TWI750241B - Photosensitive composition and method for forming hardened film - Google Patents

Abstract

The present invention provides a photosensitive composition capable of suppressing the generation of foreign matter in the photosensitive composition and capable of satisfactorily analyzing a fine pattern, and a method for forming a cured film using the photosensitive composition. In the present invention, an amine (E) is prepared in a photosensitive composition containing an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (S), and an oxime is used in combination The ester compound (C1) and the compound (C2) other than the oxime ester compound are used as the photopolymerization initiator (C), and the amount of chloride ions in the photosensitive composition shall be 1000 mass ppm or less.

Description

Photosensitive composition and method for forming cured film

The present invention relates to a photosensitive composition and a method for forming a cured film.

In a display device such as a liquid crystal display device, a material such as an insulating film must efficiently transmit light emitted from a light source such as a backlight device. Therefore, in order to form an insulating film, a material capable of forming a film having excellent transparency is required.

Usually such a transparent insulating film is patterned on a substrate. As a method of forming a patterned transparent insulating film, it is known to use, for example, an alkali-soluble resin having an oxetane ring, a polymerizable polyfunctional compound, and an α-aminoalkylphenone-based photopolymerization initiator. The method of the negative photosensitive composition of an agent (refer patent document 1).

In addition, in recent years, with the increase in the number of production units of liquid crystal displays, the production volume of color filters is also increasing. From the viewpoint of further improving productivity, a high-sensitivity product capable of patterning with a low exposure amount is expected. Photosensitive composition.

However, colorants are contained in various functional films included in color filters. When a colorant is contained in a photosensitive composition, when the α-aminoalkylphenone-based photopolymerization initiator described in Patent Document 1 is used, there is a problem that it is difficult to obtain a sufficiently high sensitivity.

Under such circumstances, as a high-sensitivity photosensitive composition, the present applicant proposed a photosensitive composition containing an oxime ester compound of a specific structure as a photopolymerization initiator (refer to Patent Documents 2 and 3).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-173678

[Patent Document 2] Japanese Patent Laid-Open No. 2012-189996

[Patent Document 3] Japanese Patent Laid-Open No. 2012-189997

However, in a photosensitive composition containing an oxime ester compound as a photopolymerization initiator, although the sensitivity is good, on the other hand, there is a problem that foreign matter is easily generated in the photosensitive composition, or that it is difficult to analyze a fine pattern during development. .

The present invention has been made in view of the above circumstances, and its object is to provide a photosensitive composition capable of suppressing the generation of foreign matter in the photosensitive composition and capable of satisfactorily analyzing a fine pattern, and a cured film using the photosensitive composition. forming method.

The inventors of the present invention found that by formulating an amine (E) in a photosensitive composition containing an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (S) ), and the oxime ester compound (C1) and the compound (C2) other than the oxime ester compound are used in combination as the photopolymerization initiator (C), and the amount of chloride ions in the photosensitive composition is 1000 mass ppm or less , and the above problems can be solved, thereby completing the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention is a photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a solvent (S), and an amine (E) ), and the photopolymerization initiator (C) contains an oxime ester compound (C1) and a compound (C2) other than the oxime ester compound, and the amount of chloride ions in the photosensitive composition is 1000 mass ppm or less.

A second aspect of the present invention is a method for forming a cured film, comprising: applying the photosensitive composition of the first aspect on a substrate to form a coating film; and exposing the coating film to light.

ADVANTAGE OF THE INVENTION According to this invention, the formation method of the cured film using the photosensitive composition which can suppress generation|occurence|production of the foreign material in a photosensitive composition, and can analyze a fine pattern favorably, and this photosensitive composition can be provided.

≪Photosensitive composition≫

The photosensitive composition contains an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a solvent (S), and an amine (E).

The photopolymerization initiator (C) contains an oxime ester compound (C1) and a compound (C2) other than the oxime ester compound.

Moreover, the amount of chloride ions in the photosensitive composition is 1000 mass ppm or less.

The amount of chloride ions can be measured by ion chromatography according to the following method.

(Ion chromatography measurement conditions)

Column: IonPac AS17-C (manufactured by Thermo Scientific Dionex)

Eluent: mixed solution of water and acetonitrile

Injection volume: 1 μL

The previously known photosensitive composition containing the oxime ester compound (C1) contains chloride ions mainly derived from the oxime ester compound (C1). Therefore, the content of the chloride ion in the conventional photosensitive composition is more than 1000 mass ppm in many cases.

Therefore, the inventors of the present invention conducted research and found that the photosensitive composition has a relatively high chlorine content The amount of compound ions is related to the generation of foreign matter in the photosensitive composition.

In addition, the photosensitive composition containing only the oxime ester compound (C1) as the photopolymerization initiator (C) has good sensitivity, but on the other hand, it is difficult to analyze a fine pattern during development after exposure.

The inventors of the present invention have also studied this aspect, and as a result, they found that the photopolymerization initiator (C) can be used for photosensitivity by using the oxime ester compound (C1) in combination with a compound other than the oxime ester compound (C1). The composition resolves fine patterns.

As mentioned above, the said photosensitive composition can suppress the generation|occurence|production of the foreign material in a photosensitive composition, and can analyze a fine pattern favorably.

Hereinafter, essential or optional components contained in the photosensitive composition will be described.

<Alkali-soluble resin (A)>

The alkali-soluble resin means that a resin film having a thickness of 1 μm is formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass and immersed in a KOH aqueous solution having a concentration of 0.05% by mass for 1 Within minutes, the film thickness of 0.01μm or more dissolves the resin.

As a suitable example of an alkali-soluble resin (A), the resin (A1) which has a Cardo structure is mentioned. By using the photosensitive composition containing the resin (A1) having a Cardo structure as the alkali-soluble resin (A), it is easy to form a cured film having a good balance of heat resistance, mechanical properties, solvent resistance, chemical resistance, and the like.

It does not specifically limit as resin (A1) which has a Cardo structure, A conventionally well-known resin can be used. Among them, the resin represented by the following formula (a-1) is preferable.

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

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

In addition, in the above formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, methylenesuccinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Base methylene tetrahydrophthalic anhydride, chloro bridge anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, etc.

Moreover, in said formula (a-1), Z ^a represents the residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. As an example of a tetracarboxylic dianhydride, a pyromellitic dianhydride, a benzophenone tetracarboxylic dianhydride, a biphenyl tetracarboxylic dianhydride, a biphenyl ether tetracarboxylic dianhydride, etc. are mentioned.

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

The mass-average molecular weight (Mw: measured value obtained in terms of polystyrene by gel permeation chromatography (GPC), the same in this specification) of the resin (A1) having a Cardo structure is preferably 1000 or more and 40000 or less, more preferably 2000 or more and 30000 or less. By setting it as the said range, favorable developability can be obtained, and sufficient heat resistance and film strength can be obtained.

A copolymer (A2) obtained by polymerizing at least an unsaturated carboxylic acid (a1) can also be suitably used as the alkali-soluble resin (A) from the viewpoint of easily forming a film having excellent mechanical strength and adhesion to a substrate.

Examples of the unsaturated carboxylic acid (a1) include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; maleic acid, fumaric acid, methyl maleic acid, and methyl fumaric acid. Dicarboxylic acids such as enedioic acid and methylenesuccinic acid; acid anhydrides of these dicarboxylic acids; etc. Among these, (meth)acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the obtained resin, ease of acquisition, and the like. These unsaturated carboxylic acids (a1) can be used individually or in combination of 2 or more types.

基、異

基、三環壬基、三環癸基、四環十二烷基等。該等含有脂環式環氧基之不飽和化合物(a2)可單獨使用或組合2種以上使用。 The copolymer (A2) may be a copolymer of an unsaturated carboxylic acid (a1) and an alicyclic epoxy group-containing unsaturated compound (a2). As an alicyclic epoxy group containing unsaturated compound (a2), if it is an unsaturated compound which has an alicyclic epoxy group, it will not specifically limit. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. As a monocyclic alicyclic group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. In addition, as the polycyclic alicyclic group, there may be mentioned:

base, different

base, tricyclononyl, tricyclodecyl, tetracyclododecyl, etc. These alicyclic epoxy group-containing unsaturated compounds (a2) may be used alone or in combination of two or more.

Specifically, as an alicyclic epoxy group containing unsaturated compound (a2), the compound represented by following formula (a2-1) - (a2-15) is mentioned, for example. Among these, in order to make developability moderate, compounds represented by the following formulae (a2-1) to (a2-5) are preferred, and the following formulae (a2-1) to (a2-3 are more preferred) ) represented by the compound.

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent aliphatic saturated hydrocarbon group with 1 to 6 ^{carbon atoms, R a22} represents a divalent hydrocarbon group with 1 to 10 carbon atoms, t It represents an integer of 0 or more and 10 or less. As R ^a21 , it is preferably a linear or branched alkylene group, such as methylene, ethylidene, propylidene, tetramethylene, ethylethylidene, pentamethylene, hexamethylene methyl. As R ^a22 , for example, methylene, ethylidene, propylidene, tetramethylene, ethylethylidene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH are preferable. ₂ -Ph-CH ₂ - (Ph represents a phenylene group).

The copolymer (A2) may be a combination of an alicyclic group-containing unsaturated compound (a3) that does not have an epoxy group, the above-mentioned unsaturated carboxylic acid (a1), and the above-mentioned alicyclic epoxy group-containing unsaturated compound ( a2) Copolymers obtained by co-polymerization.

基、異

基、三環壬基、三環癸基、四環十二烷基 等。該等含有脂環式基之不飽和化合物(a3)可單獨使用或組合2種以上使用。 The alicyclic group-containing unsaturated compound (a3) is not particularly limited as long as it is an alicyclic group-containing unsaturated compound. The alicyclic group may be monocyclic or polycyclic. As a monocyclic alicyclic group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. Moreover, as a polycyclic alicyclic group, an adamantyl group, a norm

base, different

base, tricyclononyl, tricyclodecyl, tetracyclododecyl, etc. These alicyclic group-containing unsaturated compounds (a3) can be used alone or in combination of two or more.

Specifically, as an alicyclic group containing unsaturated compound (a3), the compound represented by following formula (a3-1) - (a3-7) is mentioned, for example. Among these, in order to make developability moderate, compounds represented by the following formulae (a3-3) to (a3-8) are preferred, and the following formulae (a3-3) and (a3-4) are more preferred ) represented by the compound.

In the above formula, R ^a23 represents a hydrogen atom or a methyl group, R ^a24 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a25 represents a hydrogen atom or 1 to 5 carbon atoms or less the alkyl group. As R ^a24 , preferably a single bond, linear or branched alkylene, such as methylene, ethylidene, propylidene, tetramethylene, ethylethylidene, pentamethylene , hexamethylene. As R ^a25 , for example, a methyl group and an ethyl group are preferable.

In addition, the copolymer (A2) may be an epoxy group-containing unsaturated compound (a4) that does not have an alicyclic group, the above-mentioned unsaturated carboxylic acid (a1), and the above-mentioned alicyclic epoxy group-containing unsaturated compound. A copolymer obtained by polymerizing the compound (a2) and further the above-mentioned alicyclic group-containing unsaturated compound (a3).

Examples of the epoxy group-containing unsaturated compound (a4) include glycidyl (meth)acrylate (meth)acrylic acid ring such as oil ester, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, etc. Oxyalkyl esters; α-glycidyl ethyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl ester, etc. - Epoxyalkyl acrylates; etc. Among these, in terms of copolymerization reactivity, strength of the resin after curing, etc., glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and (methyl) acrylate are preferred. ) 6,7-epoxyheptyl acrylate. These epoxy group-containing unsaturated compounds (a4) may be used alone or in combination of two or more.

Moreover, the copolymer (A2) may be a copolymer obtained by further polymerizing other compounds other than the above. Examples of such other compounds include (meth)acrylates, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds may be used alone or in combination of two or more.

Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and tertiary (meth)acrylate Linear or branched alkyl (meth)acrylates such as trioctyl; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, (meth)acrylate 2-hydroxyethyl acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate; and the like.

Examples of (meth)acrylamides include (meth)acrylamides, N-alkyl(meth)acrylamides, N-aryl(meth)acrylamides, N,N-bis(meth)acrylamides Alkyl(meth)acrylamides, N,N-aryl(meth)acrylamides, N-methyl-N-phenyl(meth)acrylamides, N-hydroxyethyl-N-methyl (meth)acrylamide, etc.

Examples of the allyl compound include allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, Acetyl Allyl esters such as allyl acetate and allyl lactate; allyloxyethanol; etc.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl vinyl ether , chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether , dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and other alkyl vinyl ethers ; Vinyl phenyl ether, vinyl cresyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl o-aminobenzyl ether, etc. Aryl ethers; etc.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, dichloroethylene Vinyl Acetate, Vinyl Methoxyacetate, Vinyl Butoxy Vinyl Acetate, Vinyl Phenyl Acetate, Vinyl Acetyl Acetate, Vinyl Lactate, Vinyl β-Phenyl Butyrate, Vinyl Benzoate, Salicylic Acid vinyl acetate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.

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

The ratio of the constituent unit derived from the above-mentioned unsaturated carboxylic acid (a1) to the copolymer (A2) is preferably It is 1 mass % or more and 50 mass % or less, More preferably, it is 5 mass % or more and 45 mass % or less.

Moreover, when the copolymer (A2) contains the structural unit derived from the above-mentioned alicyclic epoxy group-containing unsaturated compound (a2) and the structural unit derived from the above-mentioned epoxy group-containing unsaturated compound (a4) , the proportion of the constituent units derived from the alicyclic epoxy group-containing unsaturated compound (a2) in the copolymer (A2) and the constituent units derived from the above-mentioned epoxy group-containing unsaturated compound (a4) are in The total of the proportions occupied in the copolymer (A2) is preferably 20% by mass or more, more preferably 40% by mass or more and 95% by mass or less, and still more preferably 50% by mass or more and 80% by mass or less. In particular, the ratio of the constituent unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) in the copolymer (A2) alone is preferably 10% by mass or more, more preferably 20% by mass or more and 80% by mass or less. By making the ratio of the structural unit derived from the said alicyclic epoxy group containing unsaturated compound (a2) into the said range, the time-dependent stability of a photosensitive composition can be improved further.

Moreover, when the copolymer (A2) contains a structural unit derived from the alicyclic group-containing unsaturated compound (a3), the above-mentioned structural unit derived from the alicyclic group-containing unsaturated compound (a3) is copolymerized The ratio of the substance (A2) is preferably 1 mass % or more and 30 mass % or less, more preferably 5 mass % or more and 20 mass % or less.

The mass average molecular weight of the copolymer (A2) is preferably 2,000 or more and 200,000 or less, more preferably 3,000 or more and 30,000 or less. By setting it as the said range, there exists a tendency for the balance of the film forming ability of the photosensitive composition and the developability after exposure to be easily acquired.

Moreover, as the alkali-soluble resin (A), one containing at least a structural unit derived from the above-mentioned unsaturated carboxylic acid (a1) and a site having a polymerizable site with the photopolymerizable compound (B) described below can also be suitably used. Resin of the copolymer (A3) constituting the unit, or containing at least a constituting unit derived from the above-mentioned unsaturated carboxylic acid (a1), derived from the above-mentioned unsaturated compound (a2) containing an alicyclic epoxy group, and/or containing Structural unit of unsaturated compound (a4) of epoxy group and having photopolymerizable with the below-mentioned Resin of the copolymer (A4) of the constituent unit of the site where the compound (B) is polymerized. When the alkali-soluble resin (A) contains the copolymer (A3) or the copolymer (A4), the adhesion of the film formed using the photosensitive composition to the substrate, or the film obtained by using the photosensitive composition can be improved. Mechanical strength of hardened film.

