acid represented by the following formula (11).

(23)

(Wherein R &^lt; ^{1A &gt;} is a tetravalent organic group, R &lt; ^{2A &gt;} is a divalent organic group and n is a repetition number of the structural unit shown in parentheses)

In formula (11), R ^1A is a tetravalent organic group and R ^2A is a divalent organic group. The number of carbon atoms of these organic groups is preferably 2 to 50, 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 include an oxygen atom, a nitrogen atom, or a sulfur atom, an oxygen atom, a nitrogen atom, or a sulfur atom may be substituted with a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N = N- , -CH = N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS- and is included in R ^1A and R ^2A And is preferably a group selected from -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, and is more preferably included in R ^1A and R ^2A .

Polyimide resin represented by the following formula (12) is obtained by heating and / or ring closing the polyamic acid represented by the formula (11).

&Lt; EMI ID =

(Wherein R &lt; ^{1A &gt;} and R &lt; ^2A &gt; are the same as in the formula (11) and n is the number of repeating constituent units shown in parentheses)

The polyamic acid represented by the formula (11) is obtained by reacting a tetracarboxylic acid dianhydride with a diamine in a solvent. The tetracarboxylic acid dianhydride and the diamine which are the starting materials for the synthesis of the polyamic acid are not particularly limited so long as they can form the polyamic acid by the reaction of the acid anhydride group and the amino group.

The amount of the tetracarboxylic acid dianhydride and the diamine to be used in the synthesis of the polyamic acid is not particularly limited, but it is preferable to use 0.50 to 1.50 mol of diamine per mol of the tetracarboxylic acid dianhydride, more preferably 0.60 to 1.30 More preferably from 0.70 to 1.20 mol, based on the total amount of the reaction mixture.

The tetracarboxylic acid dianhydride can be appropriately selected from tetracarboxylic acid dianhydrides conventionally used as starting materials for the synthesis of polyamic acid. The tetracarboxylic acid dianhydride may be an aromatic tetracarboxylic acid dianhydride or an aliphatic tetracarboxylic acid dianhydride, but from the viewpoint of the heat resistance of the obtained polyimide resin, an aromatic tetracarboxylic dianhydride is preferable. The tetracarboxylic acid dianhydride may be used in combination of two or more.

Specific preferred examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-bis Phenyl tetracarboxylic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic dianhydride, and 3,3', 4,4'-di Phenylsulfone tetracarboxylic acid dianhydride, and the like. Of these, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, and pyromellitic dianhydride are preferable from the viewpoint of cost, availability and the like.

Further, when polyamic acid is synthesized, tetracarboxylic acid dianhydride and dicarboxylic acid anhydride may be used in combination. When these carboxylic acid anhydrides are used in combination, the properties of the obtained polyimide resin may be better. The dicarboxylic acid anhydrides include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, methylendomethylenetetrahydrophthalic anhydride, anhydrous chlorodic acid, methyltetra Phthalic anhydride, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride and the like.

The diamine can be appropriately selected from diamines conventionally used as starting materials for the synthesis of polyamic acid. The diamine may be an aromatic diamine or an aliphatic diamine, but from the viewpoint of the heat resistance of the obtained polyimide resin, an aromatic diamine is preferable. The diamines may be used in combination of two or more.

Specific preferred examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'- Bis (trifluoromethyl) biphenyl, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4 ' - diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis Bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2- Bis (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) fluorene, 9,9- And 4,4 '- [1,4-phenylenebis (1-methylethane-1,1-di )] And the like dianiline. Of these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable from the viewpoint of cost, availability and the like.

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

Examples of the organic solvent used for the reaction of the tetracarboxylic acid dianhydride with the diamine include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, Nitrogen polar solvents such as dimethylformamide, N, N-diethylformamide, N-methylcaprolactam, and N, N, N ', N'-tetramethylurea; lactone-based polar solvents such as? -propiolactone,? -butyrolactone,? -valerolactone,? -valerolactone,? -caprolactone, and? -caprolactone; Dimethyl sulfoxide; Acetonitrile; Fatty acid esters such as ethyl lactate, and butyl lactate; And ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate, and ethyl cellosolve acetate.

Among these organic solvents, from the solubility of the resulting polyamic acid or polyimide resin, it is preferable to use N-methyl-2-pyrrolidone, N, N-dimethylacetamide, Nitrogen polar solvents such as formamide, N, N-diethylformamide, N-methylcaprolactam, and N, N, N ', N'-tetramethylurea are preferable.

[Photosensitive component]

The photosensitive component is not particularly limited and includes, for example, a compound (A) such as a photo-base generator and a photo-acid generator which is decomposed by the action of light to generate at least one of a base and an acid. The photosensitive component may be used alone or in combination of two or more.

By exposing the negative radiation-sensitive composition 2 containing the compound (A), the compound (A) in the negative-tone radiation-sensitive composition 2 is decomposed and generates at least one of a base and an acid. The base or acid generated in this manner acts as an imidation catalyst and promotes the cyclization of the polyamic acid in the negative-tone radiation-sensitive composition 2.

When the negative radiation-sensitive composition 2 containing the compound (A) is exposed, the compound (A) is decomposed in the exposed portion to generate at least one of a base and an acid. The cyclization of the polyamic acid in the negative-tone radiation-sensitive composition 2 is promoted by the base or acid thus generated, and the exposed portion is insoluble in the developer. On the other hand, since the unexposed portion is soluble in a developing solution, it can be dissolved and removed in a developing solution. Therefore, by selectively exposing the negative radiation-sensitive composition 2, a desired pattern can be formed.

Examples of the compound (A) include a compound (A-1) and an oxime compound (A-2) which are decomposed by the action of light to generate an imidazole compound. Hereinafter, the compounds (A-1) and (A-2) will be described.

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

The imidazole compound from which the compound (A-1) is generated promotes the ring-opening of the polyamic acid in the negative-tone radiation-sensitive composition 2 as a basic imidization catalyst. The imidazole compound in which the compound (A-1) is generated may be imidazole, or may be a compound in which part or all of the hydrogen atoms bonded to carbon atoms in the imidazole are substituted with substituents, Compound.

(25)

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, A phosphino group, a phosphino group, a phosphonato group, or an organic group.

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 a hetero atom. The organic group may be any of linear, branched, and cyclic. This organic group is usually monovalent, but may be divalent or more in the case of forming a cyclic structure.

R ¹ and R ² may combine with each other to form a cyclic structure, or may contain a bond of a heteroatom. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used.

When the organic group represented by R ¹ , R ² or R ³ includes 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 an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═C (-R) Or -C (= NR) - (wherein R represents a hydrogen atom or an organic group), the same applies hereinafter), a carbonate bond, a sulfonyl bond, a sulfinyl bond and an azo bond. Among them, from the viewpoint of the heat resistance of the imidazole compound, an ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond, carbonate bond, Bonding is preferred.

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

Each of R ¹ , R ² and R ³ is preferably 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, desirable. Imidazoles in which R ¹ , R ² , and R ³ are both hydrogen atoms can easily act as a polyamic acid as an imidation catalyst since they have a simple structure with few steric hindrance.

The compound (A-1) is not particularly limited as long as it is a compound capable of decomposing by the action of light to generate an imidazole compound, preferably an imidazole compound represented by the formula (3). The skeleton derived from an amine which is formed at the time of exposure with respect to a compound which has conventionally been compounded in the photosensitive composition and which generates an amine by the action of light is referred to as an imidazole compound, preferably an imidazole compound represented by the formula (3) To obtain a compound to be used as the compound (A-1).

Preferred examples of the compound (A-1) include a compound represented by the following formula (4).

(26)

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitro group, R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ^{9 each} independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfo group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, R ¹⁰ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, A phosphono group, a phosphonato group, an amino group, an ammonia group, or an organic group, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may combine with each other to form a cyclic structure or may contain a heteroatom bond.)

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

Examples of the organic group represented by R ⁴ or R ⁵ in the formula (4) include those exemplified for R ¹ , R ² , and R ³ . This organic group may contain a hetero atom as in 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 each independently represent 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, an aryloxyalkyl group having 7 to 16 carbon atoms, An alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, An acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR or -OCOR (wherein R represents a hydrocarbon group)), an aryl group having 6 to 20 carbon atoms, an electron donating group and / An aryl group having 6 to 20 carbon atoms substituted with a cyano group, a benzyl group substituted with an electron-donating group and / or an electron-withdrawing group, a cyano group, and a methylthio group. More preferably, both of 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 , or R ¹⁰ in the formula (4) include those exemplified as R ¹ , R ² , and R ³ . This organic group may contain a hetero atom as in 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 combine with each other to form a cyclic structure or may contain a heteroatom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used. For example, R ^6, R ^7, R ^8, R ^9, and R ¹⁰ are, their by two combination or more, R ^6, R ^7, R ^8, R ^9, and a benzene ring, which R ¹⁰ is bonded To form a condensed ring such as naphthalene, anthracene, phenanthrene, or indene.

R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent 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, An aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide having 2 to 11 carbon atoms Group, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, an electron donating group and / A benzyl group substituted with an aryl group, an electron donating group and / or an electron withdrawing group, a cyano group, a methylthio group and a nitro group.

In addition, R ^6, R ^7, R ^8, R ^9, and R ^10, the combined of them two or more, R ^6, R ^7, R ^8, R ^9, and the benzene ring which R ¹⁰ is bonded It is also preferable that a condensed ring such as naphthalene, anthracene, phenanthrene, or indene is formed by sharing an atom, because the absorption wavelength becomes long.

Among the compounds represented by the above formula (4), the compounds represented by the following formula (5) are preferable.

(27)

(Wherein, R ^1, R ^2, and R ³ is the formula (3) and (4) agree with a. R ⁴ ~ R ⁹ is the formula (4) with a consent. R ¹¹ is a hydrogen atom or an organic group It represents. R ⁶ and it is not the case R ⁷ is where the hydroxyl group. R ^6, R ^7, R ^8, and R ⁹ is, by binding their two or more and may form a ring structure, a combination of heteroatoms It may be included.)

The compound represented by the formula (5) has a substituent group -OR &lt; ¹¹ &gt; and is therefore excellent in solubility in an organic solvent.

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

Preferred examples of the compound (A-1) include compounds represented by the following formula (6).

(28)

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, A phosphonato group, a phosphonato group, or an organic group, and R ¹² represents a hydrocarbon group which may be substituted.

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

In formula (6), R ¹² is preferably 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, an optionally substituted aryl group having 6 to 20 carbon atoms, An aralkyl group having 7 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms which may be substituted are preferable. When the aryl group or the 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 obtained by reacting an imidazole compound represented by the formula (3) with a chloroformic ester represented by the following formula (7), a reaction between the imidazole compound represented by the formula (3) Carbonate, or by reaction of a carbonyldiimidazole compound represented by the following formula (9) with an alcohol represented by the following formula (10).

