KR102128155B1 - Radiation sensitive composition and pattern forming method - Google Patents

Abstract

Provided is a radiation-sensitive composition capable of forming a pattern in which sensitivity, storage stability, applicability, developability, and safety are excellent, and the generation of foreign matter is suppressed by exposure and development, and a method for manufacturing a pattern using the same.
The radiation-sensitive composition according to the present invention contains a compound represented by the following general formula (1). In the formula, R ¹ represents a hydrogen atom or a hydroxyl group, R ² and R ³ independently represent a hydrogen atom or a C ₁ to C ₃ alkyl group, and R ⁴ and R ⁵ independently represent C ₁ to C ₃ represents an alkyl group.

Description

Radiation-sensitive composition and pattern manufacturing method {RADIATION SENSITIVE COMPOSITION AND PATTERN FORMING METHOD}

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

Microfabrication is required in the manufacture of integrated circuits, color filters, liquid crystal elements, and the like, but conventional radiation-sensitive compositions have been used to satisfy this demand. Generally, the radiation-sensitive composition has a positive type and a negative type, and usually either is dissolved in a solvent and used in solution.

The radiation-sensitive composition is coated on a substrate such as a silicon substrate or a glass substrate by a known coating method such as spin coating, roller coating, slit coating, ink jet, and then prebaked to form a radiation-sensitive composition film. After the exposure to the photosensitive wavelength range of the radiation-sensitive composition, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, etc. are exposed to particle beams, etc., and after development, dry etching is performed as necessary to form a desired pattern.

As a solvent used for the radiation-sensitive composition, various materials have been conventionally used, and are selected and used in consideration of solubility, coatability, sensitivity, developability, and pattern characteristics to be formed. For example, ethylene glycol monoethyl ether acetate is known as a solvent having excellent properties such as solubility, coating properties, and radiation-sensitive composition film-forming properties, but safety issues with respect to the human body have recently been pointed out, and safety is high. There is a demand for a solvent having excellent resin solubility and initiator solubility, and improved performance such as radiation-sensitive composition film-forming properties.

As a solution to these, 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. Hei 3-1659

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

The present invention has been made in view of the above circumstances, and has excellent sensitivity, storage stability, applicability, developability, and safety, and is capable of forming a pattern in which the occurrence of foreign matter is suppressed by exposure and development. It is an object to provide a radioactive composition and a method for producing a pattern using the same.

As a result of repeated studies of the inventors to solve the above problems, the present inventors have found that the above problems can be solved by using a specific organic solvent and have completed the present invention. Specifically, the present invention provides the following.

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

[Formula 1]

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

In a second aspect of the present invention, a radiation-sensitive composition film forming step of forming a radiation-sensitive composition film made of the radiation-sensitive composition on a substrate, an exposure process of positionally exposing the radiation-sensitive composition film, and exposure It is a pattern production method comprising a developing step of developing the radiation-sensitive composition film.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in sensitivity, storage stability, coatability, developability, and safety, and the radiation-sensitive composition which can form the pattern by which the generation|occurrence|production of the foreign material was suppressed by exposure and development, and the pattern manufacturing method using the same Can provide

≪Sensitive radiation composition≫

The radiation-sensitive composition according to the present invention contains at least a compound represented by the general formula (1). The compound represented by the general formula (1) is used as a solvent in the radiation-sensitive composition according to the present invention. The radiation-sensitive composition according to the present invention may contain only the compound represented by the above general formula (1) as a solvent, and is also referred to as an organic solvent other than the compound represented by the above general formula (1) (hereinafter referred to as "other organic solvent"). ) May be further included. That is, the radiation-sensitive composition according to the present invention contains the compound represented by the general formula (1) as at least one solvent. The compound represented by the general formula (1), in the radiation-sensitive composition according to the present invention, alone or in the form of a mixed solvent with other organic solvents, components other than the solvent (hereinafter referred to as "base component"). ) As a solvent to dissolve and/or disperse. Since the radiation-sensitive composition according to the present invention contains the compound represented by the general formula (1), sensitivity, storage stability, coatability, developability, and safety are excellent, and generation of foreign matter is suppressed by exposure and development. Pattern can be formed. The radiation-sensitive composition according to the present invention can be suitably used, for example, in the production of black matrices, color filters, black photo spacers, integrated circuits, liquid crystal devices, and the like.

[Compound represented by general formula (1)]

The compound represented by the above general formula (1) is a solvent capable of satisfactorily dissolving and/or dispersing the base component contained in the radiation-sensitive composition, and can be widely used in general radiation-sensitive compositions. Especially, when a radiation sensitive composition contains an oxime type photoinitiator, the compound represented by said general formula (1) has favorable solubility of an oxime type photoinitiator. The compounds represented by the general formula (1) can 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 groups.

It is preferable that R ² , R ³ , R ⁴ , and R ⁵ are independently a methyl group or an ethyl group.

As a specific example of the compound represented by the said general formula (1), the compound represented by each following formula is mentioned.

[Formula 2]

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

[Formula 3]

In the radiation-sensitive composition according to the present invention, the amount of the solvent is preferably an amount such that the solid content concentration of the radiation-sensitive composition is 1 to 50% by mass, and more preferably 5 to 30% by mass. Moreover, in the solvent contained in the radiation sensitive composition which concerns on this invention, it is preferable that the mass ratio of the compound represented by said general formula (1) and other organic solvents is 5:95-100:0, and it is 20:80- It is more preferable that it is 100:0. When the content of the solvent and the mass ratio of the compound represented by the general formula (1) and other organic solvents are within the above range, the resulting radiation-sensitive composition tends to be excellent in sensitivity, storage stability, coatability, developability, and safety. , The pattern formed by exposing and developing the radiation-sensitive composition is likely to be suppressed from the occurrence of foreign matter. Note that 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 a negative radiation sensitive composition, the negative radiation sensitive composition containing the compound represented by said general formula (1) and alkali-soluble resin; A radiation-sensitive polyimide precursor composition containing a compound represented by the general formula (1), a polyamic acid, and photosensitive components such as a photobase generator and a photoacid generator; Radiation-sensitive polybenzoxazole precursor composition containing the compound represented by the said general formula (1), a polybenzoxazole precursor, and photosensitive components, such as a photobase generator and a photoacid generator; And a radiation-sensitive SOG (spin-on-glass) composition containing the compound represented by the general formula (1). As a positive radiation sensitive composition, the positive radiation sensitive composition containing the compound represented by said general formula (1), alkali-soluble resin, and a quinonediazide group containing compound; Radiation-sensitive polyimide composition containing the compound represented by said general formula (1), a polyimide resin, and photosensitive components, such as a photobase generator and a photoacid generator; And a chemically amplified positive radiation-sensitive composition containing a compound represented by the general formula (1), a resin whose solubility in alkali increases by the action of an acid, and a photoacid generator. Hereinafter, among these radiation-sensitive compositions, the negative radiation-sensitive composition containing the compound represented by the general formula (1) and an alkali-soluble resin (hereinafter referred to as "negative radiation-sensitive composition 1"), the A radiation-sensitive polyimide precursor composition (hereinafter referred to as "negative radiation-sensitive composition 2") containing a compound represented by the general formula (1), a polyamic acid, and photosensitive components such as a photobase generator and a photoacid generator. .), a radiation-sensitive polybenzoxazole precursor composition containing a compound represented by the general formula (1), a polybenzoxazole precursor, and photosensitive components such as a photobase generator and a photoacid generator (hereinafter referred to as "negative". Type radiation-sensitive composition 3”), and a positive-type radiation-sensitive composition containing a compound represented by the general formula (1), an alkali-soluble resin, and a quinonediazide group-containing compound (hereinafter referred to as “positive type”). Radiation-sensitive composition 1”) will be described in detail.

<Negative radiation sensitive composition 1>

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

[Compound represented by 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 general formula (1) can be used alone or in combination of two or more.

[Alkali-soluble resin]

The alkali-soluble resin is a resin solution having a resin concentration of 20 mass% (solvent: propylene glycol monomethyl ether acetate), and a resin film having a film thickness of 1 µm is formed on a substrate, and immersed in a KOH aqueous solution having a concentration of 0.05 mass% for 1 minute. When it does, it means that it melt|dissolves more than 0.01 micrometer in film thickness.

The alkali-soluble resin is not particularly limited as long as it is a resin exhibiting the alkali-soluble properties described above, and conventionally known alkali-soluble resins can be used. Alkali-soluble resin can be used individually or in combination of 2 or more types.

As an example of a preferable alkali-soluble resin, (A1) resin which has a cardo structure is mentioned. (A1) The resin having a cardo structure is not particularly limited, and a conventionally known resin can be used. Especially, resin represented by following formula (a-1) is preferable.

[Formula 4]

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

[Formula 5]

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

[Formula 6]

Moreover, in said Formula (a-1), Y ^a represents the residue which removed the acid anhydride group (-CO-O-CO-) from dicarboxylic anhydride. Examples of dicarboxylic acid anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene anhydride tetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro anhydride Phthalic acid, glutaric anhydride, and the like.

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

Moreover, in said Formula (a-1), m represents the integer of 0-20.

(A1) The mass average molecular weight of the resin having a cardo structure is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the said range, sufficient heat resistance and film strength can be obtained while obtaining favorable developability. In addition, in this specification, a mass average molecular weight means the value by polystyrene conversion measured by gel permeation chromatography (GPC).

Moreover, (A2) epoxy resin is mentioned as another example of a preferable alkali-soluble resin. (A2) It does not specifically limit as an epoxy resin, A conventionally well-known epoxy resin can be used, and it does not have an ethylenically unsaturated group, and may have an ethylenically unsaturated group.

As an epoxy resin which does not have an ethylenically unsaturated group, for example, a resin (A2-1) obtained by at least copolymerizing 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. Among these, (meth)acrylic acid and maleic anhydride are preferred from the viewpoint of copolymerization reactivity, alkali solubility of the resulting resin, and availability. These unsaturated carboxylic acids can be used alone or in combination of two or more.

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

The proportion of the structural unit (structural unit having a carboxyl group) derived from unsaturated carboxylic acid in the resin (A2-1) is preferably 5 to 29 mass%, more preferably 10 to 25 mass%. By setting it as the said range, the developability of the negative radiation sensitive composition 1 can be made suitable.

The epoxy group-containing unsaturated compound may or may not have an alicyclic epoxy group, or may have an alicyclic epoxy group, but more preferably has an alicyclic epoxy group.

As an epoxy group-containing unsaturated compound which does not have an alicyclic epoxy group, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7- (Meth)acrylic acid epoxyalkyl esters such as epoxy heptyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate; α-alkyl acrylic acid epoxyalkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, and α-ethyl acrylic acid 6,7-epoxyheptyl; glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; And the like. Among these, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, o in terms of copolymerization reactivity, strength of the resin after curing, etc., o -Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether are preferred.

The alicyclic group of the epoxy group-containing unsaturated compound having an alicyclic epoxy group may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Moreover, as a polycyclic alicyclic group, a norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, tetracyclododecyl group, etc. are mentioned.

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 these, the compounds represented by the following formulas (a4-1) to (a4-6) are preferred, and the following formulas (a4-1) to (a4-) in order to make the developability of the negative radiation sensitive composition 1 suitable. The compound represented by 4) is more preferable.

[Formula 7]

[Formula 8]

[Formula 9]

In the above formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a5 represents 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 is preferable, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a5 , for example, methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, -CH ₂ -Ph-CH _2- ( Ph represents a phenylene group) is preferred.

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

The proportion of the structural unit (a structural unit having an epoxy group) derived from the epoxy group-containing unsaturated compound in the resin (A2-1) is preferably 5 to 90 mass%, more preferably 15 to 75 mass%. By setting it as the said range, it becomes easy to form a pattern of favorable shape.

It is preferable that the said resin (A2-1) copolymerized the alicyclic group containing unsaturated compound further.

The alicyclic group of the alicyclic group-containing unsaturated compound may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Further, examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a 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, in order to make the developability of the negative radiation sensitive composition 1 suitable, compounds represented by the following formulas (a5-3) to (a5-8) are preferred, and the following formulas (a5-3) and (a5- The compound represented by 4) is more preferable.

[Formula 10]

[Formula 11]

In the above formula, R ^a6 represents a hydrogen atom or a methyl group, R ^a7 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a8 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R ^a7 , a single bond, linear or branched alkylene group is preferable, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a8 , for example, a methyl group and an ethyl group are preferable.

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

Moreover, the said resin (A2-1) may further copolymerize other compounds than the above. Examples of such other compounds include (meth)acrylic acid esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These compounds can be used alone or in combination of two or more.

Examples of the (meth)acrylic acid esters include straight chain types such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and t-octyl (meth)acrylate. Or branched chain alkyl (meth)acrylate; Chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono (meth)acrylate, benzyl (meth)acrylate, Furfuryl (meth)acrylate; And the like.

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

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.

As vinyl ethers, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chlorethyl vinyl ether, 1-methyl-2,2-dimethylpropyl Vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl Alkyl vinyl ethers such as ether; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorphenyl ether, vinyl-2,4-dichlorphenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; And the like.

Examples of vinyl esters include vinyl butylate, vinyl isobutylate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chlorate, vinyl dichlor acetate, vinyl methoxy acetate, and vinyl butoxy acetate. , Vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutylate, vinyl benzoate, vinyl salicylate, vinyl chlorbenzoate, vinyl tetrachlorbenzoate, vinyl naphthoate, and the like.

As styrenes, Styrene; Methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chlormethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene , Alkyl styrenes such as acetoxy methyl styrene; Alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodinestyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Halostyrenes such as styrene and 4-fluoro-3-trifluoromethylstyrene; And the like.

The mass average molecular weight of the resin (A2-1) is preferably 2000 to 50,000, more preferably 5000 to 30,000. By setting it as the said range, there exists a tendency which is easy to balance the film-forming ability and developability of the negative radiation sensitive composition 1.

On the other hand, as an epoxy resin having an ethylenically unsaturated group, for example, a resin obtained by reacting an carboxyl group of a resin obtained by at least polymerizing an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, and an epoxy group of an epoxy group-containing unsaturated compound (A2-2), Alternatively, a resin (A2-3) obtained by reacting an epoxy group of a resin obtained by at least polymerizing an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound and a carboxyl group of an unsaturated carboxylic acid can be used.

As an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, the compound illustrated by the said resin (A2-1) is mentioned. Therefore, the resin (A2-1) is exemplified as a resin obtained by at least polymerizing an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound.

The proportion of the structural unit (structural unit having a carboxyl group) derived from the unsaturated carboxylic acid occupied by the resins (A2-2) and (A2-3) is preferably 5 to 60 mass%, and 10 to 40 mass% It is more preferable. By setting it as the said range, the developability of the negative radiation sensitive composition 1 can be made suitable.

Moreover, it is preferable that the ratio of the structural unit (constitutional unit which has an epoxy group) derived from the epoxy group-containing unsaturated compound which occupies the said resin (A2-2) and (A2-3) is 5 to 90 mass %, and it is 15 to 75 mass % Is more preferable. By setting it as the said range, it becomes easy to form a pattern of favorable shape.