The copolymer (A3) and the copolymer (A4) may be (meth)acrylates, (meth)acrylamides, and allyl compounds described as other compounds about the copolymer (A2). , vinyl ethers, vinyl esters, styrenes, etc. and then copolymerized copolymers.

It is preferable that the structural unit which has a site|part which can be polymerized with a photopolymerizable compound (B) has an ethylenically unsaturated group as a site|part which can be polymerized with a photopolymerizable compound (B). Copolymerization having such a structural unit can be obtained by combining at least a part of the carboxyl groups contained in the polymer containing the structural unit derived from the above-mentioned unsaturated carboxylic acid (a1) with the above-mentioned alicyclic-containing The unsaturated compound (a2) of an epoxy group and/or the unsaturated compound (a4) containing an epoxy group are reacted and prepared. In addition, the copolymer (A4) can be obtained by combining a structural unit derived from the above-mentioned unsaturated carboxylic acid (a1) with an alicyclic epoxy group-derived unsaturated compound (a2) and/or an epoxy group-containing compound At least a part of the epoxy group in the copolymer of the structural unit of an unsaturated compound (a4) reacts with unsaturated carboxylic acid (a1), and prepares.

The ratio of the constituent unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A3) is preferably 1 mass % or more and 50 mass % or less, more preferably 5 mass % or more and 45 mass % or less. The ratio of the constituent unit having a polymerizable site with the photopolymerizable compound (B) in the copolymer (A3) is preferably 1 mass % or more and 45 mass % or less, more preferably 5 mass % or more and 40 mass % %the following. When the copolymer (A3) contains each structural unit in such a ratio, it becomes easy to obtain the photosensitive composition which can form the film which is excellent in the adhesiveness with a board|substrate.

The ratio of the constituent unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A4) is preferably 1 mass % or more and 50 mass % or less, more preferably 5 mass % or more and 45 mass % or less. Copolymer The ratio of the constituent units derived from the alicyclic epoxy group-containing unsaturated compound (a2) and/or the epoxy group-containing unsaturated compound (a4) in (A4) is preferably 20% by mass or more, More preferably, it is 50 mass % or more and 95 mass % or less, and still more preferably 60 mass % or more and 80 mass % or less.

The ratio of the constituent unit having a polymerizable site with the photopolymerizable compound (B) in the copolymer (A4) is preferably 1 mass % or more and 45 mass % or less, more preferably 5 mass % or more and 40 mass % %the following. When the copolymer (A4) contains each structural unit in such a ratio, it becomes easy to obtain the photosensitive composition which can form the film which is excellent in the adhesiveness with a board|substrate.

The mass average molecular weight of the copolymer (A3) and the copolymer (A4) is preferably 2,000 or more and 50,000 or less, and more preferably 5,000 or more and 30,000 or less. By setting it as the said range, there exists a tendency for the balance of the film forming ability of the photosensitive composition and the developability after exposure to be easily acquired.

The content of the alkali-soluble resin (A) is preferably 40% by mass or more and 85% by mass or less, more preferably 45% by mass or more with respect to the mass of the photosensitive composition excluding the mass of the solvent (S) described below. and 75% by mass or less. Moreover, the alkali-soluble resin (A) when the total amount of the content of the alkali-soluble resin (A), the content of the photopolymerizable compound (B), and the content of the photopolymerization initiator (C) is 100 parts by mass It is preferable to mix|blend as a photosensitive composition so that content of the photopolymerizable compound (B) in a photosensitive composition may become 5 mass parts or more and 50 mass parts or less.

As described above, the amount of chloride ions in the photosensitive composition is 1000 mass ppm or less. Therefore, the amount of chloride ions in the alkali-soluble resin (A) must also be reduced to some extent.

As a method of reducing the amount of chloride ions in the alkali-soluble resin (A), washing with water, an organic solvent, an aqueous solution of an organic solvent, etc., or preparing a solution of the alkali-soluble resin (A) and then using the solution obtained The method of contacting with anion exchange resin, etc.

<Photopolymerizable compound (B)>

As the photopolymerizable compound (B), a monolithic ethylenically unsaturated group can be preferably used body. The monomers with ethylenically unsaturated groups include monofunctional monomers and polyfunctional monomers.

As a monofunctional monomer, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, methylenesuccinic acid, methylenesuccinic anhydride, methylcis Butenedioic acid, methyl maleic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ( Ethyl meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate ) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy phthalate -2-hydroxypropyl, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, (methyl) ) 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, half (meth)acrylate of phthalic acid derivatives, etc. These monofunctional monomers may 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, (Meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate base) acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-Hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(methyl) Acrylates, diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (ie, Toluene diisocyanate, trimethylhexamethylene diisocyanate, or the reaction product of hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate), methylenebis(meth)acrylamide, Polyfunctional monomers such as (meth)acrylamide methylene ether, polyol and N-methylol (meth)acrylamide condensate, triacrylate formal, and the like. These polyfunctional monomers may be used alone or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, the amount of trifunctional or more is preferred in terms of the tendency to improve the adhesion of the photosensitive composition to the substrate and the strength of the photosensitive composition after curing. The functional monomer is more preferably a tetrafunctional or more multifunctional monomer, and more preferably a 5 functional or more multifunctional monomer.

The content of the photopolymerizable compound (B) in the composition is preferably 1 mass % or more and 50 mass % or less, more preferably with respect to the mass of the photosensitive composition excluding the mass of the solvent (S) described below. It is 5 mass % or more and 40 mass % or less. By setting it as the said range, there exists a tendency for the balance of sensitivity, developability, and analysis property to be easily acquired.

As described above, the amount of chloride ions in the photosensitive composition is 1000 mass ppm or less. Therefore, the amount of chloride ions in the photopolymerizable compound (B) must also be reduced to some extent.

As a method for reducing the amount of chloride ions in the photopolymerizable compound (B), preparation of an alkali by washing with water, an organic solvent, an aqueous solution of an organic solvent, or the like, or by distillation and recrystallization, can be exemplified. A method of contacting the obtained solution with an anion exchange resin after the solution of the soluble resin (A).

<Photopolymerization initiator (C)>

The photosensitive composition contains a photopolymerization initiator (C). The photopolymerization initiator (C) combination contains the oxime ester compound (C1) and the compound (C2) other than the oxime ester compound. Hereinafter, the oxime ester compound (C1) and the compound (C2) will be described.

(Oxime ester compound (C1))

The photosensitive composition must contain the oxime ester compound (C1) as a photopolymerization initiator. The oxime ester compound (C1) is not particularly limited as long as it acts as a photopolymerization initiator and contains an esterified oxime group and acts as a photopolymerization initiator.

Typically, as the oxime ester compound (C1), a compound represented by the following formula (1) can be suitably used. Include

(In formula (1), R ¹ , R ² , and R ³ are each independently a valent organic group having a bond to a carbon atom. n0 is 0 or 1)

the indicated compound. Therefore, the sensitivity of the photosensitive composition is excellent.

However, when only the oxime ester compound (C1) is used as the photopolymerization initiator (C), it is difficult to analyze a fine pattern. On the other hand, when the oxime ester compound (C1) and the compound (C2) other than the oxime ester compound are used together as the photopolymerization initiator (C), it has good sensitivity, and it becomes easy to modify a fine pattern by development.

The photopolymerization initiator (C) may contain two or more oxime ester compounds (C1) in combination.

-1-基等。 In the formula (1) ^{, examples of the organic group suitable for R 1} include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic aryl group, an alkoxycarbonyl group, and a saturated aliphatic group. Ethyloxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted benzyl, optionally substituted phenoxycarbonyl, optionally substituted benzyloxy group, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthylcarboxyl, optionally substituted naphthoxycarbonyl, optionally substituted Naphthyloxy with substituent, naphthylalkyl with optional substituent, heterocyclic group with optional substituent, heterocyclic carbonyl with optional substituent, amine substituted with 1 or 2 organic groups base, morpholin-1-yl, and piper

-1-Base, etc.

In addition, as R ¹ , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferred. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in ^{R 1 may have.}

When R ¹ is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Moreover, when R<^1> is an alkyl group, a straight chain may be sufficient as it, and a branched chain may be sufficient as it. Specific examples when R ¹ is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl base, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-octyl Decyl, and isodecyl, etc. Moreover, when R<^1> is an alkyl group, an ether bond (-O-) may be contained in an alkyl group in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc.

When R ¹ is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Moreover, when R<^1> is an alkoxy group, a straight chain may be sufficient as it, and a branched chain may be sufficient. Specific examples when R ¹ is an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a second butoxy group. , third butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy and the like. Moreover, when R<^1> is an alkoxy group, an ether bond (-O-) may be contained in an alkoxy group in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy group, propoxyethoxyethoxy, and methoxypropoxy, etc.

When R ¹ is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. As a ^{specific example when R<1>} is a cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. are mentioned. Specific examples when R ¹ 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 ¹ is a saturated aliphatic alkoxy group or a saturated aliphatic alkoxy group, the carbon number of the saturated aliphatic alkanoyl group or saturated aliphatic alkoxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. Specific examples when R ¹ is a saturated aliphatic group include acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethyl group. Propyl radical, n-hexyl radical, n-heptyl radical, n-octyl radical, n-nonyl radical, n-decyl radical, n-decyl radical, n-dodecyl radical, n-tdecyl radical, n-tetradecyl radical Carbonyl, n-pentadecyl, and n-hexadecyl, etc. Specific examples in the case where R ¹ is a saturated aliphatic alkoxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, and n-pentanoyloxy , 2,2-dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecanyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecyloxy, n-hexadecanoyloxy, and the like.

When R ¹ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when R ¹ is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy Carbonyl, second-butoxycarbonyl, third-butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second-pentoxycarbonyl, third-pentoxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy ylcarbonyl, n-octoxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyl Oxycarbonyl, etc.

When R ¹ is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. Moreover, when R<^1> is a naphthyl alkyl group, it is preferable that it is 11 or more and 20 or less, and, as for the carbon number of a naphthyl alkyl group, it is more preferable that it is 11 or more and 14 or less. Specific examples when R ¹ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when R ¹ is naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthalene base) ethyl. When R ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on a phenyl group or a naphthyl group.

唑、異

唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡

、嘧啶、嗒

、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚

、苯并咪唑、苯并三唑、苯并唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞

、

啉、喹

啉、哌啶、哌

、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。於R¹為雜環基之情形時，雜環基可進而具有取代基。 When R ¹ is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, O, or the monocyclic ring is condensed with each other or the monocyclic ring and a benzene ring. into the heterocyclic group. When the heterocyclic group is a condensed ring, the number of condensed rings is at most three. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole,

azole, iso

azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine

, pyrimidine, ta

, benzofuran, benzothiophene, indole, isoindole, indole

, Benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthaloline

,

linen, quinoline

Linen, piperidine, piperidine

, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. When R ¹ is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ¹ is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as when ^{R 1 is a heterocyclic group.}

When R ¹ is an amino group substituted with one or two organic groups, suitable examples of the organic group include: an alkyl group having 1 to 20 carbon atoms, an alkyl group having 3 to 10 carbon atoms Cycloalkyl, saturated aliphatic aliphatic group with 2 or more and 21 or less carbon atoms, optionally substituted phenyl group, optionally substituted benzyl group, optionally substituted with 7 or more and 20 or less carbon atoms phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyl, optionally substituted naphthylalkyl having 11 to 20 carbon atoms, and heterocyclic groups. Specific examples of these suitable organic groups are the same as ^{R 1 .} Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine N-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, benzene amino, naphthyl amino, acetyl amino, propionyl amino, n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino , n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino, etc.

-1-基、鹵素原子、硝基、及氰基等。 Examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclic group contained in R ¹ further have a substituent include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, and a saturated aliphatic amide. group, saturated aliphatic alkoxy, alkoxycarbonyl, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted benzyl, Optionally substituted phenoxycarbonyl, optionally substituted benzyloxy, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted Substituent naphthyl, optionally substituted naphthyloxycarbonyl, optionally substituted naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, optionally substituted Substituents of heterocyclylcarbonyl, amino, amino substituted with 1 or 2 organic groups, morpholin-1-yl, piper

-1-yl group, halogen atom, nitro group, cyano group and the like.

In the case where ^{the phenyl group, naphthyl group, and heterocyclic group contained in R 1} further have substituents, the number of the substituents is not limited to the extent that it does not hinder the purpose of the present invention, and is preferably 1 or more and 4 or less. When a ^{phenyl group, a naphthyl group, and a heterocyclic group contained in R 1} have a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent is an alkyl group, it is preferably 1 or more and 20 or less carbon atoms, and more preferably 1 or more and 6 or less carbon atoms. When the substituent is an alkyl group, it may be a straight chain or a branched chain. Specific examples when the substituent is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl base, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-octyl Decyl, and isodecyl, etc. Moreover, when a substituent is an alkyl group, an ether bond (-O-) may be contained in an alkyl group in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc.

When the substituent is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Moreover, when a substituent is an alkoxy group, a straight chain may be sufficient as it, and a branched chain may be sufficient. Specific examples when the substituent is an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a second butoxy group. , third butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy , n-heptyloxy, n-octyloxy, isooctyloxy, second octyloxy, third octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy, etc. . Moreover, when a substituent is an alkoxy group, an alkoxy group may contain an ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy group, propoxyethoxyethoxy, and methoxypropoxy, etc.

When the substituent is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably 3 or more and 10 or less, and more preferably the number of carbon atoms is 3 or more and 6 or less. As a specific example when a substituent is a cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. are mentioned. Specific examples when the substituent 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 substituent is a saturated aliphatic alkoxy group or a saturated aliphatic alkoxy group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably the number of carbon atoms is 2 or more and 7 or less. Specific examples in the case where the substituent is a saturated aliphatic group include acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethyl group. Propyl radical, n-hexyl radical, n-heptyl radical, n-octyl radical, n-nonyl radical, n-decyl radical, n-decyl radical, n-dodecyl radical, n-tdecyl radical, n-tetradecyl radical Carbonyl, n-pentadecyl, and n-hexadecyl, etc. Specific examples in the case where the substituent is a saturated aliphatic alkoxyl group include acetyloxyl, propionyloxy, n-butyryloxy, 2-methylpropionyloxy, n-pentyloxyl , 2,2-dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecanyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecyloxy, n-hexadecanoyloxy, and the like.

When the substituent is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably the number of carbon atoms is 2 or more and 7 or less. When the substituent is an alkoxycarbonyl group Specific examples include: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, second butoxycarbonyl, third Butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second pentyloxycarbonyl, third pentoxycarbonyl, n-hexyloxycarbonyl, n-heptoxycarbonyl, n-octoxycarbonyl, isooctyl Oxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl and the like.

When the substituent is an optionally substituted phenylalkyl group, it is preferably 7 or more and 20 or less carbon atoms, more preferably 7 or more and 10 or less carbon atoms. Moreover, when a substituent is the naphthyl alkyl group which may have a substituent, it is preferable that carbon number is 11 or more and 20 or less, and it is more preferable that carbon number is 11 or more and 14 or less. Specific examples when the substituent is an optionally substituted phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when the substituent is an optionally substituted naphthylalkyl group include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-naphthylmethyl. -(β-naphthyl)ethyl.