[Chemical Formula 29]

(Equation (7) to (10), R ^1, R ^2, and R ³ is a formula (3) and copper. R ¹² is the formula (6) and consent).

Specific examples of the compound particularly preferable as the compound (A-1) are shown below.

(30)

(Oxime compound (A-2))

The oxime compound (A-2) is decomposed by the action of light to generate at least one of a base and an acid. The cyclization of the polyamic acid in the negative-tone radiation-sensitive composition 2 is promoted by the base or acid generated by decomposition of the compound (A-2).

Preferred examples of the compound (A-2) include a compound represented by the following formula (D1).

(31)

( ^Wherein R ^d1 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a carbazolyl group which may have a substituent, and R ^d2 is a group having 1 to 10 carbon atoms R ^d3 is a hydrogen atom or a group represented by -CO-R ^d5 , and R ^d5 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted group having a substituent And 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 a phenyl group which may have a substituent, a naphthyl group which may have a substituent, A trityl group, and a phenanthrenyl group which may have a substituent. Among these groups, a phenyl group which may have a substituent or a naphthyl group which may have a substituent is preferable, and a phenyl group which may have a substituent is more preferable.

When the aryl group has a substituent, the number of substituents bonded to the aryl group is not particularly limited. When the aryl group has plural substituents, the plural substituents may be the same or different. The kind of the substituent that the aryl group may have is not particularly limited within the range not hindering the object of the present invention. Preferable examples of the substituent include an organic group, an amino 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 within the scope of not impairing the object of the present invention, and is suitably selected from various organic groups. Preferable examples of the organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, A phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, An amino group substituted with an organic group, a morpholin-1-yl group, and a piperazin-1-yl group. The carbon number of the substituent does not include the carbon number of the substituent further having a substituent.

When the organic group is an alkyl group, the number of carbon atoms thereof is preferably from 1 to 20, more preferably from 1 to 6. When the organic group is an alkyl group, it may be linear or branched. Specific examples of the organic group being an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- N-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-hexyl, - decyl group, and isodecyl group. When the organic group is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When the organic group is an alkoxy group, the number of carbon atoms thereof is preferably from 1 to 20, more preferably from 1 to 6. When the organic group is an alkoxy group, it may be a linear chain or branched chain. Specific examples of the organic group as the alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, A tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, a n-decyloxy group, and an isodecyloxy group. When the organic group is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group, and And a methoxypropyloxy group.

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

When the organic group is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms thereof is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of the organic group saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, - pentadecanoyl group, and n-hexadecanoyl group. Specific examples of the organic group-containing saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2- Hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group, n-tridecanoyloxy group, n-pentadecanoyloxy group and n-hexadecanoyloxy group.

When the organic group is an alkoxycarbonyl group, the carbon number thereof is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of the case where the organic group is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, An n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group, and the like.

When the organic group is a phenylalkyl group, the number of carbon atoms thereof is preferably from 7 to 20, more preferably from 7 to 10. When the organic group is a naphthylalkyl group, the number of carbon atoms thereof is preferably from 11 to 20, more preferably from 11 to 14. Specific examples of the organic group as the phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the organic ganganate alkyl group include? -Naphthylmethyl group,? -Naphthylmethyl group, 2- (? -Naphthyl) ethyl group and 2- (? - naphthyl) ethyl group. When the organic group is a phenylalkyl group or a naphthylalkyl group, the organic group may further have a substituent on the phenyl group or the naphthyl group.

When the organic group is a heterocyclyl group, the heterocyclyl group may be a 5- or 6-membered monocyclic ring containing 1 or more N, S, or O, or a heterocyclyl group condensed with such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, the number of rings is 3 or less. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Benzoimidazole, benzothiazole, benzothiazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, isoindoline, quinazoline, Phthalazine, cinnolin, and quinoxaline. When the organic group is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When the organic group is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group bonded to the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic group having 2 to 20 carbon atoms A phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having a carbon number of 7 to 20 which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, A naphthylalkyl group having from 11 to 20 carbon atoms, and a heterocyclyl group. When R ^d1 is an aryl group which may have a substituent, specific examples of these preferred organic groups are the same as specific examples of organic groups in which the aryl group may have a substituent. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino, dimethylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, an n-pentylamino group, an n-hexylamino group, an n-heptylamino group, an n-octylamino group, an n-nonylamino group, a n-decylamino group, a phenylamino group, a naphthylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, And a tolyl amino group.

In the case where R ^d1 is an aryl group which may have a substituent, ^examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclyl group contained in the organic group bonded to the aryl group as a substituent further have a substituent include those having 1 to 6 carbon atoms An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms A dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.

When R ^d1 is an aryl group which may have a substituent, when the phenyl group, the naphthyl group and the heterocyclyl group contained in the organic group bonded to the aryl group as a substituent further have a substituent, the number of the substituent may be And is not limited within the range that does not hinder the purpose, but is preferably 1 to 4. When R ^d1 is an aryl group which may have a substituent, when the phenyl group, the naphthyl group and the heterocyclyl group contained in the organic group bonded to the aryl group as a substituent have plural substituents, the plural substituents may be the same .

In the case where R ^d1 is an aryl group which may have a substituent, the substituent of the aryl group is chemically stable, but there are few steric hindrance, and the compound represented by the formula (D1) can be easily synthesized, D1) from the viewpoint of high solubility in a solvent, a group selected from the group consisting of a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms More preferably a nitro group or an alkyl of 1 to 6 carbon atoms, particularly preferably a nitro group or a methyl group.

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

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(In the formula (D1-1), R ^d4 is a group selected from the group consisting of an organic group, an amino 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, preferred examples of the organic group are the same as the examples of the organic group in which the aryl group may have a substituent, when R ^d1 is an aryl group which may have a substituent.

R ^d4 is a position, R ^d4 and the binding position of, the position of the coupling hand of the main skeleton of the phenyl group and the oxime compound is the 1-position, and a methyl group on the phenyl group bonded to the phenyl group in the case of a two-position, the 4-position , Or 5 position is preferable, and 5 position is more preferable. Q is preferably an integer of 0 to 3, more 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, the carbon number thereof is 1 to 10. This carbon number does not include the carbon number of the substituent. The number of carbon atoms of the aliphatic hydrocarbon group is preferably from 1 to 9, more preferably from 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 chain, branched chain, cyclic, or a combination thereof, preferably a linear chain.

Preferred examples of R ^d1 in the formula (D1) are a linear aliphatic hydrocarbon group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, An n-octyl group, an n-nonyl group, and an n-decyl group.

Preferable examples of the case where R ^d1 is a cyclic aliphatic hydrocarbon group include a cyclopentyl group and a cyclohexyl group.

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

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

The substituent of the aliphatic hydrocarbon group may have 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 1 or 2 substituents An aryl group, and a phenanthryl group are exemplified, and a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

The substituent of the aliphatic hydrocarbon group may have 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 1 or 2 substituents A halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, which may be the same or different, 2 to 7 saturated aliphatic acyl groups, and the like.

When R ^d1 is an aliphatic hydrocarbon group, specific examples of the above-described substituent groups described above as the substituent group that the aliphatic hydrocarbon group may have are the same as the substituent groups that the aryl group may have in the case where R ^d1 is an aryl group within the ^above- .

When R ^d1 is a carbazolyl group which may have a substituent, the kind of the substituent is not particularly limited within the range not hindering the object of the present invention. Examples of preferable substituents which the carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, A saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group having a carbon number of 7 to 20 which may have a substituent, a substituent A naphthyl group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthylcarbonyl group which may have a substituent A naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent and a carbon number of 11 to 20, a heterocyclyl group which may have a substituent, An amino group, an amino group substituted with an organic group of 1 or 2, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.

When R ^d1 is a carbazolyl group which may have a substituent, examples of the preferable substituent which the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl 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 benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent , A naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having a substituent which may have a substituent, a heterocyclyl group which may have a substituent, And a heterocyclylcarbonyl group which may have a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which the carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenylalkyl group which may have a substituent, Examples of the substituent group of the aryl group in the case where R ^d1 is an aryl group which may have a substituent group and the examples of the substituent group of the aryl group in the case where R ^d1 may have a substituent group are given as examples of the naphthylalkyl group which may be taken together with the heterocyclyl group which may have a substituent, same.

Examples of the substituent in the case where the phenyl group, the naphthyl group and the heterocyclyl group contained in the substituent of the carbazolyl group in R ^d1 further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; Halogen; A nitro group; And cyano group. When the phenyl group, the naphthyl group and the heterocyclyl group contained in the substituent possessed by the carbazolyl group further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, desirable. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

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

When R ^d2 is an aliphatic hydrocarbon group, the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 6, 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 chain, branched chain, cyclic, or a combination thereof, preferably a linear chain.

Preferable examples of R ^d2 in the case of a linear aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a n-hexyl group, an n-nonyl group, and an n-decyl group. Of these, a methyl group is particularly preferable.

Examples of the case where R ^d2 is an aryl group which may have a substituent include a phenyl group which may have a substituent, a naphthyl group which may have a substituent, an anthryl group which may have a substituent and a phenanthrenyl group which may have a substituent . Among these groups, a phenyl group which may have a substituent or a naphthyl group which may have a substituent is preferable, and a phenyl group which may have a substituent is more preferable.

The substituent of the aryl group in R ^d2 is not particularly limited within the range not hindering the object of the present invention. Examples of preferred substituents which the aryl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, A saturated aliphatic acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, , A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group having a carbon number of 7 to 20 which may have a substituent, a naphthyl group which may have a substituent, A naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent A heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, an amino group substituted with an organic group of 1 or 2, a morpholine- A 1-yl group, and a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.

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 acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenylalkyl group which may have a substituent, Examples of the substituent group that the aryl group may have, when R ^d1 is an aryl group which may have a substituent, with respect to the naphthylalkyl group, the heterocyclyl group which may have a substituent, and the amino group substituted by the organic group of 1 or 2, .

Examples of the substituent in the case where the phenyl group, naphthyl group and heterocyclyl group contained in the substituent of the aryl group in R ^d2 further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; A halogen atom; A nitro group; And cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent possessed by the aryl group further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, but is preferably 1 to 4 . When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^d3 in the formula (D1) is a hydrogen atom or a group represented by -CO-R ^d5 . 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 substituent which the aryl group may have is the same as the substituent which the aryl group may have, when 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 2 or more substituents. In this case, the substituents of the aryl group may be the same or different. As R ^d5 , a hydrogen atom, an acetyl group, a propionyl group, and a benzoyl group are preferable, and a hydrogen atom, an acetyl group, and a benzoyl group are more preferable.

The compound represented by the formula (D1) is preferably a compound represented by the formula (D1) wherein R ^d1 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, And R ^d2 is a group represented by the following formula (D1-2), or a compound wherein R ^d1 is a group represented by the following formula (D1-3) in the formula (D1) in that it is suppressed that a high transparency resin obtained, and in, R ^d1 is of 1 to 10 carbon atoms which may have a substituent, an aliphatic hydrocarbon group, or an aryl group which may have a substituent in the formula (d1), to the R ^d2 More preferably a group represented by formula (D1-2).