The mass average molecular weights of the resins (A2-2) and (A2-3) are preferably from 2000 to 50000, more preferably from 5000 to 30000. By setting it as the said range, there exists a tendency which is easy to balance the film-forming ability and developability of the negative radiation sensitive composition 1.

In addition to the above, (A2) epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, Epoxy (meth)acrylate obtained by reacting an epoxy group of an epoxy resin such as polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, amine epoxy resin, dihydroxybenzene type epoxy resin, and (meth) acrylic acid Resin etc. can also be used.

It is preferable that content of alkali-soluble resin is 5 to 90 mass% with respect to the solid content of negative radiation sensitive composition 1, and it is more preferable that it is 10 to 85 mass %. By setting it as the said range, there exists a tendency which is easy to balance the film-forming ability and developability of the negative radiation sensitive composition 1.

[Photopolymerizable monomer]

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

As a monofunctional monomer, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxy Methoxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, Citraconic acid, citraconic anhydride, crotonic acid, 2-acryl amide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylic Rate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropylphthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth) Acrylate, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth) ) Acrylates, and half (meth)acrylates of phthalic acid derivatives. These monofunctional monomers can be used alone or in combination of two or more.

On the other hand, as a polyfunctional monomer, 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, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin Di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol Tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth) Acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene Glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycylate Dietherether (meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), reactant of trimethylhexamethylene diisocyanate with hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylenebis ( And polyfunctional monomers such as a meth)acrylamide, a (meth)acrylamide methylene ether, a condensate of a polyhydric alcohol and N-methylol (meth)acrylamide, and triacrylic formal. These polyfunctional monomers can be used alone or in combination of two or more.

The content of the photopolymerizable monomer is preferably 1 to 45% by mass, and more preferably 5 to 40% by mass with respect to the solid content of the negative radiation sensitive composition 1. By setting it as the said range, there exists a tendency which is easy to balance the sensitivity, developability, and resolution.

[Photopolymerization initiator]

It does not specifically limit as a photoinitiator, A conventionally well-known photoinitiator can be used. The photoinitiators can be used alone or in combination of two or more.

Specifically as a photoinitiator, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl )-2-hydroxy-2-methylpropan-1-one, bis(4-dimethylaminophenyl)ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulf Fide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid , Benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2,4-diethyl tea Oxyxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthiochine Xanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyro Nitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimida Sol dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4,5- Triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (i.e., mihila ketone), 4,4'-bisdiethylaminobenzophenone (i.e. ethyl Mihila ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin -n-butyl ether, benzoin isobutyl ether, Benzoinbutyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p- Dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2- Isopropylthioxanthone, dibenzosveron, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9 -Acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl -4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-tri Azine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl) Ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s -Triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl )-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3- Bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis -Trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy) Styrylphenyl-s-triazine, "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade name, manufactured by BASF), "NCI-831" (trade name, manufactured by ADEKA ) And the like. These photoinitiators can be used individually or in combination of 2 or more types.

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

As a preferable example of an oxime type photoinitiator, the photoinitiator represented by following formula (c-1) is mentioned.

[Formula 12]

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

^Examples of the heterocyclic group for R ^c1 include a 5-membered ring or more, preferably a 5-membered ring or a 6-membered ring heterocyclic group containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of the heterocyclic group include a nitrogen-containing 5-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, pyrazinyl group, pyrimidyl group, and pyridazinyl group; Nitrogen-containing sulfur groups such as thiazolyl group and isothiazolyl group; Nitrogen-containing oxygen groups such as oxazolyl group and isooxazolyl group; Sulphate groups such as thienyl groups and thiopyranyl groups; Oxygen-containing groups such as furyl group and pyranyl group; And the like. Among these, it is preferable to contain one nitrogen atom or a 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 cyclic aromatic group in R ^c1 include naphthyl group, anthryl group, and phenanthryl group. Moreover, a phenyl group is mentioned as an aromatic group in R ^c1 .

The heterocyclic group, fused cyclic aromatic group, or aromatic group may have a substituent. In particular, when R ^c1 is an aromatic group, it is preferable to have a substituent. Examples of such substituents 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, and these may be substituted with a halogen atom, or 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 among these, the alkylene portion of the alkyl group and the alkoxy group is an ether bond, a thioether bond, or an ester bond May be interrupted. Moreover, 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, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, methoxy group, ethoxy group, and pro And aeration time.

A heterocyclic ring is mentioned as a ring structure which R ^c6 and R ^c7 can combine and form. Examples of the heterocycle include a 5-membered ring containing at least a nitrogen atom, preferably a 5- to 7-membered heterocycle. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include a piperidine ring, a morpholine ring, and a thiomorpholine ring. Among these, morpholine rings are preferable.

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

R ^c9 and R ^c10 each independently represent an alkyl group, and these may be substituted with a halogen atom, and may be interrupted by an ether bond, a thioether bond, or an ester bond. Preferred carbon numbers and specific examples thereof are the same as described for R ^c1 above.

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

In the formula (c-1), R ^c2 represents a monovalent organic group. As this organic group, groups represented by -R ^c11 , -OR ^c11 , -COR ^c11 , -SR ^c11 , and -NR ^c11 R ^c12 are preferable. 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, and alkyl of the alkyl group and aralkyl group among them The ren moiety may be interrupted by an unsaturated bond, ether bond, thioether bond or ester bond. Moreover, R ^c11 and R ^c12 may combine and form a ring structure together with a nitrogen atom.

The alkyl group for R ^c11 and R ^c12 is preferably 1 to 20 carbon atoms, and more preferably 1 to 5 carbon atoms. Examples of the alkyl group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group , tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isode And straight-chain or branched-chain groups such as real machines. Moreover, this alkyl group may have a substituent. Examples of the one having a substituent include methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

The alkenyl group in R ^c11 and R ^c12 is preferably 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the alkenyl group include a straight chain or branched chain group such as vinyl group, allyl group, butenyl group, ethenyl group, and propynyl group. Moreover, this alkenyl group may have a substituent. As an example of what has a substituent, 2-(benzooxazol-2-yl)ethenyl group etc. are mentioned.

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

The aralkyl group for R ^c11 and R ^c12 is preferably 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, phenylethyl group, and phenylethenyl group.

^Examples of the heterocyclic group in R ^c11 and R ^c12 include a 5-membered ring or more, preferably a 5-7-membered heterocyclic group containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom. . The heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include pyrrolyl group, pyridyl group, pyrimidyl group, furyl group, thienyl group, and the like.

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

Moreover, a heterocyclic ring is mentioned as a ring structure which R ^c11 and R ^c12 can combine and form. Examples of the heterocycle include a 5-membered ring containing at least a nitrogen atom, preferably a 5- to 7-membered heterocycle. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include a piperidine ring, a morpholine ring, and a thiomorpholine ring.

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

In the 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 that may have a substituent. Examples of the substituent include the same group as in the case of R ^c1 above. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, naphthyl group, anthryl group, and phenanthryl group.

[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. As such an alkylene group, methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, n-pentylene group, isopentylene group, sec-pentylene group, etc. And straight-chain or branched-chain groups. Among these, 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, if} the structure of R ^c14 is represented by the following formula (c-3), it is preferable from the viewpoint of improving the solubility of the photopolymerization initiator.

[Formula 14]

In the formula (c-3), R ^c17 and R ^c18 each independently represent an alkyl group having 1 to 5 carbon atoms. As such an alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pen And til groups and tert-pentyl groups. Among these, R ^c17 and R ^c18 are most preferably methyl groups.

The heterocyclic group in R ^c3 includes a 5-membered ring or more, preferably a 5-membered ring or a 6-membered ring heterocyclic group containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of the heterocyclic group include a nitrogen-containing 5-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, pyrazinyl group, pyrimidyl group, and pyridazinyl group; Nitrogen-containing sulfur groups such as thiazolyl group and isothiazolyl group; Nitrogen-containing oxygen groups such as oxazolyl group and isooxazolyl group; Sulphate groups such as thienyl groups and thiopyranyl groups; Oxygen-containing groups such as furyl group and pyranyl group; And the like. Among these, it is preferable to contain one nitrogen atom or a 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.

Moreover, the heterocyclic group may have a substituent. Examples of the substituent include the same group as in the case of R ^c1 above.

In the formula (c-1), R ^c4 represents a monovalent organic group. Especially, it is preferable that it is a C1-C5 alkyl group. As such an alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pen And til groups and tert-pentyl groups. Among these, R ^c4 is most preferably a methyl group.

Moreover, as another preferable example of an oxime type photoinitiator, the photoinitiator represented by following formula (c-4) proposed by Unexamined-Japanese-Patent No. 2010-15025 is mentioned.

[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. . The hydrogen atom of the alkyl group, aryl group, arylalkyl group, and heterocyclic group further includes OR ^c41 , COR ^c41 , SR ^c41 , NR ^c42 R ^c43 , CONR ^c42 R ^c43 , -NR ^c42 -OR ^c43 , -NCOR ^c42 -OCOR ^c43 , -C(=N-OR ^c41 )-R ^c42 , -C(=N-OCOR ^c41 )-R ^c42 , CN, halogen atom, -CR ^c41 =CR ^c42 R ^c43 , -CO-CR ^c41 =CR ^c42 R ^c43 , a carboxyl group, or an epoxy group may be substituted. 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. .

The methylene group of the alkylene portion of the substituent in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 , and R ^c43 is an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond Or, it may be interrupted 1 to 5 times by a urethane bond, the alkyl portion of the substituent may have a branch chain, cyclic alkyl, the alkyl terminal of the substituent may be an unsaturated bond, and R ^c32 and R ^c33 , And R ^c42 and R ^c43 may be bonded to each other to form a ring structure.

In the formula (c-4), R ^c23 and R ^c24 are each independently 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, halogen atom, or hydroxyl group. a and b respectively independently represent the integer of 0-4.

R ^c23 may combine with one of the carbon atoms of the adjacent benzene ring via -X ^c2 -to form a ring structure, or R ^c23 and R ^c24 may combine to form a ring structure.

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

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

In the formula (c-4), as the alkyl group for R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 , and R ^c43 , methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group and the like.

In the formula (c-4), the aryl groups for R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 , and R ^c43 include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, and a naphthyl group. , Anthryl groups, phenanthrenyl groups, and the like.

In the formula (c-4), the arylalkyl groups for R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 , and R ^c43 are benzyl group, chlorobenzyl group, α-methylbenzyl group, α, and alpha-dimethylbenzyl groups, phenylethyl groups, and phenylethenyl groups.

In the formula (c-4), as the heterocyclic groups for R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 , and R ^c43 , a pyridyl group, ^pyrimidyl group, furyl group, thienyl group, tetrahydro Furyl group, dioxolanyl group, benzooxazol-2-yl group, tetrahydropyranyl group, pyrrolidyl group, imidazolidil group, pyrazolidil group, thiazolidil group, isothiazolidil group, oxazolidil group, isooxazolidil group , 5 to 7 membered rings such as piperidyl group, piperazyl group, and morpholinyl group.

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

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

In the formula (c-4), halogen atoms which may substitute for R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 , and R ^c43 , and halogen atoms in R ^c24 and R ^c25 include a fluorine atom, Chlorine atom, bromine atom, and iodine atom.

The methylene group of the alkylene portion of the substituent may be interrupted 1 to 5 times by an unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane bond. In this case, one or two or more types of linking groups to be interrupted may be contributed, or two or more consecutively interrupted groups to be interrupted continuously. Moreover, the alkyl part of the said substituent may have a branch chain, cyclic alkyl may be sufficient, and the alkyl terminal of the said substituent may be an unsaturated bond.

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

[Formula 16]

( ^Wherein , R ^d1 is a group selected from the group consisting of monovalent organic groups, amino groups, halogen atoms, nitro groups, and cyano groups, i is an integer from 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 R ^d3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

In the formula (2), when R ^d1 is a monovalent organic group, R ^d1 is not particularly limited within a range that does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferred examples when 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, and a phenoxy which may have a substituent. Timing, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naph which may have a substituent Thoxy group, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, 1 Or an amino group substituted with the organic group of 2, morpholine-1-yl group, piperazin-1-yl group, etc. are mentioned. When i is an integer of 2-4, R ^d1 may be same or different. Moreover, the carbon number of the substituent which the substituent further has is not included in the carbon number of a substituent.

When R ^d1 is an alkyl group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Moreover, when R ^d1 is an alkyl group, a straight chain or a branch chain may be sufficient. Specific examples when R ^d1 is an alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and iso Pentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, and the like. Moreover, when R ^d1 is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

When R ^d1 is an alkoxy group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Moreover, when R ^d1 is an alkoxy group, a straight chain or a branch chain may be sufficient. As a specific example when R ^d1 is an alkoxy group, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy Period, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-oc And a thyloxyl group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. Moreover, when R ^d1 is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, and And methoxypropyloxy groups.

When R ^d1 is a cycloalkyl group or a cycloalkoxy group, 3 to 10 carbon atoms are preferable and 3 to 6 carbon atoms are more preferable. Specific examples when 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. Specific examples when 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 carbon number is preferably 2 to 20, and more preferably 2 to 7. Specific examples when R ^d1 is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, and n-hexa Noyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, and n-pentadecanoyl groups, and n-hexadecanoyl groups. Specific examples when R ^d1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, and 2,2-dimethylpro Panoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group , n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^d1 is an alkoxycarbonyl group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when R ^d1 is an alkoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert -Butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group , sec-octyloxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group.

When R ^d1 is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, and more preferably 7 to 10. Moreover, when R ^d1 is a naphthyl alkyl group, 11-20 are preferable and its carbon number is more preferably 11-14. As a specific example when R ^d1 is a phenylalkyl group, a benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group are mentioned. Specific examples when R ^d1 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-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 is a 5-membered or 6-membered monocycle in which the total number of N, S, and O is 1 or more, or such monocycles, or a heterocycle in which these monocycles and benzene rings are condensed. It is a cyclyl group. When the heterocyclyl group is a condensed ring, it is assumed to be up to 3 rings. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, Phthalazine, synnoline, 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, and a substituent group. A phenyl group which may be substituted, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbons which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, and 11 to 10 carbon atoms which may have a substituent. And a naphthyl alkyl group of 20 and a heterocyclyl group. Specific examples of these preferred organic ^groups are the same as R ^d1 . As a specific example of the amino group substituted by the organic group of 1 or 2, methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n- Butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n- Butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group, etc. Can be mentioned.

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

Among R ^d1 , a nitro group, a C1-C6 alkyl group, or a C1-C6 carbon atom, from the viewpoint of chemical stability, low steric hindrance, easy synthesis of an oxime ester compound, and high solubility in a solvent, etc. A group selected from the group consisting of an alkoxy group and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, 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 5 position is preferable, and 5 position is more preferable. Moreover, as for i, the integer of 0-3 is preferable, the integer of 0-2 is more preferable, and 0 or 1 is especially preferable.