唑、異

唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡

、嘧啶、嗒

、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚

、苯并咪唑、苯并三唑、苯并

唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞

、

啉、及喹

啉等。 When the substituent is a heterocyclic group which may have a substituent, the above-mentioned heterocyclic group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or the monocyclic ring or the monocyclic ring. A heterocyclic group formed by the condensation of a ring with a benzene ring. When the above heterocyclic group is a condensed ring, the number of condensed rings is at most 3. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole,

azole, iso

azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine

, pyrimidine, ta

, benzofuran, benzothiophene, indole, isoindole, indole

, benzimidazole, benzotriazole, benzo

azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthaloline

,

Linen, and quinoline

Lin et al.

When the substituent is an amino group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 3 or more carbon atoms and Cycloalkyl group of 10 or less, saturated aliphatic group of carbon atoms of 2 or more and 20 or less, phenyl group which may have substituents, benzyl group which may have substituents, carbon atoms which may have substituents of 7 or more and 20 or less phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyl, optionally substituted naphthylalkyl having 11 to 20 carbon atoms, and heterocyclic groups Wait. Specific examples of these suitable organic groups are the same as those exemplified above for the substituents. Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine N-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, benzene amino, naphthyl amino, acetyl amino, propionyl amino, n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino , n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino, etc.

-1-基、及苯基所組成之群中之基所取代之苯甲醯基；具有碳原子數1以上且6以下之烷基之單烷基胺基；具有碳原子數1以上且6以下之烷基之二烷基胺基；嗎啉-1-基；哌

-1-基；鹵素原子；硝基；氰基。於上述取代基所含之苯基、萘基、及雜環基等進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於苯基、萘基、及雜環基等具有複數個取代基之情形時，複數個取代基可相同亦可不同。 Among the above-mentioned substituents, examples of the substituent in the case where a phenyl group, a naphthyl group, a heterocyclic group, etc. further have a substituent group include: an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 or more carbon atoms; Alkoxy groups of at least 6 and less than 6; saturated aliphatic aliphatic groups with 2 or more and 7 or less carbon atoms; alkoxycarbonyl groups with 2 or more and 7 or less carbon atoms; saturated aliphatic groups with 2 or more and 7 or less carbon atoms phenyloxy; phenyl; naphthyl; benzyl; naphthyl;

-1-yl group and benzyl group substituted by a group in the group consisting of phenyl group; monoalkylamine group having an alkyl group having 1 to 6 carbon atoms; having 1 to 6 carbon atoms Dialkylamino of the following alkyl groups; Morpholin-1-yl; Piper

-1-yl; halogen atom; nitro; cyano. When the phenyl group, naphthyl group, heterocyclic group, etc. contained in the above-mentioned substituent group further has a substituent group, the number of the substituent group is not limited to the extent that it does not hinder the purpose of the present invention, and is preferably 1 more than 4 and less than 4. When a phenyl group, a naphthyl group, a heterocyclic group, etc. have a plurality of substituents, the plurality of substituents may be the same or different.

Among the organic groups, R ^{1 is} preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 or more and 20 or less carbon atoms, more preferably an alkyl group having 1 or more and 8 or less carbon atoms, particularly preferably an alkyl group having 1 or more and 4 or less carbon atoms, most preferably Preferably methyl. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms in the alkylene group contained in the optionally substituted phenylsulfanylalkyl group on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, particularly preferably 2. Among the phenylsulfanylalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylsulfanyl)ethyl is preferred.

Moreover, as R ¹ , a group represented by ^{-A c1} -CO-OA ^{c2 is also preferable.} A ^c1 is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A ^b2 is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ^c1 is an alkylene group, the alkylene group may be linear or branched, preferably linear. When A ^c1 is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, particularly preferably 1 or more and 4 or less.

Suitable examples of A ^c2 include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Suitable specific examples of A ^c2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl , phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl, etc.

Suitable specific examples of the group represented by -A ^c1 -CO-OA ^c2 include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-Butoxycarbonylethyl, 2-n-pentoxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methyl Oxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl, 3-n-pentoxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, 3-phenoxycarbonyl-n-propyl and the like.

R ¹ has been described above, but R ^{1 is} preferably a group represented by the following formula (c1a) or (c1b).

(In formulas (c1a) and (c1b), R ⁷ and R ⁸ are each an organic group, p is an integer of 0 or more and 4 or less, and when R ⁷ and R ⁸ are present at adjacent positions on the benzene ring, R ⁷ and R ⁸ can be bonded to each other to form a ring, p is an integer of 1 or more and 8 or less, r is an integer of 1 or more and 5 or less, s is an integer of 0 or more and (r+3) or less, and R ⁹ is an organic base)

Examples of the organic groups of ^{R 7} and R ⁸ in the formula (c1a) are the same as those of ^{R 1 .} As R ⁷ , an alkyl group or a phenyl group is preferable. When R ⁷ is an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, R ^{7 is} most preferably methyl.

When R ⁷ and R ^{8 are} bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (c1a) in which R ⁷ and R ⁸ form a ring include naphthalene-1-yl, 1,2,3,4-tetrahydronaphthalene-5-yl, and the like. In the above formula (c1a), p is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

In the above formula (c1b), R ⁹ is an organic group. Examples of the organic group include the same groups described for R ¹ in the organic group.

^Among the organic groups as R 9 , alkyl groups are preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. As R ⁹ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like can be preferably exemplified, and among these, a methyl group is more preferred.

In the above formula (c1b), r is an integer of 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (c1b), s is 0 or more and (r+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, particularly preferably 0. In the above formula (c1b), q is an integer of 1 or more and 8 or less, preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, particularly preferably 1 or 2.

In formula (1), R ² is an organic group. As the organic group, an aryl group which may have a substituent or a heteroaryl group which may have a substituent is preferable. As an aryl group which may have a substituent, the phenyl group which may have a substituent is mentioned, for example. As a heteroaryl group which may have a substituent, the carbazolyl group which may have a substituent is mentioned, for example.

-1-基、鹵素原子、硝基、及氰基等。 In R ² , the substitution that the aryl group, the heteroaryl group, the phenyl group, or the carbazolyl group may have is not particularly limited within the range that does not hinder the purpose of the present invention. Examples of suitable substituents that an aryl group, a heteroaryl group, a phenyl group, or a carbazolyl group may have on a carbon atom include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, and a saturated aliphatic group. aliphatic alkoxy, saturated aliphatic alkoxy, alkoxycarbonyl, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted benzyl group, optionally substituted phenoxycarbonyl, optionally substituted benzyloxy, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyl, optionally substituted naphthyloxycarbonyl, optionally substituted naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, Heterocyclylcarbonyl, amine group, amine group substituted with 1 or 2 organic groups, morpholin-1-yl, piperyl which may have substituents

-1-yl group, halogen atom, nitro group, cyano group and the like.

When R ² is a heteroaryl group or a carbazolyl group, there are suitable substituents that the heteroaryl group can have on a heteroatom such as a nitrogen atom, and a suitable substituent that the carbazolyl group can have on the nitrogen atom. For example, an alkyl group, a cycloalkyl group, a saturated aliphatic aryl group, an alkoxycarbonyl group, an optionally substituted phenyl group, an optionally substituted benzyl group, and an optionally substituted phenoxycarbonyl group may be mentioned. , optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyl, optionally substituted naphthoxycarbonyl, optionally substituted naphthylalkyl, optionally substituted A heterocyclic group having a substituent, a heterocyclic carbonyl group which may have a substituent, and the like. Among these substituents, an alkyl group is preferred, an alkyl group having 1 to 20 carbon atoms is more preferred, an alkyl group having 1 to 6 carbon atoms is still more preferred, and an ethyl group is particularly preferred.

Specific examples of the substituent which the aryl group, the heteroaryl group, the phenyl group, or the carbazolyl group may have are the alkyl group, the alkoxy group, the cycloalkyl group, the cycloalkoxy group, the saturated aliphatic aryl group, the saturated aliphatic group Alkyloxy, alkoxycarbonyl, optionally substituted phenylalkyl, optionally substituted naphthylalkyl, optionally substituted heterocyclyl, and amine substituted with one or two organic groups The base is the same as described ^{for R 1 .}

Among the above-mentioned substituents, the substituents in the case of further having a substituent such as a phenyl group, a naphthyl group, a heterocyclic group, etc. are the same as those described ^{for R 1 .}

R ² is preferably a group represented by the following formula (1-1) or (1-2) from the viewpoint of excellent sensitivity of the photosensitive composition, more preferably the following formula (1-1) The group represented by ) is particularly preferably a group represented by the following formula (1-1) in which A is S.

(R ⁴ is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen atom, a nitro group, and a cyano group, A is S or O, and n is an integer of 0 or more and 4 or less)

(R ⁵ and R ⁶ are respectively a monovalent organic group)

When a photosensitive composition is used to form a pattern, the pattern is likely to be colored due to the heating in the step of baking after the pattern is formed. However, in the photosensitive composition, when ^{the oxime ester compound represented by the formula (1) in which R 2} is a group represented by the above formula (1-1) and A is a group of S is used as a photopolymerization initiator, Coloring of the pattern caused by heating is easily suppressed.

-1-基、及苯基所組成之群中之基所取代之苯甲醯基；具有碳原子數1以上且6以下之烷基之單烷基胺基；具有碳原子數1以 上且6以下之烷基之二烷基胺基；嗎啉-1-基；哌

-1-基；鹵素；硝基；氰基。 ^{When R 4} in the formula (1-1) is an organic group, it can be selected from various organic groups within a range that does not inhibit the purpose of the present invention. ^{Suitable examples when R 4} in the formula (1-1) is an organic group include: an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; carbon Saturated aliphatic alkoxy group with 2 to 7 atoms; alkoxycarbonyl group with 2 to 7 carbon atoms; saturated aliphatic alkoxy group with 2 to 7 carbon atoms; phenyl group; naphthyl group; benzyl; naphthyl;

-1-yl group and benzyl group substituted by a group in the group consisting of phenyl group; monoalkylamine group having an alkyl group having 1 to 6 carbon atoms; having 1 to 6 carbon atoms Dialkylamino of the following alkyl groups; Morpholin-1-yl; Piper

-1-yl; halogen; nitro; cyano.

-1-基、及苯基所組成之群中之基所取代之苯甲醯基；硝基，更佳為：苯甲醯基；萘甲醯基；2-甲基苯基羰基；4-(哌

-1-基)苯基羰基；4-(苯基)苯基羰基。 Among R ⁴ , preferably: a benzyl group; a naphthyl group; an alkyl group selected from the group consisting of 1 or more and 6 or less carbon atoms, morpholin-1-yl, piper

-1-yl and benzyl substituted by groups in the group consisting of phenyl; nitro, more preferably: benzyl; naphthyl; 2-methylphenylcarbonyl; 4- (piper

-1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl.

Moreover, in Formula (1-1), n is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. In the case when n is 1, is preferably bonded with R ⁴ position with respect to the R ⁴ phenyl group are bonded with the bonding of the bonded atoms and A is bonded to the para position.

^{R 5} in the formula (1-2) can be selected from various organic groups within a range that does not hinder the purpose of the present invention. Suitable examples of R ⁵ include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a saturated aliphatic aliphatic group having 2 to 20 carbon atoms. , Alkoxyalkyl with 2 or more and 20 or less carbon atoms, alkoxycarbonyl with 2 or more and 20 or less carbon atoms, phenyl group which may have substituents, benzyl group which may have substituents, Substituent phenoxycarbonyl group, optionally substituted phenylalkyl group having 7 to 20 carbon atoms, optionally substituted naphthyl, optionally substituted naphthylcarboxyl, optionally substituted A naphthyloxycarbonyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclic group, and an optionally substituted heterocyclic carbonyl group, and the like.

In R ⁵ , an alkyl group having 1 to 20 carbon atoms and an alkoxyalkyl group having 2 to 20 carbon atoms are preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. , and an alkoxyalkyl group having 2 or more and 6 or less carbon atoms, particularly preferably an ethyl group and an ethoxyethyl group.

^{R 6} in the formula (1-2) is not particularly limited as long as the object of the present invention is not inhibited, and can be selected from various organic groups. Specific examples of groups suitable for R ⁶ include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocycle. base. As R ⁶ , among these groups, an optionally substituted phenyl group or an optionally substituted thienyl group is more preferable, and a 2-methylphenyl group or a thienyl group is particularly preferable.

-1-基、鹵素、硝基、及氰基等。於R⁴、R⁵、或R⁶所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於R⁴、R⁵、或R⁶所含之苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 Examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclic group contained in R ⁴ , R ⁵ , or R ^{6 further have a substituent include an alkyl group having 1 to 6 carbon atoms, a carbon} Alkoxy group having 1 to 6 atoms, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, and 2 to 7 carbon atoms Saturated aliphatic alkoxy group, monoalkylamine group having an alkyl group having 1 to 6 carbon atoms, dialkylamine group having an alkyl group having 1 to 6 carbon atoms, morpholine-1- base, piper

-1-yl, halogen, nitro, and cyano, etc. When the phenyl group, naphthyl group, and heterocyclic group contained in R ⁴ , R ⁵ , or R ⁶ further have substituents, the number of the substituents is not limited to the extent that the purpose of the present invention is not hindered. , preferably 1 or more and 4 or less. When a ^{phenyl group, a naphthyl group, and a heterocyclic group contained in R 4} , R ⁵ , or R ⁶ have a plurality of substituents, the plurality of substituents may be the same or different.

In formula (1), R ³ is an organic group. Although it does not specifically limit as an organic group, Preferably it is an alkyl group and an aryl group. The alkyl group is preferably an alkyl group having 1 or more and 11 or less carbon atoms. The aryl group is a phenyl group which may have a substituent. The substituents in the optionally substituted phenyl group are the same as those described ^{for R 1 .}

As R ³ , an alkyl group having 1 to 6 carbon atoms and a phenyl group are more preferable, a methyl group, an ethyl group, and a phenyl group are particularly preferable, and a methyl group and an ethyl group are most preferable.

As a suitable specific example of the oxime ester compound represented by Formula (1) demonstrated above, the following compounds are mentioned.

As the compound represented by the formula (1), it is also preferable to use an oxime ester compound represented by the following formula (c1).

(R ^c1 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, n1 is an integer of 0 or more and 4 or less, n2 is 0 or 1, and R ^c2 is A phenyl group which may have a substituent, or a carbazolyl group which may have a substituent, R ^c3 is an alkyl group having 1 to 6 carbon atoms)

-1-基、鹵素、硝基、及氰基等。於n1為2以上且4以下之整數之情形時，R^c1可相同亦可不同。又，取代基之碳原子數中不包括取代基所進而具有之取代基之碳原子數。 In formula (c1), R ^c1 is not particularly limited as long as the object of the present invention is not inhibited, and can be appropriately selected from various organic groups. Suitable examples in the case where R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acid group, a saturated aliphatic acid group, and an alkoxycarbonyl group. , a phenyl group that can have a substituent, a phenoxy group that can have a substituent group, a benzyl group that can have a substituent group, a phenoxycarbonyl group that can have a substituent group, a benzyloxy group that can have a substituent group, Substitutable phenylalkyl, optional substituted naphthyl, optional substituted naphthyl, optional substituted naphthyl, optional substituted naphthyloxycarbonyl, optional substituted naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, amino group, amino group substituted with one or two organic groups, morpholin-1-yl, and Piper

-1-yl, halogen, nitro, and cyano, etc. When n1 is an integer of 2 or more and 4 or less, R ^c1 may be the same or different. In addition, the carbon number of the substituent which the substituent further has is not included in the carbon number of a substituent.