(33)

R ^d6 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen atom, a nitro group, and a cyano group; A is S or O; It is an integer of 4.)

When R ^d6 in formula (D1-2) is an organic group, it can be selected from various organic groups within the range not hindering the object of the present invention. Preferable examples of R ^d6 in the formula (D1-2) when R ^d6 is an organic group include alkyl groups having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; A saturated aliphatic acyl group having 2 to 7 carbon atoms; An alkoxycarbonyl group having 2 to 7 carbon atoms; A saturated aliphatic acyloxy group having 2 to 7 carbon atoms; A phenyl group; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; A halogen atom; A nitro group; And cyano group.

Among R ^d6 , a benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A nitro group is preferable, a benzoyl group; A naphthoyl group; A 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; And a 4- (phenyl) phenylcarbonyl group is more preferable.

In 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 binding position R ^d6 is a phenyl group which is bonded R ^d6 is preferably a para position relative to the bonding hands binding to the oxygen atom or a sulfur atom.

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

Examples of the substituents on the case, a phenyl group, a naphthyl group, and the heterocyclyl included in R ^d6 group having a substituent in addition, ah saturated aliphatic group having 1 to 6 carbon atoms alkyl group, a C 1 -C 6 alkoxy group, having 2 to 7 of the An alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, A piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group and the heterocyclyl group contained in R ^d6 further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^d6 have a plurality of substituents, the plurality of substituents may be the same or different.

(34)

(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 the expression (12) can be selected from various types of organic devices ^insofar as the object of the present invention is not impaired. Preferable examples of R ^d7 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, , A phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyl group which may have a substituent A naphthylalkyl group having a carbon number of 11 to 20 which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

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 the formula (12) is not particularly limited within a range not hindering the object of the present invention, and can be selected from various organic devices. Specific examples of the group represented by R ^d8 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. Of these groups, R ^d8 is more preferably a phenyl group which may have a substituent and a naphthyl group which may have a substituent, particularly preferably a 2-methylphenyl group and a naphthyl group.

The substituent in the case where the phenyl group, the naphthyl group and the heterocyclyl group have further substituents included in R ^d7 or R ^d8 includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 2 to 7 carbon atoms A saturated aliphatic acyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, A morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group. When the phenyl group, the naphthyl group and the heterocyclyl group contained in R ^d7 or R ^d8 further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, desirable. When the phenyl group, the naphthyl group, and the heterocyclyl 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 the formula (D1) can be synthesized, for example, 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, an aromatic compound represented by the following formula (1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (1-2) To obtain a ketone compound represented by the following formula (1-4), which is obtained by subjecting the obtained ketone compound (1-3) to oxycondensing with hydroxylamine. In the following formula (1-2), Hal is a halogen atom, and R ^d1 , R ^d2 , and R ^{d3 in the} following formulas (1-1), (1-2), (1-3) And R ^d2 are the same as in formula (D1).

<Scheme 1>

(35)

The compound represented by the 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 scheme 1 and the acid anhydride ((R ^d5 CO) ₂ O) represented by the following formula (1-5) (R ^d5 COHal, Hal is a halogen atom) represented by the following formula (6) to obtain an oxime ester compound represented by the following formula (1-7). R ^d1 , R ^d2 and R ^d5 in the following formulas (1-4), (1-5), (1-6) and (1-7) are the same as in the formula (1).

<Scheme 2>

(36)

The compound represented by the formula (D1) is a ketone compound represented by R ^d2 -CO-R ^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, (= N-OH) -R ^d1 by oxalization with a hydroxylamine according to the method described in R ^d2 -C (= N-OH) -R ^d1 .

When 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 the formula (D1) is preferably R ^d2 -C (= N- OH) -R ^d1 can be obtained as a compound represented by R ^d2 -C (= NO-CO-R ^d5 ) -R ^d1 by acylating an oxime compound represented by the formula

When p is 1 and R ^d3 is a hydrogen atom, the compound represented by formula (D1) can be synthesized, for example, according to scheme 3 below. Specifically, a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (2-2) is reacted with a ketone compound represented by the following formula (2-1) To obtain a ketoxime compound represented by the formula (2-3), followed by obtaining a ketoxime compound represented by the following formula (2-3). In the following formulas (2-1) and (2-3), R ^d1 and R ^d2 are the same as in formula (D1).

<Scheme 3>

(37)

The compound represented by the 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 the formula (2-3) obtained by the method described in the scheme 3 and the acid anhydride ((R ^d5 CO) ₂ O) represented by the following formula (2-4) (R ^d5 COHal, Hal is a halogen atom) represented by the following formula (5) to obtain an oxime ester compound represented by the following formula (2-6). R ^d1 , R ^d2 , and R ^d5 in the following formulas (2-3), (2-4), (2-5), and (2-6) are the same as in formula (D1).

<Scheme 4>

(38)

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

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

(47)

(48)

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

The content of the photosensitive component in the negative-tone radiation-sensitive composition 2 is not particularly limited within the range not hindering the object of the present invention. The content of the photosensitive component in the negative-tone radiation-sensitive composition 2 is preferably from 1 to 50 parts by mass, more preferably from 1 to 30 parts by mass, per 100 parts by mass of the polyamic acid.

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

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

In the negative-tone radiation-sensitive composition 2, the content of the solvent is preferably such that the solid concentration of the negative-tone radiation-sensitive composition 2 is 1 to 50 mass%, more preferably 5 to 40 mass% . In the solvent contained in the negative radiation-sensitive composition 2, the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0, more preferably 20:80 to 100 : 0 is more preferable. By setting the content of the solvent and the mass ratio of the compound represented by the formula (1) to the other organic solvent within the above range, the negative-tone radiation sensitive composition 2 is excellent in sensitivity, storage stability, coatability, developability and safety And the pattern formed by exposure and development of the negative radiation-sensitive composition 2 tends to suppress the generation of foreign matter.

[Other ingredients]

The negative radiation-sensitive composition 2 may contain various additives, if necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, a defoaming agent, and a surfactant.

&Lt; Negative radiation sensitive composition 3 &gt;

The negative-tone radiation-sensitive composition 3 is a radiation-sensitive polybenzoxazole precursor composition containing a compound represented by the general formula (1), a polybenzoxazole precursor, and a photosensitive component.

[Compound represented by the general formula (1)

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

[Polybenzoxazole Precursor]

The polybenzoxazole precursors may be used alone or in combination of two or more. As a starting material for synthesis of the polybenzoxazole precursor, an aromatic diamine diol and a dicarbonyl compound having a specific structure are used. Hereinafter, the aromatic diamine diol and the dicarbonyl compound will be described.

(Aromatic diamine diol)

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

(49)

( ^Wherein R ^a1 is a tetravalent organic group containing at least one aromatic ring, and with respect to the combination of two amino groups and hydroxyl groups contained in the aromatic diamine diol represented by the formula (21), in each combination, an amino group and a hydroxyl group Is bonded to two adjacent carbon atoms on the aromatic ring included in R ^a1 .)

In formula (21), R ^a1 is a tetravalent organic group containing at least one aromatic ring, and the number of carbon atoms thereof is preferably from 6 to 50, more preferably from 6 to 30. R ^a1 may be an aromatic group, and two or more aromatic groups may be bonded through a bond including a hetero atom such as an aliphatic hydrocarbon group and a halogenated aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, and a nitrogen atom. ^Examples of the bond included in R ^a1 include a hetero atom such as an oxygen atom, a sulfur atom and a nitrogen atom include -CONH-, -NH-, -N = N-, -CH = N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, and examples thereof include -O-, -CO-, -SO-, -SO ₂ -, -S -, and -SS- are preferable.

The aromatic ring included in R ^a1 may be an aromatic heterocyclic ring. The aromatic ring bonded to the amino group and the hydroxyl group in R ^a1 is preferably a benzene ring. When the amino group and the ring bonding to the hydroxyl group in R ^a1 are a condensed ring containing two or more rings, the ring bonding with the amino group and the hydroxyl group in the condensed ring is preferably a benzene ring.

Preferable examples of R ^a1 include groups represented by any of the following formulas (1-1) to (1-9).

(50)

(In the formula (1-1), X ¹ represents an alkylene group having 1 to 10 carbon atoms, a fluorinated alkylene group having 1 to 10 carbon atoms, -O-, -S-, -SO-, -SO ₂ -, -CO- , -COO-, -CONH-, and a single bond. In the formulas (1-2) to (1-5), Y ¹ may be the same or different and is -CH ₂ -, -O-, -S-, -SO-, -SO ₂ -, -CO-, and a single bond.

The group represented by any of the formulas (1-1) to (1-9) may have one or plural substituents on the aromatic ring. Preferable 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 fluorinated alkyl group having 1 to 6 carbon atoms, and a fluorinated alkoxy group having 1 to 6 carbon atoms. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.