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

In R ^d2 , the substituent group of the phenyl group or carbazolyl group is not particularly limited as long as it does not impair the object of the present invention. Examples of preferred substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkoxy having 3 to 10 carbon atoms. Group, 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, or a substituent A phenylthio group, 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, or a naph which may have a substituent A naphthoxy group which may have a butyl group, 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 naphthyloxy group which may have a substituent, or a substituent having 11 to 20 carbon atoms. Tylalkyl group, heterocyclyl group which may have a substituent, heterocyclylcarbonyl group which may have a substituent, amino group, amino group substituted with 1 or 2 organic groups, morpholine-1-yl group, and piperazin-1-yl group, halogen And an 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, and a saturated aliphatic acyl group having 2 to 20 carbon atoms. , Alkoxycarbonyl group having 2 to 20 carbon atoms, phenyl group which may have substituent, benzoyl group which may have substituent, phenoxycarbonyl group which may have substituent, phenylalkyl group having 7 to 20 carbon atoms which may have substituent, and substituent A naphthyl group, a naphthyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthyl alkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent The heterocyclylcarbonyl group etc. which are mentioned are mentioned. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

For a specific example of the substituent which the phenyl group or carbazolyl group may have, 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, The naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, and the amino group substituted with the organic group of 1 or 2 are the same as R ^d1 .

In R ^d2 , examples of the substituent when the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent group of the phenyl group or carbazolyl group 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; Phenyl group; Naphthyl group; Benzoyl group; 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 morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; Monoalkylamino groups having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholine-1-yl group; Piperazine-1-diary; Halogen atom; Nitro group; And cyano groups. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent having the phenyl group or carbazolyl group further have a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but is 1 to 4 is preferred. When a phenyl group, a naphthyl group, and a heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

In R ^d2 , since the negative radiation sensitive composition 1 is excellent in sensitivity, a group represented by the following formula (3) or (4) is preferable, a group represented by the following formula (3) is more preferable, and the following formula (3) ) And a group in which A is S is particularly preferred.

[Formula 17]

(R ^d4 is a group selected from the group consisting of monovalent organic groups, amino groups, halogen atoms, nitro groups, and cyano groups, A is S or O, and k is an integer from 0 to 4.)

[Formula 18]

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

When R ^d4 in Formula (3) is an organic group, it can be selected from various organic groups within a range that does not impair the object of the present invention. In Formula (3), a preferable example when R ^d4 is an organic group 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; Phenyl group; Naphthyl group; Benzoyl group; 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 morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; Monoalkylamino groups having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholine-1-yl group; Piperazine-1-diary; Halogen atom; Nitro group; And cyano groups.

In R ^d4 , a benzoyl group; 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 morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; Nitro group is preferable, Benzoyl group; Naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; 4-(phenyl)phenylcarbonyl group is more preferable.

Moreover, in 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 Formula (4) can be selected from various organic groups within a range that does not impair the object of the present invention. Preferred 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, and a substituent. A benzoyl group, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbons which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, and a naph which may have a substituent And a alkoxycarbonyl group, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

In 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 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 groups. Specific examples of the group preferable as 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.

As a substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group included in R ^d4 , R ^d5 , or R ^d6 further has a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or carbon number 2 to 7 saturated aliphatic acyl groups, 2 to 7 alkoxycarbonyl groups, 2 to 7 saturated aliphatic acyloxy groups, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkyl having an alkyl group having 1 to 6 carbon atoms And amino groups, morpholine-1-yl groups, piperazin-1-yl groups, halogen atoms, nitro groups, and cyano groups. When a phenyl group, a naphthyl group, and a heterocyclyl group included in R ^d4 , R ^d5 , or R ^d6 further has a substituent, the number of the substituents is not limited to the extent that does not impair the object of the present invention, 1-4 are 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 Formula (2) is a hydrogen atom or a C1-C6 alkyl group. 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 composed of the compound represented by formula (2) is particularly excellent in sensitivity.

When the j is 0, the oxime ester compound represented by the formula (2) can be synthesized according to the following scheme 1, for example. Specifically, the aromatic compound represented by the following formula (d1-1) is acylated by a Friedel Crafts reaction using the halocarbonyl compound represented by the following formula (d1-2), and the following formula (d1-3) The ketone compound represented by is obtained, and the obtained ketone compound (d1-3) is oxidized with hydroxylamine to obtain an oxime compound represented by the following formula (d1-4), followed by an oxime compound of formula (d1-4), The acid anhydride represented by the following formula (d1-5) ((R ^d3 CO) ₂ O) or the acid halide represented by the following formula (d1-6) (R ^d3 COHal, Hal is a halogen atom.) The oxime ester compound represented by (d1-7) can be obtained. In addition, in the following formula (d1-2), Hal is a halogen atom, and the following formulas (d1-1), (d1-2), (d1-3), (d1-4), and (d1-7) In, R ^d1 , R ^d2 , R ^d3 , and i are the same as formula (2).

<Scheme 1>

[Formula 19]

When j is 1, the oxime ester compound represented by Formula (2) can be synthesized according to the following scheme 2, for example. Specifically, the ketone compound represented by the following formula (d2-1) is reacted with a nitrite ester represented by the following formula (d2-2) in the presence of hydrochloric acid (RONO, R is an alkyl group having 1 to 6 carbon atoms.) A ketoxime compound represented by the formula (d2-3) is obtained, followed by a ketoxime compound represented by the following formula (d2-3) and an acid anhydride represented by the following formula (d2-4) ((R ^d3 CO) ₂ O), Alternatively, an acid halide represented by the following formula (d2-5) (R ^d3 COHal, Hal is a halogen atom.) can be reacted to obtain an oxime ester compound represented by the following formula (d2-6). In addition, in the following formulas (d2-1), (d2-3), (d2-4), (d2-5), and (d2-6), R ^d1 , R ^d2 , R ^d3 , and i are It is the same as Formula (2).

<Scheme 2>

[Formula 20]

Moreover, in the oxime ester compound represented by Formula (2), when j is 1, R ^d1 is a methyl group, and R ^d1 is bonded to the para position with respect to a methyl group bound to the benzene ring to which R ^d1 is bound, for example For example, the compound represented by the following formula (d2-7) can also be synthesized by the same method as Scheme 1 by oximeization and acylation. In addition, in following formula (d2-7), R ^d2 is the same as Formula (2).

[Formula 21]

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

[Formula 22]

Another preferable example of the oxime-based photopolymerization initiator is "IRGACURE OXE01" (trade name, manufactured by BASF).

It is preferable that content of a photoinitiator is 0.3-20 mass% with respect to the solid content of negative radiation sensitive composition 1, and it is more preferable that it is 0.5-15 mass %. By setting it as the said range, sufficient heat resistance and chemical-resistance can be obtained and the coating film forming ability can be improved and hardening defect can be suppressed.

[coloring agent]

The negative radiation sensitive composition 1 may contain a colorant. By containing a coloring agent, the negative radiation sensitive composition 1 is preferably used, for example, for forming a color filter of a liquid crystal display. Moreover, the negative radiation sensitive composition 1 is preferably used for forming a black matrix in a color filter or forming a black photo spacer, for example, by including a light blocking agent as a colorant. Coloring agents can be used alone or in combination of two or more.

Although it does not specifically limit as a coloring agent, For example, the compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists), specifically the following color index (CI) It is desirable to use numbered ones.

CI Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the number is described.), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55 , 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117 , 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185 ;

CI Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the number is described.), 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 number is described."), 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 number is described.), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15 , 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1 , 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1 , 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166 , 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216 , 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265;

CI Pigment Blue 1 (Hereinafter, "CI Pigment Blue" is the same and only the number is described.), 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.

Moreover, when using a coloring agent as a light-shielding agent, it is preferable to use a black pigment as a light-shielding agent. Examples of the black pigment include organic oxides, inorganic substances such as metal oxides, complex oxides, metal sulfides, metal sulfates, and metal carbonates such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver. 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 blacks 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. Moreover, you may use resin-coated carbon black.

Since the resin-coated carbon black has a lower conductivity than the carbon black without the resin coating, when used as a black matrix for a liquid crystal display display, it is possible to manufacture a low power consumption display with low current leakage and high reliability.

Moreover, in order to adjust the color tone of carbon black, you may add the said organic pigment suitably as an auxiliary pigment.

Moreover, when using a pigment as a coloring agent, you may use a pigment and dye together. Examples of dyes that can be used in combination with the pigment include xanthene dyes, cyanine dyes, azo dyes, anthraquinone dyes, dioxazine dyes, and triphenylmethane dyes.

Moreover, in order to disperse|distribute a coloring agent uniformly in a radiation sensitive resin composition, you may use a dispersing agent further. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

In addition, the inorganic pigments and the organic pigments may be used alone or in combination, but when used in combination, the organic pigment is used in a range of 10 to 80 parts by mass relative to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferable, and it is more preferable to use it in the range of 20-40 mass parts.

The content of the colorant is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, with respect to the solid content of the negative radiation sensitive composition 1.

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

The negative radiation sensitive composition 1 may contain other organic solvents. Other organic solvents may be used alone or in combination of two or more. As other organic solvents, 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 Ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, (Poly)alkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; (Poly)alkylene 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, propylene glycol monoethyl ether acetate, etc. 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; Alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropionate ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid Other esters such as methyl, ethyl acetoacetate, and ethyl 2-oxobutanoate; And aromatic hydrocarbons such as toluene and xylene.

In the negative radiation-sensitive composition 1, the amount of the solvent is preferably an amount such that the solid content concentration of the negative radiation-sensitive composition 1 is 1 to 50% by mass, and more preferably 5 to 30% by mass. . Moreover, in the solvent contained in the negative radiation sensitive composition 1, it is preferable that the mass ratio of the compound represented by the said general formula (1) and other organic solvents is 5:95-100:0, and 20:80-100 : 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 other organic solvents in the above range, the negative radiation sensitive composition 1 is excellent in sensitivity, storage stability, coatability, developability, and safety. It is easy to become, and the pattern formed by exposing and developing the negative radiation sensitive composition 1 is likely to be suppressed from the occurrence of foreign matter.

[Other ingredients]

The negative radiation sensitive composition 1 may contain various additives as needed. Examples of the additives include sensitizers, curing accelerators, fillers, adhesion promoters, antioxidants, agglomeration inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants, and the like.

<Negative radiation-sensitive composition 2>

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

[Compound represented by 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 general formula (1) can 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 tetracarboxylic dianhydride and diamine, and is appropriately selected from polyamic acids conventionally known as precursors for polyimide resins. The polyamic acid may be used alone or in combination of two or more.

As a preferable polyamic acid, the polyamic acid represented by following formula (11) is mentioned, for example.

[Formula 23]

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

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

The polyimide resin represented by the following formula (12) is obtained by closing the polyamic acid represented by the above formula (11) by heating or a catalyst.

[Formula 24]

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

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

The amount of tetracarboxylic dianhydride and diamine used in synthesizing the polyamic acid is not particularly limited, but it is preferable to use 0.50 to 1.50 moles of diamine per 1 mole of tetracarboxylic dianhydride, and 0.60 to 1.30 It is more preferable to use moles, and it is particularly preferable to use 0.70 to 1.20 moles.

The tetracarboxylic dianhydride can be appropriately selected from tetracarboxylic dianhydride conventionally used as a synthetic raw material for polyamic acid. The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride, but from the viewpoint of heat resistance of the resulting polyimide resin, an aromatic tetracarboxylic dianhydride is preferred. You may use tetracarboxylic dianhydride in combination of 2 or more type.

As a preferable specific example of aromatic tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-ratio Phenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid 2 anhydride, and 3,3',4,4'-di And phenyl sulfone tetracarboxylic acid anhydride. Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable from the price, availability, and the like.

Moreover, when synthesize|combining a polyamic acid, you may use together tetracarboxylic dianhydride and dicarboxylic anhydride. When these carboxylic anhydrides are used in combination, the properties of the resulting polyimide resin may be better. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene anhydride tetrahydrophthalic anhydride, chlorendic anhydride, methyltetra Hydrophthalic anhydride, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, and the like.

The diamine can be appropriately selected from diamines conventionally used as a synthetic raw material for polyamic acids. The diamine may be an aromatic diamine or an aliphatic diamine, but from the viewpoint of heat resistance of the resulting polyimide resin, an aromatic diamine is preferred. Diamine may be used in combination of 2 or more type.

Preferred specific examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2 '-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(4-aminophenoxy City)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[ 4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 -Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, And 4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline. Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable from the price, ease of availability, and the like.

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

Examples of the organic solvent used for the reaction of tetracarboxylic dianhydride and diamine include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide and N,N- Nitrogen-containing polar solvents such as dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea; lactone-based polar solvents such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-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, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethyl Preference is given to nitrogen-containing polar solvents such as formamide, N,N-diethylformamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea.

[Photosensitive component]

The photosensitive component is not particularly limited, and examples thereof include compounds (A) that decompose under the action of light, such as photobase generators and photoacid generators, to generate at least one of a base and an acid. The photosensitive components may be used alone or in combination of two or more.

By exposing the negative-type radiation-sensitive composition 2 containing the compound (A), the compound (A) in the negative-type radiation-sensitive composition 2 decomposes and generates at least one of a base and an acid. The base or acid generated in this way acts as an imidization catalyst, and promotes ring closure of the polyamic acid in the negative radiation sensitive composition 2.

When the negative radiation sensitive composition 2 containing the compound (A) is exposed, the compound (A) decomposes in the exposed portion to generate at least one of a base and an acid. The base or acid generated in this way promotes ring closure of the polyamic acid in the negative radiation sensitive composition 2, and the exposed portion becomes insoluble in the developer. On the other hand, since the unexposed portion is soluble in the developer, it can be dissolved and removed in the developer. Therefore, a desired pattern can be formed by selectively exposing the negative radiation sensitive composition 2.

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

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

The imidazole compound in which the compound (A-1) is generated is a basic imidization catalyst, and promotes ring closure of the polyamic acid in the negative radiation sensitive composition 2. The imidazole compound in which the compound (A-1) occurs may be an imidazole, or a compound in which part or all of the hydrogen atoms bonded to carbon atoms in the imidazole are substituted with substituents, and imidazole represented by the following formula (3) It is preferred to be a compound.

[Formula 25]

(In the formula, 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 sulfonato group, It represents a phosphino group, a phosphinyl 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. Moreover, this organic group may be either linear, branched, or cyclic. The organic group is usually monovalent, but may be bivalent or higher in the case of forming a cyclic structure.

R ¹ and R ² may be bonded to form a cyclic structure, or may contain a bond of a hetero atom. A heterocycloalkyl group, heteroaryl group, etc. are mentioned as a cyclic structure, and a condensed ring may be sufficient.

When the organic group represented by R ¹ , R ² , or R ³ contains a hetero atom, examples of the hetero atom include an oxygen atom, a nitrogen atom, and a silicon atom. As a specific example of the bond containing a hetero atom, ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond (-N=C(-R)- Or -C(=NR)- (wherein R represents a hydrogen atom or an organic group). Hereinafter, it is the same), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like. Among them, from the viewpoint of heat resistance of the imidazole compound, ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond, carbonate bond, sulfonyl bond, sulfinyl Bonding is preferred.