When R ^c1 is an alkyl group, it is preferably 1 or more and 20 or less carbon atoms, more preferably 1 or more and 6 or less carbon atoms. Moreover, when R ^c1 is an alkyl group, a straight chain may be sufficient as it, and a branched chain may be sufficient. Specific examples when R ^c1 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl base, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-octyl Decyl, and isodecyl, etc. In addition, when R ^c1 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc.

When R ^c1 is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. Moreover, when R ^c1 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R ^c1 is an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a second butoxy group. , third butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy and the like. Moreover, when R ^c1 is an alkoxy group, an ether bond (-O-) may be contained in an alkoxy group in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy group, propoxyethoxyethoxy, and methoxypropoxy, etc.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, it is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less carbon atoms. Specific examples when R ^c1 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 ^c1 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 ^c1 is a saturated aliphatic alkoxy group or a saturated aliphatic alkoxy group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably the number of carbon atoms is 2 or more and 7 or less. Specific examples when R ^c1 is a saturated aliphatic acid group include acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethyl group. Propyl radical, n-hexyl radical, n-heptyl radical, n-octyl radical, n-nonyl radical, n-decyl radical, n-decyl radical, n-dodecyl radical, n-tdecyl radical, n-tetradecyl radical Carbonyl, n-pentadecyl, and n-hexadecyl, etc. Specific examples when R ^c1 is a saturated aliphatic alkoxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, and n-pentanoyloxy , 2,2-dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecanyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecyloxy, n-hexadecanoyloxy, and the like.

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably the number of carbon atoms is 2 or more and 7 or less. Specific examples when R ^c1 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy Carbonyl, second-butoxycarbonyl, third-butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second-pentoxycarbonyl, third-pentoxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy ylcarbonyl, n-octoxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyl Oxycarbonyl, etc.

When R ^c1 is a phenylalkyl group, it is preferable that it has 7 or more and 20 or less carbon atoms, and it is more preferable that it is 7 or more and 10 or less carbon atoms. Moreover, when R ^c1 is a naphthyl alkyl group, it is preferable that carbon number is 11 or more and 20 or less, and it is more preferable that carbon number is 11 or more and 14 or less. Specific examples when R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when R ^c1 is naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthalene base) ethyl. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or the naphthyl group.

唑、異

唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡

、嘧啶、嗒

、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚

、苯并咪唑、苯并三唑、苯并

唑、苯并噻 唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞

、

啉、及喹

啉等。於R^c1為雜環基之情形時，雜環基可進而具有取代基。 When R ^c1 is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, O, or the monocyclic ring is condensed with each other or the monocyclic ring and a benzene ring. into the heterocyclic group. When the heterocyclic group is a condensed ring, the number of condensed rings is at most three. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole,

azole, iso

azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine

, pyrimidine, ta

, benzofuran, benzothiophene, indole, isoindole, indole

, benzimidazole, benzotriazole, benzo

azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthaloline

,

Linen, and quinoline

Lin et al. When R ^c1 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^c1 is an amine group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 3 to 10 carbon atoms. Cycloalkyl, saturated aliphatic aliphatic group with 2 or more and 20 or less carbon atoms, optionally substituted phenyl group, optionally substituted benzyl group, optionally substituted with 7 or more and 20 or less carbon atoms phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyl, optionally substituted naphthylalkyl having 11 to 20 carbon atoms, and heterocyclic groups. Specific examples of these suitable organic groups are the same as ^{R c1.} Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine N-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, benzene amino, naphthyl amino, acetyl amino, propionyl amino, n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino , n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino, etc.

-1-基、鹵素、硝基、及氰基等。於R^c1所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以 下。於R^c1所含之苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 Examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclic group contained in R ^c1 further have a substituent include an alkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms. alkoxy, saturated aliphatic alkoxy group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic alkoxy group with 2 to 7 carbon atoms, Monoalkylamine group having an alkyl group having 1 to 6 carbon atoms, dialkylamine group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piper

-1-yl, halogen, nitro, and cyano, etc. When the phenyl group, naphthyl group, and heterocyclic group contained in R ^c1 further have substituents, the number of the substituents is not limited to the extent that it does not hinder the purpose of the present invention, and is preferably 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^c1 have plural substituents, the plural substituents may be the same or different.

R ^c1 is preferably selected from an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms in terms of chemical stability, less steric hindrance and easy synthesis of an oxime ester compound, etc. A group in the group consisting of the following alkoxy group and a saturated aliphatic acyl group having 2 or more and 7 or less carbon atoms is more preferably an alkyl group having 1 or more and 6 or less carbon atoms, and particularly preferably a methyl group.

About R ^c1 bonded to the upper position of the phenyl, in the primary position of R ^c1 are bonded with a phenyl-phenyl oxime ester compound of the backbone of bonding to a key, the set position of methyl In the case of 2 bits, preferably 4 bits or 5 bits, more preferably 5 bits. Moreover, n1 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.

R ^c2 is an optionally substituted phenyl group or an optionally substituted carbazolyl group. Moreover, when R ^c2 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.

-1-基、鹵素、硝基、及氰基等。 In R ^c2 , the substitution of the phenyl group or the carbazolyl group is not particularly limited in the range that does not inhibit the purpose of the present invention. Examples of suitable substituents that the phenyl group or the carbazolyl group may have on carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, Cycloalkyl having 3 or more and 10 or less carbon atoms, cycloalkoxy having 3 or more and 10 or less carbon atoms, saturated aliphatic acyl group having 2 or more and 20 or less carbon atoms, 2 or more and 20 or less carbon atoms alkoxycarbonyl group, saturated aliphatic alkoxy group having 2 to 20 carbon atoms, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted Substitutable benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, optionally substituted phenylalkyl group with 7 to 20 carbon atoms, optionally substituted Substituent naphthyl, optionally substituted naphthyloxy, optionally substituted naphthyl, optionally substituted naphthoxycarbonyl, optionally substituted naphthyloxy, optionally substituted naphthyl alkyl groups with 11 or more and 20 carbon atoms, optionally substituted heterocyclic groups, optionally substituted heterocyclic carbonyl groups, amine groups, amine groups substituted with one or two organic groups, Morpholin-1-yl, and piper

-1-yl, halogen, nitro, and cyano, etc.

When R ^c2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 3 or more carbon atoms and Cycloalkyl group of 10 or less, saturated aliphatic acyl group with 2 or more and 20 or less carbon atoms, alkoxycarbonyl group with 2 or more and 20 or less carbon atoms, phenyl group which may have substituents, benzene which may have substituents Carboxylic group, optionally substituted phenoxycarbonyl group, optionally substituted phenylalkyl group having 7 to 20 carbon atoms, optionally substituted naphthyl, optionally substituted naphthylcarboxyl , optionally substituted naphthyloxycarbonyl, optionally substituted naphthyl alkyl with 11 to 20 carbon atoms, optionally substituted heterocyclic group, and optionally substituted heterocyclic carbonyl, etc. . Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

Specific examples of the substituent that the phenyl group or the carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acid group, an alkoxycarbonyl group, and a saturated aliphatic acid group. group, an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclic group, and an amine group substituted with one or two organic groups, the same as ^{R c1.}

-1-基、及苯基所組成之群中之基所取代之苯甲醯基；具有碳原子數1以上且6以下之烷基之單烷基胺基；具有碳原子數1以上且6以下之烷基之二烷基胺基；嗎啉-1-基；哌

-1-基；鹵素；硝基；氰基。於苯基、或咔唑基所具有之取代基所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 In R ^c2 , examples of the substituent in the case where the phenyl group, the phenyl group, the naphthyl group, and the heterocyclic group contained in the substituent group of the carbazolyl group further have a substituent group include the following: Alkyl having 1 or more and 6 or less; Alkoxy having 1 or more and 6 or less carbon atoms; Saturated aliphatic aryl group having 2 or more and 7 or less carbon atoms; Alkoxycarbonyl group having 2 or more and 7 or less carbon atoms ; Saturated aliphatic alkoxy group with 2 or more and 7 or less carbon atoms; phenyl group; naphthyl group; benzyl group; naphthyl group; -1-yl, piper

-1-yl group and benzyl group substituted by a group in the group consisting of phenyl group; monoalkylamine group having an alkyl group having 1 to 6 carbon atoms; having 1 to 6 carbon atoms Dialkylamino of the following alkyl groups; Morpholin-1-yl; Piper

-1-yl; halogen; nitro; cyano. When a phenyl group, a phenyl group, a naphthyl group, and a heterocyclic group contained in the substituent group of the carbazolyl group further have a substituent group, the number of the substituent groups is within the range that does not hinder the purpose of the present invention. Although not limited, 1 or more and 4 or less are preferable. When a phenyl group, a naphthyl group, and a heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c2 is preferably a group represented by the following formula (c2) or (c3), more preferably a group represented by the following formula (c2), in terms of easily obtaining a photopolymerization initiator excellent in sensitivity. The group represented is particularly preferably a group represented by the following formula (c2) in which A is S.

(R ^c4 is a group selected from the group consisting of a monovalent organic group, an amine group, a halogen, a nitro group, and a cyano group, A is S or O, and n3 is an integer of 0 or more and 4 or less)

(R ^c5 and R ^c6 are each a monovalent organic group)

-1-基、及苯基所組成之群中之基所取代之苯甲醯基；具有碳原子數1以上且6以下之烷基之單烷基胺基；具有碳原子數1以上且6以下之烷基之二烷基胺基；嗎啉-1-基；哌

-1-基；鹵素；硝基；氰基。 ^{When R c4} in formula (c2) is an organic group, it can be selected from various organic groups within a range that does not inhibit the purpose of the present invention. ^{Suitable examples when R c4} in the formula (c2) is an organic group include: an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; Saturated aliphatic alkoxy group with 2 or more and 7 or less; alkoxycarbonyl group with 2 or more and 7 or less carbon atoms; saturated aliphatic alkoxy group with 2 or more and 7 or less carbon atoms; phenyl; naphthyl; benzyl Acyl group; naphthoyl group; selected from an alkyl group having 1 or more and 6 or less carbon atoms, morpholin-1-yl, piper

-1-yl group and benzyl group substituted by a group in the group consisting of phenyl group; monoalkylamine group having an alkyl group having 1 to 6 carbon atoms; having 1 to 6 carbon atoms Dialkylamino of the following alkyl groups; Morpholin-1-yl; Piper

-1-yl; halogen; nitro; cyano.

-1-基、及苯基所組成之群中之基所取代之苯甲醯基；硝基，更佳為：苯甲醯基；萘甲醯基；2-甲基苯基羰基；4-(哌

-1-基)苯基羰基；4-(苯基)苯基羰基。 In R ^c4 , preferably: benzyl group; naphthyl group; selected from alkyl groups having 1 or more and 6 or less carbon atoms, morpholin-1-yl, piper

-1-yl and benzyl substituted by groups in the group consisting of phenyl; nitro, more preferably: benzyl; naphthyl; 2-methylphenylcarbonyl; 4- (piper

-1-yl)phenylcarbonyl; 4-(phenyl)phenylcarbonyl.

Moreover, in Formula (c2), n3 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. In the case when n3 is 1, R ^c4 is preferably bonded to the position relative to the bonded phenyl group of R ^c4 and bonded to oxygen atoms or sulfur atoms is bonded to the para position.

^{R c5} in the formula (c3) can be selected from various organic groups within a range that does not hinder the purpose of the present invention. Suitable examples of R ^c5 include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a saturated aliphatic aryl group having 2 to 20 carbon atoms. , Alkoxyalkyl with 2 or more and 20 or less carbon atoms, alkoxycarbonyl with 2 or more and 20 or less carbon atoms, phenyl group which may have substituents, benzyl group which may have substituents, Substituent phenoxycarbonyl group, optionally substituted phenylalkyl group having 7 to 20 carbon atoms, optionally substituted naphthyl, optionally substituted naphthylcarboxyl, optionally substituted A naphthyloxycarbonyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclic group, and an optionally substituted heterocyclic carbonyl group, and the like.

In R ^c5 , preferably an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 or more and 6 or less carbon atoms, particularly preferably an ethyl group or an ethoxyethyl group.

^{R c6} in formula (c3) is not particularly limited as long as the object of the present invention is not inhibited, and can be selected from various organic groups. Specific examples of groups suitable for R ^c6 include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocycle. base. As R ^c6 , among these groups, an optionally substituted phenyl group or an optionally substituted thienyl group is more preferable, and a 2-methylphenyl group or a thienyl group is particularly preferable.

-1-基、鹵素、硝基、及氰基等。於R^c4、R^c5、或R^c6所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於R^c4、R^c5、或R^c6所含之苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 Examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclic group contained in R ^c4 , R ^c5 , or R ^{c6 further have a substituent include an alkyl group having 1 to 6 carbon atoms, a carbon} Alkoxy group having 1 to 6 atoms, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, and 2 to 7 carbon atoms Saturated aliphatic alkoxy group, monoalkylamine group having an alkyl group having 1 to 6 carbon atoms, dialkylamine group having an alkyl group having 1 to 6 carbon atoms, morpholine-1- base, piper

-1-yl, halogen, nitro, and cyano, etc. When the phenyl group, naphthyl group, and heterocyclic group contained in R ^c4 , R ^c5 , or R ^c6 further have substituents, the number of the substituents is not limited as long as the purpose of the present invention is not hindered. , preferably 1 or more and 4 or less. When a ^{phenyl group, a naphthyl group, and a heterocyclic group contained in R c4} , R ^c5 , or R ^c6 have a plurality of substituents, the plurality of substituents may be the same or different.

^{R c3} in formula (c1) is an alkyl group having 1 or more and 6 or less carbon atoms. As R ^c3 , a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

When p is 0, the oxime ester compound represented by formula (c1) can be synthesized according to the following reaction scheme 1, for example. Specifically, the aromatic compound represented by the following formula (c1-1) is converted into an aromatic compound represented by the following formula (c1-1) by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (c1-2). Acylation is performed to obtain a ketone compound represented by the following formula (c1-3), and the obtained ketone compound (c1-3) is oximeated with hydroxylamine to obtain a ketone compound represented by the following formula (c1-4) Then, the hydroxyl group in the oxime compound of formula (c1-4) is carboxylated to obtain an oxime ester compound represented by the following formula (c1-7). As the acylation agent, an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (c1-5), or an halide (R ^c3 COHal) represented by the following formula (c1-6) is preferably used, Hal is halogen). Furthermore, in the following formula (c1-2), Hal is a halogen, and in the following formulas (c1-1), (c1-2), (c1-3), (c1-4), and (c1- In 7), R ^c1 , R ^c2 , R ^c3 , and n1 are the same as formula (c1).

When n2 is 1, the oxime ester compound represented by the formula (c1) can be synthesized according to the following reaction scheme 2, for example. Specifically, in the presence of hydrochloric acid, a ketone compound represented by the following formula (c2-1) and a nitrite (RONO, R is 1 or more carbon atoms and 6 or less alkyl group) reaction to obtain a ketoxime compound represented by the following formula (c2-3), and then, the hydroxyl group in the ketoxime compound represented by the following formula (c2-3) is carboxylated, and An oxime ester compound represented by the following formula (c2-6) can be obtained. As the acylating agent, an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (c2-4) or an halide (R ^c3 COHal) represented by the following formula (c2-5) is preferably used, Hal is halogen). Furthermore, in the following formulae (c2-1), (c2-3), (c2-4), (c2-5), and (c2-6), R ^c1 , R ^c2 , R ^c3 , and n1 It is the same as formula (c1).