Specific examples of the compound represented by the formula (21) include 2,4-diamino-1,5-benzene diol, 2,5-diamino-1,4-benzene diol, 2,5- 1,4-benzene diol, 2,6-diamino-1,5-dihydroxynaphthalene, 1-fluoro-1,4-benzene diol, 2,5-diamino- Diamino-2,6-dihydroxynaphthalene, 2,6-diamino-3,7-dihydroxynaphthalene, 1,6-diamino-2,5-dihydroxynaphthalene, Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, 2,3'-diamino-3,2'-dihydro Dihydroxybiphenyl, 4,4'-diamino-4,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-6,6'-ditrifluoromethyl Biphenyl, 3,3'-diamino-4,4'-dihydroxy-6,6'-ditrifluoromethylbiphenyl, 2,3'-diamino-3,2'-dihydroxy- Dihydroxy-6,6'-ditrifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethylbiphenyl, Diamino-3,3'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'- Di-trifluoromethylbiphenyl, 2,3'-diamino-3,2'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 3,4'-diamino-4,3 ' Dihydroxy-5,5'-ditrifluoromethylbiphenyl, bis (4-amino-3-hydroxyphenyl) methane, bis Di-hydroxydiphenylmethane, bis (4-amino-3-hydroxy-6-trifluoromethyl) methane, bis Dihydroxy-6,6'-ditrifluoromethyldiphenylmethane, bis (4-amino-3-hydroxyphenyl) methane, 3,4'- (3-amino-4-hydroxyphenyl) difluoromethane, 3,4'-diamino-4,3'-dihydroxydiphenyl difluoromethane, bis 3-hydroxy-6-trifluoromethane Phenyl) difluoromethane, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) difluoromethane, 3,4'-diamino-4,3'-dihydroxy- (4-amino-3-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) ether, 3,4'-diamino- Dihydroxydiphenyl ether, bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) ether, bis (3-amino- Di (4-amino-3-hydroxyphenyl) ketone, bis (3 Amino-4-hydroxyphenyl) ketone, 3,4'-diamino-4,3'-dihydroxydiphenyl ketone, bis (4-amino- , Bis (3-amino-4-hydroxy-6-trifluoromethyl) ketone, 3,4'-diamino-4,3'-dihydroxy (4-amino-3-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) propane Amino-3-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxy- (3-amino-4-hydroxy-6-trifluoromethylphenyl) propane, 2,2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) propane, 2, (3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (3-amino-3-hydroxyphenyl) hexafluoropropane, 2,2- Amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hex (3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino- (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2- (3-amino-4-hydroxyphenyl) sulfone, 3,4'-diamino-4,3'-dihydroxydiphenyl sulfone (3-amino-4-hydroxy-6-trifluoromethyl) sulfone, 3,4'-diamino (4-amino-3-hydroxyphenyl) sulfide, bis (3-amino-4-hydroxyphenyl) sulfide, bis ) Sulfide, 3,4'-diamino-4,3'-dihydroxydiphenyl sulfide, bis (4-amino- (3-amino-4-hydroxy-6-trifluoromethyl) sulfide, 3,4'-diamino-4,3'-dihydroxy- Amino-3-hydroxyphenyl benzoate, (3-amino-4-hydroxyphenyl) 3 (3-amino-3-hydroxyphenyl) Amino-3-hydroxyphenyl benzoate, (3-amino-4-hydroxyphenyl) Hydroxyphenyl benzoate, N- (4-amino-3-hydroxyphenyl) 4-amino-3-hydroxybenzamide, N- Amino-3-hydroxyphenyl) benzamide, N- (3-amino-4-hydroxyphenyl) Phenylbenzamide, 2,4'-bis (4-amino-3-hydroxyphenoxy) biphenyl, 2,4 ' Bis (4-amino-3-hydroxyphenoxy) biphenyl, 4,4'-bis (3-amino-4-hydroxyphenoxy) biphenyl, (4-amino-3-hydroxyphenoxy) phenyl] ether, di [4- , 4'-bis (4-amino-3-hydroxyphenoxy) benzophenone, 2,4'-bis Amino-3-hydroxyphenoxy) benzophenone, 4,4'-bis (3-amino-4-hydroxyphenoxy) benzophenone, 2,4'- ) Octafluorobiphenyl, 2,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 4,4'-bis Phenyl, 4,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 2,4'-bis (4-amino-3-hydroxyphenoxy) octafluorobenzophenone, 2 , 4'-bis (3-amino-4- Hydroxyphenoxy) octafluorobenzophenone, 4,4'-bis (3-amino-4-hydroxyphenoxy) octafluorobenzophenone, 4,4'- Phenoxy) octafluorobenzophenone, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 2,2- Phenoxy] phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxynaphthyl) Hydroxyphenyl) hexafluoropropane, 2,8-diamino-3,7-dihydroxydibenzofuran, 2,8-diamino-3,7-dihydroxyfluorene, 2,6- Diamino-3,7-dihydroxychalcone, 9,9-bis- (4-amino-3-hydroxyphenyl) fluorene, and 9,9- ) Fluorene.

Of these, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferable in that a polybenzoxazole resin excellent in transparency can be formed.

(Dicarbonyl compound)

As the synthesis raw material of the polybenzoxazole precursor, a dicarbonyl compound represented by the following formula (22) is used together with the aromatic diamine diol described above. A polybenzoxazole precursor is obtained by condensing the above-mentioned aromatic diamine diol with a dicarbonyl compound represented by the following formula (22).

(51)

(Wherein R ^a2 is a divalent organic group and A represents a hydrogen atom or a halogen atom.)

R ^a2 in the formula (22) may be an aromatic group, an aliphatic group, or a combination of an aromatic group and an aliphatic group. It is preferable that R ^a2 is a group containing an aromatic group and / or an alicyclic group in view of good heat resistance, mechanical properties, chemical resistance and the like of the resulting polybenzoxazole resin. The aromatic group contained 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, an oxygen atom, a nitrogen atom, or a sulfur atom may be a divalent nitrogen-containing heterocyclic group, -CONH-, -NH-, -N = N-, A group selected from -CH═N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, which may be included in R ^a2 , -, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, more preferably included in R ^a2 .

In formula (22), it is preferable that one of the two A's is a hydrogen atom and the other is a halogen atom, but both A's are hydrogen atoms or both A's 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 a dicaldehyde compound in which both of A's are hydrogen atoms is used as the dicarbonyl compound represented by the formula (22), a polybenzoxazole intermediate represented by the following formula (10) is produced.

(52)

( ^Wherein R ^a1 and R ^a2 are the same as those of the formulas (21) and (22), and n is the number of repeating units represented by the formula (10).)

As the dicarbonyl compound represented by the formula (22), when a dicarboxylic acid dihalide in which both A are halogen atoms is used, a polybenzoxazole intermediate represented by the following formula (20) is produced.

(53)

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

Hereinafter, the dialdehyde compound and the dicarboxylic acid dihalide, which are preferable compounds as the dicarbonyl compound, will be described.

· Dialdehyde compounds

The dialdehyde compound used as a raw material of the polybenzoxazole precursor is a compound represented by the following formula (2-1). The dialdehyde compound may be used singly or in combination of two or more.

(54)

( ^Wherein R ^a2 is the same as in the formula (22)).

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

(55)

(Wherein X ² represents an alkylene group having 1 to 10 carbon atoms, a fluorinated alkylene group having 1 to 10 carbon atoms, -O-, -S-, -SO-, -SO ₂ -, -CO-, -COO- , -CONH-, and a single bond. When X ² is plural, a plurality of X ² may be the same or different, and each of Y ² may be the same or different, and - CH ₂ -, -O-, -S-, -SO-, -SO ₂ -, -CO-, and a single bond, p and q are each an integer of 0 to 3 .)

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

(56)

(Wherein X ² represents an alkylene group having 1 to 10 carbon atoms, a fluorinated alkylene group having 1 to 10 carbon atoms, -O-, -S-, -SO-, -SO ₂ -, -CO-, -COO- , -CONH-, and a single bond. When X ² is plural, plural X ² may be the same or different, and each of Y ² may be the same or different, -CH ₂ - is one selected from, -CO-, and Z is a group consisting of a single _{bond, -CH 2 - -, -O-,} -S-, -SO-, -SO 2., -CH 2 CH ₂ -, and -CH = CH-, and p is an integer of 0 to 3, respectively.

The aromatic ring or alicyclic ring included in the group represented by R ^a2 may have one or plural substituents on the ring. Preferable 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 fluorinated alkyl group having 1 to 6 carbon atoms, and a fluorinated alkoxy group having 1 to 6 carbon atoms. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.

When the dialdehyde compound represented by the formula (2-1) is an aromatic dialdehyde, preferred examples thereof include benzene dialdehydes, pyridine dialdehydes, pyrazinedialdehydes, pyrimidinedialdehydes, naphthalenedialdehydes, (1-methylene (1-methylene) biphenyl) benzene, [1,4-phenylenebis (1-methylpyridine) (Formylphenoxy) phenyl] sulfide, bis [4- (formylphenoxy) phenyl] propane, bis [ Methylphenoxy) phenyl] sulfone, and fluofluorene di aldehyde.

Specific examples of the benzene dialdehyde include phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 3-fluorophthalaldehyde, 4-fluorophthalaldehyde, 2-fluoroisophthalaldehyde, 4-fluoroisophthalaldehyde, 4-trifluoromethylphthalaldehyde, 2-trifluoromethylisophthalaldehyde, 2-fluoroterephthalaldehyde, 3-trifluoromethylphthalaldehyde, 4-trifluoromethylphthalaldehyde, 2- Isophthalaldehyde, 5-trifluoromethylisophthalaldehyde, 2-trifluoromethylterephthalaldehyde, 3,4,5,6-tetrafluorophthalaldehyde, 2,4,5,6-tetrafluoro And 2,3,5,6-tetrafluoroterephthalaldehyde, and the like.

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

Specific examples of the pyrazine dialdehyde include pyrazine-2,3-dialdehyde, pyrazine-2,5-dialdehyde, and pyrazine-2,6-dialdehyde.

Specific examples of the pyrimidinedialdehydes include pyrimidine-2,4-dialdehyde, pyrimidine-4,5-dialdehyde, and pyrimidine-4,6-dialdehyde.

Specific examples of the naphthalene dialdehyde include naphthalene-1,5-dialdehyde, naphthalene-1,6-dialdehyde, naphthalene-2,6-dialdehyde, naphthalene- 4,6,7,8-hexafluoronaphthalene-1,5-dialdehyde, 2,3,4,5,6,8-hexafluoronaphthalene-1,6-dialdehyde, 1,3,4, Hexafluoronaphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene-2,6-dialdehyde, 1,5-bis (trifluoromethyl) naphthalene- (Trifluoromethyl) naphthalene-3,7-di aldehyde, 1-trifluoromethyl-2,4,5-triazine, , 6,8-pentafluoronaphthalene-3,7-dialdehyde, 1-bis (trifluoromethyl) methoxy-2,4,5,6,8-pentafluoronaphthalene-3,7-dialdehyde , 1,5-bis (trifluoromethyl) -2,4,6,8-tetrafluoronaphthalene-3,7-dialdehyde, and 1,5-bis [bis (Trifluoromethyl) methoxy] -2,4,6,8-tetrafluoronaphthalene-3,7-dialdehyde, and the like.

Specific examples of the biphenyldialdehyde include biphenyl-2,2'-dialdehyde, biphenyl-2,4'-dialdehyde, biphenyl-3,3'-dialdehyde, biphenyl- -Dialdehyde, 6,6'-difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-2,4'-dialdehyde, 6,6'-difluorobiphenyl 6,6'-difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-4,4'-dialdehyde, 6,6'- Ditrifluoromethylbiphenyl-2,2'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-2,4'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl- 3,3'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-3,4'-dialdehyde, and 6,6'-ditrifluoromethylbiphenyl-4,4'-dialdehyde And the like.

Specific examples of diphenyl ether dialdehydes include diphenyl ether-2,4'-dialdehyde, diphenyl ether-3,3'-dialdehyde, diphenyl ether-3,4'-dialdehyde, and di Phenyl ether-4,4'-dialdehyde and the like.

Specific examples of the diphenylsulfone dialdehyde include diphenylsulfone-3,3'-dialdehyde, diphenylsulfone-3,4'-dialdehyde, diphenylsulfone-4,4'-dialdehyde and the like, .

Specific examples of the diphenyl sulfide dialdehyde include diphenyl sulfide-3,3'-dialdehyde, diphenyl sulfide-3,4'-dialdehyde, and diphenyl sulfide-4,4'- Dialdehyde, and the like.