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

As R ¹ , R ² , and R ³ , each independently, 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 are preferable, and the hydrogen atom is more preferable. desirable. Since imidazole, wherein R ¹ , R ² , and R ³ are all hydrogen atoms, has a simple structure with little steric hindrance, it can easily act on the polyamic acid as an imidization catalyst.

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). For a compound that has been conventionally blended with a photosensitive composition and generates amine by the action of light, a skeleton derived from an amine generated during exposure is an imidazole compound, preferably an imidazole compound represented by the formula (3) above The compound used as compound (A-1) is obtained by substituting with a skeleton derived from.

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

[Formula 26]

(In the formula, R ¹ , R ² , and R ³ are each independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, phosphino group, Represents a sulfonato group, a phosphinyl group, a phosphonato group, or an organic group R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, and a nitro Represents a group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ is 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 sulfino group, a sulfo group, a sulfonato group, a phosphino group, It represents a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group.R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ combine two or more of them to form a cyclic structure. It may be formed, or may contain a bond of a hetero atom.)

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

In Formula (4), what was illustrated about R ¹ , R ² , and R ³ is mentioned as an organic group represented by R ⁴ or R ⁵ . The organic group may contain a hetero atom, as in the case of R ¹ , R ² , and R ³ . Moreover, this organic group may be either linear, branched, or cyclic.

R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, an aryloxyalkyl group having 7 to 16 carbon atoms, or 7 to 20 carbon atoms. Aralkyl group, a C2-C11 alkyl group having a cyano group, a C1-C10 alkyl group having a hydroxyl group, a C1-C10 alkoxy group, a C2-C11 amide group, a C1-C10 alkylthio group, An acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR or -OCOR (where R represents a hydrocarbon group)), an aryl group having 6 to 20 carbon atoms, an electron donating group and/or electron withdrawing It is preferable that the aryl group having 6 to 20 carbon atoms substituted with an adult group, a benzyl group substituted with an electron donating group and/or an electron withdrawing group, a cyano group, or a methylthio group. More preferably, both R ⁴ and R ⁵ are hydrogen atoms, or R ⁴ is a methyl group and R ⁵ is a hydrogen atom.

In Formula (4), examples of R ¹ , R ² , and R ³ include organic groups represented by R ⁶ , R ⁷ , R ⁸ , R ⁹ , or R ¹⁰ . This organic group may contain a hetero atom as in the case of R ¹ and R ² . Moreover, this organic group may be either linear, branched, or cyclic.

In R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ , two or more of them may combine to form a cyclic structure, or may contain a bond of a hetero atom. A heterocycloalkyl group, heteroaryl group, etc. are mentioned as a cyclic structure, and a condensed ring may be sufficient. For example, R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are two or more of them, and a benzene ring to which R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ is bonded You may share the atom of and form a condensed ring, such as naphthalene, anthracene, phenanthrene, and 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, or 7 carbon atoms. Aryloxyalkyl group having 16 to 16, aralkyl group having 7 to 20 carbon atoms, alkyl group having 2 to 11 carbon atoms having cyano group, alkyl group having 1 to 10 carbon atoms having hydroxyl group, alkoxy group having 1 to 10 carbon atoms, 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, 6 carbon atoms substituted with electron donating groups and/or electron withdrawing groups It is preferable that it is a benzyl group, a cyano group, a methylthio group, a nitro group substituted with the aryl group of 20-20, an electron donating group, and/or an electron withdrawing group.

Moreover, as R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ , two or more of them are bonded, and R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ of the benzene ring When an atom is shared to form a condensed ring such as naphthalene, anthracene, phenanthrene, and indene, it is preferable from the viewpoint of long wavelength absorption.

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

[Formula 27]

(In the formula, R ¹ , R ² , and R ³ are synonymous with formulas (3) and (4). R ⁴ to R ⁹ are synonymous with formula (4). R ¹¹ is a hydrogen atom or an organic group.) There is no case where R ⁶ and R ⁷ are hydroxyl groups R ⁶ , R ⁷ , R ⁸ , and R ⁹ may have two or more of them bonded to form a cyclic structure, or to form a hetero atom bond. You may include it.)

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

In Formula (5), when R ¹¹ is an organic group, those exemplified for R ¹ , R ² , and R ³ are mentioned as the organic group. This organic group may contain a hetero atom. Moreover, this organic group may be either linear, branched, or 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.

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

[Formula 28]

(In the formula, R ¹ , R ² , and R ³ are each independently hydrogen atom, halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, phosphino group, It represents a sulfonato group, a phosphinyl group, a phosphonato group, or an organic group. 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), as R ¹² , 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 aryl group having 6 to 20 carbon atoms which may be substituted, which may be substituted An aralkyl group having 7 to 20 carbon atoms is mentioned, and an aralkyl group having 7 to 20 carbon atoms which may be substituted is preferable. When the said aryl group or aralkyl group is substituted, a halogen atom, a nitro group, a C1-C4 alkyl group, or a C1-C4 alkoxy group is mentioned as a substituent.

The compound represented by the formula (6) is a reaction of the imidazole compound represented by the formula (3) and the chloroformate ester represented by the following formula (7), the imidazole compound represented by the formula (3) and the di represented by the following formula (8) It can be synthesized by a reaction of a carbonate or a reaction of a carbonyldiimidazole compound represented by the following formula (9) and an alcohol represented by the following formula (10).

[Formula 29]

(In formulas (7) to (10), R ¹ , R ² , and R ³ are synonymous with formula (3). R ¹² is synonymous with formula (6).)

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

[Formula 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. Closing of the polyamic acid in the negative-type radiation-sensitive composition 2 is promoted by the base or acid generated by the decomposition of the compound (A-2).

As a preferable compound (A-2), the compound represented by following formula (D1) is mentioned.

[Formula 31]

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

In the case where 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, or an unsubstituted group. And a phenanthrenyl group which may have a trill group and 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 that are attached to the aryl group is not particularly limited. When the aryl group has a plurality of substituents, the plurality of substituents may be the same or different. The kind of the substituent which an aryl group may have is not specifically limited in the range which does not inhibit the objective of this invention. Preferred 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 type of the organic group is not particularly limited as long as it does not impair the object of the present invention and is appropriately selected from various organic groups. Preferred examples of the organic group include alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, saturated aliphatic acyl group, alkoxycarbonyl group, saturated aliphatic acyloxy group, phenyl group which may have a substituent, phenoxy group which may have a substituent, and substituent A benzoyl group which may have, 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, and a substituent A naphthoyl group which may have, 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 2 of And an amino group substituted with an organic group, a morpholine-1-yl group, and a piperazin-1-yl group. The carbon number of the substituent which the substituent further has is not included in the carbon number of a substituent.

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

When the organic group is an alkoxy group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Moreover, when an organic group is an alkoxy group, it may be linear or branched. As a specific example when the organic group is an alkoxy group, a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy Group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. Moreover, when an organic group is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, and And methoxypropyloxy groups.

When the organic group is a cycloalkyl group or a cycloalkoxy group, 3 to 10 carbon atoms are preferable, and 3 to 6 carbon atoms are more preferable. Specific examples of the case where the organic group is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the case where the organic group 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 the organic group is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the carbon number is preferably 2 to 20, and more preferably 2 to 7. Specific examples of the case where the organic group is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, and n-hexanoyl group , n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n -Pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples of the case where the organic group is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropano Iloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, and n-tridecanoyloxy groups, n-tetradecanoyloxy groups, n-pentadecanoyloxy groups, and n-hexadecanoyloxy groups.

When the organic group is an alkoxycarbonyl group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when the organic group is an alkoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert- Butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, and sec-octyloxycarbonyl groups, tert-octyloxycarbonyl groups, n-nonyloxycarbonyl groups, isononyloxycarbonyl groups, n-decyloxycarbonyl groups, and isodecyloxycarbonyl groups.

When the organic group is a phenylalkyl group, the carbon number is preferably 7 to 20, and more preferably 7 to 10. Moreover, when an organic group is a naphthyl alkyl group, 11-20 are preferable and its carbon number is more preferable 11-14. Specific examples of the case where the organic group 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 the organic group is a naphthyl alkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-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 is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclyl group condensed between these monocyclic groups or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, it is assumed to be up to 3 rings. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, Phthalazine, synnoline, 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 an organic group of 1 or 2, 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, and a saturated aliphatic group having 2 to 20 carbon atoms. Actual group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbons which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent And a naphthyl alkyl group having 11 to 20 carbon atoms, a heterocyclyl group, and the like. Specific examples of these preferred organic groups are the same as the specific 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. As a specific example of the amino group substituted with the organic group of 1 or 2, methylamino group, dimethylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di -n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group , n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naph And a soil amino group.

When R ^d1 is an aryl group which may have a substituent, the phenyl group, the naphthyl group, and the heterocyclyl group included in the organic group bonded as a substituent to the aryl group further include a substituent having 1 to 6 carbon atoms. Monoalkylamino group having 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, or a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms , Dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholine-1-yl group, piperazin-1-yl group, halogen atom, nitro group, and cyano group.

When R ^d1 is an aryl group which may have a substituent, when the phenyl group, naphthyl group, and heterocyclyl group included in the organic group bonded as a substituent to the aryl group further has a substituent, the number of the substituents of the present invention Although it is not limited in the range which does not impair a purpose, 1-4 are preferable. When R ^d1 is an aryl group which may have a substituent, when the phenyl group, naphthyl group, and heterocyclyl group included in the organic group bonded as a substituent to the aryl group has a plurality of substituents, the plurality of substituents may be the same It may be different.

In the case where R ^d1 is an aryl group which may have a substituent, as the substituent possessed by the aryl group, the point in which the substituent is chemically stable, there are few steric hindrances, and the synthesis of the compound represented by formula (D1) is easy. 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 from the viewpoint of high solubility in the solvent of the compound represented by D1) The nitro group or alkyl having 1 to 6 carbon atoms is more preferable, and a nitro group or a methyl group is particularly preferable.

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

[Formula 32]

(In 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 from 0 to 4.)

When R ^d4 is an organic group, a preferable example of the organic group is the same as the example of the organic group that the aryl group may have as 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. Moreover, as for q, the integer of 0-3 is preferable, the integer of 0-2 is more preferable, and 0 or 1 is especially preferable.

In Formula (D1), when R ^d1 is an aliphatic hydrocarbon group which may have a substituent, the number of carbon atoms is 1 to 10. The carbon number of the substituent is not included in this carbon number. 1-9 are preferable and, as for carbon number of the said aliphatic hydrocarbon group, 1-8 are more preferable. 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 linear, branched, cyclic, or a combination of these structures, and is preferably linear.

In the formula (D1), preferred examples when R ^d1 is a straight-chain aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-hept A til group, an n-octyl group, an n-nonyl group, and an n-decyl group.

Preferred examples when R ^d1 is a cyclic aliphatic hydrocarbon group include a cyclopentyl group and a cyclohexyl group.

Preferred examples in the case where R ^d1 is a structure of a combination of a linear aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group are cyclohexylmethyl group, cyclopentylmethyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, 3-cyclohexyl -n-propyl group and 3-cyclopentyl-n-propyl group are mentioned, and among these groups, 2-cyclohexylethyl group and 2-cyclopentylethyl group are preferable.

When R ^d1 is an aliphatic hydrocarbon group, the substituents that 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, and a substituent group. An aryl group, an aryloxy 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, or 1 to 2 carbon atoms of 1 to 6 carbon atoms. And amino groups substituted with alkyl and aryl groups which may have 1 or 2 substituents. In addition, the carbon number of these substituents is not included in the carbon number of the aliphatic hydrocarbon group.

The substituent having 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 a substituent of 1 or 2 In the case of an amino group substituted with an aryl group to be used, examples of the aryl group included in these groups include phenyl group, naphthyl group, anthryl group, and phenanthryl group, preferably phenyl group and naphthyl group, and more preferably phenyl group.

The substituent having 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 a substituent of 1 or 2 In the case of an amino group substituted with an aryl group, as the substituent which the aryl group contained in these groups may have, a hydroxyl group, 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 carbon number And 2 to 7 saturated aliphatic acyl groups.

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

When R ^d1 is a carbazolyl group which may have a substituent, the type of the substituent is not particularly limited within a range that does not impair the object of the present invention. Examples of preferred substituents that 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, and a carbon number. Saturated aliphatic acyl group having 2 to 20, alkoxycarbonyl group having 2 to 20 carbon atoms, saturated aliphatic acyloxy group having 2 to 20 carbon atoms, phenyl group which may have a substituent, phenoxy group which may have a substituent, and phenyl thi which may have a substituent Ogi, a phenylcarbonyl 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 substituent A naphthyl group which may have, a naphthoxy group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a naphtho which may have a substituent Iloxy group, a naphthyl alkyl group having 11 to 20 carbon atoms which may have a substituent, heterocyclyl group which may have a substituent, heterocyclylcarbonyl group which may have a substituent, amino group, amino group substituted with an organic group of 1 or 2, morpholine And a -1-yl group, and 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 preferred substituents that the carbazolyl group may have on a nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 to 20 carbon atoms. Saturated aliphatic acyl group, a C2-20 alkoxycarbonyl 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, or a phenylalkyl group of 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 11 to 20 carbon atoms 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.

About specific examples of the substituent which the carbazolyl group may have, 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, and a substituent Regarding the naphthyl alkyl group which may have, the heterocyclyl group which may have a substituent, and the amino group substituted with the organic group of 1 or 2, with the example of the substituent which an aryl group has when R ^d1 is an aryl group which may have a substituent, same.

In R ^d1 , examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group included in the substituent group of the carbazolyl group 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; Phenyl group; Naphthyl group; Benzoyl group; 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 morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; Monoalkylamino groups having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholine-1-yl group; Piperazine-1-diary; Halogen; Nitro group; And cyano groups. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent having the carbazolyl group further have a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but is 1 to 4 desirable. When a phenyl group, a naphthyl group, and a heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

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

When R ^d2 is an aliphatic hydrocarbon group, 1 to 6 carbon atoms are preferable and 1 is more preferable as the carbon number of the aliphatic hydrocarbon group. 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 linear, branched, cyclic, or a combination of these structures, and is preferably linear.

Preferred examples when R ^d2 is a straight-chain aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl groups and n-decyl groups. Among these, a methyl group is particularly preferable.

Examples when 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. Can. 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.

In R ^d2 , the substituent group of the aryl group is not particularly limited as long as it does not impair the object of the present invention. Examples of the preferable substituent which the aryl group may have on a 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, and 2 carbon atoms. Saturated aliphatic acyl group having 20 to 20, alkoxycarbonyl group having 2 to 20 carbon atoms, saturated aliphatic acyloxy group having 2 to 20 carbon atoms, phenyl group which may have a substituent, phenoxy group which may have a substituent, phenylthio 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, and a substituent A naphthoxy group which may have, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a substituent A heterocyclyl group which may have, 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-1-yl group, and a piperazin-1-yl group, a halogen atom, a nitro group And cyano groups.