In the oxime ester compound represented by the formula (c1), n2 is 1, R ^c1 is a methyl group, and R ^c1 is bonded to the para position with respect to the methyl group of the benzene ring to which R ^{c1 is bonded.} In this case, the compound represented by the following formula (c2-7) can also be synthesized by, for example, oximation and acylation by the same method as in Reaction Scheme 1. In addition, in following formula (c2-7), R ^{c2 is the} same as formula (c1).

Among the oxime ester compounds represented by the formula (c1), particularly suitable compounds include the following PI-1 to PI-42.

Moreover, the oxime ester compound represented by following formula (c4) is also preferable as a photoinitiator.

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, R ^c8 and R ^c9 are respectively a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R ^c8 and R ^c9 can be bonded to each other to form a ring, R ^c10 is a monovalent organic group, R ^c11 is an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group, and n4 is 0 or more and an integer below 4, n5 is 0 or 1)

Here, as the oxime compound for producing the oxime ester compound of the formula (c4), a compound represented by the following formula (c5) is suitable.

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4 , and n5 are the same as formula (c4))

In formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c7 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by _{-(CO) n5} - on the pyrene ring in the formula (c4). In formula (c4), R ^c7 is not particularly limited to the bonding position of the perylene ring. In the case where the compound represented by the formula (c4) has one or more R ^{c7 , it is preferable that one of the one or more R c7} is bonded from the viewpoint of easy synthesis of the compound represented by the formula (c4), etc. 2 in the ring. When R ^c7 is plural, the plural R ^c7 may be the same or different.

-1-基等。 When R ^c7 is an organic group, R ^c7 is not particularly limited in a range that does not inhibit the purpose of the present invention, and can be appropriately selected from various organic groups. Suitable examples when R ^c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acid group, a saturated aliphatic acid group, and an alkoxycarbonyl group. , a phenyl group that can have a substituent, a phenoxy group that can have a substituent group, a benzyl group that can have a substituent group, a phenoxycarbonyl group that can have a substituent group, a benzyloxy group that can have a substituent group, Substitutable phenylalkyl, optional substituted naphthyl, optional substituted naphthyl, optional substituted naphthyl, optional substituted naphthyloxycarbonyl, optional substituted naphthyloxy, optionally substituted naphthylalkyl, optionally substituted heterocyclic group, optionally substituted heterocyclic carbonyl, optionally substituted amine group, substituted with one or two organic groups, olin-1-yl, and piper

-1-Base, etc.

When R ^c7 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. In addition, when R ^c7 is an alkyl group, it may be a straight chain or a branched chain. Specific examples when R ^c7 is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl base, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, isononyl, n-octyl Decyl, and isodecyl, etc. In addition, when R ^c7 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc.

When R ^c7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. In addition, when R ^c7 is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R ^c7 is an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a second butoxy group. , third butoxy, n-pentyloxy, isopentyloxy, second pentyloxy, third pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, second Octyloxy, tertiary octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, isodecyloxy and the like. Moreover, when ^Rc7 is an alkoxy group, an ether bond (-O-) may be contained in an alkoxy group in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy group, propoxyethoxyethoxy, and methoxypropoxy, etc.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the carbon number of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. Specific examples when R ^c7 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 ^c7 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 ^c7 is a saturated aliphatic alkoxy group or a saturated aliphatic alkoxy group, the carbon number of the saturated aliphatic alkanoyl group or saturated aliphatic alkoxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less. Specific examples in the case where R ^c7 is a saturated aliphatic acid group include acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentyl group, and 2,2-dimethyl group. Propyl radical, n-hexyl radical, n-heptyl radical, n-octyl radical, n-nonyl radical, n-decyl radical, n-decyl radical, n-dodecyl radical, n-tdecyl radical, n-tetradecyl radical Carbonyl, n-pentadecyl, and n-hexadecyl, etc. Specific examples when R ^c7 is a saturated aliphatic alkoxy group include acetyloxy, propanoyloxy, n-butanoyloxy, 2-methylpropanoyloxy, and n-pentanoyloxy , 2,2-dimethylpropionyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecanyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecyloxy, n-hexadecanoyloxy, and the like.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. Specific examples when R ^c7 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy Carbonyl, second-butoxycarbonyl, third-butoxycarbonyl, n-pentoxycarbonyl, isopentyloxycarbonyl, second-pentoxycarbonyl, third-pentoxycarbonyl, n-hexyloxycarbonyl, n-heptyloxy ylcarbonyl, n-octoxycarbonyl, isooctyloxycarbonyl, second octyloxycarbonyl, third octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyloxycarbonyl, and isodecyl Oxycarbonyl, etc.

When R ^c7 is a phenylalkyl group, the carbon number of the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. Moreover, when R ^c7 is a naphthyl alkyl group, the carbon number of the naphthyl alkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. Specific examples when R ^c7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when R ^c7 is naphthylalkyl include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthalene base) ethyl. When R ^c7 is a phenylalkyl group or a naphthylalkyl group, R ^c7 may further have a substituent on the phenyl group or the naphthyl group.

唑、異

唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡

、嘧啶、嗒

、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚

、苯并咪唑、苯并三唑、苯并

唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞

、

啉、喹

啉、哌啶、哌

、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。於R^c7為雜環基之情形時，雜環基可進而具有取代基。 When R ^c7 is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, O, or the monocyclic ring is condensed with each other or the monocyclic ring and a benzene ring. into the heterocyclic group. When the heterocyclic group is a condensed ring, the number of condensed rings is at most three. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole,

azole, iso

azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine

, pyrimidine, ta

, benzofuran, benzothiophene, indole, isoindole, indole

, benzimidazole, benzotriazole, benzo

azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthaloline

,

linen, quinoline

Linen, piperidine, piperidine

, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc. When R ^c7 is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ^c7 is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as when ^{R c7 is a heterocyclic group.}

When R ^c7 is an amine group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 3 to 10 carbon atoms. Cycloalkyl, saturated aliphatic aliphatic group with 2 or more and 21 or less carbon atoms, optionally substituted phenyl group, optionally substituted benzyl group, optionally substituted with 7 or more and 20 or less carbon atoms phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyl, optionally substituted naphthylalkyl having 11 to 20 carbon atoms, and heterocyclic groups. Specific examples of these suitable organic groups are the same as ^{R c7 .} Specific examples of the amino group substituted with one or two organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamine N-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, benzene amino, naphthyl amino, acetyl amino, propionyl amino, n-butyl amino, n-pentyl amino, n-hexyl amino, n-heptyl amino, n-octyl amino , n-decylamino, benzylamino, α-naphthylamino, and β-naphthylamino, etc.

-1-基、鹵素、硝基、及氰基等。於R^c7所含之苯基、萘基、及雜環基進而具有取代基之情形時，該取代基之個數於不阻礙本發明之目的之範圍內並無限定，較佳為1以上且4以下。於R^c7所含之苯基、萘基、及雜環基具有複數個取代基之情形時，複數個取代基可相同亦可不同。 Examples of substituents when the phenyl group, naphthyl group, and heterocyclic group contained in R ^c7 further have a substituent include an alkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms. alkoxy, saturated aliphatic alkoxy group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic alkoxy group with 2 to 7 carbon atoms, Monoalkylamine group having an alkyl group having 1 to 6 carbon atoms, dialkylamine group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piper

-1-yl, halogen, nitro, and cyano, etc. In the case where ^{the phenyl group, naphthyl group, and heterocyclic group contained in R c7} further have substituents, the number of the substituents is not limited as long as the purpose of the present invention is not hindered, and it is preferably 1 or more and 4 or less. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ^c7 have plural substituents, the plural substituents may be the same or different.

Among the groups described above, when R ^c7 is a nitro group or a ^{group represented by R c12} -CO-, the sensitivity tends to increase, which is preferable. R ^c12 is not particularly limited as long as the object of the present invention is not inhibited, and can be selected from various organic groups. Examples of groups suitable for R ^c12 include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclic group. . As R ^c12 , among these groups, 2-methylphenyl, thiophen-2-yl, and α-naphthyl are particularly preferred.

Moreover, when ^Rc7 is a hydrogen atom, there exists a tendency for transparency to become favorable, and it is preferable. Furthermore, when R ^c7 is a hydrogen atom and R ^c10 is a group represented by the formula (c4a) or (c4b) described below, the transparency tends to be more favorable.

In formula (c4), R ^c8 and R ^c9 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to each other to form a ring. Among these groups, R ^c8 and R ^{c9 are} preferably chain alkyl groups which may have a substituent. When R ^c8 and R ^c9 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c8 and R ^c9 are unsubstituted chain alkyl groups, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, particularly preferably 1 more than 6 and less than 6. Specific examples when R ^c8 and R ^c9 are chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertiary Butyl, n-pentyl, isopentyl, second pentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, second octyl, third octyl, n-nonyl, Isononyl, n-decyl, and isodecyl, etc. In addition, when R ^c8 and R ^c9 are alkyl groups, the alkyl group may also contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, and propoxyethyl oxyethyl, and methoxypropyl, etc.

When R ^c8 and R ^c9 are chain alkyl groups having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, particularly preferably 1 or more and 6 or less. In this case, the carbon number of the substituent is not included in the carbon number of the chain alkyl group. The chain alkyl group having a substituent is preferably a straight chain.

The substitution which an alkyl group may have is not specifically limited in the range which does not inhibit the objective of this invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. As a cyclic organic group, a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group are mentioned. Specific examples of the cycloalkyl group are the same as those suitable for the case where ^{R c7 is a cycloalkyl group.} Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group. Specific examples of the heterocyclic group are the same as suitable examples when ^{R c7 is a heterocyclic group.} When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of preferable substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.

When R ^c8 and R ^c9 are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. As a cyclic organic group, an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group are mentioned. When R ^c8 and R ^c9 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as when ^{R c8} and R ^{c9 are chain alkyl groups.}

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, or a group formed by the bonding of a plurality of benzene rings through carbon-carbon bonds, or a group formed by the condensation of a plurality of benzene rings. . When the aromatic hydrocarbon group is a phenyl group or a group formed by the bonding or condensation of a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, and is preferably 3 or less, more preferably 2 or less, preferably 1. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group.

基、異

基、三環壬基、三環癸基、四環十二烷基、及金剛烷基等。 When R ^c8 and R ^c9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norm

base, different

base, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl, etc.

唑、異

唑、噻唑、噻二唑、異噻唑、咪唑、吡唑、三唑、吡啶、吡

、嘧啶、嗒

、苯并呋喃、苯并噻吩、吲哚、異吲哚、吲哚

、苯并咪唑、苯并三唑、苯并

唑、苯并噻唑、咔唑、嘌呤、喹啉、異喹啉、喹唑啉、酞

、

啉、喹

啉、哌啶、哌

、嗎啉、哌啶、四氫吡喃、及四氫呋喃等。 When R ^c8 and R ^c9 are heterocyclic groups, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or the monocyclic rings or each other, or the monocyclic ring and benzene. Heterocyclic group formed by ring condensation. When the heterocyclic group is a condensed ring, the number of condensed rings is at most three. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclic group include furan, thiophene, pyrrole,

azole, iso

azole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyridine

, pyrimidine, ta

, benzofuran, benzothiophene, indole, isoindole, indole

, benzimidazole, benzotriazole, benzo

azole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthaloline

,

linen, quinoline

Linen, piperidine, piperidine

, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran, etc.

R ^c8 and R ^c9 may be bonded to each other to form a ring. The group comprising ^{the ring formed by R c8} and R ^c9 is preferably a cycloalkylene group. When R ^c8 and R ^{c9 are} bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.

環、及嘧啶環等。 When ^{the group formed by the bonding of R c8} and R ^c9 is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring which can be condensed with a cycloalkylene ring include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, Thiophene ring, pyrrole ring, pyridine ring, pyridine

rings, and pyrimidine rings.

^{Among R c8} and R ^c9 described above, examples of suitable groups include groups represented by ^{formula -A 1} -A ^{2 .} In the formula, A ¹ is a linear alkyl group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The ^{number of carbon atoms of the linear alkyl group of A 1} is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less. When A ² is in the case of a halogen atom, preferably fluorine atom, chlorine atom, bromine atom, iodine atom, more preferably a fluorine atom, a chlorine atom, a bromine atom. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, more preferably a fluorine atom, a chlorine atom, and a bromine atom. The halogenated alkyl group may be straight-chain or branched, but straight-chain is preferred. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups ^{R c8} and R ^{c9 have as substituents.} When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups ^{R c8} and R ^{c9 have as substituents.}

Suitable specific examples of R ^c8 and R ^c9 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methoxyethyl, 3 -Methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl base, 2-ethoxyethyl, 3-ethoxyn-propyl, 4-ethoxyn-butyl, 5-ethoxyn-pentyl, 6-ethoxyn-hexyl, 7-ethoxy n-heptyl, and alkoxyalkyl groups such as 8-ethoxyn-octyl; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl , 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl cyanoalkyl groups; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-octyl Butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl and other phenylalkyl groups; 2-cyclohexylethyl, 3-cyclohexyl Hexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl , 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl Cycloalkylalkyl such as pentyl-n-octyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl , 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4 - Ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl, and 8-ethoxycarbonyl-n-octyl alkanes Oxycarbonylalkyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-butyl Octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, Halogenated alkyl groups such as 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

As R ^c8 and R ^c9 , suitable groups among the above are: ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl , 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3,4,4,5 ,5,5-heptafluoro-n-pentyl.

-1-基等。該等基之具體例與針對R^c7之說明相同。又，作為R^c10，亦較佳為環烷基烷基、芳香環上可具有取代基之苯氧基烷基、芳香環上可具有取代基之苯基硫基烷基。苯氧基烷基、及苯基硫基烷基可具有之取代基與R^c7 所含之苯基可具有之取代基相同。 Examples of suitable organic groups for R ^c10 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acid group, an alkoxycarbonyl group, a saturated aliphatic group, as in ^{the case of R c7.} Ethyloxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted benzyl, optionally substituted phenoxycarbonyl, optionally substituted benzyloxy group, optionally substituted phenylalkyl, optionally substituted naphthyl, optionally substituted naphthyloxy, optionally substituted naphthylcarboxyl, optionally substituted naphthoxycarbonyl, optionally substituted Naphthyloxy with substituent, naphthylalkyl with optional substituent, heterocyclic group with optional substituent, heterocyclic carbonyl with optional substituent, amine substituted with 1 or 2 organic groups base, morpholin-1-yl, and piper

-1-Base, etc. Specific examples of these groups are the same as those described ^{for R c7.} Moreover, R ^{c10 is} also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent which the phenoxyalkyl group and the phenylsulfanylalkyl group may have is the same as the substituent which the phenyl group contained in ^{R c7 may have.}

^{Among the} organic groups, R c10 is preferably an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, or a cycloalkylalkyl group or an optionally substituted phenylthioalkyl group on the aromatic ring. The alkyl group is preferably an alkyl group having 1 or more and 20 or less carbon atoms, more preferably an alkyl group having 1 or more and 8 or less carbon atoms, particularly preferably an alkyl group having 1 or more and 4 or less carbon atoms, most preferably Preferably methyl. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2. Among the cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms in the alkylene group contained in the optionally substituted phenylsulfanylalkyl group on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, particularly preferably 2. Among the phenylsulfanylalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylsulfanyl)ethyl is preferred.