Specific examples of the diphenyl ketone dialdehyde include diphenyl ketone-3,3'-dialdehyde, diphenyl ketone-3,4'-dialdehyde, and diphenyl ketone-4,4'-dialdehyde. .

Specific examples of bis (formylphenoxy) benzenes include benzene 1,3-bis (3-formylphenoxy) benzene, 1,4-bis (3-formylphenoxy) -Bis (4-formylphenoxy) benzene, and the like.

Specific examples of the [1,4-phenylene bis (1-methylethylidene)] bisbenzaldehyde include 3,3 '- [1,4-phenylene bis (1-methylethylidene)] bis (4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, and 4,4 '- [1,4- )] Bisbenzaldehyde and the like.

Specific examples of the 2,2-bis [4- (formylphenoxy) phenyl] propane include 2,2-bis [4- (2-formylphenoxy) phenyl] propane, 2,2- Bis [4- (3-formylphenoxy) phenyl] propane, 2,2-bis [4- Phenyl] hexafluoropropane, and 2,2-bis [4- (4-formylphenoxy) phenyl] hexafluoropropane.

Specific examples of the bis [4- (formylphenoxy) phenyl] sulfide include bis [4- (3-formylphenoxy) phenyl] sulfide and bis [4- ) Phenyl] sulfide, and the like.

Specific examples of the bis [4- (formylphenoxy) phenyl] sulfone include bis [4- (3-formylphenoxy) phenyl] sulfone and bis [4- ] Sulfone, and the like.

Specific examples of the fluoranedialdehyde include fluorene-2,6-dialdehyde, fluorene-2,7-dialdehyde, dibenzofuran-3,7-dialdehyde, 9,9- (3-formylphenyl) fluorene, 9,9-bis (3-formylphenyl) fluorene, and 9- .

Also, diphenylalkanedialdehyde or diphenylfluoroalkanedialdehyde represented by the following formula can be preferably used as an aromatic dialdehyde compound.

(57)

Further, a compound having an imide bond represented by the following formula can also be preferably used as an aromatic dialdehyde compound.

(58)

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, cyclohexane-1,3-dialdehyde, Bicyclo [2.2.2] heptane-2,5-di aldehyde, bicyclo [2.2.2] octane-2,5-di aldehyde, bicyclo [2.2.2] octa- 2.2.1] hept-5-ene-2,3-dialdehyde, tricyclo [5.2.1.0 ^2,6 ] decane- Tricyclo [5.2.1.0 ^2,6 ] dec-4-ene-8,9-dialdehyde, perhydronaphthalene-2,3-dialdehyde, perhydronaphthalene-1,4-di Aldehyde, perhydronaphthalene-1,6-dialdehyde, perhydro-1,4-methanonaphthalene-2,3-dialdehyde, perhydro-1,4-methanonaphthalene- Hydro-1,4-methanonaphthalene-7,8-dialdehyde, perhydro-1,4: 5,8- Dimethanonaphthalene-2,3-dialdehyde, perhydro-1,4: 5,8-dimethanonaphthalene-2,7-dialdehyde, perhydro-1,4: 5,8: 9,10- Tricyclohexyl-4,4'-dialdehyde, dicyclohexyl ether-3, 4'-dialdehyde, dicyclohexylmethane-3,3'-dialdehyde, Dicyclohexylmethane-3,4'-dialdehyde, dicyclohexylmethane-4,4'-dialdehyde, dicyclohexyldifluoromethane-3,3'-dialdehyde, dicyclohexyldifluoromethane- 3,4'-dialdehyde, dicyclohexyldifluoromethane-4,4'-dialdehyde, dicyclohexyl sulfone-3,3'-dialdehyde, dicyclohexyl sulfone-3,4'-dialdehyde, Dicyclohexyl sulfone-4,4'-dialdehyde, dicyclohexyl sulfide-3,3'-dialdehyde, dicyclohexyl sulfide-3,4'-dialdehyde, dicyclohexyl sulfide-4,4 '-Dialdehyde, dicyclohexylketone-3,3'-dial Bis (3-formylcyclohexyl) propane, 2,2-bis (4) -isobutyl ketone-4,4'-dodecylhexyl ketone-3,4'-dialdehyde, dicyclohexylketone- -Formylcyclohexyl) propane, 2,2-bis (3-formylcyclohexyl) hexafluoropropane, 2,2-bis (4-formylcyclohexyl) hexafluoropropane, 1,3-bis (3-formylcyclohexyl) benzene, 1,4-bis (3-formylcyclohexyl) benzene, 1,4- Cyclohexylene bis (1-methylethylidene)] biscyclohexanecarbaldehyde, 4 '- [1,4-cyclohexylenebis (1-methylethylidene)] biscyclohexanecarbaldehyde, Bis [4- (3-formylcyclohexyl) cyclohexyl] propane, 4'- [1,4-cyclohexylenebis (1-methylethylidene)] biscyclohexanecarbaldehyde, 2,2- Cyclohexyl] propane, 2,2-bis [4- (3-formylcyclohexyl) cyclohexyl] hexafluoropropane, 2 , Bis [4- (4-formylphenoxy) cyclohexyl] hexafluoropropane, bis [4- (3- formylcyclohexyloxy) cyclohexyl] (4-formylcyclohexyloxy) cyclohexyl] sulfide, bis [4- (3-formylcyclohexyloxy) cyclohexyl] sulfone, bis [4- , 2,2'-bicyclo [2.2.1] heptane-5,6'-dialdehyde, 2,2'-bicyclo [2.2.1] heptane-6,6'-dialdehyde, Diformamide adamantane and the like.

Of the above-mentioned dialdehyde compounds, isophthalaldehyde is preferred because it is easy to synthesize and obtain, and polybenzoxazole resins excellent in heat resistance and mechanical properties are easily obtained.

· Dicarboxylic dihalide

The dicarboxylic acid dihalide used as a raw material of the polybenzoxazole precursor is a compound represented by the following formula (2-2). The dicarboxylic acid dihalide may be used alone, or two or more dicarboxylic acid dihalides may be used in combination.

[Chemical Formula 59]

( ^Wherein R ^a2 is the same as in the 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, more preferably a chlorine atom.

Preferable examples of the compound represented by the formula (2-2) include a compound in which the two aldehyde groups of the aforementioned compound are substituted with a halocarbonyl group, preferably a chlorocarbonyl group, as a preferable example of the dialdehyde compound.

Of the dicarboxylic acid dihalides described above, terephthalic acid dichloride is preferable because it is easy to synthesize and obtain, and to easily obtain a polybenzoxazole resin excellent in heat resistance and mechanical properties.

(Production method of polybenzoxazole precursor)

In the present invention, the polybenzoxazole precursor is produced by reacting the above-mentioned aromatic diamine diol and a dicarbonyl compound in a solvent according to a known method. Hereinafter, as a typical example of the production method of the polybenzoxazole precursor, a production method in the case where the dicarbonyl compound is a dialdehyde compound and a production method in the case where the dicarbonyl compound is a dicarboxylic acid halide will be described.

· Reaction of an aromatic diamine diol with a dialdehyde compound

The reaction of the aromatic diamine diol and the dialdehyde compound is carried out in a solvent. The reaction between an aromatic diamine diol and a dialdehyde compound is a reaction of forming a Schiff base and can be carried out according to a well-known method. The reaction temperature is not particularly limited, but is preferably 20 to 200 占 폚, more preferably 20 to 160 占 폚, and particularly preferably 100 to 160 占 폚.

The reaction of the aromatic diamine diol and the dialdehyde compound may be carried out by adding an entrainer to the solvent and refluxing and dehydrating. The entrainer is not particularly limited and is appropriately selected from an organic solvent which forms an azeotropic mixture with water and forms a two-phase system with water at room temperature. Preferable examples of the entrainer include esters such as isobutyl acetate, allyl acetate, n-propyl propionate, isopropyl propionate, n-butyl propionate, and isobutyl propionate; Ethers such as dichloromethyl ether and ethyl isoamyl ether; Ketones such as ethyl propyl ketone; And aromatic hydrocarbons such as toluene.

The reaction time of the aromatic diamine diol and the dialdehyde compound is not particularly limited, but is preferably about 2 to 72 hours.

The amount of the dialdehyde compound used in preparing the polybenzoxazole precursor is preferably 0.5 to 1.5 moles, more preferably 0.7 to 1.3 moles, per 1 mole of the aromatic diamine diol.

The amount of the solvent to be used is not particularly limited as long as the reaction between the aromatic diamine diol and the dialdehyde compound proceeds satisfactorily. Typically, a solvent having a mass of 1 to 40 times, preferably 1.5 to 20 times the sum of the mass of the aromatic diamine diol and the mass of the dialdehyde compound is used.

The reaction of the aromatic diamine diol and the dialdehyde compound is preferably carried out until the number average molecular weight of the resulting polybenzoxazole precursor becomes 1,000 to 20,000, preferably 1,200 to 5,000.

· Reaction of aromatic diamine diol with dicarboxylic dihalide

The reaction of the aromatic diamine diol and the dicarboxylic acid dihalide is carried out in a solvent. The reaction temperature is not particularly limited, but is usually -20 to 150 占 폚, more preferably -10 to 150 占 폚, and particularly preferably -5 to 70 占 폚. In the reaction of an aromatic diamine diol and a dicarboxylic acid dihalide, hydrogen halide is by-produced. In order to neutralize such hydrogen halide, a small amount of an alkali metal hydroxide such as triethylamine, pyridine, N, N-dimethyl-4-aminopyridine or the like, or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added .

The reaction time of the aromatic diamine diol and the dicarboxylic acid dihalide is not particularly limited, but is preferably about 2 to 72 hours.

The amount of the dicarboxylic acid dihalide used when preparing the polybenzoxazole precursor is preferably 0.5 to 1.5 moles, more preferably 0.7 to 1.3 moles, per 1 mole of the aromatic diamine diol.

The amount of the solvent to be used is not particularly limited as long as the reaction between the aromatic diamine diol and the dicarboxylic acid dihalide proceeds satisfactorily. Typically, a solvent having a mass of 1 to 40 times, preferably 1.5 to 20 times the mass of the aromatic diamine diol and the dicarboxylic acid dihalide is used.

The reaction between the aromatic diamine diol and the dicarboxylic acid dihalide is preferably carried out until the number average molecular weight of the resultant polybenzoxazole precursor becomes 1,000 to 20,000, preferably 1,200 to 5,000.

By the above-described method, a solution of the polybenzoxazole precursor is obtained. In the case of preparing the negative radiation-sensitive composition 3, the solution of the polybenzoxazole precursor can be used as it is. The polybenzoxazole precursor obtained by removing at least a part of the solvent from the polybenzoxazole precursor solution at a low temperature at which the conversion from the polybenzoxazole precursor to the polybenzoxazole resin does not occur under reduced pressure Pastes or solids may also be used. A solution of the polybenzoxazole precursor in which the solids concentration is adjusted by adding a suitable amount of a solvent or the like to the solution of the polybenzoxazole precursor obtained by the above reaction may be used for the preparation of the negative radiation sensitive composition 3 .