About the specific example of the substituent which an aryl group may have, even if it has an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a phenyl alkyl group which may have a substituent, a substituent Regarding the naphthyl alkyl group, the heterocyclyl group which may have a substituent, and the amino group substituted with the organic group of 1 or 2, when R ^d1 is an aryl group which may have a substituent, examples of the substituent which the aryl group may have Same as

In R ^d2 , examples of the substituent when the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent having the aryl group 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; Phenyl group; Naphthyl group; Benzoyl group; 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 morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; Monoalkylamino groups having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholine-1-yl group; Piperazine-1-diary; Halogen atom; Nitro group; And cyano groups. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent having the aryl group further have a substituent, the number of the substituents is not limited within the range not impairing the object of the present invention, but 1 to 4 is preferred. . When a phenyl group, a naphthyl group, and a heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^d3 in Formula (D1) is a hydrogen atom or a group represented by -CO-R ^d5 . 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 the aforementioned R ^d1 is an aryl group which may have a substituent. When R ^d5 is an aryl group which may have a substituent, the aryl group may have two or more 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.

As a compound represented by Formula (D1), in terms of the base generating efficiency or acid generating efficiency of this compound, in Formula (D1), an aliphatic hydrocarbon group having 1 to 10 carbon atoms which R ^d1 may have a substituent or a substituent It is an aryl group which may have, and a compound in which R ^d2 is a group represented by the following formula (D1-2) or a compound in which R ^d1 is a group represented by the following formula (D1-3) in the formula (D1) is preferred, and is colored In view of this suppression and obtaining a highly transparent resin, in formula (D1), R ^d1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent or an aryl group which may have a substituent, and R ^d2 is The compound represented by the formula (D1-2) is more preferable.

[Formula 33]

(In formula (D1-2), R ^d6 is a group selected from the group consisting of monovalent organic groups, amino groups, halogen atoms, nitro groups, and cyano groups, A is S or O, and r is 0 to 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 a range that does not impair the object of the present invention. Preferred examples when R ^d6 is an organic group in the formula (D1-2) 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; Phenyl group; Naphthyl group; Benzoyl group; 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 morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; Monoalkylamino groups having an alkyl group having 1 to 6 carbon atoms; A dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Morpholine-1-yl group; Piperazine-1-diary; Halogen atom; Nitro group; And cyano groups.

In R ^d6 , a benzoyl group; 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 morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; Nitro group is preferable, Benzoyl group; Naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; 4-(phenyl)phenylcarbonyl group is more preferable.

Moreover, 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), it is preferable that A is S.

As a substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group included in R ^d6 further has a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a saturated aliphatic group having 2 to 7 carbon atoms. Actual group, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholine-1- And diary, piperazin-1-yl group, halogen atom, nitro group, and cyano group. When a phenyl group, a naphthyl group, and a heterocyclyl group included in R ^d6 further has a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but 1 to 4 is preferred. When phenyl group, naphthyl group, and heterocyclyl group contained in R ^d6 have a plurality of substituents, the plurality of substituents may be the same or different.

[Formula 34]

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

R ^d7 in Formula (12) can be selected from various organic groups within a range that does not impair the object of the present invention. Preferred 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, and a substituent. A benzoyl group, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbons which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, and a naph which may have a substituent And a alkoxycarbonyl group, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

In R ^d7 , 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 ^d8 in Formula (12) is not particularly limited within a range that does not impair the object of the present invention, and can be selected from various organic groups. Specific examples of the group preferable as 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. As R ^d8 , among these groups, a phenyl group which may have a substituent and a naphthyl group which may have a substituent are more preferable, and a 2-methylphenyl group and a naphthyl group are particularly preferable.

As a substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^d7 or R ^d8 further has a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 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, Morpholine-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group. When a phenyl group, a naphthyl group, and a heterocyclyl group included in R ^d7 or R ^d8 further has a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but is 1 to 4 desirable. When a phenyl group, a naphthyl group, and a 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 formula (D1) can be synthesized according to scheme 1 below, for example, when p is 0, R ^d2 is an aryl group which may have a substituent, and R ^d3 is a hydrogen atom. Specifically, the aromatic compound represented by the following formula (1-1) is acylated by a Friedel Crafts reaction using the halocarbonyl compound represented by the following formula (1-2), and the following formula (1-3) The ketone compound represented by is obtained, and the obtained ketone compound (1-3) is oxidized with hydroxylamine to obtain an oxime compound represented by the following formula (1-4). Further, in the following formula (1-2), Hal is a halogen atom, and in the following formulas (1-1), (1-2), (1-3), and (1-4), R ^d1 , And R ^d2 is the same as formula (D1).

<Scheme 1>

[Formula 35]

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

<Scheme 2>

[Formula 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. According to the method described above, it can be oxime-oxidized with hydroxylamine to obtain a compound represented by R ^d2 -C(=N-OH)-R ^d1 .

Moreover, when the compound represented by Formula (D1) is p is 0, R ^d2 is a C1-C10 aliphatic hydrocarbon group, and R ^d3 is a group represented by -CO-R ^d5 , R ^d2 -C(=N- The oxime compound represented by OH)-R ^d1 can be obtained as a compound represented by R ^d2 -C(=NO-CO-R ^d5 )-R ^d1 by acylating according to the method described in Scheme 2.

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

<Scheme 3>

[Formula 37]

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

<Scheme 4>

[Formula 38]

Among the oxime compounds represented by formula (D1), compounds of the following formula are mentioned as particularly preferable compounds.

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

[Formula 45]

[Formula 46]

[Formula 47]

[Formula 48]

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

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

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

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

In the negative radiation-sensitive composition 2, the amount of the solvent is preferably an amount such that the solid content concentration of the negative radiation-sensitive composition 2 is 1 to 50% by mass, and more preferably 5 to 40% by mass. . Moreover, in the solvent contained in the negative radiation sensitive composition 2, the mass ratio of the compound represented by the general formula (1) and other organic solvents is preferably 5:95 to 100:0, and 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) and other organic solvents in the above range, the negative radiation sensitive composition 2 is excellent in sensitivity, storage stability, coatability, developability, and safety. It is easy to become, and the pattern formed by exposing and developing the negative radiation sensitive composition 2 is likely to be suppressed from the occurrence of foreign matter.

[Other ingredients]

The negative radiation sensitive composition 2 may contain various additives as needed. Examples of the additives include sensitizers, curing accelerators, fillers, adhesion promoters, antioxidants, agglomeration inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants, and the like.

<Negative radiation sensitive composition 3>

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

[Compound represented by 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 general formula (1) can be used alone or in combination of two or more.

[Polybenzoxazole precursor]

The polybenzoxazole precursor can be used alone or in combination of two or more. As a synthetic raw material for the polybenzoxazole precursor, an aromatic diamine diol and a dicarbonyl compound having a specific structure are used. Hereinafter, an aromatic diamine diol and a dicarbonyl compound are demonstrated.

(Aromatic diaminediol)

In this invention, the compound represented by following formula (21) is used as aromatic diamine diol. Aromatic diamine diol may be used individually by 1 type, or may be used in combination of 2 or more type.

[Formula 49]

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

In formula (21), R ^a1 is a tetravalent organic group containing one or more aromatic rings, and the carbon number is preferably 6-50, more preferably 6-30. R ^a1 may be an aromatic group, or two or more aromatic groups may be a contributing bond via an aliphatic hydrocarbon group and a halogenated aliphatic hydrocarbon group, or a bond including a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom. As a bond containing hetero atoms such as oxygen atom, sulfur atom, and nitrogen atom contained in R ^a1 , -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, and the like, and -O-, -CO-, -SO-, -SO ₂ -, -S -, and -SS- are preferred.

The aromatic ring contained in R ^a1 may be an aromatic heterocycle. It is preferable that the aromatic ring bonded to the amino group and hydroxyl group in R ^a1 is a benzene ring. When the ring bonding to the amino group and hydroxyl group in R ^a1 is a condensed ring containing two or more rings, it is preferable that the ring bonding to the amino group and hydroxyl group in the condensed ring is a benzene ring.

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

[Formula 50]

(In Formula (1-1), X ¹ is 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. Y ¹ in Formulas (1-2) to (1-5) may be the same or different, and -CH. ₂ -, -O-, -S-, -SO-, -SO ₂ -, -CO-, and a single bond selected from the group consisting of single bonds.)

The group represented by any of the formulas (1-1) to (1-9) may have one or more substituents on the aromatic ring. As a preferable example of a substituent, a fluorine atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 fluorinated alkyl group, and a C1-C6 fluorinated alkoxy group are preferable. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferable that it is a perfluoroalkyl group or a perfluoroalkoxy group.

Specific examples of the compound represented by the formula (21) include 2,4-diamino-1,5-benzenediol, 2,5-diamino-1,4-benzenediol, and 2,5-diamino-3 -Fluoro-1,4-benzenediol, 2,5-diamino-3,6-difluoro-1,4-benzenediol, 2,6-diamino-1,5-dihydroxynaphthalene, 1 ,5-diamino-2,6-dihydroxynaphthalene, 2,6-diamino-3,7-dihydroxynaphthalene, 1,6-diamino-2,5-dihydroxynaphthalene, 4,4 '-Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, 2,3'-diamino-3,2'-dihydride Hydroxybiphenyl, 3,4'-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- 6,6'-ditrifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethylbiphenyl, 4,4'-diamino -3,3'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-ditrifluoromethyl Biphenyl, 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(3-amino-4-hydroxyphenyl)methane, 3,4'-diamino-4 ,3'-dihydroxydiphenylmethane, bis(4-amino-3-hydroxy-6-trifluoromethyl)methane, bis(3-amino-4-hydroxy-6-trifluoromethyl)methane , 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenylmethane, bis(4-amino-3-hydroxyphenyl)difluoromethane, bis (3-amino-4-hydroxyphenyl)difluoromethane, 3,4'-diamino-4,3'-dihydroxydiphenyldifluoromethane, bis(4-amino-3-hydroxy- 6-trifluoromethylphenyl)difluoromethane, bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)difluoromethane , 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyldifluoromethane, bis(4-amino-3-hydroxyphenyl)ether, bis (3-amino-4-hydroxyphenyl) ether, 3,4'-diamino-4,3'-dihydroxydiphenyl ether, bis(4-amino-3-hydroxy-6-trifluoromethylphenyl )Ether, bis(3-amino-4-hydroxy-6-trifluoromethylphenyl) ether, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyl Diphenyl ether, bis(4-amino-3-hydroxyphenyl) ketone, bis(3-amino-4-hydroxyphenyl) ketone, 3,4'-diamino-4,3'-dihydroxydiphenyl Ketone, bis(4-amino-3-hydroxy-6-trifluoromethyl) ketone, bis(3-amino-4-hydroxy-6-trifluoromethyl) ketone, 3,4'-diamino- 4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenylketone, 2,2-bis(4-amino-3-hydroxyphenyl)propane, 2,2-bis(3-amino -4-hydroxyphenyl)propane, 2-(3-amino-4-hydroxyphenyl)-2-(4'-amino-3'-hydroxyphenyl)propane, 2,2-bis(4-amino- 3-hydroxy-6-trifluoromethylphenyl)propane, 2,2-bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)propane, 2-(3-amino-4-hydroxy- 6-trifluoromethylphenyl)-2-(4'-amino-3'-hydroxy-6'-trifluoromethylphenyl)propane, 2,2-bis(3-amino-4-hydroxy-5-tri Fluoromethylphenyl)propane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2- (3-amino-4-hydroxyphenyl)-2-(4'-amino-3'-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxy-6-tri Fluoromethylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)hexafluoropropane, 2-(3-amino-4-hydroxy-6- Trifluoromethylphenyl)-2-(4'-amino-3'-hydroxy-6'-trifluoromethylphenyl)hexafluoropropane, 2,2-ratio S(3-amino-4-hydroxy-5-trifluoromethylphenyl)hexafluoropropane, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)sulfone , 3,4'-diamino-4,3'-dihydroxydiphenylsulfone, bis(4-amino-3-hydroxy-6-trifluoromethyl)sulfone, bis(3-amino-4-hydroxy Hydroxy-6-trifluoromethyl)sulfone, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenylsulfone, bis(4-amino-3- Hydroxyphenyl)sulfide, bis(3-amino-4-hydroxyphenyl)sulfide, 3,4'-diamino-4,3'-dihydroxydiphenylsulfide, bis(4-amino-3 -Hydroxy-6-trifluoromethyl)sulfide, bis(3-amino-4-hydroxy-6-trifluoromethyl)sulfide, 3,4'-diamino-4,3'-dihydride Hydroxy-6,6'-ditrifluoromethyldiphenylsulfide, (4-amino-3-hydroxyphenyl)4-amino-3-hydroxyphenylbenzoate, (3-amino-4-hydroxyphenyl )3-amino4-hydroxyphenylbenzoate, (3-amino-4-hydroxyphenyl)4-amino-3-hydroxyphenylbenzoate, (4-amino-3-hydroxyphenyl)3-amino- 4-hydroxyphenylbenzoate, N-(4-amino-3-hydroxyphenyl)4-amino-3-hydroxybenzamide, N-(3-amino-4-hydroxyphenyl)3-amino4- Hydroxyphenylbenzamide, N-(3-amino-4-hydroxyphenyl)4-amino-3-hydroxyphenylbenzamide, N-(4-amino-3-hydroxyphenyl)3-amino-4- Hydroxyphenylbenzamide, 2,4'-bis(4-amino-3-hydroxyphenoxy)biphenyl, 2,4'-bis(3-amino-4-hydroxyphenoxy)biphenyl, 4, 4'-bis(4-amino-3-hydroxyphenoxy)biphenyl, 4,4'-bis(3-amino-4-hydroxyphenoxy)biphenyl, di[4-(4-amino-3 -Hydroxyphenoxy)phenyl]ether, di[4-(3-amino-4-hydroxyphenoxy)phenyl]ether, 2,4'-bis(4-amino-3-hydroxyphenoxy)benzophenone , 2,4'-bis(3-amino-4-hydroxyphenoxy)benzophenone, 4,4'-bis(4-amino-3-hydroxyphenoxy)benzophene Paddy, 4,4'-bis(3-amino-4-hydroxyphenoxy)benzophenone, 2,4'-bis(4-amino-3-hydroxyphenoxy)octafluorobiphenyl, 2,4' -Bis(3-amino-4-hydroxyphenoxy)octafluorobiphenyl, 4,4'-bis(4-amino-3-hydroxyphenoxy)octafluorobiphenyl, 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(4-amino-3-hydroxyphenoxy)octafluorobenzophenone, 4,4'-bis(3-amino-4- Hydroxyphenoxy)octafluorobenzophenone, 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(3-amino-4- Hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-amino-4 -Hydroxyphenoxy)phenyl]hexafluoropropane, 2,8-diamino-3,7-dihydroxydibenzofuran, 2,8-diamino-3,7-dihydroxyfluorene, 2, 6-diamino-3,7-dihydroxyxanthene, 9,9-bis-(4-amino-3-hydroxyphenyl)fluorene, and 9,9-bis-(3-amino-4-hydride And oxyphenyl)fluorene.