Moreover, as R ^c10 , a group represented by ^{-A 3} -CO-OA ^{4 is also preferable.} A ³ is a divalent organic group, preferably a divalent hydrocarbon group, preferably an alkylene group. A ⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be straight-chain or branched, preferably straight-chain. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, particularly preferably 1 or more and 4 or less.

As preferred embodiments of the A ^4, include: an alkyl group of 10 or less and the number of 7 or more and 20 or less of the arylalkyl, and the number of carbon atoms of 6 or more and 20 or less carbon atoms, an aromatic hydrocarbon group having 1 or more carbon atoms. As preferred specific examples of the A ^4, include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl , phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl, etc.

Suitable specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-Butoxycarbonylethyl, 2-n-pentoxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methyl Oxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl, 3-n-pentoxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, 3-phenoxycarbonyl-n-propyl and the like.

Above for R ^c10 has been described, but as R ^c10, preferred is represented by the following formula (C4A) or (C4b) group.

(In formulas (c4a) and (c4b), R ^c13 and R ^c14 are each an organic group, n6 is an integer of 0 or more and 4 or less, and when R ^c13 and R ⁸ are present at adjacent positions on the benzene ring, R ^c13 and R ^c14 can be bonded to each other to form a ring, n7 is an integer of 1 or more and 8 or less, n8 is an integer of 1 or more and 5 or less, n9 is an integer of 0 or more and (n8+3) or less, R ^c15 is an organic base)

Examples of the organic groups of ^{R c13} and R ^c14 in the formula (c4a) are the same as those of ^{R c7.} As R ^c13 , an alkyl group or a phenyl group is preferable. When R ^c13 is an alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, R ^{c13 is} most preferably a methyl group. When R ^c13 and R ^{c14 are} bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (c4a) in which R ^c13 and R ^c14 form a ring include naphthalene-1-yl, 1,2,3,4-tetrahydronaphthalene-5-yl, and the like. In the above formula (c4a), n6 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.

In the above formula (c4b), R ^c15 is an organic group. As an organic group, the same group as the organic group demonstrated ^{about Rc7 is mentioned.} Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. As R ^c15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and the like can be preferably exemplified, and among these, a methyl group is more preferred.

In the above formula (c4b), n8 is an integer of 1 or more and 5 or less, preferably 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (c4b), n9 is 0 or more and (n8+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, particularly preferably 0. In the above formula (c4b), n7 is an integer of 1 or more and 8 or less, preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, particularly preferably 1 or 2.

In formula (c4), R ^c11 is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. As ^{a substituent which may be possessed when R c11} is an alkyl group, a phenyl group, a naphthyl group and the like can be preferably exemplified. Moreover, as ^{a substituent which may be possessed when R c7} is an aryl group, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group, a halogen atom and the like can be preferably exemplified.

In formula (c4), as R ^c11 , hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, etc. can be preferably exemplified , among these, methyl or phenyl is more preferred.

The compound represented by the formula (c4) is obtained by converting the oxime group (>C=N-OH) contained in the compound represented by the aforementioned formula (c5) into the oxime ester represented by ^{>C=NO-COR c11.} Manufactured by the method based on the steps. And R ^c11 are the same as the formula (c4) R ^c11.

Conversion of the oxime group (>C=N-OH) to ^{the oxime ester group represented by >C=NO-COR c11} is performed by reacting the compound represented by the aforementioned formula (c5) with an acylating agent.

The acid anhydride represented by ^{(R c11} CO) ₂ ^{O, or the acid halide represented by R c11} COHal (Hal is a halogen atom) can be mentioned as an acylation agent that provides the acyl group represented by ^{-COR c11.}

When n5 is 0, the compound represented by the general formula (c4) can be synthesized according to the following reaction scheme 3, for example. In Reaction Scheme 3, a fortium derivative represented by the following formula (c3-1) was used as a raw material. When R ^c7 is a nitro group or a monovalent organic group, the fortium derivative represented by the formula (c3-1) can introduce a substituent into the fortium derivative substituted with ^{R c8} and R ^{c9 at the 9-position by a known method.} obtained by R ^c7. For example, when R ^c8 and R ^{c9 are alkyl groups, the phenyl derivatives substituted by R c8} and R ^{c9 at the} 9-position can be treated as described in Japanese Patent Laid-Open No. 06-234668 in the presence of alkali metal hydroxides. It is obtained by reacting fluoride with an alkylating agent in an aprotic polar organic solvent. Also, by adding an alkylating agent such as a halogenated alkyl group, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tertiary butoxide to an organic solvent solution of fenugreek Alkylation reaction can be carried out to obtain 9,9-alkyl-substituted perylene.

The fortium derivative represented by the formula (c3-3) can be obtained ^{by introducing the acyl group represented by -CO-R c10} into the fortium derivative represented by the formula (c3-1) by the Friedel-Crafts acylation reaction. The acylation agent for introducing the acylation group represented by -CO-R ^c10 may be a halocarbonyl compound or an acid anhydride. As the acylation agent, a halocarbonyl compound represented by the formula (c3-2) is preferred. In formula (c3-2), Hal is a halogen atom. The position at which the acyl group is introduced into the perylene ring can be selected by appropriately changing the conditions of the Friedel-Crafts reaction, or the method of protecting and deprotecting the position other than the acyl group.

^{Then, the group represented by -CO-R c10} in the obtained stilbene derivative represented by the formula (c3-3) is converted into the group represented by -C(=N-OH)-R ^c10 , and the formula is obtained. The oxime compound represented by (c3-4). The method of converting the group represented by -CO-R ^c10 to the group represented by -C(=N-OH)-R ^c10 is not particularly limited, but oximation with hydroxylamine is preferable. The oxime compound of the formula (c3-4) and the acid anhydride ((R ^c11 CO) ₂ O) represented by the following formula (c3-5), or the halide (R ^c11 COHal) represented by the following formula (c3-6) , Hal is a halogen atom) reaction, and the compound represented by the following formula (c3-7) can be obtained.

Furthermore, in formulas (c3-1), (c3-2), (c3-3), (c3-4), (c3-5), (c3-6), and (c3-7), R ^c7 , R ^c8 , R ^c9 , R ^c10 , and R ^{c11 are the} same as formula (c4).

^{Moreover, in Reaction Scheme 3, R c10} contained in each of formula (c3-2), formula (c3-3), and formula (c3-4) may be the same or different. ^{That is, R c10} in formula (c3-2), formula (c3-3), and formula (c3-4) can be chemically modified during the synthesis process shown in Reaction Scheme 3. Examples of chemical modification include esterification, etherification, amidation, amidation, halogenation, substitution of a hydrogen atom in an amine group with an organic group, and the like. The chemical modifications to which R ^c10 can be subjected are not limited to these.

When n5 is 1, the compound represented by the formula (c4) can be synthesized according to the following reaction scheme 4, for example. In Reaction Scheme 4, a fortium derivative represented by the following formula (c4-1) was used as a raw material. _{The perylene derivative represented by the formula (c4-1) is prepared by introducing -CO-CH 2} -R ^c10 into the compound represented by the formula (c3-1) by the same method as in Reaction Scheme 3 by Friedel-Crafts reaction. It is obtained by expressing the acid base. As an acylation agent, a carboxylate halide represented by the formula (c3-8): Hal-CO-CH ₂ -R ^{c10 is preferred. Next, the methylene group present between R c10} and the carbonyl group in the compound represented by the formula (c4-1) is oximeated to obtain a ketoxime compound represented by the following formula (c4-3). The method for oximation of a methylene group is not particularly limited, but preferably a nitrite (RONO, R is 1 or more and 6 carbon atoms) represented by the following general formula (c4-2) in the presence of hydrochloric acid. The following alkyl) reaction method. Next, a ketoxime compound represented by the following formula (c4-3), an acid anhydride (R ^c11 CO) ₂ O) represented by the following formula (c4-4), or a ketoxime compound represented by the following formula (c4-5) The compound represented by the following formula (c4-6) can be obtained by reacting the halide (R ^{c11 COHal, Hal is a halogen atom).} Furthermore, in the following formulae (c4-1), (c4-3), (c4-4), (c4-5), and (c4-6), R ^c7 , R ^c8 , R ^c9 , and R ^c10 , and R ^{c11 are the} same as formula (c4).

When n5 is 1, there exists a tendency to further reduce the generation|occurence|production of the foreign material in the pattern formed using the photosensitive composition containing the compound represented by Formula (c4).

^{Moreover, in Reaction Scheme 4, R c10} contained in each of formula (c3-8), formula (c4-1), and formula (c4-3) may be the same or different. ^{That is, R c10} in the formula (c3-8), the formula (c4-1), and the formula (c4-3) can be chemically modified during the synthesis process shown in Reaction Scheme 4. Examples of chemical modification include esterification, etherification, amidation, amidation, halogenation, substitution of a hydrogen atom in an amine group with an organic group, and the like. The chemical modifications to which R ^c10 can be subjected are not limited to these.

<Reaction Scheme 4> [Chemical 29]

Suitable specific examples of the compound represented by the formula (c4) include the following PI-43 to PI-83.

[Chemical 30]

[Chemical 31]

As described above, the amount of chloride ions in the photosensitive composition is 1000 mass ppm or less. Therefore, the amount of chloride ions in the photopolymerization initiator (C) must also be reduced to some extent.

In this respect, the oxime ester compound (C1) is particularly likely to contain chloride ions due to its production method. Therefore, purification of the oxime ester compound (C1) is important.

As a method for reducing the amount of chloride ions in the oxime ester compound (C1), there can be mentioned: 1) Synthesize the oxime ester compound (C1) by a method including the step of using aluminum chloride to carry out the Friedel-Crafts reaction, and adjust the amount of aluminum chloride to be used in a manner that minimizes the content of chloride ions in the oxime ester compound. method; 2) in the synthesis of the compound represented by the oxime ester compound (C1), a method of using an acid without chlorine atom; 3) in the synthesis of the compound represented by the oxime ester compound (C1), in the Friedel-Crafts acid A method of using an acid anhydride as an acylating agent in the acylation reaction or oxime group; 4) purifying the oxime by one or more methods selected from the group consisting of distillation, recrystallization, water washing, and column chromatography The method for the crude and refined product of the compound represented by the ester compound (C1); 5) The solution obtained by dissolving the crude and refined product of the compound represented by the oxime ester compound (C1) in a hydrophobic organic solvent is washed with water, Method for recovering the compound represented by the oxime ester compound (C1) in the washed solution; and 6) dissolving the crude and refined product of the compound represented by the oxime ester compound (C1) in a hydrophobic organic compound by an anion exchange resin A method of recovering the oxime ester compound (C1) after the solution obtained in the solvent is treated.

(Compound (C2))

In the photosensitive composition, as a photopolymerization initiator (C), a compound (C2) other than the oxime ester compound is contained in addition to the above-mentioned oxime ester compound (C1). The kind of compound (C2) is not particularly limited as long as it is not an oxime ester compound and can function as a photopolymerization initiator.

、2-氯-9-氧硫

、2,4-二甲基-9-氧硫

、1-氯-4-丙氧基-9-氧硫

、硫

、2-氯硫

、2,4-二乙基硫

、2-甲基硫

、2-異丙基硫

、2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌、偶氮二異丁腈、過氧化苯甲醯、氫過氧化異丙苯、2-巰基苯并咪唑、2-巰基苯并

唑、2-巰基苯并噻唑、2-(鄰氯苯基)-4,5-二(間甲氧基苯基)-咪唑基二聚物、2-(鄰氯苯基)-4,5-二苯基咪唑基二聚物、二苯甲酮、2-氯二苯甲酮、4,4'-雙二甲胺基二苯甲酮、4,4'-雙二乙胺基二苯甲酮、4,4'-二氯二苯甲酮、3,3-二甲基-4-甲氧基二苯甲酮、苯偶醯、安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香正丁醚、安息香異丁醚、安息香丁醚、苯乙酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對第三丁基苯乙酮、對二甲胺基苯乙酮、對第三丁基三氯苯乙酮、對第三丁基二氯苯乙酮、α,α-二氯-4-苯氧基苯乙酮、9-氧硫

、2-甲基-9-氧硫

、2-異丙基-9-氧硫

、二苯并環庚酮、4-二甲胺基苯甲酸戊酯、9-苯基吖啶、1,7-雙-(9-吖啶基)庚烷、1,5-雙-(9-吖啶基)戊烷、1,3-雙-(9-吖啶基)丙烷、對甲氧基三

、2,4,6-三(三氯甲基)-均三

、2-甲基-4,6-雙(三氯甲基)-均三

、2-[2-(5-甲基呋喃-2-基)乙烯 基]-4,6-雙(三氯甲基)-均三

、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-均三

、2-[2-(4-二乙胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-均三

、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-均三

、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-均三

、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-均三

、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-均三

、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯基-均三

、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯基-均三

、2,4-雙-三氯甲基-6-(3-溴-4-甲氧基)苯乙烯基苯基-均三

、2,4-雙-三氯甲基-6-(2-溴-4-甲氧基)苯乙烯基苯基-均三

等。該等光聚合起始劑可單獨使用或組合2種以上使用。 Specific examples of the compound (C2) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyl Ethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one , bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(benzyloxyimino)-1-[4-(phenylthio) Phenyl]-1-octanone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 4-benzyl-4'-methyldimethyl sulfide, 4-dimethyl Aminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl Benzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, methyl o-benzyl benzoate, 2,4-Diethyl-9-oxosulfur

, 2-chloro-9-oxosulfur

, 2,4-dimethyl-9-oxothio

, 1-chloro-4-propoxy-9-oxothio

,sulfur

, 2-chlorosulfur

, 2,4-diethyl sulfide

, 2-methyl sulfide

, 2-isopropyl sulfide

, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzyl peroxide, isohydroperoxide Propylbenzene, 2-mercaptobenzimidazole, 2-mercaptobenzo

azole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)-imidazolyl dimer, 2-(o-chlorophenyl)-4,5 -Diphenylimidazolyl dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminodiphenyl ketone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether , benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichlorobenzene Ethyl ketone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, alpha ,α-Dichloro-4-phenoxyacetophenone, 9-oxothio

, 2-methyl-9-oxothio

, 2-isopropyl-9-oxothio

, Dibenzocycloheptanone, Amyl 4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9 -acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxytris

, 2,4,6-tris(trichloromethyl)-tris

, 2-methyl-4,6-bis(trichloromethyl)-mesotri

, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-mesotri

, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-mesotri

, 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-mesotri

, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-mesotri

, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-mesotri

, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-mesotri

, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-mesotri

, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-mesotri

, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-mesotri

, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy) styrylphenyl-mesotri

, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-mesotri

Wait. These photopolymerization initiators may be used alone or in combination of two or more.

Among these, in terms of maintaining good sensitivity and easily improving resolution, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)-imidazolylbis polymer, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer and other imidazole compounds; or 2,2-diethoxyacetophenone, p-dimethylacetophenone, 2 -Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinyl Phenyl)-butan-1-one and other alkyl phenone compounds. Among the alkyl phenone compounds, preferably 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-di α-aminoalkylphenone compounds such as methylamino-1-(4-morpholinophenyl)-butan-1-one.

The compound (C2) is preferably purified in the same manner as the oxime ester compound (C1), and the chloride ion is reduced.

The content of the photopolymerization initiator (C) is preferably 0.5 mass % or more and 30 mass % or less, more preferably 1 mass % with respect to the mass of the photosensitive composition excluding the mass of the solvent (S) described later. % or more and 20 mass % or less. By making content of a photoinitiator (C) into the said range, the photosensitive composition which is hard to produce the defect of a pattern shape can be obtained.