Examples of the organic solvent used for the reaction between the aromatic diamine diol and the dicarbonyl compound include N, N-dimethylacetamide, N, N-diethylacetamide, N, N- Nitrogen polar solvents such as dimethylformamide, N, N-diethylformamide, N, N, 2-trimethylpropionamide, N-methylcaprolactam, and N, N, N ', N'-tetramethylurea; lactone-based polar solvents such as? -propiolactone,? -butyrolactone,? -valerolactone,? -valerolactone,? -caprolactone, and? -caprolactone; Dimethyl sulfoxide; Acetonitrile; Fatty acid esters such as ethyl lactate, and butyl lactate; And ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate, and ethyl cellosolve acetate.

Among these organic solvents, from the solubility of the polybenzoxazole precursor and the polybenzoxazole resin to be produced, it is possible to use N-methyl-2-pyrrolidone, N, N-dimethylacetamide, Examples of N, N, N ', N'-tetramethylurea and the like include N, N-dimethylformamide, N, N-diethylformamide, N, Nitrogen polar solvents are preferred.

[Photosensitive component]

The photosensitive component is not particularly limited and, as in the case of the negative radiation-sensitive composition 2, at least one of a base and an acid is decomposed by the action of light such as a photo-base generator and photo- (A). &Lt; / RTI &gt; The photosensitive component may be used alone or in combination of two or more.

By exposing the negative radiation-sensitive composition 3 containing the compound (A), the compound (A) in the negative-tone radiation-sensitive composition 3 is decomposed to generate at least one of a base and an acid. The base or acid generated in this manner acts on the polybenzoxazole precursor in the negative-tone radiation-sensitive composition 3 and promotes the conversion to the polybenzoxazole resin.

When the negative radiation-sensitive composition 3 containing the compound (A) is exposed, the compound (A) is decomposed in the exposed portion to generate at least one of a base and an acid. The conversion of the polybenzoxazole precursor to the polybenzoxazole resin in the negative-tone radiation-sensitive composition 3 is promoted by the base or acid thus generated, and the exposed portion is insoluble in the developer. On the other hand, since the unexposed portion is soluble in a developing solution, it can be dissolved and removed in a developing solution. Thus, by selectively exposing the negative radiation-sensitive composition 3, a desired pattern can be formed.

As the compound (A), for example, a compound (A-1) or an oxime compound (A-2) which is decomposed by the action of light to generate an imidazole compound may be used as the negative radiation- . The imidazole compound from which the compound (A-1) is generated accelerates the conversion of the polybenzoxazole precursor to the polybenzoxazole resin in the negative-tone radiation-sensitive composition 3. Further, the conversion of the polybenzoxazole precursor to the polybenzoxazole resin in the negative-tone radiation-sensitive composition 3 is promoted by the base or acid generated by decomposition of the compound (A-2). Details of the compound (A-1) and the compound (A-2) are the same as those described for the negative-tone radiation-sensitive composition 2.

The content of the photosensitive component in the negative-tone radiation-sensitive composition 3 is not particularly limited within the range not hindering the object of the present invention. The content of the photosensitive component in the negative-tone radiation-sensitive composition 3 is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, per 100 parts by mass of the polybenzoxazole precursor.

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

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

In the negative-tone radiation-sensitive composition 3, the content of the solvent is preferably such that the solid concentration of the negative-tone radiation-sensitive composition 3 is 1 to 50 mass%, more preferably 5 to 40 mass% . In the solvent contained in the negative-tone radiation-sensitive composition 3, the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0, more preferably 20:80 to 100 : 0 is more preferable. By setting the content of the solvent and the mass ratio of the compound represented by the general formula (1) to the other organic solvent within the above range, the negative-tone radiation-sensitive composition 3 is excellent in sensitivity, storage stability, coating property, developability and safety And the pattern formed by exposure and development of the negative radiation-sensitive composition 3 tends to be inhibited from the generation of foreign matter.

[Other ingredients]

The negative radiation-sensitive composition 3 may contain various additives, if necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, a defoaming agent, and a surfactant.

&Lt; Positive radiation sensitive composition 1 &gt;

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

[Compound represented by the general formula (1)

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

[Alkali-soluble resin]

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

The content of the alkali-soluble resin is preferably 5 to 90% by mass, more preferably 10 to 85% by mass with respect to the solid content of the positive-tone radiation-sensitive composition 1. Within the above range, the positive radiation-sensitive composition 1 tends to have a balance of film-forming ability and developability.

[Quinone diazide group-containing compound]

The quinone diazide group-containing compound is not particularly limited, but a compound having at least one phenolic hydroxyl group and a full esterified product or a partially esterified product of a quinone diazide group-containing sulfonic acid are preferable. Such a quinonediazide group-containing compound is obtained by reacting a compound having at least one phenolic hydroxyl group and a quinonediazide group-containing sulfonic acid in an appropriate solvent such as dioxane with an alkali such as triethanolamine, alkali metal carbonate, In the presence of a condensation agent to give a fully esterified or a partially esterified product. The quinone diazide group-containing compounds may be used alone or in combination of two or more.

Examples of the compound having at least one phenolic hydroxyl group include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone ;

Hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4- (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) Hydroxyphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) Dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis Dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis 2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl- Trisphenol-type compounds such as 4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane and bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane;

(2,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2,6-bis Linear type 3-core phenol compounds;

Bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5- Hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5- Hydroxyphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4- Hydroxyphenyl] methane, bis [2-hydroxy-3- (2-hydroxy-3- Methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane and the like Morphological 4 nuclei phenol compound;

Bis [4-hydroxy-3- (4-hydroxvbenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4- 5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy- Linear 5-core phenolic compounds such as methylphenol;

Bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- ( (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) propane, 2- 2- (4'-hydroxyphenyl) propane, 2- (2, 3, 4-trihydroxyphenyl) propane, 2- Hydroxyphenyl) -2- (4'-hydroxy-3 ', 5'-dimethylphenyl) -2- (4'-hydroxyphenyl) propane, 2- Bisphenol-type compounds such as propane, 4,4 '- [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol;

1- [1- (3-methylphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] ) Isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;

Condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane; And the like.

Examples of the quinone diazide group-containing sulfonic acid include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, orthoanthraquinonediazide sulfonic acid, have.

The content of the quinone diazide group-containing compound is preferably 10 to 95% by mass, more preferably 15 to 90% by mass based on the solid content of the positive-tone radiation-sensitive composition 1. Within the above range, the sensitivity of the positive radiation-sensitive composition 1 can be improved.

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

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

In the positive-tone radiation-sensitive composition 1, the content of the solvent is preferably such that the solid concentration of the positive-tone radiation-sensitive composition 1 is 1 to 50 mass%, more preferably 5 to 30 mass% . In the solvent contained in the positive radiation-sensitive composition 1, the mass ratio of the compound represented by the general formula (1) to the other organic solvent is preferably 5:95 to 100: 0, more preferably 20:80 to 100: : 0 is more preferable. When the content of the solvent and the mass ratio of the compound represented by the general formula (1) to the other organic solvent are in the above ranges, the positive radiation-sensitive composition 1 is excellent in sensitivity, storage stability, coatability, developability and safety And the pattern formed by exposure and development of the positive radiation-sensitive composition 1 tends to be inhibited from the generation of foreign matter.

[Other Polymers]

The positive radiation-sensitive composition 1 may contain other polymers. Other polymers may be used alone or in combination of two or more. Examples of other polymers include the polyamic acid described in the negative-tone radiation-sensitive composition 2, the polybenzoxazole precursor described in the negative-tone radiation-sensitive composition 3, the polymer having a structure represented by the following formula (31) .

The polymer having a structure represented by the general formula (31) as a main component can be a polymer having an imide ring, an oxazole ring or other ring structure by heating or a suitable catalyst. Polyamic acid or polyamic acid ester of a polyimide precursor, and polyhydroxyamide of a polybenzoxazole precursor. Here, the main component means that the structural unit represented by the general formula (31) is contained in an amount of 50 mol% or more of the total structural units of the polymer. More preferably 70 mol% or more, and more preferably 90 mol% or more.

(60)

In the general formula (31), R ¹ and R ² may be the same or different and represent a divalent to octavalent organic group having 2 or more carbon atoms. R ³ and R ⁴ may be the same or different and each represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms. l and m each represent an integer of 0 to 2, and p and q represent an integer of 0 to 4. However, p + q &gt; 0.

In the general formula (31), R ¹ represents a divalent to octavalent organic group having 2 or more carbon atoms, and represents a structural component of an acid. Examples of the acid in which R ¹ is divalent include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalene dicarboxylic acid and bis (carboxyphenyl) propane, cyclohexanedicarboxylic acid, And aliphatic dicarboxylic acids such as adipic acid. Examples of the acid in which R ¹ is trivalent include tricarboxylic acids such as trimellitic acid and trimesic acid. Examples of the acid in which R ¹ is tetravalent include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid and diphenylsulfone tetracarboxylic acid, , Aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and diester compounds in which two hydrogen atoms of the carboxyl group are substituted with a methyl group or an ethyl group. Also, examples of the acid include those having a hydroxyl group such as hydroxyphthalic acid and hydroxytrimellitic acid. Two or more of these acid components may be used, but it is preferable that the residue of the tetracarboxylic acid is contained in an amount of 1 to 40 mol%. From the viewpoint of solubility in an alkali developing solution and photosensitivity, it is preferable that the acid residue contains an acid residue having a hydroxyl group in an amount of 50 mol% or more.

R ¹ preferably has an aromatic ring in view of heat resistance, 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 octavalent organic group having 2 or more carbon atoms and represents a structural component of a diamine. It is preferable that R ² has an aromatic ring in view of heat resistance. Specific examples of the diamine include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane , Bis (aminophenoxyphenyl) sulfone, bis (amino-hydroxy-phenyl) hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diamino Phenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, compounds obtained by substituting at least a part of the hydrogen atoms of these aromatic rings with an alkyl group or halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine and hexamethylenediamine . Two or more of these diamine components may be used, but from the viewpoint of solubility in an alkali developing solution, it is preferable that the diamine contains a residue of a diamine having a hydroxyl group in an amount of 60 mol% or more.

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 viewpoints of the solubility in the alkali developing solution and the solution stability of the positive-tone radiation-sensitive composition 1, it is preferable that 10 mol% to 90 mol% of each of R ³ and R ⁴ is hydrogen. It is more preferable that R ³ and R ⁴ each contain at least one monovalent hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.

In formula (31), l and m represent the number of carboxyl groups or ester groups, and each independently represent an integer of 0 to 2. Preferably 1 or 2. P and q in the general formula (31) independently represent an integer of 0 to 4, and p + q &gt;

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

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

Further, for example, in order to improve the adhesiveness with the substrate, an aliphatic group having a siloxane structure may be copolymerized within a range not lowering the heat resistance. Concretely, a copolymer of 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane and bis (p-amino-phenyl) octamethylpentasiloxane as a diamine component can be given.