Among these, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane is preferable from the viewpoint of being able to form a polybenzoxazole resin excellent in transparency.

(Dicarbonyl compound)

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

[Formula 51]

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

R ^a2 in Formula (22) may be an aromatic group, an aliphatic group, or a combination of aromatic groups and aliphatic groups. It is preferable that R ^a2 is a group containing an aromatic group and/or an alicyclic group from the viewpoint 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 the carbon atom and the hydrogen atom. When R ^a2 contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, nitrogen atom, or sulfur atom is 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 or -O As a group selected from -, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, it is more preferably contained in R ^a2 .

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

As a dicarbonyl compound represented by Formula (22), when a dialdehyde compound in which both A are hydrogen atoms is used, a polybenzoxazole intermediate represented by Formula (10) below is prepared.

[Formula 52]

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

As a dicarbonyl compound represented by Formula (22), when both of A are dicarboxylic acid dihalides having halogen atoms, a polybenzoxazole intermediate represented by Formula (20) below is prepared.

[Formula 53]

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

Hereinafter, the dialdehyde compound which is a preferable compound as a dicarbonyl compound, and dicarboxylic acid dihalide are demonstrated.

· Dialdehyde compounds

The dialdehyde compound used as a raw material for a polybenzoxazole precursor is a compound represented by the following formula (2-1). As the dialdehyde compound, one type may be used alone, or two or more types may be used in combination.

[Formula 54]

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

The following groups are mentioned as a preferable aromatic group or aromatic ring-containing group as R ^a2 in Formula (2-1).

[Formula 55]

(In the formula, X ² is 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 selected from the group consisting of single bonds, when X ² is plural, plural X ² may be the same or different, Y ² may be the same or different, respectively,- CH ₂ -, -O-, -S-, -SO-, -SO ₂ -, -CO-, and a single bond selected from the group consisting of single bonds p and q are each an integer of 0 to 3 .)

The following groups are mentioned as an alicyclic group or alicyclic containing group preferable as R ^a2 in Formula (2-1).

[Formula 56]

(In the formula, X ² is 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 one bond selected from the group consisting of single bonds, when X ² is plural, plural X ² may be the same or different, and Y ² may be the same or different, respectively. -CH ₂ -, -O-, -S-, -SO-, -SO ₂ -, -CO-, and a single bond selected from the group consisting of single bonds Z is -CH ₂ -, -CH ₂ CH ₂ -, and -CH=CH- are 1 species selected from the group consisting of p, each being an integer of 0 to 3.)

The aromatic ring or alicyclic group included in the group preferable as R ^a2 may have one or more substituents on the ring. As a preferable example of a substituent, a fluorine atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C6 fluorinated alkyl group, and a C1-C6 fluorinated alkoxy group are preferable. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferable that it is 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 benzenedialdehydes, pyridinedialdehydes, pyrazinedialdehydes, pyrimidinedialdehydes, naphthalenedialdehydes, and bis Phenyldialdehydes, diphenyletherdialdehydes, diphenylsulfonedialdehydes, diphenylsulfidedialdehydes, bis(formylphenoxy)benzenes, [1,4-phenylenebis(1-methyle Thiliden)]bisbenzaldehydes, 2,2-bis[4-(formylphenoxy)phenyl]propanes, bis[4-(formylphenoxy)phenyl]sulfide, bis[4-(former) Milphenoxy)phenyl]sulfones, and fluorenedialdehydes.

Specific examples of the benzenedialdehydes include phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 3-fluorophthalaldehyde, 4-fluorophthalaldehyde, 2-fluoroisophthalaldehyde, 4-fluoroisophthalaldehyde, 5-fluoroisophthalaldehyde, 2-fluoroterephthalaldehyde, 3-trifluoromethylphthalaldehyde, 4-trifluoromethylphthalaldehyde, 2-trifluoromethylisophthalaldehyde, 4-trifluoromethyl Isophthalaldehyde, 5-trifluoromethylisophthalaldehyde, 2-trifluoromethylterephthalaldehyde, 3,4,5,6-tetrafluorophthalaldehyde, 2,4,5,6-tetrafluoro Sophthalaldehyde, and 2,3,5,6-tetrafluoro terephthalaldehyde, etc. are mentioned.

Examples of pyridine dialdehydes include pyridine-2,3-dialdehyde, pyridine-3,4-dialdehyde, and pyridine-3,5-dialdehyde.

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

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

Specific examples of naphthalenedialdehydes include naphthalene-1,5-dialdehyde, naphthalene-1,6-dialdehyde, naphthalene-2,6-dialdehyde, naphthalene-3,7-dialdehyde, 2,3, 4,6,7,8-hexafluoronaphthalene-1,5-dialdehyde, 2,3,4,5,6,8-hexafluoronaphthalene-1,6-dialdehyde, 1,3,4, 5,7,8-hexafluoronaphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene-2,6-dialdehyde, 1,5-bis(trifluoromethyl)naphthalene-2,6- Dialdehyde, 1-trifluoromethylnaphthalene-3,7-dialdehyde, 1,5-bis(trifluoromethyl)naphthalene-3,7-dialdehyde, 1-trifluoromethyl-2,4,5 ,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] And -2,4,6,8-tetrafluoronaphthalene-3,7-dialdehyde.

As specific examples of biphenyldialdehydes, biphenyl-2,2'-dialdehyde, biphenyl-2,4'-dialdehyde, biphenyl-3,3'-dialdehyde, biphenyl-4,4 '-Dialdehyde, 6,6'-difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-2,4'-dialdehyde, 6,6'-difluorobiphenyl -3,3'-dialdehyde, 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 the diphenyl ether dialdehydes include diphenyl ether-2,4'-dialdehyde, diphenyl ether-3,3'-dialdehyde, diphenyl ether-3,4'-dialdehyde, and di And phenyl ether-4,4'-dialdehyde.

Specific examples of diphenylsulfone dialdehydes include diphenylsulfone-3,3'-dialdehyde, diphenylsulfone-3,4'-dialdehyde, and diphenylsulfone-4,4'-dialdehyde, and the like. Can be lifted.

Specific examples of diphenyl sulfide dialdehydes include diphenyl sulfide-3, 3'-dialdehyde, diphenyl sulfide-3,4'-dialdehyde, and diphenyl sulfide-4,4'-. And dialdehydes.

Specific examples of diphenyl ketone dialdehydes include diphenyl ketone-3,3'-dialdehyde, diphenylketone-3,4'-dialdehyde, and diphenylketone-4,4'-dialdehyde. Can be lifted.

Specific examples of bis(formylphenoxy)benzenes include benzene1,3-bis(3-formylphenoxy)benzene, 1,4-bis(3-formylphenoxy)benzene, and 1,4 -Bis(4-formylphenoxy)benzene, etc. are mentioned.

[1,4-Phenylenebis(1-methylethylidene)] As specific examples of the bisbenzaldehyde, 3,3'-[1,4-phenylenebis(1-methylethylidene)]bis Benzaldehyde, 3,4'-[1,4-phenylenebis(1-methylethylidene)]bisbenzaldehyde, and 4,4'-[1,4-phenylenebis(1-methylethylidene) )]Bisbenzaldehyde and the like.

As specific examples of 2,2-bis[4-(formylphenoxy)phenyl]propanes, 2,2-bis[4-(2-formylphenoxy)phenyl]propane, 2,2-bis[ 4-(3-formylphenoxy)phenyl]propane, 2,2-bis[4-(4-formylphenoxy)phenyl]propane, 2,2-bis[4-(3-formylphenoxy) And phenyl]hexafluoropropane and 2,2-bis[4-(4-formylphenoxy)phenyl]hexafluoropropane.

As specific examples of bis[4-(formylphenoxy)phenyl]sulfides, bis[4-(3-formylphenoxy)phenyl]sulfide, and bis[4-(4-formylphenoxy) )Phenyl]sulfide.

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

Specific examples of the fluorene dialdehyde include fluorene-2,6-dialdehyde, fluorene-2,7-dialdehyde, dibenzofuran-3,7-dialdehyde, and 9,9-bis(4- Formylphenyl)fluorene, 9,9-bis(3-formylphenyl)fluorene, 9-(3-formylphenyl)-9-(4'-formylphenyl)fluorene, and the like. .

Moreover, diphenyl alkane dialdehyde represented by the following formula or diphenyl fluoro alkane dialdehyde can also be preferably used as an aromatic dialdehyde compound.

[Formula 57]

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

[Formula 58]

When the dicarbonyl compound represented by Formula (2-1) is an alicyclic dialdehyde containing an alicyclic group, preferred examples thereof include cyclohexane-1,4-dialdehyde, cyclohexane-1,3-dialdehyde, Bicyclo[2.2.1]heptan-2,5-dialdehyde, bicyclo[2.2.2]octane-2,5-dialdehyde, bicyclo[2.2.2]octa-7-ene-2,5-di Aldehyde, bicyclo[2.2.1]heptan-2,3-dialdehyde, bicyclo[2.2.1]hepta-5-ene-2,3-dialdehyde, tricyclo[5.2.1.0 ^2,6 ]decane- 3,4-dialdehyde, tricyclo[5.2.1.0 ^2,6 ]deca-4-en-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-2,7-dialdehyde, per 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-trimethanoanthracene-2,3-dialdehyde, bicyclohexyl-4,4'-di Aldehyde, 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'-di Aldehyde, dicyclohexylsulfone-3,3'-dialdehyde, dicyclohexylsulfone-3,4'-dialdehyde, dicyclohexylsulfone-4,4'-dialdehyde, dicyclohexylsulfide-3,3 '-Dialdehyde, dicyclohexyl sulfide-3,4'-dialdehyde, dicyclohexyl sulfide-4,4'-dialdehyde, dicyclohexylketone-3,3'-dialdehyde, dicyclohexylketone -3,4'-dialdehyde, dicyclohexylketone-4,4'-dialdehyde, 2,2-bis(3-formylcyclohexyl)propane, 2,2- Bis(4-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-bis(4-formylcyclohexyl)benzene, 3,3'-[1, 4-cyclohexylenebis(1-methylethylidene)]biscyclohexanecarbaldehyde, 3,4'-[1,4-cyclohexylenebis(1-methylethylidene)]biscyclohexanecarval Dehydr, 4,4'-[1,4-cyclohexylenebis(1-methylethylidene)]biscyclohexanecarbaldehyde, 2,2-bis[4-(3-formylcyclohexyl)cyclohexyl ]Propane, 2,2-bis[4-(4-formylcyclohexyl)cyclohexyl]propane, 2,2-bis[4-(3-formylcyclohexyl)cyclohexyl]hexafluoropropane, 2, 2-bis[4-(4-formylphenoxy)cyclohexyl]hexafluoropropane, bis[4-(3-formylcyclohexyloxy)cyclohexyl]sulfide, bis[4-(4-formal Milcyclohexyloxy)cyclohexyl]sulfide, bis[4-(3-formylcyclohexyloxy)cyclohexyl]sulfone, bis[4-(4-formylcyclohexyloxy)cyclohexyl]sulfone, 2,2'-bicyclo[2.2.1]heptan-5,6'-dialdehyde, 2,2'-bicyclo[2.2.1]heptan-6,6'-dialdehyde, and 1,3-di Formyl adamantane and the like.

Among the dialdehyde compounds described above, isophthalaldehyde is preferable from the viewpoint of easy synthesis and availability, and easy to obtain a polybenzoxazole resin excellent in heat resistance and mechanical properties.

Dicarboxylic acid dihalide

The dicarboxylic acid dihalide used as a raw material for the polybenzoxazole precursor is a compound represented by the following formula (2-2). Dicarboxylic acid dihalide may be used individually by 1 type, or may be used in combination of 2 or more type.

[Formula 59]

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

In Formula (2-2), as Hal, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a chlorine atom is more preferable.

As a preferable compound as a compound represented by Formula (2-2), a preferable example of a dialdehyde compound includes a compound in which two aldehyde groups of the above-mentioned compounds are substituted with halocarbonyl groups, preferably chlorocarbonyl groups.

Among the dicarboxylic acid dihalides described above, terephthalic acid dichloride is preferred from the viewpoint of easy synthesis and availability, and easy to obtain a polybenzoxazole resin excellent in heat resistance and mechanical properties.

(Method for producing polybenzoxazole precursor)

In the present invention, the polybenzoxazole precursor is produced by reacting the above-described aromatic diaminediol and dicarbonyl compound in a solvent according to a known method. Hereinafter, as a representative example of a method for producing a polybenzoxazole precursor, a method for producing when the dicarbonyl compound is a dialdehyde compound and a method for producing when the dicarbonyl compound is a dicarboxylic acid halide will be described.

· Reaction of aromatic diaminediol and dialdehyde compound

The reaction of the aromatic diamine diol and the dialdehyde compound is carried out in a solvent. The reaction of the aromatic diamine diol and the dialdehyde compound is a reaction of forming a CiF base, and can be carried out according to a known method. Although the reaction temperature is not particularly limited, usually 20 to 200°C is preferable, 20 to 160°C is more preferable, and 100 to 160°C is particularly preferable.

The reaction of the aromatic diamine diol and the dialdehyde compound may be performed while adding an entrainer to the solvent and dehydrating at reflux. The entrainer is not particularly limited, and is suitably selected from organic solvents that form an azeotropic mixture with water and form a two-phase system with water at room temperature. Preferred examples of the entrainer include esters such as isobutyl acetate, allyl acetate, n-propyl propionic acid, isopropyl propionate, n-butyl propionic acid, 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 between the aromatic diamine diol and the dialdehyde compound is not particularly limited, but is typically 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 aromatic diaminediol.

The amount of the solvent 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, is used with respect to the sum of the mass of the aromatic diaminediol and the mass of the dialdehyde compound.

It is preferable that the reaction of the aromatic diamine diol and the dialdehyde compound is performed until the number average molecular weight of the resulting polybenzoxazole precursor is 1000 to 20000, preferably 1200 to 5000.

· Reaction of aromatic diaminediol and dicarboxylic acid dihalide

The reaction of the aromatic diamine diol and dicarboxylic acid dihalide is carried out in a solvent. Although reaction temperature is not specifically limited, Usually, -20-150 degreeC is preferable, -10-150 degreeC is more preferable, -5-70 degreeC is especially preferable. Hydrogen halide is by-product in the reaction of an aromatic diamine diol and a dicarboxylic acid dihalide. In order to neutralize such hydrogen halide, an organic base such as triethylamine, pyridine and N,N-dimethyl-4-aminopyridine, or an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide may be added in a small amount in the reaction solution. .

Although the reaction time of aromatic diamine diol and dicarboxylic acid dihalide is not specifically limited, Typically, about 2 to 72 hours is preferable.

The amount of dicarboxylic acid dihalide used in preparing the polybenzoxazole precursor is preferably 0.5 to 1.5 mol, more preferably 0.7 to 1.3 mol, per 1 mol of aromatic diaminediol.

The amount of the solvent 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, is used with respect to the sum of the mass of the aromatic diamine diol and the mass of the dicarboxylic acid dihalide.