The content of the oxime ester compound (C1) in the photopolymerization initiator (C) is easy to achieve good performance at the same time. In terms of sensitivity and good analytical properties, it is preferably 10% by mass or more and 99.5% by mass or less, more preferably 30% by mass or more and 97% by mass or less, relative to the mass of the photopolymerization initiator (C). It is especially preferable that it is 50 mass % or more and 95 mass % or less. The content of the compound (C2) in the photopolymerization initiator (C) is preferably 0.5 mass % or more and 90 mass % or less, more preferably 1 mass % or more and 60 mass % or less, particularly preferably 10 mass % or more And 40 mass % or less.

唑、2-巰基苯并咪唑、2-巰基-5-甲氧基苯并噻唑、3-巰基丙酸、3-巰基丙酸甲酯、季戊四醇四巰基乙酸酯、3-巰基丙酸酯等硫醇化合物等。該等光起始助劑可單獨使用或組合2種以上使用。 Moreover, you may combine a photoinitiator auxiliary agent with a photoinitiator (C). Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Isoamyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'- Bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl 9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzothiazol

azole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, 3-mercaptopropionate, etc. Thiol compounds, etc. These photoinitiating aids may be used alone or in combination of two or more.

<Colorant (D)>

The photosensitive composition may contain a coloring agent (D). It does not specifically limit as a coloring agent (D). As the colorant (D), it is preferable to use, for example, a compound classified as a pigment (Pigment) in the color index (CI; issued by The Society of Dyers and Colourists), and specifically, it is preferable to use a compound with the following notes. The color index (CI) number of the compound.

Examples of yellow pigments that can be suitably used include 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, and 185.

Examples of orange pigments that can be suitably used include 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, and 73.

Examples of violet pigments that can be suitably used include CI Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39 , 40, and 50.

Examples of red pigments that can be suitably used include 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, and 265.

Examples of blue pigments that can be suitably used include 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, and 66.

Examples of pigments with hues other than the above that can be suitably used include green pigments such as CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 37; CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26 , CI Pigment Brown 28 and other brown pigments; CI Pigment Black 1, CI Pigment Black 7 and other black pigments.

Moreover, the photosensitive composition may contain a light-shielding agent as a coloring agent (D). The photosensitive composition containing the sunscreen agent can be suitably used for the formation of black matrix or black column spacer in liquid crystal display panels, or the alignment for the division of light-emitting layers in organic EL (Electroluminescence, electroluminescence) elements Formation.

In the case of using the colorant (D) as the opacifying agent, it is preferable to use a black pigment or a violet pigment as the opacifying agent. Examples of black pigments and violet pigments include carbon black, perylene-based pigments, lactamide-based pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, regardless of organic or inorganic substances. Various pigments such as metal oxides, composite oxides, metal sulfides, metal sulfates or metal carbonates.

As the carbon black, known carbon blacks such as chimney black, furnace black, thermal black, and lamp black can be used. In addition, resin-coated carbon black may also be used.

As carbon black, the carbon black which performed the process to introduce|transduce an acidic group is also preferable. The acidic group introduced into the carbon black is a functional group which exhibits the acidity of Bronsted's definition. As a specific example of an acidic group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned. Acidic groups introduced into carbon black can also form salts. The cation that forms a salt with the acidic group is not particularly limited as long as the object of the present invention is not inhibited. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and preferred are alkali metal ions such as sodium ions, potassium ions, and lithium ions, or ammonium ions.

In the carbon black that has been subjected to the above-described treatment of introducing an acid group, the feeling of use is achieved. From the viewpoint of the high resistance of the light-shielding cured film formed from the optical composition, it is preferable to have a carboxylic acid group, a carboxylate group, a sulfonic acid group, and a sulfonate group selected from the group consisting of a sulfonate group. Carbon black with one or more functional groups.

The method of introducing an acidic group to carbon black is not particularly limited. As a method of introducing an acidic group, the following method is mentioned, for example.

1) A method of introducing a sulfonic acid group to carbon black by a direct substitution method using concentrated sulfuric acid, oleum, chlorosulfonic acid, etc., or an indirect substitution method using sulfite, hydrogen sulfite, or the like.

2) A method of coupling an organic compound having an amine group and an acidic group with carbon black diazo.

3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by the etherification method of Williamson.

4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.

5) A method of deprotecting carbon black after Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.

Among these methods, the method 2) is preferable in terms of easy and safe introduction and treatment of the acidic group. The organic compound having an amine group and an acidic group used in the method 2) is preferably a compound having an amine group and an acidic group bonded to an aromatic group. Examples of such compounds include aminobenzenesulfonic acid such as sulfanilic acid, and aminobenzoic acid such as 4-aminobenzoic acid.

The molar number of the acidic group introduced into carbon black is not particularly limited within a range that does not inhibit the purpose of the present invention. The molar number of the acidic group introduced into carbon black is preferably 1 mmol or more and 200 mmol or less, and more preferably 5 mmol or more and 100 mmol or less with respect to 100 g of carbon black.

Carbon black into which an acid group is introduced can also be subjected to coating treatment with resin. When a photosensitive composition containing carbon black coated with resin is used, light-shielding and insulating properties are easily formed A light-shielding cured film with excellent properties and low surface reflectivity. In addition, the coating process by resin does not adversely affect the dielectric constant of the light-shielding cured film formed using the photosensitive composition in particular. Examples of resins that can be used for the coating of carbon black include phenol-based resins, melamine resins, xylene resins, diallyl phthalate resins, glycerol resins, epoxy resins, and alkylbenzene resins. Curable resin; or polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polystilbene, polyparaphenylene terephthalate Amine, polyamide imide, polyimide, polyamine bismaleimide, polyether polyphenylene, polyarylate, polyether ether ketone and other thermoplastic resins. The coating amount of the carbon black with the resin is preferably 1 mass % or more and 30 mass % or less with respect to the total of the mass of the carbon black and the mass of the resin.

Moreover, as a light-shielding agent, a perylene type pigment is also preferable. Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (d-1), a perylene-based pigment represented by the following formula (d-2), and a perylene-based pigment represented by the following formula (d-3). Said perylene pigment. Among the commercially available products, the product names K0084 and K0086 manufactured by BASF, or Pigment Black 21, 30, 31, 32, 33, and 34, etc., can be preferably used as the perylene-based pigments.

In formula (d-1), R ^d1 and R ^d2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^d3 and R ^d4 each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or an ethyl group. Acrylic base.

In formula (d-2), R ^d5 and R ^d6 each independently represent an alkylene group having 1 or more and 7 or less carbon atoms.

In formula (d-3), R ^d7 and R ^d8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may also contain a hetero atom of N, O, S, or P. When R ^d7 and R ^d8 are alkyl groups, the alkyl groups may be linear or branched.

The compound represented by the above formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) can be used, for example, Japanese Patent Laid-Open No. 62-1753, Japanese Patent Application Laid-Open No. 62-1753 It was synthesized by the method described in Japanese Patent Publication No. 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines are used as raw materials, and a heating reaction is performed in water or an organic solvent. Then, the obtained crude product is reprecipitated in sulfuric acid, or recrystallized in water, an organic solvent, or a mixed solvent thereof, whereby the target product can be obtained.

In order to disperse the perylene-based pigment well in the photosensitive composition, the average particle diameter of the perylene-based pigment is preferably 10 nm or more and 1000 nm or less.

Moreover, a lactamide type pigment may be contained as a light-shielding agent. As a lactamide type pigment, the compound represented by following formula (d-4) is mentioned, for example.

In the formula (d-4), X ^d represents a double bond, and as geometric isomers, each independently is an E body or a Z body, and R ^d9 independently represents a hydrogen atom, a methyl group, a nitro group, a methoxy group, and a bromine atom. , a chlorine atom, a fluorine atom, a carboxyl group, or a sulfo group, R ^d10 each independently represents a hydrogen atom, a methyl group, or a phenyl group, and R ^d11 each independently represents a hydrogen atom, a methyl group, or a chlorine atom.

The compound represented by formula (d-4) may be used alone or in combination of two or more.

R ^{d9 is preferably bonded to the 6-position of the indolinone ring, and R d11 is} preferably bonded to the indolinone ring in terms of easy production of the compound represented by the formula (d-4). 4 digits. From the same viewpoint, R ^d9 , R ^d10 , and R ^{d11 are} preferably hydrogen atoms.

The compound represented by the formula (d-4) has an EE body, a ZZ body, and an EZ body as geometric isomers, and may be any of these single compounds or a mixture of these geometric isomers.

The compound represented by the formula (d-4) can be produced, for example, by the method described in International Publication No. 2000/24736 and International Publication No. 2010/081624.

In order to disperse the lactamide-based pigment well in the composition, the average particle diameter of the lactamide-based pigment is preferably 10 nm or more and 1000 nm or less.

Furthermore, fine particles mainly composed of a silver-tin (AgSn) alloy (hereinafter referred to as "AgSn alloy fine particles") can also be preferably used as a light-shielding agent. The AgSn alloy fine particles only need to have an AgSn alloy as the main component, and as other metal components, for example, Ni, Pd, Au and the like may be contained.

The average particle diameter of the AgSn alloy fine particles is preferably 1 nm or more and 300 nm or less.

When the AgSn alloy is represented by the chemical formula AgxSn, the range of x that can obtain chemically stable AgSn alloy is 1≦x≦10, and the range of x that can simultaneously obtain chemical stability and blackness is 3≦x≦4.

Here, if the mass ratio of Ag in the AgSn alloy is obtained within the range of x above, in the case of x=1, it becomes Ag/AgSn=0.4762; in the case of x=3, it becomes 3·Ag/ Ag3Sn=0.7317; in the case of x=4, it becomes 4·Ag/Ag4Sn=0.7843; in the case of x=10, it becomes 10·Ag/Ag10Sn=0.9008.

Therefore, the AgSn alloy is chemically stable when it contains 47.6 mass % or more and 90 mass % or less of Ag, and when it contains 73.17 mass % or more and 78.43 mass % or less of Ag, it is effective relative to the amount of Ag. Obtain chemical stability and blackness.

The AgSn alloy fine particles can be produced by a general fine particle synthesis method. Examples of the fine particle synthesis method include a gas phase reaction method, a spray thermal decomposition method, an atomization method, a liquid phase reaction method, a freeze drying method, a hydrothermal synthesis method, and the like.

AgSn alloy fine particles have high insulating properties, but in order to further improve the insulating properties according to the application of the photosensitive composition, the surface may be covered with an insulating film. As a material of such an insulating film, a metal oxide or an organic polymer compound is suitable.

As the metal oxide, an insulating metal oxide can be suitably used, for example, silicon oxide (silica), aluminum oxide (alumina), zirconia (zirconia), yttria (yttria), and titanium oxide (titania) can be suitably used )Wait.

Moreover, as an organic polymer compound, the resin which has insulating property can be used suitably, for example, a polyimide, a polyether, a polyacrylate, a polyamine compound, etc. can be used suitably.

In order to sufficiently improve the insulating properties of the surface of the AgSn alloy fine particles, the thickness of the insulating film is preferably 1 nm or more and 100 nm or less, and more preferably 5 nm or more and 50 nm or less.

The insulating film can be easily formed by a surface modification technique or a surface coating technique. In particular, if an alkoxide such as tetraethoxysilane and aluminum triethoxide is used, an insulating film with a uniform thickness can be formed at a relatively low temperature, which is preferable.

As the light-shielding agent, the above-mentioned perylene-based pigments, lactamide-based pigments, and AgSn alloy fine particles may be used alone, or may be used in combination.

In addition, the light-shielding agent may contain pigments of hues such as red, blue, green, and yellow in addition to the above-mentioned black pigment or violet pigment for the purpose of adjusting the color tone. Pigments of hues other than black pigments and violet pigments can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as pigments for hues other than black pigments and violet pigments. The usage-amount of the pigment of other hues other than the black pigment or the violet pigment is preferably 15 mass % or less, more preferably 10 mass % or less, with respect to the total mass of the light-shielding agent.

In order to disperse the said coloring agent uniformly in a composition, a dispersing agent can be used further. As such a dispersant, a polyethylenimine-based, polyurethane resin-based, and acrylic resin-based polymer dispersant is preferably used. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

Furthermore, the decomposition|disassembly of a dispersing agent may generate|occur|produce a corrosive gas from the cured film of the photosensitive composition. Therefore, it is also preferable to disperse the colorant without using a dispersant.

In addition, the inorganic pigment and the organic pigment may be used independently, or two or more types may be used in combination, and in the case of combined use, it is preferably 10 parts by mass or more and 80 parts by mass relative to the total amount of 100 parts by mass of the inorganic pigment and the organic pigment. The organic pigment is used in a range of not more than 20 parts by mass, more preferably not more than 20 parts by mass and not more than 40 parts by mass.

In addition to the pigment, a dye may be used as a colorant (D) in the photosensitive composition. The dye may be appropriately selected from known materials.

染料、花青染料、萘醌染料、醌亞胺染料、次甲基染料、酞菁染料等。 Examples of dyes that can be used in the photosensitive composition of the present embodiment include azo dyes, metal zirconium salt azo dyes, anthraquinone dyes, triphenylmethane dyes,

Dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, phthalocyanine dyes, etc.

Moreover, these dyes can be used as a colorant (D) by being laked (salified) and dispersed in an organic solvent or the like.

In addition to these dyes, for example, Japanese Patent Laid-Open No. 2013-225132, Japanese Patent Laid-Open No. 2014-178477, Japanese Patent Laid-Open No. 2013-137543, and Japanese Patent Laid-Open No. 2011-38085 can also be preferably used. Dyes and the like described in Gazette No. 2014-197206 and the like.

In addition, these dyes can also be used in combination with the above-mentioned pigments (eg, perylene-based pigments, lactamide-based pigments, AgSn alloy fine particles, etc.).

The amount of the coloring agent (D) used in the photosensitive composition can be appropriately selected within a range that does not hinder the purpose of the present invention. Typically, it is preferably 5 with respect to the mass of the entire solid content of the photosensitive composition. % by mass or more and 70% by mass or less, more preferably 25% by mass or more and 60% by mass or less.

The colorant (D) is preferably added to the photosensitive composition after being prepared as a dispersion liquid dispersed at an appropriate concentration in the presence or absence of a dispersant.

In addition, in this specification, the usage-amount of the said coloring agent (D) can be defined as the value including the dispersing agent which exists.

As described above, the amount of chloride ions in the photosensitive composition is 1000 mass ppm or less. Therefore, the amount of chloride ions in the colorant (D) must also be reduced to some extent.

As a method of reducing the amount of chloride ions in the colorant (D), washing with water, an organic solvent, an aqueous solution of an organic solvent, or the like is exemplified. In the case where the colorant is a dye, the amount of chloride ions can also be reduced by contacting the obtained solution with an anion exchange resin after preparing a dye solution, and recovering the dye from the solution.

<Amine (E)>

The photosensitive composition contains an amine (E). By containing an amine (E) in a photosensitive composition, it becomes easy to prepare the photosensitive composition which has the favorable analytical property which can analyze a fine pattern.

The amine (E) may be formulated in the photosensitive composition alone, or may be formulated in the photosensitive composition as an impurity contained in other components other than the amine (E).