The content of the other polymer in the positive-tone radiation-sensitive composition 1 is not particularly limited within the range not hindering the object of the present invention. The content of the other polymer in the positive-tone radiation-sensitive composition 1 is preferably 1 to 300 parts by mass, more preferably 1 to 200 parts by mass, per 100 parts by mass of the alkali-soluble resin.

[Other ingredients]

The positive radiation-sensitive composition 1 may contain various additives, if necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, a defoaming agent, and a surfactant.

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

The radiation sensitive composition according to the present invention is prepared by mixing each of the above components with a stirrer. In addition, it may be filtered using a membrane filter or the like so that the prepared radiation sensitive composition becomes uniform.

«Pattern manufacturing method»

The method for producing a resist pattern according to the present invention includes the steps of forming a radiation-sensitive composition film on a substrate, which comprises a radiation-sensitive composition according to the present invention, and a step of exposing the radiation- And a developing step of developing the exposed radiation sensitive composition film.

First, in the step of forming a radiation-sensitive composition film, a non-contact type coating device such as a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, a spinner (rotary coating device), or a curtain flow coater , The radiation sensitive composition according to the present invention is applied and, if necessary, the solvent is removed by drying to form a radiation sensitive composition film.

In the step of forming the radiation-sensitive composition film, a radiation-sensitive composition film (dry film) formed of the radiation-sensitive composition formed on the support film is attached to the substrate to form a radiation- . The dry film can be formed by applying the above radiation sensitive composition onto a support film by a conventional method and then drying it.

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

Subsequently, in the development step, the exposed radiation-sensitive composition film is developed with a developer 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 ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

<Material>

Details of each component used in Examples and Comparative Examples are as follows.

· Alkali-soluble resin

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

Acrylic resin 1: Methacrylic acid (MAA), tricyclodecanyl methacrylate (TCDMA), 2,3-epoxycyclohexylmethyl methacrylate (ECHM) and glycidyl methacrylate (GMA) were dissolved in MAA / TCDMA / ECHM / GMA = 15/20/40/25 (mass ratio), and an acrylic resin having a structural unit represented by the following formula (weight average molecular weight 10,000), obtained by addition polymerization by a conventional method,

(61)

Acrylic resin 2: Acrylic resin (mass average molecular weight: 15,000) obtained by addition polymerization of benzyl methacrylate (BzMA) and methacrylic acid (MAA) at BzMA / MAA = 80/20 (mass ratio)

· 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: &quot; IRGACURE OXE02 &quot; (trade name, manufactured by BASF)

Colorant 1: Carbon dispersion "CF Black" (trade name, manufactured by Mikuni Color Company, solids content: 25%, solvent: 3-methoxybutyl acetate)

Colorant 2: Black pigment A pigment dispersion (solid content: 15% by mass, manufactured by BASF) having an average particle diameter of 90 to 190 nm was prepared by dispersing Experimental Black 582 (trade name, manufactured by BASF) Solvent: propylene glycol monomethyl ether acetate)

Colorant 3: R254 (CI Pigment Red 254) / Y139 (CI Pigment Yellow) (mixing mass ratio: 85/15) was used in combination with a dispersant and acrylic resin 2 (solid content ratio to pigment: 10% (Solid content: 18 mass%, solvent: propylene glycol monomethyl ether acetate) prepared so as to have an average particle diameter of 90 to 190 nm,

Colorant 4: A pigment prepared from pigment G36 (CI Pigment Green 36) / Y150 (CI Pigment Yellow 150) (mixing mass ratio: 70/30) to have an average particle diameter of 90 to 190 nm Dispersion (solid content 18% by mass, solvent: propylene glycol monomethyl ether acetate)

Colorant 5: Pigment prepared from pigment B156 (CI Pigment Blue 156) / V23 (CI Pigment Violet 23) (mixing weight ratio: 90/10) so as to have an average particle diameter of 90 to 190 nm Dispersion (solid content 15% by mass, solvent: propylene glycol monomethyl ether acetate)

· Surfactants

Surfactant 1: &quot; Granol 440 &quot; (trade name, available from Kyowa Chemical Industry Co., Ltd.)

Compounds 1 to 4: Compounds represented by the following formulas (E1) to (E4)

(62)

· Other organic solvents

MBA: 3-methoxybutylacetate

PGMEA: Propylene glycol monomethyl ether acetate

EEP: ethyl 3-ethoxypropionate

EL: Ethyl lactate

NMP: N-methyl-2-pyrrolidone

GBL:? -Butyrolactone

Cardo Resin 1 was synthesized according to the following prescription.

235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid 72.0 g, and the mixture was heated and dissolved at 90 to 100 占 폚 while blowing air at a rate of 25 ml / min. Next, the solution was slowly heated in a cloudy state, and completely dissolved by heating at 120 ° C. At this time, the solution gradually became a transparent point group, but stirring was continued. During this time, the acid value was measured, and the heating and stirring were continued until the temperature was less than 1.0 mgKOH / g. The acid value required 12 hours to reach the target value. The mixture was then cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following structural formula (a-4) which was colorless transparent and solid.

(63)

Subsequently, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained and dissolved. Then, 80.5 g of benzophenonetetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed The temperature was gradually raised, and the reaction was carried out at 110 to 115 ° C for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain Cardos resin 1. The disappearance of the acid anhydride group was confirmed by IR spectrum. This cardo resin 1 corresponds to the compound represented by the aforementioned general formula (a-1).

&Lt; Preparation of transparent resist &

The alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, and the surfactant were mixed with a solvent having the composition shown in Table 2 in accordance with the composition and blending amount (unit: parts by mass) shown in Table 1 to obtain a solid content concentration of 20% Of a negative radiation sensitive composition was prepared.

[bow]

A negative radiation-sensitive composition was spin-coated on a glass base material having a thickness of 680 mm x 880 mm x 0.7 mm and the coating film was dried at 100 占 폚 for 120 seconds to form a photosensitive resin layer having a thickness of 1.2 占 퐉. Subsequently, the photosensitive resin layer was exposed at an exposure dose of 100 mJ / cm 2. Subsequently, an aqueous solution containing 0.04% by mass of KOH and 0.1% by mass of a surfactant EMULGEN A60 (manufactured by Kao Corporation) was used as a developing solution, subjected to a shower phenomenon at 23 DEG C for 60 seconds, Takano). The results are shown in Table 2.

[Sensitivity]

A negative radiation-sensitive composition was spin-coated on a glass base material having a thickness of 680 mm x 880 mm x 0.7 mm and the coating film was dried at 100 占 폚 for 120 seconds to form a photosensitive resin layer having a thickness of 1.2 占 퐉. Subsequently, the photosensitive resin layer was exposed at various exposure amounts using a mask of a line-and-space pattern. Subsequently, 0.04% by mass of KOH and 0.1% by mass of a surfactant EMULGEN A60 (manufactured by Kao Corporation) were used as a developer and a shower phenomenon was performed at 23 DEG C for 60 seconds. The exposure amount at which the CD (Critical Dimension) of the obtained line pattern became CD + 1 占 퐉 of the mask was determined and evaluated according to the following criteria. The results are shown in Table 2.

?: Less than 100 mJ / cm 2,?: 100 to 140 mJ / cm 2, ×: more than 140 mJ / cm 2

[Precipitates]

The negative radiation-sensitive composition was subjected to aging treatment at -5 占 폚 for 2 weeks, followed by spin-coating on a glass substrate having a size of 10 cm in length and 10 cm, and the number of foreign substances precipitated was counted and evaluated according to the following criteria. The results are shown in Table 2.

?: 0 to 2,?: 3 to 10, X: 11 or more

[Change in viscosity]

The viscosity of the negative-tone radiation-sensitive composition subjected to the aging treatment at 40 ° C for 2 weeks was measured and the amount of change from the initial viscosity of 5 mPa · s was determined and evaluated according to the following criteria. The results are shown in Table 2.

?: Change amount is less than 0.5 mPa.s,?: Change amount is 0.5 to 2 mPa.s, X: Change amount is more than 2 mPa.s

[Irregular application]

The negative radiation-sensitive composition was spin-coated on a glass substrate having a thickness of 680 mm x 880 mm x 0.7 mm, and when the coating film was dried at 100 캜 for 120 seconds, whether coating unevenness such as pin irregularity or uneven spinning occurred Visually, and evaluated by the following criteria. The results are shown in Table 2.

?: No coating irregularity occurred,?: Irregular coating irregularity occurred locally, X: Coating irregularity occurred on the entire surface

As can be seen from Table 2, the negative-tone radiation-sensitive compositions of the examples containing the compound represented by the above-mentioned general formula (1) were excellent in sensitivity, storage stability and applicability, Can be formed.

On the other hand, the negative-tone radiation-sensitive compositions of the comparative example which do not contain the compound represented by the general formula (1) are inferior in sensitivity and storage stability, and are more inferior in coating property, / Or more foreign matter was generated in the pattern formed by exposure and development.

<Preparation of Black Matrix Resist, Color Filter Resist, and Black Photo Spacer Resist>

The alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, the colorant, and the surfactant were mixed with a solvent having the composition shown in Tables 4 to 8 according to the composition and blending amount (unit: parts by mass) shown in Table 3 Was converted to solid content), and a solid content concentration of 18 mass% was prepared.

The obtained negative-tone radiation-sensitive compositions were evaluated for foreign matters, sensitivity, viscosity variation, and coating unevenness in the same manner as in the above-mentioned "production of transparent resist". The results are shown in Tables 4-8.

[Agglomerate]

The negative radiation-sensitive composition was subjected to aging treatment at 40 占 폚 for 2 weeks, followed by spin-coating on a glass substrate having an aspect ratio of 10 cm, and the number of aggregated foreign matters was counted and evaluated according to the following criteria. The results are shown in Tables 4-8.

?: 0 to 2,?: 3 to 10, X: 11 or more

In the uppermost stage of Table 3, BM represents Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-4, and R represents Examples 3-1 to 3-7 and Comparative Example 3 -1 to 3-4, G is Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-4, B is Examples 5-1 to 5-7 and Comparative Example 5 -1 to 5-4, and BPS represents Examples 6-1 to 6-7 and Comparative Examples 6-1 to 6-4.

As can be seen from Tables 4 to 8, the negative-tone radiation-sensitive compositions of the examples containing the compound represented by the general formula (1) had excellent sensitivity, storage stability and applicability, , It was possible to form a pattern in which the generation of foreign matter was suppressed.

On the other hand, the negative-tone radiation-sensitive compositions of the comparative example not containing the compound represented by the general formula (1) had inferior storage stability, more foreign matter was generated in the patterns formed by exposure and development, Depending on the solvent, the coating properties were inferior. In addition, the negative-tone radiation-sensitive composition of Comparative Example containing a light-shielding agent as a colorant had inferior sensitivity.