The reaction of the aromatic diamine diol and dicarboxylic acid dihalide is preferably carried out until the number average molecular weight of the resulting polybenzoxazole precursor is 1000 to 20000, preferably 1200 to 5000.

By the method described above, a solution of the polybenzoxazole precursor is obtained. When the negative radiation sensitive composition 3 is prepared, a solution of a polybenzoxazole precursor can be used as it is. In addition, the polybenzoxazole precursor obtained by removing at least a portion of the solvent from the solution of the polybenzoxazole precursor at a low temperature such that conversion of the polybenzoxazole precursor to the polybenzoxazole resin under reduced pressure does not occur. You can also use pastes or solids. Further, an appropriate amount of a solvent or the like is added to the solution of the polybenzoxazole precursor obtained by the above reaction, and the solution of the polybenzoxazole precursor whose solid content concentration is adjusted can also be used for the preparation of the negative radiation sensitive composition 3. .

Examples of the organic solvent used for the reaction of the aromatic diaminediol and the dicarbonyl compound include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide and N,N- Nitrogen-containing 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 β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-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 polybenzoxazole precursor or polybenzoxazole resin, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N,N,2-trimethylpropionamide, N-methylcaprolactam, and N,N,N',N'-tetramethylurea 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, it is decomposed by the action of light, such as a photobase generator or a photoacid generator, to generate at least one of a base and an acid. The compound (A) to be mentioned is mentioned. The photosensitive components 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 radiation sensitive composition 3 decomposes to generate at least one of a base and an acid. The base or acid generated in this way acts on the polybenzoxazole precursor in the negative-type radiation-sensitive composition 3 to promote conversion to polybenzoxazole resin.

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

As the compound (A), as in the case of the negative radiation-sensitive composition 2, 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 is mentioned. Can. The imidazole compound in which compound (A-1) occurs promotes the conversion of the polybenzoxazole precursor in the negative radiation sensitive composition 3 to polybenzoxazole resin. In addition, conversion of the polybenzoxazole precursor in the negative radiation sensitive composition 3 to the polybenzoxazole resin is promoted by the base or acid generated by the decomposition of the compound (A-2). The details of the compound (A-1) and the compound (A-2) are the same as those described for the negative radiation sensitive composition 2.

The content of the photosensitive component in the negative-type radiation-sensitive composition 3 is not particularly limited as long as it does not impair the object of the present invention. The content of the photosensitive component in the negative-type radiation-sensitive composition 3 is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 mass of the polybenzoxazole precursor.

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

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

In the negative radiation sensitive composition 3, the content of the solvent is preferably an amount such that the solid content concentration of the negative radiation sensitive composition 3 is 1 to 50 mass%, and more preferably 5 to 40 mass%. . Moreover, in the solvent contained in the negative radiation sensitive composition 3, the mass ratio of the compound represented by the general formula (1) and other organic solvents is preferably 5:95 to 100:0, and 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) and other organic solvents in the above range, the negative radiation sensitive composition 3 is excellent in sensitivity, storage stability, coatability, developability, and safety. It is easy to become, and the pattern formed by exposing and developing the negative radiation sensitive composition 3 is likely to be suppressed from the occurrence of foreign matter.

[Other ingredients]

The negative radiation sensitive composition 3 may contain various additives as needed. Examples of the additives include sensitizers, curing accelerators, fillers, adhesion promoters, antioxidants, agglomeration inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants, and the like.

<Positive radiation-sensitive composition 1>

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

[Compound represented by 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 general formula (1) can be used alone or in combination of two or more.

[Alkali-soluble resin]

As an alkali-soluble resin, what was illustrated by the negative radiation sensitive composition 1 can be used.

It is preferable that content of alkali-soluble resin is 5 to 90 mass% with respect to the solid content of positive radiation sensitive composition 1, and it is more preferable that it is 10 to 85 mass %. By setting it as the said range, there exists a tendency which is easy to balance the film-forming ability and developability of the positive radiation sensitive composition 1.

[Compound containing quinonediazide group]

The quinonediazide group-containing compound is not particularly limited, but a complete ester or partial esterified product of a compound having at least one phenolic hydroxyl group and a quinonediazide group-containing sulfonic acid is preferable. Such a quinonediazide group-containing compound contains a compound having one or more phenolic hydroxyl groups and a quinonediazide group-containing sulfonic acid in a suitable solvent such as dioxane, and alkalis such as triethanolamine, alkali carbonate, and alkali hydrogen carbonate. It can be obtained by condensation in the presence and complete esterification or partial esterification. The quinonediazide group-containing compound can be used alone or in combination of two or more.

Examples of the compound having one or more phenolic hydroxyl groups include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone. ;

Tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxy Phenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4 -Hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2, 5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)- 3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)- 2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4- Hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxy Trisphenol type compounds such as phenylmethane and bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane;

2,4-bis(3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenol, 2,6-bis(2,5-dimethyl-4-hydroxybenzyl)-4-methylphenol, etc. Linear trinuclear phenol compounds;

1,1-bis[3-(2-hydroxy-5-methylbenzyl)-4-hydroxy-5-cyclohexylphenyl]isopropane, bis[2,5-dimethyl-3-(4-hydroxy- 5-methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane, bis[3-(3,5-dimethyl -4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis [3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4- Hydroxy-5-ethylphenyl]methane, bis[2-hydroxy-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane, bis[2-hydroxy-3-(2 -Hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[2,5-dimethyl Linear type 4 nucleus phenol compounds such as -3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane;

2,4-bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxy Hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxybenzyl]-4 -Linear 5 nucleus phenol compounds, such as methylphenol;

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

1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl )Isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene and other polynuclear branched compounds;

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

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

The content of the quinonediazide group-containing compound is preferably 10 to 95% by mass, more preferably 15 to 90% by mass, with respect to the solid content of the positive radiation sensitive composition 1. By setting it as the said range, the sensitivity of positive radiation sensitive composition 1 can be made favorable.

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

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

In the positive radiation-sensitive composition 1, the amount of the solvent is preferably an amount such that the solid content concentration of the positive radiation-sensitive composition 1 is 1 to 50% by mass, and more preferably 5 to 30% by mass. . Moreover, in the solvent contained in the positive radiation sensitive composition 1, the mass ratio of the compound represented by the general formula (1) and other organic solvents is preferably 5:95 to 100:0, and 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) and other organic solvents in the above range, the positive radiation sensitive composition 1 is excellent in sensitivity, storage stability, coatability, developability, and safety. It is easy to become, and the pattern formed by exposing and developing the positive radiation sensitive composition 1 is likely to be suppressed from the occurrence 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 the other polymers include the polyamic acid described in the negative radiation-sensitive composition 2, the polybenzoxazole precursor described in the negative radiation-sensitive composition 3, or the polymer represented by the following general formula (31). Can be mentioned.

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 cyclic structure by heating or a suitable catalyst. Preferably, it is a polyamic acid or polyamic acid ester of a polyimide precursor, and a polyhydroxyamide of a polybenzoxazole precursor. Here, the main component means that the structural unit represented by the general formula (31) has 50 mol% or more of the total structural units of the polymer. It is preferable to contain 70 mol% or more, and it is more preferable to contain 90 mol% or more.

[Formula 60]

In General Formula (31), R ¹ and R ² may be the same or different, respectively, 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, respectively, and represent hydrogen or a monovalent organic group having 1 to 20 carbon atoms. l and m represent the integer of 0-2, p and q represent the integer of 0-4. However, it is p + q> 0.

In 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, naphthalenedicarboxylic acid, and bis(carboxyphenyl)propane, cyclohexanedicarboxylic acid, And aliphatic dicarboxylic acids such as adipic acid. Tricarboxylic acids, such as trimellitic acid and trimesic acid, are mentioned as an acid in which R<^1> is trivalent. Examples of the acid in which R ¹ is tetravalent include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenylsulfonetetracarboxylic acid. , Aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, and diester compounds in which two hydrogen atoms of these carboxyl groups are methyl groups or ethyl groups. Moreover, the acid which has hydroxyl groups, such as hydroxyphthalic acid and hydroxy trimellitic acid, is also mentioned. You may use 2 or more types of these acid components, but it is preferable to contain 1 to 40 mol% of the residue of tetracarboxylic acid. Moreover, it is preferable to contain 50 mol% or more of the residue of the acid which has a hydroxyl group from a point of solubility or photosensitive property to an alkali developing solution.

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

In General Formula (31), R ² represents a divalent to octavalent organic group having 2 or more carbon atoms, and represents the structural component of diamine. R ² preferably has an aromatic ring from the viewpoint of heat resistance. Specific examples of diamines 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 in which at least a part of hydrogen in these aromatic rings is substituted with an alkyl group or a halogen atom, and aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and hexamethylenediamine Can. Two or more of these diamine components may be used, but from the viewpoint of solubility in an alkali developer, it is preferable to contain 60 mol% or more of the residue of the diamine having a hydroxyl group.

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

Moreover, l and m of general formula (31) represent the number of a carboxyl group or an ester group, and respectively independently represent the integer of 0-2. It is preferably 1 or 2. P and q of general formula (31) each independently represent the integer of 0-4, and p+q>0.

The number of 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, , It is more preferably in the range of 20 to 100.

The number of structural units represented by the general formula (31) can be easily calculated by measuring the mass average molecular weight by gel permeation chromatography (GPC), light scattering, X-ray incineration scattering, 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 structural units represented by the general formula (31) = Mm/M. The number of structural units represented by the general formula (31) refers to a value calculated using the GPC measurement by the simplest polystyrene conversion.

Moreover, in order to improve adhesiveness with a board|substrate, for example, you may copolymerize the aliphatic group which has a siloxane structure in the range which does not lower heat resistance. Specifically, examples of the diamine component include a copolymer of 1 to 10 mol% of bis(3-aminopropyl)tetramethyldisiloxane, bis(p-amino-phenyl)octamethylpentasiloxane, and the like.

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

[Other ingredients]

The positive radiation sensitive composition 1 may contain various additives as needed. Examples of the additives include sensitizers, curing accelerators, fillers, adhesion promoters, antioxidants, agglomeration inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants, and the like.

<Method for preparing radiation-sensitive composition>

The radiation-sensitive composition according to the present invention is prepared by mixing each component with a stirrer. Moreover, you may filter using a membrane filter etc. 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 a step of forming a radiation-sensitive composition film comprising a radiation-sensitive composition film comprising the radiation-sensitive composition according to the present invention on a substrate, and selectively exposing the radiation-sensitive composition film It includes an exposure process to be performed, and a developing process for developing the exposed radiation-sensitive composition film.

First, in the radiation-sensitive composition film forming step, for example, on a substrate, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or curtain flow coater may be used. Using, 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 radiation-sensitive composition film forming step, the radiation-sensitive composition film is formed on the substrate by attaching a radiation-sensitive composition film (dry film) made of the radiation-sensitive composition formed on the support film to the substrate. It can also form. A dry film can be formed by apply|coating the said radiation sensitive composition on a support film by a conventional method, and drying it.

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

Subsequently, in the developing step, a predetermined pattern is formed by developing the radiation-sensitive composition film after exposure with a developer. 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

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

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

[Formula 61]

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

· Photopolymerizable monomer

Photopolymerizable monomer 1: dipentaerythritol hexaacrylate (DPHA)

· Photopolymerization initiator

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

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

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

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

Coloring agent 1: Carbon dispersion liquid "CF Black" (trade name, Mikuni pigment company, solid content 25%, solvent: 3-methoxybutyl acetate)

Coloring agent 2: Black pigment Experimental Black 582 (trade name, manufactured by BASF) using a dispersing agent and dispersing with a bead mill by a conventional method to prepare a pigment dispersion liquid having an average particle diameter of 90 to 190 nm (solid content 15% by mass, Solvent: Propylene glycol monomethyl ether acetate)

Coloring agent 3: R254 (CI pigment red 254)/Y139 (CI pigment yellow) (mixed mass ratio: 85/15), dispersant and acrylic resin 2 (solid content ratio to pigment: 10 mass%) are used in combination, Dispersed with a bead mill by, to prepare a pigment dispersion liquid having an average particle diameter of 90 to 190 nm (solid content 18 mass%, solvent: propylene glycol monomethyl ether acetate)

Colorant 4: Pigment prepared from G36 (CI Pigment Green 36)/Y150 (CI Pigment Yellow 150) (mixed mass ratio: 70/30) in the same manner as Colorant 3, so that the average particle diameter of the pigment is 90 to 190 nm Dispersion (18% by mass of solid content, solvent: propylene glycol monomethyl ether acetate)

Colorant 5: Pigment prepared from B156 (CI Pigment Blue 156)/V23 (CI Pigment Violet 23) (mixed mass ratio: 90/10) in the same manner as Colorant 3, so that the average particle diameter of the pigment is 90 to 190 nm Dispersion (15% by mass solid content, solvent: propylene glycol monomethyl ether acetate)

· Surfactants

Surfactant 1: ``Granol 440'' (trade name, Kyoeisha Chemical Co., Ltd.)

Compounds 1-4: compounds represented by the following formulas (E1) to (E4), respectively

[Formula 62]

· Other organic solvents

MBA: 3-methoxybutyl acetate

PGMEA: Propylene glycol monomethyl ether acetate

EEP: 3-ethoxypropionate ethyl

EL: ethyl lactate

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

The cardo resin 1 was synthesized according to the following prescription.

First, in a 500 mL four-neck flask, 235 g of bisphenolfluorene-type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 of acrylic acid g was injected, and it was heated and dissolved at 90 to 100°C while blowing air at a rate of 25 ml/min. Next, the solution was gradually heated as it was cloudy, and heated to 120°C to completely dissolve. At this time, the solution gradually became a transparent consistency, but stirring was continued as it was. In the meantime, the acid value was measured and heating and stirring continued until it became less than 1.0 mgKOH/g. It took 12 hours until the acid value reached the target value. Then, the mixture was cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following structural formula (a-4), which is a colorless, transparent and solid phase.

[Formula 63]

Subsequently, after adding and dissolving 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained, 80.5 g of benzophenone tetracarboxylic acid anhydride and 1 g of tetraethylammonium bromide are mixed. Then, the temperature was gradually increased and reacted at 110 to 115°C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydro phthalic anhydride were mixed and reacted at 90°C for 6 hours to obtain cardo 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 general formula (a-1) described above.

<Production of transparent resists>

Alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, and surfactant are mixed with a solvent having the composition shown in Table 2 according to the composition and compounding amount (unit: parts by mass) shown in Table 1, and the solid content concentration is 20 mass%. A negative radiation-sensitive composition was prepared.

[bow]

A negative-type radiation-sensitive composition was spin-coated on a glass substrate having a thickness of 680 mm × 880 mm × 0.7 mm, and the coating film was dried at 100°C for 120 seconds to form a photosensitive resin layer having a thickness of 1.2 µm. Next, the photosensitive resin layer was exposed with an exposure amount of 100 mJ/cm 2. Subsequently, an aqueous solution containing 0.04% by mass of KOH and 0.1% by mass of surfactant Emulgen A60 (manufactured by Kao) was used as a developer, and shower development was performed at 23°C for 60 seconds, and the foreign matter in the obtained pattern was subjected to an automatic optical inspection device ( (Made by Takano). Table 2 shows the results.