Examples of impurities containing an amine (E) include an alkali-soluble resin (A) containing a nitrogen atom in the form of an amide bond, a photopolymerizable compound (B) containing a nitrogen-containing compound, and a light containing a nitrogen-containing compound. Polymerization initiator (C), colorant (D) containing nitrogen-containing compound, amide bond (-CO-NH-), urethane bond (-O-CO-NH-), urea Bond (-NH-CO-NH-) resins and other colorants (D), additives such as dispersants or dispersing aids, and solvents (S) containing nitrogen-containing polar organic solvents.

When the amine (E) is formulated in the photosensitive composition as an impurity contained in the photopolymerization initiator (C), it is preferable to use an imidazole compound or an alkyl group as the compound (C2). α-aminoalkylphenone compounds of benzophenone compounds.

、嗎啉、吡咯、及咪唑等環式胺；苯胺、甲苯胺、及苯二胺等芳香族胺等。 Suitable specific examples of the amine (E) include ammonia, methylamine, ethylamine, ethanolamine, propylamine, isopropylamine, n-butylamine, n-pentylamine, n-hexylamine, diamine Methylamine, diethylamine, diethanolamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, trimethylamine, triethylamine , triethanolamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, ethylenediamine, 1,3-propanediamine, 1,4 - Chain aliphatic amines such as butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine; pyrrolidine, piperidine, piperidine

, cyclic amines such as morpholine, pyrrole, and imidazole; aromatic amines such as aniline, toluidine, and phenylenediamine, etc.

Content of the amine (E) in the photosensitive composition is not specifically limited in the range which does not inhibit the objective of this invention.

The content of the amine (E) in the photosensitive composition is preferably 5000 mass ppm or less, more preferably 3000 mass ppm or less. The content of the amine (E) in the photosensitive composition may be 2000 mass ppm or less, 1000 mass ppm or less, or 500 mass ppm or less.

The content of the amine (E) in the photosensitive composition is preferably at least 50 mass ppm, more preferably at least 100 mass ppm, particularly preferably at least 200 mass ppm, from the viewpoint of easily obtaining the desired effect.

When the content of the amine (E) in the photosensitive composition is 5000 mass ppm or less, it becomes easy to reduce the unevenness of the film thickness of the coating film when the coating film is formed using the photosensitive composition.

The content of the amine (E) in the photosensitive composition can be measured by ion chromatography.

<Solvent (S)>

The photosensitive composition contains a solvent (S) for the purpose of improving coatability or adjusting viscosity. In addition, a liquid amine compound is not contained in a solvent (S).

Specific examples of the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (poly) Alkylene glycol monoalkyl ethers; Ethylene Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), (Poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Other ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and other lactic acid alkyl esters; 2 -Hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropionate, 3-methoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate ester, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-Methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, propyl acetate n-butyl acid, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, Ethyl acetate, ethyl 2-oxybutyrate and other esters; Aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N,N-dimethylformamide , N,N-Dimethylacetamide, N,N-Dimethylisobutylacetamide, N,N-Diethylacetamide, N,N-Diethylformamide, N-methylacetamide Nitrogen-containing polar organic solvents such as caprolactam, 1,3-dimethyl-2-imidazolidinone, pyridine, and N,N,N',N'-tetramethylurea; etc.

Among them, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, lactic acid alkyl esters, and the above-mentioned other esters are preferable, and the above-mentioned other esters are more preferable. Alkylene glycol monoalkyl ether acetates, other ethers mentioned above, and other esters mentioned above.

Moreover, it is also preferable that the solvent (S) contains a nitrogen-containing polar organic solvent from the viewpoints of the solubility of each component, the dispersibility of the colorant (D), and the like. The nitrogen-containing polar organic solvent is preferably N,N,N',N'-tetramethylurea.

These solvents may be used alone or in combination of two or more.

Among the above-mentioned solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol are preferred. Methyl ethyl ether, cyclohexanone, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are particularly preferably used.

The content of the solvent (S) is preferably such that the solid content concentration of the photosensitive composition is 5 mass % or more and 99 mass % or less, more preferably the solid content concentration of the photosensitive composition is 15 mass % or more and 50 mass % or more. mass % or less.

As described above, the amount of chloride ions in the photosensitive composition is 1000 mass ppm or less. Therefore, the amount of chloride ions in the solvent (S) must also be reduced to some extent.

As a method of reducing the amount of chloride ions in the solvent (S), distillation, treatment with an anion exchange resin, and the like are exemplified.

<Other ingredients>

The photosensitive composition may contain additives such as surfactants, adhesion improving agents, thermal polymerization inhibitors, antifoaming agents, and silane coupling agents as necessary. Any of the additives can be used previously known.

It is preferable that the photosensitive composition contains a silane coupling agent from the viewpoint of being easy to form a cured film having a favorable shape and excellent adhesion to a substrate. As the silane coupling agent, those previously known can be used without particular limitation.

Examples of surfactants include compounds of anionic, cationic, and nonionic systems, examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monoethyl ether, and the like, and examples of antifoaming agents include polysiloxane-based, fluorine-based compounds, etc.

<Preparation method of photosensitive composition>

The photosensitive composition described above can be obtained by mixing each of the above-mentioned components in a specific amount, respectively. Afterwards, it is obtained by uniformly mixing with a mixer. Furthermore, a filter can also be used to make the obtained mixture more homogeneous.

Moreover, in order to reduce the chloride ion content of a photosensitive composition to a desired value, you may process a photosensitive composition with an anion exchange resin.

≪Method of suppressing foreign matter in film formed using photosensitive composition≫

The photosensitive composition used in the method of suppressing foreign matter in the film formed using the photosensitive composition contains the above-mentioned alkali-soluble resin (A), photopolymerizable compound (B), photopolymerizable compound, respectively. Starter (C), solvent (S), and amine (E). The photosensitive composition may further contain optional components such as a colorant (D).

By making the quantity of the chloride ion in this photosensitive composition 1000 mass % or less, generation|occurrence|production of the foreign material in the film formed using the photosensitive composition can be suppressed.

The amount of foreign matter is the amount of foreign matter detected by a foreign matter detector in a film having a thickness of 1 μm obtained by spin-coating the photosensitive composition on a 10 cm×10 cm substrate, followed by drying.

By the above-described method, the number of foreign objects described above can be suppressed to less than 1,000.

≪How to form a cured film≫

A cured film is formed by hardening the thin film formed using the photosensitive composition demonstrated above by exposure.

As a use of a cured film, an insulating film is mentioned. When the photosensitive composition does not contain a colorant (D), a transparent insulating film is formed. When the photosensitive resin composition contains a colorant (D), a colored insulating film is formed. In particular, when the colorant (D) is a light-shielding agent, a light-shielding insulating film is formed.

Suitable examples of the light-shielding black insulating film include those for various image display devices. The panel has black partition walls or black column spacers in the black matrix.

Moreover, when the photosensitive resin composition contains chromatic coloring agent (D), such as RGB, a colored cured film can be formed in the area|region divided by a black matrix, and a color filter can be manufactured.

For example, the above-mentioned black matrix or a color filter including a colored cured film can be suitably used in various display devices.

As a suitable manufacturing method of a cured film, the method which consists of the process of apply|coating the above-mentioned photosensitive composition on a board|substrate, forming a coating film, and exposing the coating film can be mentioned.

When forming a cured film using a photosensitive composition, the photosensitive composition is apply|coated to the board|substrate selected by the use of a cured film, and a coating film is formed. The method of forming the coating film is not particularly limited, and for example, a contact transfer type coating device such as a roll coater, a reverse coater, and a bar coater, a spinner (rotary coating device), a curtain type coating device, etc. can be used. A non-contact coating apparatus such as a coater is used.

If necessary, the applied photosensitive composition is dried to constitute a coating film. The drying method is not particularly limited, but for example, (1) drying on a hot plate at a temperature of 80° C. or higher and 120° C. or lower, preferably 90° C. or higher and 100° C. or lower, for 60 seconds or more and 120 seconds or less. (2) The method of placing it at room temperature for more than a few hours and less than a few days; (3) The method of placing it in a hot air heater or infrared heater for more than tens of minutes and less than a few hours to remove the solvent Wait.

Next, the coating film is exposed to light. Exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light. Exposure can be performed selectively by position, for example, by a method of exposing through a negative mask. The amount of energy rays to be irradiated varies depending on the composition of the photosensitive resin composition, but is preferably about 40 mJ/cm ² or more and 200 mJ/cm ² or less, for example.

In the case where the coating film is selectively exposed to light, it is patterned into a desired shape by developing the exposed film with a developing solution. The development method is not particularly limited, and for example, a dipping method, a spray method, or the like can be used. The developer can be appropriately selected according to the composition of the photosensitive composition. As the developer, for example, alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts can be used.

The cured film formed by the entire surface exposure, or the developed patterned cured film may be post-baked at a temperature of 120° C. or higher and 250° C. or lower as needed.

The cured film formed as described above has a small content of foreign matter and can be finely patterned, and thus can be suitably used for various applications.

[Example]

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

[Example]

In Examples and Comparative Examples, 100 parts by mass of the oxime ester compound (C1) of the type described in Table 1 and 25 parts by mass of the compound (C2) of the type described in Table 1 so that the solid content was 15% by mass parts, 310 parts by mass of alkali-soluble resin (solid content 55% by mass, solvent: 3-methoxybutyl acetate), 175 parts by mass of dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), and carbon 3-methoxybutyl acetate was added to a mixture of 450 parts by mass of a black dispersion liquid (CF Black, manufactured by Yukoku Color Co., Ltd.), and the mixture was stirred until uniform to obtain a photosensitive composition.

As the alkali-soluble resin, the same resin as the resin A-1 described in paragraphs [0063] to [0064] of Japanese Patent Laid-Open No. 2010-32940 was used.

For the obtained photosensitive composition, the content of amine is determined by ion chromatography, and The chloride ion content was determined by ion chromatography. Table 1 describes the amine content and chloride ion content of each photosensitive composition.

The types of amines E1, E2, and E3 in Table 1 are as follows.

E1: Morpholine

E2: Triethylamine

E3: Imidazole

In addition, the amine content in the photosensitive composition of Examples 1-3, Examples 6-11, Comparative Examples 1-6, and Comparative Examples 8-12 was adjusted by the degree of refinement|purification of the compound (C2).

The amine content in the photosensitive compositions of Example 4, Example 5, and Comparative Example 7 was obtained by using a compound (C2) that does not substantially contain amine, and adding a specific amount of triethylamine to the photosensitive composition And adjust.

In addition, the chloride ion content in each photosensitive composition is adjusted by the degree of refinement|purification of the oxime ester compound (C1).

In Examples and Comparative Examples, the following C1a and the following C1b were used as the oxime ester compound (C1).

In Examples and Comparative Examples, the following C2a, C2b, and C2c were used as the compound (C2).

C2a: 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one

C2b: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one

C2c: 2-(o-Chlorophenyl)-4,5-diphenylimidazolyl dimer

About the obtained photosensitive composition, foreign matter, analytical property, sensitivity, and coating property were evaluated according to the following methods. These evaluation results are described in Table 1.

(Foreign body evaluation)

Using a spin coater, the photosensitive resin composition was applied to a glass of 10 cm×10 cm to form a coating film. Next, the coating film was heated at 100° C. for 120 seconds with a hot plate to remove the solvent from the coating film, thereby obtaining a coating film having a film thickness of 1 μm.

The number of foreign substances in the obtained coating film was measured by a foreign substance detector, and it was determined that the number of foreign substances was 1000 or more as ×, and the number of foreign substances less than 100 was determined to be ○.

(analytical evaluation)

Using a spin coater, the photosensitive resin composition was applied to a glass of 10 cm×10 cm to form a coating film. Next, the coating film was heated at 100° C. for 120 seconds with a hot plate to remove the solvent from the coating film, thereby obtaining a coating film having a film thickness of 1 μm.

The obtained coating film was exposed ^{at an exposure amount of 50 mJ/cm 2 through a} photomask in which lines with line widths of 2, 4, 6, 8, 10, 12, 14, 16, 18, and 20 μm were drawn.

After exposure, the coating film was developed for 60 seconds using a KOH aqueous solution having a concentration of 0.05 mass %, and the smallest line width in the drawn pattern was confirmed.

The case where the minimum line width was 10 μm or more was judged as ×, and the case where the minimum line width was less than 10 μm was judged as ○.

(sensitivity evaluation)

Using a spin coater, the photosensitive resin composition was applied to a glass of 10 cm×10 cm to form a coating film. Next, the coating film was heated at 100° C. for 120 seconds with a hot plate to remove the solvent from the coating film, thereby obtaining a coating film having a film thickness of 1 μm.

The obtained coating film was exposed ^{to light with an exposure amount of 50 mJ/cm 2 through a} mask on which lines with a line width of 20 μm were drawn.

After exposure, the coating film was developed for 60 seconds using a KOH aqueous solution having a concentration of 0.05 mass %, and the drawn pattern was confirmed.

The same operation was performed with exposure amounts of 25mJ/cm ² , 75mJ/cm ² and 100mJ/cm ^{2 .}

The case where a pattern of the desired size was obtained with an exposure amount of 75 mJ/cm ² or more was determined as ×, and the case where a pattern of the desired size was obtained with an exposure amount of 50 mJ/cm ² or less was determined as ○.

(Applicability evaluation)

The film thickness of the coating film used for the foreign matter measurement was measured at 10 points, and the difference between the maximum film thickness and the minimum film thickness was calculated. In addition, any photosensitive composition is a level which does not have a problem with coatability. This evaluation is a comparison of the coating properties within the range without problems.

The case where the film thickness difference was 0.1 μm or more was judged as ◯, and the case where the film thickness difference was less than 0.1 μm was judged as ⊚.

As can be seen from Table 1, when the alkali-soluble resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C), the solvent (S), and the amine (E) are contained, and the photopolymerization initiator (C) ) In the photosensitive compositions of Examples containing an oxime ester compound (C1) and a compound (C2) other than the oxime ester compound, and the amount of chloride ions in the photosensitive composition is 1,000 mass ppm or less, foreign matter protection is achieved at the same time. Suppression and good resolution.

Claims (6)

A photosensitive composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a solvent (S), and an amine (E), and wherein the photopolymerization is initiated The starting agent (C) contains an oxime ester compound (C1), a compound (C2) other than the above-mentioned oxime ester compound, and the above-mentioned compound (C2) is one selected from the group consisting of alkyl phenone compounds and imidazole compounds Above, the above-mentioned amine (E) is one or more selected from the group consisting of chain-like aliphatic amines, cyclic amines, and aromatic amines, and the above-mentioned cyclic amines are selected from pyrrolidine, piperidine

, morpholine, and one or more of the group consisting of pyrrole, and the amount of chloride ions in the photosensitive composition is 1000 mass ppm or less. A photosensitive composition containing an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D), a solvent (S), and an amine (E) , and the above-mentioned photopolymerization initiator (C) contains an oxime ester compound (C1) and a compound (C2) other than the above-mentioned oxime ester compound, and the above-mentioned compound (C2) is selected from the group consisting of alkyl phenone compounds and imidazole compounds. One or more of the group, and the amount of chloride ions in the photosensitive composition is 1000 mass ppm or less. The photosensitive composition of Claim 1 which further contains a coloring agent (D). The photosensitive composition of any one of Claims 1-3 whose content of the said amine (E) in the said photosensitive composition is 5000 mass ppm or less. A method for forming a cured film, comprising: applying the photosensitive composition according to any one of claims 1 to 4 on a substrate to form a coating film; and exposing the coating film to light. The method for forming a cured film according to claim 5, comprising subjecting the coating film to position-selective exposure, and then developing the exposed coating film.