<Preparation of positive-tone radiation-sensitive composition>

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

[Presence or absence of precipitate]

The prepared positive-tone radiation-sensitive composition was filtered with a 0.2 탆 membrane filter and allowed to stand at 40 캜, and the presence or absence of precipitates in the positive-tone radiation-sensitive composition at the passage of 2 months was examined. The results are shown in Table 9.

[Sensitivity change]

The presence or absence of the sensitivity change of the positive-tone radiation-sensitive composition after 3 months was examined. That is, the case where the positive radiation-sensitive composition immediately after preparation is applied to the substrate and dried, and the minimum exposure amount (sensitivity) when the positive radiation-sensitive composition which has been prepared and applied for 3 months has been applied to the substrate and dried has been compared , &Quot; o &quot;, and &quot; x &quot;, respectively. The results are shown in Table 9.

[Cross-sectional shape]

The prepared positive radiation-sensitive composition was slit-coated on a glass substrate and dried at 90 캜 for 90 seconds on a hot plate to form a resist film having a film thickness of 1.3 탆. Using a stepper, Thereafter, the resist film was heated on a hot plate at 110 DEG C for 90 seconds, developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), washed with water for 30 seconds and dried, Respectively. The results are shown in Table 9. The undercut means that the width of the lowermost portion of the resist pattern in contact with the glass substrate in the cross section of the resist pattern is narrower than the width of the uppermost portion of the resist pattern.

?: No undercut occurred at the contact portion between the glass substrate and the resist pattern.

X: Undercut occurred at the contact portion between the glass substrate and the resist pattern.

[Application state]

The positive-tone radiation-sensitive composition thus prepared was slit-coated on a glass substrate and dried at 90 ° C for 90 seconds on a hot plate. The film thickness was measured to find that the film was uniformly applied in the plane as "good" And those that were not coated were determined as &quot; defective &quot;. The results are shown in Table 9.

As can be seen from Table 9, the positive radiation-sensitive compositions of the examples containing the compound represented by the above-mentioned general formula (1) were excellent in storage stability, developability and applicability.

On the other hand, the positive-tone radiation-sensitive compositions of the comparative examples not containing the compound represented by the general formula (1) were inferior in storage stability, developability and applicability.

<Preparation of negative type radiation sensitive resin composition containing polyamic acid>

654.4 g of pyromellitic acid dianhydride (PMDA), which is a tetracarboxylic acid dianhydride, and 4,4'-dicyclohexylmethane diisocyanate, were added to a separable flask having a capacity of 5 L equipped with a stirrer, a stirrer, a reflux condenser and a nitrogen gas- 672.8 g of diaminodiphenyl ether (ODA) and a solvent having the composition shown in Table 10 were charged. Nitrogen was introduced from the nitrogen gas introducing tube into the flask, and the inside of the flask was changed to nitrogen atmosphere. Then, the tetracarboxylic acid dianhydride and the diamine were reacted with each other at 50 DEG C for 20 hours while stirring the content of the flask 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 radiation sensitive resin composition having a solid content concentration of 30 mass%.

The obtained negative-tone radiation-sensitive resin composition was evaluated for foreign matter, viscosity change, and coating irregularity in the same manner as in &quot; production of transparent resist &quot;. The results are shown in Table 10.

As can be seen from Table 10, the negative-tone radiation-sensitive resin composition of the example containing the compound represented by the above-mentioned general formula (1) was excellent in storage stability and coating property, This suppressed pattern could be formed.

On the other hand, the negative-tone radiation-sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) has inferior storage stability and coating property, and more foreign matter is generated in the patterns formed by exposure and development Respectively.

<Preparation of polybenzoxazole precursor-containing negative-tone radiation-sensitive resin composition>

2 mmole of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as an aromatic diamine diol and 1 ml of a solvent having the composition shown in Table 11 were added to an Erlenmeyer flask containing a rotor, The contents of the flask were then stirred for 5 minutes using a magnetic stirrer. Then, 2 mmole of isophthalaldehyde, which is a dicarbonyl compound, was placed in a flask, and the content of the flask was refluxed for 3 hours under nitrogen atmosphere to carry out the reaction. Then, the reaction solution was dehydrated by vacuum distillation to obtain a polybenzoxazole precursor solution.

To the obtained polybenzoxazole 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 concentration of 30 mass% Respectively.

The obtained negative-tone radiation-sensitive resin composition was evaluated for foreign matter, viscosity change, and coating irregularity in the same manner as in &quot; production of transparent resist &quot;. The results are shown in Table 11.

As can be seen from Table 11, the negative-tone radiation-sensitive resin composition of the example containing the compound represented by the general formula (1) was excellent in storage stability and coating property, This suppressed pattern could be formed.

On the other hand, the negative-tone radiation-sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) has inferior storage stability and coating property, and more foreign matter is generated in the patterns formed by exposure and development Respectively.

&Lt; Preparation of positive photosensitive radiation-containing resin composition containing polyamic acid &gt;

[Synthesis of hydroxyl group-containing acid anhydride (a)] [

18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and 34.2 g (0.3 mol) of allyl glycidyl ether were added to 100 g of GBL Dissolved and cooled to -10 &lt; 0 &gt; C. 22.1 g (0.11 mol) of anhydrous trimellitic acid 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 dropwise addition, the mixture was stirred at 0 ° C for 5 hours. This solution was concentrated with a rotary evaporator and poured into 1 L of toluene to obtain a hydroxyl group-containing acid anhydride (a) represented by the following formula.

&Lt; EMI ID =

[Synthesis of Polymer A]

Under nitrogen flow, 4.40 g (0.022 mol) of 4,4'-diaminophenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 50 g of NMP. Thereto was added 21.4 g (0.030 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1, followed by reaction at 20 ° C for 1 hour and subsequent reaction at 40 ° C for 2 hours. Thereafter, 0.65 g (0.006 mol) of 4-aminophenol was added, and the mixture was further reacted at 40 DEG C for 45 minutes. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropwise addition, the mixture was stirred at 40 占 폚 for 3 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the precipitate of the polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 45 캜 for 80 hours to obtain a polymer A, which is a polyimide precursor. The mass average molecular weight of the polymer A was measured by GPC and it was confirmed that the number of the structural units represented by the general formula (31) was within the range of 10 to 500.

[Synthesis of novolac resin A]

(0.35 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g of formaldehyde solution (0.93 mol) of 37 wt% of formaldehyde, 0.63 g (0.005 mol) of oxalic acid dihydrate, 264 g of isobutyl ketone was poured, and the mixture was immersed in an oil bath. The reaction solution was refluxed for 4 hours to effect polycondensation reaction. Thereafter, the temperature of the oil bath was raised over 3 hours, and thereafter the inside of the flask was depressurized to remove volatile components, and the dissolved resin was cooled to room temperature to obtain a polymer solid of novolac resin A. According to GPC, the novolak resin A had a weight average molecular weight of 4,000.

[Preparation of composition]

6 g of a solid of polymer A, 4 g of novolak resin A, 2 g of quinone diazide compound A represented by the following formula, 6.0 g of HMOM-TPHAP (trade name, manufactured by Honsyu Chemical Industry Co., Ltd.), BIR- (Manufactured by Organic Materials Co., Ltd.) and 0.3 g of vinyltrimethoxysilane were weighed and dissolved in a solvent having the composition shown in Table 12 to obtain a positive radiation-sensitive resin composition having a solid content concentration of 30 mass% .

The obtained positive-tone radiation-sensitive resin composition was evaluated for foreign matters, viscosity change, and coating unevenness in the same manner as in &quot; production of transparent resist &quot;. The results are shown in Table 12.

(65)

[Wherein D is H or a 1,2-naphthoquinonediazide-5-sulfonyl group, and the average esterification ratio of D with the 1,2-naphthoquinonediazide-5-sulfonyl group is 59.9% . In addition, since there is a variation in the number of substitution or substitution position of D depending on the molecule, the average ratio (average esterification ratio (%)) in which D is 1,2-naphthoquinonediazide-5-sulfonyl group . Hereinafter, it is the same.]

As can be seen from Table 12, the positive-tone radiation-sensitive resin composition of the example containing the compound represented by the general formula (1) was excellent in storage stability and coating property, This suppressed pattern could be formed.

On the other hand, the positive radiation-sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) has poor storage stability and coating property, and more foreign matter is generated among the patterns formed by exposure and development Respectively.

<Preparation of positive-tone radiation-sensitive resin composition containing polyamic acid>

6 g of a solid of polymer A, 4 g of novolak resin A, 2 g of quinone diazide compound B represented by the following formula, 6.0 g of HMOM-TPHAP (trade name, manufactured by Honsyu Chemical Industry Co., Ltd.), BIR- (Manufactured by Organic Materials Co., Ltd.) and 0.3 g of vinyltrimethoxysilane were weighed and dissolved in a solvent having the composition shown in Table 13 to obtain a positive radiation-sensitive resin composition having a solid content concentration of 30 mass% . Polymer A and novolac resin A were obtained in &quot; Preparation 1 of positive-tone radiation-sensitive resin composition containing polyamic acid. &Quot;

The obtained positive-tone radiation-sensitive resin composition was evaluated for foreign matters, viscosity change, and coating unevenness in the same manner as in &quot; production of transparent resist &quot;. The results are shown in Table 13.

(66)

[Wherein D is H or a 1,2-naphthoquinonediazide-5-sulfonyl group, and the average esterification ratio by D, a 1,2-naphthoquinonediazide-5-sulfonyl group is 54.7% .]

As can be seen from Table 13, the positive-tone radiation-sensitive resin composition of the example containing the compound represented by the above-mentioned general formula (1) was excellent in storage stability and coating property, This suppressed pattern could be formed.

On the other hand, the positive radiation-sensitive resin composition of the comparative example which does not contain the compound represented by the general formula (1) has poor storage stability and coating property, and more foreign matter is generated among the patterns formed by exposure and development Respectively.

Claims (4)

A radiation-sensitive composition containing a compound represented by the following general formula (1).
[Chemical Formula 1]

(Wherein R ¹ represents a hydrogen atom or a hydroxyl group, R ² and R ³ independently represent a hydrogen atom or a C ₁ -C ₃ alkyl group, R ⁴ and R ⁵ independently represent C ₁ To C &lt; ₃ &gt;). The method according to claim 1,
Wherein the compound represented by the general formula (1) is at least one compound represented by each of the following formulas (E1) to (E4).
(2)

The method according to claim 1,
A radiation-sensitive composition containing the compound represented by the general formula (1) as at least one kind of solvent. A radiation-sensitive composition film forming process for forming a radiation-sensitive composition film comprising the radiation-sensitive composition according to any one of claims 1 to 3 on a substrate,
An exposure step of exposing the radiation sensitive composition film to positional selective exposure,
And a development step of developing the exposed radiation sensitive composition film.