[Sensitivity]

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

○: less than 100 mJ/cm 2, △: 100 to 140 mJ/cm 2, ×: more than 140 mJ/cm 2

[Precipitation]

After the aging treatment of the negative radiation sensitive composition at -5°C for 2 weeks, spin coating was applied to a glass substrate having a width of 10 cm and the number of precipitated foreign substances was counted and evaluated according to the following criteria. Table 2 shows the results.

○: 0 to 2, △: 3 to 10, ×: 11 or more

[Viscosity change]

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

○: Change amount less than 0.5 mPa·s, △: Change amount 0.5 to 2 mPa·s, ×: Change amount exceeds 2 mPa·s

[Coating unevenness]

Whether or not coating unevenness such as pin unevenness or radiation unevenness occurred when spin-coating a negative radiation-sensitive composition on a glass substrate having a thickness of 680 mm × 880 mm × 0.7 mm and drying the coating film at 100° C. for 120 seconds. It was confirmed visually and evaluated based on the following criteria. Table 2 shows the results.

(Circle): Coating unevenness did not arise, (triangle|delta): Coating unevenness occurred locally, x: Coating unevenness occurred in the whole surface.

As can be seen from Table 2, the negative radiation-sensitive composition of the example containing the compound represented by the general formula (1) is excellent in sensitivity, storage stability, and coatability, and by exposure and development, foreign matter It was possible to form a pattern in which the occurrence of is suppressed.

On the other hand, the negative radiation sensitive composition of the comparative example that does not contain the compound represented by the general formula (1) has inferior sensitivity and storage stability, and, according to the solvent used, further inferior in applicability, and / Or more foreign matter has occurred in the pattern formed by exposure and development.

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

Alkali-soluble resins, photopolymerizable monomers, photopolymerization initiators, colorants, and surfactants are mixed with solvents having the compositions shown in Tables 4 to 8 according to the composition and compounding amount (unit: parts by mass) shown in Table 3 (colorants) The compounding quantity of the solid content conversion), and the negative radiation sensitive composition of solid content concentration 18 mass% was prepared.

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

[Agglomeration]

After aging the negative radiation sensitive composition at 40°C for 2 weeks, spin coating was applied to a 10 cm wide glass substrate, and the number of aggregated foreign matter was counted and evaluated according to the following criteria. The results are shown in Tables 4-8.

○: 0 to 2, △: 3 to 10, ×: 11 or more

In addition, in the uppermost part 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 represents Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-4, and B represents Examples 5-1 to 5-7 and Comparative Examples 5 -1 to 5-4, and BPS shows 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 radiation-sensitive composition of the example containing the compound represented by the general formula (1) is excellent in sensitivity, storage stability, and coatability, and is exposed and developed. , It was possible to form a pattern in which the occurrence of foreign matter was suppressed.

On the other hand, in the negative radiation sensitive composition of the comparative example that does not contain the compound represented by the general formula (1), storage stability is inferior, and more foreign matter is generated among patterns formed by exposure and development, and used. Depending on the solvent, the coatability was further inferior. Moreover, the sensitivity of the negative radiation sensitive composition of the comparative example containing a light-shielding agent as a coloring agent was inferior.

<Preparation of positive radiation sensitive composition>

2 g of the esterification reaction product of 1 mol of 2,4,4,4'-tetrahydroxybenzophenone and 3 mol of naphthoquinone-1,2-diazide-5-sulfonylchloride and 8 g of cresol novolak resin , Dissolved in 40 g of the solvent of the composition shown in Table 1 to prepare a positive radiation sensitive composition. The following evaluation test was performed about the positive radiation sensitive composition obtained in this way.

[Presence or absence of precipitate]

The prepared positive-type radiation-sensitive composition was filtered through a 0.2 μm membrane filter at 40° C., and the presence or absence of precipitates in the positive-type radiation-sensitive composition at a time point of 2 months was examined. Table 9 shows the results.

[Sensitivity change]

The presence or absence of a change in sensitivity of the positive radiation-sensitive composition after 3 months was investigated. That is, the minimum exposure amount (sensitivity) of the case where the positive radiation-sensitive composition immediately after preparation is applied to the substrate and dried is compared with the case where the positive radiation-sensitive composition 3 months elapsed after preparation is applied to the substrate and dried. , When there was no change at all, "○", and when the sensitivity was lowered, "X". Table 9 shows the results.

[Sectional shape]

The prepared positive radiation-sensitive composition was slit-coated on a glass substrate, and dried with a hot plate at 90° C. for 90 seconds to form a resist film having a film thickness of 1.3 μm, and a stepper was used to expose the film through a predetermined mask. Then, it was heated on a hot plate at 110° C. for 90 seconds, then developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), and the cross-sectional shape of the resist pattern obtained by washing and drying for 30 seconds was observed, and the following criteria It was evaluated as. Table 9 shows the results. In addition, undercut means that the width of the lowermost portion of the resist pattern in contact with the glass substrate is narrower than the width of the uppermost portion of the resist pattern in the cross section of the resist pattern.

(Circle): Undercut is not formed in the contact part of a glass substrate and a resist pattern.

X: An undercut is formed in the contact portion between the glass substrate and the resist pattern.

[Application status]

When the prepared positive-type radiation-sensitive composition is slit-coated on a glass substrate, the film thickness of the product dried at 90° C. for 90 seconds with a hot plate is measured, and the case where the coating is uniformly applied in-plane is “good”, uniformly in-plane What was not applied was set as "poor". Table 9 shows the results.

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

On the other hand, the positive-type radiation-sensitive composition of the comparative example not containing the compound represented by the general formula (1) was inferior in storage stability, developability, and coatability.

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

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

The obtained negative-type radiation-sensitive resin composition was evaluated in the same manner as in "Production of a transparent resist" to evaluate foreign matter, viscosity change, and coating unevenness. Table 10 shows the results.

As can be seen from Table 10, the negative-type radiation-sensitive resin composition of the example containing the compound represented by the general formula (1) is excellent in storage stability and coatability, and by exposure and development, foreign matter is generated. This suppressed pattern could be formed.

On the other hand, the negative radiation sensitive resin composition of the comparative example that does not contain the compound represented by the general formula (1) is inferior in storage stability and coatability, and more foreign matter is generated in the pattern formed by exposure and development. Did.

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

To an Erlenmeyer flask containing a rotor, 2 mmol of 2,2'-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, which is an aromatic diaminediol, and 1 ml of a solvent having the composition shown in Table 11 were added. Then, the contents of the flask were stirred for 5 minutes using a magnetic stirrer. Thereafter, 2 mmol of the dicarbonyl compound, isophthalaldehyde, was placed in the flask, and the contents of the flask were refluxed for 3 hours under a nitrogen atmosphere to react. Subsequently, the reaction solution was dehydrated by distillation under reduced pressure to obtain a polybenzoxazole precursor solution.

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

The obtained negative-type radiation-sensitive resin composition was evaluated in the same manner as in "Production of a transparent resist" to evaluate foreign matter, viscosity change, and coating unevenness. Table 11 shows the results.

As can be seen from Table 11, the negative radiation-sensitive resin composition of the example containing the compound represented by the general formula (1) is excellent in storage stability and coatability, and by exposure and development, foreign matter is generated. This suppressed pattern could be formed.

On the other hand, the negative radiation sensitive resin composition of the comparative example that does not contain the compound represented by the general formula (1) is inferior in storage stability and coatability, and more foreign matter is generated in the pattern formed by exposure and development. Did.

<Preparation 1 of positive-type radiation-sensitive resin composition containing polyamic acid>

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

Under nitrogen stream, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF) 18.3 g (0.05 mol) and allyl glycidyl ether 34.2 g (0.3 mol) were added to 100 g of GBL. Dissolve and cool to -10 °C. 22.1 g (0.11 mol) of trimellitic anhydride dissolved in 50 g of GBL was added dropwise thereto. At this time, the dropping speed was adjusted so that the temperature of the reaction solution did not exceed 0°C. After completion of dropping, the mixture was stirred at 0°C for 5 hours. The solution was concentrated with a rotary evaporator and charged into 1 L of toluene to obtain a hydroxyl group-containing acid anhydride (a) represented by the following formula.

[Formula 64]

[Synthesis of Polymer A]

Under nitrogen stream, 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. To this, 21.4 g (0.030 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added, reacted at 20°C for 1 hour, and then reacted at 40°C for 2 hours. Then, 0.65 g (0.006 mol) of 4-aminophenol was added, and further reacted at 40°C for 45 minutes. Then, a solution of 7.14 g (0.06 mol) of N,N-dimethylformamide dimethylacetal diluted with 5 g of NMP was added dropwise over 10 minutes. After dripping, it stirred at 40 degreeC for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and precipitation of the polymer solid was collected by filtration. The polymer solid was dried in a vacuum dryer at 45°C for 80 hours to obtain polymer A as a polyimide precursor. The mass average molecular weight of polymer A was measured by GPC, and it was confirmed that the number of structural units represented by the general formula (31) was within the range of 10 to 500.

[Synthesis of Novolac Resin A]

Under nitrogen stream, m-cresol 70.2 g (0.65 mol), p-cresol 37.8 g (0.35 mol), 37% by weight aqueous formaldehyde solution 75.5 g (formaldehyde 0.93 mol), oxalic acid dihydrate 0.63 g (0.005 mol), methyl After injection of 264 g of isobutyl ketone, the mixture was immersed in an oil bath, and a polycondensation reaction was performed for 4 hours while refluxing the reaction solution. Thereafter, the temperature of the oil bath was raised over 3 hours, after which the pressure in the flask was reduced, volatiles were removed, and the dissolved resin was cooled to room temperature to obtain a polymer solid of novolac resin A. According to GPC, the mass average molecular weight of the novolac resin A was 4,000.

[Preparation of composition]

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

About the obtained positive radiation sensitive resin composition, it carried out similarly to "the manufacture of a transparent resist," and evaluated the foreign material, a viscosity change, and coating unevenness. Table 12 shows the results.

[Formula 65]

[In the above formula, D is H or 1,2-naphthoquinonediazide-5-sulfonyl group, and the average esterification rate of D by 1,2-naphthoquinonediazide-5-sulfonyl group is 59.9%. . In addition, since there is a variation in the number of substitutions and substitution positions of D depending on the molecule, as described above, D represents an average ratio (average esterification ratio (%)) of 1,2-naphthoquinonediazide-5-sulfonyl groups. . Hereinafter, it is the same.]

As can be seen from Table 12, the positive-type radiation-sensitive resin composition of the example containing the compound represented by the general formula (1) is excellent in storage stability and coatability, and by exposure and development, foreign matter is generated. This suppressed pattern could be formed.

On the other hand, the positive-type radiation-sensitive resin composition of the comparative example that does not contain the compound represented by the general formula (1) is inferior in storage stability and coatability, and more foreign matter is generated among patterns formed by exposure and development. Did.

<Preparation 2 of positive-type radiation-sensitive resin composition containing polyamic acid>

6 g of solid of polymer A, 4 g of novolac resin A, 2 g of quinonediazide compound B represented by the following formula, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 6.0 g, BIR-PC (trade name, Asahi 1 g of Organic Materials Industry Co., Ltd. and 0.3 g of vinyl trimethoxysilane were weighed and dissolved in a solvent having a composition shown in Table 13 to obtain a positive radiation sensitive resin composition having a solid content concentration of 30 mass%. . In addition, the polymer A and the novolac resin A were obtained in "Preparation 1 of a polyamic acid-containing positive radiation sensitive resin composition."

About the obtained positive radiation sensitive resin composition, it carried out similarly to "the manufacture of a transparent resist," and evaluated the foreign material, a viscosity change, and coating unevenness. Table 13 shows the results.

[Formula 66]

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

As can be seen from Table 13, the positive-type radiation-sensitive resin composition of the example containing the compound represented by the general formula (1) is excellent in storage stability and coatability, and by exposure and development, foreign matter is generated. This suppressed pattern could be formed.

On the other hand, the positive-type radiation-sensitive resin composition of the comparative example that does not contain the compound represented by the general formula (1) is inferior in storage stability and coatability, and more foreign matter is generated among patterns formed by exposure and development. Did.

Claims (8)

It contains the compound represented by the following general formula (1), provided that the combination of propylene glycol monomethyl ether acetate and N,N-dimethylacetamide, the combination of propylene glycol monomethyl ether acetate and N,N-diethylacetamide, And a combination of propylene glycol monomethyl ether acetate and N,N-dimethylpropionamide.
[Formula 1]

(In the formula, R ¹ represents a hydrogen atom or a hydroxyl group, R ² and R ³ independently represent a hydrogen atom or a C ₁ to C ₃ alkyl group, and R ⁴ and R ⁵ independently represent C ₁ -Represents a C ₃ alkyl group.) According to claim 1,
The radiation-sensitive composition in which the compound represented by the general formula (1) is at least one of the compounds represented by the formulas (E1) to (E4).
[Formula 2]

According to claim 1,
Radiation-sensitive composition containing the compound represented by the general formula (1) as at least one kind of solvent. As a radiation-sensitive composition containing a compound represented by the following general formula (1),

(In the formula, R ¹ represents a hydrogen atom or a hydroxyl group, R ² and R ³ independently represent a hydrogen atom or a C ₁ to C ₃ alkyl group, and R ⁴ and R ⁵ independently represent C ₁ -Represents a C ₃ alkyl group.)
The said radiation sensitive composition contains the compound represented by said general formula (1) as at least 1 type of solvent,
The compound represented by the general formula (1) is at least one of the compounds represented by the following formulas,
The radiation-sensitive composition further contains or does not contain organic solvents other than the compound represented by the general formula (1),
The mass ratio of the compound represented by the general formula (1) and the organic solvent is 5:95 to 100:0,
The said radiation sensitive composition does not contain a coloring agent, The radiation sensitive composition.

The method of claim 4,
The radiation-sensitive composition in which the compound represented by the general formula (1) is at least one of the compounds represented by the following formulas (E1) and (E3).

As a radiation-sensitive composition containing a compound represented by the following general formula (1) and a colorant,

(In the formula, R ¹ represents a hydrogen atom or a hydroxyl group, R ² and R ³ independently represent a hydrogen atom or a C ₁ to C ₃ alkyl group, and R ⁴ and R ⁵ independently represent C ₁ -Represents a C ₃ alkyl group.)
The compound represented by the general formula (1) is at least one of the compounds represented by the following formulas, and the radiation-sensitive composition.

The method of claim 6,
The radiation-sensitive composition in which the compound represented by the general formula (1) is at least one of the compounds represented by the following formulas (E1) and (E3).

A radiation-sensitive composition film forming step of forming a radiation-sensitive composition film comprising the radiation-sensitive composition according to any one of claims 1 to 7 on a substrate,
An exposure step of selectively exposing the radiation-sensitive composition film;
A pattern production method comprising a developing process for developing the exposed radiation-sensitive composition film.